JP2023092472A - Exterior film for interior display device - Google Patents

Abstract

To provide an exterior film which is suitable for exterior of an interior display device, is flexible, is excellent in discoloration resistance against ultraviolet rays and heat while keeping excellent transparency, and is made of a polyester elastomer resin composition.SOLUTION: An exterior film of an interior display device is composed of a polyester elastomer resin composition which contains 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 polyether unit and/or an aliphatic polyester unit, contains with respect to 100 pts.mass of the polyester block copolymer (A), 0.01-3 pts.mass of an alkali metal salt (B) of an aliphatic carboxylic acid having 10 or more and 20 or less carbon atoms, 0.2-20 pts.mass of an ethylene copolymer (C) having a carboxylic acid metal base at a side chain, 0.05 pts.mass or more and 1.0 pts.mass or less of a hindered phenolic radical scavenger (D) composed of carbon, hydrogen and oxygen, and 0.05-1.0 pts.mass of a peroxide decomposer (E), and has total light transmittance when a sheet with thickness of 2 mm is measured of 5% or more, a haze value (cloud degree) of 95% or less, and surface hardness according to JIS K 7215 of 20-50 D.SELECTED DRAWING: None

Description

The present invention relates to an exterior film for an interior display device.

CMF (color, material, finish) design in automobile design plays a role in conveying the concept of the vehicle and expanding the choices of the user. In automobile cabins, for example, the use of synthetic leather instead of genuine leather is increasing for seat materials, and vinyl chloride and urethane resin are being used as synthetic leather materials, and various synthetic resins are being used. Leather materials are required to have good tactile sensation and designability because they are touched by people, so flexible materials are required.

In particular, automobile interior parts are installed in the interior of the vehicle. Since the heat deterioration caused by the high temperature in the vehicle interior is a major factor in deterioration, materials that are resistant to discoloration due to ultraviolet rays and heat are required.

In addition, many display devices are also used in buildings (stores, hotels, general houses, etc.), and the materials used for the exterior of such interior display devices in vehicle interiors and buildings improve visibility. It is required to have high transparency for the purpose of being visible to the public, good tactile sensation and designability, and no reduction in transparency, hue, and mechanical strength due to ultraviolet rays that enter the room through glass windows and the like.

According to Patent Document 1, a polycarbonate resin is used for the exterior of the instrument panel of the driver's seat of an automobile. There have been proposals for interior parts with a high degree of design in which a display body consisting of light figures and characters is displayed as a watermark on the surface of the skin (exterior) as necessary, and according to Patent Document 2, translucency is According to Patent Document 3, a vehicle interior part using a smoke-colored acrylic resin for the exterior, a vehicle display device using a translucent urethane resin for the exterior, and a translucent olefin-based thermoplastic according to Patent Document 4 An example of the use of elastomers is given.

Japanese Patent No. 5301847 Japanese Patent No. 6350332 Japanese Patent No. 4900877 Japanese Patent No. 6677666

In Patent Document 1, a polycarbonate resin is used for the exterior of the interior display device, but a hard material such as polycarbonate resin is useful for structural parts, but as an exterior film, it has a poor tactile feel and is difficult to design. Gender may be limited.

In Patent Document 2, a translucent acrylic resin is used for the exterior, but since it is more flexible than polycarbonate resin, it provides a good tactile sensation. Excessive heat shrinkage occurs when exposed to

In Patent Document 3, a translucent urethane resin is used for the exterior, but since it is a material that is more flexible than polycarbonate resin, it has a good tactile feel, but it is thought that it has better heat resistance than acrylic resin. However, since it contains urethane bonds (-N-H-C=O-) in its structure, it is considered that it is greatly discolored by light and ultraviolet rays due to its structure.

In Patent Document 4, a translucent olefin-based thermoplastic elastomer is used for the exterior. It is thought that discoloration due to UV rays is small, but the display part is unclear due to scattering of light due to the finely dispersed rubber component. In addition, it is considered that due to the structure of the olefinic elastomer, the heat resistance is poorer than that of the urethane elastomer and the polyester elastomer.

Therefore, the present inventors focused on a flexible polyester elastomer resin composition, and thought that a film made of a specific polyester elastomer resin composition could be preferably used as an exterior film for an interior display device. made diligent efforts.

An object of the present invention is to provide a film made of a polyester elastomer resin composition which is suitable for an exterior film of an interior display device and which is flexible and has excellent color resistance to ultraviolet rays and heat while maintaining excellent transparency. to do.

(1) High melting point crystalline polymer segment (a) composed of crystalline aromatic polyester units (10 to 50% by mass) and low melting point polymer segment (b) composed of aliphatic polyether units and/or aliphatic polyester units 90 to 50% by mass of the polyester block copolymer (A), relative to 100 parts by mass of the polyester block copolymer (A), an alkali metal salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms (B ) 0.01 to 3 parts by mass, 0.2 to 20 parts by mass of an ethylene copolymer (C) having a carboxylic acid metal group in the side chain, and a hindered phenolic radical scavenger (D) consisting of carbon, hydrogen and oxygen. A polyester elastomer resin composition containing 0.05 parts by mass or more and 1.0 parts by mass or less and 0.05 to 1.0 parts by mass of a peroxide decomposer (E). An interior display device characterized by having a total light transmittance of 5% or more, a haze value (cloudiness) of 95% or less, and a surface hardness of 20 to 50D according to JIS K7215, as measured by a sheet with a thickness of 2 mm. exterior film.
(2) The polyester elastomer resin composition contains 0.05 to 2.5 parts by mass of an ultraviolet absorber (F) and 0.05 part by mass of a hindered amine compound (G) per 100 parts by mass of the polyester block copolymer (A). 01 to 2.5 parts by mass of the exterior film for an interior display device according to (1).
(3) The exterior film for an interior display device according to (1) or (2), wherein the hindered amine compound (G) has a tertiary amine series.
(4) The ultraviolet absorber (F) is one or more selected from the group consisting of benzotriazole-based compounds, triazine-based compounds, and cyanoacrylate-based compounds, according to (2) or (3). Exterior film for interior display devices.
(5) The exterior film for an interior display device according to any one of (1) to (4), which is used for the interior of an automobile.
(6) The exterior film for an interior display device according to any one of (1) to (5), which is used for instrument panels and skins.

It is possible to provide an exterior film made of a polyester elastomer resin composition that is suitable for an interior display device, is flexible, maintains excellent transparency, and is excellent in discoloration resistance to ultraviolet light and heat.

The exterior film of the interior display device of the present invention comprises a polyester elastomer resin composition. The polyester elastomer resin composition used for the exterior film of the interior display device of the present invention has a total light transmittance of 5% or more and a haze value (cloudiness) of 95% or less, as measured by a sheet having a thickness of 2 mm. The surface hardness according to JIS K7215 is 20-50D. As described below, total light transmittance and haze value (haze) are measured according to ASTM D1003. Surface hardness is measured according to JIS K7215 as described above.

A polyester elastomer resin composition having a total light transmittance of 5% or more and a haze value (haze) of 95% or less as measured on a sheet with a thickness of 2 mm is visually transparent or semi-transparent. It is transparent but has translucency, and when this sheet is placed on the printed matter, the characters can be read sufficiently. It includes even those that can be seen very clearly. In addition, when the light source, the printed matter, and the sheet of 2 mm thickness are stacked in this order, the printed matter cannot be seen at all when the light source is not illuminated, but the printed matter can be seen when the light source is illuminated. A sheet with a thickness of 2 mm that has a total light transmittance of less than 5% and a haze value (haze) of greater than 95% is opaque and has neither translucency nor transparency. When the sheet is put down, the letters cannot be read at all. Also, when the light source, the printed matter, and the sheet with a thickness of 2 mm are stacked in this order, even when the light source emits light, it cannot be seen at all. Sheets with a thickness of more than 2 mm are cut to a thickness of 2 mm, and sheets with a thickness of less than 2 mm are overlapped to a thickness of 2 mm.

Polyester elastomer resin compositions having a surface hardness of 20 to 50D according to JIS K7215 measured on a 2 mm thick sheet include those that deform greatly when pressed with a finger, and those that deform slightly when pressed with a finger. If the surface hardness is less than 20D, the strength is insufficient, and if the surface hardness is greater than 50D, a soft feel cannot be obtained.

The polyester elastomer resin composition of the present invention comprises 10 to 50 parts by mass of a high melting point crystalline polymer segment (a) comprising crystalline aromatic polyester units and a low polyether comprising aliphatic polyether units and/or aliphatic polyester units. A polyester block copolymer (A) containing 90 to 50 parts by mass of a melting point polymer segment (b), and an aliphatic carboxylic acid having 10 to 20 carbon atoms per 100 parts by mass of the polyester block copolymer (A) 0.01 to 3 parts by mass of an alkali metal salt (B) of, 0.2 to 20 parts by mass of an ethylene copolymer (C) having a carboxylic acid metal group in the side chain, a hindered phenol system consisting of carbon, hydrogen and oxygen It contains 0.05 to 1.0 parts by mass of a radical scavenger (D) and 0.05 to 1.0 parts by mass of a peroxide decomposing agent (E). The polyester elastomer resin composition of the present invention preferably contains 0.05 to 2.5 parts by mass of an ultraviolet absorber (F) and 0.01 to 2.5 parts by mass of a hindered amine compound (G).

The polyester block copolymer (A) in the present invention comprises a high melting point crystalline polymer segment (a) composed of crystalline aromatic polyester units and a low melting point polymer segment (a) composed of aliphatic polyether units and/or aliphatic polyester units. coalescence segment (b).

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 terephthalic acid. and/or polybutylene terephthalate derived from dimethyl terephthalate and 1,4-butanediol, but also 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 diols having a molecular weight of 300 or less, such as ethylene glycol and trimethylene. Aliphatic diols such as glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol and decamethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and tricyclodecanedimethylol; xylylene glycol; -hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxy)phenyl]sulfone, 1,1-bis Polyesters derived from aromatic diols such as [4-(2-hydroxyethoxy)phenyl]cyclohexane, 4,4′-dihydroxy-p-terphenyl, 4,4′-dihydroxy-p-quarterphenyl, etc., or these It may be a copolyester in which two or more dicarboxylic acid components and diol components are used in combination. It is also possible to copolymerize trifunctional or higher polyfunctional carboxylic acid components, polyfunctional oxyacid components, polyfunctional hydroxy components, and the like in an amount of 5 mol % or less.

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

Aliphatic polyesters include poly(ε-caprolactone), polyenantholactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate. Poly(tetramethylene oxide) glycol, ethylene oxide adducts of poly(propylene oxide) glycol, poly(ε-caprolactone), and poly(ε-caprolactone) have ), polybutylene adipate, polyethylene adipate and the like are preferred. The number average molecular weight of these low-melting polymer segments is preferably about 300 to 6000 in the copolymerized state.

The copolymerization amount of the high melting point crystalline polymer segment (a) in the polyester block copolymer (A) in the present invention 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, crystallinity will be 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 desired transparency of the present invention cannot be sufficiently exhibited.

The polyester block copolymer (A) in the invention can be produced by a known method. For example, a method of subjecting a lower alcohol diester of a dicarboxylic acid, an excessive amount of a low molecular weight glycol, and a low melting point polymer segment component to a transesterification reaction in the presence of a catalyst, and polycondensing the resulting reaction product. Alternatively, a dicarboxylic acid, an excess amount of glycol and a low melting point polymer segment component are esterified in the presence of a catalyst, and the resulting reaction product is polycondensed. Alternatively, a high-melting-point crystalline segment is prepared in advance, and a low-melting-point segment component is added thereto to effect randomization by transesterification. A method of linking a high melting point crystalline segment and a low melting point polymer segment with a chain linking agent. Furthermore, when poly(ε-caprolactone) is used for the low melting point polymer segment, any method such as addition reaction of ε-caprolactone monomer to the high melting point crystalline segment may be employed.

The polyester elastomer resin composition in the present invention contains 0.01 to 3 parts by mass of an alkali metal salt (B) of an aliphatic carboxylic acid having 10 to 20 carbon atoms. It preferably has 10 or more and 18 or less carbon atoms, more preferably 10 or more and 15 or less carbon atoms. Aliphatic carboxylic acid is a compound in which a carboxyl group is attached to a linear or branched aliphatic group, and part of the bond includes an unsaturated group, an alicyclic group, an aromatic group, a hydroxyl group, or a phosphate ester group. You may have other substituents such as 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), tuberculostearic acid (19 carbon atoms), arachidic acid (20 carbon atoms), and the like. Among them, capric acid, lauric acid, myristic acid, tridecylic acid, myristic acid, and pentadecylic acid are preferred. Among alkali metal salts, sodium salts are preferred in terms of solubility in polyester elastomers and good crystal nucleation. The alkali metal salts (B) of aliphatic carboxylic acids having 10 to 20 carbon atoms may be used singly or in combination of two or more.

The alkali metal salt (B) of an aliphatic carboxylic acid having 10 to 20 carbon atoms is an aliphatic It is a carboxylic acid alkali metal salt. Alkali metal salts of aliphatic carboxylates having 9 or less carbon atoms are preferable in that they can improve transparency even when mixed in small amounts, but they cause bleeding out due to their short carbon chains. On the other hand, an aliphatic carboxylic acid alkali metal salt having a carbon number of more than 20 is preferable in terms of suppressing bleed-out due to its long carbon chain, inhibiting the crystallinity of the polyether ester block copolymer, and improving transparency. However, a large amount of addition is necessary to obtain sufficient transparency, and a large amount of addition causes bleeding out.

The amount of the alkali metal salt (B) of an aliphatic carboxylic acid having 10 to 20 carbon atoms is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyester block copolymer (A). . The amount of the alkali metal salt (B) of an aliphatic carboxylic acid having 10 to 20 carbon atoms to be added is more preferably 0.05 to 2 parts by mass, still more preferably 0.1 to 1 part by mass.

If the amount of the alkali metal salt (B) of an aliphatic carboxylic acid having 10 to 20 carbon atoms exceeds 3 parts by mass, a large amount of gas is generated during processing, possibly affecting moldability.

The polyester elastomer resin composition in the present invention contains an ethylene copolymer (C) having a carboxylic acid metal group in the side chain. The ethylenic copolymer (C) having a carboxylic acid metal group in the side chain is a copolymer of ethylene and an ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid. , alkaline earth metal ions, zinc ions, etc. These are commercially available, for example, as "Surlyn" from DuPont or "Himilan" from Mitsui-Dow Polychemicals. Among them, those neutralized with alkali metal ions such as sodium, potassium and lithium are preferable.

The ethylene copolymer (C) having a carboxylic acid metal group in these side chains is 0.2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyester block copolymer (A). Preferably, 0.5 to 15 parts by mass, particularly preferably 1 to 10 parts by mass.

If the amount of the ethylene copolymer (C) having a carboxylic acid metal group in the side chain is less than 0.2 parts by mass, the translucency and transparency are insufficient, and if it is 20 parts by mass or more, phase separation occurs. , it is thought that the mechanical properties, translucency, transparency, and separation from the mold during molding are reduced.

The polyester elastomer resin composition in the present invention contains a hindered phenolic radical scavenger (D) consisting of carbon, hydrogen and oxygen and a peroxide decomposer (E). The hindered phenol-based radical scavenger (D) and the peroxide decomposer (E) comprising carbon, hydrogen and oxygen are used as antioxidants for suppressing thermal discoloration of the polyester elastomer resin composition. In addition, since the hindered phenol-based radical scavenger (D) and the peroxide decomposer (E) consisting of carbon, hydrogen and oxygen act as nucleating agents, an alkali metal salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms Transparency is improved by using together with (B) and an ethylene-based copolymer (C) having a carboxylic acid metal group in a side chain.

The amount of the hindered phenol-based radical scavenger (D) composed of carbon, hydrogen and oxygen is 0.05 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the polyester block copolymer (A). be. It is preferably 0.05 to 0.50 parts by mass, more preferably 0.05 to 0.25 parts by mass, and most preferably 0.05 to 0.15 parts by mass.

The amount of the peroxide decomposer (E) is 0.05 parts by mass to 1.0 parts by mass with respect to 100 parts by mass of the polyester block copolymer (A). It is preferably 0.05 to 0.75 parts by mass, more preferably 0.05 to 0.50 parts by mass, and most preferably 0.05 to 0.30 parts by mass.

The amounts of the hindered phenol radical scavenger (D) consisting of carbon, hydrogen and oxygen and the peroxide decomposer (E) are If the content of the oxide decomposer (E) is less than 0.05 parts by mass, the effect of preventing thermal deterioration is poor. When the amount of the hindered phenolic radical scavenger (D) consisting of carbon, hydrogen and oxygen and the peroxide decomposer (E) exceeds 1.0 parts by mass, bleed out, discoloration due to heat, initial color tone, and appearance problems arise.

The hindered phenol radical scavenger (D) consisting of carbon, hydrogen and oxygen is preferably added during polymerization, but may be added to the polyester block copolymer after polymerization.

The resin composition of the present invention may contain an antioxidant other than the hindered phenol-based radical scavenger (D) consisting of carbon, hydrogen and oxygen and the peroxide decomposer (E). , a hindered phenolic radical scavenger (D) consisting of hydrogen and oxygen, and a peroxide decomposer (E) only.

Examples of the hindered phenolic radical scavenger (D) consisting of carbon, hydrogen and oxygen 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-hydroxy-benzenepropanoic acid, pentaerythritol tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate, 3-(4-hydroxy-3, 5-diisopropylphenyl)octyl propionate 2,4-dimethyl-6(-1-methylpentadecyl)phenol, bis(3-t-butyl-4-hydroxy-5-methylbenzenepropanoate)ethylene bis(oxyethylene) , 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 4,4′,4″-(1-methylpropanyl-3-indene) Tris(6-t-butyl-m-cresol), 6,6'-di-t-butyl-4,4'-butylidenedi-m-cresol, octadecyl 3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and the like.

Phosphorus-based peroxide decomposers and sulfur-based peroxide decomposers are preferable as the peroxide decomposer (E). Among the phosphorus-based peroxide decomposers, there are peroxide decomposers that have hygroscopicity, so from the viewpoint of handling, sulfur-based antioxidants are more preferable.

Phosphorus-based peroxide decomposers 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(monononylphenyl)phosphite, triphenoxyphosphine, isodecylphos Phyto, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl ]methyl]phosphonate, trisnonylphenyl phosphite, tricresylphosphite, triethylphosphite, tris(2-ethylhexyl)phosphite, tridecylphosphite, trilaurylphosphite, tris(tridecyl)phosphite, trioleylphosphite Phyto, diphenylmono(2-ethylhexyl)phosphite, diphenylmonodecylphosphite, diphenylmono(tridecyl)phosphite, trilauryltrithiophosphite, diethylhydrogenphosphite, bis(2-ethylhexyl)hydrogenphosphite, dilaurylhydrogen Phosphites, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene Diphenylphosphite, bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, tristearyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) Phosphite, triisooctylphosphite, triisodecylphosphite, trioctadecylphosphite, tetraphenyltetratridecylpentaerythritol tetraphosphite, diethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphoric acid, phenyldiisodecylphosphite, diphenyldecylphosphite, diphenylisodecylphosphite, diphenyl(tridecyl)phosphite, tris(cyclohexylphenyl)phosphite, tris(4-phenylphenol)phosphite, diphenylnonylphenylphosphite, di(nonylphenyl) dinonylphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl 4,4'-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl) pentaerythritol di Phosphite, bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogenphosphite, diisodecylpentaerythritol phosphite, tris(2,4-di-t- butylphenyl)phosphite, cyclic neopentanetetraylbi(2,4-di-t-butylphenyl)phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triphenylphosphite Phyto, 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 neopentanetetraylbi(2,4-di-t-butyl-4-methylphenyl)phosphite, cyclic and neopentanetetrayl bis(octadecyl) phosphite.

Sulfur-based peroxide decomposers include dilaurylthiopropionate, distearyltheodipropionate, laurylstearyltheodipropionate, dimyristylthiodipropionate, and dioctadecyl 3,3'-thiodipropionate. , dioctadecyl 3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate dilauryl-3,3-thiodipropionate, dimyristyl-3,3'-thiodipropionate, dilauryl thiodipropionate, ditridecyl thiodipropionate, dimistil thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodipropionate, distearyl-β,β'-thiodibutyrate, 3,3' Thiodipropionic acid, pentaerythritol tetra(β-laurylthiopropionate), bis[3,3′-bis(4′hydroxy-3′-tert-butylphenyl)butyric acid]glycol ester, thiodiethylene- bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate.

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 before the ultraviolet light acts on the polymer chain, the ultraviolet absorber itself absorbs the ultraviolet light and converts it into harmless substances such as heat. It is used to prevent deterioration of the polymer chain itself. The hindered amine-based compound (G) is used to supplement radicals generated by ultraviolet rays. The hindered amine compound (G) preferably has a tertiary amine series. When the class of amine is primary or secondary, the weather resistance is improved, but discoloration due to heat may occur.

Since the ultraviolet absorber (F) and the hindered amine compound (G) have different mechanisms for suppressing discoloration due to light, their combination produces a synergistic effect. In addition, since the addition of the ultraviolet absorber (F) and the hindered amine compound (G) acts as a nucleating agent, an alkali metal salt (B) of an aliphatic carboxylic acid having 10 to 20 carbon atoms and a carboxylic acid metal base on the side chain Transparency improves by using together with the ethylene-based copolymer (C) having

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, p- t-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-amyl-phenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzylphenyl)benzotriazole , 2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)-5-chlorobenztriazole, 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, phenyl salicylate and the like.

The ultraviolet absorber (F) is preferably one or more selected from the group consisting of benzotriazole-based compounds, triazine-based compounds, and cyanoacrylate-based compounds. Among them, in order to improve appearance, an ultraviolet absorber having a low absorbance in the wavelength region of 360 mm or more, which is the wavelength in the visible light region, is preferable.

As the hindered amine compound (G), a polymer 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-4-piperidyl) sebacate, dimethyl succinate 1-(2-hydroxyethyl)-4-hydroxy-2 , 2,6,6-tetramethylpiperidine polycondensate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl-malonate bis(1,2,2,6 ,6-pentamethyl-4-piperidyl), bis (1,2,2,6,6,-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate , 2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanedioate bis[1,2,2,6,6-pentamethyl-4-piperidinyl ] etc. can be mentioned.

Among the hindered amine compounds (G), the amine series is preferably tertiary. Most preferred is a structure in which all atoms bonded to nitrogen atoms are carbon atoms.

The blending amount of the ultraviolet absorber (F) and the hindered amine compound (G) is preferably 0.1 to 2.5 parts by mass each with respect to 100 parts by mass of the polyester block copolymer (A). More preferably 0.1 to 2.0 parts by mass, particularly preferably 0.1 to 1.0 parts by mass.

The polyester elastomer resin composition in the present invention may contain a light stabilizer other than the ultraviolet absorber (F) and the hindered amine compound (G), but the ultraviolet absorber (F) and the hindered amine compound (G) is preferably contained.

The polyester elastomer resin composition in the present invention may contain a coloring agent (H). Both pigments and dyes can be used as the coloring agent (H). Among them, pigments are preferable from the viewpoint of durability and weather resistance. The pigment is not particularly limited, and one or more of various conventionally known inorganic pigments, organic pigments, etc. can be appropriately selected and used to achieve a desired hue. Examples of pigments include inorganic pigments and organic pigments such as carbon black, titanium black, ultramarine, organic metal salts, metal oxides, metal sulfides, metal nitrides, metal oxalates, metal carbonates, and titanium dioxide. .

As for the particle size of organic pigments, inorganic pigments, etc., the average primary particle size is preferably in the range of 10 nm to 100 μm, more preferably 10 nm to 50 μm, from the viewpoint of color development, concealability and handling properties. . If it is less than 10 nm, the handleability becomes difficult, and if it is 100 μm or more, when it is made into a sheet, there is a possibility that unevenness increases and the haze value increases.

The average primary particle size of the pigment is obtained by observing with a scanning microscope (SEM) or transmission microscope (TEM), measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating the average value. be able to.

Examples of organic pigments include C.I. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185, C.I. I. Pigment Orange 36, 71, C.I. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264, C.I. I. Pigment Violet 19, 23, 32, C.I. I. Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66, C.I. I. Pigment Brown 25, 28, C.I. I. Pigment Green 7, 36, 37, C.I. I. Pigment Black 1 and the like.

As metal oxides, metals forming oxides include zinc, magnesium, aluminum, iron, titanium, silicon, antimony, tin, copper, manganese, cobalt, vanadium, bismuth, niobium, molybdenum, ruthenium, tungsten, palladium, silver, platinum, and the like. Furthermore, composite metal oxides include ITO (indium tin oxide), ATO (antimony trioxide), AZO (aluminum-doped zinc oxide), and the like.

In order to improve the dispersibility of the pigment, a pigment dispersant, a spreading agent, and the like may be added as appropriate.
When the coloring agent (H) is blended, the blending amount is preferably less than 1.5 parts by mass, more preferably less than 1.0 parts by mass, per 100 parts by mass of the polyester block copolymer (A). If it is 1.5 parts by mass or more, the haze value increases, and it is thought that the composition becomes opaque.

Various other additives can be added to the polyester elastomer resin composition of the present invention. Examples of additives include the polyether ester block copolymer (A) in the present invention, an aliphatic carboxylic acid alkali metal salt (B) having 10 to 20 carbon atoms, and an ethylene copolymer having a carboxylic acid metal group in the side chain. Other than coalescence (C), hindered phenolic radical scavengers (D) consisting of carbon, hydrogen and oxygen, peroxide decomposers (E), coloring agents (H), flame retardants, inorganic fillers, stabilizers, and aging What is widely used as an additive to the polyester block copolymer as an inhibitor is the feature of the present invention (the total light transmittance measured on a sheet with a thickness of 2 mm is 5% or more, the haze value (cloudiness) is It can be added within the range of 95% or less and not impairing the surface hardness of 20 to 50D) according to JIS K7215.

Other additives include coloring pigments, inorganic and organic fillers, coupling agents, tackiness improvers, quenchers, stabilizers such as metal deactivators, polyfunctional glycidyl group-containing styrene polymers, and the like. can also be added. Alternatively, heat stabilizers, light stabilizers, cross-linking agents, dispersants, lubricants, anti-slip agents, nucleating agents, foaming agents, antibacterial agents, deodorants, adsorbents, conductive agents, flame retardants, etc. may also be contained. good.

The polyester elastomer resin composition in the present invention comprises a polyether ester block copolymer (A), an aliphatic carboxylic acid alkali metal salt having 10 to 20 carbon atoms (B), and an ethylene-based polymer having a carboxylic acid metal group in the side chain. The total content of the copolymer (C), the hindered phenol-based radical scavenger (D) consisting of carbon, hydrogen and oxygen, the peroxide decomposer (E) and the colorant (H) should account for 80% by mass or more. is preferred. (A), (B), (C), (D), (E) or (A), (B), (C), (D), (E), (F), (G) or (A) ), (B), (C), (D), (E), (H) or (A), (B), (C), (D), (E), (F), (G), The total of (H) is more preferably 90% by mass or more, and even more preferably 95% by mass or more.

The method for producing the polyester elastomer resin composition of the present invention is not particularly limited. Ethylene copolymer with a base, hindered phenol radical scavenger consisting of carbon, hydrogen and oxygen, peroxide decomposer, UV absorber, hindered amine compound and other additives are mixed together and screwed together. A method of supplying to a type extruder and melt-kneading, or a screw type extruder, a polyester block copolymer is first supplied and melted, and an aliphatic carboxylic acid alkali having 10 to 20 carbon atoms is further supplied from another supply port. Metal salts, ethylene-based copolymers having carboxylic acid metal groups in side chains, hindered phenol-based radical scavengers composed of carbon, hydrogen and oxygen, peroxide decomposers, ultraviolet absorbers, hindered amine-based compounds and other additives A method of feeding and kneading materials can be employed as appropriate.

The film of the present invention is made of a polyester elastomer resin composition and has a total light transmittance of 5% or more when a sheet having a thickness of 2 mm is used. It is preferably 10% or more, more preferably 30% or more, still more preferably 60% or more. In addition, as described above, the total light transmittance is an aliphatic carboxylic acid alkali metal salt (B) having 10 to 20 carbon atoms, an ethylene copolymer (C) having a carboxylic acid metal group in a side chain, a coloring A desired total light transmittance can be appropriately selected by appropriately blending the agent (H) within the range of the present invention.

The film of the present invention is made of a polyester elastomer resin composition, and has a haze value of 95% or less when a sheet having a thickness of 2 mm is used. It is preferably 70% or less, more preferably 60% or less, still more preferably 30% or less. As described above, the haze value is an aliphatic carboxylic acid alkali metal salt (B) having 10 to 20 carbon atoms, an ethylene copolymer (C) having a carboxylic acid metal group in a side chain, and a coloring agent (H). is appropriately blended within the scope of the present invention, a desired haze value can be appropriately selected.

The film of the present invention is made of a polyester elastomer resin composition, and has a color difference ΔE of 10 or less when a heat discoloration test described later (heat treatment at 110 ° C. for 250 hours) is performed using a 2 mm thick sheet. preferable. More preferably, the color difference ΔE is 8 or less, and most preferably 5 or less. If the color difference ΔE is 10 or more in the thermodiscoloration test described later (heat treatment at 110° C. for 250 hours), the appearance may be affected when used for a long time in a high temperature environment.

The film of the present invention is made of a polyester elastomer resin composition, and a 2 mm thick sheet is used for the weather resistance test described later (black panel temperature: 63 ° C., no rain, illuminance: 255 w / m ² for 150 hours). is preferably 10 or less. Furthermore, the color difference ΔE is preferably 8 or less, and most preferably 5 or less. If the color difference ΔE is 10 or more, it is considered that the appearance will be affected when used for a long time in a harsh environment including ultraviolet rays.

In the case of lowering the visibility of the display element when it is not emitting light, a method of incorporating the coloring agent (H) into the film of the present invention as described above, or a method of forming a smoke print layer or a mask print layer on the surface or the surface of the film of the present invention. , a method of producing a film having a uniform thickness by slush molding a polyester elastomer and a predetermined pigment, but any known method may be used. By lowering the transmittance of the exterior film, the display element can be hidden by the exterior film when the display element is not emitting light, and the exterior film can be highlighted.

The film of the present invention is made of a polyester elastomer resin composition and is an exterior film for an interior display device. The term "for interior use" in the present invention refers to an environment that is not directly exposed to sunlight, wind and rain, but is expected to be exposed to strong ultraviolet rays through glass. Specifically, it is under the environment such as inside a building (a store, a hotel, a general house, etc.) or inside a car.

The display device of the present invention has a display element including a light source, and a film arranged so as to overlap the display element. The light source used for the display element is not particularly limited, but a backlight It may be a conventionally known configuration including a liquid crystal element, an electroluminescence element, an LED, or the like having a

The exterior film in the present invention means a film that decorates and protects the portion visible from the outside of the display element and that can be touched by people.

The interior display device according to the present invention is preferably used for automobile interiors, and is mainly used around windshields and side windows. The interior display device of the present invention is used for, for example, an instrument panel, an outer skin, etc., and is preferably used for an instrument panel. The instrument panel portion includes, for example, a meter panel such as a speedometer and a tachometer, a navigation panel such as a car navigation system, and a control panel such as an overhead control panel. Covers include door trims, front panels, glove box panels, shifter panels, and the like.

The method for producing the film of the present invention is not particularly limited, but may be known methods such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding, and in-mold molding. Examples of extrusion molding include a melt casting method, a T-die method, an inflation method, and the like.

The thickness of the film of the present invention is preferably 50 µm or more and 2 mm or less, more preferably 100 µm or more and 1 mm or less, in order to impart flexibility. The surface condition may be smooth or uneven (in the case of a shape having unevenness, it may be a geometric shape or a leather-like shape. Among them, it is particularly preferable to have large unevenness of 200 μm or more and 500 μm or less, It is a textured shape in which fine unevenness of 1 μm or more and 10 μm or less is formed.)
The method of providing unevenness is not particularly limited, but may be a known method such as an imprint transfer method or a resin coating method.

The film of the present invention has coatings and additives to improve wear resistance and scratch resistance, adjust touch and gloss, sterilize and deodorize, and improve conductivity and flame retardancy within the range that does not impair flexibility. may also be added, and a coating agent may be applied thinly (with a thickness of several μm to several tens of μm) on the surface. Depending on the purpose, instead of being added to the layer forming the main part of the film of the present invention, it is added to the coating (coating agent) located on the surface of the surface film, or to the adhesive layer or laminate layer located on the back surface of the film. You may add.

Furthermore, the film of the present invention can achieve excellent durability. That is, since it is a film made of a polyester elastomer, it is excellent in heat resistance, light resistance, chemical resistance, oil resistance, bending fatigue resistance, and the like. Because of its excellent heat resistance and weather resistance, it is less likely to be restricted by the atmosphere in which it is used, and can be used indoors under high temperatures or in vehicles. It also has excellent chemical resistance and oil resistance, so it does not deteriorate easily even if it is used with oily hands or in an environment where machine oil or the like adheres. In addition, since it has excellent resistance to bending fatigue, it can be applied to next-generation flexible display devices and flexible modules.

The film of the present invention may be partly composed of polyester elastomer, other thermoplastic elastomer, or other highly transparent member (substrate) in accordance with the configuration of the display device, if thickness is required. The thickness of the polyester elastomer layer at that time is preferably 10 to 300 μm, more preferably 20 to 100 μm. This polyester elastomer layer and the above-described highly transparent base material are laminated to form a multi-layered film, and the highly transparent base material prevents the strength of the film from being lowered. Examples of highly transparent substrates include films, sheets, and plates made of polyolefin resins such as polyethylene and polypropylene, polyesters, polycarbonates, acrylics, and the like. The surface is made of thin polyester elastomer, which provides an excellent balance between high-class appearance, tactile sensation, and clarity. It is also an excellent film.

The film of the present invention may have a multi-layer structure, and the substrate that supports and is laminated with a film made of a polyester elastomer or the like includes a piezoelectric film, a mirror film, a conductive film, a metal deposition film, and a circuit pattern. It may be a film, a touch panel, or the like. The appearance of the film is not limited to the leather-like appearance described above, and may be wood grain, wallpaper, metal, stone, tile, or the like.

Moreover, the film of the present invention further has the advantage of being excellent in moldability and heat-sealability. For example, since the film of the present invention is a polyester elastomer, it has excellent adhesion to glass or resin glass arranged on the surface, and is particularly excellent in thermal adhesiveness and curved surface conformability. That is, the film of the present invention can be firmly adhered to any display element without gaps, so that a display device having a desired shape can be easily formed. From this point of view, the surface film is preferably made of a thermoplastic material. Moreover, although it has excellent heat-sealability, an adhesive may be used in order to further improve adhesion.

The effects of the present invention will be described below with reference to examples. All percentages and parts in the examples are based on mass unless otherwise specified. Moreover, the physical properties shown in the examples were measured as follows.

- Using a melting point differential scanning calorimeter (DSC Q1000 manufactured by TA Instruments), the top temperature of the melting peak when heated at a heating rate of 10°C/min in a nitrogen gas atmosphere was measured.

・Surface hardness (Shore D scale)
Measured according to JIS K-7215.

· Moldability Using an electric injection molding machine (NEX-1000) manufactured by Nissei Plastic Industry Co., Ltd., prepare a test piece of 125 mm × 75 mm and a thickness of 2 mm at 220 ° C (mold temperature: 40 ° C). At the time, the moldability was confirmed. The moldability was determined by the amount of release and generated gas as shown below.
Releasability ◯: No problem with mold release, Δ: Some problem with mold release, ×: Problem with mold release Amount of gas generated ◯: Small, ×: Large.

・ Total light transmittance and haze value Using an electric injection molding machine (NEX-1000) manufactured by Nissei Plastic Industry Co., Ltd., under the conditions of 220 ° C. (mold temperature: 40 ° C.), 125 mm × 75 mm, thickness 2 mm A test piece was produced. The surface roughness of the test piece was measured using VK-9700 manufactured by KEYENCE and found to be 0.46 μm. Using the test piece, the total light transmittance and haze value were measured according to ASTM D1003 using a DIRECT READING HAZEMETER manufactured by Toyo Seiki Seisakusho.

·Evaluation of translucency An LED light source, paper, and the above-described test piece (125 mm x 75 mm, thickness 2 mm) were stacked in this order from the bottom. As for translucency, whether characters printed on the paper can be read by turning on and off the light source of the LED was judged as shown below.
Good: Characters can be read clearly with the LED light source ON.
Δ: Characters can be read with the LED light source ON.
x: Characters cannot be read with the LED light source ON.

・ Color change (color difference ΔE) measurement Using an electric injection molding machine (NEX-1000) manufactured by Nissei Plastic Industry Co., Ltd., at 220 ° C (mold temperature: 40 ° C), 125 mm × 75 mm, thickness 2 mm A test piece was prepared. Using the test piece, according to JIS Z8722, using an SM-T color meter (light source: C, viewing angle: 2 degrees view) manufactured by Suga Test Instruments Co., Ltd., pressing with a white plate, L *, a *, b* was measured. L*, a*, and b* were measured before and after the thermal denaturation test and weather resistance test, which will be described later, and the color difference ΔE was calculated.
The formula for calculating ΔE is ΔE=[(ΔL*) ² +(Δa*) ² +(Δb*) ² ] ^1/2 .

・Thermal discoloration test A test piece of 125 mm × 75 mm and a thickness of 2 mm prepared under the conditions shown above was heat-treated at 110 ° C. for 250 hours using an Espec GPH (H)-202 type gear oven. The color tone of the test piece was visually observed and the color difference ΔE was calculated with the SM-T color meter.

Weather resistance test A test piece of 125 mm x 75 mm and 2 mm in thickness prepared under the conditions described above was treated for 150 hours using a S80HB sunshine weather meter manufactured by Suga Test Instruments Co., Ltd. (black panel temperature: 63 ° C., No rain, illuminance: 255 w/m ² ). The color tone of the treated test piece was visually observed and the color difference ΔE was calculated with the SM-T color meter.

Reference Example Production of polyester block copolymer (A-1) 686 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of about 1400, which will be the melting point polymer segment, 316 parts of 1,4-butanediol, and 0.1 part of titanium tetrabutoxide are reacted together with a helical ribbon stirring blade. The mixture was placed in a container and heated at 190 to 225° C. for 3 hours to carry out an esterification reaction while distilling reaction water out of the system. After adding 0.1 part by mass of "IRGANOX" 1330 (a hindered phenolic radical scavenger made by BASF made of carbon, hydrogen and oxygen) (D-1) with respect to 100 parts by mass of the polyester block copolymer component, The temperature was raised to 245° C., 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 resulting polymer was extruded into water in the form of a strand and cut into pellets.

Production of polyester block copolymer (A-2) A low-melting point polymer composed of 234 parts of terephthalic acid, an aliphatic polyether unit and/or an aliphatic polyester unit, which becomes a high-melting point crystalline polymer segment composed of a crystalline aromatic polyester. 754 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of about 2000, which will be a coalescing segment, 228 parts of 1,4-butanediol, and 0.2 parts of titanium tetrabutoxide were added to a reaction vessel equipped with a helical ribbon stirring blade. The mixture was charged and heated at 190 to 225° C. for 3 hours to carry out an esterification reaction while distilling reaction water out of the system. 0.5 parts by mass of "IRGANOX" 1330 (IR1330, a hindered phenolic radical scavenger made by BASF made of carbon, hydrogen and oxygen) (D-1) was added to 100 parts by mass of the polyester block copolymer component. After that, the temperature was raised to 245° C., the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was carried out for 3 hours and 30 minutes under these conditions. The resulting polymer was extruded into water in the form of a strand and cut into pellets.

Production of polyester block copolymer (A-3) 374 parts of terephthalic acid to be a high melting point crystalline polymer segment made of crystalline aromatic polyester, a low melting point polymer made of aliphatic polyether units and / or aliphatic polyester units 610 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of about 1400, which will be coalescing segments, 335 parts of 1,4-butanediol, and 0.2 parts of titanium tetrabutoxide were added to a reaction vessel equipped with a helical ribbon stirring blade. The mixture was charged and heated at 190 to 225° C. for 3 hours to carry out an esterification reaction while distilling reaction water out of the system. After adding 0.1 part by mass of "IRGANOX" 1330 (a hindered phenolic radical scavenger made by BASF made of carbon, hydrogen and oxygen) (D-1) with respect to 100 parts by mass of the polyester block copolymer component, The temperature was raised to 245° C., 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 resulting polymer was extruded into water in the form of a strand and cut into pellets.

Production of polyester block copolymer (A-4) 374 parts of terephthalic acid terephthalic acid, which is a high-melting crystalline polymer segment composed of a crystalline aromatic polyester, and a low molecular weight polymer composed of aliphatic polyether units and/or aliphatic polyester units. 610 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of about 1,400 as a melting point polymer segment, 335 parts of 1,4-butanediol, 0.2 parts of titanium tetrabutoxide, and a reaction vessel equipped with a helical ribbon stirring blade and heated at 190 to 225° C. for 3 hours to carry out an esterification reaction while distilling reaction water out of the system. "IRGANOX" 1098 (Hindered phenol-based radical scavenger (not composed of carbon, hydrogen and oxygen) containing secondary amine manufactured by BASF) (D-3) 0.05 for 100 parts by mass of polyester block copolymer component After the mass parts were added, the temperature was raised to 245° C., 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 resulting polymer was extruded into water in the form of a strand and cut into pellets.

Table 1 shows the compositions of A-1, A-2, A-3 and A-4, and the amount and physical properties of the hindered phenolic radical scavenger used.

In the polyester block copolymers (A-1), (A-2), (A-3), and (A-4) shown in Reference Examples, during polymerization, (D-1) or (D-3) of the radical scavenger (D) is contained, but in the examples shown below, the formulation for 100 parts by mass of the polyester block copolymer component (A) excluding the radical scavenger (D) added during polymerization showing the ratio.

Examples 1-7
The polyester block copolymers (A-1), (A-2), and (A-3) obtained in Reference Examples were added with a hindered phenol-based radical scavenger ("IRGANOX" manufactured by BASF) consisting of carbon, hydrogen and oxygen. 1010) (D-2), an alkali metal salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms (NS-3A (sodium laurate) manufactured by Nitto Kasei Kogyo Co., Ltd.) (B-1), a carboxylic acid in the side chain Ethylene-based copolymer having a sodium base (“Surlyn” AD8610 manufactured by DuPont) (C-1) or (“Himilan” 1707 manufactured by Mitsui-Dow Polychemicals Co., Ltd.) (C-2), phosphorus-based peroxide decomposition agent (ADEKA Co., Ltd. "ADEKA STAB" PEP-8) (E-1) or sulfur-based peroxide decomposer (Daiichi Kogyo Seiyaku Co., Ltd. "Lasmit" LG) (E-2), benzotriazole-based ultraviolet absorption agent (BASF "Tinuvin" 234) (F-1), triazine-based UV absorber (BASF "Tinuvin" 1557) (F-2), cyanocrate UV absorber (BASF "Uvinul" 3030 ) (F-3), a hindered amine compound whose amine series is tertiary (BASF "Tinuvin" 144) (G-1), carbon black (Mitsubishi Chemical #5, average particle size 75 nm) (H -1) was dry-blended at the compounding ratio shown in Table 2, melt-kneaded using a twin-screw extruder having a cylinder diameter of 45 mm, and pelletized. After drying the pellets at 80 ° C. for 3 hours, using an electric injection molding machine (NEX-1000) manufactured by Nissei Plastic Industry Co., Ltd., under the conditions of 220 ° C. (mold temperature: 40 ° C.), 125 mm × 75 mm, thickness A test piece with a thickness of 2 mm was produced. Using the obtained sheet having a thickness of 2 mm, the total light transmittance and haze value were measured, the presence or absence of bleeding out was confirmed, and the surface hardness was measured. Furthermore, the translucency evaluation, the heat discoloration test and the weather resistance test shown above were carried out. Table 3 shows the results.

Incidentally, (D-1) and (D-3) in Table 2 are the radical scavenger (D) contained in the polyester block copolymer (A) at the time of polymerization, as shown in the reference example above. means.

Comparative Examples 1-3
To the polyester block copolymer (A-1) or (A-4) obtained in Reference Example, an alkali metal salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms (NS-3A manufactured by Nitto Kasei Kogyo Co., Ltd. ( sodium laurate)) (B-1) and (sodium stearate manufactured by Nitto Kasei Kogyo Co., Ltd. (sodium stearate)) (B-2), an ethylene copolymer having a sodium carboxylate group in the side chain (DuPont "Surlyn" AD8610 manufactured by Mitsui Dow Polychemical Co., Ltd. (C-1) or ("Himilan" 1707 manufactured by Mitsui Dow Polychemical Co., Ltd.) (C-2), phosphorus-based peroxide decomposing agent (ADEKA Co., Ltd. "ADEKA STAB" PEP- 8) (E-1) or sulfur-based peroxide decomposer (Daiichi Kogyo Seiyaku Co., Ltd. "Lasmit" LG) (E-2), triazine-based ultraviolet absorber (BASF "Tinuvin" 1557) (F- 2), a hindered amine compound (“Tinuvin” 144 manufactured by BASF) (G-1), and carbon black (#5 manufactured by Mitsubishi Chemical, average particle size 75 nm) (H-1) at a compounding ratio as shown in Table 2. and pelletized after melt kneading using a twin-screw extruder having a cylinder diameter of 45 mm. After drying the pellets at 80 ° C. for 3 hours, using an electric injection molding machine (NEX-1000) manufactured by Nissei Plastic Industry Co., Ltd., under the conditions of 220 ° C. (mold temperature: 40 ° C.), 125 mm × 75 mm, thickness A test piece with a thickness of 2 mm was produced. Using the obtained sheet having a thickness of 2 mm, the total light transmittance and haze value were measured, the presence or absence of bleeding out was confirmed, and the surface hardness was measured. Furthermore, the translucency evaluation, the heat discoloration test and the weather resistance test shown above were carried out. Table 3 shows the results.

As is clear from Examples 1 to 7 in Tables 2 and 3, 10 to 50% by mass of a high melting point crystalline polymer segment (a) composed of crystalline aromatic polyester units and aliphatic polyether units and/or aliphatic A polyester block copolymer (A) containing 90 to 50% by mass of a low-melting polymer segment (b) composed of polyester units, an aliphatic carboxylic acid metal salt (B) having 10 to 20 carbon atoms and a side chain An ethylene copolymer (C) having a carboxylic acid metal group, a hindered phenol radical scavenger (D) comprising carbon, hydrogen and oxygen, and a peroxide decomposer (E) were blended within the scope of the present invention. A resin composition, and a resin composition further containing an ultraviolet absorber (F), a hindered amine compound (G), and a colorant (H) within a suitable range, is excellent in transparency, appearance, heat discoloration resistance, and weather resistance. .

From Comparative Example 1, a hindered phenol radical scavenger (D- When 3) was contained even in a small amount, large thermal discoloration was observed. Further, from Comparative Example 2, more than 3 parts by mass and 4 parts by mass of the alkali metal salt (B) of an aliphatic carboxylic acid having 10 to 20 carbon atoms per 100 parts by mass of the polyester block copolymer (A) Bleed-out was observed when it was contained. Also, a large amount of gas was generated during molding. Further, from Comparative Example 3, when 1.5 parts by mass or more of the colorant (H) is blended with 100 parts by mass of the polyester block copolymer (A), the total light transmittance is 0% and the haze is 0%. There was a large decrease in transparency.

The film of the present invention has superior flexibility, translucency, and resistance to discoloration due to light and heat, compared to conventional translucent films used for exterior films of interior display devices. It is used for interior applications where durability is required, especially for automobile interior applications.

Claims (6)

10 to 50% by mass of a high melting point crystalline polymer segment (a) composed of crystalline aromatic polyester units and 90 to 50% by mass of a low melting point polymer segment (b) composed of aliphatic polyether units and/or aliphatic polyester units and an alkali metal salt (B) of an aliphatic carboxylic acid having 10 or more and 20 or less carbon atoms per 100 parts by mass of the polyester block copolymer (A). 01 to 3 parts by mass, 0.2 to 20 parts by mass of an ethylene copolymer (C) having a carboxylic acid metal group in the side chain, and 0.05 of a hindered phenolic radical scavenger (D) consisting of carbon, hydrogen and oxygen. Total light transmittance measured on a 2 mm thick sheet made of a polyester elastomer resin composition containing at least 1.0 parts by mass and 0.05 to 1.0 parts by mass of a peroxide decomposer (E) 5% or more, a haze value (cloudiness) of 95% or less, and a surface hardness of 20 to 50D according to JIS K7215. The polyester elastomer resin composition contains 0.05 to 2.5 parts by mass of an ultraviolet absorber (F) and 0.01 to 2 parts by mass of a hindered amine compound (G) with respect to 100 parts by mass of the polyester block copolymer (A). 2. The exterior film for an interior display device according to claim 1, containing .5 parts by mass. 3. The exterior film for an interior display device according to claim 2, wherein the hindered amine compound (G) has a tertiary amine series. The interior display device according to claim 2, wherein the ultraviolet absorber (F) is one or more selected from the group consisting of benzotriazole-based compounds, triazine-based compounds, and cyanoacrylate-based compounds. exterior film. 5. The exterior film for an interior display device according to any one of claims 1 to 4, wherein the exterior film is for automobile interior. 6. The exterior film for an interior display device according to claim 5, which is used for an instrument panel or an outer skin.