0001]The present invention relates to a superior polyester sheet to the light reflective performance.
BACKGROUND
[0002]In the display device such as a liquid crystal display and lighting signboard, but can show clearly the image by irradiating light from the rear, lighter display device, as thin is required, including a direct light source on the back changes to the backlight system includes a system of irradiating from the back is reflected is the mainstream by the reflecting plate and the reflective sheet light from the periphery. Then, in order to improve the display performance while achieving further weight and thinner, the reflection plate and the reflection sheet, thin and light with excellent mechanical strength, high reflectance, those excellent in scattering of light desired.
[0003]
　In a flat image display system such as a liquid crystal display, the reflective plate and the reflective sheet of the surface light source device, the rear reflecting sheet of a lighting signboard, as such as the back reflecting sheet of a solar cell may have reflective light, dimensional stability at low cost for reasons such as excellent, the polyester sheet is used encompasses the fine particles or pores.
[0004]
　As a method for obtaining a polyester sheet having a light reflectivity of a number by mixing inorganic particles such as barium sulfate into a polyester sheet, a polyester and inorganic particles interfacial and inorganic particles at the interface of the fine pores formed as nuclei how to use the light reflection (see Patent Document 1), by mixing the polyester and incompatible resin, fine pores to form the polyester and the incompatible resin interface and incompatible resin as nuclei how to use the light reflection at the interface (see Patent Document 2), an inert gas in a pressure vessel to form a large number of fine voids therein by impregnating the polyester at the interface of the polyester and the holes and the like method using the light reflection (see Patent Document 3).
[0005]
　However, the polyester sheet using inorganic particles such as titanium oxide, there is a limit to the improvement of the reflectance, and because there is a tendency for the inorganic particles to absorb specific wavelengths, with respect to light in the wavelength range corresponding thereto reduces the reflectivity, there is a problem that the screen becomes dark. Further, when the inside of the pores is large, another light reflecting performance is insufficient, there is a problem that may be poor in mechanical strength.
[0006]
　Particularly liquid crystal display is widely used in mobile terminals and a liquid crystal television is high brightness and power saving of the screen is always required, improvement of light reflection performance is also required for the reflection sheet. In order to improve the light reflectivity of the polyester sheet, it is necessary to increase the interface of the light reflecting in the polyester film. Therefore, efforts to form a more fine and large number of pores have been made. For example, in order to finely disperse the incompatible resin into a polyester, white polyester film formed using a styrene elastomer has been proposed in the compatibilizer (refer to Patent Documents 4 and 5).
[0007]
　But the white polyester sheet as shown in the Patent Documents 4 and 5, because the size of the dispersed phase of incompatible resin in the polyester is large, it is difficult to satisfy the high light reflectivity of which are required in recent years is there. The manufacturing process for an essential a multilayer structure is disadvantageously not complicated economical.
[0008]
　Patent Document 6 whereas, also, polyester sheet using a 4-methyl-1-pentene-based resin has been proposed. 4-methyl-1-pentene-based resin component of Hiaiyo polyester is dispersed more finely, polyester resin composition capable of forming a sheet showing a higher light reflectivity of, as well as suitable molding as reflective sheet, etc. It provides the body and the polyester sheet.
CITATION
Patent Document
[0009]
Patent Document 1: JP 2004-330727 Patent Publication
Patent Document 2: JP-A 04-239540 JP-
Patent Document 3: WO 97/01117 pamphlet
Patent Document 4: JP 2004-123784 Patent Publication
Patent Document 5: JP open 2009-40045 JP
Patent Document 6: JP 2015-214663 Patent Publication
Summary of the Invention
Problems that the Invention is to Solve
[0010]
　An object of the present invention is to provide high mechanical strength inherently possessed polyester, dimensional stability, while maintaining excellent properties such as durability, the polyester sheet having excellent light reflection performance than conventional polyester sheet .
Means for Solving the Problems
[0011]
　The present inventors have made intensive studies and as a result, the polyester (A), a specific meeting the requirements 4-methyl-1-pentene polymer (B), and the compatibilizer (C) is contained at a specific ratio the polyester sheet made of a resin composition, found that it is possible to solve the above problems, and have completed the present invention.
[0012]
　That is, the present invention relates to the following [1] to [10].
[1] Polyester (A), a polyester sheet comprising 4-methyl-1-pentene polymer (B) and compatibilizer and (C), wherein (A), (B) and (C) content ratio, (a), (B) , total is 100 parts by weight of (C), (a) is 60 to 98.9 parts by weight, (B) 1 to 25 parts by weight, (C ) is 0.1 to 15 parts by mass, further, the (B) satisfies the following requirements (a) ~ (d), a polyester sheet.
(A) 4-methyl-1-pentene constitutional unit derived from a 100 to 90 mole%, at least selected from ethylene and carbon atoms 3 ~ 20 alpha-olefin (except 4-methyl-1-pentene) sum 0-10 mol% of structural units derived from one α- olefin.
(B) differential scanning calorimetry (DSC) in the measured heat of fusion .DELTA.Hm (Unit: J / g) and the melting point Tm (unit: ° C.) The following requirements (1), satisfying the (2).
[0013]
　　　　(1) .DELTA.Hm ≧ 0.5 ×
　　　　Tm-76 (2) melting point Tm: 200 ~ 260 ° C.
(c) in compliance with ASTM D1238 260 ° C., a melt flow rate measured at 5kg loading condition (MFR) of 0.1 ~ 500g / 10 minutes.
(D) 13 meso diad fraction as measured by C-NMR (m) 98.5 to 100 percent.
[2] The (B) satisfies at least one of the following requirements (e) and (f), a polyester sheet according to [1].
(E) a silicone oil in compliance with ASTM D1525, test load 10 N, Vicat softening temperature measured at a Atsushi Nobori rate of 50 ° C. / h is 145 ~ 220 ° C..
(F) 23 ° C. decane-soluble component quantity less 5 wt%.
[3] polyester sheet according to the melting point Tm of the 4-methyl-1-pentene polymer (B) is 230 ~ 245 ° C. [1] or [2].
[4] The polyester (A) is a polyester sheet according to any one of polyethylene terephthalate [1] to [3].
[5] Polyester sheet according to any one of those obtained through a step of stretching treatment [1] to [4].
[6] The (C) is a polyester sheet according to any one of a polar group-modified styrene elastomer [1] to [5]
[7] wherein the polar group-modified styrene-based elastomer, a polar group-modified styrene - ethylene / butylene - polyester sheet according to a styrene copolymer [6].
[8] polyester sheet according to the polarity in the range styrene content of 5-20% by weight of the base-modified styrene elastomer (C) [6] or [7].
[9] biaxially is a stretched sheet, [1] a polyester sheet according to any one of to [8].
[10] a liquid crystal display, a reflecting sheet of a lighting signboard or solar cell, a polyester sheet according to any one of [1] to [9].
The invention's effect
[0014]
　Polyester sheet of the present invention has mechanical strength inherent polyester, dimensional stability, and durability, and show a high degree of light reflectance.
DESCRIPTION OF THE INVENTION
[0015]
　Hereinafter, the present invention will be described in detail.
[0016]
　 Polyester sheet
　a polyester sheet of the present invention include polyester (A), 4-methyl-1-pentene-based polymer (B), the compatibilizer (C) is as essential components. These content ratio is, (A), (B) , is taken as 100 parts by weight of total, (A) is 60 to 98.9 parts by weight, preferably 60 to 94 parts by weight of (C), (B ) is 1 to 25 parts by weight, preferably 5 to 25 parts by weight, (C) from 0.1 to 15 parts by weight, preferably 1 to 15 parts by weight.
[0017]
　Hereinafter, a good component described be added to these components and optionally.
[0018]
　[Polyester (A)]
　Polyester (A) used in the present invention, antimony catalyst, germanium catalyst, in the presence of a known polyester polymerization catalyst such as titanium-based catalysts, the polymerization of monomers comprising dicarboxylic acid and diol it can be produced by.
[0019]
　The dicarboxylic acid component, for example, in an aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, phthalic acid, include diphenic acid and ester derivatives thereof, and in the aliphatic dicarboxylic acid, adipic acid, sebacic acid, Dodekajion acid, eicosanoic acid, dimer acid and ester derivatives, the alicyclic dicarboxylic acids, include 1,4-cyclohexanedicarboxylic acid and ester derivatives thereof, and polyfunctional acids, trimellitic acid, pyromellitic trimellitic acid and its esters derivatives thereof as a representative example.
[0020]
　As the diol component, for example, ethylene glycol, propanediol, butanediol, neopentyl glycol, pentanediol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyethylene glycol, tetramethylene glycol and polyethylene glycol, and the like polyethers such as polytetramethylene glycol may be mentioned as typical examples.
[0021]
　Polyester (A) used in the present invention, mechanical strength, heat resistance, when considering the manufacturing cost, a polyester having a basic structure of polyethylene terephthalate is preferred.
[0022]
　[4-methyl-1-pentene polymer (B)]
　according to the present invention 4-methyl-1-pentene polymer (B) satisfies the following requirements (a) ~ (d), preferably further below it may be met if necessary one or more of the requirements (e) and (f).
[0023]
　The following describes each requirement.
[0024]
　(Requirement (a))
　according to the present invention 4-methyl-1-pentene polymer (B) is a structural unit derived from 4-methyl-1-pentene is 100 to 90 mol%, of ethylene and carbon atoms 3 ~ 20 alpha-olefin of at least one constituent unit derived from olefins selected from (4-methyl-1-excluding pentene) is 0 to 10 mol%.
[0025]
　According to the present invention 4-methyl-1-pentene polymer (B), for example, if 4-methyl-1-pentene homopolymer (4-methyl-1-pentene constitutional unit derived from the 100 mol% ), or 4-methyl-1-pentene and copolymers with other olefins can be mentioned, as long as the effect of the present invention, including its any meaning.
[0026]
　Constitutional unit derived from 4-methyl-1-pentene according to the present invention 4-methyl-1-pentene polymer (B) is preferably 92 to 100 mol%, more preferably 95 to 100 mol%, sum of at least one constituent unit derived from olefins selected from ethylene and carbon atoms 3 ~ 20 alpha-olefin (except 4-methyl-1-pentene) is preferably from 0 to 8 mol%, more preferably it is 0 to 5 mol%.
[0027]
　If according to the present invention 4-methyl-1-pentene polymer (B) is a copolymer, specifically as α- olefin of 4-methyl-1 3 to 20 carbon atoms which pentene copolymer are propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Among these preferable are 4-methyl-1-a α- olefin having 6 to 20 carbon atoms excluding pentene, more preferably from α- olefin of 8 to 20 carbon atoms. These α- olefins can be used singly or in combination of two or more.
[0028]
　4-methyl-1-pentene constitutional unit derived from in accordance with the present invention 4-methyl-1-pentene polymer (B), and, of ethylene and carbon atoms 3 ~ 20 alpha-olefin (4-methyl - the amount of the at least one structure unit derived from olefins selected from 1-except-pentene) can be adjusted by the amount of each of the olefins to be added during the polymerization reaction.
[0029]
　(Requirement (b))
　in the present invention, 4-methyl-1-pentene polymer (B) is a heat of fusion .DELTA.Hm (Unit: J / g) as measured by differential scanning calorimetry (DSC) and melting point Tm (unit: ° C.) the following requirements (1), satisfying the (2).
[0030]
　　　　　(1) .DELTA.Hm ≧ 0.5 ×
　　　　　Tm-76 (2) melting point Tm: 200 ~ 260 ℃
　in the requirement (1), differential scanning calorimetry (DSC) (heating rate: 10 ° C. / min) is measured by heat of fusion ΔHm that is preferably 5 ~ 80 J / g, more preferably 10 ~ 60J / g. Further, in the above requirement (2), differential scanning calorimetry (DSC) (heating rate: 10 ° C. / min) melting point Tm as measured by preferably 210 ~ 245 ° C., more preferably 215 ~ 240 ° C., more preferably 220 ~ 235 ° C..
[0031]
　The requirement (1) indicates that according to the present invention 4-methyl-1-pentene polymer (B) has a melting heat quantity as compared with conventional 4-methyl-1-pentene polymer ing. Specifically, according to the present invention 4-methyl-1-pentene polymer (B) it is known 4-methyl-1-pentene polymer, for example, described in Example of Patent Document 6 4- compared methyl-1-pentene, decene-1 copolymer, the heat of fusion in the same degree of melting point (Tm) (ΔHm) is large, that has the characteristics of high crystallinity. The known 4-methyl-1-pentene polymer, since the melting point because the melting heat of high smaller was generally according to the present invention 4-methyl-1-pentene polymer (B) it can be said that exhibit excellent characteristics.
[0032]
　4-methyl-1-pentene polymer (B) is by satisfying the requirements (1), in sheet obtained becomes high porosity of the pores was found to improve brightness. Although not clear about this reason, open-porous consisting of the improvement of interfacial peeling-releasing property due to crystallinity is high improvement and improvement by reducing high temperature deformation degree, pores shape retention after open pores It is presumed to be due to the.
[0033]
　Heat of fusion ΔHm of 4-methyl-1-pentene polymer according to the present invention (B) can be obtained within the scope of the defined by the manufacturing method described later. The melting point Tm can also be adjusted by adjusting the amount of the structural units of 4-methyl-1-pentene in the requirement (a).
[0034]
　Note that the melting point (Tm) is not less than the lower limit, the dimensional stability of the resulting sheet, preferably in the heat resistance, it is more than the above upper limit is preferred in the impact strength and toughness of the resulting sheet.
[0035]
　(Requirement (c))
　according to the present invention 4-methyl-1-pentene polymer (B) is, 260 ° C. in conformity with ASTM D1238, a melt flow rate measured at 5kg loading condition (MFR) is 0. 1 ~ 500g / 10min, preferably from 100 ~ 500g / 10min.
[0036]
　When MFR is in the above range is preferred in terms of dispersibility in the polyester during manufacturing a molded body.
[0037]
　MFR can be adjusted by coexistence of hydrogen in the reactor during the polymerization reaction.
[0038]
　(Requirement (d))
　according to the present invention 4-methyl-1-pentene polymer (B) is 13 meso diad fraction as measured by C-NMR (m) 98.5 to 100%, preferably 99 it is ~ 100%.
[0039]
　By meso diad fraction (m) exceeds the lower limit, the polyester (A) and 4-methyl-1-pentene polymer (B) and peeling and opening of the interface, holes shape retention after opening sex is sufficient.
[0040]
　Meso diad fraction of 4-methyl-1-pentene polymer (B) (m) can be adjusted by the type of olefin polymerization catalyst described below.
[0041]
　(Requirement (e))
　according to the present invention 4-methyl-1-pentene polymer (B) is preferably a silicone oil in compliance with ASTM D1525, test load 10 N, at a Atsushi Nobori rate of 50 ° C. / h measured Vicat softening temperature of 145 ~ 220 ° C., preferably from 0.99 ~ 210 ° C., more preferably 155 ~ 200 ° C., more preferably 160 ~ 190 ° C..
[0042]
　If Vicat softening temperature is in the above range, since the higher the shape retention at high temperatures preferred.
[0043]
　Vicat softening temperature, the type of olefin polymerization catalyst, ethylene and the structural unit content derived from at least one olefin selected from α- olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) it can be adjusted by.
[0044]
　(Requirement (f))
　according to the present invention 4-methyl-1-pentene polymer (B) is preferably, 23 ° C. decane-soluble component quantity less 5 wt%, preferably 3 wt% or less, more preferably 1wt % or less. 23 The ° C. decane soluble part amount, as described in detail in examples described later, 4-methyl-1 of the pentene-based polymer (B), after 1 hour heating dissolved in n- decane 145 ° C. 23 ℃ shows a partial dissolved in n- decane solution side after lowering the temperature to.
[0045]
　By 23 ° C. decane-soluble component quantity falls within the above range, it becomes possible to suppress the outflow of the low molecular weight component (contaminant), suitably used for applications in which the resulting polyester sheet is required high purity be able to.
[0046]
　[4-methyl-1-producing method of pentene polymer (B)]
　according to the present invention 4-methyl-1-pentene polymer (B) is, for example, JP 2015-183141, JP 2016-098257 , it can be prepared by methods described in WO 2014/050817.
[0047]
　[Compatibilizer (C)]
　compatibilizing agent used in the present invention (C) is 4-methyl-1-pentene polymer in the polyester (A) (B) degree of dispersion adjustment and - the interface peeling It is used for the purpose of adjusting the opening properties.
[0048]
　There is no particular limitation on the kind and manufacturing process of the compatibilizer (C), such as polystyrene, styrene-based elastomer, a polar group-modified styrene-based elastomer is used.
[0049]
　Styrene elastomer may be used in the present invention, the monovinyl substituted aromatic hydrocarbon (styrene aromatic hydrocarbons) and a copolymer component, examples include styrene - ethylene - butylene - styrene block copolymer (SEBS ), styrene - ethylene - propylene - styrene block copolymer (SEPS), styrene - ethylene - propylene - styrene block copolymer (SEPS), a styrene - butylene - Butajiren - styrene block copolymer (SBBS), a styrene - butadiene rubber (SBR), styrene - isoprene rubber (SIR), styrene - ethylene copolymer, styrene - butadiene - styrene copolymer (SBS), styrene - isoprene - styrene copolymer (SIS), poly (alpha-methyl styrene ) - polybutadiene - poly alpha-methyl styrene) (α-MeSBα-MeS), poly (alpha-methylstyrene) - polyisoprene - poly (alpha-methylstyrene) (α-MeSIα-MeS) can be exemplified, and further, the above-exemplified conjugated diene compound constituting the copolymer was specifically include aspects Butajiren or isoprene is hydrogenated. Among these styrene - butadiene rubbers, styrene - isoprene rubber, styrene - hydrogenated butadiene rubbers, styrene - hydrogenated isoprene rubber is preferably used.
[0050]
　Polar group-modified styrene-based elastomers include those portions of the styrene elastomer is modified with a polar monomer. Modification can be performed by a conventionally known method.
[0051]
　As the polar monomer used for the modification include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenic unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or derivatives thereof, vinyl ester compounds , vinyl chloride, vinyl group-containing organosilicon compound, a carbodiimide compound, and the like. Among these, unsaturated carboxylic acid or its derivatives are particularly preferred.
[0052]
　Examples of the unsaturated carboxylic acid or a derivative thereof, an unsaturated compound having a carboxylic acid group of one or more esters of a compound and an alkyl alcohol having a carboxylic acid group, there may be mentioned an unsaturated compound having one or more carboxylic anhydride groups can, unsaturated group include a vinyl group, a vinylene group, an unsaturated cyclic hydrocarbon group. These compounds can be used known ones, as is not particularly limited specific compounds, such as acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic [TM] (Endoshisu - bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid) unsaturated carboxylic acids such as, or derivatives thereof, such as acid halides, amides, imides, anhydrides , esters, and the like. Specific examples of such derivatives, for example malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and the like glycidyl maleate. These unsaturated carboxylic acids and / or derivatives thereof, can either be used alone, it may be used in combination of two or more thereof. Of these, unsaturated dicarboxylic acids or their anhydrides are preferred, particularly maleic anhydride is preferably used, relative to the styrene-based elastomer 100 parts by mass of the above, usually 1 to 100 parts by weight of polar monomer preferably it is obtained by graft polymerization in an amount of 5 to 80 parts by weight.
[0053]
　Examples of the polar group-modified styrene-based elastomer may be a commercially available product. Specific ones, Dynaron (trademark, JSR Corporation) 8630P, Tuftec (TM, manufactured by Asahi Kasei Corporation) M1913, and the like. It polar group modified styrene-based elastomer may be used alone, it may be used in combination of two or more thereof.
[0054]
　Polar group-modified styrene-based elastomer used in the present invention preferably satisfies the following requirements (i) and (ii).
[0055]
　(I) a melt flow rate (MFR; JIS K7210,230 ℃, 2.12kgf) is usually 1 ~ 100 g / 10min, preferably from 10 ~ 50g / 10min. When MFR is in the above range, the polyester (A), 4-methyl-1-pentene polymer (B) and the melt viscosity, it is close fluidity, expresses good dispersibility as a compatibilizer.
[0056]
　(Ii) styrene content, usually 1 to 35 wt%, preferably 5 to 20 mass%. If the styrene content is less than 1 wt%, polyester compatibility decreases with (A), also exceeds 35 mass%, the compatibility with the 4-methyl-1-pentene polymer (B) lowering increases.
[0057]
　[Other Components]
　The polyester sheets of the present invention, depending on the application, the above-mentioned polyester (A), 4-methyl-1-pentene polymer (B) and compatibilizer (C) other than the resin Alternatively polymer and / or resin additives is an object may be added optionally in a range not to impair the present invention.
[0058]
　Polyester sheet of the present invention, the above-described (A), (B), (C) if it contains other resins or polymers other than the component, other resins or polymers, polystyrene, acrylic resin, polyphenylene sulfide resins, polyether ether ketone resin, polyester resin, polysulfone, polyphenylene oxide, polyimide, polyetherimide, acrylonitrile-butadiene-styrene copolymer (ABS), ethylene-alpha-olefin copolymer rubber, conjugated diene rubber, a phenol resin , melamine resins, polyester resins, silicone resins, and epoxy resins.
[0059]
　If the polyester sheet contains other resins or polymers of these, the total content of other resins or polymers, the above-described (A), (B), 100 parts by weight of the total of the component (C) , preferably 0.1 to 30 parts by weight.
[0060]
　The additive for even better resins have been added to the polyester sheet of the present invention, for example, pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, UV absorbers, antimicrobial agents , surfactants, antistatic agents, weathering stabilizers, heat stabilizers, slip agents, antiblocking agents, foaming agents, crystallization aids, antifogging, (transparent) nucleating agent, antioxidant, hydrochloric acid absorber , impact modifier, crosslinking agent, co-crosslinking agent, crosslinking aid, adhesive, softening agents, and processing aids. These additives, also alone, can be used in combination or in appropriate combination.
[0061]
　As the pigment, inorganic content (titanium oxide, iron oxide, chromium oxide, cadmium sulfide), organic pigments (azo lake, thioindigo, phthalocyanine, anthraquinone) and the like. The dye azo, anthraquinone, triphenylmethane and the like. The addition amount of these pigments and dyes are not particularly limited, the above-described (A), (B), 100 parts by weight of the total of the component (C) in total, generally 5 parts by mass or less, preferably 0.1 ~ is 3 parts by weight.
[0062]
　Glass fibers as the filler, carbon fibers, silica fibers, metal (stainless steel, aluminum, titanium, copper, etc.) fibers, carbon black, silica, glass beads, silicates (calcium silicate, talc, clay, etc.), metal oxides ( iron oxide, titanium oxide, alumina, etc.), carbonates (calcium sulfate of the metal, barium) and various metals (magnesium sulfate, silicon, aluminum, titanium, copper, etc.) powder, mica, glass flake and the like. These fillers may be either singly or in combination of two or more thereof.
[0063]
　Examples of the lubricant, a wax (carnauba wax wax), higher fatty acids (such as stearic acid), higher alcohols (stearyl alcohol, etc.), and higher fatty acid amide (stearic acid amide, etc.).
[0064]
　As the plasticizer, aromatic carboxylic acid esters (dibutyl phthalate), aliphatic carboxylic acid esters (methyl acetyl ricinoleate, etc.), aliphatic Jiarubon ester (adipic acid - propylene glycol type polyester), aliphatic tricarboxylic acid ester (triethyl citrate and the like), phosphoric acid triester (triphenyl phosphate, etc.), epoxy fatty acid ester (epoxy butyl stearate, etc.), petroleum resins.
[0065]
　The release agent, a lower of higher fatty acids (C1 ~ 4) alcohol esters (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4 ~ 30) (hydrogenated castor oil, etc.), glycol esters of fatty acids, such as liquid paraffin and the like.
[0066]
　As the antioxidant, phenol (2,6-di -t- butyl-4-methylphenol), polycyclic phenol (2,2'-methylenebis (4-methyl -6-t-butylphenol), phosphorus-based (tetrakis (2,4-di -t- butyl-phenyl) -4,4-biphenylene phosphonate, etc.), antioxidants like amine-based (N, N-diisopropyl -p- phenylenediamine) It is.
[0067]
　As the flame retardants, organic flame retardant (nitrogen-containing, sulfur-containing, silicon-Motokei, phosphorous-based, etc.), an inorganic flame retardant (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.) and the like.
[0068]
　As the ultraviolet absorber, benzotriazole-based, benzophenone-based, salicylic acid-based, acrylate-based, and the like.
[0069]
　Antibacterial agents, quaternary ammonium salts, pyridine based compounds, organic acids, organic acid esters, halogenated phenol, and organic iodine.
[0070]
　As the surfactant can be exemplified nonionic, anionic, surfactants cationic or amphoteric. Nonionic surfactants, higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol polyethylene glycol type nonionic surfactants of ethylene oxide adducts, polyethylene oxide, fatty esters of glycerol , fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and polyhydric alcohol type nonionic surfactants such as fatty amides of alkanolamines and the like, as an anionic surfactant is, for example, sulfuric acid ester salts such as alkali metal salts of higher fatty acids, alkyl benzene sulfonates, alkyl sulfonates, sulfonate salts such as paraffin sulfonate, Include a phosphoric acid ester salts such as grade alcohol phosphate ester salt, the cationic surfactants, such as quaternary ammonium salts such as alkyl trimethyl ammonium salts. Examples of the amphoteric surfactant, higher alkyl amino acid salts amino acid type duplex surfactants such as higher alkyl dimethyl betaines, such as betaine type amphoteric surfactants such as higher alkyl time hydroxyethyl betaine.
[0071]
　As the antistatic agent, said surfactant, fatty acid esters, polymeric antistatic agent. As the fatty acid ester include stearic acids and esters of oleic acid, polyether ester amides as polymer type antistatic agent.
[0072]
　The filler, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, UV absorbers, antimicrobial agents, surfactants, amount of various additives such as antistatic agents, to impair the object of the present invention may be in free range, can be appropriately selected depending on the application, but are not limited to, the above-described (a), (B), 100 parts by weight total of the component (C), respectively, 0. is preferably 1 to 30 parts by weight.
[0073]
　Polyester sheet of the present invention contains a polyester (A), a predetermined mixing ratio as described above 4-methyl-1-pentene polymer (B) and compatibilizer and (C), 4-methyl-1 - at least a portion of the pentene polymer (B) is favorably shows a state of being dispersed in finely and uniformly resin composition.
[0074]
　[Polyester production method of Sheet]
　Although method for producing a polyester sheet of the present invention is not particularly limited, for example, after drying the polyester (A), dry polyester (A), 4-methyl-1-pentene polymer ( B), after the compatibilizing agent (C) and other optional components were mixed in the proportion of the added above, to obtain a polyester resin composition by melt-kneading the polyester by molding a polyester resin composition obtained sheet it is possible to obtain. The method of melt kneading is not particularly limited, it is generally possible to perform using a melt kneading apparatus such as an extruder which is commercially available.
[0075]
　If melt-kneading, for example, a cylinder temperature of a portion performing kneading at a kneading machine is usually 250 ~ 310 ° C., preferably 260 ~ 290 ° C.. Temperature kneading is insufficient due to the low and insufficient melting than 250 ° C., not seen improvement in the physical properties of the resin composition. On the other hand, if the temperature is higher than 310 ° C., the polyester (A), 4-methyl-1-pentene-based polymer (B), thermal decomposition occurs compatibilizer (C), deterioration of physical properties of the resin composition there is a case that occurs. The kneading time is usually 0.1 to 30 minutes, particularly preferably 1 to 5 minutes. Kneading time is not performed sufficiently kneading the less than 0.1 minutes, and when the kneading time exceeds 30 minutes polyester (A), 4-methyl-1-pentene-based polymer (B), compatibilizer which may occur thermal decomposition of the agent (C).
[0076]
　Thus a polyester resin composition prepared typically shows a state in which at least part are finely dispersed in the resin composition of the 4-methyl-1-pentene polymer (B).
[0077]
　Polyester sheet of the present invention can be produced without being particularly limited by the known method of manufacturing a sheet from the resin composition, specifically, for example, sheet obtained by various molding methods object can be suitably produced by the (unstretched sheet) is stretched, more preferably, can be produced by biaxially stretching the resulting sheet by extrusion molding.
[0078]
　Method for producing a non-stretched sheet is not particularly limited, it is generally possible to perform by using a device that is commercially available. Unstretched sheet, for example, the polyester (A), 4-methyl-1-pentene-based polymer (B), a polyester resin composition consisting of other optional components as needed compatibilizer (C) and the pellet of goods, dried by vacuum drying if necessary, and supplied to an extruder having a T die, can be created by extruding. Or polyester (A), 4-methyl-1-pentene-based polymer (B), and supplies the compatibilizer (C) and other components in each extruder, preparing the polyester resin composition in an extruder and by performing extrusion and subsequently it may be an unstretched sheet. Unstretched sheet may be a sheet of a single layer or a laminated sheet comprising a layer of the polyester resin composition.
[0079]
　In the step of stretching, the unstretched sheet is stretched with a stretching device. Preferably, the unstretched sheet, 2 is biaxially stretched using a biaxial stretching apparatus. Sheet of the present invention obtained through the step of stretching treatment, having a large number of fine pores. In this stretching step, the polyester (A) in unstretched sheet made of a polyester resin composition described above, the polyester (A) is finely dispersed in the 4-methyl-1-pentene polymer (B ) interface delamination and occurs which fine voids in the polyester-based sheet is formed many by.
[0080]
　Conditions of stretching is not particularly limited, for example, when using a polyethylene terephthalate polyester (A), after heating the unstretched sheet is 70 ~ 90 ℃, 2 ~ 5 times in the longitudinal direction, the longitudinal preferably stretched 2-5 times in the direction perpendicular to the direction. Stretching method is not particularly limited, it is generally possible to perform by using a device that is commercially available. Also, when performing the biaxial stretching, longitudinal, a method of sequential stretching in a direction perpendicular to the longitudinal direction, may be either a method of stretching in the longitudinal and vertical directions simultaneously.
[0081]
　Sheet was subjected to stretching treatment continues, the mechanical strength, in order to increase the dimensional stability and the like, the sheet edge clip in a fixed state such as heat treatment is performed for 1 to 120 seconds 0.99 ~ 240 ° C., orientation performing the removal of the strain stretch and promotion of crystallization are preferable. The heat treatment step is also referred to as a heat. During the heat treatment step may be subjected to 1-10% relaxation treatment in the longitudinal direction and the vertical direction as needed.
[0082]
　Further, the sheet obtained through the step of stretching treatment, for imparting functions such as light stability and anti-blocking properties, may be provided a coating layer. Furthermore polyester sheet of the present invention may be a laminate of the same or other species sheet.
[0083]
　[Shape and characteristics of the polyester sheet]
　While polyester sheet is not particularly thick limitations of the present invention, practically preferably in the range of 0.001 mm ~ 10 mm. Luminance measured by later-described conditions are preferably in the range 40-100%.
[0084]
　Polyester sheet of the present invention, open-porous in the dispersed phase around which is reduced, because the peeling resistance is obtained by using a conventionally greatly improved to have a resin composition, a homogeneous fine pores can be made by dispersing the, excellent in reflectivity and scattering of light, without causing strength reduction unit and holes and the like in a part, it is expected to exhibit uniform properties over the entire surface.
[0085]
　[Polyester sheet applications]
　polyester sheet of the present invention can be used without limitation to conventional polyester sheet applications, from its excellent light reflection performance, reflective sheet of the flat type image display device such as a liquid crystal display, lighting Signs reflecting sheet can be suitably used for various reflection sheet applications such as the back reflecting sheet of a solar cell.
Example
[0086]
　Hereinafter, a more detailed description of the present invention based on examples, the present invention is not limited to these examples. Measurement method in Examples and Comparative Examples of the present invention is as follows.
[0087]
　[Comonomer
　content] 4-methyl-1-pentene polymer of ethylene and carbon atoms 3 ~ 20 alpha-olefin (4-methyl-1 except pentene) from at least one member selected alpha-olefin the content of constituent units derived from (comonomer) is the following apparatus and conditions, 13 was calculated from the C-NMR spectrum.
[0088]
　Using Bruker BioSpin made AVANCEIIIcryo-500 type nuclear magnetic resonance device, the solvent is o- dichlorobenzene / benzene -d 6 (4/1 v / v) mixed solvent, sample concentration 55 mg / 0.6 mL, measured temperature is 120 ° C., the observed nucleus 13 C (125 MHz), a single pulse proton broadband decoupling sequence, pulse width 5.0μ sec (45 ° pulse), repetition time 5.5 sec, the integration number 64 times, benzene -d 6 to 128ppm of measured as a reference value for the chemical shift. Using the integral value of the main chain Mechinshigunaru was calculated comonomer content by the following equation.
[0089]
　Comonomer content (%) = [P / ( P + M)] × 100
　where P denotes the total peak area of the comonomer backbone Mechinshigunaru, M denotes the total peak area of the 4-methyl-1-pentene backbone Mechinshigunaru .
[0090]
　Mp (Tm), heat of fusion (.DELTA.Hm)]
　using a Seiko Instruments Inc. DSC measurement apparatus (DSC220C), and filled with samples of about 5mg to measurement aluminum pan, was heated to 280 ° C. at 10 ° C. / min. After holding for 5 minutes at 280 ° C., the temperature was lowered to 20 ° C. at 10 ° C. / min. After holding at 20 ° C. 5 min, the temperature was raised to 280 ° C. at 10 ° C. / min. The apex of the observed crystal melting peak during the second heating was as the melting point (Tm). Moreover, to calculate the heat of fusion ΔHm from the integrated value of the crystal melting peak.
[0091]
　[Melt Flow Rate
　(MFR)] compliance with 260 ° C. to ASTM D1238, measured under the conditions of 5kg load.
[0092]
　[Meso diad fraction]
　4-methyl-1-pentene polymer meso diad isotacticity (meso diad fraction) (m) is, any two head-to-tail bonded 4-methyl in the polymer chain -1- when expressing a pentene unit chain in plan zigzag structure, defined as the percentage direction are the same for the isobutyl branches, 13 was determined by the following formulas C-NMR spectra.
[0093]
　Meso diad isotacticity (m) (%) = [m / (m + r)] × 100
[wherein, m, head r is represented by the following formula - attached at the tail 4-methyl-1 It shows the absorption intensity originating from the main chain methylene of pentene units. ]
[0094]
[Formula 1]

[0095]
　 13 C-NMR spectra using a Bruker BioSpin made AVANCEIIIcryo-500 type nuclear magnetic resonance device, the solvent is o- dichlorobenzene / benzene -d6 (4/1 v / v) mixed solvent, sample concentration 60 mg / 0.6 mL, measurement temperature 120 ° C., the observed nucleus 13 C (125 MHz), a single pulse proton broadband decoupling sequence, pulse width 5.0μ sec (45 ° pulse), repetition time 5.5 sec, benzene the 128ppm of -d6 was measured as a reference value of the chemical shift.
[0096]
　Peak area, delimiting the region of 41.5 ~ 43.3ppm at the minimum point of the peak profile, high magnetic field side of the first region, were classified downfield in the second region.
[0097]
　In the first region, 4-methyl-1-but main chain methylene of pentene units 2 in the chain resonates represented by (m), the integrated value regarded as 4-methyl-1-pentene homopolymer "m" and the. In the second region, and resonance 4-methyl-1-backbone methylene pentene units 2 in the chain represented by (r), and the integrated value "r". Incidentally, it was below the detection limit of less than 0.01%.
[0098]
　[Decane-soluble
　component] 4-methyl-1 sample 5g pentene polymer n- decane 200mL the mixture was heated for 1 hour dissolution at 145 ° C.. Allowed to cool to 23 ° C., and allowed to stand for 30 minutes. Thereafter, the precipitate (n- decane-insoluble portion) was filtered off. Put filtrate into approximately 3 volumes of acetone to precipitate a component that was dissolved in n- decane. The precipitate was separated by acetone Kararo, and then dried. Even the filtrate side was concentrated to dryness The residue was observed. n- decane-soluble portion content was determined by the following equation.
[0099]
　n- decane soluble part amount (wt%) = [precipitates weight / sample weight] × 100
　[unstretched sheet solution of 4-methyl-1-pentene polymer average dispersion diameter and the maximum particle size of (B) measurement method]
　the size of the dispersed phase of the 4-methyl-1-pentene polymer in the unstretched sheet (B) is a cross-sectional (end view, sheet TD direction cross-section) of the sheet was observed by SEM cut out. The average dispersion diameter of the dispersed phase, was defined as the average value of any of the dispersed phase 10 points was confirmed by SEM. Maximum particle diameter, of the observed particles in the visual field 60 [mu] m × 70 [mu] m, was used the largest value is the average value of the maximum diameter and minimum diameter.
[0100]
　[Measurement method for average pore area of the stretched sheet]
　The obtained cross-section (end view, sheet TD cross section) of the stretched sheet was observed by SEM cut out. The average pore area was an average value of any of the holes 10 has been identified in the SEM.
[0101]
　[Measurement method of light reflectance of the stretched sheet (luminance)
　light reflectivity of the stretched sheet was measured by a spectrophotometer (manufactured by Hitachi High-Tech Science). Longitudinal, direction perpendicular to the longitudinal direction, to measure the light reflectance of a wavelength of 550 nm, and the average value was used.
[0102]
　[Example
　1] <4-methyl -1-pentene polymer (B)>
　at room temperature under a nitrogen stream, made of SUS polymerization vessel in which with a stirrer having an inner volume of 1L, purified decane 425 mL, diisobutylaluminum hydride decane solution (2.0 mmol / mL of aluminum atom basis) was 0.5 mL (1 mol) charged. Then added 0.0005mmol decane slurry solution of prepolymerized catalyst component prepared above and (C) in terms of zirconium atom was 50NmL charged with hydrogen (first hydrogen loading). Then, it was charged continuously at a constant rate to the 4-methyl-1-pentene 250mL and 1-decene 3.3mL mixed solution of over 2 hours the polymerization vessel. The instrumentation and the polymerization initiator input start time, the temperature was raised from the start of polymerization to 30 minutes over 45 ° C., and held for 4 hours at 45 ° C.. 1 hour after the start of polymerization, the hydrogen after two hours each were 50NmL charged (second hydrogen loading). After 4.5 hours from the polymerization initiation, the temperature was lowered to room temperature and after depressurizing to obtain a solid material was immediately filtered a polymer liquid containing a white solid. The solid matter dried under reduced pressure for 8 hours at 80 ° C., to obtain a polymer [B-1]. The yield was 131g. Of the polymer [B-1] 13 C-NMR, GPC, the results of MFR and decane soluble part measurements are shown in Table 1.
[0103]
　
　Polyethylene terephthalate polyester (A) (manufactured by Mitsui Chemicals, Inc. Mitsui PET, brand name: J005PC, IV = 0.62dl / g ) and, 0.99 ° C. using a vacuum dryer, 16 hours and dried conditions. The dried polyethylene terephthalate 80 parts by weight, 4-methyl-1-pentene polymer as (B), the above-mentioned polymer 15 parts by mass of [B-1], the polar group-modified styrene as compatibilizer (C) - ethylene / butylene - styrene copolymer (JSR Corporation, brand name: Dynalon 8630P, MFR (JIS K7210,230 ℃, 2.16kgf): 15g / 10min, density: 0.89 g / cm 3 , styrene content: 15 %) were blended at the composition ratio of 5 parts by weight.
[0104]
　Moreover The mixture biaxial extruder (manufactured TECHNOVEL Ltd., φ = 25mm, L / D = 40, cylinder temperature: 270 ° C., screw rotational speed: 1800 rpm) were melt-kneaded in, and an unstretched sheet having a thickness of 100μm .
[0105]
　
　Using a biaxial stretching apparatus (manufactured by Bruckner), after heating the unstretched sheet to 100 ° C., longitudinally 3-fold, 3-fold in a direction perpendicular to the longitudinal direction, the stretching speed 300 mm / sec It was successively stretched at the conditions. 200 ° C. The stretched sheet was subjected to heat treatment at for 60 seconds. The thickness of the stretched sheet is 11 [mu] m, light reflectance wavelength 550nm was 56%.
[0106]
　[Comparative Example
　1] 4-methyl-1-a-pentene polymer, 4-methyl-1-pentene, 1-decene copolymer (manufactured by Mitsui Chemicals, Inc. TPX (registered trademark), brand name: DX820, mp: 233 ℃, MFR (ASTM D1238,260 ℃ , 5kgf): except using 180 g / 10min), granulation was performed and film in the same manner as above example 1. The thickness of the stretched sheet was 12.5 .mu.m, light reflectance wavelength 550nm was 53%. Towards the stretched film of Example 1 is more average pore area is large, it can be seen light reflectance is high.
[0107]
　[Comparative Example
　2] 4-methyl-1 as pentene polymer, 4-methyl-1-pentene, 1-decene copolymer (manufactured by Mitsui Chemicals, Inc. TPX (registered trademark), brand name: DX818, mp: 232 ℃, MFR (ASTM D1238,260 ℃ , 5kgf): except for using 28 g / 10min) was subjected to granulation and film in the same manner as above example 1. The thickness of the stretched sheet was 11.5 .mu.m, light reflectance wavelength 550nm was 40%.
[0108]
　As can be seen from larger maximum particle size of the pre-stretch sheet is large variation in the dispersed particle size of the dispersed phase in the sheet before stretching, the resulting stretched sheet was uneven opening state. This is presumed to have led to a reduction in luminance.
[0109]
　[Comparative Example 3]
　in place of 4-methyl-1-pentene polymer, homopolypropylene (Prime Polypro (registered trademark), brand name: J108M, except using the same method as described above [Example 1] in granulation was performed and film. the thickness of the stretched and heat-fixed stretched sheet is 11.5 .mu.m, PP is melted at light reflectance wavelength 550nm was 35%. heat-setting step (heat treatment step) and will be, it is once estimated that opening the hole has closed.
[0110]
[Table 1]

[0111]
In Table 1, ND means no data.

WE CLAIM

Polyester (A), a polyester sheet comprising 4-methyl-1-pentene polymer (B) and compatibilizer and (C), wherein (A), the content ratio of (B) and (C) , (a), (B) , when the total 100 parts by mass of (C), (a) is 60 to 98.9 parts by weight, (B) is 1 to 25 parts by weight, (C) 0 a .1 to 15 parts by weight, further, the (B) satisfies the following requirements (a) ~ (d), a polyester sheet.
(A) 4-methyl-1-pentene constitutional unit derived from a 100 to 90 mole%, at least selected from ethylene and carbon atoms 3 ~ 20 alpha-olefin (except 4-methyl-1-pentene) sum 0-10 mol% of structural units derived from one α- olefin.
(B) differential scanning calorimetry (DSC) in the measured heat of fusion .DELTA.Hm (Unit: J / g) and the melting point Tm (unit: ° C.) The following requirements (1), satisfying the (2).
　　　　(1) .DELTA.Hm ≧ 0.5 ×
　　　　Tm-76 (2) melting point Tm: 200 ~ 260 ° C.
(c) in compliance with ASTM D1238 260 ° C., a melt flow rate measured at 5kg loading condition (MFR) of 0.1 ~ 500g / 10 minutes.
(D) 13 meso diad fraction as measured by C-NMR (m) 98.5 to 100 percent.
[Requested item 2]
　Wherein (B) satisfies at least one of the following requirements (e) and (f), a polyester sheet according to claim 1.
(E) a silicone oil in compliance with ASTM D1525, test load 10 N, Vicat softening temperature measured at a Atsushi Nobori rate of 50 ° C. / h is 145 ~ 220 ° C..
(F) 23 ° C. decane-soluble component quantity less 5 wt%.
[Requested item 3]
　The 4-methyl-melting point Tm of pentene polymer (B) is a polyester sheet according to claim 1 or 2 is 230 ~ 245 ° C..
[Requested item 4]
　The polyester (A) is a polyester sheet according to any one of claims 1 to 3, which is a polyethylene terephthalate.
[Requested item 5]
　Polyester sheet according to any one of claims 1 to 4 is obtained through a step of stretching treatment.
[Requested item 6]
　Wherein (C) is a polyester sheet according to any one of claims 1 to 5, which is a polar group-modified styrene-based elastomer
[Requested item 7]
　The polar group modified styrene-based elastomer, a polar group-modified styrene - ethylene / butylene - polyester sheet according to claim 6 which is a styrene copolymer.
[Requested item 8]
　Polyester sheet according to the polar group-modified claim 6 or claim 7 styrene content of the styrene elastomer is in the range of 5 to 20 wt%.
[Requested item 9]
　A biaxially oriented sheet, polyester sheet according to any one of claims 1-8.
[Requested item 10]
　Liquid crystal display, a reflecting sheet of a lighting signboard or solar cell, a polyester sheet according to any one of claims 1-9.