JP2014125588A - Polyester composition and polyester molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-heat storage black spun-dyed polyester composition, the polyester composition showing a black color and capable of preventing temperature rise of the polyester composition by solar radiation.SOLUTION: There is provided a polyester composition containing practically no carbon black and black pigments other than carbon black of 0.05 to 40 mass% based on the polyester composition.

Description

  The present invention relates to a black polyester composition. More specifically, the present invention relates to a polyester composition suitable for various industrial products that contain substantially no carbon black and are required to suppress the temperature rise of the surface by solar radiation, and a polyester molded article comprising the same.

  Polyesters, particularly polyethylene terephthalate, polyethylene naphthalate and polytetramethylene terephthalate are widely used in fibers, films or other molded articles because of their excellent mechanical, physical and chemical performance.

  In general, a black polyester molded product is generally obtained by adding carbon black. When carbon black is added, a polyester / molded article with an excellent jet black hue can be obtained. However, since carbon black has a high absorbance even in the infrared region, the temperature of the molded article rises due to infrared rays contained in sunlight. It has the characteristic to do. For example, when a carbon black-containing polyester fiber is used as an interior material of a car, there is a drawback that the interior temperature reaches a high temperature due to solar radiation in summer and the comfort is greatly impaired.

  When the molded product is a fiber, a polyester fabric can be produced by dyeing a polyester fabric with a black disperse dye. However, the dyeing process requires high-temperature heat treatment, and the wastewater treatment of the dyeing solution is expensive. From the viewpoints of energy saving and productivity, black original polyester that does not require dyeing is desired.

  In order to eliminate such heat storage properties of carbon black, non-heat storage inorganic black pigments have been studied. (For example, refer to the prior art documents 1 to 8.) However, as for the thing excellent in heat storage, the hue of the polyester obtained is mostly gray rather than black, and the blackness is not a sufficient level. The obtained polyester that exhibits excellent blackness has insufficient heat storage. The reality is that a black pigment having both heat storage and blackness has not been obtained. In addition, many of these inorganic black pigments use harmful chromium compounds, and there are problems in terms of the environment.

JP 2000-072990 A JP 2001-311049 A JP 2004-083616 A JP 2000-264639 A JP 2003-238164 A JP 2002-331611 A JP 2007-197570 A JP 2010-150354 A

  The present invention has been made in view of the above background, and the object thereof is substantially free of carbon black, and the surface temperature of a polyester molded product is irradiated by irradiation with visible light including infrared rays such as sunlight and various illumination lights. An object of the present invention is to provide a black polyester composition and a black polyester molded article capable of suppressing the increase.

As a result of intensive studies in view of the above-described prior art, the present inventors have reached the present invention. That is, in the present invention, the main repeating unit is selected from the group consisting of ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, ethylene-2,6-naphthalate, trimethylene-2,6-naphthalate and tetramethylene-2,6-naphthalate. A polyester composition comprising at least one selected polyester and a black pigment other than carbon black, containing 0.05 to 40% by mass of the black pigment other than carbon black with respect to the polyester composition, and carbon black as a polyester It is a polyester composition which does not contain substantially with respect to a composition, Comprising: It satisfy | fills following formula (I), It is the polyester molded article obtained by melt-molding this. The present invention can also solve the above problems.
Color-L ≦ 30 (I)
[In the above formula, Col-L represents the hue L ^* value according to the L ^* a ^* b ^* system of the CIE color difference system of the polyester composition. ]

  According to the present invention, it is possible to obtain a polyester composition that is black and does not absorb light in the near infrared region without using carbon black. As a result, various industrial products that can suppress the temperature rise of the polyester composition by solar radiation can be obtained. The polyester molded product obtained by melt-molding the polyester composition of the present invention has the property that it is difficult to store heat with sunlight, so it is used for car interior materials such as car seats and dashboards, and for summer clothing such as black clothing, and for industrial use. It can be used widely.

Hereinafter, the polyester composition of the present invention will be described in detail.
<About the polyester which comprises the polyester composition of this invention, and its manufacturing method>
As the polyester polymer constituting the polyester composition of the present invention, a general-purpose polyester polymer is used. Among them, the main repeating unit of polyester is selected from the group consisting of ethylene terephthalate, ethylene-2,6-naphthalate, trimethylene terephthalate, trimethylene-2,6-naphthalate, butylene terephthalate, butylene-2,6-naphthalate. It is preferable. Considering the point that it is particularly excellent in physical properties and suitable for mass production, it is preferable that the main repeating unit constituting the polyester is ethylene terephthalate, trimethylene terephthalate, butylene terephthalate, ethylene-2,6-naphthalate, which is industrially inexpensive. Therefore, the main repeating unit is most preferably ethylene terephthalate.

  As a main repeating unit of polyester, it represents that the specific repeating unit contains 80 mol% or more with respect to all the repeating units which comprise polyester. In particular, it is preferably 85 mol% or more. In particular, a polyester containing 90 mol% or more is preferable. Moreover, if it is a small amount in the polyester polymer, it may be a copolymer containing an appropriate third component.

As the third component dicarboxylic acid, orthophthalic acid, isophthalic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylsulfonedicarboxylic acid, 4,4′-biphenyletherdicarboxylic acid, 1,2-bis ( Phenoxy) ethane-p, p'-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid, alkali metal salt of 5-sodium sulfoisophthalic acid, alkali metal earth metal salt of 5-sodium sulfoisophthalic acid, 5-sodium sulfoisophthalic acid Quaternary ammonium salts, aromatic dicarboxylic acids represented by quaternary phosphonium salts of 5-sodium sulfoisophthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid , Sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid Aliphatic dicarboxylic acids exemplified by aliphatic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, decanedicarboxylic acid, tricyclo [5.2.1.0 ^2,6 ] decanedicarboxylic acid Or these ester forming derivatives are preferable. Further, a tri- or higher functional carboxylic acid component such as trimellitic acid, trimesic acid and pyromellitic acid may be copolymerized. The dicarboxylic acid may contain a substituent or an alicyclic structure in the molecular chain, and two or more kinds may be used at the same time.

  The ester-forming derivatives are dialkyl esters, such as dimethyl esters, diethyl esters, dipropyl esters, dibutyl esters, dihexyl esters, etc., diaryl esters, such as diphenyl esters, dinaphthyl esters, etc., dicarboxylic acid chlorides, dicarboxylic acid bromides And dicarboxylic acid halides represented by dicarboxylic acid iodide and the like.

Examples of the third component glycol include diethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1 , 6-hexanediol, 1,8-octamethylene glycol, 1,10-decamethylene glycol, alkylene glycol such as 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc. Aliphatic glycols, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexa Dimethanol, 1,4-cyclohexane diethanol, tricyclo [5.2.1.0 ^{2, 6]} de or alicyclic glycols exemplified in Kanji methanol, etc., catechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenyl methyl Bisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p -Hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2,5-naphthalenediol, glycols obtained by adding ethylene oxide to these glycols (for example, 1,3-bis ( 4-β-hydroxyethoxyphenyl) Propane, 1,3-bis (4-beta-hydroxy-ethoxy) propane) aromatic group-containing glycol exemplified in the like. Moreover, the said glycol may contain a substituent and an alicyclic structure in a molecular chain, and may use 2 or more types simultaneously.

  As a method for producing the polyester used in the present invention, a generally known production method is used. That is, first, a glycol ester of dicarboxylic acid and / or a low polymer thereof is produced by a direct esterification reaction of a dicarboxylic acid component such as terephthalic acid and a glycol component such as ethylene glycol. Alternatively, a dicarboxylic acid glycol ester and / or a low polymer thereof is produced by a transesterification reaction in the presence of a dicarboxylic acid component such as dimethyl terephthalate, a diol component such as ethylene glycol, and a transesterification catalyst.

Next, this low polymer is heated under reduced pressure in the presence of a polymerization catalyst and subjected to a polycondensation reaction until a predetermined degree of polymerization is obtained, whereby the desired polyester is produced. For example, as the polyester polymer used in the present invention, terephthalic acid, naphthalene-2,6-dicarboxylic acid or an ester-forming derivative thereof can be polymerized under appropriate reaction conditions in the presence of a catalyst. Further, if one or more appropriate third components are added before completion of the polycondensation of the polyester, a copolyester is produced. As will be described later, by using a specific compound for the transesterification catalyst, the hue L ^* of the resulting polyester can be made more black. Therefore, in producing the polyester composition of the present invention, the dimethyl terephthalate For example, it is preferable to employ a method of transesterification in the presence of a dicarboxylic acid component, a diol component such as ethylene glycol, and a transesterification catalyst.

<About transesterification catalyst>
The transesterification catalyst is not particularly limited, and a conventionally known transesterification catalyst can be used. For example, lithium, sodium, potassium, magnesium, calcium, strontium, barium, titanium, manganese, cobalt, zinc, and an aluminum compound can be used. Examples of such compounds include oxides, acetates, carboxylates, hydrides, alcoholates, halides, carbonates, sulfates and the like of each metal compound. Moreover, these compounds may use 2 or more types together.

  When the transesterification catalyst is magnesium, calcium, manganese, or aluminum, the catalytic amount of the transesterification reaction is preferably in the range of 5 to 200 mmol% with respect to the number of moles of the dicarboxylic acid component used as a raw material. More preferably, it is the range of 10-100 mmol%, Most preferably, it is the range of 15-50 mmol%. When it is less than 5 mmol%, the reaction rate of transesterification is slow, which is not preferable for production. When the amount exceeds 200 mmol%, the catalyst causes thermal deterioration, and therefore, it may not be possible to have a sufficient degree of polymerization and a sufficient mechanical strength as a molded article, which is not preferable.

Since the polyester composition of the present invention is required to be black, it is desirable to use a titanium compound or a manganese compound as a catalyst for the transesterification reaction. When a titanium compound is used as a transesterification reaction catalyst, the polyester obtained becomes deep yellow, and when a manganese compound is used, the polyester obtained becomes light gray and finally the CIE color difference L ^* a of the polyester composition obtained. ^* B ^{* It} is good for decreasing the hue L ^* (hereinafter simply referred to as the hue L ^* ) by the system and consequently increasing the blackness.

  When the catalyst for the transesterification reaction is a titanium compound, the catalyst amount for the transesterification reaction is preferably in the range of 5 to 1000 mmol% with respect to the number of moles of the dicarboxylic acid component. More preferably, it is the range of 10-750 mmol%. When it is less than 5 mmol%, the reaction rate of transesterification is slow, which is not preferable for production. Moreover, since the dark color property of obtained polyester becomes inadequate, it is not preferable. When it exceeds 1000 mmol%, the catalyst causes thermal deterioration, which is not preferable. By satisfying these requirements, a transesterification product capable of achieving an intrinsic viscosity sufficient to obtain a molded article can be obtained.

<About polymerization catalyst>
The polymerization catalyst is not particularly limited, and antimony, titanium, germanium, aluminum, zirconium, and tin compounds can be used. Examples of such a compound include antimony, titanium, germanium, aluminum, zirconium, tin oxide, acetate, carboxylate, hydride, alcoholate, halide, carbonate, sulfate and the like. Moreover, these compounds may use 2 or more types together. Moreover, it is also possible to use the metal compound used for this invention as a catalyst as a polymerization catalyst.

  When the polymerization reaction catalyst is an antimony compound, the catalyst amount is preferably in the range of 10 to 200 mmol% with respect to the number of moles of the dicarboxylic acid component used as a raw material. More preferably, it is the range of 15-150 mmol%, More preferably, it is the range of 20-100 mmol%, Most preferably, it is the range of 25-80 mmol%. If it is less than 5 mmol%, the reaction rate of melt polymerization is slow, which is not preferable for production. Moreover, since the solid-phase polymerization rate also falls, it is not preferable. If it exceeds 200 mmol%, the catalyst causes thermal degradation of the polyester when melted, which is not preferable.

Since the polyester composition of the present invention is required to have a black color, it is desirable to use a titanium compound or an antimony compound as a catalyst for the melt polymerization reaction. When a titanium compound is used as a melt polymerization reaction catalyst, the resulting polyester becomes dark yellow, and when an antimony compound is used, the resulting polyester becomes gray and ultimately reduces the hue L * of the resulting polyester, resulting in a black color. Good to increase the properties. By adopting these catalysts, the hue L ^* of the final polyester is lowered, the hue L ^* is realized to be 30 or less, and as a result, it is favorable for increasing the blackness.

  When the catalyst for the polymerization reaction is titanium, the catalyst amount is preferably in the range of 5 to 1000 mmol% with respect to the number of moles of the dicarboxylic acid component used as a raw material. More preferably, it is the range of 10-750 mmol%. If it is less than 5 mmol%, the reaction rate of melt polymerization is slow, which is not preferable for production. Moreover, since the dark color property of obtained polyester becomes inadequate, it is not preferable. When it exceeds 1000 mmol%, the catalyst causes thermal deterioration, which is not preferable. It is also preferable to use an antimony compound and a titanium compound which have high polymerization activity and are easily available.

<About titanium catalyst>
The titanium compound of the catalyst used here is preferably an organic titanium compound containing a polyester-soluble titanium element. The organic titanium compound is preferably a titanium complex compound, more specifically, tetraalkoxytitanium or tetraphenoxytitanium, hexaalkyldititanate, or octaalkyltrititanate having an alkyl group having 1 to 10 carbon atoms. Is mentioned. Examples of specific compounds of tetraalkoxytitanium include tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, and tetra-n-butoxytitanium. Preferred examples of the other titanium compounds include tetraphenoxy titanium, hexabutyl dititanate, and octabutyl trititanate.

  Other titanium complex compounds include titanium lactate, titanium acetate, tetrakisacetylacetonatotitanium, tetrakis (2,4-hexanedionato) titanium, tetrakis (3,5-heptanedionato) titanium, bisacetylacetonatodimethoxytitanium, bisacetyl Acetonatodiethoxytitanium, bisacetylacetonatobis (n-propoxy) titanium, bisacetylacetonatodiisopropoxytitanium, diacetylacetonatodibutoxytitanium, titanium dihydroxybisglycolate, titanium dihydroxybislactate, titanium dihydroxybis (2 -Hydroxypropionate), dimethoxybis (triethanolaminato) titanium, diethoxybis (triethanolaminato) titanium, diisopropoxybis (triethanol Minato) titanium, di-n-propoxy-bis (triethanolaminato) titanium or dibutoxybis (triethanolaminato) can be exemplified preferably titanium. These compounds can be used as a polymerization catalyst during the production of the polyester.

<About DEG (diethylene glycol)>
The DEG contained in the polyester used in the present invention is preferably in the range of 0.40 ≦ DEG ≦ 2.00% by weight. Here, DEG indicates mass% of diethylene glycol contained in the polyester. Since DEG affects the ease of molding of polyester, it is desirable to control by the target molded product (fiber, molded product, film). However, when the DEG exceeds 2.0% by weight, the mechanical properties of the obtained molded product are deteriorated, which is not preferable. As will be described later, the polyester composition of the present invention is used in various molded products such as films, sheets, various packaging containers, and fibers. In that case, the minimum mechanical strength is often required, although the situation varies depending on the individual application. Therefore, even if the temperature rise can be suppressed by sunlight, the final object of the present invention may not be achieved if the mechanical strength is extremely inferior. More preferably, the content of DEG is 0.45 to 1.00% by mass, and still more preferably 0.50 to 0.80% by weight.

<About black pigment>
The polyester composition of the present invention contains 0.05% by mass to 40% by mass of black pigment other than carbon black with respect to the polyester composition, and substantially does not contain carbon black with respect to the polyester composition. Features. When it is less than 0.05% by mass, the blackness of the resulting polyester composition is insufficient, which is not preferable. When it exceeds 40 mass%, the process condition at the time of melt-molding the polyester deteriorates, which is not preferable. The addition amount of the black pigment other than the carbon black is preferably 0.1 to 30% by mass from the viewpoint of maintaining the blackness and not adversely affecting the physical properties of the melt moldability and the mechanical strength of the molded product. 0.5-20 mass% is more preferable, and 0.8-10 mass% is the most preferable. Note that black is an achromatic color, a color such as an eyelid or a corner, and light is not evenly perceived over the entire band in the human visible region, or a state close to it, or a state that can be felt by humans. Represents. Hexadecimal notation used for web color designation is # 0000, and RGB (RGB color model) notation (0, 0, 0) used for image representation on a cathode ray tube, liquid crystal display, digital camera, etc. This is a case where (0, 0, 0, 100) is expressed in CMYK (CMYK color model) and N1 is expressed in Munsell color system.

  The amount of carbon black added to the polyester composition of the present invention is substantially not contained and is 0 ppm. If it exceeds 0 ppm, the carbon black added to the polyester composition has a property of absorbing not only electromagnetic waves having a wavelength in the visible light region but also electromagnetic waves having a wavelength in the infrared region. Since the ultimate temperature of the surface temperature of a polyester composition increases significantly, it is not preferable. Here, “substantially not contained” means that it is less than the detection limit even by instrumental analysis, or is acceptable in the field of polyester and polyester compositions as a result of contamination, and is 0.5 ppm or less. More preferably, it means 0.1 ppm or less, more preferably 0.01 ppm or less. Here, as a method for quantifying carbon black in the polyester composition, JIS standard K6277, rubber-carbon black quantification-thermal decomposition method, and chemical decomposition method can be appropriately applied.

<About the types of black pigments>
The black pigment used in the polyester composition of the present invention preferably satisfies the following general formula (II).
0 ≦ (inorganic black pigment) / (organic black pigment) ≦ 0.5 (II)
[In the above formula, (inorganic black pigment) indicates mass% of inorganic black pigment other than carbon black contained in the polyester composition. (Organic black pigment | dye) shows the mass% of the organic black pigment | dye contained in a polyester composition. ]

When the ratio exceeds 0.5, the blackness and hue L ^* of the resulting polyester composition are insufficient, which is not preferable. The ratio is preferably 0.2 or less, and more preferably 0. That is, the case where it mix | blends with an organic black pigment | dye alone in a polyester composition is a more preferable aspect at the point which does not absorb the light of the wavelength of a near infrared region, maintaining the blackness of a polyester composition.

<About the types of inorganic black pigments>
About an inorganic black pigment | dye, a conventionally well-known infrared reflective black-type pigment can be used.

<About the types of organic black pigments>
As the organic black dye, one or two or more dyes selected from a blue color adjusting dye, a yellow color adjusting dye, a purple color adjusting dye, a red color adjusting dye, and an orange color adjusting dye are used. Here, the blue color adjusting dye is a color adjusting dye that is generally marketed and is indicated as “Blue” and has a maximum absorption wavelength of about 580 to 620 nm. . The purple color-matching dye here is a color-matching dye that is generally marketed and is described as “Violet” and has a maximum absorption wavelength of about 560 to 580 nm. . Here, the red color-matching dye is a color-matching dye that is generally marketed and is indicated as “Red” and has a maximum absorption wavelength of about 480 to 580 nm. . Here, the orange color adjusting dye is a color adjusting dye that is generally marketed and is labeled “Orange”. Here, the yellow color adjusting dye is a color adjusting dye which is generally marketed and is labeled “Yellow”.

  As these color adjusting pigments, solvent dyes and disperse dyes are particularly preferable, and blue color adjusting pigments include C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 25, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 45, C.I. I. Solvent Blue 55, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 78, C.I. I. Solvent Blue 83, C.I. I. Solvent Blue 87, C.I. I. Solvent Blue 94 and the like. Examples of purple color adjusting pigments include C.I. I. Solvent Violet 8, C.I. I. Solvent Violet 13, C.I. I. Solvent Violet 14, C.I. I. Solvent Violet 21, C.I. I. Solvent Violet 27, C.I. I. Solvent Violet 28, C.I. I. Solvent Violet 36 etc. are mentioned. Examples of red color adjusting pigments include C.I. I. Solvent Red 24, C.I. I. Solvent Red 25, C.I. I. Solvent Red 27, C.I. I. Solvent Red 30, C.I. I. Solvent Red 49, C.I. I. Solvent Red 52, C.I. I. Solvent Red 100, C.I. I. Solvent Red 109, C.I. I. Solvent Red 111, C.I. I. Solvent Red 121, C.I. I. Solvent Red 135, C.I. I. Solvent Red 168, C.I. I. Solvent Red 179 etc. are mentioned. Examples of the orange color adjusting dye include C.I. I. Solvent Orange 60 etc. are mentioned. Examples of yellow color adjusting pigments include C.I. I. Solvent Yellow 33, C.I. I. Solvent Yellow 93, C.I. I. Disperse Yellow 54, C.I. I. Disperse Yellow 160, C.I. I. Disperse Yellow 201 etc. are mentioned.

Among the color adjusting dyes, the quinoline compound, the anthraquinone compound, and the perinone compound have good heat resistance as the dye, and can suppress thermal decomposition of the dye when melt-molding the polyester composition. The polyester composition is preferable in terms of maintaining good blackness and hue L ^* . The organic black dye used in the present invention may be prepared by mixing and mixing a plurality of these blue color-changing dyes, purple color-changing dyes, red color-changing dyes, orange color-changing dyes, and yellow color-changing dyes. preferable. In particular, the combinations shown below, that is, 1) a combination of a blue color-changing dye, a purple color-changing dye, and a yellow color-changing dye 2) a blue color-changing dye, a yellow color-changing dye, and a red color-changing dye Combination 3) A combination of at least one of a blue color-changing dye, a yellow color-changing dye, and an orange color-changing dye is a combination of a visible light absorption spectrum characteristic and a polyester composition as described below. Since the hue L * can be reduced to a specific value or less, this is a more preferable embodiment.

<Physical properties of organic black pigment>
The absorbance of the organic black pigment used in the present invention measured in a hexafluoroisopropanol solution at a concentration of 20 mg / L and an optical path length of 1 cm preferably satisfies all of the following formulas (1) to (5).
A400 ≧ 0.1 (1)
A500 ≧ 0.1 (2)
A600 ≧ 0.1 (3)
A700 ≦ 0.1 (4)
A800 ≦ 0.1 (5)
[In the above formula, A400, A500, A600, A700 and A800 represent the absorbance in the visible light absorption spectrum at wavelengths of 400 nm, 500 nm, 600 nm, 700 nm and 800 nm, respectively. ]

When A400 of Formula (1) is less than 0.1, the hue of the resulting polyester composition becomes bright and blackness becomes insufficient, which is not preferable. When A500 of formula (2) is less than 0.1, the hue of the obtained polyester composition becomes bright and blackness becomes insufficient, which is not preferable. When A600 of formula (3) is less than 0.1, the hue of the resulting polyester composition becomes bright and the blackness becomes insufficient, which is not preferable. When A700 in formula (4) exceeds 0.1, the resulting polyester composition absorbs near infrared rays, which is not preferable because the temperature reached when irradiated with infrared rays increases. A700 in the formula (4) is preferably 0.05 or less. When A800 in formula (5) exceeds 0.1, the resulting polyester composition absorbs near infrared rays, which is not preferable because the temperature reached when irradiated with infrared rays increases. A800 in the formula (5) is preferably 0.05 or less. By satisfying these requirements in the visible light absorption spectrum, the blackness and the hue L ^* are sufficiently black, and absorption of light in the near infrared region can be suppressed.

<Thermal stability of organic black pigment>
The thermal decomposition temperature of the organic black pigment used in the present invention is preferably 300 ° C. or higher. More preferably, the temperature is 320 ° C. or higher and 340 ° C. or higher. When the temperature is below this temperature, thermal decomposition occurs during the polyester polymerization / molding reaction, and the desired black color may not be obtained. Also, the pyrolysis product of the organic black pigment is not preferable because it may adversely affect the physical properties of the final polyester composition, particularly the melt moldability and mechanical properties.

<Black pigment addition time>
Here, the addition timing of the black pigment other than carbon black in the production of the polyester is not particularly limited, but it can be added at any stage where the polymerization reaction is completed before the start of the transesterification reaction. Moreover, when the addition method by the kneading | mixing mentioned later is employ | adopted, it is also possible to add just before shaping | molding process after superposition | polymerization of polyester.

<Adding method of black pigment>
Furthermore, examples of methods for adding black pigments other than carbon black to polyester include a method of directly adding a black pigment, and a method of dissolving and dispersing in a solvent capable of dissolving and dispersing the black pigment. it can. In the case of the method of adding as a solution, the solvent to be dissolved is a solvent such as methanol, ethanol, propanol, butanol, acetone, tetrahydrofuran, 1,4-dioxane, toluene or xylene, or a solvent such as ethylene glycol, propylene glycol or butylene glycol. Examples of the diol component constituting the polyester include a solvent, water, and a mixed solution of these solvents. As the solvent, ethylene glycol is preferable because of its excellent solubility and dispersibility.

<Dry addition method of black pigment>
Moreover, as a manufacturing method of this polyester composition, the addition method by kneading | mixing to polyester of a molten state is employable. The method of kneading is not particularly limited, but it is preferable to use a normal uniaxial or biaxial kneader. More preferably, in order to suppress a decrease in the degree of polymerization of the resulting polyester composition, a method of using a vented uniaxial or biaxial kneader can be exemplified.

  The conditions during the kneading are not particularly limited. For example, the melting point is higher than the melting point of the polyester and the residence time is within 1 hour, preferably 1 minute to 30 minutes. Moreover, the supply method of the black pigment | dye and polyester to a kneading machine is not specifically limited. For example, a method of supplying black pigment and polyester separately to a kneader by a dry method, a method of appropriately mixing and supplying black pigment and polyester, and the like can be mentioned.

<Hue of polyester composition: Color-L (L ^* )>
In the polyester composition of the present invention, the hue L ^* value based on the CIE color difference L ^* a ^* b ^* system needs to be 30 or less.
Color-L ≦ 30 (I)
[In the above formula, Col-L represents the hue L ^* value according to the L ^* a ^* b ^* system of the CIE color difference system of the polyester composition. ]

When the L ^* value is 30 or less, it becomes clear that the polyester composition of the present invention has a sufficient blackness, and even in a polyester molded product obtained by melt molding, the polyester composition has a sufficient blackness. Can be achieved. L * is preferably 0 or more and 30 or less, more preferably 0 or more and 26 or less. In the polyester composition of the present invention, while exhibiting such L ^* value, that is, blackness (non-whiteness), by not absorbing electromagnetic waves in the near-infrared region, the solar radiation that is the effect of the invention The property which suppresses the temperature rise of a polyester composition, and the polyester molded product which carried out the melt molding of the polyester composition can show | play the property which is hard to store heat with sunlight. In order to achieve the effects of such an invention, it is important to select a black pigment to be blended in the polyester composition as described above. In addition, it may be important to select a polyester mode in which L ^* does not become a large value even before blending the black pigment by appropriate selection of the catalyst.

<Intrinsic viscosity of polyester composition, etc.>
The intrinsic viscosity (solvent: orthochlorophenol, measurement temperature: 35 ° C.) of the polyester composition of the present invention is not particularly limited, but is preferably in the range of 0.3 to 1.5 dL / g. When the intrinsic viscosity is less than 0.3 dL / g, the mechanical properties of the resulting polyester fiber are insufficient, and when it exceeds 1.5 dL / g, the melt moldability is lowered, which is not preferable. The viscosity is more preferably in the range of 0.55 to 1.3 dL / g, and still more preferably in the range of 0.6 to 0.8 dL / g. It is also possible to produce a master chip containing the black pigment of the present invention at a high concentration and knead it with polyester to obtain the polyester composition / polyester molded product of the present invention.
The polyester composition of the present invention contains a small amount of additives as required, such as lubricants, phosphorus compound stabilizers, radical scavengers, antioxidants, solid phase polymerization accelerators, color adjusters, fluorescent whitening agents, antibacterial agents An agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a light shielding agent, a flame retardant, or a matting agent may be included.

  Moreover, the polyester composition of the present invention can be melt-molded to obtain polyester molded products such as films, molded products, and fibers. There is no limitation in particular as a manufacturing method when manufacturing the polyester molded product of this invention by melt molding, A conventionally well-known method is used. The production method for producing the polyester fiber of the present invention by melt spinning is not particularly limited, and conventionally known melt spinning methods are used. For example, it is preferable to produce a dried polyester composition by melt spinning at a temperature in the range of 270 ° C. to 300 ° C., and the spinning speed of the melt spinning can be 400 to 9000 m / min. It is possible to increase the strength of the material. Also, the shape of the die used at the time of spinning is not particularly limited, and any of circular shape, irregular shape, solid shape or hollow shape can be adopted. Furthermore, the polyester fiber of the present invention is preferably subjected to an alkali weight reduction treatment in order to enhance the texture.

  The present invention will be further described in the following examples, but the scope of the present invention is not limited by these examples. Various characteristics were measured by the following methods.

(A) Intrinsic viscosity:
A dilute solution obtained by dissolving a polyester composition chip in orthochlorophenol at 100 ° C. for 60 minutes was determined from a value measured at 35 ° C. using an Ubbelohde viscometer.

(A) Metal element content / phosphorus element content in the polyester composition:
The amount of metal element in the polyester composition was such that a granular polyester composition sample was heated and melted on a steel plate, and then a test molded body having a flat surface was prepared with a compression press. Using this test molded body, it was determined using a fluorescent X-ray apparatus (Model 3270E manufactured by Rigaku Corporation).

(C) Thermal storage test:
The polyester composition is melt-spun by a conventional method and then stretched to obtain a polyester fiber. The polyester fiber was prepared by a conventional method using a cylindrical knitting machine to produce a tubular net test sample, and the heat storage temperature of the test sample was measured. After the cylindrical knitted sample was allowed to stand for 12 hours in a room controlled at a measurement atmosphere: 20 ° C. and relative humidity = 60%, and stabilized, the cylindrical knitted sample and the infrared lamp (Toshiba: infrared drying bulb 125W) The distance was set to 30 cm. The time when a current of 100 V was passed through the infrared lamp was taken as the test start time, and the fabric temperature 10 minutes after the start of the test was measured as the ultimate temperature. Due to the high and low temperatures, the property of suppressing the temperature rise of the polyester composition by solar radiation, and the polyester molded product obtained by melt-molding the polyester composition can be evaluated for the property of being difficult to store heat with sunlight. .

[Reference Example 1] Measurement of light absorption spectrum of organic black dye, preparation of organic black dye A The color adjusting dye shown in Table 1 was made into a 20 mg / L hexafluoroisopropanol solution at room temperature and filled in a quartz cell having an optical path length of 10 mm. The blank cell was filled with only hexafluoroisopropanol, and a light absorption spectrum in the region of 300 nm to 820 nm was measured using a Hitachi spectrophotometer U-3010 type. When two or more kinds of organic black pigments were mixed, the total concentration was 20 mg / L. Absorbance at 400 nm, 500 nm, 600 nm, 700 nm, and 800 nm was measured. The results are shown in Table 1. Furthermore, the thermal mass reduction start temperature of the powder for color matching shown in Table 1 was measured. The results are shown in Table 1. In addition, when adding these organic black pigment | dye in an Example and a comparative example, it used by making it melt | dissolve and disperse | distribute so that it might become 0.1 mass% with respect to the glycol solution used as a raw material at the temperature of 100 degreeC.

[Example 1]
Manufacture of polyester composition chip Manganese acetate tetrahydrate as a catalyst in a mixture of 194.2 parts by weight of dimethyl terephthalate (hereinafter referred to as DMT) and 124.2 parts by weight of ethylene glycol (200 mol% relative to DMT) 0.049 parts by mass (20 mmol% relative to DMT) was charged into a SUS container. The ester exchange reaction was carried out while raising the temperature from 140 ° C. to 245 ° C. under normal pressure, and it was confirmed that almost the theoretical amount of methanol had been distilled off, and the ester exchange reaction was terminated. The internal temperature at the end of the reaction was 240 ° C. Thereafter, 0.042 trimethyl phosphate (30 mmol% relative to DMT) and 0.116 parts by mass of antimony trioxide (40 mmol% relative to DMT) were added to the reaction product, followed by 1.94 parts by mass of black dye A (the amount of the final polyester composition) The black pigment A was transferred to a reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port, and a distillation apparatus. The internal temperature of the reaction vessel was raised to 285 ° C., and a polycondensation reaction was performed at a high vacuum of 30 Pa or less to obtain a polyester composition having an intrinsic viscosity of 0.64 dL / g. Furthermore, it was made into a chip according to a conventional method. In addition, although content of the carbon black in a polyester composition was evaluated by the method mentioned above, it was below the detection limit.

-Manufacture of polyester tube sample The polyester composition chip sample was dried at 160 ° C for 6 hours under a nitrogen stream, melt-spun and stretched under the conditions of a spinning temperature of 285 ° C, a nozzle hole diameter of 0.27 mm, and a hole number of 24, and 84 dtex (24fil ) Polyester fiber was obtained. The obtained polyester fiber was prepared by a conventional method using a tubular knitting machine to create a tubular net test sample, and the heat storage temperature of the test sample was measured. The reached temperature was 59 ° C. Table 2 shows the evaluation results of the polyester composition and the cylindrical net sample.

[Examples 2-6, Comparative Examples 1-2]
In Example 2, it carried out like Example 1 except having changed the kind and quantity of the dyeing agent, and the kind and quantity of the additive into those described in Table 2. Table 2 shows the evaluation results of the polyester composition and the cylindrical net sample. In addition, although content of the carbon black in a polyester composition was evaluated by the method mentioned above, all except the comparative example 1 were below the detection limit.

  Advantageous Effects of Invention According to the present invention, it is possible to provide a non-heat storage black original polyester composition that is a polyester composition that exhibits black color and that can suppress a temperature increase due to heat storage of the polyester composition due to solar radiation. It becomes. As a result, it is possible to produce non-heat storage black polyester molded products such as various molded products (films, sheets, various packaging containers, fibers, car dashboards, various housings) that can suppress the temperature rise by sunlight. it can.

Claims (4)

A polyester in which the main repeating unit is at least one selected from the group consisting of ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, ethylene-2,6-naphthalate, trimethylene-2,6-naphthalate and tetramethylene-2,6-naphthalate. And a polyester composition comprising a black pigment other than carbon black, containing 0.05 to 40% by mass of the black pigment other than carbon black relative to the polyester composition, and substantially containing the carbon black relative to the polyester composition A polyester composition characterized by satisfying the following formula (I):
Color-L ≦ 30 (I)
[In the above formula, Col-L represents the hue L ^* value according to the L ^* a ^* b ^* system of the CIE color difference system of the polyester composition. ] The polyester composition according to claim 1, wherein the black pigment satisfies the following general formula (II).
0 ≦ (inorganic black pigment) / (organic black pigment) ≦ 0.5 (II)
[In the above formula, (inorganic black pigment) indicates mass% of inorganic black pigment other than carbon black contained in the polyester composition. (Organic black pigment | dye) shows the mass% of the organic black pigment | dye contained in a polyester composition. ] 3. The polyester composition according to claim 2, wherein the organic black dye has an absorbance according to an ultraviolet-visible absorption spectrum between wavelengths of 300 to 820 nm measured in a hexafluoroisopropanol solution having a concentration of 20 mg / L and an optical path length of 1 cm. The polyester composition according to claim 2, wherein all of the formulas (1) to (5) are satisfied.
A400 ≧ 0.1 (1)
A500 ≧ 0.1 (2)
A600 ≧ 0.1 (3)
A700 ≦ 0.1 (4)
A800 ≦ 0.1 (5)
[In the above formula, A400, A500, A600, A700 and A800 represent the absorbance in the visible light absorption spectrum at wavelengths of 400 nm, 500 nm, 600 nm, 700 nm and 800 nm, respectively. ]   The polyester molded article obtained by shape | molding the polyester composition of any one of Claims 1-3.