HK1224689B - Polyester resin, injection-molded article, polyester sheet, and polyester container - Google Patents
Polyester resin, injection-molded article, polyester sheet, and polyester container Download PDFInfo
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- HK1224689B HK1224689B HK16112804.3A HK16112804A HK1224689B HK 1224689 B HK1224689 B HK 1224689B HK 16112804 A HK16112804 A HK 16112804A HK 1224689 B HK1224689 B HK 1224689B
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Description
Technical Field
The present invention relates to a polyester resin obtained by copolymerizing a specific diol having a pentacyclopentadecane skeleton, and an injection-molded article, a polyester sheet and a polyester container using the polyester resin.
Background
Polyethylene terephthalate (hereinafter, abbreviated as "PET") is a polyester resin widely used for sheets, films, containers and the like because of its excellent characteristics of transparency, mechanical strength, chemical resistance and recyclability.
In particular, a transparent molded article of PET produced by injection molding is highly demanded for applications such as sundries and containers because it is lightweight, has excellent functionality such as impact resistance, and has a large degree of freedom in designing the shape.
Further, PET transparent sheets have excellent environmental suitability such as not generating dioxin upon incineration, being recyclable, and not generating environmental hormones, and thus demand in the field of foods is expanding due to such advantages.
Further, PET transparent containers have excellent environmental suitability, such as being lightweight and easy to use, being able to confirm functionality of contents, being free from dioxin generation during incineration, being able to be recycled, and the like, and thus demand in the food field or the cosmetic field is expanding due to such advantages.
However, since PET has a glass transition temperature of about 80 ℃ and is not sufficiently high in heat resistance, it cannot be used as a material suitable for high-temperature sterilization such as boiling sterilization, heating cooking using a microwave oven, or the like. In addition, when a thick molded article is obtained, whitening occurs due to high crystallinity of the molded article obtained by post-molding a sheet, and transparency is impaired. Therefore, modification by copolymerization has been widely attempted.
As an example of the modification, it has been proposed to obtain an amorphous polyester resin having reduced crystallinity and improved whitening of a molded article by copolymerizing isophthalic acid with PET or 1, 4-cyclohexanedimethanol. However, these resins all have a glass transition temperature of less than 100 ℃ and show little improvement in heat resistance.
For the above-mentioned applications requiring heat resistance, polyethylene naphthalate (hereinafter, abbreviated as "PEN") is used, but since its crystallinity is equivalent to that of PET, transparency may be lost even when the molded article is thick.
As another example of modification by copolymerization, patent documents 1 and 2 disclose polyester resins obtained by copolymerizing diols having a pentacyclopentadecane skeleton. In particular, patent document 1 describes a polyester resin in which dicarboxylic acid units are mainly units derived from aliphatic dicarboxylic acids, and diol units other than diols having a pentadecane skeleton are units derived from aliphatic diols. Patent document 2 describes a polyester resin obtained by copolymerizing a diol having a pentacyclopentadecane skeleton as a diol unit, the diol unit being composed of an aromatic dicarboxylic acid unit or an aliphatic dicarboxylic acid unit as a dicarboxylic acid unit.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2007-238856
Patent document 2: japanese laid-open patent publication No. 58-174419
Disclosure of Invention
Problems to be solved by the invention
The polyester resin described in patent document 1 has a glass transition temperature of 130 ℃ or lower, and therefore, is difficult to be applied to applications requiring high heat resistance, and has a problem that transparency and mechanical strength are insufficient depending on the composition of the resin.
The polyester resin described in patent document 2, which is obtained by copolymerizing a diol having a pentacyclopentadecane skeleton, is expected to be used in applications where higher heat resistance is required, because the heat resistance is rather lowered when the copolymerization ratio is more than 49 mol%.
Thus, no polyester resin suitable for applications requiring both high heat resistance and low crystallinity has been known.
Patent documents 1 and 2 do not disclose any application of the polyester resin described above to the production of a molded article by injection molding or application of a molded article of the polyester resin to an application requiring high heat resistance such as boiling sterilization.
In patent documents 1 and 2, there is no description at all on the application of a polyester resin obtained by copolymerizing a diol having a pentacyclopentadecane skeleton to the production of a sheet and a molded article of the sheet, or the evaluation of the transparency or heat resistance of the sheet.
In patent documents 1 and 2, there is no description at all that is given about the applicability of a polyester resin obtained by copolymerizing a diol having a pentacyclopentadecane skeleton to the production of containers and the evaluation of the transparency and heat resistance of the containers.
The present invention has been made in view of the above-mentioned problems of the prior art. That is, an object of the present invention is to provide a polyester resin having high heat resistance and excellent transparency and mechanical properties, and an injection-molded article, a polyester sheet and a polyester container using the same.
Means for solving the problems
The present inventors have made extensive studies and found that a polyester resin obtained by copolymerizing a specific diol having a pentacyclopentadecane skeleton in a specific composition range has high heat resistance, transparency and excellent mechanical properties. Further, it has been found that an injection-molded article, a polyester sheet and a polyester container using the polyester resin are excellent in transparency and mechanical properties and further excellent in heat resistance.
Namely, the present invention is as follows.
[1]
A polyester resin, wherein,
the polyester resin contains a diol unit and a dicarboxylic acid unit,
50 to 95 mol% of the diol units are units derived from pentacyclopentadecane dimethanol represented by the following formula (I) and/or pentacyclopentadecane dimethanol represented by the following formula (II), 50 to 100 mol% of the dicarboxylic acid units are units derived from aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) a measured value of a glass transition temperature measured by a differential scanning calorimeter is 131 ℃ or more, and a heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less;
(2) the Intrinsic Viscosity (IV) measured at 25 ℃ using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane at a mass ratio of 6:4 is 0.2 to 1.2dl/g,
[2]
the polyester resin according to [1], wherein the unit derived from an aromatic dicarboxylic acid is at least one unit derived from terephthalic acid, isophthalic acid, and 2, 6-naphthalenedicarboxylic acid.
[3]
The polyester resin according to [1] or [2], wherein the unit derived from an aromatic dicarboxylic acid is 80 to 100 mol% of the dicarboxylic acid unit.
[4]
The polyester resin according to any one of [1] to [3], wherein the diol unit contains 5 to 50 mol% of a unit derived from ethylene glycol.
[5]
An injection-molded body, wherein,
the injection-molded article is obtained from a polyester resin containing a diol unit and a dicarboxylic acid unit,
50 to 95 mol% of the diol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the following formula (I) and/or pentacyclopentadecane dimethanol represented by the following formula (II), 50 to 100 mol% of the dicarboxylic acid units are units derived from aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) a measured value of a glass transition temperature measured by a differential scanning calorimeter is 131 ℃ or more, and a heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less;
(2) the Intrinsic Viscosity (IV) measured at 25 ℃ using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane at a mass ratio of 6:4 is 0.2 to 1.2dl/g,
[6]
the injection-molded article according to [5], wherein the unit derived from an aromatic dicarboxylic acid of the polyester resin is at least one unit derived from at least one selected from terephthalic acid, isophthalic acid, and 2, 6-naphthalenedicarboxylic acid.
[7]
The injection-molded article according to [5] or [6], wherein the unit derived from an aromatic dicarboxylic acid in the dicarboxylic acid units of the polyester resin is 80 to 100 mol%.
[8]
The injection-molded article according to any one of [5] to [7], wherein the diol unit of the polyester resin contains 5 to 50 mol% of a unit derived from ethylene glycol.
[9]
The injection-molded article according to any one of [5] to [8], wherein 50 to 90 mol% of the diol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the formula (I) and/or pentacyclopentadecane dimethanol represented by the formula (II), 10 to 50 mol% of the diol units are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from terephthalic acid.
[10]
The injection-molded article according to any one of [5] to [8], wherein 5 to 50 mol% of the diol units of the polyester resin are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from 2, 6-naphthalenedicarboxylic acid.
[11]
The injection-molded article according to any one of [5] to [10],
the polyester resin satisfies the following condition (3):
(3) a test piece (1A type multipurpose test piece) having a shape conforming to JIS K7162 (tensile property test method) obtained by injection molding of the polyester resin is immersed in boiling water at 100 ℃ for 30 minutes, and then the dimensional change rate after immersion in boiling water is 0.50% or less in the thickness direction and the width direction and 0.60% or less in the entire length direction, as calculated from the following formula (1),
formula (1):
ΔM＝|M-M0|/M0×100
wherein Δ M is the rate of change in size [% ]]；M0The size of the product is [ mm ] before immersion in boiling water](ii) a M is the size [ mm ] after immersion in boiling water]。
[12]
A polyester sheet, wherein,
the polyester sheet is obtained by molding a polyester resin containing a diol unit and a dicarboxylic acid unit,
50 to 95 mol% of the diol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the following formula (I) and/or pentacyclopentadecane dimethanol represented by the following formula (II), 50 to 100 mol% of the dicarboxylic acid units are units derived from aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) a measured value of a glass transition temperature of the polyester resin measured by a differential scanning calorimeter is 131 ℃ or more, and a heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less;
(2) the polyester resin has a measured value of Intrinsic Viscosity (IV) measured at 25 ℃ of 0.2 to 1.2dl/g using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane in a mass ratio of 6:4,
[13]
the polyester sheet according to [12], wherein the unit derived from an aromatic dicarboxylic acid in the polyester resin is a unit derived from at least one selected from terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid.
[14]
The polyester sheet according to [12] or [13], wherein 80 to 100 mol% of the dicarboxylic acid units in the polyester resin are units derived from an aromatic dicarboxylic acid.
[15]
The polyester sheet according to any one of [12] to [14], wherein the diol unit of the polyester resin contains 5 to 50 mol% of a unit derived from ethylene glycol.
[16]
The polyester sheet according to any one of [12] to [15], wherein 50 to 90 mol% of the diol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the formula (I) and/or pentacyclopentadecane dimethanol represented by the formula (II), 10 to 50 mol% of the diol units are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from terephthalic acid.
[17]
The polyester sheet according to any one of [12] to [15], wherein 5 to 50 mol% of the diol units of the polyester resin are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from 2, 6-naphthalenedicarboxylic acid.
[18]
The polyester sheet according to any one of [12] to [17], wherein,
the polyester resin satisfies the following conditions (4) and (5):
(4) the total light transmittance of the sheet with the thickness of 0.20mm and the sheet with the thickness of 0.35mm is measured by more than 86%;
(5) a square test piece of 120mm in the longitudinal direction x 120mm in the transverse direction was cut out from a sheet of 0.20mm in thickness with the extrusion direction being the longitudinal direction and the width direction being the transverse direction, a mark line of 100mm in length was marked on the center line of the test piece in the longitudinal direction and the transverse direction, respectively, after the test piece was heated in a drier for 30 minutes, the maximum temperature (heat resistance temperature) at which the change rate of the length of the mark line after heating does not exceed 0.5% in the longitudinal direction and the transverse direction, calculated from the following formula (2), was 110 ℃ or higher,
formula (2):
ΔL＝|L-L0|/L0×100
wherein Δ L is the rate of change [% of the length of the reticle]；L0Is the length of the marked line before heating [ mm ]](ii) a L is the length of the heated reticle [ mm ]]。
[19]
A polyester container, wherein,
the polyester container is obtained by molding a polyester resin containing a diol unit and a dicarboxylic acid unit,
50 to 95 mol% of the diol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the following formula (I) and/or pentacyclopentadecane dimethanol represented by the following formula (II), 50 to 100 mol% of the dicarboxylic acid units are units derived from aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) a measured value of a glass transition temperature of the polyester resin measured by a differential scanning calorimeter is 131 ℃ or more, and a heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less;
(2) the polyester resin has a measured value of Intrinsic Viscosity (IV) measured at 25 ℃ of 0.2 to 1.2dl/g using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane in a mass ratio of 6:4,
[20]
the polyester container according to [19], wherein the unit derived from an aromatic dicarboxylic acid in the polyester resin is a unit derived from at least one selected from terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid.
[21]
The polyester container according to [19] or [20], wherein 80 to 100 mol% of the dicarboxylic acid units in the polyester resin are units derived from an aromatic dicarboxylic acid.
[22]
The polyester container according to any one of [19] to [21], wherein the glycol unit of the polyester resin contains 5 to 50 mol% of a unit derived from ethylene glycol.
[23]
The polyester container according to any one of [19] to [22], wherein 50 to 90 mol% of the diol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the formula (I) and/or pentacyclopentadecane dimethanol represented by the formula (II), 10 to 50 mol% of the diol units are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from terephthalic acid.
[24]
The polyester container according to any one of [19] to [22], wherein 5 to 50 mol% of the diol units in the polyester resin are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from 2, 6-naphthalenedicarboxylic acid.
[25]
The polyester container according to any one of [19] to [24],
the following condition (6) is satisfied:
(6) the highest temperature (heat-resistant temperature) at which the height retention rate of the heated container becomes 98% or more, which is calculated from the following formula (3), is 100 ℃ or more after heating the polyester container having the following shape in a dryer for 30 minutes,
< Container shape >
A polyester sheet having a thickness of 0.35mm was thermoformed by a vacuum pressure molding machine at a draw ratio of 0.36 to obtain a container having an opening of 70mm X70 mm, a height of 25mm and a capacity of about 100mL,
< formula (3) >
ΔH＝H/H0×100
Wherein Δ H is the height-holding ratio [% ], of the container]；H0Is the height of the container before heating [ mm ]](ii) a H is the height of the heated container [ mm ]]。
[26]
The polyester container according to any one of [19] to [25], wherein the molding is a hollow molding of the polyester resin.
[27]
The polyester container according to any one of [19] to [25], wherein the molding is thermoforming of a sheet made of the polyester resin.
Effects of the invention
The polyester resin of the present invention has excellent transparency and mechanical properties, and also has excellent heat resistance. The injection-molded article, the polyester sheet and the polyester container of the present invention have excellent transparency and mechanical properties, and also have excellent heat resistance.
Drawings
Fig. 1 is a diagram showing the shape and size of a test piece (strip-shaped injection molded article) used for measuring the deflection temperature under load of the molded article.
FIG. 2 is a view showing the shape and size of a test piece (disc-shaped injection-molded article) used for measuring the transparency of a molded article.
FIG. 3 is a view showing the shape and size of a test piece (a type 1A multipurpose test piece described in the test method for tensile properties in JIS K7162) used for measuring the boiling resistance of a molded article.
Fig. 4 is a view showing the size and reticle distance (reticle length) of a test piece used for evaluating heat resistance of a sheet.
FIG. 5 is a view showing the cross-sectional shape and size of a molded article used for measuring the heat-resistant temperature of a container.
Detailed Description
Hereinafter, an embodiment for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The following embodiments are illustrative of the present invention, and the present invention is not limited to the following embodiments. The present invention can be appropriately modified and implemented within the scope of the gist thereof.
< first embodiment >
[ polyester resin ]
The polyester resin of the present embodiment is a polyester resin containing a diol unit and a dicarboxylic acid unit. In the polyester resin of the present embodiment, 50 to 95 mol% of the diol units are units derived from pentacyclopentadecane dimethanol represented by the following formula (I) and/or pentacyclopentadecane dimethanol represented by the following formula (II), 50 to 100 mol% of the dicarboxylic acid units are units derived from aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) a measured value of a glass transition temperature measured by a differential scanning calorimeter is 131 ℃ or more, and a heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less;
(2) the Intrinsic Viscosity (IV) measured at 25 ℃ using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane at a mass ratio of 6:4 is 0.2 to 1.2 dl/g.
With the above-described configuration, the polyester resin of the present embodiment has high heat resistance and is excellent in transparency and mechanical properties. In particular, the resin composition has high heat resistance as compared with conventional transparent resins such as conventionally known heat-resistant transparent polyester resins, polystyrene, and acrylonitrile-styrene copolymers, and is excellent in transparency and mechanical properties. Therefore, the present invention can be suitably used for various applications such as food containers, cosmetic containers, medical devices, optical materials, automobile parts, baby products such as feeding bottles and pacifiers, and the like. Thus, the polyester resin of the present embodiment is extremely valuable in industrial use.
In the present embodiment, the proportion of the unit derived from pentacyclopentadecane dimethanol represented by the above formula (I) and/or (II) is 50 mol% or more, preferably 51 mol% or more, more preferably 55 mol% or more, and still more preferably 60 mol% or more of the total diol units. When the proportion of the units derived from pentacyclopentadecane dimethanol is 50 mol% or more based on the total diol units, the effect of raising the glass transition temperature of the polyester resin and the effect of suppressing crystallinity can be sufficiently obtained. On the other hand, the proportion of the unit derived from pentacyclopentadecane dimethanol is 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less, and still more preferably 80 mol% or less of the total diol units. When the proportion of units derived from pentacyclopentadecane dimethanol is 95 mol% or less in the total diol units, a significant increase in the melt viscosity of the polyester resin can be avoided, and a resin having a sufficient molecular weight can be obtained when the polyester resin is synthesized by melt polymerization, so that the polyester container produced from the resin has excellent mechanical properties. Further, the above ratio is 95 mol% or less, and it is possible to prevent the occurrence of moldability problems such as difficulty in sufficiently transferring a metal mold during injection molding. In addition, the molding can be performed at an appropriate resin preheating temperature during molding, and the coloring of the molded article and the deterioration of mechanical properties due to thermal aging of the resin can be prevented.
Accordingly, the proportion of the unit derived from pentacyclopentadecane dimethanol represented by the above formula (I) and/or (II) is in the range of 50 to 95 mol%, preferably in the range of 50 to 90 mol%, more preferably in the range of 51 to 90 mol%, still more preferably in the range of 51 to 85 mol%, still more preferably in the range of 55 to 85 mol%, yet more preferably in the range of 55 to 80 mol%, and yet more preferably in the range of 60 to 80 mol% in the total diol units. By containing the units derived from pentacyclopentadecane dimethanol in the above-mentioned ratio, the glass transition temperature of the polyester resin can be greatly increased, and excellent heat resistance can be obtained. In addition, since crystallinity is reduced, transparency is not lost even when a thick molded article is formed.
Specific examples of the pentacyclopentadecane dimethanol represented by the above formula (I) include: 4, 10-bis (hydroxymethyl) pentacyclic [6.5.1.13，6.02，7.09，13]Pentadecane, 4, 11-bis (hydroxymethyl) pentacyclic [6.5.1.1 ]3，6.02，7.09，13]Pentadecane, 4, 12-bis (hydroxymethyl) pentacyclic [6.5.1.1 ]3，6.02，7.09，13]Pentadecane, and stereoisomers thereof.
Specific examples of the pentacyclopentadecane dimethanol represented by the above formula (II) include: 5, 12-bis (hydroxymethyl) pentacyclic [9.2.1.14，7.02，10.03，8]Pentadecane, 5, 13-bis (hydroxymethyl) pentacyclic [9.2.1.14，7.02，10.03，8]Pentadecane, 6, 12-bis (hydroxymethyl) pentacyclic [9.2.1.14，7.02，10.03，8]Pentadecane, and stereoisomers thereof.
The pentacyclopentadecane dimethanol mentioned above may be a single compound selected from these compounds, or may contain a plurality of compounds.
The diol units contained in the polyester resin of the present embodiment may contain diol units derived from other than the pentacyclopentadecane dimethanol units. The diol units other than pentacyclopentadecane dimethanol units are not limited to the following, and examples thereof include units derived from aliphatic diols, alicyclic diols, polyether compounds, bisphenols and alkylene oxide adducts thereof, aromatic dihydroxy compounds and alkylene oxide adducts thereof, and the like.
The aliphatic diols include, for example, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, propylene glycol, and neopentyl glycol, although not limited to the following. The alicyclic glycols are not limited to the following, but include, for example, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 1, 3-decahydronaphthalenedimethanol, 1, 4-decahydronaphthalenedimethanol, 1, 5-decahydronaphthalenedimethanol, 1, 6-decahydronaphthalenedimethanol, 2, 7-decahydronaphthalenedimethanol, bicycloheptane dimethanol, tricyclodecanedimethanol, 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 5-hydroxymethyl-5-ethyl-2- (1, 1-dimethyl-2-hydroxyethyl) -1, 3-dioxane, etc. Examples of the polyether compounds include, but are not limited to, polyethylene glycol, polypropylene glycol, and polybutylene glycol. Examples of the bisphenols include, but are not limited to, 4,4 '- (1-methylethylidene) bisphenol (bisphenol a), 4, 4' -methylenebisphenol (bisphenol F), 4,4 '-cyclohexylidene bisphenol (bisphenol Z), and 4, 4' -sulfonyl bisphenol (bisphenol S). The aromatic dihydroxy compound is not limited to the following, but examples thereof include hydroquinone, resorcinol, 4 ' -dihydroxybiphenyl, 4 ' -dihydroxydiphenyl ether, and 4,4 ' -dihydroxydiphenyl benzophenone. These may be contained alone as a diol unit, or two or more of these may be contained in combination.
From the viewpoint of heat resistance, mechanical properties, and easy availability of the polyester resin, units derived from ethylene glycol, 1, 3-propanediol, and 1, 4-butanediol are preferred, and units derived from ethylene glycol are more preferred.
When the diol unit derived from ethylene glycol is contained as a diol unit other than the unit derived from pentacyclopentadecane dimethanol, the proportion of the unit derived from ethylene glycol is preferably 1 to 50 mol%, more preferably 5 to 50 mol%, even more preferably 10 to 50 mol%, even more preferably 15 to 49 mol%, and particularly preferably 20 to 45 mol% in the diol unit, from the viewpoint of improving the heat resistance and mechanical properties of the polyester resin.
The polyester resin of the present embodiment contains a unit derived from an aromatic dicarboxylic acid as a dicarboxylic acid unit. The proportion of the unit derived from the aromatic dicarboxylic acid is 50 to 100 mol%, preferably 80 to 100 mol%, and more preferably 100 mol% of the total dicarboxylic acid units.
By containing the units derived from the aromatic dicarboxylic acid in the above-described ratio, the polyester resin of the present embodiment can be made excellent in heat resistance and mechanical properties.
Examples of the unit derived from an aromatic dicarboxylic acid include, but are not limited to, terephthalic acid, isophthalic acid, phthalic acid, 1, 3-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 2-methylterephthalic acid, biphenyldicarboxylic acid, and tetrahydronaphthalenedicarboxylic acid. These dicarboxylic acid units may be contained alone or in combination of two or more. Further, the ester compound may be used in the form of an ester of a dicarboxylic acid and an alcohol having 1 to 6 carbon atoms.
From the viewpoint of heat resistance, mechanical properties, and easy availability of the polyester resin, units derived from terephthalic acid, isophthalic acid, and 2, 6-naphthalenedicarboxylic acid are preferred, and from the viewpoint of economy, units derived from terephthalic acid and isophthalic acid are more preferred.
The dicarboxylic acid unit contained in the polyester resin of the present embodiment is not particularly limited as far as it is a dicarboxylic acid unit other than the unit derived from the aromatic dicarboxylic acid (unit derived from another dicarboxylic acid).
The units derived from other dicarboxylic acids are not limited to those described below, but examples thereof include units derived from aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and the like.
The aliphatic dicarboxylic acids include, but are not limited to, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decaalkanedicarboxylic acid, dodecanedicarboxylic acid, and the like. The alicyclic dicarboxylic acids are not limited to the following, but include, for example, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 3-decahydronaphthalenedicarboxylic acid, 1, 4-decahydronaphthalenedicarboxylic acid, 1, 5-decahydronaphthalenedicarboxylic acid, 1, 6-decahydronaphthalenedicarboxylic acid, 2, 7-decahydronaphthalenedicarboxylic acid, bicycloheptanedicarboxylic acid, tricyclodecanedicarboxylic acid, pentacyclopentadecanedicarboxylic acid, 3, 9-bis (1, 1-dimethyl-2-carboxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 5-carboxy-5-ethyl-2- (1, 1-dimethyl-2-carboxyethyl) -1, 3-dioxane, and the like. These dicarboxylic acid units may be contained alone or in combination of two or more. Further, the ester may be used in the form of an ester of a dicarboxylic acid and an alcohol having 1 to 6 carbon atoms.
The polyester resin of the present embodiment may contain a unit derived from a monool, a unit derived from a polyol, a unit derived from a monocarboxylic acid, a unit derived from a polycarboxylic acid, and a unit derived from an oxo acid in order to adjust melt viscoelasticity, molecular weight, or the like, within a range not to impair the object of the present embodiment.
Examples of the monool include, but are not limited to, butanol, hexanol, and octanol. Examples of the polyhydric alcohol include, but are not limited to, trimethylolpropane, glycerol, 1,3, 5-pentanetriol, and pentaerythritol. The monocarboxylic acid is not limited to the following, but examples thereof include benzoic acid, propionic acid, and butyric acid. Examples of the polycarboxylic acid include, but are not limited to, trimellitic acid and pyromellitic acid. Examples of the oxo acid include, but are not limited to, glycolic acid, lactic acid, hydroxybutyric acid, 2-hydroxyisobutyric acid, and hydroxybenzoic acid.
The method for producing the polyester resin of the present embodiment is not particularly limited, and conventionally known polyester production methods can be applied. Specifically, for example, melt polymerization methods such as an ester exchange method and a direct esterification method, and solution polymerization methods can be cited.
In producing the polyester resin of the present embodiment, a general transesterification catalyst, esterification catalyst, polycondensation catalyst, and the like used in producing polyester resins can be used. Although not limited to the following, examples of the catalyst include compounds of metals such as zinc, lead, cerium, cadmium, manganese, cobalt, lithium, sodium, potassium, calcium, nickel, magnesium, vanadium, aluminum, titanium, antimony, germanium, and tin (for example, fatty acid salts, carbonates, phosphates, hydroxides, chlorides, oxides, and alkoxides), and magnesium. These may be used alone or in combination of two or more.
Among the above catalysts, compounds of manganese, cobalt, zinc, titanium, calcium, antimony and germanium are preferable, compounds of manganese, antimony and germanium are more preferable, and manganese (II) acetate tetrahydrate (manganese diacetate tetrahydrate), antimony (III) oxide (antimony trioxide) and germanium (IV) oxide (germanium dioxide) are more preferable.
The amount of the catalyst used is not limited to the following, but is preferably 1 to 1000ppm, more preferably 5 to 500ppm, and still more preferably 10 to 250ppm as the amount of the metal component relative to the raw material of the polyester resin.
In the production of the polyester resin of the present embodiment, a phosphorus compound can be used as an additive. Examples of the phosphorus compound include, but are not limited to, phosphoric acid, phosphorous acid, phosphoric acid esters, and phosphorous acid esters.
Examples of the phosphate ester include, but are not limited to, methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, diphenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, and triphenyl phosphate. Examples of the phosphite include methyl phosphite, ethyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and triphenyl phosphite. These may be used alone or in combination of two or more.
Phosphoric acid is particularly preferable from the viewpoint of enabling the polyester resin to contain a phosphorus compound quantitatively.
The amount of the phosphorus compound used is not limited to the following, but is preferably 10 to 300ppm, more preferably 20 to 200ppm, and still more preferably 30 to 100ppm, as the concentration of phosphorus atoms in the polyester resin. When the phosphorus compound is contained in the above range, the polyester resin of the present embodiment tends to be inhibited from being colored during molding or being colored during use in a high-temperature environment, and is preferable from the viewpoint of preventing problems such as a significant decrease in polymerization rate and an insufficient increase in polymerization degree.
The phosphorus compound may be added at any time point in the production of the polyester resin. Although not limited to the following, the phosphorus compound can be added at the time of charging the raw materials, at the start, in the middle, or at the end of the transesterification or esterification reaction, or at the start, in the middle, or at the end of the polycondensation reaction.
In the production of the polyester resin of the present embodiment, various additives such as various stabilizers such as a heat stabilizer, a light stabilizer, an anti-etherifying agent, and an antioxidant, a colorant, a mold release agent, and a polymerization regulator may be added to the polyester resin in a range not to impair the object of the present embodiment. These are appropriately selected depending on the reaction rate, color tone of the polyester resin, safety, thermal stability, weather resistance, solubility of the polyester resin itself, and the like.
The polyester resin of the present embodiment may contain various additives such as various stabilizers including a heat stabilizer, a light stabilizer, an anti-etherifying agent, and an antioxidant, a coloring agent, a release agent, a plasticizer, an ultraviolet absorber, an extender, a delustering agent, a drying regulator, an antistatic agent, an anti-settling agent, a surfactant, a flow improver, a drying oil, waxes, a filler, a reinforcing material, a surface smoothing material, a leveling agent, a curing reaction accelerator, a tackifier, and a molding aid, as long as the object of the present embodiment is not impaired. In addition, it may be mixed with other resins.
The polyester resin of the present embodiment has a measured value of glass transition temperature as measured by a differential scanning calorimeter of 131 ℃ or higher, and a heat quantity of a crystallization exothermic peak at the time of temperature reduction of 5J/g or lower. The glass transition temperature was measured at a temperature rise rate of 20 ℃ per minute, and the heat quantity of the exothermic peak of crystallization at the time of temperature decrease was measured at a temperature decrease rate of 5 ℃ per minute. When the glass transition temperature is 131 ℃ or higher, the polyester resin of the present embodiment has significantly improved heat resistance as compared with PET, and can withstand heat treatment at 100 ℃ or higher or use in a high-temperature environment. That is, when the polyester resin is formed into an injection molded article, significant deformation can be prevented even if boiling sterilization is performed for a long time, and excellent dimensional stability can be exhibited. Further, if the glass transition temperature is 140 ℃ or higher, for example, even when the injection molded article is sterilized by heating under pressure (retorting) at 121 ℃, significant deformation does not occur, and further excellent dimensional stability tends to be obtained. Further, if the glass transition temperature is 150 ℃ or higher, the dimensional stability of the injection-molded article during the pressure-heat sterilization tends to be further improved. From the above-mentioned viewpoint, the glass transition temperature is preferably 140 ℃ or higher, and more preferably 150 ℃ or higher.
Further, since the heat quantity of the crystallization exothermic peak at the time of temperature reduction is 5J/g or less, the crystallinity of the polyester resin of the present embodiment is sufficiently reduced, whitening due to the progress of crystallization is suppressed, and transparency is not lost even in the case of producing a thick molded article. From the above-mentioned viewpoints, the heat quantity of the crystallization exothermic peak at the time of temperature decrease is preferably 3J/g or less, more preferably 1J/g or less, and still more preferably 0.1J/g or less.
The polyester resin of the present embodiment has a measured value of Intrinsic Viscosity (IV) measured at 25 ℃ of 0.2 to 1.2dl/g using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane in a mass ratio of 6: 4. When the intrinsic viscosity is within the above range, the polyester resin of the present embodiment exhibits sufficient mechanical properties, and the melt viscosity of the polyester resin during molding is also suitable, resulting in good moldability. That is, the intrinsic viscosity is 0.2dl/g or more, preferably 0.3dl/g or more, more preferably 0.4dl/g or more, still more preferably 0.43dl/g or more, and still more preferably 0.46dl/g or more. When the intrinsic viscosity is 0.2dl/g or more, a resin having sufficient mechanical properties and excellent impact resistance can be obtained. The intrinsic viscosity is not more than 1.2dl/g, preferably not more than 1.0dl/g, more preferably not more than 0.8 dl/g. By setting the intrinsic viscosity to 1.2dl/g or less, it is possible to avoid a significant increase in the melt viscosity of the polyester resin, prevent the occurrence of moldability problems such as difficulty in sufficiently performing transfer to a metal mold during injection molding, and further, to perform molding at an appropriate resin preheating temperature during molding, thereby preventing the coloring of a molded article or the reduction in mechanical properties due to thermal aging of the resin. From the above viewpoint, the intrinsic viscosity is preferably in the range of 0.3 to 1.0dl/g, more preferably in the range of 0.4 to 0.8 dl/g.
The polyester resin of the present embodiment can be used for injection molded articles, extrusion molded articles such as sheets and films, bottles, foams, adhesives, paints, and the like.
The sheet or film may be a single layer or a plurality of layers, may be unstretched or stretched in one direction or two directions, or may be laminated on a steel sheet or the like. The bottle body can be a single layer or a plurality of layers, and can be a direct blowing type bottle body, an injection blow molding type bottle body or injection molding. The foam may be a bead foam or an extruded foam.
The polyester resin of the present embodiment can be suitably used for applications requiring high heat resistance. Specific examples of the application include, but are not limited to, transparent containers that can be used for storage of high-temperature products, heating for sterilization or cooking, high-temperature filling of contents, and the like, medical devices and infant products that require high-temperature sterilization, packaging materials for products that are exported beyond the equator, electronic materials that are exposed to severe temperatures, automobile parts, and various industrial masks.
< second embodiment >
Hereinafter, a second embodiment of the present invention will be described. The same contents as those of the first embodiment described above will not be described repeatedly.
[ injection-molded article ]
The injection molded article of the present embodiment is an injection molded article obtained from a polyester resin containing a diol unit and a dicarboxylic acid unit. In the injection-molded article of the present embodiment, 50 to 95 mol% of the diol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the formula (I) and/or pentacyclopentadecane dimethanol represented by the formula (II), 50 to 100 mol% of the dicarboxylic acid units are units derived from an aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) the measured value of the glass transition temperature measured by a differential scanning calorimeter is 131 ℃ or more, and the heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less.
(2) The Intrinsic Viscosity (IV) measured at 25 ℃ using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane at a mass ratio of 6:4 is 0.2 to 1.2 dl/g.
With the above configuration, the injection-molded article of the present embodiment is transparent and excellent in heat resistance, and has dimensional stability such as no appearance defect or no large dimensional change even after boiling sterilization. That is, the injection-molded article of the present embodiment has more excellent heat resistance than an injection-molded article using a conventionally known heat-resistant transparent polyester resin or a conventional transparent resin such as polystyrene or an acrylonitrile-styrene copolymer, and does not cause a poor appearance or a large dimensional change even after boiling sterilization. Therefore, it can be suitably used for applications requiring sterilization treatment at high temperature, such as food and drink containers, cosmetic containers, medical instruments, baby products such as feeding bottles and pacifiers. Further, the injection molding is extremely useful because of its property, such that the degree of freedom of the shape of the molded article is large and the production efficiency is high.
As described above, the polyester resin used in the second embodiment of the present invention is the same as that described in the first embodiment.
As the combination of the diol unit and the dicarboxylic acid unit of the polyester resin used for the injection-molded article of the present embodiment, preferred are: a resin containing, as a diol unit, the above-mentioned unit derived from pentacyclopentadecane dimethanol and a unit derived from ethylene glycol, and, as a dicarboxylic acid unit, a unit derived from terephthalic acid and/or a unit derived from 2, 6-naphthalenedicarboxylic acid.
In the case where the dicarboxylic acid unit mainly contains a unit derived from terephthalic acid, the proportion of the unit derived from pentacyclopentadecane dimethanol in the diol unit is preferably 50 to 90 mol%, more preferably 51 to 85 mol%, even more preferably 51 to 80 mol%, and even more preferably 55 to 80 mol% of the total diol units, from the viewpoint of further improving the heat resistance and mechanical properties of the polyester resin. The proportion of the units derived from ethylene glycol in the diol units is preferably 10 to 50 mol%, more preferably 15 to 49 mol%, even more preferably 20 to 49 mol%, and even more preferably 20 to 45 mol% of the total diol units. The proportion of the unit derived from terephthalic acid in the dicarboxylic acid unit is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and still more preferably 90 to 100 mol%.
In addition, when the dicarboxylic acid unit mainly contains a unit derived from 2, 6-naphthalenedicarboxylic acid, higher heat resistance tends to be obtained.
In the case where the dicarboxylic acid unit contains a unit derived from 2, 6-naphthalenedicarboxylic acid, the proportion of the unit derived from pentacyclopentadecane dimethanol in the diol unit is preferably 50 to 90 mol%, more preferably 51 to 90 mol%, even more preferably 51 to 80 mol%, and even more preferably 55 to 80 mol% of the total diol units, from the viewpoint of heat resistance and transparency. The proportion of the units derived from ethylene glycol in the diol units is preferably 5 to 50 mol%, more preferably 10 to 50 mol%, even more preferably 15 to 49 mol%, even more preferably 20 to 49 mol%, and even more preferably 20 to 45 mol% of the total diol units, from the viewpoint of heat resistance and mechanical properties. The proportion of the unit derived from 2, 6-naphthalenedicarboxylic acid in the dicarboxylic acid unit is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and still more preferably 90 to 100 mol%, from the viewpoint of heat resistance.
The polyester resin used for the injection-molded article of the present embodiment preferably satisfies the following condition (3):
(3) in a test in which a type 1A multipurpose test piece (test piece having a shape shown in fig. 3) described in a test method conforming to tensile characteristics in JIS K7162, which was produced by injection molding by the following molding method, was immersed in boiling water at 100 ℃ for 30 minutes, the dimensional change rate after immersion in boiling water, which was calculated from the following formula (1), was 0.50% or less in the thickness direction and the width direction and 0.60% or less in the entire length direction. The injection molding is carried out by using an injection molding machine (model: SE130DU-HP, manufactured by Sumitomo heavy machinery industries, Ltd.) under the conditions of a cylinder temperature of 230 to 260 ℃ and a mold temperature of 60 ℃.
Formula (1):
ΔM＝|M-M0|/M0×100
(wherein. DELTA.M is the rate of change in size [% ])]；M0Is the size [ mm ] before immersion in boiling water](ii) a M is the size [ mm ] after immersion in boiling water]。)
Regarding the dimensional change rate after immersion in boiling water, the dimensional change rate in the thickness direction was measured at 9 positions 10mm, 30mm, 50mm, 70mm, 85mm, 100mm, 120mm, 140mm, and 160mm from the end of the test piece on the center axis of the dotted line shown in fig. 3, and the dimensional change rate in the thickness direction was calculated from the obtained measurement values according to the above formula (1), and the arithmetic mean of these numbers was taken as the dimensional change rate in the thickness direction.
The dimensional change rate in the width direction was measured before and after 9 portions of the test piece of fig. 3, which were 10mm, 30mm, 50mm, 70mm, 85mm, 100mm, 120mm, 140mm, and 160mm from the end of the test piece, were immersed in boiling water, and the dimensional change rate was calculated from the obtained measurement values according to the above formula (1), and the arithmetic mean of these numbers was taken as the dimensional change rate in the width direction.
The dimensional change rate in the entire length direction is measured for the dimension in the entire length direction before and after immersion in boiling water on the central axis shown by the broken line in fig. 3, and the dimensional change rate in the entire length direction is calculated from the obtained measurement value based on the above formula (1).
In the above test, it is preferable that the dimensional change rate after immersion in boiling water is 0.50% or less in the thickness direction or width direction, or 0.60% or less in the entire length direction, because significant deformation tends to be prevented particularly when the shape of the injection molded article is complicated in the long-term boiling sterilization. From the above-described viewpoint, the dimensional change rate after immersion in boiling water in the above test is preferably 0.40% or less, and more preferably 0.30% or less, in the thickness direction and the width direction. In the entire length direction, it is preferably 0.50% or less, and more preferably 0.40% or less.
The injection molded article of the present embodiment can be produced by a conventionally known injection molding method. For example, a method of supplying a polyester resin to an injection molding machine including an injection device and a mold clamping device, injecting the resin heated and melted at a melting temperature into a mold having a predetermined shape, and cooling and solidifying the resin in the mold to obtain a molded article can be mentioned.
The injection molded article of the present embodiment can also be multilayered with another resin by coinjection molding.
In the injection molding of the present embodiment, various stabilizers such as a heat stabilizer, a light stabilizer, an anti-etherifying agent and an antioxidant, and various additives such as a coloring agent, a mold release agent, a plasticizer, an ultraviolet absorber, an extender, a delustering agent, a drying regulator, an antistatic agent, an anti-settling agent, a surfactant, a flow improver, a drying oil, waxes, a filler, a reinforcing material, a surface smoothing material, a leveling agent, a curing reaction accelerator, a tackifier and a molding aid may be added to the injection molding within a range not to impair the object of the present embodiment. In addition, it can be mixed with other resins.
The injection molded article of the present embodiment has heat resistance such that it is transparent and can withstand boiling sterilization, and therefore can be suitably used for applications requiring high-temperature sterilization treatment, such as food and beverage containers, cosmetic containers, medical instruments, baby products such as feeding bottles and pacifiers. And can also be used in applications where electronic materials, automobile parts, and the like are used under severe temperature conditions.
< third embodiment >
A third embodiment of the present invention will be explained below. The same contents as those of the first to second embodiments described above will be omitted here.
[ polyester sheet ]
The polyester sheet of the present embodiment is obtained by molding a polyester resin containing a diol unit and a dicarboxylic acid unit. In the polyester sheet of the present embodiment, 50 to 95 mol% of the diol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the formula (I) and/or pentacyclopentadecane dimethanol represented by the formula (II), 50 to 100 mol% of the dicarboxylic acid units are units derived from an aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) a measured value of the glass transition temperature of the polyester resin measured by a differential scanning calorimeter is 131 ℃ or more, and the heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less;
(2) the polyester resin has a measured value of Intrinsic Viscosity (IV) measured at 25 ℃ of 0.2 to 1.2dl/g using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane in a mass ratio of 6: 4.
With the above configuration, the polyester sheet of the present embodiment is excellent in transparency and heat resistance. That is, the polyester sheet of the present embodiment has more excellent heat resistance than a sheet obtained by molding a conventional transparent resin such as a conventionally known heat-resistant transparent polyester resin, polystyrene, or an acrylonitrile-styrene copolymer. Therefore, the polyester sheet of the present embodiment and the molded article obtained by molding the sheet can be suitably used in operations such as sterilization at high temperature and high-temperature filling of contents, and can be suitably used in the fields of food, cosmetics, containers and packaging materials in the medical field. Further, the resin composition can be used for industrial materials such as building materials, optical materials, and automobile parts. Therefore, the industrial utility value is extremely high.
As described above, the polyester resin used in the third embodiment of the present invention is the same as that described in the first embodiment.
In addition, the preferable combination of the diol unit and the dicarboxylic acid unit of the polyester resin used in the third embodiment of the present invention is the same as that described in the second embodiment.
The polyester sheet of the present embodiment is not limited to the following, but can be produced by a conventionally known method such as extrusion molding or calender molding. Further, the multilayer sheet can be formed by a conventionally known lamination technique such as a coextrusion method, an extrusion lamination method, a coextrusion lamination method, and a dry lamination method. For such lamination, an adhesive or an adhesive resin applied between resins can be used.
In the production of the polyester sheet of the present embodiment, various additives such as various stabilizers such as a heat stabilizer, a light stabilizer, an anti-etherifying agent, and an antioxidant, a coloring agent, a mold release agent, a plasticizer, an ultraviolet absorber, an extender, a delustering agent, a drying regulator, an antistatic agent, an anti-settling agent, a surfactant, a flow improver, drying oil, waxes, a filler, a reinforcing material, a surface smoothing material, a leveling agent, a curing reaction accelerator, a tackifier, and a molding aid may be added to the polyester sheet in such a range that the object of the present embodiment is not impaired. In addition, it can be mixed with other resins.
In the present embodiment, the polyester resin used for the polyester sheet preferably satisfies the following conditions (4) and (5):
(4) the total light transmittance of the sheet with the thickness of 0.20mm and the sheet with the thickness of 0.35mm is measured by more than 86%;
(5) a square test piece of 120mm in the longitudinal direction x 120mm in the transverse direction was cut out from a sheet of 0.20mm in thickness with the extrusion direction as the longitudinal direction and the width direction as the transverse direction, a mark line of 100mm in length was marked on the center line of the test piece in the longitudinal direction and the transverse direction, respectively, and after the test piece was heated in a drier for 30 minutes, the maximum temperature (heat resistance temperature) at which the change rate of the length of the mark line after heating does not exceed 0.5% in the longitudinal direction and the transverse direction, which was calculated from the following formula (2), was 110 ℃ or higher.
Formula (2):
ΔL＝|L-L0|/L0×100
(wherein. DELTA.L is the rate of change [% ] in the length of the reticle]；L0Is the length of the marked line before heating [ mm ]](ii) a L is the length of the heated reticle [ mm ]]。)
As described above, the polyester sheet of the present embodiment is preferably a polyester resin having a total light transmittance of 86% or more as measured in accordance with JIS K7105 when the sheet is molded to have a thickness of 0.20 to 0.35 mm. When the total light transmittance is set to 86% or more, the visibility tends to be sufficient, and the practical value as a transparent material tends to be improved. From the above viewpoint, the total light transmittance is more preferably 88% or more, and still more preferably 90% or more.
Further, as the polyester sheet of the present embodiment, a polyester resin is preferably used, in which a square test piece of 120mm in the longitudinal direction × 120mm in the transverse direction is cut out from a sheet molded to have a thickness of 0.20mm with the extrusion direction as the longitudinal direction and the width direction as the transverse direction, and as shown in fig. 4, a mark line having a length of 100mm is marked on the center line of each of the longitudinal direction and the transverse direction of the test piece, and after the test piece is heated in a dryer for 30 minutes, the maximum temperature (hereinafter referred to as "heat-resistant temperature a") at which the rate of change in the length of the heated mark line does not exceed 0.5% in the longitudinal direction and the transverse direction, is not less than 110 ℃. When the heat-resistant temperature a is 110 ℃ or higher, heat resistance that can sufficiently withstand heat treatment at 100 ℃ or higher or use in a high-temperature environment tends to be imparted. From the above-mentioned viewpoint, the heat-resistant temperature A is preferably 115 ℃ or higher, and more preferably 120 ℃ or higher.
The thickness of the polyester sheet of the present embodiment can be appropriately set according to the application, and is usually 0.05mm to 10 mm. As a specific example, although not limited to the following, the sheet is used in a thickness of 0.10mm to 3mm in a sheet for food use, and is used in a thickness of 1mm or more in a thick sheet for building material use, electronic material use, commodity display use, and the like.
The polyester sheet of the present embodiment is not limited to the following, but can be used as a molded article having various shapes formed by secondary molding by a conventionally known method such as vacuum molding, pressure molding, and vacuum pressure molding (pressure vacuum molding). The molding method of the thermoforming is not particularly limited, and any method such as a direct method (Straight method), a hot wrap method (draw method), and a plug assist molding method (plug assist method) may be used. When conventionally known PET or PEN sheets are produced by the above method, the obtained molded article may be whitened, but the polyester sheet of the present embodiment is inhibited from being crystallized and thus is free from whitening, and a molded article having excellent transparency can be obtained.
The molded article (container shape) obtained by molding the polyester sheet of the present embodiment is preferably one in which the maximum temperature (hereinafter referred to as "heat-resistant temperature B") at which the height retention of the container after heating is 98% or more, calculated from the following formula (3), is 100 ℃ or higher after heating in a dryer for 30 minutes. When the heat-resistant temperature B is 100 ℃ or higher, heat resistance sufficient to withstand high-temperature filling of contents or use in a high-temperature environment tends to be imparted. From the above-mentioned viewpoint, the heat-resistant temperature B is preferably 105 ℃ or higher, and more preferably 110 ℃ or higher.
Formula (3):
ΔH＝H/H0×100
(wherein. DELTA.H is the height-holding ratio [% ]) of the container]；H0Is the height of the container before heating [ mm ]](ii) a H is the height of the heated container [ mm ]]
< fourth embodiment >
The fourth embodiment of the present invention will be explained below. The same contents as those of the first to third embodiments are omitted here.
[ polyester Container ]
The polyester container of the present embodiment is obtained by molding a polyester resin containing a diol unit and a dicarboxylic acid unit. In the polyester container of the present embodiment, 50 to 95 mol% of the glycol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the formula (I) and/or pentacyclopentadecane dimethanol represented by the formula (II), 50 to 100 mol% of the dicarboxylic acid units are units derived from an aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) a measured value of the glass transition temperature of the polyester resin measured by a differential scanning calorimeter is 131 ℃ or more, and the heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less;
(2) the polyester resin has a measured value of Intrinsic Viscosity (IV) measured at 25 ℃ of 0.2 to 1.2dl/g using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane in a mass ratio of 6: 4.
With the above configuration, the polyester container of the present embodiment is excellent in transparency and heat resistance. That is, the polyester container of the present embodiment has more excellent heat resistance than a container formed by molding a conventional transparent resin such as a conventionally known heat-resistant transparent polyester resin, polystyrene, or an acrylonitrile-styrene copolymer. Therefore, the present invention can be used for storage of high-temperature products, heating for sterilization or cooking, high-temperature filling of contents, transportation under a high-temperature environment, and the like, and can be suitably used for containers for food and drink, containers for cosmetic products, containers for pharmaceuticals, and the like, and thus has a very great industrial utility value.
As described above, the polyester resin used in the fourth embodiment of the present invention is the same as that described in the first embodiment.
In addition, the preferable combination of the diol unit and the dicarboxylic acid unit of the polyester resin used in the fourth embodiment of the present invention is the same as that described in the second embodiment.
The polyester container of the present embodiment can be manufactured by a conventionally known method. The production method is not limited to the following, but examples thereof include blow molding (blow molding) of the polyester resin used in the present embodiment, and thermoforming of a sheet made of the polyester resin. When conventionally known PET or PEN is produced by the above method, the obtained molded article may be whitened, but the polyester sheet used in the present embodiment is inhibited from being whitened due to its crystallinity, and a container having excellent transparency can be obtained.
In the present embodiment, the polyester resin for a polyester container preferably satisfies the following condition (6):
(6) after heating a polyester container having the shape described below in a dryer for 30 minutes, the maximum temperature (heat-resistant temperature) at which the height retention rate of the heated container becomes 98% or more, calculated from the following formula (3), is 100 ℃ or more.
< Container shape >
A polyester sheet having a thickness of 0.35mm was thermoformed by a vacuum pressure molding machine at a draw ratio of 0.36 to obtain a container having an opening of 70mm X70 mm, a height of 25mm and a capacity of about 100 mL.
< formula (3) >
ΔH＝H/H0×100
(wherein. DELTA.H is the height-holding ratio [% ]) of the container]；H0Is the height of the container before heating [ mm ]](ii) a H is the height of the heated container [ mm ]])
The polyester sheet having a thickness of 0.35mm was obtained as follows.
The polyester resin of the present embodiment was charged into a sheet manufacturing apparatus comprising an extruder (manufactured by PLAENGI CO., LTD., trade name: PSV-30 (diameter: 30mm, L/D: 36)), a T-die, a chill roll, and a winder, and a sheet having a thickness of about 0.35mm was manufactured by the T-die method.
The molding conditions are that the temperature of the charging barrel is 240 ℃, the temperature of the die head is 250 ℃, the rotating speed of the screw is 35-36 rpm, the speed of the roller (the speed of the main roller and the speed of the pinch roller) is 0.6-0.8 m/min, and the temperature of the roller is 145 ℃.
The polyester container of the present embodiment is preferably a polyester resin which is molded into a container shape as described above, and then heated in a dryer for 30 minutes, and then the maximum temperature (hereinafter referred to as "heat-resistant temperature C") at which the height retention rate of the heated container (average of the height retention rates measured at the four corners of the container) calculated from the above formula (3) is 98% or more is 100 ℃. When the heat-resistant temperature C is 100 ℃ or higher, the container can withstand high-temperature filling of contents, use in a high-temperature environment, or the like. From the above-mentioned viewpoint, the heat-resistant temperature C is preferably 105 ℃ or higher, and more preferably 110 ℃ or higher.
The hollow molding is not limited to the following, but examples thereof include injection blow molding (injection blow molding), direct blow molding (direct blow molding), and the like. The molding method of the hollow molding is not particularly limited, and may be a 1-stage (hot parison method) or a 2-stage (cold parison method). Further, the container can be multilayered by co-injection or co-extrusion with another resin.
When the polyester container of the present embodiment is produced by blow molding, various additives such as a heat stabilizer, a light stabilizer, an anti-etherifying agent, various stabilizers such as an antioxidant, a coloring agent, a mold release agent, a plasticizer, an ultraviolet absorber, an extender, a matting agent, a drying modifier, an antistatic agent, an anti-settling agent, a surfactant, a flow improving agent, drying oil, waxes, a filler, a reinforcing agent, a surface smoothing agent, a leveling agent, a curing reaction accelerator, a thickener, a molding aid, and the like may be added within a range not to impair the object of the present embodiment. In addition, it can be mixed with other resins.
The thermoforming is not limited to the following, but examples thereof include vacuum forming, pressure forming, and vacuum pressure forming (pressure vacuum forming). The molding method of the thermoforming is not particularly limited, and any method such as a direct method, a hot-wrap method, and an assist plug molding method can be used. Further, the container can be made into a multilayer by using a polyester sheet multilayered with another resin by the method described later as a coil.
The polyester sheet used for the thermoforming can be produced by a conventionally known method such as extrusion molding or calender molding. Further, the multilayer sheet can be produced by a conventionally known lamination technique such as a coextrusion method, an extrusion lamination method, a coextrusion lamination method, and a dry lamination method. For such lamination, an adhesive or an adhesive resin suitable for resin bonding can be used.
In the production of the polyester sheet used for the thermoforming, various additives such as various stabilizers such as a heat stabilizer, a light stabilizer, an anti-etherifying agent, and an antioxidant, a coloring agent, a mold release agent, a plasticizer, an ultraviolet absorber, an extender, a delustering agent, a drying regulator, an antistatic agent, an anti-settling agent, a surfactant, a flow improver, drying oil, waxes, a filler, a reinforcing material, a surface smoothing material, a leveling agent, a curing reaction accelerator, a tackifier, and a forming aid may be added within a range not to impair the object of the present embodiment. In addition, it can be mixed with other resins.
The thickness of the polyester sheet used for the thermoforming is not limited to the following, but is usually about 0.10mm to 3 mm.
Examples
The present embodiment will be described in more detail below with reference to examples, but the scope of the present embodiment is not limited by these examples.
[ evaluation method of polyester resin ]
(1) Copolymerization composition
The proportions of the diol units and the dicarboxylic acid units in the polyester resin were determined1H-NMR was calculated from the peak area ratios derived from the respective constituent units. The measurement was carried out at 500MHz using a nuclear magnetic resonance apparatus (product name: AVANCE III 500/Ascend 500, manufactured by Bruker BioSpin K.K.). Deuterated chloroform was used as a solvent. When the solubility of the polyester resin is insufficient, a proper amount of deuterated trifluoroacetic acid is added to ensure sufficient solubility.
(2) Glass transition temperature (Tg)
The glass transition temperature of the polyester resin was measured by using a differential scanning calorimeter (product name: DSC-60/TA-60WS, manufactured by Shimadzu corporation). 5-10 mg of polyester resin is put into an aluminum non-sealed container, heated to 280 ℃ at a heating rate of 20 ℃/min in a nitrogen (50 mL/min) air flow, and rapidly cooled to obtain a sample for measurement. The temperature of the sample was again raised under the same conditions, and the glass transition temperature was determined as the temperature (midpoint glass transition temperature) at which the difference between the base lines before and after the DSC curve drifted was changed by only 1/2.
(3) Crystallization heat release (Δ Hc) at cooling
The crystallization heat release at the time of cooling the polyester resin was calculated from the area of the heat generation peak which appears when the temperature was lowered at a rate of 5 ℃ per minute after measuring the Tg and holding the temperature at 280 ℃ for 1 minute.
(4) Intrinsic Viscosity (IV)
The polyester resin was dissolved in a mixed solvent of phenol/1, 1,2, 2-tetrachloroethane (6/4 by weight), and three kinds of measurement solutions (0.2g/dl, 0.4g/dl, 0.6g/dl) were prepared. The specific viscosity at each concentration was measured at a constant temperature of 25 ℃ using a relative viscometer (manufactured by Viscotek, model: Y501). Then, the obtained specific viscosity is divided by the concentration of the measurement solution, and reduced viscocity (reduced viscocity) is calculated for each concentration. The values were plotted with the reduced viscosity as the vertical axis and the solution concentration as the horizontal axis, and an approximate straight line was plotted, and the intercept when the obtained straight line was extrapolated to infinite dilution was taken as the intrinsic viscosity of the polyester resin.
[ evaluation method of injection-molded article ]
(1) Deflection temperature under load
The deflection temperature under load of the molded article was measured in accordance with JIS K7191 using a strip-shaped injection molded article having the shape and size shown in FIG. 1 as a sample. The temperature rise rate of the heat transfer medium was 120 ℃/h, the test was carried out edgewise (edgewise), the bending stress applied to the sample was carried out at 0.45MPa and 1.80MPa, and the deflection temperature under load was defined as the temperature at which the deflection of the sample reached 0.26 mm. The measurement was carried out using an automatic HDT testing apparatus (model 3A-2, manufactured by Toyo Seiki Seisaku-Sho Ltd.).
(2) Transparency of
The transparency of the molded article was evaluated by measuring the total light transmittance and the haze by the transmission method in accordance with JIS K7105 using a disc-shaped injection molded article having the shape and size shown in FIG. 2 as a sample. The measurement was carried out using a color difference and turbidity measuring apparatus (model: COH-400, manufactured by Nippon Denshoku industries Co., Ltd.).
(3) Resistance to boiling
The boiling resistance of the injection-molded article was evaluated by using a test piece (1A type multipurpose test piece) having a shape shown in fig. 3 described in the test method for tensile properties in JIS K7162. The injection-molded article was immersed in boiling water at 100 ℃ for 30 minutes, and the dimensional change rate after immersion in boiling water in the thickness direction, width direction and overall length direction was calculated from the dimensions measured before and after immersion and the following formula (1), and the boiling resistance was evaluated.
Formula (1):
ΔM＝|M-M0|/M0×100
(wherein. DELTA.M is the rate of change in size [% ])]；M0Is the size [ mm ] before immersion in boiling water](ii) a M is the size [ mm ] after immersion in boiling water]。)
The dimensions in the thickness direction and the width direction were measured using a micrometer (manufactured by Mitutoyo Co., Ltd., code No. 293-661-10), and the dimensions in the entire length direction were measured using a stainless steel ruler (manufactured by Shinwa Rules Co., Ltd.) with a scale interval of 1 mm.
In addition, if the appearance change such as warpage, cracking, whitening and the like can be visually confirmed, the test results are described.
[ evaluation method of sheet ]
(1) Transparency of
The transparency of the sheet was evaluated by cutting out a square test piece of 50mm in the longitudinal direction x 50mm in the transverse direction as a sample from a sheet having a thickness of 0.20mm and a sheet having a thickness of 0.35mm in the longitudinal direction and the transverse direction in the extrusion direction, and measuring the total light transmittance and haze by the transmission method according to jis k 7105. The measurement was carried out using a color difference and turbidity measuring apparatus (model: COH-400, manufactured by Nippon Denshoku industries Co., Ltd.).
(2) Heat resistance
The heat resistance of the sheet was evaluated by the heat resistance temperature determined in the following test method with JIS K7133 as a reference. A square test piece of 120mm in the longitudinal direction X120 mm in the transverse direction was cut out from a sheet of 0.20mm in thickness with the extrusion direction being the longitudinal direction and the width direction being the transverse direction, and markings of 100mm in length were marked on the center lines of the test piece in the longitudinal direction and the transverse direction, respectively, as shown in FIG. 4. The test piece was placed on a metal tray covered with talc, heated in a drier (model no 63, manufactured by Yamato Scientific co., ltd.) at a set test temperature (constant temperature) for 30 minutes, and the rate of change in the heated reticle distance was calculated from the reticle distance (length of the reticle) measured before and after heating and the following formula (2).
The maximum temperature at which the rate of change in the length of the heated reticle does not exceed 0.5% in both the longitudinal and transverse directions was used as the heat-resistant temperature of the sheet. The test was carried out at a temperature interval of 5 ℃. The length of the mark line was measured using a stainless steel ruler (manufactured by Shinwa Rules co., Ltd) with 0.5mm scale intervals.
Formula (2):
ΔL＝|L-L0|/L0×100
(wherein. DELTA.L is the rate of change [% ] in the length of the reticle]；L0Is the length of the marked line before heating [ mm ]](ii) a L is the length of the heated reticle [ mm ]]。)
[ evaluation methods for sheet molded article and Container ]
(1) Transparency of
The appearance of the molded article was evaluated by visual observation. The notations in the table have the following meanings.
it was confirmed that the transparent glass had sufficient transparency
X: transparency is impaired by whitening or the like
(2) Heat resistance
The heat resistance of the molded article (container produced by the method described later) was evaluated by determining the heat resistance temperature according to the following test method. The container was left to stand and heated for 30 minutes in a drier (model No. DN63, manufactured by Yamato Scientific co., ltd.) at a set test temperature (constant temperature), and the height retention rate of the heated container was calculated from the height of the container measured before and after heating and the following formula (3).
The heat-resistant temperature of the container was determined as the highest temperature at which the height retention rate of the heated container became 98% or more. The test was carried out at a temperature interval of 5 ℃. The height of the container was measured using a height gauge (height gage) (manufactured by Mitutoyo, Ltd., code No. 192-653) and was an average of the values measured at 4 places (four corners of the container).
Formula (3):
ΔH＝H/H0×100
(wherein. DELTA.H is the height-holding ratio [% ]) of the container]；H0Is the height of the container before heating [ mm ]](ii) a H is the height of the heated container [ mm ]])
[ Synthesis and evaluation of polyester resin ]
< examples 1-1 to 1-2 and comparative examples 1-1 to 1-2>
A polyester production apparatus equipped with a partial condenser, a complete condenser, a cold trap, a stirrer, a heating device, and a nitrogen gas inlet pipe was charged with the amount of the raw material monomers shown in Table 1, and the esterification reaction was carried out by raising the temperature to 245 to 260 ℃ under a nitrogen pressure of 0.3 MPa. After the reaction conversion of the dicarboxylic acid component calculated from the amount of water distilled out of the reactor reached 90% or more, antimony (III) oxide and phosphoric acid were added in the amounts shown in Table 1, and the temperature and pressure were gradually increased and reduced, and finally polycondensation was carried out at 260 to 280 ℃ under 0.1 kPa. The reaction is terminated when an appropriate melt viscosity is reached, and the polyester resin is recovered.
The evaluation results of the obtained polyester resin are shown in table 1.
[ production and evaluation of injection molded article ]
< examples 1-1 to 1-2 and comparative examples 1-1 to 1-2>
The obtained polyester resin was subjected to an injection molding machine (model: SE130DU-HP, manufactured by Sumitomo heavy machinery industries Co., Ltd.) to prepare an injection molded article under the conditions of a cylinder temperature of 230 to 260 ℃ and a mold temperature of 60 ℃.
The evaluation results of the obtained polyester resin are shown in table 1.
< comparative examples 1-3 to 1-5>
A polyester resin containing no diol unit having a pentacyclopentadecane skeleton was used: tritan (TX2001) (manufactured by Eastman Chemical company), Tritan (TX1001) (manufactured by Eastman Chemical company), or an acrylonitrile-styrene copolymer: stylac AS (T8707) (manufactured by Asahi Kasei Chemicals Corporation) was injection-molded by an injection molding machine (manufactured by Sumitomo heavy machinery industries, Ltd., model: SE130DU-HP) under temperature conditions of a cylinder temperature of 230 to 260 ℃ and a mold temperature of 60 ℃.
The evaluation results are shown in table 2.
< comparative examples 1 to 6>
An injection-molded article was prepared from PSJ-polystyrene (HF77) (PS Japan K.K.) by using an injection molding machine (model: SE130DU-HP, manufactured by Sumitomo heavy machinery industries Co., Ltd.) under the conditions of a cylinder temperature of 210 to 230 ℃ and a mold temperature of 60 ℃.
The evaluation results are shown in table 2.
[ Table 1]
The notations in the table have the following meanings.
PTA: high purity terephthalic acid
PCPDM: pentacyclopentadecane dimethanol
EG: ethylene glycol
DEG: diethylene glycol
[ Table 2]
[ Synthesis of polyester resin ]
Production examples 2-1 to 2-3
A polyester production apparatus equipped with a partial condenser, a complete condenser, a cold trap, a stirrer, a heating device, and a nitrogen gas inlet pipe was charged with the amount of the raw material monomers shown in Table 3, and the temperature was raised to 245 to 260 ℃ under a nitrogen pressure of 0.3MPa to perform an esterification reaction. After the reaction conversion of the dicarboxylic acid component calculated from the amount of water distilled out of the reactor reached 90% or more, antimony (III) oxide and phosphoric acid were added in the amounts shown in Table 3, and the temperature and pressure were gradually increased and reduced, and finally polycondensation was carried out at 260 to 280 ℃ under 0.1 kPa. The reaction is terminated when an appropriate melt viscosity is reached, and the polyester resin is recovered.
The composition of the obtained polyester resin is shown in table 3.
< production examples 2 to 4>
In a polyester production apparatus equipped with a partial condenser, a complete condenser, a cold trap, a stirrer, a heating apparatus, and a nitrogen gas introduction pipe, the raw material monomers and manganese (II) acetate tetrahydrate were charged in amounts shown in table 3, and the temperature was raised to 220 to 235 ℃ under a nitrogen pressure of 0.15MPa to perform a transesterification reaction. After the reaction conversion of the dicarboxylate component calculated from the amount of methanol distilled out of the reactor reached 90% or more, antimony (III) oxide and phosphoric acid in the amounts shown in Table 3 were added, and the temperature and pressure were gradually increased and reduced, and finally polycondensation was carried out at 260 to 280 ℃ under 0.1 kPa. The reaction is terminated when an appropriate melt viscosity is reached, and the polyester resin is recovered.
The compositions of the obtained polyester resins are shown in Table 3, and the evaluation results are shown in Table 4.
[ production and evaluation of injection molded article ]
< example 2-1, reference examples 2-1 to 2-2 and comparative example 2-1>
An injection-molded article was produced from the polyester resin obtained in production examples 2-1 to 2-4 by using an injection molding machine (model: SE130DU-HP, manufactured by Sumitomo heavy machinery industries Co., Ltd.) under the conditions of a cylinder temperature of 230 to 260 ℃ and a mold temperature of 60 ℃.
The evaluation results of the obtained injection-molded articles are shown in table 4.
< comparative examples 2-2 to 2-3>
A polyester resin containing no diol unit having a pentacyclopentadecane skeleton was used: tritan (TX 1001: manufactured by Eastman Chemical Co., Ltd.), or an acrylonitrile-styrene copolymer: stylac AS (T8707: manufactured by Asahi Kasei Chemicals Corporation) was molded into an injection-molded article by an injection molding machine (model: SE130DU-HP, manufactured by Sumitomo heavy machinery industries Co., Ltd.) under temperature conditions of a cylinder temperature of 230 to 260 ℃ and a mold temperature of 60 ℃.
The evaluation results of the resin used and the injection molded article obtained are shown in table 5.
< comparative examples 2 to 4>
An injection-molded article was prepared from PSJ-polystyrene (HF 77: manufactured by PS JAPAN Co., Ltd.) by using an injection molding machine (model: SE130DU-HP, manufactured by Sumitomo heavy machinery industries Co., Ltd.) under the conditions of a cylinder temperature of 210 to 230 ℃ and a mold temperature of 60 ℃.
The evaluation results of the resin used and the injection molded article obtained are shown in table 5.
[ Table 3]
The notations in the table have the following meanings.
PTA: high purity terephthalic acid
NDCM (NDCM): 2, 6-naphthalenedicarboxylic acid dimethyl ester
PCPDM: pentacyclopentadecane dimethanol
EG: ethylene glycol
DEG: diethylene glycol
[ Table 4]
[ Table 5]
[ Synthesis of polyester resin ]
< production example 3-1>
A polyester production apparatus equipped with a partial condenser, a complete condenser, a cold trap, a stirrer, a heating device, and a nitrogen gas inlet pipe was charged with the amount of the raw material monomers shown in Table 6, and the temperature was raised to 245 to 260 ℃ under a nitrogen pressure of 0.3MPa to perform an esterification reaction. After the reaction conversion of the dicarboxylic acid component calculated from the amount of water distilled out of the reactor reached 90% or more, antimony (III) oxide and phosphoric acid were added in the amounts shown in Table 6, and the temperature and pressure were gradually increased and reduced, and finally polycondensation was carried out at 260 to 280 ℃ under 0.1 kPa. The reaction is terminated when an appropriate melt viscosity is reached, and the polyester resin is recovered.
The compositions of the obtained polyester resins are shown in Table 6, and the evaluation results are shown in Table 7.
< production examples 3 and 2>
A polyester production apparatus equipped with a partial condenser, a complete condenser, a cold trap, a stirrer, a heating device, and a nitrogen gas inlet pipe was charged with the raw material monomers and manganese (II) acetate tetrahydrate in the amounts shown in Table 6, and the temperature was raised to 220 to 235 ℃ to perform an ester exchange reaction. After the reaction conversion of the dicarboxylate component calculated from the amount of methanol distilled out of the reactor reached 90% or more, antimony (III) oxide and phosphoric acid in the amounts shown in Table 6 were added, and the temperature and pressure were gradually increased and reduced, and finally polycondensation was carried out at 260 to 280 ℃ under 0.1 kPa. The reaction is terminated when an appropriate melt viscosity is reached, and the polyester resin is recovered.
The compositions of the obtained polyester resins are shown in Table 6, and the evaluation results are shown in Table 7.
[ production of sheet and sheet molded article ]
< example 3-1>
The polyester resin obtained in production example 3-1 was charged into a sheet production apparatus comprising an extruder (manufactured by PLAENGI CO., LTD., trade name: PSV-30 (bore diameter: 30mm, L/D: 36)), a T die, a chill roll, and a winder, and a sheet having a thickness of about 0.20mm and a sheet having a thickness of about 0.35mm were produced by the T die method.
The sheet having a thickness of about 0.20mm is molded under conditions of a cylinder temperature of 240 ℃, a die temperature of 250 ℃, a screw rotation speed of 35 to 36rpm, a roll speed (main roll speed, pinch roll speed) of 1.0 to 1.1m/min, and a roll temperature of 145 ℃.
The sheet having a thickness of about 0.35mm was molded under the same conditions as those of the sheet having a thickness of about 0.20mm except that the roll speeds (main roll speed, pinch roll speed) were changed to 0.6 to 0.8 m/min.
Then, the polyester sheet having a thickness of about 0.35mm was formed using a vacuum pressure forming machine (Manufactured by the research on shallow fields of the company, type number: FK-0431-10) was thermoformed to prepare a molded article (container) having an opening of 70mm × 70mm, a height of 25mm, and a capacity of about 100mL (draw ratio: 1.8). The molding method is compression-assisted plug molding (upper mold pressing/lower mold vacuum), and the molding conditions are sheet preheating temperature of 180 deg.C, metal mold temperature of 60 deg.C, and pressing pressure of 4kg/cm2The process is carried out as follows.
The evaluation results of the obtained sheet and the sheet molded article are shown in table 7.
< reference example 3-1>
The polyester resin obtained in production example 3-2 was charged into a sheet production apparatus composed of an extruder (manufactured by PLAENGI CO., LTD., trade name: PSV-30 (diameter: 30mm, L/D: 36)), a T die, a chill roll, and a winder, and a sheet having a thickness of about 0.20mm and a sheet having a thickness of about 0.35mm were produced by the T die method.
The sheet having a thickness of about 0.20mm is molded under conditions of a cylinder temperature of 240 ℃, a die temperature of 250 ℃, a screw rotation speed of 32 to 33rpm, a roll speed (main roll speed, pinch roll speed) of 1.0 to 1.1m/min, and a roll temperature of 125 ℃.
The sheet having a thickness of about 0.35mm was molded under the same conditions as those of the sheet having a thickness of about 0.20mm except that the roll speeds (main roll speed, pinch roll speed) were changed to 0.7 to 0.8 m/min.
Then, the polyester sheet having a thickness of about 0.35mm was thermoformed by a vacuum pressure molding machine (manufactured by Kabushiki Kaisha, type: FK-0431-10) to prepare a molded article (container) having an opening of 70mm × 70mm, a height of 25mm and a capacity of about 100mL (draw ratio: 1.8). The molding method is compression-assisted plug molding (upper mold pressing/lower mold vacuum), and the molding conditions are sheet preheating temperature of 170 deg.C, metal mold temperature of 60 deg.C, and pressing pressure of 4kg/cm2The process is carried out as follows.
The evaluation results of the obtained sheet and the sheet molded article are shown in table 7.
< comparative example 3-1>
A polyester resin containing no diol unit having a pentacyclopentadecane skeleton was fed into a sheet manufacturing apparatus comprising an extruder (produced by PLAENGI co., ltd., trade name: PSV-30 (diameter: 30mm, L/D: 36)), a T die, a chill roll, and a winder: tritan (TX1001) (manufactured by Eastman Chemical Co., Ltd.), and sheets having a thickness of about 0.20mm and sheets having a thickness of about 0.35mm were produced by the T-die method.
The sheet with a thickness of about 0.20mm is molded under the conditions of a cylinder temperature of 250 ℃, a die temperature of 260 ℃, a screw rotation speed of 34-35 rpm, a roll speed (main roll speed, pinch roll speed) of 1.0-1.1 m/min, and a roll temperature of 110 ℃.
The sheet having a thickness of about 0.35mm was molded under the same conditions as those of the sheet having a thickness of about 0.20mm except that the roll speeds (main roll speed, pinch roll speed) were changed to 0.6 to 0.8 m/min.
Further, the same method as in reference example 3-1 was repeated except that the sheet preheating temperature was changed to 160 ℃ for the above-mentioned sheet having a thickness of about 0.35mm, and the same molded article (container) as in reference example 3-1 was produced.
The evaluation results of the resin, the sheet and the sheet molded body are shown in table 8.
< comparative example 3-2>
In a sheet manufacturing apparatus composed of an extruder (manufactured by PLAENGI CO., LTD., trade name: PSV-30 (bore: 30mm, L/D: 36)), a T die, a chill roll, and a winder, acrylonitrile-styrene copolymer: stylac AS (T8707) (manufactured by Asahi Kasei Chemicals Corporation), a sheet having a thickness of about 0.20mm and a sheet having a thickness of about 0.35mm were produced by the T die method.
The sheet having a thickness of about 0.20mm is molded under conditions of a cylinder temperature of 240 ℃, a die temperature of 250 ℃, a screw rotation speed of 33 to 34rpm, a roll speed (main roll speed, pinch roll speed) of 1.0 to 1.1m/min, and a roll temperature of 103 ℃.
The sheet having a thickness of about 0.35mm was molded under the same conditions as those of the sheet having a thickness of about 0.20mm except that the roll speeds (main roll speed, pinch roll speed) were changed to 0.6 to 0.7 m/min.
Further, for the above sheet having a thickness of about 0.35mm, the mold temperature was changed to 30 ℃ and the pressing pressure was changed to 1kg/cm2Except for this, the same thermoforming method as in reference example 3-1 was carried out to produce a molded article (container) as in reference example 3-1.
The evaluation results of the resin, the sheet and the sheet molded body are shown in table 8.
< comparative examples 3 to 3>
A sheet having a thickness of about 0.20mm and a sheet having a thickness of about 0.35mm were produced by a T-die method in a sheet production apparatus comprising an extruder (piaerni co., ltd., trade name: PSV-30 (diameter: 30mm, L/D: 36)), a T-die, a chill roll, and a winder, and charged with PSJ-polystyrene (HF77) (manufactured by PS JAPAN corporation).
The sheet having a thickness of about 0.20mm is molded under conditions of a cylinder temperature of 230 ℃, a die temperature of 240 ℃, a screw rotation speed of 33 to 34rpm, a roll speed (main roll speed, pinch roll speed) of 1.0 to 1.1m/min, and a roll temperature of 96 ℃.
The sheet having a thickness of about 0.35mm was molded under the same conditions as those of the sheet having a thickness of about 0.20mm except that the roll speeds (main roll speed, pinch roll speed) were changed to 0.7 to 0.8 m/min.
Further, for the above sheet having a thickness of about 0.35mm, the sheet preheating temperature was changed to 160 ℃, the mold temperature was changed to 30 ℃, and the pressing pressure was changed to 1kg/cm2Except for this, the same thermoforming method as in reference example 3-1 was carried out to produce a molded article (container) as in reference example 3-1.
The evaluation results of the resin, the sheet and the sheet molded body are shown in table 8.
[ Table 6]
The notations in the table have the following meanings.
PTA: high purity terephthalic acid
DMT: terephthalic acid dimethyl ester
PCPDM: pentacyclopentadecane dimethanol
EG: ethylene glycol
DEG: diethylene glycol
[ Table 7]
[ Table 8]
[ Synthesis of polyester resin ]
< production example 4-1>
A polyester production apparatus equipped with a partial condenser, a complete condenser, a cold trap, a stirrer, a heating device, and a nitrogen gas inlet pipe was charged with the amount of the raw material monomers shown in Table 9, and the temperature was raised to 245 to 260 ℃ under a nitrogen pressure of 0.3MPa to perform an esterification reaction. After the reaction conversion of the dicarboxylic acid component calculated from the amount of water distilled out of the reactor reached 90% or more, antimony (III) oxide and phosphoric acid were added in the amounts shown in Table 9, and the temperature and pressure were gradually increased and reduced, and finally polycondensation was carried out at 260 to 280 ℃ under 0.1 kPa. The reaction is terminated when an appropriate melt viscosity is reached, and the polyester resin is recovered.
The compositions of the obtained polyester resins are shown in Table 9, and the evaluation results are shown in Table 10.
< production examples 4 and 2>
A polyester production apparatus equipped with a partial condenser, a complete condenser, a cold trap, a stirrer, a heating device, and a nitrogen gas inlet pipe was charged with the raw material monomers and manganese (II) acetate tetrahydrate in the amounts shown in Table 9, and the temperature was raised to 220 to 235 ℃ to perform an ester exchange reaction. After the reaction conversion of the dicarboxylate component calculated from the amount of methanol distilled out of the reactor reached 90% or more, antimony (III) oxide and phosphoric acid in the amounts shown in Table 9 were added, and the temperature and pressure were gradually increased and reduced, and finally polycondensation was carried out at 260 to 280 ℃ under 0.1 kPa. The reaction is terminated when an appropriate melt viscosity is reached, and the polyester resin is recovered.
The compositions of the obtained polyester resins are shown in Table 9, and the evaluation results are shown in Table 10.
[ production of Web sheet and Container ]
< example 4-1>
The polyester resin obtained in production example 4-1 was charged into a sheet production apparatus comprising an extruder (PLAENGI CO., LTD., trade name: PSV-30 (diameter: 30mm, L/D: 36)), T die, cooling roll, and winder, and a sheet having a thickness of about 0.35mm was produced by the T die method.
The molding conditions are that the temperature of the charging barrel is 240 ℃, the temperature of the die head is 250 ℃, the rotating speed of the screw is 35-36 rpm, the speed of the roller (the speed of the main roller and the speed of the pinch roller) is 0.6-0.8 m/min, and the temperature of the roller is 145 ℃.
Then, the polyester sheet was thermoformed using a vacuum pressure molding machine (model: FK-0431-10, manufactured by Hill Seiki K.K.) to prepare a molded article (container) having an opening of 70mm × 70mm in a cross-sectional shape shown in FIG. 5, a height of 25mm, and a capacity of about 100mL (draw ratio: 0.36).
The molding method is compression-assisted plug molding (upper mold pressing/lower mold vacuum), and the molding conditions are sheet preheating temperature of 180 deg.C, metal mold temperature of 60 deg.C, and pressing pressure of 4kg/cm2The process is carried out as follows.
The evaluation results of the obtained container are shown in table 10.
< reference example 4-1>
The polyester resin obtained in production example 4-2 was charged into a sheet production apparatus comprising an extruder (PLAENGI CO., LTD., trade name: PSV-30 (diameter: 30mm, L/D: 36)), T die, cooling roll, and winder, and a sheet having a thickness of about 0.35mm was produced by the T die method.
The molding conditions are that the temperature of the charging barrel is 240 ℃, the temperature of the die head is 250 ℃, the rotating speed of the screw is 32-33 rpm, the speed of the roller (the speed of the main roller and the speed of the pinch roller) is 0.7-0.8 m/min, and the temperature of the roller is 125 ℃.
Then, the polyester sheet was thermoformed using a vacuum pressure molding machine (model: FK-0431-10, manufactured by Hill Seiki K.K.) to prepare a molded article (container) having an opening of 70mm × 70mm in cross section as shown in FIG. 5, a height of 25mm, and a capacity of about 100mL (stretch ratio: 0.36).
The molding method is compression-assisted plug molding (upper mold pressing/lower mold vacuum), and the molding conditions are sheet preheating temperature of 170 deg.C, metal mold temperature of 60 deg.C, and pressing pressure of 4kg/cm2The process is carried out as follows.
The evaluation results of the obtained container are shown in table 10.
< comparative example 4-1>
A polyester resin containing no diol unit having a pentacyclopentadecane skeleton was fed into a sheet manufacturing apparatus comprising an extruder (produced by PLAENGI co., ltd., trade name: PSV-30 (diameter: 30mm, L/D: 36)), a T die, a chill roll, and a winder: tritan (TX1001) (Eastman Chemical Co., Ltd.), and a sheet having a thickness of about 0.35mm was produced by the T die method.
The molding conditions are that the temperature of a charging barrel is 250 ℃, the temperature of a die head is 260 ℃, the rotating speed of a screw is 34-35 rpm, the speed of a roller (the speed of a main roller and the speed of a pinch roller) is 0.6-0.8 m/min, and the temperature of the roller is 110 ℃.
The above-mentioned sheet was thermoformed in the same manner as in reference example 4-1 except that the conditions were changed to a sheet preheating temperature of 160 ℃ to prepare a molded article (container) in the same manner as in reference example 4-1.
The evaluation results of the resin and the container are shown in table 11.
< comparative example 4-2>
In a sheet manufacturing apparatus composed of an extruder (manufactured by PLAENGI CO., LTD., trade name: PSV-30 (bore: 30mm, L/D: 36)), a T die, a chill roll, and a winder, acrylonitrile-styrene copolymer: stylac AS (T8707) (manufactured by Asahi Kasei Chemicals Corporation) was used to fabricate a sheet having a thickness of about 0.35mm by the T die method.
The molding conditions are that the temperature of the material cylinder is 240 ℃, the temperature of the die head is 250 ℃, the rotating speed of the screw is 33-34 rpm, the speed of the roller (the speed of the main roller and the speed of the pinch roller) is 0.6-0.7 m/min, and the temperature of the roller is 103 ℃.
Further, the above sheet was subjected to conditions of 30 ℃ mold temperature and 1kg/cm pressure2Except for this, thermoforming was carried out in the same manner as in reference example 4-1 to produce a molded article (container) as in reference example 4-1.
The evaluation results of the resin and the container are shown in table 11.
< comparative examples 4 to 3>
A sheet having a thickness of about 0.35mm was produced by a T-die method in which PSJ-polystyrene (HF77) (manufactured by PS JAPAN corporation) was charged into a sheet production apparatus comprising an extruder (piaerni co., ltd., product name: PSV-30 (diameter: 30mm, L/D: 36)), a T-die, a chill roll, and a winder.
The molding conditions are that the temperature of the material cylinder is 230 ℃, the temperature of the die head is 240 ℃, the rotating speed of the screw is 33-34 rpm, the speed of the roller (the speed of the main roller and the speed of the pinch roller) is 0.7-0.8 m/min, and the temperature of the roller is 96 ℃.
Further, the above sheet was subjected to conditions of 160 ℃ for preheating the sheet, 30 ℃ for mold, and 1kg/cm for pressurizing pressure2Except for this, thermoforming was carried out in the same manner as in reference example 4-1 to produce a molded article (container) as in reference example 4-1.
The evaluation results of the resin and the container are shown in table 11.
[ Table 9]
The notations in the table have the following meanings.
PTA: high purity terephthalic acid
DMT: terephthalic acid dimethyl ester
PCPDM: pentacyclopentadecane dimethanol
EG: ethylene glycol
DEG: diethylene glycol
[ Table 10]
[ Table 11]
The present application is based on japanese patent application No. 2013, No. 10/11 (application No. 2013-213322), japanese patent application No. 2013, No. 10/11 (application No. 2013-213323), japanese patent application No. 2013, No. 10/11 (application No. 2013-213324), and japanese patent application No. 2013, No. 10/11 (application No. 2013-213325), which are incorporated herein by reference.
Industrial applicability
The polyester resin of the present invention can be used for various purposes. For example, it is transparent and has heat resistance capable of withstanding heat treatment at 100 ℃ or higher, and therefore can be suitably used for applications such as food containers, cosmetic containers, medical devices, baby products such as feeding bottles and pacifiers, and the like. Furthermore, the resin composition can be used for applications in which the resin composition is used under severe temperature conditions such as electronic materials and automobile parts.
The injection molded article of the present invention can be used for various applications. For example, since it is transparent and has heat resistance capable of withstanding boiling sterilization, it can be suitably used for applications requiring high-temperature sterilization treatment, such as food and beverage containers, cosmetic containers, medical instruments, baby products such as feeding bottles and pacifiers, and the like. Furthermore, the resin composition can be used for applications in which the resin composition is used under severe temperature conditions such as electronic materials and automobile parts.
The polyester sheet of the present invention and a molded article obtained by molding the sheet can be used for food applications, for example, in transparent containers requiring sterilization and sterilization, heat-resistant transparent beverage cups, takeaway dish trays, transparent containers requiring reheating, lids, and the like. In addition, in the building material applications, the present invention can be used for outdoor applications such as showcases, outdoor display boards, and simple garages, various industrial shelters, windshields, and partitions. In other fields, it can be used for labels, stickers, tapes, displays, transparent cases/boxes (bending machine-formed articles), automobile parts, electronic materials, illumination panels for vending machines, lamp covers, cover panels, packaging for equatorial-crossing outlet products, and the like.
Further, the polyester container of the present invention can be used as a transparent container suitable for storage of high-temperature products, heating for sterilization or cooking, high-temperature filling of contents, transportation in a high-temperature environment, and the like. The container produced by blow molding can be used, for example, for storing food and beverage bottles such as tea, fruit juice, soft drink, seasoning, sauce, honey, and jam; bottle for preserving cosmetic products such as cosmetics, skin care products, shampoo, detergent, etc.; a bottle for pharmaceuticals, etc. Containers produced by thermoforming a sheet can be used, for example, as food trays and cups for storing jelly, puddings, baby food, takeaway dishes, convenience food, and the like; beverage cups, medical trays, lids, cover plate packages, transparent boxes, carrying belts, and the like.
In conclusion, the industrial significance of the invention is great.
Claims (23)
1. A polyester resin, wherein,
the polyester resin contains a diol unit and a dicarboxylic acid unit,
50 to 95 mol% of the diol units are units derived from pentacyclopentadecane dimethanol represented by the following formula (I) and/or pentacyclopentadecane dimethanol represented by the following formula (II), 5 to 50 mol% of the diol units are units derived from ethylene glycol, 50 to 100 mol% of the dicarboxylic acid units are units derived from aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) a measured value of a glass transition temperature measured by a differential scanning calorimeter is 131 ℃ or more, and a heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less;
(2) the Intrinsic Viscosity (IV) measured at 25 ℃ using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane at a mass ratio of 6:4 is 0.2 to 1.2dl/g,
2. the polyester resin according to claim 1, wherein,
the unit derived from an aromatic dicarboxylic acid is at least one unit derived from terephthalic acid, isophthalic acid, and 2, 6-naphthalenedicarboxylic acid.
3. The polyester resin according to claim 1 or 2,
the unit derived from the aromatic dicarboxylic acid is 80 to 100 mol% of the dicarboxylic acid unit.
4. An injection-molded body, wherein,
the injection-molded article is obtained from a polyester resin containing a diol unit and a dicarboxylic acid unit,
50 to 95 mol% of glycol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the following formula (I) and/or pentacyclopentadecane dimethanol represented by the following formula (II), 5 to 50 mol% of glycol units are units derived from ethylene glycol, 50 to 100 mol% of dicarboxylic acid units are units derived from aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) a measured value of a glass transition temperature measured by a differential scanning calorimeter is 131 ℃ or more, and a heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less;
(2) the Intrinsic Viscosity (IV) measured at 25 ℃ using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane at a mass ratio of 6:4 is 0.2 to 1.2dl/g,
5. the injection-molded body according to claim 4, wherein,
the unit derived from an aromatic dicarboxylic acid in the polyester resin is at least one unit derived from terephthalic acid, isophthalic acid, and 2, 6-naphthalenedicarboxylic acid.
6. The injection-molded body according to claim 4 or 5,
the amount of units derived from an aromatic dicarboxylic acid in the dicarboxylic acid units of the polyester resin is 80 to 100 mol%.
7. The injection-molded body according to claim 4 or 5,
50 to 90 mol% of the diol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the formula (I) and/or pentacyclopentadecane dimethanol represented by the formula (II), 10 to 50 mol% of the diol units are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from terephthalic acid.
8. The injection-molded body according to claim 4 or 5,
5 to 50 mol% of the diol units of the polyester resin are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from 2, 6-naphthalenedicarboxylic acid.
9. The injection-molded body according to claim 4 or 5,
the polyester resin satisfies the following condition (3):
(3) a test piece having a shape described in a test method for tensile properties according to JIS K7162 obtained by injection molding of the polyester resin is immersed in boiling water at 100 ℃ for 30 minutes, and then the dimensional change rate after immersion in boiling water is 0.50% or less in the thickness direction and the width direction and 0.60% or less in the entire length direction, as calculated by the following formula (1), wherein the test piece is a 1A type multi-purpose test piece,
formula (1):
ΔM＝|M-M0|/M0×100
in the formula, Δ M is a dimensional change rate in units; m0The dimension before boiling water immersion is in mm; m is the size after immersion in boiling water, in mm.
10. A polyester sheet, wherein,
the polyester sheet is obtained by molding a polyester resin containing a diol unit and a dicarboxylic acid unit,
50 to 95 mol% of glycol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the following formula (I) and/or pentacyclopentadecane dimethanol represented by the following formula (II), 5 to 50 mol% of glycol units are units derived from ethylene glycol, 50 to 100 mol% of dicarboxylic acid units are units derived from aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) a measured value of a glass transition temperature of the polyester resin measured by a differential scanning calorimeter is 131 ℃ or more, and a heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less;
(2) the polyester resin has a measured value of Intrinsic Viscosity (IV) of 0.2 to 1.2dl/g measured at 25 ℃ using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane in a mass ratio of 6:4,
11. the polyester sheet according to claim 10, wherein,
the unit derived from an aromatic dicarboxylic acid in the polyester resin is derived from at least one or more units selected from terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.
12. The polyester sheet according to claim 10 or 11,
80 to 100 mol% of the dicarboxylic acid units in the polyester resin are units derived from an aromatic dicarboxylic acid.
13. The polyester sheet according to claim 10 or 11,
50 to 90 mol% of the diol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the formula (I) and/or pentacyclopentadecane dimethanol represented by the formula (II), 10 to 50 mol% of the diol units are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from terephthalic acid.
14. The polyester sheet according to claim 10 or 11,
5 to 50 mol% of the diol units of the polyester resin are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from 2, 6-naphthalenedicarboxylic acid.
15. The polyester sheet according to claim 10 or 11,
the polyester resin satisfies the following conditions (4) and (5):
(4) the total light transmittance of the sheet with the thickness of 0.20mm and the sheet with the thickness of 0.35mm is measured by more than 86%;
(5) a square test piece of 120mm in the longitudinal direction x 120mm in the transverse direction was cut out from a sheet of 0.20mm in thickness with the extrusion direction as the longitudinal direction and the width direction as the transverse direction, a mark line of 100mm in length was marked on the center line of the test piece in the longitudinal direction and the transverse direction, respectively, after the test piece was heated in a drier for 30 minutes, the maximum temperature of 110 ℃ or higher at which the change rate of the length of the mark line after heating does not exceed 0.5% in the longitudinal direction and the transverse direction, calculated from the following formula (2),
formula (2):
ΔL＝|L-L0|/L0×100
where Δ L is the rate of change of the length of the reticle in%; l is0The length of the marked line before heating is in mm; l is the length of the heated reticle in mm.
16. A polyester container, wherein,
the polyester container is obtained by molding a polyester resin containing a diol unit and a dicarboxylic acid unit,
50 to 95 mol% of glycol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the following formula (I) and/or pentacyclopentadecane dimethanol represented by the following formula (II), 5 to 50 mol% of glycol units are units derived from ethylene glycol, 50 to 100 mol% of dicarboxylic acid units are units derived from aromatic dicarboxylic acid, and the polyester resin satisfies the following conditions (1) and (2):
(1) a measured value of a glass transition temperature of the polyester resin measured by a differential scanning calorimeter is 131 ℃ or more, and a heat quantity of a crystallization exothermic peak at the time of temperature reduction is 5J/g or less;
(2) the polyester resin has a measured value of Intrinsic Viscosity (IV) of 0.2 to 1.2dl/g measured at 25 ℃ using a mixed solvent of phenol and 1,1,2, 2-tetrachloroethane in a mass ratio of 6:4,
17. the polyester-made container according to claim 16,
the unit derived from an aromatic dicarboxylic acid in the polyester resin is derived from at least one or more units selected from terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.
18. The polyester-made container according to claim 16 or 17,
80 to 100 mol% of the dicarboxylic acid units in the polyester resin are units derived from an aromatic dicarboxylic acid.
19. The polyester-made container according to claim 16 or 17,
50 to 90 mol% of the diol units of the polyester resin are units derived from pentacyclopentadecane dimethanol represented by the formula (I) and/or pentacyclopentadecane dimethanol represented by the formula (II), 10 to 50 mol% of the diol units are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from terephthalic acid.
20. The polyester-made container according to claim 16 or 17,
5 to 50 mol% of the diol units of the polyester resin are units derived from ethylene glycol, and 70 to 100 mol% of the dicarboxylic acid units are units derived from 2, 6-naphthalenedicarboxylic acid.
21. The polyester-made container according to claim 16 or 17,
the following condition (6) is satisfied:
(6) the highest temperature at which the height retention rate of the heated container is 98% or more, which is calculated from the following formula (3), is 100 ℃ or higher after heating the polyester container in the dryer for 30 minutes, wherein the highest temperature is a heat-resistant temperature,
the shape of the container is as follows:
a polyester sheet having a thickness of 0.35mm was thermoformed by a vacuum pressure molding machine at a draw ratio of 0.36 to obtain a container having an opening of 70mm X70 mm, a height of 25mm and a capacity of about 100mL,
formula (3):
ΔH＝H/H0×100
wherein Δ H is the height retention of the container in units; h0Is the height of the container before heating, and the unit is mm; h is the height of the heated container in mm.
22. The polyester-made container according to claim 16 or 17,
the molding is a hollow molding of the polyester resin.
23. The polyester-made container according to claim 16 or 17,
the molding is thermoforming of a sheet composed of the polyester resin.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-213325 | 2013-10-11 | ||
| JP2013-213323 | 2013-10-11 | ||
| JP2013-213322 | 2013-10-11 | ||
| JP2013-213324 | 2013-10-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1224689A1 HK1224689A1 (en) | 2017-08-25 |
| HK1224689B true HK1224689B (en) | 2018-08-03 |
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