JP2014051642A - Heat molded product containing polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat molded product containing a polyester resin composition, having high degree of crystallinity and excellent in transparency, heat resistance, bleeding resistance and strength, and to provide a manufacturing method thereof.SOLUTION: A heat molded product contains a polyester resin composition containing a polyester resin and a polyester plasticizer represented by the formula (I). RO-CO-R-CO-[(OR)O-CO-R-CO-]OR(I), where Ris an alkyl group having 1 to 4 carbon atoms, Ris an alkylene group having 2 to 4 carbon atoms, Ris an alkylene group having 2 to 6 carbon atoms, m is a number of 1 to 6 and n is a number of 1 to 12; all Rmay be same or different and all Rmay be same or different.

Description

  The present invention relates to a thermoformed article comprising a polyester resin composition. More specifically, the present invention relates to a thermoformed article comprising a polyester resin composition containing an ester compound and a polyester resin that are suitably used as a plasticizer, and a method for producing the same.

  When biodegradable resin is placed in soil, seawater, or the body of an animal, for example, it begins to degrade in a few weeks due to the action of enzymes produced by microorganisms that inhabit the natural world. Disappears. Therefore, in recent years, its use has attracted attention due to the growing environmental awareness.

  For example, in Patent Document 1, a molded product obtained by vacuum molding, pressure molding, or vacuum / pressure molding of a resin composition in which a specific (poly) glycerin ester plasticizer is blended with an aliphatic polyester is moderately soft. When the hole is punched out, it has a good cut edge and does not crack from it, and the plasticizer used does not elute in water, does not bleed even at high temperatures, and has high heat resistance. It has been reported.

  In Patent Document 2, an organic crystal nucleating agent containing an aliphatic carboxylic acid amide having an amide bond in a lactic acid polymer, a phthalic acid derivative, an isophthalic acid derivative, an adipic acid derivative, a maleic acid derivative, a citric acid derivative, an itaconic acid derivative , Lactic acid derivative, ricinoleic acid derivative, phosphoric acid ester, hydroxy polyvalent carboxylic acid ester, polyhydric alcohol ester and the like, a sheet made of a lactic acid-based polymer composition, It is disclosed that a thermoformed product excellent in heat resistance and transparency can be obtained with excellent production efficiency by performing secondary molding after 20% to 50%.

  Moreover, in patent document 3, the polyester system which has the repeating unit of a dihydric alcohol, the terminal was sealed with monobasic acid and / or monohydric alcohol, and the sum total of an acid value and a hydroxyl value is 40 or less. It is disclosed that when a plasticizer is used, a resin composition having excellent water resistance and flexibility can be obtained while maintaining the transparency of the lactic acid-based polymer because of excellent compatibility with the polymer.

  Patent Document 4 discloses an example in which an oligoester plasticizer is further blended in a resin composition in which cellulose having a crystallinity of less than 50% is blended with a composition containing a polylactic acid resin and a flame retardant. ing. It has been shown that a molded product obtained by injection molding such a resin composition is excellent in strength, flexibility, impact resistance, and flame retardancy.

JP 2002-60605 A WO 2006-121056 Japanese Patent Laid-Open No. 7-118513 JP 2011-153296 A

  Based on the conventional technology, a resin composition is prepared by adding a specific plasticizer to improve compatibility between components, and using this, a thermoformed product excellent in heat resistance, transparency, bleed resistance, etc. is prepared. It is possible to obtain efficiently. However, since the crystallinity is not yet sufficient, the strength is inferior, and the applicable applications are limited.

  An object of the present invention is to provide a thermoformed product comprising a polyester resin composition having a high crystallinity and excellent in transparency, heat resistance, bleed resistance, and strength, and a method for producing the same. is there.

The present invention relates to the following [1] to [2].
[1] A thermoformed article comprising a polyester resin and a polyester resin composition containing a polyester plasticizer represented by the following formula (I).
R ¹ O—CO—R ² —CO — [(OR ³ ) _m O—CO—R ² —CO—] _n OR ¹ (I)
Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6 And n represents a number from 1 to 12, provided that all R ² may be the same or different, and all R ³ may be the same or different.
[2] The method for producing a thermoformed product according to [1], wherein a thermoformed product crystallized to a relative crystallinity of 80% or more is obtained by the following steps (1) to (2). A method for manufacturing a thermoformed product.
Step (1) A polyester resin composition containing a polyester resin and a polyester plasticizer represented by the formula (I) is extruded from a die by an extrusion molding method to prepare a sheet, and then the glass transition temperature (Tg) of the polyester resin composition. ) Step (2) for obtaining a sheet having a relative crystallinity of less than 80% by cooling to less than the glass transition temperature (Tg) of the polyester resin composition, melting point (Tm) A process for obtaining a thermoformed product that is thermoformed in a temperature range of less than 80% and crystallized to a relative crystallinity of 80% or more.

  The thermoformed article of the present invention has an excellent effect of having a high degree of crystallinity and excellent transparency, heat resistance, bleed resistance, and strength.

FIG. 1 shows a mold used when the thermoformed product of the example was prepared.

  The thermoformed product of the present invention comprises a polyester resin composition containing a polyester resin and a polyester plasticizer, and is characterized in that the plasticizer is a specific compound.

  In general, many polyester plasticizers are polymer compounds having a high acid value or hydroxyl value. When such a compound is blended with a polyester resin, the acid group (for example, carboxyl group) or hydroxyl group of the compound causes the polyester resin to be decomposed or bleed to decompose itself. If the material is heated and molded, the transparency of the molded body tends to be lowered. Therefore, in the present invention, the compound represented by the formula (I) is used. Since the compound has few acid groups and hydroxyl groups and the end of the compound is capped, decomposition of the polyester resin is suppressed due to low reactivity with the polyester resin. In addition, since the compound has a chain structure in which each segment in the molecule has an appropriate polarity, a moderate interaction with the polyester resin is obtained and compatibility is improved. The resin composition has improved plasticity and moldability (wide temperature range that can be molded in thermoforming), and thermoformed products obtained by secondary processing (thermoforming) have good bleed resistance of plasticizers. It is excellent in transparency, heat resistance and strength. In addition, since the compatibility with the polyester resin and the plasticity are high, the orientation of the polyester molecules in the thermoforming process is promoted uniformly, and the crystallinity is improved.

[Polyester resin composition]
[Polyester resin]
The polyester resin is not particularly limited as long as it is known in the art, but preferably has biodegradability, and a biodegradable polyester resin is preferable. Specifically, polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polybutylene succinate / adipate, polyethylene succinate, polyethylene terephthalate, polylactic acid resin, polymalic acid, polyglycolic acid, polydioxanone, poly (2-oxetanone) Aliphatic polyester resins such as polybutylene succinate / terephthalate, polybutylene adipate / terephthalate, polytetramethylene adipate / terephthalate, etc .; starch, cellulose, chitin, chitosan, gluten, gelatin, zein And mixtures of natural polymers such as soybean protein, collagen, keratin and the like with the above aliphatic polyester resins or aliphatic aromatic copolyester resins. Among these, polybutylene succinate and polylactic acid resin are preferable and polylactic acid resin is more preferable because of excellent processability, economy, availability, and physical properties. In the present specification, “biodegradable” means a property that can be decomposed into a low molecular weight compound by a microorganism in nature. Specifically, JIS K6953 (ISO 14855) “controlled aerobic composting conditions”. This means biodegradability based on the “Aerobic and Ultimate Biodegradation and Disintegration Test”.

  Examples of the polylactic acid resin include commercially available polylactic acid resins (for example, Mitsui Chemical Co., Ltd .: trade names Lacia H-100, H-280, H-400, H-440, etc., Nature Works, Inc .: trade name Nature). Works PLAs / NW3001D, NW4032D, manufactured by Toyota Motor Corporation: trade name Ecoplastic U'z S-09, S-12, S-17, etc.), and polylactic acid resin synthesized from lactic acid or lactide. From the viewpoint of improving strength and heat resistance, a polylactic acid resin having an optical purity of 90% or more is preferable. For example, a polylactic acid resin (NW4032D or the like) manufactured by Nature Works with a relatively high molecular weight and high optical purity is preferable.

  Further, in the present invention, the polylactic acid resin is obtained by using a lactic acid component mainly composed of different isomers from the viewpoint of coexistence of strength and flexibility of the polyester resin composition, and improvement of heat resistance and transparency. Alternatively, stereocomplex polylactic acid composed of two types of polylactic acid may be used.

  One polylactic acid constituting the stereocomplex polylactic acid (hereinafter referred to as polylactic acid (A)) contains 90 to 100 mol% of L isomer and 0 to 10 mol% of other components including D isomer. The other polylactic acid (hereinafter referred to as polylactic acid (B)) contains 90 to 100 mol% of D isomer and 0 to 10 mol% of other components including L isomer. In addition, as other components other than L-form and D-form, dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid, lactone, etc. having a functional group capable of forming two or more ester bonds are exemplified, and unreacted Polyester, polyether, polycarbonate or the like having two or more of the functional groups in the molecule may be used.

  In the stereocomplex polylactic acid, the weight ratio of polylactic acid (A) to polylactic acid (B) [polylactic acid (A) / polylactic acid (B)] is preferably 10/90 to 90/10, and 20/80 to 80 / 20 is more preferable, and 40/60 to 60/40 is more preferable.

  Moreover, the polylactic acid resin in this invention may be contained as a polymer alloy by the blend of non-biodegradable resin other than polylactic acid resin, non-biodegradable resins, such as a polypropylene, and polylactic acid resin.

  In the present invention, a polylactic acid resin other than a polylactic acid resin (modified polylactic acid resin) composed of a lactic acid component, a dicarboxylic acid component, and a diol component is preferable from the viewpoint of resin physical properties and economy.

  The content of the polylactic acid resin in the polyester resin is preferably 80% by weight or more, more preferably 90% by weight or more, and further preferably substantially 100% by weight.

  The content of the polyester resin is not particularly limited, but is preferably 50% by weight or more, more preferably 60% by weight or more, and further preferably 70% by weight or more in the polyester resin composition.

[Plasticizer]
As the polyester plasticizer in the present invention, the following formula (I):
R ¹ O—CO—R ² —CO — [(OR ³ ) _m O—CO—R ² —CO—] _n OR ¹ (I)
Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6 And n represents a number from 1 to 12, provided that all R ² may be the same or different, and all R ³ may be the same or different.
The compound represented by these is mentioned. In the present specification, [(OR ³ ) _m O—CO—R ² —CO—] in formula (I) is also referred to as a repeating unit in formula (I).

R ¹ in formula (I) represents an alkyl group having 1 to 4 carbon atoms, and two of them exist in one molecule and exist at both ends of the molecule. R ¹ may be linear or branched as long as it has 1 to 4 carbon atoms. The number of carbon atoms of the alkyl group is preferably 1 to 4 and more preferably 1 to 2 from the viewpoint of improving the compatibility with the polyester resin and exhibiting a plasticizing effect. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and an iso-butyl group. Among them, the compatibility with a polyester resin is improved. From the viewpoint of developing a plasticizing effect, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

R ² in formula (I) represents an alkylene group having 2 to 4 carbon atoms, and a linear alkylene group is a preferred example. Specific examples include an ethylene group, a 1,3-propylene group, and a 1,4-butylene group. Among these, from the viewpoint of improving compatibility with a polyester resin and exhibiting a plasticizing effect, an ethylene group, 1 , 3-propylene group is preferable, ethylene group is more preferable, and from the viewpoint of developing a plasticizing effect and economical viewpoint, ethylene group and 1,4-butylene group are preferable, and ethylene group is more preferable. However, all R ² may be the same or different.

R ³ in formula (I) represents an alkylene group having 2 to 6 carbon atoms, and is present in the repeating unit as an oxyalkylene group. R ³ may be linear or branched as long as it has 2 to 6 carbon atoms. As carbon number of an alkylene group, 2-6 are preferable and 2-3 are more preferable from a viewpoint of improving compatibility with a polyester resin and expressing the plasticizing effect. Specifically, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,3-butylene group, 1,4-butylene group, 2-methyl-1,3 -Propylene group, 1,2-pentylene group, 1,4-pentylene group, 1,5-pentylene group, 2,2-dimethyl-1,3-propylene group, 1,2-hexylene group, 1,5-hexylene Group, 1,6-hexylene group, 2,5-hexylene group, 3-methyl-1,5-pentylene group, among others, from the viewpoint of improving the compatibility with the polyester resin and developing the plasticizing effect. , Ethylene group, 1,2-propylene group, 1,3-propylene group and 1,4-butylene group are preferable. However, all R ³ may be the same or different.

  m shows the average repeating number of an oxyalkylene group, and is a number of 1-6. When m increases, the ether group value of the compound represented by formula (I) increases, and it is oxidized and easily decomposed. From the viewpoint of improving the compatibility with the polyester resin and the viewpoint of improving the transparency of the obtained molded product, the number is 1 to 6, preferably 1 to 4, more preferably 1 to 3. A number of ~ 2 is more preferred.

  n represents the average number of repeating units (average polymerization degree), and from the viewpoint of volatility, it is preferably 1 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and still more preferably 1. 8 or more, more preferably 2 or more. Further, from the viewpoint of plasticizing efficiency, it is preferably 12 or less, more preferably 10 or less, further preferably 8 or less, further preferably 7 or less, and further preferably 6 or less. In addition, n is preferably 1 to 12, more preferably 1 to 8, more preferably from the viewpoint of improving the compatibility between the volatile resistance and the polyester resin and improving the plasticizing effect and plasticizing efficiency. Is 1.2-8, More preferably, it is 1.5-7, More preferably, it is 1.8-7. In the present specification, the average degree of polymerization can be calculated according to the method described in Examples described later.

Specific examples of the compound represented by formula (I), ^{R 1} is methyl, ^{R 2} is an ethylene group, ^{R 3} is an ethylene group, an ester of m is 2, n is 1.6, ^{R 1} there but a methyl group, ^{R 2} is an ethylene group, a ^{R 3} is an ethylene group, an ester of m is 2, n is 2.1, ^{R 1} is methyl, ^{R 2} is an ethylene group, ^{R 3} is an ethylene group An ester wherein m is 2, n is 4.3, R ¹ is a methyl group, R ² is an ethylene group, R ³ is a 1,3-propylene group, m is 1, and n is 4.4 R ¹ is a methyl group, R ² is an ethylene group, R ³ is a 1,2-propylene group, m is 1, n is an ester of 3.6, R ¹ is an ethyl group, R ² is 1, 4 - butylene group, a ^{R 3} is 1,3-propylene group, m is 1, n is 2 ester, ^{R 1} is butyl, ^{R 2} is an ethylene radical, R There an ethylene group, an ester of m is 2, n is 1.9, ^{R 1} is butyl, ^{R 2} is 1,3-propylene group, a ^{R 3} is an ethylene group, m is is 3, n 1.5 ester, R ¹ is methyl group, R ² is 1,4-butylene group, R ³ is 1,3-propylene group, m is 1, n is 4.4 ester, R ¹ is Methyl group, R ² is ethylene group, R ³ is 1,4-butylene group, m is 1, n is 4.4 ester, R ¹ is methyl group, R ² is ethylene group, R ³ is 1 , 6-hexylene group, m is 1, n is 3 ester, R ¹ is methyl group, R ² is ethylene group, R ³ is 1,2-propylene group, m is 1, n is esters of 6.5, ^{R 1} is methyl, ^{R 2} is an ethylene group, a ^{R 3} is 2-methyl-1,3-propylene group, m is 1, n is 3 Ester, and the like. These may be contained singly or two or more. Among these, R ¹ is all methyl group, R ² is ethylene group or 1,4-butylene group, R ³ is ethylene group, 1,3-propylene group, or 1,2-propylene group, m Is a compound in which n is a number of 1 to 3 and n is a number of 1 to 8, R ¹ is all methyl group, R ² is ethylene group or 1,4-butylene group, R ³ is ethylene group, 1,3- More preferred is a compound which is a propylene group or a 1,2-propylene group, wherein m is a number of 1 to 2 and n is a number of 1.8 to 7.

  The compound represented by the formula (I) is not particularly limited as long as it has the above structure, but those obtained using the following raw materials (1) to (3) are preferable.

(1) Monohydric alcohol having an alkyl group having 1 to 4 carbon atoms The monohydric alcohol having an alkyl group having 1 to 4 carbon atoms is an alcohol containing R ¹ , specifically, methanol, Examples include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 1,1-dimethyl-1-ethanol. Of these, methanol, ethanol, 1-propanol, and 1-butanol are preferred from the viewpoint of improving the compatibility with the polyester resin and exhibiting a plasticizing effect, as well as increasing the efficiency of the transesterification reaction. More preferred is methanol and even more preferred.

(2) Dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms The dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms is a dicarboxylic acid containing R ² , specifically, succinic acid, Examples include glutaric acid, adipic acid, and derivatives thereof (for example, succinic anhydride, glutaric anhydride, dimethyl succinate, dibutyl succinate, dimethyl glutarate, dimethyl adipate). Among them, succinic acid, glutaric acid, and derivatives thereof (for example, succinic anhydride, glutaric anhydride, dimethyl succinate, succinic acid are used from the viewpoint of improving the compatibility with the polyester resin and exhibiting a plasticizing effect. Dibutyl, dimethyl glutarate), succinic acid and derivatives thereof (for example, succinic anhydride, dimethyl succinate) are more preferable, and succinic acid, adipic acid and Their derivatives (eg, succinic anhydride, dimethyl succinate, dibutyl succinate, dimethyl adipate) are preferred, and succinic acid and its derivatives (eg, succinic anhydride, dimethyl succinate, dibutyl succinate) are more preferred. .

(3) Dihydric alcohol having an alkylene group having 2 to 6 carbon atoms The dihydric alcohol having an alkylene group having 2 to 6 carbon atoms is a dihydric alcohol containing R ³ , specifically, Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5 -Pentanediol, 2,2-dimethyl-1,3-propanediol, 2,5-hexanediol, 1,6-hexane Ol, 2,5-hexanediol, and 3-methyl-1,5-pentanediol. Of these, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, tetraethylene glycol, and 1,4-butane from the viewpoint of improving the compatibility with the polyester resin and exhibiting a plasticizing effect. Diols are preferred, diethylene glycol, triethylene glycol, 1,2-propanediol and 1,3-propanediol are more preferred, and diethylene glycol, 1,2-propanediol and 1,3-propanediol are even more preferred.

Therefore, as said (1)-(3),
(1) The monohydric alcohol is at least one selected from the group consisting of methanol, ethanol, 1-propanol, and 1-butanol, and (2) the group consisting of dicarboxylic acid consisting of succinic acid, glutaric acid, and derivatives thereof. (3) The group in which the dihydric alcohol is composed of diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, tetraethylene glycol, and 1,4-butanediol. It is preferably at least one selected from
(1) The monohydric alcohol is at least one selected from the group consisting of methanol and ethanol, and (2) the dicarboxylic acid is at least one selected from the group consisting of succinic acid, glutaric acid, and derivatives thereof, (3) More preferably, the dihydric alcohol is at least one selected from the group consisting of diethylene glycol, triethylene glycol, 1,2-propanediol, and 1,3-propanediol,
(1) the monohydric alcohol is methanol, (2) the dicarboxylic acid is at least one selected from the group consisting of succinic acid and derivatives thereof, and (3) the dihydric alcohol is diethylene glycol, 1,2-propanediol, And at least one selected from the group consisting of 1,3-propanediol.

Although there is no limitation in particular as a method of obtaining the compound represented by Formula (I) using said (1)-(3), For example, the method of the following aspects 1 and 2 is mentioned.
Aspect 1: (2) Step of synthesizing dicarboxylic acid ester by performing esterification reaction of (2) dicarboxylic acid with (1) monohydric alcohol (Step 1), and (3) esterifying the obtained dicarboxylic acid ester and (3) dihydric alcohol A method comprising a step of reacting (step 2): A method comprising a step of collectively reacting (1) a monohydric alcohol, (2) a dicarboxylic acid, and (3) a dihydric alcohol

  Among these, from the viewpoint of adjusting the average degree of polymerization, the method of aspect 1 in which the alcoholic decomposition of the polyester resin hardly occurs is preferable.

  The method of aspect 1 is demonstrated below.

  Aspect 1 is a method in which a dicarboxylic acid ester, which is a reaction product of a dicarboxylic acid and a monohydric alcohol, is transesterified with a dihydric alcohol. In this specification, the method of aspect 1 is also referred to as a transesterification reaction.

Specifically, first, in Step 1 of Embodiment 1, (2) dicarboxylic acid and (1) monohydric alcohol are esterified to synthesize a dicarboxylic acid ester. Examples of the esterification method include (2) a dehydration esterification method in which (1) a monohydric alcohol is added to a mixture of a dicarboxylic acid and a catalyst and stirred, and water and monohydric alcohol generated are removed from the system. It is done. In particular,
1) A method in which a monohydric alcohol vapor is blown into a dicarboxylic acid to carry out an esterification reaction, and the generated water and unreacted monohydric alcohol are both removed.
2) A method of performing an esterification reaction using excess monohydric alcohol and azeotropically removing generated water and monohydric alcohol,
3) A method of removing the water and alcohol by performing an esterification reaction and adding water or a solvent (for example, toluene) that azeotropes with water, monohydric alcohol or the like.

  Examples of the catalyst include inorganic acids such as sulfuric acid, phosphoric acid, methanesulfonic acid, and paratoluenesulfonic acid, and organic acids. Among these, paratoluenesulfonic acid is preferable. 0.05-10 mol is preferable with respect to 100 mol of dicarboxylic acids, and, as for the usage-amount of a catalyst, 0.10-3 mol is more preferable.

  The molar ratio of the monohydric alcohol to the dicarboxylic acid (monohydric alcohol / dicarboxylic acid) is preferably 2/1 to 20/1, more preferably 3/1 to 12/1, from the viewpoint of improving the reaction rate and economy. . In this case, the “reaction rate” means the rate at which the raw materials subjected to the reaction have reacted with respect to the dicarboxylic acid.

  The reaction temperature depends on the type of monohydric alcohol used, but is preferably 50 to 200 ° C, more preferably 80 to 140 ° C, from the viewpoint of improving the reaction rate and suppressing side reactions. The reaction time is preferably 0.5 to 15 hours, more preferably 1.0 to 5 hours. The reaction may be performed under reduced pressure, and the reaction pressure is preferably 2.7 to 101.3 kPa, more preferably 6.7 to 101.3 kPa.

  The resulting dicarboxylic acid ester has an alkyl esterification rate with respect to two molecular ends of preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more. In the present specification, the alkyl esterification rate can be calculated according to the method described in the examples described later.

  The dicarboxylic acid ester thus obtained is subjected to step 2. In the present invention, as the dicarboxylic acid ester, the reaction product obtained as described above may be used, but a commercially available product may be used, and the commercially available product may be subjected to Step 2. Examples of suitable commercially available products include dimethyl succinate (manufactured by Wako Pure Chemical Industries, Ltd.) and dimethyl adipate (manufactured by Wako Pure Chemical Industries, Ltd.).

  In step 2 of embodiment 1, a transesterification reaction of dicarboxylic acid ester with (3) dihydric alcohol is performed.

  Specifically, for example, (3) a dihydric alcohol is continuously added to a mixture of a dicarboxylic acid ester and a catalyst, and the resulting monohydric alcohol is removed from the system, or (3) a divalent Examples include a transesterification reaction in which a dicarboxylic acid ester is continuously added to a mixture of an alcohol and a catalyst, and the resulting monohydric alcohol is removed from the system. In any case, the reaction can proceed by shifting the equilibrium by distilling off the produced monohydric alcohol. Further, the catalyst may be added stepwise. For example, the dihydric alcohol is added to the dicarboxylic acid ester, or the dihydric alcohol is added when the dicarboxylic acid ester is added to the dihydric alcohol. It can be further added at the stage of removal from the system. In addition, the dicarboxylic acid ester used for transesterification can use the reaction mixture obtained by the above-mentioned esterification reaction, or a commercial item as it is, and can also use it after distilling and isolating.

  Examples of the catalyst include inorganic acids such as sulfuric acid, phosphoric acid, methanesulfonic acid, and paratoluenesulfonic acid, and organic acids, organic metal compounds such as tetraisopropoxy titanium and tetrabutoxy titanium, and alkalis such as sodium methoxide. An alkoxide etc. are mentioned. Of these, p-toluenesulfonic acid, tetraisopropoxy titanium, tetrabutoxy titanium, and sodium methoxide are preferable. For example, in the case of paratoluenesulfonic acid and sodium methoxide, the catalyst is used in an amount of preferably 0.05 to 10 mol, more preferably 0.10 to 5 mol, and tetraisopropoxy titanium for 100 mol of dicarboxylic acid ester. In tetrabutoxy titanium, 0.0001 to 0.1 mol is preferable, and 0.0005 to 0.05 mol is more preferable. In addition, the usage-amount of a catalyst here means the total usage-amount of the catalyst used at the process 2. FIG.

  The molar ratio of the dicarboxylic acid ester to the dihydric alcohol (dicarboxylic acid ester / dihydric alcohol) is preferably 1.1 / 1 to 10/1 from the viewpoint of controlling the molecular weight of the ester compound in the present invention. 1-4 / 1 are more preferable, and 1.3 / 1-3 / 1 are more preferable.

  The reaction temperature is preferably 50 to 250 ° C., more preferably 60 to 150 ° C., from the viewpoint of improving the reaction rate and suppressing side reactions. In this case, the “reaction rate” means the rate at which the raw materials subjected to the reaction have reacted with respect to the dihydric alcohol. The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 10 hours. The reaction may be performed under reduced pressure, and the reaction pressure is preferably 0.7 to 101.3 kPa, more preferably 2.0 to 101.3 kPa.

  The method of aspect 2 is demonstrated below.

  The method of aspect 2 is a method in which (1) a monohydric alcohol, (2) a dicarboxylic acid, and (3) a dihydric alcohol are collectively reacted in the presence of a catalyst, if necessary. This method is also called batch addition reaction.

  The raw materials can be supplied in a batch or divided, but the monohydric alcohol may be introduced into the reactor in a divided or continuous manner.

  Examples of the catalyst include inorganic acids such as sulfuric acid, phosphoric acid, methanesulfonic acid, and paratoluenesulfonic acid, and organic acids. Among these, paratoluenesulfonic acid is preferable. 0.05-10 mol is preferable with respect to 100 mol of dicarboxylic acids, and, as for the usage-amount of a catalyst, 0.10-5 mol is more preferable.

  The molar ratio of dicarboxylic acid, monohydric alcohol and dihydric alcohol (dicarboxylic acid / monohydric alcohol / dihydric alcohol) is 1.1 / 1.1 / 1 from the viewpoint of controlling the molecular weight of the ester compound in the present invention. 10/100/1 is preferable, 1.2 / 3/1 to 3/30/1 is more preferable, and 1.3 / 5/1 to 3/20/1 is more preferable.

  Further, from the viewpoint of controlling the molecular weight of the ester compound in the present invention, the molar ratio of dicarboxylic acid to dihydric alcohol (dicarboxylic acid / dihydric alcohol) is preferably 1.2 / 1 to 3/1.

  The reaction temperature depends on the type of alcohol used, but is preferably 50 to 200 ° C., and the reaction time is preferably 0.5 to 15 hours. The reaction may be performed under reduced pressure, and preferably under a pressure of 6.7 to 101.3 kPa. Moreover, after making it react for 3 to 5 hours under the temperature of 70-140 degreeC and a normal pressure (101.3kPa), after removing the water and monohydric alcohol to produce | generate, temperature 70-120 degreeC, pressure 0.7-26.7kPa May be aged for 0.5 to 3 hours.

  In the present invention, as embodiment 3, the dicarboxylic acid ester obtained after synthesizing the dicarboxylic acid ester by performing esterification reaction (dehydration esterification reaction) of (2) dicarboxylic acid and (3) dihydric alcohol. Furthermore, (1) monohydric alcohol may be esterified (dehydrated esterification).

  In addition, you may distill away the unreacted raw material and a by-product from the obtained reaction material according to a well-known method.

  Thus, a compound represented by the formula (I) is obtained.

  The compound represented by the formula (I) preferably has an acid value of 1.00 mgKOH / g or less, more preferably 0.90 mgKOH / g or less, from the viewpoint of bleed resistance and durability of the thermoformed product. Is 0.05 mgKOH / g or more, more preferably 0.1 mgKOH / g or more. From the viewpoint of bleed resistance, the hydroxyl value is preferably 10.0 mgKOH / g or less, more preferably 8.0 mgKOH / g or less, still more preferably 5.0 mgKOH / g or less, preferably 0.1 mgKOH / g. As mentioned above, More preferably, it is 0.2 mgKOH / g or more. In addition, in this specification, the acid value and hydroxyl value of a plasticizer can be measured according to the method as described in the below-mentioned Example.

  The saponification value of the compound represented by the formula (I) is preferably 500 mgKOH / g or more from the viewpoint of improving the compatibility with the polyester resin and suppressing the generation of volatile organic compounds from the polyester resin composition. 600 mgKOH / g or more is more preferable, 800 mgKOH / g or less is preferable, and 750 mgKOH / g or less is more preferable. Moreover, 500-800 mgKOH / g is preferable and 600-750 mgKOH / g is more preferable. In addition, in this specification, the saponification value of a plasticizer can be measured according to the method as described in the below-mentioned Example.

  The number average molecular weight of the compound represented by the formula (I) is preferably 500 or more, more preferably 600 or more, and still more preferably, from the viewpoint of improving volatility and plasticizing efficiency and improving thermoformability. It is 700 or more, preferably 1500 or less, more preferably 1400 or less, further preferably 1300 or less, and further preferably 1200 or less. Moreover, Preferably it is 500-1500, More preferably, it is 500-1400, More preferably, it is 500-1300, More preferably, it is 500-1200, More preferably, it is 600-1200, More preferably, it is 700-1200. When the number average molecular weight is 500 or more, the volatile resistance of the polyester resin composition becomes good, and the volatilization of the plasticizer from the resin composition is suppressed. Therefore, the bending of the molded body of the resin composition over time Reduction in physical properties such as elastic modulus, heat resistance and bleed resistance is reduced. When the molecular weight is further improved, compatibility with the polylactic acid resin is excellent, and the softening temperature and the crystallization speed are appropriately controlled. As a result, the moldable temperature range is improved. In the present specification, the number average molecular weight of the plasticizer can be calculated according to the method described in Examples described later.

  The compound represented by the formula (I) preferably has an acid value of 1.00 mgKOH / g or less, a hydroxyl value of 10.0 mgKOH / g or less, a number average molecular weight of 500 to 1500, and an acid value of 0.00. 90 mgKOH / g or less, hydroxyl value is 8.0 mgKOH / g or less, number average molecular weight is more preferably 500 to 1400, acid value is 0.90 mgKOH / g or less, hydroxyl value is 8.0 mgKOH / g or less, number The average molecular weight is more preferably 600 to 1200.

  In addition, the compound represented by the formula (I) has an alkyl esterification rate with respect to two molecular ends (from the viewpoint of improving the compatibility with the polyester resin and developing the plasticizing effect and improving the plasticizing efficiency ( The terminal alkyl esterification ratio) is preferably 85% or more, more preferably 90% or more. In the present specification, the terminal alkyl esterification rate of the plasticizer can be calculated according to the method described in Examples described later.

  The ether group value of the compound represented by the formula (I) is preferably 1 mmol / g or more from the viewpoint of improving the compatibility with the polyester resin and suppressing the generation of volatile organic compounds from the polyester resin composition. Yes, preferably 8 mmol / g or less, more preferably 6 mmol / g or less, and even more preferably 5 mmol / g or less. Moreover, 0-8 mmol / g is preferable, 0-6 mmol / g is more preferable, 1-6 mmol / g is more preferable, 1-5 mmol / g is further more preferable. In the present specification, the ether group value of the plasticizer can be calculated according to the method described in Examples described later.

From the viewpoint of compatibility with the polyester resin, the compound represented by the formula (I) has an SP (Solubility Parameter) value of preferably 10.0 or more, more preferably 10.1 or more, and still more preferably Is 10.2 or more, preferably 12.0 or less, more preferably 11.5 or less, and still more preferably 11.2 or less. Moreover, Preferably it is 10.0-12.0, More preferably, it is 10.1-11.5, More preferably, it is 10.2-11.2. In the present specification, the SP value means the following formula when the cohesive energy is ΔE and the molecular volume is V:
SP value = (ΔE / V) ^1/2 (cal ^1/2 cm ^−3/2 )
For example, as described in the examples below, using the Fedors method described in Yuji Harasaki, “Basic Science of Coatings”, p. 48, Tsuji Shoten (1988). Can be calculated.

  In the present invention, a plasticizer other than the compound represented by the formula (I) can be used in combination as long as the effects of the present invention are not impaired. The other plasticizer is not particularly limited, and is an ester compound having two or more ester groups in the molecule, wherein at least one alcohol component constituting the ester compound has 2 to 2 carbon atoms per hydroxyl group. An ester compound that is an alcohol obtained by adding 0.5 to 5 moles of an average of 3 alkylene oxides is preferable. Specific examples include plasticizers described in JP-A-2008-174718 and JP-A-2008-115372. It is done. The content of the compound represented by the formula (I) is preferably 50% by weight or more, more preferably 80% by weight or more from the viewpoint of heat resistance and molding workability in all plasticizer components contained in the composition. 90% by weight or more is more preferable, and substantially 100% by weight is further preferable.

  In addition, the content of the compound represented by the formula (I) is excellent in the plasticizing effect, but the generation of volatile organic compounds is suppressed. 1 part by weight or more, more preferably 5 parts by weight or more, preferably 50 parts by weight or less, more preferably 30 parts by weight or less. Moreover, 1-50 weight part is preferable and 5-30 weight part is more preferable.

  The plasticizer content, that is, the total content of the other plasticizers and the compound represented by the formula (I) is to improve the heat resistance, transparency and moldability of the molded article made of the polyester resin composition. From the viewpoint, it is preferably 1 part by weight or more, more preferably 5 parts by weight or more, preferably 50 parts by weight or less, more preferably 30 parts by weight or less, with respect to 100 parts by weight of the polyester resin. Moreover, Preferably it is 1-50 weight part, More preferably, it is 5-30 weight part.

  The polyester resin composition in the present invention preferably further contains a crystal nucleating agent and a hydrolysis inhibitor in addition to the polyester resin and the compound represented by the formula (I).

[Crystal nucleating agent]
Examples of the crystal nucleating agent include inorganic crystal nucleating agents and organic crystal nucleating agents. Examples of inorganic crystal nucleating agents include natural or synthetic silicate compounds, titanium oxide, barium sulfate, tricalcium phosphate, calcium carbonate, sodium phosphate and other metal salts, kaolinite, halloysite, talc, smectite, vermiculite, mica, etc. Is mentioned. Examples of the organic crystal nucleating agent include carboxylic acid amides and metal salts of phenylphosphonic acid, and carboxylic acid amides are preferable from the viewpoint of improving transparency. Examples of the carboxylic acid amide include ethylene bis fatty acid amide, alkylene bis fatty acid amide, and alkylene bishydroxy fatty acid amide. Examples of the ethylene bis fatty acid amide include ethylene bis stearic acid amide and ethylene bis oleic acid amide, and examples of the alkylene bis fatty acid amide include propylene bis fatty acid amide and butylene bis fatty acid amide. The alkylene bishydroxy fatty acid amide is preferably an alkylene bishydroxy stearic acid amide having an alkylene group having 1 to 6 carbon atoms, more preferably ethylene bis 12-hydroxy stearic acid amide.

  The content of the crystal nucleating agent is preferably 0.1 parts by weight or more, preferably 100 parts by weight or more with respect to 100 parts by weight of the polyester resin, from the viewpoint of improving the transparency of the molded article comprising the polyester resin composition or the polyester resin composition. Is 1.0 part by weight or less, more preferably 0.5 part by weight or less. Moreover, 0.1-1.0 weight part is preferable and 0.1-0.5 weight part is more preferable.

[Hydrolysis inhibitor]
Examples of the hydrolysis inhibitor include carbodiimide compounds such as polycarbodiimide compounds and monocarbodiimide compounds. From the viewpoint of improving durability and impact resistance of the polyester resin composition, polycarbodiimide compounds are preferable, and durability of the polyester resin composition is preferred. From the viewpoint of improving the properties and moldability (fluidity), a monocarbodiimide compound is preferable. Moreover, it is preferable to use monocarbodiimide and polycarbodiimide in combination from the viewpoint of further improving the durability, impact resistance, and moldability of the molded article made of the polyester resin composition.

  Examples of the polycarbodiimide compound include poly (4,4′-diphenylmethanecarbodiimide), poly (4,4′-dicyclohexylmethanecarbodiimide), poly (1,3,5-triisopropylbenzene) polycarbodiimide, poly (1,3,3). 5-triisopropylbenzene and 1,3-diisopropylbenzene) polycarbodiimide and the like, and examples of the monocarbodiimide compound include N, N′-di-2,6-diisopropylphenylcarbodiimide.

  The carbodiimide compound may be used singly or in combination of two or more in order to satisfy the durability, impact resistance and moldability of the molded article made of the polyester resin composition. Poly (4,4′-dicyclohexylmethane carbodiimide) is obtained from carbodilite LA-1 (manufactured by Nisshinbo Chemical Co., Ltd.), poly (1,3,5-triisopropylbenzene) polycarbodiimide and poly (1,3,5-tri (Isopropylbenzene and 1,3-diisopropylbenzene) polycarbodiimide is stavaxol P and stabaxol P-100 (manufactured by Rhein Chemie), and N, N'-di-2,6-diisopropylphenylcarbodiimide is stavaxol I (Rhein Chemie). Can be purchased and used.

  The content of the hydrolysis inhibitor is preferably 0.05 parts by weight or more, more preferably 100 parts by weight or more with respect to 100 parts by weight of the polyester resin, from the viewpoint of improving the transparency and moldability of the molded body made of the polyester resin composition. It is 0.10 parts by weight or more, preferably 3 parts by weight or less, more preferably 2 parts by weight or less. Moreover, 0.05-3 weight part is preferable and 0.10-2 weight part is more preferable.

  The polyester resin composition according to the present invention includes a lubricant which is a filler (inorganic filler, organic filler), a flame retardant, an antioxidant, a hydrocarbon wax, or an anionic surfactant as components other than those described above. , UV absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, antifungal agents, antibacterial agents, foaming agents and the like can be contained within a range not impairing the effects of the present invention. Similarly, other polymer materials and other resin compositions can be added within a range that does not impair the effects of the present invention.

  The polyester resin composition in the present invention can be prepared without particular limitation as long as it contains a polyester resin and a compound represented by the formula (I). For example, the polyester resin composition is represented by the polyester resin and the formula (I). A raw material containing a compound and, if necessary, various additives can be prepared by melt-kneading using a known kneader such as a closed kneader, a single or twin screw extruder, and an open roll kneader. . The raw materials can be subjected to melt kneading after being uniformly mixed in advance using a Henschel mixer, a super mixer, or the like. In preparing the polyester resin composition, in order to promote the plasticity of the polyester resin, it may be melt-mixed in the presence of a supercritical gas.

  The melt kneading temperature is preferably 170 ° C. or higher, more preferably 175 ° C. or higher, more preferably 180 ° C. or higher, preferably 240 ° C. or lower, from the viewpoint of improving the moldability and deterioration prevention of the polyester resin composition. Preferably it is 220 degrees C or less, More preferably, it is 210 degrees C or less. Moreover, Preferably it is 170-240 degreeC, More preferably, it is 175-220 degreeC, More preferably, it is 180-210 degreeC. The melt-kneading time cannot be generally determined depending on the melt-kneading temperature and the type of the kneader, but is preferably 15 to 900 seconds.

  The glass transition temperature (Tg) of the obtained melt-kneaded product is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, because the compound represented by the formula (I) works effectively as a plasticizer. Preferably it is 60 degrees C or less, More preferably, it is 55 degrees C or less. Moreover, Preferably it is 30-60 degreeC, More preferably, it is 30-55 degreeC, More preferably, it is 35-55 degreeC.

  The cold crystallization temperature (Tc) of the melt-kneaded product is preferably 50 ° C. or more, more preferably 60 ° C. or more, preferably because the compound represented by the formula (I) works effectively as a plasticizer. It is 110 degrees C or less, More preferably, it is 100 degrees C or less, More preferably, it is 90 degrees C or less. Moreover, Preferably it is 50-110 degreeC, More preferably, it is 50-100 degreeC, More preferably, it is 60-90 degreeC.

  The melting point (Tm) of the melt-kneaded product is preferably 130 ° C. or higher, more preferably 140 ° C. or higher, further preferably 150 ° C. or higher, preferably 210 ° C. or lower, from the viewpoint of heat resistance and workability of the molded body. More preferably, it is 200 degrees C or less, More preferably, it is 180 degrees C or less. Moreover, Preferably it is 130-210 degreeC, More preferably, it is 140-200 degreeC, More preferably, it is 150-180 degreeC. In addition, in this specification, the glass transition temperature (Tg), cold crystallization temperature (Tc), and melting | fusing point (Tm) of a polyester resin composition can be measured according to the method as described in the below-mentioned Example.

  The melt-kneaded product thus obtained is excellent in secondary processability such as stretchability and thermoformability, and is thus formed into a primary processed product (also referred to as a primary molded product) made of a polyester resin composition. Examples of the primary processed product include a sheet and a film, but a sheet is preferable from the viewpoint of processability to a thermoformed product. In this specification, “sheet” means a flat plate having a thickness of 0.1 mm or more, and “film” means a flat plate having a thickness of less than 0.1 mm.

  The sheet-like primary processed product can be prepared by extruding or press-molding the polyester resin composition.

  In extrusion molding, a sheet-like molded product can be obtained by melting the polyester resin composition filled in a heated extruder and then extruding it from a T die. The molded product is immediately brought into contact with a cooling roll and cooled to less than the Tg of the polyester resin composition to be in an amorphous state or a semi-crystalline state, and then pulled away from the cooling roll, and they are wound on a winding roll. The primary processed product in the present invention can be obtained. When filling the extruder, the raw materials constituting the polyester resin composition in the present invention, for example, the polyester resin and the compound represented by the formula (I), and further containing various additives as necessary are filled. After melt kneading, extrusion molding may be performed. In this specification, the amorphous state and the semi-crystalline state are an amorphous state and a relative crystallinity of 60% when the relative crystallinity obtained by the method of Test Example 1 described later is less than 60%. As mentioned above, the case of less than 80% is defined as a semi-crystalline state. Therefore, a molded body in an amorphous state or a semi-crystalline state means a molded body having a relative crystallinity of less than 80%.

  The temperature of the extruder is preferably 170 ° C. or higher, more preferably 175 ° C. or higher, and further preferably 180 ° C. or higher, from the viewpoint of uniformly mixing the polyester resin composition and preventing deterioration of the polyester resin. Is 240 ° C. or lower, more preferably 220 ° C. or lower, and further preferably 210 ° C. or lower. Moreover, 170-240 degreeC is preferable, 175-220 degreeC is more preferable, and 180-210 degreeC is further more preferable. Moreover, it is preferable to set the temperature of a cooling roll to less than Tg of a polyester resin composition from a viewpoint of obtaining the primary processed goods of an amorphous state or a semi-crystalline state, specifically, less than 40 degreeC is preferable and 30 degrees C or less Is more preferable, and 20 ° C. or less is more preferable. In the present invention, the temperature of the extruder means the barrel set temperature of the extruder.

  The time for contacting the cooling roll is preferably 0.1 to 50 seconds, more preferably 0.5 to 10 seconds, and 0.8 to 5 seconds from the viewpoint of obtaining a molded body in an amorphous state or a semicrystalline state. Is more preferable. The extrusion speed is preferably 1 to 100 m / min, more preferably 5 to 80 m / min, and even more preferably 10 to 50 m / min from the viewpoint of obtaining a molded body in an amorphous state or a semicrystalline state.

  When a sheet-like primary processed product is formed by press molding, it can be prepared by surrounding the polyester resin composition of the present invention with a frame having a sheet shape and press-molding.

  The press molding temperature and pressure are preferably 170 to 240 ° C. and 5 to 30 MPa, more preferably 175 to 220 ° C. and 10 to 25 MPa, and more preferably 180. It is preferable to press under conditions of a temperature of ˜210 ° C. and a pressure of 10 to 20 MPa. The press time cannot be determined unconditionally depending on the temperature and pressure of the press, but is preferably 1 to 10 minutes, more preferably 1 to 7 minutes, and further preferably 1 to 5 minutes.

  In addition, immediately after pressing under the above conditions, the temperature is preferably 0 to 40 ° C. and the pressure is 5 to 30 MPa, more preferably the temperature is 10 to 30 ° C. and the pressure is 10 to 25 MPa, and further preferably 10 It is preferable to press and cool under conditions of a temperature of -20 ° C and a pressure of 10-20 MPa. By pressing under this temperature condition, the polyester resin composition in the present invention can be cooled to less than its Tg to maintain an amorphous state or a semi-crystalline state. The press time cannot be determined unconditionally depending on the temperature and pressure of the press, but is preferably 1 to 10 minutes, more preferably 1 to 7 minutes, and further preferably 1 to 5 minutes.

  When preparing an amorphous or semi-crystalline sheet-like primary processed product, the thickness thereof is preferably 0.1 mm or more, more preferably from the viewpoint of obtaining a uniform molded product (secondary processed product). It is 15 mm or more, preferably 1.5 mm or less, more preferably 1.4 mm or less, and still more preferably 1.2 mm or less. Moreover, 0.1-1.5 mm is preferable, 0.1-1.4 mm is more preferable, 0.15-1.2 mm is further more preferable.

  By further processing the primary processed product thus obtained, the thermoformed product of the present invention which is a secondary processed product (also referred to as a secondary molded product) is obtained. The primary processed product in the amorphous or semi-crystalline state has a high effect of plasticizing the polyester resin by the compound represented by the formula (I) even when subjected to secondary processing such as thermoforming. Therefore, even when an additive such as a crystal nucleating agent or a hydrolysis inhibitor is blended, the bleed resistance is excellent.

  The thermoformed article of the present invention can be molded according to a known method without any particular limitation. For example, a non-crystalline or semi-crystalline sheet prepared by the above-described method may be used as a glass transition temperature (Tg) of a polyester resin composition. ) As described above, crystallization is performed by thermoforming in a temperature range below the melting point (Tm), and for example, the relative crystallinity obtained by the method of Test Example 1 described later is preferably 80% or more, more preferably A crystallized thermoformed product of 90% or more can be obtained.

  Examples of the thermoformed product in the present invention include a molded product obtained by vacuum forming or pressure forming. These can be molded according to a known method without any particular limitation. For example, the amorphous or semi-crystalline sheet of the present invention is placed in a mold in a vacuum / pressure forming machine, and the mold is polyester. The resin composition can be obtained by heating to a temperature not lower than the glass transition temperature (Tg) and lower than the melting point (Tm), and maintaining the pressure or non-pressurized state for molding.

  The mold temperature may be any temperature above the glass transition temperature (Tg) and below the melting point (Tm) of the polyester resin composition from the viewpoint of improving the crystallization speed and workability of the polylactic acid resin composition. Specifically, 120 ° C. or lower is preferable, 115 ° C. or lower is more preferable, and 110 ° C. or lower is further preferable. Moreover, 70 degreeC or more is preferable, 75 degreeC or more is more preferable, and 80 degreeC or more is further more preferable. From this viewpoint, the mold temperature is preferably 70 to 120 ° C, more preferably 75 to 115 ° C, and further preferably 80 to 110 ° C.

  The holding time in the mold is preferably 2 to 60 seconds, and preferably 3 to 30 seconds in a 90 ° C. mold, for example, from the viewpoint of improving the heat resistance and productivity of the thermoformed product made of the polyester resin composition. More preferred is 5 to 20 seconds. Since the polyester resin composition of the present invention has a high crystallization rate, a molded product having sufficient heat resistance can be obtained even with a short holding time as described above.

  The thickness of the thermoformed product of the present invention thus obtained is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.15 mm or more, from the viewpoint of obtaining a uniform molded body (secondary processed product). Preferably it is 0.2 mm or more, Preferably it is 1.5 mm or less, More preferably, it is 1.4 mm or less, More preferably, it is 1.2 mm or less. Moreover, 0.1-1.5 mm is preferable, 0.15-1.4 mm is more preferable, 0.2-1.2 mm is further more preferable.

  In the thermoformed product of the present invention, since the amorphous or semi-crystalline sheet has good thermoformability, the molding temperature range in thermoforming is widened and the fit is excellent. Moreover, since the plasticizing effect by the compound represented by the formula (I) is excellent, the obtained molded body has high crystallinity, and is excellent in heat resistance and transparency.

  The present invention also provides a method for producing the thermoformed article of the present invention.

  The production method is not particularly limited as long as it is a method including a step of thermoforming a polyester resin composition containing the polyester resin and the compound represented by formula (I), depending on the type of the molded product to be obtained. A process can be added as appropriate.

Specifically, the aspect containing the following processes is mentioned.
Step (1) A polyester resin composition containing a polyester resin and a compound represented by formula (I) is extruded from a die by an extrusion molding method to prepare a sheet, and then the glass transition temperature (Tg) of the polyester resin composition is lowered. Step (2) for cooling to obtain a sheet having a relative crystallinity of less than 80% The sheet obtained in step (1) is a temperature not lower than the glass transition temperature (Tg) of the polyester resin composition and lower than the melting point (Tm). Step of obtaining a thermoformed product that has been thermoformed in the region and crystallized to a relative crystallinity of 80% or more

  Step (1) is a step of obtaining a sheet having a relative crystallinity of less than 80%. Specifically, the polyester resin composition containing the polyester resin and the compound represented by formula (I) is preferably 170 ° C. or higher, more preferably 175 ° C. or higher, further preferably 180 ° C. or higher, preferably 240 ° C. or lower, more preferably 220 ° C. or lower, further preferably 210 ° C. or lower, preferably 170 to 240 ° C., more preferably 175 to 220 ° C., and more preferably 180 to 210 ° C. Is extruded from a die with an extruder heated to 170-240 ° C, more preferably 175-220 ° C, more preferably 180-210 ° C, and then preferably less than 40 ° C, more preferably 30 ° C or less, still more preferably The cooling roll set at 20 ° C. or lower is preferably 0.1 to 50 seconds, more preferably 0.5 to 10 seconds. More preferably may be prepared by cooling in contact from 0.8 to 5 seconds, of less than relative crystallinity of 80% sheet. Further, depending on the type of the extruder used, the raw material of the polyester resin composition may be filled in the extruder, melt-kneaded as it is, and then extruded.

  In the step (2), a sheet having a relative crystallinity of less than 80% is thermoformed and crystallized. For example, the sheet is preferably 70 ° C. or higher, more preferably 75 ° C. or higher, further preferably 80 ° C. or higher, preferably 120 ° C. or lower, more preferably 115 ° C. or lower, more preferably 110 ° C. or lower, and preferably Can be crystallized by placing it in a mold of 70 to 120 ° C., more preferably 75 to 115 ° C., and still more preferably 80 to 110 ° C., and keeping it under pressure or no pressure. The thickness of the obtained molded product is not particularly limited, but is preferably 0.1 to 1.5 mm, more preferably 0.15 to 1.4 mm. In addition, before installing the sheet | seat obtained at the process (1) in a metal mold | die, you may shape | mold, after heating a sheet | seat beforehand to the temperature of mold temperature vicinity, for example.

  The thermoformed product of the present invention thus obtained has a high crystallinity, preferably a relative crystallinity of 80% or more, more preferably 90% or more, and has good transparency, heat resistance, Because of its excellent bleed and strength, it can be used in various applications, especially blister packs and trays for daily necessities, cosmetics, home appliances, food containers such as lunch box lids, and industrial trays used for transport and protection of industrial parts. It can be used suitably.

The present invention may relate to any of the following:
<1>
A thermoformed article comprising a polyester resin and a polyester resin composition comprising a polyester plasticizer represented by the following formula (I).
R ¹ O—CO—R ² —CO — [(OR ³ ) _m O—CO—R ² —CO—] _n OR ¹ (I)
Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6 And n represents a number from 1 to 12, provided that all R ² may be the same or different, and all R ³ may be the same or different.

<2>
The thermoformed product according to <1>, wherein the polyester resin contains a polylactic acid resin.
<3>
The thermoformed product according to <2>, wherein the content of the polylactic acid resin in the polyester resin is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably substantially 100% by weight.
<4>
The content of the polyester resin is preferably 50% by weight or more, more preferably 60% by weight or more, and further preferably 70% by weight or more in the polyester resin composition, <1> to <3>. .
<5>
R ¹ in formula (I) represents an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl. The thermoformed product according to any one of <1> to <4>, which is selected from the group consisting of a group and an iso-butyl group, preferably a methyl group and an ethyl group, and more preferably a methyl group.
<6>
R ² in Formula (I) represents an alkylene group having 2 to 4 carbon atoms, and is at least one selected from the group consisting of an ethylene group, a 1,3-propylene group, and a 1,4-butylene group, The thermoformed product according to any one of <1> to <5>, wherein an ethylene group, a 1,3-propylene group, an ethylene group, or a 1,4-butylene group is preferable, and an ethylene group is more preferable.
<7>
R ³ in the formula (I) represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group. 1,3-butylene group, 1,4-butylene group, 2-methyl-1,3-propylene group, 1,2-pentylene group, 1,4-pentylene group, 1,5-pentylene group, 2,2 -From dimethyl-1,3-propylene group, 1,2-hexylene group, 1,5-hexylene group, 1,6-hexylene group, 2,5-hexylene group, and 3-methyl-1,5-pentylene group Thermoforming according to any one of <1> to <6>, which is at least one selected from the group consisting of ethylene group, 1,2-propylene group, 1,3-propylene group and 1,4-butylene group Goods.
<8>
M in formula (I) is a number of 1 to 6, preferably a number of 1 to 4, more preferably a number of 1 to 3, and even more preferably a number of 1 to 2, <1> to <7> The thermoformed product described.
<9>
N in the formula (I) is preferably 1 or more, more preferably 1.2 or more, still more preferably 1.5 or more, still more preferably 1.8 or more, further preferably 2 or more, preferably 12 or less, more The thermoformed article according to any one of <1> to <8>, which is preferably 10 or less, more preferably 8 or less, further preferably 7 or less, and further preferably 6 or less.
<10>
In the compound represented by formula (I), R ¹ is a methyl group, R ² is an ethylene group, R ³ is an ethylene group, m is 2 and n is an ester of 1.6, R ¹ is a methyl group, R ² is an ethylene group, R ³ is an ethylene group, m is an ester of 2, n is 2.1, R ¹ is a methyl group, R ² is an ethylene group, R ³ is an ethylene group, and m is 2, n is 4.3 ester, R ¹ is methyl group, R ² is ethylene group, R ³ is 1,3-propylene group, m is 1, n is 4.4 ester, R ¹ is Methyl group, R ² is ethylene group, R ³ is 1,2-propylene group, m is 1, n is 3.6 ester, R ¹ is ethyl group, R ² is 1,4-butylene group, a R ³ is 1,3-propylene group, m is 1, n is 2 ester, ^{R 1} is butyl, ^{R 2} is an ethylene group, ^{R 3} is an ethylene group There are, esters of m is 2, n is 1.9, ^{R 1} is butyl, ^{R 2} is 1,3-propylene group, a ^{R 3} is an ethylene group, m is 3, n is 1.5 Ester, R ¹ is methyl group, R ² is 1,4-butylene group, R ³ is 1,3-propylene group, m is 1, n is 4.4 ester, R ¹ is methyl group, R ² is an ethylene group, R ³ is a 1,4-butylene group, m is 1 and n is an ester of 4.4, R ¹ is a methyl group, R ² is an ethylene group, R ³ is 1,6-hexylene An ester wherein m is 1 and n is 3, R ¹ is a methyl group, R ² is an ethylene group, R ³ is a 1,2-propylene group, m is 1 and n is 6.5 ester, ^{R 1} is methyl, ^{R 2} is an ethylene group, a ^{R 3} is 2-methyl-1,3-propylene group, m is 1, n is favored ester 3 Ku, ^{R 1} are all methyl groups, ^{R 2} is an ethylene group or a 1,4-butylene group, a ^{R 3} is an ethylene group, 1,3-propylene group, or a 1,2-propylene group, m is 1 More preferred are compounds in which the number of 3 and n is a number of 1 to 8, R ¹ is all methyl groups, R ² is ethylene group or 1,4-butylene group, R ³ is ethylene group, 1,3-propylene group Or a 1,2-propylene group, wherein m is a number of 1 to 2 and n is a number of 1.8 to 7, more preferably a thermoformed article according to any one of <1> to <9>. .
<11>
The thermoformed product according to any one of <1> to <10>, wherein the compound represented by the formula (I) is preferably obtained using the following raw materials (1) to (3).
(1) Monohydric alcohol having an alkyl group having 1 to 4 carbon atoms (2) Dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms (3) Divalent alcohol having an alkylene group having 2 to 6 carbon atoms <12>
(1) The monohydric alcohol having an alkyl group having 1 to 4 carbon atoms is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 1, <1> Description, which is at least one selected from the group consisting of 1-dimethyl-1-ethanol, preferably methanol, ethanol, 1-propanol and 1-butanol, more preferably methanol and ethanol, and even more preferably methanol. Thermoformed product.
<13>
(2) Dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms is succinic acid, glutaric acid, adipic acid, and derivatives thereof (for example, succinic anhydride, glutaric anhydride, dimethyl succinate, succinic acid) One or more selected from the group consisting of dibutyl, dimethyl glutarate, and dimethyl adipate, and succinic acid, glutaric acid, and derivatives thereof (for example, succinic anhydride, glutaric anhydride, dimethyl succinate, succinic acid) Dibutyl acid, dimethyl glutarate), succinic acid and derivatives thereof (for example, succinic anhydride, dimethyl succinate) are more preferable, or succinic acid, adipic acid and derivatives thereof (for example, succinic anhydride, Dimethyl succinate, dibutyl succinate, dimethyl adipate), succinic acid and its derivatives For example, succinic anhydride, dimethyl succinate, dibutyl succinate) are more preferred, <11> or <12> thermoformed article according.
<14>
(3) A dihydric alcohol having an alkylene group having 2 to 6 carbon atoms is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl- 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propane Diol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,5-hexanediol, 1,6-hexanediol, One or more selected from the group consisting of 2,5-hexanediol and 3-methyl-1,5-pentanediol Yes, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, tetraethylene glycol, 1,4-butanediol are preferred, diethylene glycol, triethylene glycol, 1,2-propanediol, 1, The thermoformed article according to any one of <11> to <13>, wherein 3-propanediol is more preferable, and diethylene glycol, 1,2-propanediol, and 1,3-propanediol are more preferable.
<15>
(1) The monohydric alcohol is at least one selected from the group consisting of methanol, ethanol, 1-propanol, and 1-butanol, and (2) the group consisting of dicarboxylic acid consisting of succinic acid, glutaric acid, and derivatives thereof. (3) The group in which the dihydric alcohol is composed of diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, tetraethylene glycol, and 1,4-butanediol. It is preferably at least one selected from
(1) The monohydric alcohol is at least one selected from the group consisting of methanol and ethanol, and (2) the dicarboxylic acid is at least one selected from the group consisting of succinic acid, glutaric acid, and derivatives thereof, (3) More preferably, the dihydric alcohol is at least one selected from the group consisting of diethylene glycol, triethylene glycol, 1,2-propanediol, and 1,3-propanediol,
(1) the monohydric alcohol is methanol, (2) the dicarboxylic acid is at least one selected from the group consisting of succinic acid and derivatives thereof, and (3) the dihydric alcohol is diethylene glycol, 1,2-propanediol, And the thermoformed article according to <11>, more preferably at least one selected from the group consisting of 1,3-propanediol.
<16>
The thermoformed article according to any one of <11> to <15>, wherein the compound represented by the formula (I) is obtained by the method of the following aspect 1 or aspect 2.
Aspect 1: (2) Step of synthesizing dicarboxylic acid ester by performing esterification reaction of (2) dicarboxylic acid with (1) monohydric alcohol (Step 1), and (3) esterifying the obtained dicarboxylic acid ester and (3) dihydric alcohol Method aspect including the step (Step 2) of chemical reaction: Method (17) including the step of collectively reacting (1) monohydric alcohol, (2) dicarboxylic acid, and (3) dihydric alcohol
The compound represented by the formula (I) has an acid value of preferably 1.00 mgKOH / g or less, more preferably 0.90 mgKOH / g or less, preferably 0.05 mgKOH / g or more, more preferably 0.1 mgKOH. The thermoformed product according to any one of <1> to <16>, which is at least / g.
<18>
The compound represented by the formula (I) preferably has a hydroxyl value of 10.0 mgKOH / g or less, more preferably 8.0 mgKOH / g or less, still more preferably 5.0 mgKOH / g or less, preferably 0.1 mgKOH. / G or more, More preferably, it is 0.2 mgKOH / g or more, The thermoformed product in any one of <1>-<17>.
<19>
The saponification value of the compound represented by formula (I) is preferably 500 mgKOH / g or more, more preferably 600 mgKOH / g or more, preferably 800 mgKOH / g or less, more preferably 750 mgKOH / g or less, <1> to <1. 18> The thermoformed product according to any one of the above.
<20>
The number average molecular weight of the compound represented by the formula (I) is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, preferably 1500 or less, more preferably 1400 or less, and still more preferably 1300 or less. The thermoformed article according to any one of <1> to <19>, which is more preferably 1200 or less.
<21>
The compound represented by formula (I) preferably has an acid value of 1.00 mgKOH / g or less, a hydroxyl value of 10.0 mgKOH / g or less, a number average molecular weight of 500 to 1500, and an acid value of 0.90 mgKOH. / G or less, a hydroxyl value of 8.0 mgKOH / g or less, and a number average molecular weight of 500 to 1400 are more preferred, an acid value of 0.90 mgKOH / g or less, a hydroxyl value of 8.0 mgKOH / g or less, and a number average The thermoformed article according to any one of <1> to <20>, further preferably having a molecular weight of 600 to 1200.
<22>
The compound represented by formula (I) is a thermoformed article according to any one of <1> to <21>, wherein the terminal alkyl esterification rate is preferably 85% or more, more preferably 90% or more.
<23>
The ether group value of the compound represented by the formula (I) is preferably 1 mmol / g or more, preferably 8 mmol / g or less, more preferably 6 mmol / g or less, and further preferably 5 mmol / g or less. 1> to <22>.
<24>
The compound represented by the formula (I) has an SP (Solubility Parameter) value of preferably 10.0 or more, more preferably 10.1 or more, further preferably 10.2 or more, preferably The thermoformed article according to any one of <1> to <23>, which is 12.0 or less, more preferably 11.5 or less, and still more preferably 11.2 or less.
<25>
The content of the compound represented by the formula (I) is preferably 1 part by weight or more, more preferably 5 parts by weight or more, preferably 50 parts by weight or less, more preferably 100 parts by weight of the polyester resin. The thermoformed product according to any one of <1> to <24>, which is 30 parts by weight or less.
<26>
The thermoformed article according to any one of <1> to <25>, wherein the polyester resin composition further contains a crystal nucleating agent.
<27>
The crystal nucleating agent is preferably an inorganic crystal nucleating agent or an organic crystal nucleating agent, more preferably an organic crystal nucleating agent, more preferably a metal salt of a carboxylic acid amide and phenylphosphonic acid, still more preferably a carboxylic acid amide, ethylene Bis fatty acid amide, alkylene bis fatty acid amide, alkylene bishydroxy fatty acid amide are more preferred, alkylene bishydroxy stearic acid amide having an alkylene group having 1 to 6 carbon atoms is more preferred, ethylene bis 12-hydroxy stearic acid amide is more preferred, <26> The thermoformed product described.
<28>
The content of the crystal nucleating agent is preferably 0.1 parts by weight or more, preferably 1.0 parts by weight or less, more preferably 0.5 parts by weight or less with respect to 100 parts by weight of the polyester resin. 26> or <27>.
<29>
The thermoformed article according to any one of <1> to <28>, wherein the polyester resin composition further contains a hydrolysis inhibitor.
<30>
<29> The thermoformed article according to <29>, wherein the hydrolysis inhibitor is preferably a polycarbodiimide compound or a monocarbodiimide compound.
<31>
The content of the hydrolysis inhibitor is preferably 0.05 parts by weight or more, more preferably 0.10 parts by weight or more, preferably 3 parts by weight or less, more preferably 2 parts by weight with respect to 100 parts by weight of the polyester resin. The thermoformed product according to <29> or <30>, which is not more than parts by weight.
<32>
<1> to <31>, wherein the polyester resin composition is prepared by melt-kneading a polyester resin and a compound represented by the formula (I), and if necessary, a raw material containing various additives. Thermoformed product.
<33>
The melt kneading temperature is preferably 170 ° C. or higher, more preferably 175 ° C. or higher, further preferably 180 ° C. or higher, preferably 240 ° C. or lower, more preferably 220 ° C. or lower, still more preferably 210 ° C. or lower. 32>.
<34>
The glass transition temperature (Tg) of the obtained melt-kneaded product is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, preferably 60 ° C. or lower, more preferably 55 ° C. or lower, <32> or <33>.
<35>
The cold crystallization temperature (Tc) of the obtained melt-kneaded product is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, preferably 110 ° C. or lower, more preferably 100 ° C. or lower, and further preferably 90 ° C. or lower. The thermoformed product according to any one of <32> to <34>.
<36>
The melting point (Tm) of the obtained melt-kneaded product is preferably 130 ° C. or higher, more preferably 140 ° C. or higher, further preferably 150 ° C. or higher, preferably 210 ° C. or lower, more preferably 200 ° C. or lower, still more preferably. Is a thermoformed article according to any one of <32> to <35>, which is 180 ° C. or lower.
<37>
The thermoformed product according to any one of <1> to <36>, wherein the polyester resin composition is formed into a primary processed product selected from a sheet and a film.
<38>
<37> The thermoformed product according to <37>, wherein the primary processed product is prepared by extrusion molding or press molding a polyester resin composition.
<39>
The primary processed product is made into an amorphous state or a semi-crystalline state by filling the polyester resin composition into an extruder, extruding from a T die, and contacting a cooling roll to cool to less than Tg of the polyester resin composition. <37> or <38>.
<40>
The temperature of the extruder is preferably 170 ° C. or higher, more preferably 175 ° C. or higher, more preferably 180 ° C. or higher, preferably 240 ° C. or lower, more preferably 220 ° C. or lower, and further preferably 210 ° C. or lower. <39> The thermoformed article according to the description.
<41>
The temperature of the cooling roll is preferably less than 40 ° C, more preferably 30 ° C or less, and further preferably 20 ° C or less, and the thermoformed product according to <39> or <40>.
<42>
The thermoformed product according to <37> or <38>, wherein the primary processed product is formed by surrounding and pressing the polyester resin composition with a frame having a sheet shape.
<43>
The press molding temperature and pressure are preferably 170 to 240 ° C. and 5 to 30 MPa, more preferably 175 to 220 ° C. and 10 to 25 MPa, and more preferably 180. <42> The thermoformed product according to <42>, which is under a condition of a temperature of ˜210 ° C. and a pressure of 10 to 20 MPa.
<44>
Furthermore, the temperature is preferably 0 to 40 ° C., and the pressure is 5 to 30 MPa, more preferably the temperature is 10 to 30 ° C., the pressure is 10 to 25 MPa, and further preferably the temperature is 10 to 20 ° C. <43> The thermoformed product according to <43>, which is pressed under a pressure of ˜20 MPa to be in an amorphous state or a semicrystalline state.
<45>
The thickness of the amorphous or semi-crystalline sheet-like primary processed product is preferably 0.1 mm or more, more preferably 0.15 mm or more, preferably 1.5 mm or less, more preferably 1.4 mm or less. The thermoformed article according to <39> or <44>, more preferably 1.2 mm or less.
<46>
The thickness of the amorphous or semi-crystalline film-like primary processed product is preferably 0.01 mm or more, more preferably 0.02 mm or more, further preferably 0.03 mm or more, preferably less than 0.1 mm. Hereinafter, the thermoformed article according to <39> or <44>, more preferably 0.09 mm or less, and still more preferably 0.08 mm or less.
<47>
The thermoformed product according to any one of <37> to <46>, which is formed into a secondary processed product by further processing the primary processed product.
<48>
<47> The thermoformed article according to <47>, wherein the amorphous or semi-crystalline sheet is thermoformed in a temperature range not lower than the glass transition temperature (Tg) and lower than the melting point (Tm) of the polyester resin composition.
<49>
A sheet in an amorphous state or a semi-crystalline state is placed in a mold in a vacuum / pressure forming machine, and the inside of the mold is above the glass transition temperature (Tg) of the polyester resin composition and below the melting point (Tm). <48> The thermoformed product according to <48>, wherein the thermoformed product is heated to a temperature of and maintained in a pressurized or non-pressurized state.
<50>
The mold temperature is preferably 120 ° C. or lower, more preferably 115 ° C. or lower, further preferably 110 ° C. or lower, more preferably 70 ° C. or higher, more preferably 75 ° C. or higher, and further preferably 80 ° C. or higher, <49> Thermoformed product.
<51>
The thermoformed article according to any one of <48> to <50>, which is a thermoformed article having a relative crystallinity of preferably 80% or more, more preferably 90% or more.
<52>
The thickness of the thermoformed product is preferably 0.1 mm or more, more preferably 0.15 mm or more, further preferably 0.2 mm or more, preferably 1.5 mm or less, more preferably 1.4 mm or less, and still more preferably. The thermoformed article according to any one of <48> to <51>, which is 1.2 mm or less.
<53>
A method for producing a thermoformed product, comprising the following steps (1) and (2).
Step (1) A polyester resin composition containing a polyester resin and a compound represented by formula (I) is extruded from a die by an extrusion molding method to prepare a sheet, and then the glass transition temperature (Tg) of the polyester resin composition is lowered. Step (2) for cooling to obtain a sheet having a relative crystallinity of less than 80% The sheet obtained in step (1) is a temperature not lower than the glass transition temperature (Tg) of the polyester resin composition and lower than the melting point (Tm). <54> a step of obtaining a thermoformed article that is thermoformed in the region and crystallized to a relative crystallinity of 80% or more.
The step (1) is preferably a polyester resin composition containing a polyester resin and a compound represented by the formula (I), preferably 170 ° C. or higher, more preferably 175 ° C. or higher, more preferably 180 ° C. or higher, preferably Is 240 ° C. or lower, more preferably 220 ° C. or lower, more preferably 210 ° C. or lower, and is preferably 170 ° C. or higher, more preferably 175 ° C. or higher, more preferably 180 ° C. or higher, preferably 240 ° C. Or less, more preferably 220 ° C. or less, more preferably 210 ° C. or less, extruded from a die, and then preferably set to less than 40 ° C., more preferably 30 ° C. or less, and even more preferably 20 ° C. or less. The cooling roll is preferably 0.1 to 50 seconds, more preferably 0.5 to 10 seconds, still more preferably 0.8. 5 seconds in contact with cooling, <53> The method according.
<55>
In the step (2), the sheet obtained in the step (1) is preferably 70 ° C. or higher, more preferably 75 ° C. or higher, further preferably 80 ° C. or higher, preferably 120 ° C. or lower, more preferably 115 ° C. or lower, More preferably, the method according to <53> or <54>, wherein the method is installed in a mold of 110 ° C. or lower and kept in a pressurized or non-pressurized state.
<56>
<1>-<52> The thermoformed product according to any one of <1> to <52>, which is suitable for clear cases such as daily necessities, cosmetics, and home appliances, packaging containers such as transparent windows of paper boxes, and stationery items such as clear holders and ID card cases.
<57>
(1) Blister packs or trays for products selected from daily necessities, cosmetics and household appliances, (2) food containers, or (3) industrial trays used for transporting and protecting industrial parts, < Use of thermoformed product according to any one of 1> to <52>, <56>.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, unless otherwise indicated, the part in an example is a weight part. “Normal pressure” indicates 101.3 kPa, and “normal temperature” indicates 15 to 25 ° C.

[Weight average molecular weight of polylactic acid resin (Mw)]
The weight average molecular weight (Mw) is measured by GPC (gel permeation chromatography) under the following measurement conditions.
<Measurement conditions>
Column: GMHHR-H + GMHHR-H
Column temperature: 40 ° C
Detector: RI
Eluent: Chloroform Flow rate: 1.0 mL / min
Sample concentration: 1 mg / mL
Injection volume: 0.1 mL
Conversion standard: Polystyrene

[Optical purity of polylactic acid]
The optical purity is determined according to the D-body content measurement method described in “Voluntary Standards for Food Containers and Packaging Made of Synthetic Resins such as Polyolefins, Third Edition, Revised June 2004, Part 3 Sanitation Test Method P12-13”. Measure under the measurement conditions. Specifically, sodium hydroxide / methanol is added to precisely weighed polylactic acid, set in a water bath shaker set at 65 ° C., and hydrolyzed until the resin content becomes a homogeneous solution. Dilute hydrochloric acid is added to the completed alkaline solution to neutralize it, and the decomposition solution is made up to volume with pure water, and then a fixed volume is separated into a volumetric flask and diluted with a high-performance liquid chromatography (HPLC) mobile phase solution to obtain a pH. Is adjusted to a range of 3-7, filtered into a volumetric flask, filtered through a membrane filter (0.45 μm), and this adjusted solution is quantified for D-lactic acid and L-lactic acid by HPLC. Obtain the optical purity of lactic acid.
<HPLC measurement conditions>
Column: Optical resolution column
Sumichiral OA6100 (46mmφ × 150mm, 5μm), Precolumn manufactured by Sumika Chemical Analysis Co., Ltd .: Optical resolution column
Sumichiral QA6100 (4mmφ × 10mm, 5μm), Sumika Chemical Analysis Center column temperature: 25 ° C
Mobile phase: 1.5% copper sulfate aqueous solution containing 2.5% methanol Mobile phase flow rate: 1.0 mL / min Detector: UV detector (UV254 nm)
Injection volume: 20 μL

[Melting point of polylactic acid resin and polyester resin composition]
The melting point of the polylactic acid resin is determined from the crystal melting endothermic peak temperature by the temperature rising method of differential scanning calorimetry (DSC, manufactured by Perkin Elmer, Diamond DSC) based on JIS-K7121. The melting point is measured by increasing the temperature from 20 ° C. to 250 ° C. at a temperature increase rate of 10 ° C./min.

[Acid value, hydroxyl value, and saponification value of polyester plasticizer]
Acid value: Analysis is performed according to the test method of JIS K 0070, except that toluene / ethanol = 2/1 (volume ratio) is used as a titration solvent.
Hydroxyl value: Analysis is performed according to the test method of JIS K 0070, except that acetic anhydride / pyridine = 1/4 (volume ratio) is used as the acetylating reagent and the addition amount is 3 mL.
Saponification value: Analysis is performed according to the test method of JIS K 0070, except that the temperature of the water bath is 95 ° C. and the heating time is 1 hour.

[Molecular weight of polyester plasticizer, terminal alkyl esterification rate, and ether group value]
Molecular weight: In this specification, the molecular weight of the polyester plasticizer means the number average molecular weight, and is calculated from the acid value, hydroxyl value, and saponification value according to the following formula.
Average molecular weight M = (M ₁ + M ₂ −M ₃ × 2) × n + M ₁ − (M ₃ −17.01) × 2 + (M ₃ −17.01) × p + (M ₂ −17.01) × q + 1. 01 × (2-pq)
q = hydroxyl value × M ÷ 56110
2-pq = acid value × M ÷ 56110
Average degree of polymerization n = saponification number × M ÷ (2 × 56110) −1
Terminal alkyl esterification rate: The molecular terminal alkyl esterification rate (terminal alkyl esterification rate) can be calculated from the following formula. The larger the value of the molecular terminal alkyl esterification rate, the free carboxyl group or hydroxyl group There are few, and it shows that the molecular terminal is fully alkylesterified.
Terminal alkyl esterification rate (%) = (p ÷ 2) × 100
Where M ₁ : molecular weight of dibasic acid ester M ₂ : molecular weight of dihydric alcohol M ₃ : molecular weight of monohydric alcohol p: number of terminal alkyl ester groups in one molecule q: number of terminal hydroxyl groups in one molecule Base value: From the following formula, the ether group value which is the number of millimoles (mmol) of the ether group in 1 g of the ester compound and plasticizer is calculated.
Ether group value (mmol / g) = (m−1) × n × 1000 ÷ M
Where m: average number of repeating oxyalkylene groups (m-1 represents the number of ether groups in one molecule of dihydric alcohol)

[Calculation of SP value of polyester plasticizer]
In the present specification, the SP (Solubility Parameter) value of the polyester plasticizer means an amount defined by the following formula when the aggregation energy is ΔE and the molecular volume is V.
SP value = (ΔE / V) ^1/2 (cal ^1/2 cm ^−3/2 )
In the present invention, the calculation is performed using the Fedors method described in Yuji Harasaki, “Basic Science of Coating”, p. 48, Tsubaki Shoten (1988).

[Glass transition point and cold crystallization temperature of polyester resin composition]
In accordance with JIS K 7121, a portion of the amorphous sheet is cut out, precisely weighed 7.5 mg, sealed in an aluminum pan, and then used at 25 ° C. to 200 ° C. using a DSC device (Perkin Elmer Diamond DSC). The glass transition temperature (° C) and the cold crystallization temperature (° C) are measured.

Production example 1 of polyester plasticizer
A four-necked flask (with a stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube) was charged with 363 g (3.42 mol) of diethylene glycol and 6.6 g of a methanol solution containing 28 wt% sodium methoxide as a catalyst (sodium methoxide 0). 0.034 mol) was added, and methanol was distilled off while stirring at normal pressure and 120 ° C. for 0.5 hour. Thereafter, 1000 g (6.84 mol) of dimethyl succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 3 hours, and methanol produced by the reaction was distilled off at normal pressure and 120 ° C. Next, the mixture was cooled to 75 ° C., the pressure was gradually reduced from normal pressure to 6.7 kPa over 1.5 hours to distill off methanol, and then the pressure was returned to normal pressure. Further, 28 wt% sodium methoxide was used as a catalyst. A methanol solution containing 5.8 g (sodium methoxide 0.030 mol) was added, and the pressure was gradually reduced from normal pressure to 2.9 kPa over 2 hours at 100 ° C. to distill methanol. Then, after cooling to 80 ° C., 18 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by filtration under reduced pressure. The filtrate was pressured at 0.3 kPa and the temperature was raised from 70 ° C. to 190 ° C. over 1 hour to distill off the remaining dimethyl succinate to obtain a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 0.94 mol with respect to 100 mol of dicarboxylic acid ester.

Production example 2 of polyester plasticizer
In a four-necked flask (with a stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube) 581 g (5.47 mol) of diethylene glycol and 9.1 g of methanol solution containing 28 wt% sodium methoxide as a catalyst (sodium methoxide 0) 0.047 mol), and methanol was distilled off with stirring at normal pressure and 120 ° C. for 0.5 hour. Thereafter, 1200 g (8.21 mol) of dimethyl succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours, and methanol produced by the reaction was distilled off at normal pressure and 120 ° C. Next, the mixture was cooled to 75 ° C., the pressure was gradually reduced from normal pressure to 6.7 kPa over 1.5 hours to distill off methanol, and then the pressure was returned to normal pressure. Further, 28 wt% sodium methoxide was used as a catalyst. The methanol solution containing 9.8 g (0.051 mol of sodium methoxide) was added, and the pressure was gradually reduced from normal pressure to 2.9 kPa over 2 hours at 100 ° C. to distill methanol. Then, after cooling to 80 ° C., 28 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by vacuum filtration. The filtrate was pressured at 0.3 kPa and the temperature was raised from 70 ° C. to 170 ° C. over 2.5 hours to distill off the remaining dimethyl succinate to obtain a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 1.2 mol with respect to 100 mol of dicarboxylic acid ester.

Production example 3 of polyester plasticizer
In a four-necked flask (with a stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube), 521 g (6.84 mol) of 1,3-propanediol and 5.9 g of a methanol solution containing 28 wt% sodium methoxide as a catalyst (Sodium methoxide 0.031 mol) was added, and methanol was distilled off with stirring at normal pressure and 120 ° C. for 0.5 hour. Thereafter, 1500 g (10.26 mol) of dimethyl succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour, and methanol produced by the reaction was distilled off at normal pressure and 120 ° C. Next, the mixture was cooled to 60 ° C., 5.6 g of 28 wt% sodium methoxide-containing methanol solution (0.029 mol of sodium methoxide) was added, the temperature was raised to 120 ° C. over 2 hours, and then the pressure was applied over 1 hour. The methanol was gradually distilled off from normal pressure to 3.7 kPa. Then, after cooling to 80 ° C., 18 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by filtration under reduced pressure. The filtrate was raised at a pressure of 0.1 kPa and the temperature was raised from 85 ° C. to 194 ° C. over 2.5 hours to distill off the remaining dimethyl succinate to obtain a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 0.58 mol with respect to 100 mol of dicarboxylic acid ester.

Production example 4 of polyester plasticizer
In a four-necked flask (with a stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube), 1,64 g (10.0 mol) of 1,2-propanediol and 14.0 g of methanol solution containing 28 wt% sodium methoxide as a catalyst (Sodium methoxide 0.073 mol) was added, and methanol was distilled off while stirring at normal pressure and 120 ° C. for 0.5 hour. Thereafter, 2200 g (15.05 mol) of dimethyl succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2.5 hours, and methanol produced by the reaction was distilled off at normal pressure and 120 ° C. Next, the mixture was cooled to 75 ° C., the pressure was gradually reduced from normal pressure to 6.7 kPa over 0.5 hours to distill off methanol, and then the pressure was returned to normal pressure. Further, 28 wt% sodium methoxide was used as a catalyst. 6.4 g of methanol solution (0.033 mol of sodium methoxide) was added, and methanol was distilled by gradually lowering the pressure from normal pressure to 5.3 kPa over 1 hour at 110 ° C. After cooling to 75 ° C. and returning to normal pressure, 8.4 g of a 28 wt% sodium methoxide-containing methanol solution (0.044 mol of sodium methoxide) was added again as a catalyst, and the pressure was increased to 110 ° C. under a pressure of 2 Methanol was distilled off gradually from normal pressure to 1.6 kPa over time. Then, after cooling to 80 ° C., 47 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by filtration under reduced pressure. The filtrate was heated at a pressure of 0.4 kPa and the temperature was raised from 115 ° C. to 200 ° C. over 1 hour, and the remaining dimethyl succinate was distilled off to obtain a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 1.82 mol with respect to 100 mol of dicarboxylic acid ester.

Production example 5 of polyester plasticizer
In a four-necked flask (with a stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube), 955 g (12.6 mol) of 1,2-propanediol and 15.4 g of a methanol solution containing 28 wt% sodium methoxide as a catalyst (Sodium methoxide 0.080 mol) was added, and methanol was distilled off while stirring at normal pressure and 120 ° C. for 0.5 hour. Thereafter, 2567 g (17.56 mol) of dimethyl succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours, and methanol produced by the reaction was distilled off at normal pressure and 120 ° C. Next, the mixture was cooled to 75 ° C., the pressure was gradually reduced from normal pressure to 6.7 kPa over 0.5 hours to distill off methanol, and then the pressure was returned to normal pressure. Further, 28 wt% sodium methoxide was used as a catalyst. 8.1 g of methanol solution (0.042 mol of sodium methoxide) was added and methanol was distilled at 110 ° C. by gradually lowering the pressure from normal pressure to 5.3 kPa over 1 hour. After cooling to 75 ° C. and returning to normal pressure, 10.8 g of a 28 wt% sodium methoxide-containing methanol solution (0.056 mol of sodium methoxide) was added again as a catalyst. Methanol was distilled off gradually from normal pressure to 1.6 kPa over time. Then, after cooling to 80 ° C., 47 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by filtration under reduced pressure. The filtrate was heated at a pressure of 0.8 kPa and the temperature was raised from 102 ° C. to 200 ° C. over 3 hours to distill off the remaining dimethyl succinate to obtain a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 1.71 mol with respect to 100 mol of dicarboxylic acid ester.

Production example 6 of polyester plasticizer
In a four-necked flask (with a stirrer, thermometer, distillation tube, nitrogen blowing tube) 369 g (3.47 mol) of diethylene glycol and 5.6 g of methanol solution containing 28 wt% sodium methoxide as a catalyst (0.029 mol of sodium methoxide) ) And methanol was distilled off while stirring at a pressure of 3.6 kPa and 84 ° C. for 0.5 hour. Thereafter, 1600 g (6.95 mol) of dibutyl succinate obtained in the same manner as in Production Example 10 at a pressure of 2.7 kPa and 79 ° C. was dropped over 2.5 hours, and 1-butanol produced by the reaction was distilled off. . Next, after returning to normal pressure, 2.1 g of a 28 wt% sodium methoxide-containing methanol solution (0.011 mol of sodium methoxide) was added, and the state was maintained at 85 ° C. and 2.1 kPa over 1.5 hours. The temperature was gradually raised and reduced to 146 ° C. and 1.1 kPa to distill 1-butanol produced by the reaction. Then, after cooling to 80 ° C., 11 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by vacuum filtration to obtain a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 0.58 mol with respect to 100 mol of dicarboxylic acid ester.

Production example 7 of polyester plasticizer
In a four-necked flask (with a stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube), 999 g (9.41 mol) of diethylene glycol and 23.6 g of a methanol solution containing 28 wt% sodium methoxide as a catalyst (sodium methoxide 0) .122 mol) was added, and methanol was distilled off while stirring at normal pressure (101.3 kPa) and 120 ° C. for 0.5 hour. Thereafter, 4125 g (28.2 mol) of dimethyl succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 3 hours, and methanol produced by the reaction was distilled off at normal pressure and 120 ° C. Next, the mixture was cooled to 75 ° C., the pressure was gradually reduced from normal pressure to 6.7 kPa over 2 hours to distill off methanol, and the pressure was returned to normal pressure. Further, 28 wt% sodium methoxide-containing methanol was used as a catalyst. 4.4 g of solution (0.023 mol of sodium methoxide) was added, and methanol was distilled at 100 ° C. by gradually lowering the pressure from normal pressure to 2.9 kPa over 2 hours. Then, after cooling to 80 ° C., 41 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by filtration under reduced pressure. The filtrate was raised at a pressure of 0.3 kPa and the temperature from 70 ° C. to 190 ° C. over 4 hours, and the remaining dimethyl succinate was distilled off to obtain a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 0.51 mol with respect to 100 mol of dicarboxylic acid ester.

Production Example 8 for Polyester Plasticizer
In a four-necked flask (with a stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube), neopentyl glycol 263.5 g (2.53 mol), bis (2-ethylhexyl) adipate 1500 g (4.05 mol) 2-ethyl ester produced by the reaction while adding 5.6 g of methanol solution containing 28 wt% sodium methoxide (0.029 mol of sodium methoxide) as a catalyst and reacting at a pressure of 3.7 kPa and 120 ° C. for 1.5 hours. Hexanol was distilled off. Next, after cooling to 75 ° C., the pressure is returned to normal pressure. Further, 3.0 g (sodium methoxide 0.016 mol) of 28 wt% sodium methoxide-containing methanol solution is added as a catalyst, and the pressure is 0.4 kPa and the temperature is increased. Was raised from 92 ° C. to 160 ° C. over 1 hour to distill 2-ethylhexanol. Then, after cooling to 80 ° C., 19 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by vacuum filtration. The filtrate was raised at a pressure of 0.3 kPa and the temperature was raised from 166 ° C. to 214 ° C. over 2 hours to distill off 504 g of residual bis (2-ethylhexyl) adipate to obtain a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 1.11 mol with respect to 100 mol of dicarboxylic acid ester.

Production Example 9 for Polyester Plasticizer
In a four-necked flask (with a stirrer, thermometer, Deanstalc apparatus, nitrogen blowing tube), 2515 g (19.3 mol) of 2-ethylhexanol (manufactured by Kanto Chemical Co., Inc.), 877 g of succinic acid (manufactured by Wako Pure Chemical Industries, Ltd.) 7.43 mol) and 14.1 g (0.0742 mol) of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.), from a pressure of 16 kPa and 80 ° C. to a pressure of 12 kPa and 90 ° C. Until the reaction was continued for 7 hours, water was distilled off. Thereafter, 32 g of KYOWARD 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by filtration under reduced pressure. The filtrate was charged into a four-necked flask (with a stirrer, thermometer, distillation tube and nitrogen blowing tube), and the residual 2-ethylhexanol was changed from a pressure of 0.7 kPa and 95 ° C. to a pressure of 0.5 kPa and 185 ° C. Then, 16 g of Kyoward 500SH was added again and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by vacuum filtration to obtain bis (2-ethylhexyl) succinate. Next, 467 g (1.36 mol) of this bis (2-ethylhexyl) succinate and 250 g (2.36 mol) of diethylene glycol were added to a four-necked flask (with a stirrer, thermometer, dropping funnel, distillation tube and nitrogen blowing tube). ), And 2.2 g of methanol solution containing 28 wt% sodium methoxide (0.011 mol of sodium methoxide) as a catalyst, and gradually decreasing the pressure from 2.7 kPa to 0.9 kPa at 110 ° C. over 45 minutes. Then, 2-ethylhexanol produced by the reaction was distilled off. After cooling to 80 ° C., 1953 g (5.70 mol) of bis (2-ethylhexyl) succinate and 5.0 g of 28 wt% sodium methoxide-containing methanol solution (0.026 mol of sodium methoxide) were added again. The pressure was gradually lowered while increasing the temperature from 110 ° C. and 0.8 kPa to 5.5 ° C. over 5.5 hours, and 2-ethylhexanol produced by the reaction was distilled off. Then, after cooling to 80 ° C., 10.5 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by filtration under reduced pressure. The filtrate was gradually reduced in temperature from 178 ° C. and 0.3 kPa to 220 ° C. and 0.1 kPa over 4.5 hours, and the remaining bis (2-ethylhexyl) succinate was distilled. Leaving a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 0.53 mol with respect to 100 mol of dicarboxylic acid ester.

Production Example 10 for Polyester Plasticizer 10
In a four-necked flask (with stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube), 763.6 g (10.04 mol) of 1,3-propanediol and methanol solution 17 containing 28 wt% sodium methoxide as a catalyst 17 0.5 g (sodium methoxide 0.091 mol) was added, and methanol was distilled off while stirring at 120 ° C. under normal pressure for 0.5 hour. Thereafter, 2622 g (15.05 mol) of dimethyl adipate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour, and methanol produced by the reaction was distilled off at normal pressure and 120 ° C. Next, the mixture was cooled to 70 ° C., 6.2 g of 28 wt% sodium methoxide-containing methanol solution (0.032 mol of sodium methoxide) was added, and methanol was distilled off at 100 ° C. for 1 hour at a pressure of 5.2 kPa. . Again, it cooled to 70 degreeC, 5.2g (sodium methoxide 0.027mol) 28 weight% sodium methoxide containing methanol solution was put, and methanol was distilled off over 1 hour at the pressure of 1.6 kPa and 100 degreeC. Then, after cooling to 80 ° C., 67 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by vacuum filtration. The filtrate was heated at a pressure of 0.4 kPa and the temperature was raised from 135 ° C. to 200 ° C. over 1 hour to distill off the remaining dimethyl adipate, thereby obtaining a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 1.0 mol with respect to 100 mol of dicarboxylic acid ester.

Production Example 11 for Polyester Plasticizer 11
4. A 4-necked flask (with a stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube) in 308 g (3.42 mol) of 1,4-butanediol, and a methanol solution containing 28 wt% sodium methoxide as a catalyst 6 g (0.034 mol of sodium methoxide) was added, and methanol was distilled off while stirring at normal pressure and 120 ° C. for 0.5 hour. Thereafter, 750 g (5.13 mol) of dimethyl succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour, and methanol produced by the reaction was distilled off at normal pressure and 120 ° C. Next, the mixture was cooled to 75 ° C., the pressure was gradually reduced from normal pressure to 6.7 kPa over 1 hour to distill off methanol, and then returned to normal pressure. Further, 28 wt% sodium methoxide-containing methanol as a catalyst. 1.7 g of solution (0.009 mol of sodium methoxide) was added, and methanol was distilled by gradually lowering the pressure from normal pressure to 2.9 kPa over 1 hour at 100 ° C. After cooling to 70 ° C., 1.7 g of a 28 wt% sodium methoxide-containing methanol solution (0.009 mol of sodium methoxide) was added again, and the pressure was increased from normal pressure to 2.9 kPa over 1 hour at 100 ° C. The methanol was distilled off gradually. Thereafter, 23 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 90 ° C. under a pressure of 4.0 kPa, followed by vacuum filtration. The filtrate was heated at a pressure of 0.4 kPa and the temperature was raised from 85 ° C. to 180 ° C. over 1 hour to distill off the remaining dimethyl succinate, thereby obtaining a room temperature yellow solid. In addition, the usage-amount of the catalyst was 1.0 mol with respect to 100 mol of dicarboxylic acid ester.

  The acid value, hydroxyl value, and saponification value of the obtained ester plasticizer were measured, and the number average molecular weight, terminal alkyl esterification rate, average polymerization degree (n), and ether group value were calculated based on the above formula. . The SP value was also calculated according to the above method. The results are shown in Tables 1-2.

Examples 1-11 and Comparative Examples 1-4
Preparation of Polyester Resin Composition As a polyester resin composition, the composition raw materials shown in Tables 3 and 4 were rotated at a rotational speed of 100 r / min and a melt kneading temperature 190 with a twin screw extruder (Ikegai Iron Works, PCM-45). The mixture was melt-kneaded at 0 ° C., strand cut was performed, and polylactic acid resin composition pellets were obtained. The obtained pellets were dried at 70 ° C. under reduced pressure for 1 day, and the water content was adjusted to 500 ppm or less.

Preparation of Amorphous Sheet This pellet was melt-kneaded at a rotation speed of 120 r / min and a melt-kneading temperature of 200 ° C. with a T-die twin-screw extruder (TEX44αII manufactured by Nippon Steel Works), and a sheet having a thickness of 0.3 mm The composition was extruded from a T-die and contacted with a chill roll controlled at a surface temperature of 20 ° C. for 2 seconds to obtain an amorphous sheet having a relative crystallinity of less than 80% (thickness 0.3 mm).

Preparation of thermoformed article Next, using a single vacuum / pressure forming machine (FVS-500P WAKITEC, manufactured by Wakisaka Seisakusho), the cut amorphous sheet was attached to a guide, and the heater part was set to 400 ° C. By changing the holding time in the sheet, the temperature of the sheet surface becomes 70 to 90 ° C, and after heating and softening the sheet to a state where thermoforming is possible, use the upper and lower molds in which the sheet is set at a surface temperature of 90 ° C. Then, vacuum forming was performed, and after holding for 10 seconds in the mold, the mold was removed to obtain a thermoformed product. The sheet surface temperature was measured by directly measuring the sheet surface temperature after heating with a surface thermometer. The mold used is shown in FIG.

The raw materials in Tables 3 and 4 are as follows.
<Polyester resin>
NW4032D: Polylactic acid resin, manufactured by Nature Works LLC, poly-L-lactic acid, NatureWorks 4032D, optical purity 98.5%, melting point 164 ° C., weight average molecular weight 141000, residual monomer 1200 ppm
PET: Polyethylene terephthalate, TSUNAMI GS2, manufactured by Eastman Chemical Co., Ltd., glass transition temperature 81 ° C.
<Plasticizer>
Production Examples 1 to 11: Polyester plasticizers Riquemar PL-019 described in Tables 1 and 2: Glycerin diacetomonocaprylate, Riken Vitamin Co., Ltd. ATBC: Tributyl acetyl citrate, Asahi Kasei Finechem Co., Ltd. <Crystal Nucleating Agent>
SLIPAX H: Ethylene bis 12-hydroxystearic acid amide, manufactured by Nippon Kasei Co., Ltd. <Hydrolysis inhibitor>
Carbodilite LA-1: Polycarbodiimide, manufactured by Nisshinbo Chemical Co., Ltd.

  The characteristics of the obtained molded body were evaluated according to the methods of Test Examples 1 to 5 below. The results are shown in Tables 3 and 4.

Test Example 1 <Evaluation of crystallinity>
7.5 mg of an amorphous sheet and a thermoformed product are precisely weighed, sealed in an aluminum pan, and then used as a 1st RUN using a DSC apparatus (Diamond DSC manufactured by PerkinElmer Co., Ltd.) at a heating rate of 20 ° C./min. The temperature was raised to 200 ° C. and held at 200 ° C. for 5 minutes, then the temperature was lowered from 200 ° C. to 20 ° C. at a temperature drop rate of −20 ° C./minute, held at 20 ° C. for 1 minute, and then further heated to 2nd RUN. The temperature was raised from 20 ° C to 200 ° C at a rate of ° C / min. The absolute value ΔHcc of the cold crystallization enthalpy of the polylactic acid resin observed at 1st RUN was obtained, and the crystal melting enthalpy ΔHm observed at 2nd RUN was obtained. From the obtained value, the relative crystallinity (%) was obtained by the following formula.
Relative crystallinity (%) = {(ΔHm−ΔHcc) / ΔHm} × 100

Test Example 2 <Transparency Evaluation>
A part of the amorphous sheet and the thermoformed product is cut out, and using an integrating sphere light transmittance measuring device (haze meter, HM-150 type, manufactured by Murakami Color Research Laboratory Co., Ltd.) defined in JIS-K7105, Haze is used. The value was measured and used as an index of transparency. It shows that it is excellent in transparency, so that the value of Haze value is small.

Test Example 3 <Evaluation of heat resistance>
50 cc of water at 25 ° C. is put into the main body part (φ81 mm, height 51 mm, made of low foamed PS containing PP) of a commercially available container (trade name: Yubumi 90, Shino CPC Kasei Co., Ltd.), and the resulting thermoformed product (lid) Was firmly fitted, and the range was raised with a microwave oven at 600 W for 60 seconds, and the heat resistance was evaluated in the following three stages. The surface temperature of the thermoformed product immediately after the test was 95 ° C.
3: Almost no deformation 2: Slight deformation 1: Large deformation

Test Example 4 <Evaluation of bleed resistance>
The thermoformed product was left in a thermostatic chamber at 70 ° C. for 1 week, and the presence or absence of a plasticizer bleed on its surface was evaluated by the following three stages for bleed resistance by visual observation and touch.
3: No bleed is observed 2: Slight bleed is observed 1: Clearly bleed is observed

Test Example 5 <Evaluation of rigidity (elastic modulus)>
A sample piece having a width of 1 cm and a length of 4 cm is cut from the flat part of the top surface of the thermoformed product, and the frequency is increased by a dynamic viscoelasticity measuring device (EXSTAR6000 manufactured by SII Nanotechnology) based on JIS-K7198. The storage elastic modulus (E ′) in the temperature range of −20 ° C. to 80 ° C. was measured at a temperature rate of 2 ° C./min, and the storage elastic modulus (GPa) at 25 ° C. was determined.

  As is apparent from the results of Tables 3 and 4, the plasticizer represented by the formula (I) is excellent in compatibility with the polylactic acid resin and polyethylene terephthalate, so that the thermoformed product of the present invention has high crystallinity and excellent It showed transparency and had good heat resistance and bleed resistance. Further, the thermoformed product containing the plasticizer had a high elastic modulus and good rigidity. On the other hand, since the plasticizers used in Comparative Examples 3 and 4 have poor compatibility with the resin, they are poor in transparency as compared with the present invention, bleed is observed during storage, and the elastic modulus is greatly reduced. there were. Further, the plasticizers used in Comparative Examples 1 and 2 had insufficient compatibility with the resin, the transparency was lowered, and bleeding was observed during storage.

  Further, the thermoformability of the thermoformed product of the present invention was evaluated according to Test Example 6 below. The results are shown in Tables 5 and 6.

Test Example 6 <Evaluation of thermoformability>
The thermoformability was evaluated by using a single vacuum / pressure forming machine (manufactured by Wakisaka Seisakusho Co., Ltd., FVS-500P WAKITEC), attaching the amorphous sheet to the guide, and setting the heater temperature to 400 ° C. By changing the holding time, the sheet was heated until the temperature of the sheet surface reached the temperature shown in Tables 5 and 6. When the sheet heated to each temperature is vacuum molded using upper and lower molds set at 90 ° C., held in the mold for 10 seconds, the vacuum molded body is taken out, and the case where it can be easily fitted is designated as “A”. Other than that, it was designated as “B”. The sheet surface temperature was measured by directly measuring the sheet surface temperature after heating with a surface thermometer. The mold used is the same as described above.

  As is apparent from the results of Tables 5 and 6, since the plasticizer represented by the formula (I) is excellent in compatibility with the polylactic acid resin and polyethylene terephthalate, the resin composition containing the plasticizer represented by the formula (I) The product had a wide temperature range (molding temperature range) in which sufficient fit could be obtained even when the sheet surface temperature changed due to different holding times in the heating zone, and was excellent in thermoformability.

  The thermoformed product of the present invention is excellent in transparency, heat resistance and bleed resistance, and further excellent in rigidity, so it is suitable for various applications such as food containers, packaging materials for household and household appliances, trays for industrial parts, etc. Can be used for

Claims (11)

A thermoformed article comprising a polyester resin and a polyester resin composition comprising a polyester plasticizer represented by the following formula (I).
R ¹ O—CO—R ² —CO — [(OR ³ ) _m O—CO—R ² —CO—] _n OR ¹ (I)
Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6 And n represents a number from 1 to 12, provided that all R ² may be the same or different, and all R ³ may be the same or different.   The thermoformed article according to claim 1, wherein the polyester plasticizer has an acid value of 1.00 mgKOH / g or less, a hydroxyl value of 10.0 mgKOH / g or less, and a number average molecular weight of 500 to 1500.   The thermoformed article according to claim 1 or 2, wherein the solubility parameter of the polyester plasticizer by the Fedoros method is 10.0 to 12.0. The thermoformed product according to any one of claims 1 to 3, wherein the polyester plasticizer is obtained by using the following (1) to (3).
(1) Monohydric alcohol having an alkyl group having 1 to 4 carbon atoms (2) Dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms (3) Divalent alcohol having an alkylene group having 2 to 6 carbon atoms   The thermoformed article according to any one of claims 1 to 4, wherein the polyester resin is a polylactic acid resin. The method for producing a thermoformed product according to any one of claims 1 to 5, wherein a thermoformed product crystallized to a relative crystallinity of 80% or more is obtained by the following steps (1) to (2). A method for manufacturing a thermoformed product.
Step (1) A polyester resin composition containing a polyester resin and a polyester plasticizer represented by the formula (I) is extruded from a die by an extrusion molding method to prepare a sheet, and then the glass transition temperature (Tg) of the polyester resin composition. ) Step (2) for obtaining a sheet having a relative crystallinity of less than 80% by cooling to less than the glass transition temperature (Tg) of the polyester resin composition, melting point (Tm) A process for obtaining a thermoformed product that is thermoformed in a temperature range of less than 80% and crystallized to a relative crystallinity of 80% or more.   The thermoformed article according to any one of claims 1 to 5, further comprising an organic crystal nucleating agent.   The thermoformed article according to claim 7, wherein the organic crystal nucleating agent is a carboxylic acid amide.   The thermoformed article according to claim 8, wherein the carboxylic acid amide is an alkylene bishydroxystearic acid amide having an alkylene group having 1 to 6 carbon atoms. The thermoformed product according to any one of claims 1 to 5 and 7 to 9, wherein R ² in the formula (I) is an ethylene group.   The thermoformed article according to any one of claims 1 to 5, and 7 to 10, wherein n in the formula (I) is 2 or more.

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