JP2001288346A - Polyester composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester composition reduced in the formation of THF in a production step of a polymer, a compounding step or a molding and processing step. SOLUTION: This polyester composition comprises a polyester having units represented by general formulae (I) and (II) (wherein, respective symbols have each the same meaning as that in the specification) and a silicon compound having a silanol group. The amount of the unit represented by general formula (II) is >0 and <=100 mol% in the polymer and the amount of a polyoxyalkylene group represented by general formula (IV) (wherein, respective symbols have each the same meaning as that in the specification) in the whole polyoxyalkylene groups represented by R3 is 20-100 mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composition, and more particularly, to a process for producing tetrahydrofuran (hereinafter, also referred to as THF) in a polyester production step, a compounding step, and a molding / processing step, in which the production is small. The present invention relates to a polyester composition having a low THF content in a molded article used.

[0002]

2. Description of the Related Art Poly-1,4-tetramethyleneoxy glycol (hereinafter also referred to as PTMG) and / or 1,4-tetramethylene glycol (hereinafter also referred to as TMG) are used as glycol components, and terephthalic acid and / or 2 Polyesters containing 2,6-naphthalenedicarboxylic acid as an acid component and ethylene glycol (hereinafter also referred to as EG) as a copolymer component exhibit rubbery elasticity and are therefore generally referred to as thermoplastic elastomers. These thermoplastic elastomers are widely used in the fields of electric products, automobile products, films, fibers, and the like, because they are excellent in color tone, heat resistance, and mechanical properties, and are easy to mold and process.

However, the polyesters glycol component PTMG and TMG, such as the following, the manufacturing process of the polymer, compounding step and the molding and processing step, the polyester butanol end groups (-CH ₂ CH ₂ CH ₂ CH
The cyclization reaction of ₂ OH) is a problem that THF produces. For example,

[0004]

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[0005] The THF formation reaction is affected by the polymerization catalyst, acid, temperature and the like, and the reaction is accelerated.

In reaction A, only one molecule of THF is produced from one butanol end group. In reaction B, even if one butanol end group is changed to one molecule of THF, one new butanol end group is generated,
(N + 1) molecules of THF are generated until the polymer terminal becomes a carboxyl group. Therefore, as the molecular weight of PTMG is large and the content of PTMG in the polymer is large, the amount of THF produced increases.

The problems of the generated THF are as follows. Manufacturing Process (Polycondensation Process) THF generated during polyester manufacturing is released through an exhaust system and causes environmental pollution such as rivers and air. Compounding step The compounding step is a step of kneading stabilizers, pigments, fillers, and the like for the purpose of adding a new function to the polyester. When THF is generated in the step,
This causes poisoning, odor, air pollution and, in some cases, fires to workers. Molding / working process During molding / working, THF is generated and the same problem as the compounding process occurs. In molded / processed products THF in a product oozes out to the product surface during use, contaminating other products in contact and causing corrosion.

The following means (1) to (3) can be considered as a method for suppressing the formation of THF. (1) Method for modifying butanol terminal group Since the formation of THF is caused by a ring closure reaction of the butanol terminal group, it is preferable to modify the butanol terminal group to a stable form.
For example, the following reaction is exemplified.

[0009]

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Here, R-X is a compound active on a hydroxyl terminal group such as an aliphatic or aromatic carboxylic acid, an ester or an acid anhydride thereof, an epoxy compound, an isocyanate compound and the like. The means in each step are as follows.

A) Polycondensation Step The method of blocking a butanol terminal group by adding a stabilizer (RX) in the polyester polycondensation step is the simplest and most convenient method. However, in this method, since the butanol terminal group active in the polycondensation reaction is blocked, it is difficult to adjust the molecular weight, and a high molecular polyester cannot be obtained. In addition, the reaction rate decreases and it takes a long time to produce polyester, which causes problems such as an increase in cost due to a decrease in productivity and a decrease in physical properties due to thermal degradation.

B) Compounding step A method of adding a stabilizer (R-X) in the compounding step and melt-kneading to stabilize the butanol end groups is also a simple and convenient method. However, since the residence time of the melt-kneading is short, the reaction between the stabilizer and the butanol end group occurs unevenly. That is, complete stabilization of the terminal group cannot be expected. Therefore, unreacted stabilizers remain in the product, which oozes out on the product surface, impairing printability and adhesion, and contaminating other products.

C) Molding / Processing Step In the molding / processing step, a method of applying a stabilizer to the polyester or mixing and melt-molding the polyester can be considered, but the same problem as in the compounding step occurs.

(2) Inactivation method using a catalyst A catalyst used for polyester polycondensation is indispensable for a reaction in which THF is generated from a butanol terminal group, and this accelerates the reaction. Therefore, inactivating the catalyst after completion of the polycondensation has a very large effect in suppressing the formation of THF. In general, a phosphorus compound is used for inactivating the catalyst. The means in each step are as follows.

A) Polycondensation step Since the polycondensation reaction does not proceed if the catalyst is inactivated before or during the polymerization reaction, it is necessary to add a deactivating agent such as a phosphorus compound after the polycondensation to inactivate the catalyst. Is common. However, this method inactivates the catalyst by adding and mixing an inactivating agent to the melt having a high melt viscosity, and thus the inactivation is not uniform. In order to completely inactivate the inactivation, it is necessary to carry out melt mixing for a long time, resulting in an increase in cost due to a decrease in productivity and a decrease in physical properties due to thermal degradation.

B) Compounding step and molding / processing step A method of impregnating, coating or mixing a polyester resin with a catalyst inactivating agent or injecting it in the compounding step or molding / processing step to inactivate the catalyst during melt-kneading. Is a simple and convenient means. However, in this method, since the residence time required for melt-kneading is short, the inactivation becomes uneven and the TH
The F suppression effect becomes incomplete. In addition, since the unreacted inactivator remains in the product, it causes printability and adhesiveness to be impaired and contamination of other products.

(3) Adjustment of polymerization temperature during polyester production (during polycondensation) The production of THF from the butanol end group is affected by the polymerization temperature, and the higher the temperature, the more the amount of THF produced. Therefore, setting the polymerization temperature of the polyester to a low temperature is an effective means for suppressing the formation of THF. However, the polymerization temperature is determined by the melting point of the polyester,
Even if the temperature is equal to or higher than the melting point, when the polymerization temperature is lowered, the melt has a high melt viscosity, and there is a limit in terms of equipment such as stirring and mixing and stirring load. Also, when the polymerization temperature is lowered, the reaction rate of the polycondensation is reduced, the polymerization time is greatly extended, and the production is lowered, thereby causing a cost increase.

As described above, any of the conventional methods has the advantage of being simple, but has many problems and is not practical as a technique for suppressing the production of THF.

[0019]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a polymer production process, a compounding process, and a molding / processing process.
The production of THF is reduced, so that the exhaust gas does not pollute the environment such as rivers and the atmosphere, does not cause harm to workers, and furthermore, exudes to the obtained product surface and corrodes. Another object of the present invention is to provide a polyester composition containing a polyester having a TMG unit or a PTMG unit so as not to contaminate other products to be contacted.

[0020]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and have found that TMG or glycol obtained by chemically modifying both ends of PTMG is used as a polymerization component.
And the incorporation of a specific silicon compound to suppress the production of THF in the polyester,
The present invention has been completed.

That is, the present invention is as follows. A repeating unit represented by the following general formula (I) and
Having a repeating unit represented by the general formula (II),
In the polymer, a repeating unit represented by the general formula (II)
More than 0 mol% and 100 mol% or less, the general formula
R in (II) ^ThreeHas the following general formula (III) and
Polyoxyalkylene group represented by the following general formula (IV)
And R^ThreeFor all polyoxyalkylene groups represented by
To obtain a polyoxyalkylene represented by the general formula (IV)
A polyester having 20 to 100 mol% of a len group;
Polyester containing lanol group-containing silicon compound
Ter composition.

[0022]

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[0023]

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[0024]

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[0025]

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Wherein R ¹ and R ² represent an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group, an arylene group or an arylalkylene group, p represents an integer of 0 to 60, and r represents 1 to 50. And q and s are each 0 to
Represents an integer of 50, q + s is 1 or more, and R ⁴ , R ⁵
Represents the same or different and represents a hydrogen atom or an alkyl group. ] The polyester composition according to the above, wherein the reduced viscosity of the polyester is 0.1 dl / g or more. The polyester composition as described above, wherein the silicon compound has at least 10 ¹⁸ silanol groups / g. The polyester composition as described above, wherein the silicon compound having a silanol group is silicon dioxide. The polyester composition according to the above or the above, wherein the content of the silicon compound is 0.1% by weight or more.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyester composition of the present invention contains a polyester and a silicon compound having a silanol group.

Hereinafter, the present invention will be described in detail. The polyester used in the present invention has the repeating units of the above general formulas (I) and (II).

The alkylene group having 2 to 20 carbon atoms for R ¹ in the above general formulas (I) and (II) may be linear or branched, and preferably has 2 to 10 carbon atoms. Specific examples include ethylene, propylene, tetramethylene, hexamethylene, octamethylene, nonamethylene, and the like.

The cycloalkylene group represented by R ¹ in the general formulas (I) and (II) preferably has 5 carbon atoms.
To 20, specifically 1,4-cyclohexylene, 1,3-cyclopentylene, 1,8-cyclooctylene and the like.

The arylene group represented by R ¹ in the general formulas (I) and (II) preferably has 6 to 20 carbon atoms.
Specific examples thereof include 1,4-phenylene, 1,3-phenylene, 4,4′-biphenylene, 2,6-naphthylene, and 2,6-anthracenylene.

The arylalkylene group represented by R ¹ in the general formulas (I) and (II) preferably has 7 carbon atoms.
To 30 and the alkylene portion thereof may be either a straight chain or a branched chain. Specifically, 1,4-tolylene, 1,4-
Xylylene, 1-methylphenylene, 1-methylnaphthylene, 2-ethylnaphthylene and the like are exemplified.

Among these R ¹ , 1,4-phenylene and 2,6-naphthylene are preferred.

The alkyl group represented by R ⁴ and R ⁵ in the general formula (IV) may be either linear or branched, and preferably has 1 to 6 carbon atoms. Specifically, methyl, ethyl, propyl, butyl and the like are exemplified.

In the general formula (III), p is preferably 1
It is an integer of 0 to 40.

In the general formula (IV), q is preferably 1 to
An integer of 10, r is preferably an integer of 10 to 40, and s is preferably an integer of 1 to 10. Further, (q + s) is preferably 2 to 20, more preferably 2 to 16.

In the polyester used in the present invention,
Is a group represented by R in the above general formula (II) ^ThreeIs the above general formula
(III) and a polio represented by the above general formula (IV)
A xyalkylene group;^ThreeAll polyoxy represented by
The alkylene group is represented by the above general formula (IV)
The ratio of the polyoxyalkylene group is 20 to 100 mol
%, Preferably 30-100 mol%, more preferably 4%
0 to 100 mol%. Represented by the above general formula (IV)
Less than 20 mol% of polyoxyalkylene groups
Effect of suppressing the formation of THF in polyester
Less is. Accordingly, the poly (III) represented by the general formula (III)
The ratio of the lioxyalkylene group is R^ThreeAll poly indicated by
80 mol% or less with respect to the oxyalkylene group, preferably
At most 70 mol%, more preferably at most 60 mol%.
is there.

In the polyester used in the present invention, the proportion of the repeating unit represented by the general formula (II) in the polymer is more than 0 mol% and 100 mol% or less, preferably 10 to 100 mol%. Mol%, more preferably 20 to 100 mol%, particularly preferably 30 to 100 mol%.
Mol%.

The polyester used in the present invention comprises, as a glycol component, a glycol represented by the following general formula (V) (hereinafter also referred to as PTMC, including the case where r = 1):
Use In the general formula (V), R ⁴ , R ⁵ ,
q, r and s have the same meanings as in the case of the above general formula (IV).

[0040]

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As shown in the following reaction, the glycol (PTMC) represented by the general formula (V) is poly (1,4-tetramethylene glycol) (hereinafter also referred to as PTMG, including the case where r = 1). To a hydroxyl terminal group of the above by ring-opening addition of an alkylene oxide such as ethylene oxide (hereinafter also referred to as EO) or propylene oxide (hereinafter also referred to as PO). The alkylene oxides may be used alone or in a combination of two or more.

[0042]

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(Wherein, R represents R ⁴ and / or R ⁵ )

In the glycol (PTMC) represented by the general formula (V) obtained by the above reaction, the PTM
The ratio at which the hydroxyl end group of G is capped with an alkylene oxide such as EO or PO is preferably 20 to 1
The amount is 00 mol%, preferably 30 to 100 mol%, particularly preferably 40 to 100 mol%. If the capped ratio is less than 20 mol%, the resulting polyester contains many uncapped PTMG units, so that the effect of suppressing the formation of THF is reduced.

In the above reaction, the amount of the alkylene oxide such as EO and PO and the addition reaction conditions depend on the amount used.
The rate at which the hydroxyl end groups of poly 1,4-tetramethylene glycol (PTMG) are capped is different. Theoretically, alkylene oxides such as EO and PO are PT
If 2 moles per 1 mole of MG, both hydroxyl end groups of PTMG will be completely capped, but in practice, it will compete with its own polymerization reaction such as EO, PO, etc.
It is difficult to completely cap both hydroxyl end groups of MG. In particular, it is more difficult when the amounts of EO and PO are small. However, if too large, the ether bond in the obtained polyester increases, heat resistance and weatherability deteriorate, and further,
Water absorption and hygroscopicity are increased, and there are adverse effects such as a decrease in hydrolysis resistance and deformation of a molded product. Therefore, E
The amount of the alkylene oxide such as O and PO to be used is preferably 1 to 30 mol, more preferably 1.5 to 25 mol, particularly preferably 2 to 1 mol of poly 1,4-tetramethylene glycol (PTMG). ２０20 mol.

In the glycol (PTMC) represented by the above general formula (V) obtained by the above reaction,
Addition amount of alkylene oxide such as EO and PO (that is,
q + s) is 1 mol or more, preferably 2 mol or more, more preferably 2 to 20 mol.

The glycol (PTMC) represented by the above general formula (V) obtained here may be directly subjected to a polymerization reaction without isolation, but in this case, unreacted PTMG is contained. May have been

The molecular weight of the polyoxyalkylene group represented by the general formula (IV) is preferably about 400 to 400.
It is 4000, more preferably 600 to 4000, and particularly preferably 800 to 3000. If the molecular weight is less than 400, the resulting polyester is inferior in properties such as flexibility, elongation, and rubbery elasticity. On the other hand, if it exceeds 4,000, the production cost of PTMC is high, phase separation occurs, and strength and elongation are increased. Mechanical properties such as degree may be inferior.

In the polyester used in the present invention, examples of the acid component to be used include an acid component corresponding to R ¹ in the repeating units represented by the above general formulas (I) and (II). Specifically, terephthalic acid,
Isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,
Examples include 4′-biphenyldicarboxylic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, dimer acid, and the like. Of these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable.

In the polyester used in the present invention, the glycol (PTM) of the above general formula (V) used
C), poly 1,4-tetramethylene glycol (PTM
Glycols other than G) include all glycol components capable of forming a polyester. In particular,
Ethylene glycol, propylene glycol, 1,3-
Trimethylene glycol, 1,4-tetramethylene glycol, 1,5-pentamethylene glycol, 1,6-
Hexamethylene glycol, 1,4-cyclohexane dimethanol, polyethylene glycol, polypropylene glycol and the like can be mentioned.

The above polyester may use a hydroxycarboxylic acid as a polymerization component. Examples thereof include p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxy-6-carboxynaphthalene, and 3-hydroxy-carboxylic acid.
Examples thereof include 6-carboxynaphthalene, glycolic acid, lactic acid, and the like, and ester-forming derivatives thereof. Among these, p-hydroxybenzoic acid and m-hydroxybenzoic acid are preferred.

The polyester may be a cyclic ester as a polymerization component. Examples thereof include ε-caprolactone, valerolactone, enantholactone, glycoxide, and lactide. Of these, ε-caprolactone is preferred.

In addition to the above components, it is also possible to use a polyfunctional component such as trimellitic acid, pyromellitic acid, glycerin, trimethylenepropane or the like as long as the linearity of the polyester is not substantially impaired. It is.

In the present invention, preferred polyesters are specifically shown as follows. (1) homopolymer terephthalic acid // PTMC 2,6-naphthalenedicarboxylic acid // PTMC adipic acid // PTMC sebacic acid // PTMC (2) copolymer terephthalic acid / isophthalic acid // PTMC terephthalic acid / 2,6-naphthalene Dicarboxylic acid // PT
MC 2,6-naphthalenedicarboxylic acid / isophthalic acid // PT
MC adipic acid / sebacic acid // PTMC terephthalic acid // PTMC / ethylene glycol terephthalic acid // PTMC / TMG terephthalic acid // PTMC / 1,3-propylene glycol terephthalic acid // PTMC / cyclohexanedimethanol 2,6-naphthalene Dicarboxylic acid // PTMC / ethylene glycol 2,6-naphthalenedicarboxylic acid // PTMC / 1,3-
Propylene glycol 2,6-naphthalenedicarboxylic acid // PTMC / cyclohexanedimethanol 2,6-naphthalenedicarboxylic acid // PTMC / TMG 2,6-naphthalenedicarboxylic acid // PTMC / ethylene glycol 2,6-naphthalenedicarboxylic acid // PTMC / cyclohexanedimethanol adipic acid // PTMC / ethylene glycol adipic acid // PTMC / 1,3-propylene glycol adipic acid // PTMC / hexamethylene dimethanol sebacic acid // PTMC / ethylene glycol sebacic acid // PTMC / 1 , 3-propylene glycol sebacic acid // PTMC / hexamethylene dimethanol terephthalic acid / isophthalic acid // PTMC / TMG terephthalic acid / isophthalic acid // PTMC / ethylene glycol terephthalic acid / isophthalic acid // PTMC / cyclohexanedimethanol 2,6-naphthalenedicarboxylic acid / isophthalic acid // PT
MC / TMG 2,6-naphthalenedicarboxylic acid / isophthalic acid // PT
MC / ethylene glycol 2,6-naphthalenedicarboxylic acid / isophthalic acid // PT
MC / cyclohexanedimethanol, terephthalic acid / 2,6-naphthalenedicarboxylic acid // PT
MC / TMG terephthalic acid / 2,6-naphthalenedicarboxylic acid // PT
MC / ethylene glycol terephthalic acid / 2,6-naphthalenedicarboxylic acid // PT
MC / cyclohexane dimethanol

The amount of the copolymer component is not particularly limited as long as it does not impair the inherent properties of the homopolyester.
It is at most 7 mol%, preferably at most 6 mol%. If the copolymerization exceeds 7 mol%, the melting point, mechanical properties, and the like of the polyester are greatly changed and generally tend to be poor.

The reduced viscosity of the polyester used in the present invention is 0.1 dl / g or more, especially 0.2 to 2.5 dl / g.
g is preferred. In the present invention, the reduced viscosity is determined by using phenol / tetrachloroethane (60/40, weight ratio) as a solvent and a resin concentration of 0.2 g / 100 ml.
It is measured at a temperature of 30 ° C. using an Ostwald viscometer.

For the production of the polyester, a conventionally known polyester production method is employed. Specifically, a transesterification reaction is carried out between an ester of dicarboxylic acid (preferably dimethyl ester) and a glycol component in the presence of a catalyst. Then, transesterification method of producing polyester by performing polycondensation; direct esterification of dicarboxylic acid and glycol component in the presence of a catalyst or under non-catalytic conditions and then conducting polycondensation to produce polyester Chemical method.

In the above reaction, a catalyst may be used. For example, Mg, Ca, Sr, Zn, Cd, Pb, M
oxides such as n, Co, Ti, Sn, Sb, and Ge, and compounds such as carboxylate, carbonate, and alkoxide;
Among them, compounds of Ti, Sb, Ge, Sn, Mn, Co, and Zn are preferably used.

In the above reaction, stabilization with a phosphorus compound is performed for the purpose of avoiding side effects of the catalyst (for example, a decrease in heat resistance and hydrolysis resistance).
Examples of the phosphorus compound used herein include phosphoric acid, phosphorous acid and esters thereof; phosphonic acid, phosphinic acid and esters thereof; alkylphosphonic acid, arylphosphonic acid and esters thereof; alkylphosphinic acid and aryl Examples thereof include phosphinic acid and esters thereof, and a phosphorus compound that can be generally used in producing a polyester can be used.

The addition time of the phosphorus compound is generally after the end of transesterification or after the end of the esterification reaction, but the addition time can be arbitrarily selected according to the purpose.

Further, many kinds of stabilizers, pigments, fillers, release agents, etc. can be added to the above polyester for the purpose of improving heat resistance, light resistance, coloring of resin, physical properties and releasability. is there.

The polyester used in the present invention is a polyester obtained by capping the hydroxyl end group of poly 1,4-tetramethylene glycol (PTMG) with an alkylene oxide such as ethylene oxide (EO) or propylene oxide (PO). Since the glycol (PTMC) of the general formula (V) is used as a glycol component, the proportion having a butanol terminal group is small. Therefore, it is considered that the production of THF caused by the ring closure reaction of the butanol terminal group can be reduced.

The polyester composition of the present invention contains a silicon compound having a silanol group (—Si—OH) in addition to the above polyester. The silicon compound suppresses the formation of THF by a ring closure reaction of the butanol end group of the polyester.

The reaction mechanism is as follows. Since the polymerization catalyst (for example, Ti) of the polyester accelerates the THF generation reaction, it is presumed that the catalyst coordinated to the butanol terminal group becomes the active site of the reaction.

[0065]

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However, when a silicon compound having a silanol group is present, the silanol group coordinates to the butanol terminal group as shown below.

[0067]

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The coordination ability to the butanol end group is considered to be much higher for the silanol group than for the polyester polymerization catalyst (eg, Ti). The following equilibrium exists:

[0069]

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That is, it is considered that by adding a certain amount or more of the silicon compound, a silanol group coordinates to a butanol terminal group, thereby inhibiting the coordination of the polymerization catalyst (eg, Ti). In other words, the coordination of the silanol groups of the silicon compound to the butanol end groups results in THF
It is thought to suppress the production reaction.

The silicon compound used in the present invention has preferably at least 10 ¹⁸ / g, more preferably at least 10 ¹⁹ / g, particularly preferably at least 10 ²⁰ / g. If the number of silanol groups is less than 10 ¹⁸ / g, the effect of suppressing the formation of THF from the polyester may be poor. The upper limit is not particularly limited, but is preferably about 10 ³⁰ .

In the present invention, the number of silanol groups in the silicon compound is measured by the following method. (1) Method of measuring the number of silanol groups in an inorganic silicon compound Using a thermogravimetric analyzer TGA-50 manufactured by Shimadzu Corporation under a dry air atmosphere of 20 ml / min, at a temperature rising rate of 10 ° C./min from room temperature to 1000 The temperature was raised to 200 ° C., and the remaining sample weights at 200 ° C. and 900 ° C. were determined from the thermogravimetric analysis chart and calculated by the following equation. Number of silanol groups (pieces / g) = 2 × ｛(W−W ₁ ) / 18
W｝ × 6.02 × 10 ²³ W: weight of residual sample at 200 ° C. W ₁ : weight of residual sample at 900 ° C.

(2) Method for measuring the number of silanol groups in the organosilicon compound The number of silanol groups in 1 g of the organosilicon compound can be calculated by the following equation. Number of silanol groups (pieces / g) = (N / W) × 6.02 × 1
0 ²³ N: Number of silanol groups in one molecule of organosilicon compound W: Molecular weight of organosilicon compound

The above-mentioned silicon compounds having a silanol group used in the present invention can be generally classified into inorganic compounds and organic compounds. Inorganic silicon compounds having a silanol group Inorganic silicon compounds having a silanol group include, in general, silicon dioxide, hydrated silicon dioxide, hydrated amorphous silicon dioxide, fumed colloidal silica, fume colloidal silica, and the like. Among them, those having a silanol group number of 10 ¹⁸ / g or more are used. Among them, hydrous silicon dioxide and hydrous amorphous silicon dioxide are suitably used in the present invention. Both compounds can be purchased commercially and used, for example, Nipsil E-200A and Nipsil G-30 manufactured by Nippon Silica Industry Co., Ltd.
0, Nipgel CX-200, Nipgel CX-8
00, Nip Gel AZ-200, Nip Gel BY-
601 and the like.

Organosilicon Compounds Having Silanol Groups There are many organosilicon compounds having silanol groups. Representative examples are trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, tripentylsilanol, trihexylsilanol, and triheptylsilanol. , Trioctylsilanol, dimethylsilanediol, diethylsilanediol, dipropylsilanediol, dibutylsilanediol, dipentylsilanediol, dihexylsilanediol, diheptylsilanediol, dioctylsilanediol, methylsilanetriol, ethylsilanetriol, propylsilanetriol , Butylsilanetriol, pentylsilanetriol, hexylsilanetriol, heptylsilane Triol, octylsilanetriol, triphenylsilanol, trinaphthylsilanol, diphenylsilanediol, dinaphthylsilanediol, phenylsilanetriol, naphthylsilanetriol, and the like. Among them, those having a silanol group number of 10 ¹⁸ / g or more Is used. Among these, methylsilanetriol, ethylsilanetriol, dimethylsilanediol, diethylsilanediol, phenylsilanetriol, naphthylsilanetriol, diphenylsilanediol, and dinaphthylsilanediol are preferred.

In the present invention, the number of silanol groups in the polyester composition is preferably at least 10 ¹⁵ , more preferably at least 10 ¹⁷ , particularly preferably at least 10 ¹⁸ . If the number of silanol groups is less than 10 ^{15, the} effect of suppressing the formation of THF from the polyester may be poor.

The content of the silicon compound in the polyester composition of the present invention varies depending on the type, the number of silanol groups, the type of polyester used, and the like, but the number of silanol groups in the polyester composition is 10 ¹⁵ or more. Such an amount is preferable. For example, when the silicon compound is silicon dioxide, it is preferably at least 0.1% by weight, more preferably at least 0.2% by weight in the composition. The higher the content, the greater the effect of suppressing the production of THF. However, even if it increases unnecessarily, the effect will not be commensurate with the increase and the cost will increase. Problems such as roughening occur.

In the case of an organic silicon compound,
Preferably at least 0.05% by weight, more preferably 0.1% by weight.
% By weight or more, particularly preferably 0.2% by weight or more.
The higher the content, the greater the effect of suppressing the production of THF. However, even if it increases unnecessarily, the effect is not commensurate with the increase and the cost increases.

The above silicon compound is added to the polyester by the following method. (1) Polyester production step (polycondensation step) This is a method of adding a silicon compound when producing a polyester from dicarboxylic acid and its diester and glycol. The silicon compound can be added in any process from the time when the polyester production raw materials are charged into the reactor to the time when the polycondensation ends and the polymer is taken out.

(2) Compounding step The addition of the silicon compound is also possible in the compounding step. The silicon compound can be applied to the polyester resin or compounded as a master pellet at the same time as the polyester resin. Furthermore, it is also possible to add during the compounding step.

(3) Molding Step It is also possible to add a silicon compound to the resin by applying it to the resin during the molding of the polyester.

Among the above-mentioned steps (1) to (3), the addition of the silicon compound to the polyester during the production of the polyester (during the polycondensation) is carried out because the addition operation is simple and uniform mixing is possible. Particularly, it is preferable to supply the polyester raw material to the reactor. In addition, the silicon compound can be added in the as-acquired form as it is, or in a state previously dispersed or dissolved in glycol used as a raw material of the polyester, or in the form of a master pellet containing the silicon compound, in any state. It is.

In the present invention, the formation of THF can be further suppressed by adding a silicon compound to the polyester in addition to using the polyester as described above.

[0084]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the measuring method of the generated THF amount is shown.

1. Method of measuring THF The THF was measured by dissolving 1 g of resin in 10 ml of m-cresol, adding the solution to 20 ml of methanol to precipitate the resin, and then subjecting the supernatant to gas chromatography.
It was measured by GC-14B (manufactured by Shimadzu Corporation). The amount of THF in the resin used toluene as an internal standard compound.

2. Definition of ΔTHF (ppm / min) ΔTHF (ppm / min) = ([THF] ₂ − [TH
F] ₁ ) / 30 [THF] ₁ : The amount of THF (ppm) in the resin determined by the above-mentioned THF measurement method after drying the resin at 120 ° C. under reduced pressure for 16 hours. [THF] ₂ : 3 g of the resin dried under reduced pressure with [THF] ₁ was placed in an ampoule tube, and the vacuum replacement with nitrogen was repeated three times.
The pressure was adjusted to 100 mmHg with nitrogen, and the tube was sealed. Place the sealed ampoule in an oil bath set at 245 ° C.
After holding for 0 minutes, the resin was quenched in liquid nitrogen and the resin was taken out. The THF content (ppm) determined by the THF measurement method described above.

3. Meaning of ΔTHF (ppm) ΔTHF is an index of the amount of THF generated in a compounding step or a molding / processing step. Therefore, the smaller the ΔTHF, the smaller the compounding process or molding / forming process.
This means that the amount of THF generated in the processing step and the amount of THF in the molded / processed product are small. This ΔTHF
Varies depending on the copolymerization ratio of TMG and / or PTMG with other glycol components or the molecular weight of PTMG. In general, the larger the copolymerization ratio of TMG and PTMG, and the larger the molecular weight of PTMG, the greater the ΔT
HF increases. In the present invention, ΔTHF is preferably 100 ppm / min or less, more preferably 7 ppm / min.
It is 0 ppm / min or less.

The number of silanol groups in the silicon compound is as follows:
It was calculated by the method described above.

Example 1 In a transesterification reactor, 9580 parts of dimethyl terephthalate (hereinafter also referred to as DMT), 7380 parts of TMG, PTMC having a molecular weight of 1000 and 2 moles of EO were added to PTMC having a molecular weight of 1090 (PTMC). -1) to 1240
Parts, 120 parts of nip gel CX-800 having 3.035 × 10 ²¹ silanol groups / g, 12 parts of titanium tetrabutoxide as a catalyst and 24 parts of Ionox 330 (manufactured by Ciba Geigy) as a stabilizer,
A transesterification reaction was performed at 120 ° C. to 220 ° C. for 90 minutes. After the reaction is completed, the contents are transferred to a polycondensation reactor and
The temperature was raised from 20 ° C. to 245 ° C. in 60 minutes. During this time, the degree of vacuum in the reactor was set to 0.15 mmHg, and
It was polycondensed for 05 minutes. The reduced viscosity of the obtained polyester resin was 1.098 dl / g, and the content of silicon dioxide was 1% by weight. The resin was dried under reduced pressure at 120 ° C. for 16 hours and then heat-treated at 245 ° C. for 30 minutes. The amount of THF was increased from 8 ppm to 182 ppm by the heat treatment.
THF was 5.8 ppm / min.

Examples 2 to 4 and Comparative Examples 1 to 12 In Example 1, the PTMCs shown in Table 1 were used in place of PTMC-1. The polyester was obtained in the same manner as in Example 1 except that the polyester was changed as shown in Table 1. Table 2 shows the reduced viscosity and silicon dioxide content of the obtained polyester resin. After drying under reduced pressure at 120 ° C. for 16 hours, heat treatment was performed at 245 ° C. for 30 minutes, and the amounts of THF and ΔTHF before and after the heat treatment are also shown in Table 2.

Example 5 In a transesterification reactor, 6,000 parts of dimethyl 2,6-naphthalenedicarboxylate (hereinafter also referred to as DMN), 30 parts of
10 parts of TMG, 580 of PTMC-2 shown in Table 1
0 parts, 240 parts of nip gel BY-601 having 1.919 × 10 ²¹ silanol groups / g, 12 parts of titanium tetrabutoxide as a catalyst, and 24 parts of Ionox 330 as a stabilizer were added to the ester in the same manner as in Example 1. Exchange reaction and polycondensation were performed. The reduced viscosity of the obtained polyester resin was 1.358 dl / g, and the content of silicon dioxide was 2% by weight. The resin was dried under reduced pressure at 120 ° C. for 16 hours and then heat-treated at 245 ° C. for 30 minutes. The amount of THF was increased from 2 ppm to 554 ppm by the heat treatment, and ΔTHF was 18.4 ppm / min.

Comparative Examples 13 to 15 Polyesters were obtained in the same manner as in Example 5, except that the kind and amount of PTMC and the presence or absence of the silicon compound were changed as shown in Table 2. . Table 2 shows the reduced viscosity and silicon dioxide content of the obtained polyester resin. After drying under reduced pressure at 120 ° C. for 16 hours, heat treatment was performed at 245 ° C. for 30 minutes, and the amounts of THF and ΔTHF before and after the heat treatment are also shown in Table 2.

[0093]

[Table 1]

[0094]

[Table 2]

Example 6, Comparative Example 16 After drying the resin obtained in Example 3 and Comparative Example 7 under reduced pressure,
Solid injection molding machine SAV-100-7 manufactured by Yamashiro Manufacturing Co., Ltd.
5 at a molding temperature of 240 ° C and a thickness of 2mm, 100m
An m square plate was fabricated. About the obtained flat plate, the THF content, hardness, tensile strength, elongation, tear strength and Vicat softening point before and after molding were measured. Table 3 shows the results.

[0096]

[Table 3]

The hardness, tensile strength, elongation, tear strength and Vicat softening point of the obtained flat plate were measured by the following methods. Hardness (Shore D) Measured according to ASTM D2240. Tensile strength Measured according to ASTM D638. Elongation Measured according to ASTM D638. Tear strength Measured according to ASTM D624. Vicat softening point Measured according to ASTM D1525.

[0098]

As is apparent from the above description, the polyester composition of the present invention suppresses the formation of THF in the polymer production process, compounding process and molding / processing process.
Therefore, the exhaust gas does not pollute the environment such as rivers and the atmosphere, and does not cause harm to workers.
It does not leach onto the resulting product surface and corrode or contaminate other products in contact.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Hiroshi Hashimoto 10-24 Toyocho, Tsuruga City, Fukui Prefecture Inside the Tsuruga Plant of Toyobo Co., Ltd. (72) Seiji Endo 10-24 Toyocho Tsuruga City, Fukui Prefecture Toyobo Co., Ltd. Tsuruga Plant F-term (reference) 4J002 CF031 CF041 CF051 CF061 CF081 EX046 FD206 4J029 AA03 AB01 AC01 AC02 BF08 CA02 CA04 CA06 CB05A CB06A CB10A CC06A JC713

Claims (5)

[Claims] 1. A compound having a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II), wherein the repeating unit represented by the general formula (II) is
In the polymer, more than 0 mol% and 100 mol% or less;
R ³ in the general formula (II) is represented by the following general formula (II)
I) and a polyoxyalkylene group represented by the following general formula (IV), wherein the polyoxyalkylene group represented by the general formula (IV) is 20 to 100 with respect to all polyoxyalkylene groups represented by R ^3. A polyester composition containing a mol% of a polyester and a silicon compound having a silanol group. Embedded image Embedded image Embedded image Embedded image [Wherein, R ¹ and R ² are an alkylene group having 2 to 20 carbon atoms;
Represents a cycloalkylene group, an arylene group or an arylalkylene group, p represents an integer of 0 to 60, and r represents 1 to 60
It is an integer of 50, q and s each represent an integer of 0 to 50, q + s is 1 or more, and R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or an alkyl group. ] 2. The reduced viscosity of the polyester is 0.1 dl /
The polyester composition according to claim 1, wherein the amount is not less than g. 3. The polyester composition according to claim 1, wherein the silicon compound has at least 10 ¹⁸ silanol groups / g. 4. A silicon compound having a silanol group,
The polyester composition according to claim 3, which is silicon dioxide. 5. The polyester composition according to claim 3, wherein the content of the silicon compound is 0.1% by weight or more.