JPS63284220A - Manufacture of modified polyester - Google Patents

Abstract

PURPOSE:To obtain a polyester which gives a molded product excellent in surface smoothness and improved in lubricating properties and release properties, by reacting a specific modified polyorganosiloxane and a specific compound with terephthalic acid and an alkylene glycol added thereto. CONSTITUTION:In the manufacture of a polyester by reacting a difunctional carboxylic acid comprising as a main component terephthalic acid or a derivative thereof capable of forming an ester with an alkylene glycol or a derivative thereof capable of forming an ester, a modified polyorganosiloxane of formula I having an average molecular weight of 1,000-6,000 or a derivative thereof capable of forming an ester is added in an amount of 0.5-5wt.% per unit weight of the polymer that will be produced in any stage before the completion of the reaction, and further a compound of formula II is added in an amount with will satisfy formula III [wherein W is the amount (ppm) of A derived from the above compound for the polymer that will be produced].

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing modified polyester, and more specifically to a method for producing a modified polyester, and more specifically to provide a molded article, especially a film, which has excellent surface flatness and improved slipperiness and mold release properties. This invention relates to a method for producing modified polyester.

Prior art and its problems Polyester, especially polyethylene terephthalate, has been widely used for slick films, fibers, etc. due to its excellent mechanical and chemical properties. However, when manufacturing molded products, particularly films, that take full advantage of its transparency, process defects often occur during the molding and processing steps. This is often due to a high coefficient of friction.

Conventionally, methods to reduce the coefficient of friction of polyester include adding inorganic particles or precipitating catalysts to create fine irregularities in the surface of the molded product. Many methods have been proposed.

However, the fundamental problem with this method is that the affinity between the fine particles and polyester is not sufficient, and for example, voids occur around the fine particles during the film forming process, resulting in poor transparency and abrasion resistance of the resulting film. The problem lies in the fact that sexuality, etc., is not something to be satisfied with.

In addition, another method has been proposed in which smoothness is imparted by applying a coating agent. This method has the advantage of overcoming the above-mentioned problems of the method in which fine particles are present in polyester, but on the other hand, it requires a special processing step in the conventional film forming process, resulting in high costs. .

Further, when imparting mold releasability using a coating agent, a special processing step is similarly required.

Furthermore, as another method for lowering the coefficient of friction of polyester, there is an organic substance that imparts a low coefficient of friction to polyester.
For example, a method of mixing polyorganosiloxane is known. However, in the case of this method, it is difficult to find an organic substance that has good polymer compatibility and has a large effect of imparting a low coefficient of friction.

OBJECT OF THE INVENTION The object of the present invention is to improve the above-mentioned problems and to provide a polyester molded product with excellent surface flatness, slipperiness, and release properties without requiring almost any change in the manufacturing process of conventional polyester molded products, especially polyester films. The object of the present invention is to provide a gA manufacturing method for modified polyester that provides molded articles, particularly films, with improved moldability.

Structure/Effects of the Invention According to the present invention, an object of the present invention is to react a difunctional carboxylic acid, mainly terephthalic acid, or an ester-forming derivative thereof with at least one alkylene glycol or an ester-forming derivative thereof. When producing a polyester, at any stage until the reaction is completed, a modified polyorganosiloxane having an average molecular weight of 1,000 to 6,000 represented by the following formula (I) RRR + 1 1 or an ester thereof at least one formable derivative per weight of the produced polymer,
0.5 to 5% by weight, and at least one compound represented by the following formula (II) is added to the compound represented by the following formula (II).
I) 10 (ppn)<W≦8000 (pplm)
This is achieved by a method for producing a modified polyester characterized by adding a satisfactory amount of -.---(III).

The difunctional carboxylic acid or its ester-forming derivative used in the present invention is mainly terephthalic acid or its lower alkyl ester, but other acid components include, for example, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid.

p-β-oxydiethoxybenzoic acid, cepatic acid.

Adipic acid, succinic acid, oxalic acid, diphenyl-4,4
One or more of .degree.-dicarboxylic acid, diphenyl ether-4,4"-dicarboxylic acid, 5-sodium sulfoisophthalic acid, trimellitic acid, lower alkyl or glycol esters thereof, or the like may be used in combination. Such a combined acid component is 30% per total acid component.
The proportion is preferably at most mol %, more preferably at most 20 mol %, especially at most 15 mol %.

Further, examples of the alkylene glycol used in the present invention include ethylene glycol, trimethylene glycol, and tetramethylene glycol.

Examples include pentamethylene glycol, hexamethylene glycol, etc., but among these, ethylene glycol and tetramethylene glycol are particularly preferred. In the present invention, such alkylene glycols can also be used in combination with alkylene glycols or other diols, and are preferred, for example. ! When S-like ethylene glycol or tetramethylene glycol is the main glycol component, other glycol components include, for example, ethylene glycol (when tetramethylene glycol is the main glycol component), propylene glycol, trimethylene glycol, and tetramethylene glycol.

(when ethylene glycol is the main glycol component), neopentyl glycol, hexamethylene glycol, pentamethylene glycol.

One type or two or more types of 1.4-cyclohexanediol, 1.4-cyclohexane dimetatool, bisphenol A, hydroquinone, etc. can be used in combination. The proportion of the glycol component used in combination is preferably 30 mol% or less, more preferably 20 mol% or less, particularly 15 mol% or less, based on the total acid components.

The modified polyorganosiloxane used in the present invention is
Represented by the following formula (I), with an average molecular weight of 1,000 to e, ooo
This is a modified polyorganosiloxane. Examples of lower alkyl for R in the above formula (I) include methyl and ethyl, with methyl being particularly preferred, and phenyl as the aryl for R.

Specific examples of such modified polyorganosiloxanes include:
α,ω-bis(dimethyl-2-hydroxyethylsiloxy)-polydimethylsiloxane.

α,ω-Bis(dimethyl-3-hydroxypropylsiloxy)-polydimethylsiloxane, α,ω-bis(dimethyl-2-hydroxyethoxysiloxy)-polydimethylsiloxane, α-(dimethyl-2-hydroxyethoxysiloxy)- ω-(dimethyl-3-hydroxypropylsiloxy)-polydimethylsiloxane: α-(dimethyl-2-hydroxyethylsiloxy)-polydimethylsiloxane, α-(dimethyl-3-hydroxypropylsiloxy)-polydimethylsiloxane, α- (dimethyl-
Examples include 2-hydroxyethoxysiloxy)-polydimethylsiloxane, α,ω-bis(dimethyl-2-hydroxyethylsiloxy)-polydiphenylsiloxane, and α-(dimethyl-2-hydroxyethylsiloxy)-polydiphenylsiloxane.

The modified polyorganosiloxane may be used as an alkali metal salt (eg, sodium salt, potassium salt, etc.) or as a lower alkyl ester (eg, methyl ester).

It is presumed that a part of the modified polyorganosiloxane in the present invention forms a block copolymer with polyester, and the rest is in a blended state.

As mentioned above, the modified polyorganosiloxane needs to have a molecular weight of 1,000 to 6,000.

If this molecular weight is less than 1,000, the thermal stability of the modified polyester will deteriorate, and for example, the intrinsic viscosity will decrease significantly during melt molding, which is undesirable.If this molecular weight is more than 6,000, This is not preferable because the surface of the molded product, especially the film, becomes rough.

Modified polyorganosiloxane can be added at any stage until the reaction of polyester production is completed. For example, terephthalic acid or dimethyl terephthalate is subjected to an esterification or transesterification reaction with ethylene glycol, and the reaction product is When producing polyester through a polycondensation reaction, the modified polyorganosiloxane may be added at the polycondensation reaction stage, at the esterification or transesterification stage, or at the stage of charging the starting materials. This is the period until the initial polycondensation reaction is completed, and among these, the earliest possible period is more preferable.

The amount of modified polyorganosiloxane added is 0.5 to 5% by weight, preferably 0.8 to 4% by weight, based on the weight of the produced polymer.
Weight%. If this amount added is less than 0.5% by weight,
The effect of improving slipperiness and mold releasability is insufficient, and if it exceeds 5% by weight, the thermal stability of the modified polyester decreases, which is not preferable.

The compound used in combination with the modified polyorganosiloxane in the present invention is a compound represented by the following formula (n). A in the above formula (I[)
When is a nitrogen atom (N), it is a quaternary ammonium compound represented by the following formula (II-1), and when is a phosphorus atom (P), it is a quaternary phosphonium compound represented by the following formula (II-2). .

Examples of the alkyl group for R1 to R4 in these formulas include methyl, ethyl, propyl, n-butyl, hexyl, octyl, capryl, and decyl.

Examples of the aryl group include dodecyl, and examples of the aryl group include phenyl and benzyl. Further, as an anion of X, halogen (for example, bromine) is used.

(chlorine, etc.), droxide, etc.

Specific examples of quaternary ammonium compounds include tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetrao-9-1-luammonium bromide, benzyltriethylammonium bromide, tricaprylmethylammonium chloride, triethyldecyl Ammonium bromide, triethyldodecyl ammonium chloride, tetraphenylammonium bromide, tetramethylammonium hydroxide, tetraethylammonium doroxide.

Tetra n-butylammonium hydroxide.

Tetraoctylammonium hydroxide, benzyltriethylammonium hydroxide.

Tricaprylmethylammonium droxide.

Triethyldecyl ammonium hydroxide.

Triethyldecyl ammonium hydroxide.

Examples include tetraphenylammonium hydroxide. Among these, particularly preferred are tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra n-butylammonium hydroxide, and tetraoctylammonium hydroxide.

Specific examples of quaternary phosphonium compounds include ethyltrioctylphosphonium bromide and hexadecyltributylphosphonium bromide.

Hexadecyltributylphosphonium chloride.

Tetrabutylphosphonium iodide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, ethyltrihexylphosphonium bromide, butyltrioctylphosphonium chloride, butyltrihexylphosphonium iodide, cyclohexyltributylphosphonium bromide, benzyltributylphosphonium chloride, benzyl Triphenylphosphonium chloride, tetraphenylphosphonium iodide, tetraphenylphosphonium bromide,
Tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide.

Preferred examples include tetramethylphosphonium hydroxide and tetraethylphosphonium hydroxide.

In the present invention, by using a quaternary ammonium compound and/or a quaternary phosphonium compound in combination, the modified polyorganosiloxane is dispersed in the obtained polyester or its molded product, although the reason is not clear. In addition, the contact angle between the film and water as measured by the method described below increases.

In the present invention, the amount of the compound represented by formula (It) added is 11 (I) based on the weight of nitrogen atoms and phosphorus atoms (W>10 to 80,001) relative to the resulting polymer. When a quaternary ammonium compound is used as the above compound, the weight (W) in terms of nitrogen atom is 1
It is preferably in the range of 0 to 3600 ppn+,
Furthermore, when using a quaternary phosphonium compound, the weight (W) in terms of phosphorus atom is 20 to 80% of the resulting polymer.
If the amount of the above-mentioned compound added is too small, the effect of improving the dispersibility of the modified polyorganosiloxane in the polyester will be poor;
If it is too large, by-products will be generated in large quantities and the quality of the produced polyester will deteriorate, which is not preferable.

The quaternary ammonium compound and/or the quaternary phosphonium compound can be added at any stage until the reaction for polyester production is completed. this house'! It is preferable to add the modified polyorganosiloxane before starting the fi condensation reaction and after adding the modified polyorganosiloxane.

In the present invention, the modified polyester is produced by conventionally known methods or means accumulated in the art, except for using a modified polyorganosiloxane and a quaternary ammonium compound and/or a quaternary phosphonium compound. can be used.

At that time, a reaction catalyst can be used, and additives such as stabilizer 1 colorant, lubricant, B fuel agent, ultraviolet absorber, etc. can be added as necessary.

In particular, in order to further enhance the thermal stability of the modified polyester, it is preferable to add a stabilizer that is conventionally known or used. This stabilizer is
Examples include phosphorus compounds (for example, sulfuric acid, arsenous acid, phosphinic acid, esters thereof, etc.), hindered phenol compounds, and the like.

The modified polyester thus obtained has an intrinsic viscosity (ortsk-rollophenol, 35°C) of 0.4 or more, and even 0.
．． It is preferable that it is 5 or more.

The modified polyester of the present invention is a polymer with a small coefficient of friction, and molded products thereof, particularly films, have good surface slipperiness and excellent surface flatness. In addition, this modified polyester can contain a small proportion of inert fine particles (lubricant) within a range that satisfies the surface flatness required for the film, and this can synergistically increase the slipperiness. , and it is preferable to do so. Conventionally known methods can be used to incorporate inert fine particles into polyester. When inert fine particles are added, preferred examples of the fine particles include calcium carbonate, titanium oxide, kaolin, clay, and calcium terephthalate.

According to the modified polyester of the present invention, excellent flatness can be achieved, for example, by using conventional manufacturing processes as they are without providing special processing steps for imparting slipperiness and mold release properties in the production of films. A film with improved slip properties and mold release properties can be obtained.

Example Hereinafter, the present invention will be explained in more detail with reference to Examples.

Note that parts in the examples mean parts by weight.

Moreover, each characteristic value was measured by the following method.

1) Intrinsic viscosity It is determined from the solution viscosity measured at 35°C after dissolving a polymer in orthochlorophenol.

2) Coefficient of Dynamic Friction A The value between films is measured by the STM-D-1894B method.

3) Film surface roughness Ra) Measured according to JIS 80601. Stylus 2 surface scaler (SURFCO) manufactured by Tokyo Seimitsu@! 3B) with a needle radius of 2μ and a load fi of 0.07. A chart (film surface roughness curve) is drawn under the conditions of , and from the obtained film surface roughness curve, a part of the measuring length is extracted in the direction of its center line, and the center line of this extracted part is set as the X axis, When the roughness curve is expressed as Y=f(x) with the direction of vertical magnification as the Y axis, the value (Ra; μ) given by the following equation is defined as the film surface roughness.

L Ra = -/l f(x) I dXO In the present invention, the standard length is 0.25+m+, 8 measurements are taken, and the average value of the 5 measurements excluding 3 from the largest value is Ra.
represents.

4) Adhesive strength with removable Scotch adhesive tape #54 was measured by the r-shaped peeling method, and if the width was 50 g/am or less (O); 50 to 15
0 t/C1l width (△); 150 g/an
Evaluate as (width or more).

5) Contact angle The degree of forward contact between the film and water is measured using a contact angle meter (Kyowa Interface Science CA-A model).

Example 1 100 parts dimethyl terephthalate (DMT), 58 parts ethylene glycol, average molecular weight 415. α of f300.

ω-bis(dimethyl-2-hydroxyethoxysiloxy)-polydimethylsiloxane 3.0 parts, manganese acetate 0
．． 038 parts of antimony trioxide and 0.041 parts of antimony trioxide were charged into a reactor, and transesterification was carried out while stirring and distilling off methanol until the internal temperature reached 240"C. After the transesterification reaction was completed, tetraethyl Add 0.038 parts of ammonium hydroxide, then
0.097 part of trimethyl phosphate is added, and the reaction product is subsequently heated to 280 °C under high vacuum.
Polycondensation is carried out under the conditions of °C to increase the intrinsic viscosity [η]')
Q. Obtain a modified polyester of 63.

This modified polyester was dried at 180°C, then melt-extruded to form a film, and then biaxially stretched at 90°C at a stretch ratio of 3.5 times in the weave direction and 4° in the transverse direction, and then further 21
Heat setting was performed at 0° C. for 20 seconds to obtain a biaxially stretched film with a thickness of 15 μm. The slip properties, surface roughness, and peelability of this biaxially stretched film are as shown in Table 1. Moreover, this film showed a contact angle with water of 90 degrees and had good water repellency.

From the results in Table 1, it can be said that this modified polyester is a polymer with excellent properties.

Examples 2 to 4 In Example 2, α,
ω-bis(dimethyl-3-hydroxypropylsiloxy)-polydimethylsiloxane, in Example 3 α-(dimethyl-2-hydroxyethoxysiloxy)-polydimethylsiloxane, and in Example 4 α-(dimethyl-3-
Hydroxypropylsiloxy)-polydimethylsiloxane was used, and the molecular weight and addition amount of the modified polyorganosiloxane were as shown in Table 1. In addition, as the quaternary ammonium compound, in Examples 2 and 3, tetran- Butylammonium hydroxide was used, and tetraphenylammonium bromide was used in Example 4, and the amounts of quaternary ammonium compounds added are shown in Table 1.
Example 1 was carried out in the same manner as in Example 1 except that the procedure was as shown in Example 1.

The results are shown in Table-1.

From the results in Table 1, it can be said that the modified polyesters of Examples 2 to 4 are polymers with excellent properties.

Comparative Example 1 The same procedure as Example 1 was carried out except that tetraethylammonium hydroxide was not added. The results are shown in Table-1.

Comparative Examples 2 to 4 α,ω-bis(dimethyl-2-droxyethoxysiloxy)-polydimethylsiloxane was used as the modified polyorganosiloxane, and its molecular weight and amount added were changed as shown in Table 1. The same procedure as in Example 1 was carried out except for this. The results are shown in Table-1.

In Comparative Example 2, the amount of modified polyorganosiloxane was small, and no effect on the slipperiness of the film was observed.
Furthermore, in Comparative Example 3, the molecular weight of the modified polyorganosiloxane was small and the amount thereof was too large, resulting in poor thermal stability of the polymer, and it can be said that the polyester is not suitable for film production. In addition, in Comparative Example 4, the dispersibility of the modified polyorganosiloxane in polyester was poor;
The film surface is roughened.

Comparative Example 5 The same procedure as Example 1 was carried out except that the modified polyorganosiloxane and the quaternary ammonium compound were not added. The results are shown in Table-1.

Example 5 15 ffi amount percent of calcium carbonate (average particle size 2.5 μm) was added to 85 weight percent of ethylene glycol, mixed and stirred, and then crushed using a sand grinder to obtain calcium carbonate with an average particle size of 0.6 μm. A processed product was obtained.

During the production of polyester, after the transesterification reaction was completed, 0.66 parts of the ethylene glycol slurry of calcium carbonate obtained above was added with stirring (calcium carbonate concentration = 0.1% by weight to polymer). It was carried out in exactly the same manner as in Example 1.

The results are shown in Table-2.

Comparative Example 6 The same procedure as Example 5 was carried out except that the modified polyorganosiloxane and the quaternary ammonium compound were not added. The results are shown in Table-2.

Comparison Solid Line Example 7 Modified polyorganosiloxane and quaternary ammonium compound were not added, and 0.66 parts to 3°3 parts kg of ethylene glycol slurry of calcium carbonate (calcium carbonate concentration 20, 5% by weight to polymer) The same procedure as in Example 5 was performed except for changing to . The results are shown in Table-2.

This film had good slip properties, but the surface was rough.

Example 6 100 parts of dimethyl terephthalate (DMT), 58 parts of ethylene glycol, α with an average molecular weight of 5,600.

ω-bis(dimethyl-2-droxyethoxysiloxy)-polydimethylsiloxane 3.0 parts, manganese acetate 0
．． 038 parts of antimony trioxide and 0.041 parts of antimony trioxide were each charged into a reactor, and the transesterification reaction was carried out while stirring and distilling off methanol until the internal temperature reached 240°C.
After the transesterification reaction was completed, 0.133 parts of tetrabutylphosphonium bromide was added, followed by 0.097 parts of trimethylphosphate-1. Subsequently, the reaction product was heated to a final temperature of 280° C. under high vacuum.
Polycondensation reaction is carried out under the conditions of , and the intrinsic viscosity ([η] )
Obtain a modified polyester of 0.64.

After drying this modified polyester at 180°C, it was melt-extruded to form a film, and then stretched at 90°C in the longitudinal direction at a stretching ratio of 3.5 times.
Biaxially stretched in the transverse direction at a stretching ratio of 4.0 times, and further stretched at 210
Heat setting was performed at °C for 20 seconds to obtain a biaxially stretched film with a thickness of 15 μm. The slipperiness, surface roughness and peelability of this biaxially stretched film are as shown in Table 3. Further, this film showed a contact angle with water of 89.0 degrees, and had good potability.

From the results shown in Table 3, it can be said that this modified polyester is a polymer with excellent properties.

Example 7 Average molecular weight i as modified polyorganosiloxane,
2.0 parts of α,ω-bis(dimethyl-3-hydroxypropylsiloxy)-polydimethylsiloxane of ooo,
In addition, except for using 0.096 parts of tetraphenylphosphonium chloride as the quaternary phosphonium halide,
The same procedure as in Example 6 was carried out. The results are shown in Table 3. From the results in Table 3, it can be said that this modified polyester is a polymer with excellent properties.

Comparative Example 8 The same procedure as Example 7 was carried out except that no quaternary phosphonium halide was added. The results are shown in Table-3.

Comparative Example 9 The same procedure as Example 6 was carried out except that modified polyorganosiloxane and quaternary phosphonium halide were not added.

The results are shown in Table-3.

Procedural amendment July/Sun, 1985

Claims (1)

[Claims] 1. When producing a polyester by reacting a difunctional carboxylic acid, mainly terephthalic acid, or its ester-forming derivative with at least one alkylene glycol or its ester-forming derivative, At any stage until the reaction is completed, the following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) [However, in the formula, R is lower alkyl or aryl,
R_1 is -O-(CH_2)-_lOH or -(CH
_2) -_mOH (where l, m are numbers from 2 to 10), R_2 is the same as R or R_1, and n
represents the degree of polymerization. ] At least one modified polyorganosiloxane or its ester-forming derivative having an average molecular weight of 1,000 to 6,000 expressed by 0% per weight of the produced polymer.
．． 5 to 5% by weight, and further the following formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) [In the formula, A is a nitrogen atom (N) or a phosphorus atom (P), and R
_1, R_2, R_3 and R_4 each represent an alkyl group, an aryl group or a hydrogen atom, X represents an anion, and a represents the number of charges of X. ] At least one compound represented by the following formula (III) 10 (ppm)<W≦8000 (ppm)...(III)
[Wherein, W is A due to the above compound to the produced polymer
(indicates the amount (ppm)). 2. The above compound has the following formula (II-1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... (II-1) [In the formula, R_1, R_2, R_3, R_4, X and a are the same as above. ] It is a quaternary ammonium compound represented by the following formula (III-1): 10(ppm)<W<3600(ppm)...(III-
1) [In the formula, W is the same as above] The manufacturing method according to claim 1, which satisfies the following. 3. The above compound has the following formula (II-2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... (II-2) [In the formula, R_1, R_2, R_3, R_4, X and a are the same as above. ] It is a quaternary phosphonium compound represented by the following formula (III-2): 20 (ppm)<W<8000 (ppm)...(III-
2) [In the formula, W is the same as above] The manufacturing method according to claim 1, which satisfies the following.