JPH0641407A - Modified polyester and film - Google Patents

Abstract

PURPOSE:To obtain the modified polyester excellent in bondability, transparency, and recovery from curling by incorporating given amounts of specific compounds into a polyester. CONSTITUTION:The polymer comprises a polyester [e.g. poly(ethylene terephthalate)] and, incorporated therein, 1-30wt.% ester-forming phosphonium sulfonate compound represented by formula I (wherein A is an aromatic or aliphatic group; X1 is an ester-forming functional group; X2 is H or the same as X1; R1 to R4 each is an alkyl or an aryl; and n is a positive integer) (e.g. tetrabutylphosphonium 3,5-dicarbomethoxybenzenesulfonate) and l-20wt.% compound which is either a dicarboxylic acid containing an ether linkage or an ester-forming derivative thereof and is represented by formula II (wherein R5 is a 4C or higher divalent hydrocarbon group; R6 and R7 each is H or an alkyl; i and j each is 2-4; q is 0 or 1; p is 1-3; and k+m>=4, provided that either may be 0) (e.g. poly(oxyethylene)dicarboxylic acid).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified polyester and a film, and more particularly to a modified polyester and a film having excellent adhesiveness, transparency and flatness. More specifically, the present invention relates to a modified polyester and a film having excellent adhesiveness, transparency and flatness, which are suitable for a photographic support, packaging, general industry, magnetic tape and the like.

[0002]

2. Description of the Prior Art Polyester, especially polyethylene terephthalate, polybutylene terephthalate or poly-
1,4-Cyclohexane dimethylene terephthalate and polyesters mainly containing these have excellent physical and chemical properties, and are widely used as fibers, films or sheets, and molded articles thereof. There is.

In particular, polyester films have excellent heat resistance, chemical resistance, and mechanical properties, and are therefore used in many applications such as magnetic tape, electricity, photography, packaging, and drawing. Has been.

However, since polyester itself is generally inactive, there is a problem that adhesiveness and printability with hydrophilic ink are poor. Conventionally, a method of subjecting the film surface to corona discharge treatment or coating an adhesive substance to improve the adhesiveness of the polyester film is known. However, these methods have drawbacks that not only the process is complicated and the cost is increased, but also the transparency of the film is lowered.

Therefore, these steps are not required, and
Attempts have been made to improve the adhesion from the film itself. For example, in JP-A-52-151365, polyalkylene glycol is used to copolymerize a polyether segment to improve the adhesiveness and printability of the film, but the characteristics are not sufficient.

On the other hand, as a photographic support, a plastic film made of triacetyl cellulose and polyester represented by polyethylene terephthalate is generally used. However, although the polyester film has excellent mechanical properties, transparency, and dimensional stability, in the roll form, the curling curl remains strongly, so that the handleability after development is poor, and the film for X-rays and plate making Its scope has been limited to use in sheet-like form, such as film for use.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned drawbacks of the prior art. In particular, it has excellent adhesiveness without the need for extra high-order processing, transparency, and winding. It is an object of the present invention to provide a modified polyester and a film which have good curl recovery properties and mechanical properties.

[0008]

The above-mentioned object of the present invention is to provide a polyester with 1 to 3 ester-forming phosphonium sulfonate compound represented by the following formula (I).
1 to 2% by weight of an ether bond-containing dicarboxylic acid or ester-forming derivative represented by the following formula (II):
It can be achieved by a modified polyester and a film characterized by containing 0% by weight.

[0009]

[Chemical 2]

(Wherein A is an aromatic group or an aliphatic group, X ₁ is an ester-forming functional group, X ₂ is the same as or different from X ₁ or a hydrogen atom,
R ₁ , R ₂ , R ₃ and R ₄ are the same or different functional groups selected from an alkyl group and an aryl group, and n is a positive integer. R ₅ is a divalent hydrocarbon group having 4 or more carbon atoms, R _5
6 , R ₇ are the same or different and represent hydrogen or an alkyl group. Note that i and j may be 2 to 4, q may be 0 or 1 and p may be 1 to 3, respectively, and k and m may be 0, and k + m is 4 or more. ).

The polyester in the present invention is a polyester mainly composed of an aromatic dicarboxylic acid or an alicyclic dicarboxylic acid and diol. Examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid and phthalic acid. , 1,4-naphthalenedicarboxylic acid, 1,
5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4
Examples thereof include aromatic dicarboxylic acids such as ′ -diphenyl ether dicarboxylic acid and 4,4′-diphenyl sulfone dicarboxylic acid, and examples of the alicyclic dicarboxylic acid component include 1,4-cyclohexanedicarboxylic acid. You can Two or more of these acid components may be used in combination,
Further, aliphatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid and dodecanedioic acid, and oxyacids such as hydroxyethoxybenzoic acid may be partially copolymerized.
Examples of the diol component include ethylene glycol
1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,2-butanediol
1,3-butanediol, 1,4-butanediol
1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-
Cyclohexane dimethanol, 1,4-cyclohexane dimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2'-bis (4'-β-hydroxyethoxyphenyl) propane,
Examples thereof include aliphatic, alicyclic and aromatic diols such as bis (4′-β-hydroxyethoxyphenyl) sulfone. These diol components may be used alone or in combination of two or more. Further, the polyester may be copolymerized with another compound such as a trifunctional or higher functional compound or a monofunctional compound in an amount range in which the polymer is substantially linear. As a typical example of polyester,
Examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexane dimethylene terephthalate.

The ester-forming phosphonium sulfonate compound of the present invention is represented by the following formula (I).

[0013]

[Chemical 3]

In the formula, A represents an aromatic group or an aliphatic group, of which the aromatic group is preferable. X ₁ represents an ester-forming functional group, and specific examples thereof include -OCOR 'and -C.
OOH, -COOR ', - (CH 2) a OH, -O- (CH 2) b [O (CH
₂ ) _b ] _d -OH, -CO- [O (CH ₂ ) _b ] _d -OH (however,
R'is a lower alkyl group or a phenyl group, a and d are integers of 1 or more, and b is an integer of 2 or more. ) Etc. can be mentioned. X ₂ represents an ester-forming functional group or a hydrogen atom which is the same as or different from X _1, and is preferably an ester-forming functional group. R ₁ , R ₂ , R ₃
And R ₄ represent the same or different groups selected from the group consisting of alkyl groups and aryl groups. n is a positive integer.

Specific examples of the sulfonic acid phosphonium salt compound include 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid ethyltributylphosphonium salt,
3,5-Dicarboxybenzenesulfonic acid benzyltributylphosphonium salt, 3,5-dicarboxybenzenesulfonic acid phenyltributylphosphonium salt, 3,5
-Tetraphenylphosphonium dicarboxybenzene sulfonate, 3,5-dicarboxybenzene sulfonic acid butyl triphenylphosphonium salt, 3,5-dicarboxybenzene sulfonic acid benzyl triphenylphosphonium salt, 2,6-dicarboxynaphthalene-4 -Sulfonic acid tetrabutylphosphonium salt, and their methyl or β-hydroxyethyl ester, 4- (β-hydroxyethoxy) benzenesulfonic acid phosphonium salt and the like can be mentioned. Among them, 3,5- is particularly preferable. Examples include dicarboxybenzene sulfonic acid tetrabutylphosphonium salt, 3,5-dicarboxybenzene sulfonic acid phenyltributylphosphonium salt, and their methyl or β-hydroxyethyl esters. That. The amount of the ester-forming phosphonium sulfonate compound is 1 to polyester.
It should be 30% by weight, preferably 3 to 20% by weight, more preferably 5 to 17% by weight, and particularly preferably 9 to 15% by weight.

If the amount of the ester-forming phosphonium sulfonate compound is less than 1% by weight based on the polyester, sufficient adhesive performance and curl curl recovery cannot be obtained, which is not preferable. On the other hand, when it exceeds 30% by weight, the adhesiveness reaches saturation, and on the contrary, high-molecular-weight polyester cannot be obtained, which makes it difficult to form a film or lowers the mechanical strength of the obtained film.

The ether bond-containing dicarboxylic acid or ester-forming derivative in the present invention is represented by the following formula (II).

[0018]

[Chemical 4]

Here, R ₅ is a divalent hydrocarbon group having 4 or more carbon atoms and may contain halogen, oxygen and sulfur.
For example, straight chain or side chain aliphatic hydrocarbon groups such as tetramethylene, hexylene, and 2,2-dimethylpropylene, aliphatic hydrocarbon groups having aliphatic rings such as cyclohexylene, and aromatic hydrocarbons such as phenylene. Groups and the like. R ₆ and R ₇ are the same or different and represent hydrogen or an alkyl group. Further, i and j may be 2 to 4, q may be 0 or 1, p may be 1 to 3, k and m may be 0, and k + m is 4 or more. When k + m is less than 4, heat resistance and mechanical properties are deteriorated, and curling curl recovery is insufficient. The preferred value of k + m is 30 to 500, more preferably k.
+ M is 60 to 300. When k + m exceeds 500, transparency is deteriorated, which is not preferable. The average molecular weight of the ether bond-containing dicarboxylic acid or ester-forming derivative is preferably in the range of 1,000 to 25,000, more preferably 2,000 to 20,000, and particularly preferably 3,000 to 10,000. .

Particularly preferred ether bond-containing dicarboxylic acid or ester-forming derivative is represented by the following formula.

R ₆ OOCCH ₂ O (C ₂ H ₄ O) _m CH ₂ COOR ₇ (wherein R ₆ and R ₇ are the same or different groups and represent hydrogen or an alkyl group. M is 30 to 500) Specific examples of this compound include polyethyleneoxydiglycolic acid and its alkyl ester.

The amount of the ether bond-containing dicarboxylic acid or ester-forming derivative in the present invention must be 1 to 20% by weight, preferably 3% by weight, based on the polyester.
˜17% by weight, more preferably 6 to 15% by weight. If it is less than 1% by weight, the adhesive performance and curl curl recovery are insufficient, and if it exceeds 20% by weight, mechanical properties and heat resistance are deteriorated, which is not preferable.

In the present invention, the method for copolymerizing or incorporating the ester-forming phosphonium sulfonate compound and the ether bond-containing dicarboxylic acid or the ester-forming derivative into the polyester is not particularly limited. The method and timing of blending or addition to the polyester are arbitrary and are not particularly limited, and may be blended and added to the polyester in the powder or molten state. Alternatively, they may be blended and added at any time after the reaction, in the molten state, pellet state, or before molding. In particular, it is preferable to mix and add during the polyester synthesis reaction before the reaction and after the reaction.

As a specific method for producing the modified polyester of the present invention, for example, a polyethylene terephthalate modified polyester comprising a terephthalic acid component and an ethylene glycol component will be described. Terephthalic acid, ester-forming sulfonic acid phosphonium salt compound (for example, 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt) and an ether bond-containing dicarboxylic acid are directly esterified with ethylene glycol, or Dimethyl terephthalate, ester-forming phosphonium sulfonate compounds (eg,
3,5-dicarbomethoxybenzenesulfonic acid tetrabutylphosphonium salt) and an ester-forming derivative of an ether bond-containing dicarboxylic acid, and a first-step reaction for transesterifying ethylene glycol with the first-step reaction. A second step of subjecting the reaction product of step 1 to polycondensation reaction, or B. Terephthalic acid or its ester-forming derivative,
After the completion of the reaction in the first step in which the ester-forming phosphonium sulfonate compound and ethylene glycol are directly esterified or transesterified, the polyester is prepared by the second step in which the reaction product is subjected to a polycondensation reaction. Examples include a method in which an ether bond-containing dicarboxylic acid or an ester-forming derivative is added during arbitrary production until production.

At this time, a conventionally known alkali metal, alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, titanium compound or the like is used as a reaction catalyst, and a phosphorus compound or the like may be used as a coloring preventing agent. .

The glass transition temperature of the modified polyester of the present invention is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher. If the glass transition temperature of the modified polyester is less than 30 ° C., the heat resistance of the formed film is lowered and the film is thermally deformed, which is not preferable. The intrinsic viscosity of the modified polyester of the present invention is preferably 0.3 or more, more preferably 0.35 or more, and particularly preferably 0.4 or more in order to enhance the strength of the formed film.

In order to further improve the adhesiveness, transparency and curl curl recovery which are the objects of the present invention,
Polyalkylene glycol can be further used in combination. For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. can be mentioned. Further, such a polyalkylene glycol may be an organic group having an ester-forming functional group at one end, may have a hydrocarbon group such as an alkyl group, and both ends may have an alkyl group or the like. It may be blocked with a hydrocarbon group. Examples thereof include polyethylene glycol monomethyl ether and polyethylene glycol dimethyl ether. The preferable average molecular weight of the polyalkylene glycol is 300 to 2
0000, and more preferably 400 to 15000
These polyalkylene glycols may be used alone or in combination of two or more. The amount of these polyalkylene glycols is 0.1 to 15 relative to polyester.
The range of wt% is suitable, preferably 0.5 to 10 wt%, more preferably 1 to 8 wt%.

The modified polyester and film of the present invention may optionally contain an organic lubricant such as a flame retardant, a heat stabilizer, an ultraviolet absorber, a pigment, a dye, a fatty acid ester and a wax, or an antifoaming agent such as polysiloxane. May be blended, for the purpose of further improving the slipperiness, clay, mica, titanium oxide, calcium carbonate, kaolin, silica, calcium phosphate, barium sulfate, alumina, or acrylic, styrene, etc. You may mix.

The modified polyester of the present invention can be dried and then melt-extruded to give an unstretched sheet, which is then biaxially stretched and heat-set to give a desired film. The biaxial stretching may be either longitudinal and transverse sequential stretching or biaxial simultaneous stretching, and the stretching ratio is not particularly limited, but usually 2.0 to 5.0 times in the longitudinal and transverse directions is suitable. Further, after the longitudinal and transverse stretching, it may be re-stretched in either the longitudinal or transverse direction.

Further, from the modified polyester of the present invention,
Fibers and other molded products can be manufactured according to a conventional method.

[0031]

EXAMPLES The present invention will now be described in more detail by way of examples. The characteristics in the examples were measured as follows.

A. Intrinsic viscosity of polyester: [η] was measured at 25 ° C using an o-chlorophenol solvent.

B. Glass transition temperature of polyester (T
g), melting point (Tm) Measured by a differential scanning calorimeter.

C. Transparency ASTM-D10 is a film obtained from polyester.
The film haze was measured according to 03-59.

D. Adhesiveness Aluminum was vapor-deposited on the surface of a film obtained from polyester, and cellophane tape was pressure-bonded to the vapor-deposited surface, and the state when peeled off was evaluated. ⊚: No peeling on the cellophane tape side. ◯: 20% or less of the portion peeled off to the cellophane tape side. Δ: 20% to 70% of the portion is peeled off to the cellophane tape side. X: 70% or more of the portion was peeled off to the cellophane tape side.

E. Breaking strength 10 mm width x 5 from a film obtained from polyester
A sample having a length of 0 mm was prepared and measured at a pulling speed of 300 mm / min.

F. Winding curl recovery 35mm width x 1 from a film obtained from polyester
A sample with a length of 33 mm is made, wound on a winding core having a diameter of 10 mm, treated at 70 ° C. × 30% RH × 72 hr, then released from the winding core and immersed in distilled water at 40 ° C. for 30 minutes,
The sample is hung vertically, a load of 30 g is applied, and the sample is dried for 5 minutes in an air thermostat at 50 ° C. Place the processed film sample on a flat surface, and for the original sample length of 133 mm,
The recovery of the sample length was evaluated.

G. Thermal shrinkage 10mm width x 2 from the film obtained from polyester
A sample with a length of 50 to 300 mm is made, the sample is weighted with a 3 g clip, and the sample is treated in a hot air oven set at 150 ° C. The sample length before and after the treatment is measured to determine the heat shrinkage rate. I asked.

Example 1 100 parts by weight of dimethyl terephthalate, 10 parts by weight of 3,5-dicarbomethoxybenzenesulfonic acid tetrabutylphosphonium salt, 70 parts by weight of ethylene glycol and calcium acetate as a transesterification reaction catalyst of 0. 1 part by weight and 0.03 part by weight of antimony trioxide as a polycondensation reaction catalyst were added, and an ester exchange reaction was carried out according to a conventional method, and then 0.05 part by weight of trimethyl phosphate was added. Then, as an ether bond-containing dicarboxylic acid, an average molecular weight of 4
000 polyethyleneoxydicarboxylic acid {HOOCCH ₂ O
10 parts by weight of (C ₂ H ₄ O) _n CH ₂ COOH} was added, and then the temperature was gradually raised and the pressure was reduced, and finally the polycondensation reaction was performed at 280 ° C. and 1 mmHg or less to obtain a polyester. The intrinsic viscosity measured at 25 ° C. using an o-chlorophenol solvent was 0.60.

The obtained polyester was formed into a film at 280 ° C. by a film molding machine, and then stretched at a longitudinal stretching ratio of 3.6 times and a transverse stretching ratio of 3.8 times by a biaxial stretching machine, and then at 190 ° C.
Then, the film was heat treated in order to obtain a film having a thickness of 80μ. The haze of the film was 1.1%, the adhesiveness was good, and the curl curl recovery was evaluated. The film was almost flat without curling. Further, the heat shrinkage rate at 150 ° C. was 1.3%.

Comparative Example 1 Polyethyleneoxydiglycol was prepared in the same manner as in Example 1.
A 3,5-dicarboxybenzenesulfonic acid tetraphosphonium salt copolymerized polyester and a film were obtained without adding acid. Although the intrinsic viscosity of polyester is 0.59 and the haze of the film is as good as 0.9%,
Both the adhesiveness and curl curl recovery were poor.

Examples 2-9, Comparative Examples 2-4 As shown in Tables 1 and 2, various ester-forming phosphonium sulfonate compounds and ether bond-containing dicarboxylic acids were prepared in the same manner as in Example 1. The type and amount were changed to obtain polyester and film.

The results are shown in Tables 3 and 4. Examples 2 to
9 is within the object range of the present invention, the film haze,
Both the adhesiveness and the curl curl recovery were good. On the other hand, Comparative Example 2 did not use the ester-forming phosphonium sulfonate compound, and although the haze of the film was good, both the adhesiveness and curl curl recovery were poor. In addition, in Comparative Example 3, the amount of the ester-forming phosphonium sulfonate compound was the same as that in Comparative Example 4.
The amount of ether bond-containing dicarboxylic acid was out of the range of the present invention, and both had poor adhesiveness and curl curl recovery.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

The abbreviations in the table indicate the following compounds. SIP-B: 3,5-dicarbomethoxybenzenesulfonic acid tetrabutylphosphonium salt SIP-PB: 3,5-dicarbomethoxybenzenesulfonic acid phenyltributylphosphonium salt PEOA: polyethyleneoxydiglycolic acid HOOCCH ₂ O (CH ₂ CH ₂ O) _n CH ₂ COOH PEG: Polyethylene glycol PEGM: Polyethylene glycol monomethyl ether

[0049]

As described above, the present invention provides a modified polyester and a film containing a specific amount of an ester-forming phosphonium sulfonate compound and an ether bond-containing dicarboxylic acid or an ester-forming derivative with respect to the polyester. It has excellent adhesiveness, transparency, and curl curl recovery property, and is preferably used for a photographic support, packaging, general industry, magnetic tape and the like.

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Claims (2)

[Claims] 1. A polyester-containing phosphonium sulfonate compound represented by the following formula (I) in an amount of 1 to 30% by weight and an ether bond-containing dicarboxylic acid or ester represented by the following formula (II) relative to polyester. Modified polyester containing 1 to 20% by weight of a forming derivative (In the formula, A is an aromatic group or an aliphatic group, X ₁ is an ester-forming functional group, X ₂ is the same or different from X ₁ , an ester-forming functional group or a hydrogen atom, R ₁ , R ₂ , R ₃
And R ₄ are the same or different functional groups selected from an alkyl group and an aryl group, and n is a positive integer. R ₅ is a divalent hydrocarbon group having 4 or more carbon atoms, and R ₆ and R ₇ are the same or different groups and represent hydrogen or an alkyl group. Note that i
And j may be 2 to 4, q may be 0 or 1 and p may be 1 to 3, respectively, and k and m may be 0, k
+ M is 4 or more. ). 2. A film made of the polyester according to claim 1.