JPH01103651A - Polyester composition - Google Patents

Abstract

PURPOSE:To provide a polyester composition which can give a film, a fiber, etc. excellent in lubricity, blocking resistance, abrasion resistance, workability, etc., by adding a specified carbon black-grafted polymer to a polyester. CONSTITUTION:Carbon black is reacted with a polymer reactive with it at 0-350 deg.C to produce a carbon black-grafted polymer. Desirable polymers reactive with carbon black are those containing an aziridine group, an oxazoline group, an N-hydroxyalkylamide group or the like (e.g., styrene/isopropenyloxazoline copolymer). The obtained polymer is added to a polyester to produce a polyester composition. This composition can be suitably used in the production of magnetic tapes, packaging films, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to polyester compositions. More specifically, it does not contain carbon black graft polymer obtained by a specific method, has lubricating properties, smoothness, anti-blocking properties,
The present invention relates to a polyester composition that is suitable for molded products such as films and fibers and has excellent abrasion resistance, uniformity, antistatic properties, and workability.

(Prior Art) Polyester, particularly polyethylene terephthalate, is widely used as molded products such as films and fibers. However, when polyester is used as molded products such as films and fibers, there are problems with slipperiness, smoothness, blocking resistance, abrasion resistance, uniformity, and antistatic properties. The above problem also significantly reduces workability during molding, and tends to lead to various troubles.

Conventionally, as a method for solving these problems, it has been proposed to add fine particles of finely powdered silica, talc, carbon black, etc. to polyester. For example, Japanese Patent Application Laid-open No. 71357/1984 has proposed a method for adding a specific carbon black to polyester.

(Problems to be Solved by the Invention) However, according to the prior art, polyester compositions to which carbon black is added have poor slip properties because carbon black inherently has poor dispersibility even if a specific carbon black is used. smoothness, blocking resistance, abrasion resistance,
There is a limit to the improvement in uniformity and antistatic properties, and therefore it is difficult to obtain a polyester composition that is completely satisfactory in terms of workability during molding.

(Means for solving the problem) In view of the current situation, the inventors of the present invention have improved slipperiness, smoothness,
We have conducted extensive research to develop a polyester composition suitable for molded products such as films and fibers that has excellent blocking resistance, abrasion resistance, uniformity, antistatic properties, and workability. As a result, it was discovered that a polyester composition containing a carbon black graft polymer obtained by a specific method can achieve the above object, and the present invention was completed. That is, the present invention relates to a polyester composition containing a CB graft polymer obtained by reacting carbon black (hereinafter referred to as CB) with a polymer having reactivity with CB under conditions of SO °C to 350 °C. It is something.

In the present invention, tamene to obtain a CB graft polymer,
Functional groups on the CB surface (-OH, -COOH1C=.

etc.). As the polymer having reactivity with CB, any polymer having a reactive group that can easily react with a functional group present on the surface of CB can be used without particular limitation. Examples of reactive groups that can easily react with functional groups present on the CB surface include aziridine groups, oxazo phosphorus groups, N-hydroxyalkylamide groups, epoxy groups,
Examples include isocyanate groups, vinyl groups, silicon-based hydrolyzable groups, amine groups, etc. Polymers having reactivity with CB include vinyl-based polymers having one or more of the above-mentioned reactive groups in the molecule; Examples include polyester and polyether. In order to obtain a polymer having such reactivity with CB, for example, a polymerizable monomer having the above-mentioned reactive group in the molecule is required, and other polymerizable monomers are added according to a known procedure. A method of polymerization or a method of reacting a compound having the above-mentioned reactive group in the molecule with a polymer having a group capable of reacting with the compound can be appropriately employed. In the present invention, one or more selected from aziridine groups, oxazoline groups, N-hydroxyalkylamide groups, epoxy groups, and isocyanate groups are used in terms of reactivity with functional groups present on the surface of KCB. It is preferable to use a polymer having as a reactive group, more preferably a polymer having one or more selected from aziridine group, oxazoline group, and N-hydroxyalkylamide group as reactive group. When reacting CB with a polymer having reactivity with CB, substances such as polymer components other than the polymer, polymerizable monomers, organic solvents, etc. may be present in the reaction system.

As a specific example of reacting CB with a polymer having reactivity with CB, for example, 5 to 400 parts by weight, preferably 20 parts by weight of a polymer having reactivity with CB per 100 parts by weight of CB.
~300 parts by weight and 0 to 2 polymers that have no reactivity with CB
0 to 200 parts by weight of a polymerizable monomer and 0 to 200 parts by weight of an organic solvent are stirred and mixed under a temperature condition of 4-O<0>C to 350<0>C, preferably 70<0>C to 300<0>C. In this reaction, CB and #pH are important factors, and in polymers containing highly reactive oxazoline groups and aziridine groups, p
Even if H is 8 or more, a graft compound can be easily obtained, but when the reactivity is low like an epoxy group-containing polymer, the usable pH of CB is.

The pH range is from 2 to 6, preferably from 2 to 4.

In the present invention, polyester is used for films, fibers, etc., and is composed of an aliphatic and/or aromatic polycarboxylic acid and/or polycarboxylic acid ester component and an aliphatic and/or aromatic polyol component. A resin obtained by self-polycondensation of a resin obtained by condensation or a compound having a carboxylic acid and/or carboxylic acid ester group component and a hydroxyl group component in one molecule, or a resin obtained by polycondensation together with the above two components. Specific examples include polyethylene terephthalate, polybutylene terephthalate, polyarylate resin, and polyoxybenzoyl.

The CB graft polymer in the present invention has a weight ratio of 0.001 to 20 in the polyester composition, preferably a polyester having excellent smoothness, uniformity, lubricity, anti-blocking property, and antistatic property. On the other hand, if it exceeds 20% by weight, it is undesirable because it adversely affects the smoothness and strength when processed into films or fibers, and furthermore, the system may break during processing.

Examples of methods for incorporating the CB graft polymer into polyester include the following methods.

(2) A method in which a CB graft polymer is added to a transesterified product of dimethyl terephthalate and ethylene glycol, and polycondensation is performed to obtain the desired polyester composition.

■ A method in which CB graft polymer is added to polyester obtained from dimethyl terephthalate and ethylene glycol and mixed with stirring.

(Effects of the Invention) As understood from the above explanation, the polyester composition of the present invention has excellent lubricity, smoothness, blocking resistance, and abrasion resistance by containing the CB graft polymer obtained by a specific method. , provides molded products such as films and fibers with excellent uniformity, antistatic properties, workability, etc. Therefore, the polyester composition of the present invention can be used for housings of various devices, magnetic tapes, packaging films, processing systems, etc.

(Examples) Hereinafter, the present invention will be explained in detail using Examples, but the present invention is not limited to the following Examples. still,
In the examples, parts indicate parts by weight, and % by weight.

Reference Example 1 A flask equipped with a stirrer, an inert gas introduction tube, a reflux condenser, and a thermometer was charged with 10 parts of deionized water in which 0.2 parts of polyvinyl alcohol had been dissolved.

A mixture prepared in advance by dissolving 16 parts of benzoyl peroxide in a polymerizable monomer consisting of 196 parts of styrene and 4 parts of impropenyl oxazoline was added thereto, and stirred at high speed to form a uniform suspension. Next, this polymer suspension was filtered and washed while blowing nitrogen gas, and then dried to obtain a polymer having an oxazoline group as a reactive group.

40 parts of a polymer having an oxazoline group as a reactive group and 20 parts of CB MA-600 (manufactured by Mitsubishi Chemical Industries, Ltd.) were mixed at 160°C for 1 hour using a Laboplastomill (manufactured by Toyo Seiki Ltd.).
After reacting by kneading for 15 minutes at 0.00 rpm, the mixture was cooled and pulverized to obtain a CB graft polymer (1).

Reference Example 2 The same flask as used in Reference Example 1 was charged with 200 parts of toluene and 200 parts of methyl isobutyl ketone, and heated to 80° C. while blowing nitrogen gas. A mixture of 4 parts of benzoyl peroxide dissolved in a polymerizable monomer consisting of 190 parts of styrene and 10 parts of 2-(1-aziridinyl)ethyl methacrylate prepared in advance was added thereto.
The mixture was added dropwise through the dropping funnel over a period of time, and stirring was continued for an additional 5 hours to carry out a polymerization reaction, followed by cooling to obtain a polymer solution.

2000 parts of methanol was added to 100 parts of this polymer solution, reprecipitation was carried out, and the mixture was dried to obtain a polymer having an aziridine group as a reactive group.

20 parts of a polymer having an aziridine group as a reactive group and Styron-6, which is polystyrene without a reactive group.
20 parts of 66 (manufactured by Asahi Kasei Kogyo ■, Mn-40000) and C
20 parts of BMA-600 was reacted in the same manner as in Reference Example 1, then cooled and pulverized to obtain a CB graft polymer (2).

Reference Example 3 Cyclohexane 4 was added to the same flask used in Reference Example 1.
60 parts and 2 parts of Rheodol 5P-810 (manufactured by Kao ■) were added, and the temperature was raised to 75°C while blowing nitrogen gas. There, 60 parts of acrylamide prepared in advance, N-
A mixture of a polymerizable monomer consisting of 15.2 parts of vinylpyrrolidone and 1.6 parts of N-hydroxyethylmethacrylamide, to which 140 parts of deionized water and 2 parts of ammonium persulfate were added was added through a dropping funnel over 1.5 hours. Drop and then add 0.
Stirring was continued for 5 hours to carry out the polymerization reaction. After cooling, cyclohexane was removed, and the polymer was dried at 80 to 100°C under reduced pressure to obtain a polymer having N-hydroxyalkylamide groups as reactive groups.

45 parts of a polymer having an N-hydroxyalkylamide group as a reactive group and 15 parts of CB MA-10OR (manufactured by Mitsubishi Chemical Corporation) were reacted in the same manner as in Reference Example 1, and then cooled.
The CB graft polymer (3) was obtained by pulverization.

Reference Example 4 217 parts of toluene was charged into the same flask as used in Reference Example 1, and heated to 90° C. while blowing nitrogen gas. To the polymerizable monomers prepared in advance consisting of 480 parts of styrene and 20 parts of n-butyl acrylate, 5.44 parts of thioglycolic acid and 1 part of azobisisobutyronitrile were added.
．． A mixture of 32 parts and 32 parts was added dropwise through the dropping funnel over a period of 2 hours, and stirring was continued for an additional 5 hours to carry out a polymerization reaction.

Next, 185.1 parts of this reaction product (solution containing a prepolymer having a carboxyl group at the end) K 2-p
2.95 parts of -phenylene-bis-2-oxazoline was added and reacted at 80°C for 2 hours to obtain a solution (non-volatile content: 70 parts) of a polymer having an oxazoline group as a terminal reactive group.

57.1 parts of a solution of a polymer having an oxazoline group at the end (70% non-volatile content) and 20 parts of CB MA-10OR were kneaded for 15 minutes at 160°C and 1100 rpm using a Laboplastomill for reaction and desorption. After removing the solvent, the mixture was cooled and ground to obtain a CB graft polymer (4).

Reference Example 5 Into the same flask as used in Reference Example 1, a terminal carboxyl group-containing linear saturated polyester Alloplatz 0B-63 (
Nippon Shokubai Chemical Co., Ltd., molecular weight Mn=6000, non-volatile content 50 parts) 200 parts, 2-1)-phenylene-bis-2
- 3.6011 l of oxazoline was added and reacted at 110°C for 2 hours to obtain a solution (non-volatile content: 50%) of a polymer having an oxazoline group as a terminal reactive group. Solution of polymer having oxazoline group at the end (non-volatile content 50%) 80
．． 0 parts of CB MA-10OR and 20 parts of CB MA-10OR were cross-reacted under the same conditions as in Reference Example 4 to form a CB graft polymer (5 parts).
) was obtained.

Reference Example 6 In Reference Example 1, the polymerizable monomer used was styrene 15
A polymer having an epoxy group as a reactive group was obtained by repeating the same method as in Reference Example 1 except that 0 part, 45 parts of methyl methacrylate, and 5 parts of glycidyl methacrylate were used.

40 parts of a polymer having an epoxy group as a reactive group and CB
20 parts of MA-10OR (manufactured by Mitsubishi Chemical Industries, Ltd.) were kneaded and reacted for 15 minutes at 220°C and 1100 rpm using a Labo Plastomill, and then cooled and pulverized to obtain a CB graft polymer (6). .

Reference Example 7 217 parts of toluene was charged into the same flask as used in Reference Example 1, and heated to 90° C. while blowing nitrogen gas. A mixture of 4.61 parts of mercaptoethanol and 1.32 parts of azobisisobutyronitrile dissolved in a polymerizable monomer consisting of 480 parts of styrene and 20 parts of n-butyl acrylate prepared in advance was added thereto. The mixture was added dropwise through the dropping funnel over a period of 2 hours, and stirring was continued for an additional 5 hours to carry out a polymerization reaction. Next, this reaction product (hydro@P toluylene diisocyanate 2.38#- was added to the terminal and heated at 80°C.
The mixture was reacted for 30 minutes to obtain a solution (non-volatile content: 70%) of a polymer having an isocyanate group as a terminal reactive group.

57.1 parts of a solution of a polymer having an isocyanate group as a reactive group at the end (70% non-volatile content) and 20 parts of CB MA-10OR (manufactured by Mitsubishi Chemical Corporation) that had been pre-dried at 200°C for 2 hours were prepared in a laboratory. 160℃ using plastomill
, kneaded for 15 minutes at 100 rpm to remove the solvent as well as the reaction, cool, and grind to form the CB graft polymer (
7) was obtained.

Reference Example 8 32 parts of methanol and 0.35 parts of sodium hydroxide were placed in an autoclave equipped with a stirrer, a thermometer, and an ethylene oxide supply device, and the temperature was raised to 110°C.
While stirring and maintaining the pressure at 5-8 to 9/d, 88 parts of ethylene oxide was added dropwise, and after aging for 30 minutes, the reaction temperature was further raised to 150°C and 352 parts of ethylene oxide was added for 5 hours. The mixture was added dropwise over a period of time, and then aged for 1 hour to obtain a 10 mol adduct of ethylene oxide with methoxylated one end. 47.2 parts of this 10 mole adduct of methoxylated ethylene oxide at one end and 0.0 parts of sodium hydroxide.
62 parts of ethylene oxide were placed in the same autoclave as above, the temperature was raised to 150°C, and 616 parts of ethylene oxide was added to 5 parts of ethylene oxide.
The mixture was added dropwise over a period of time, and then aged for 1 hour to complete polymerization to synthesize polyethylene glycol with methoxylated one end.

Into the same autoclave as used above, 400 parts of distilled water, 100 parts of nine-end methoxylated polyethylene glycol obtained by the above reaction, and 10 parts of platinum/palladium catalyst were charged, the temperature was kept at 90-95°C, and the pressure was 10 kg/ Stirring was continued for 30 hours while adding compressed air as needed to maintain i, and the reaction was continued to obtain an aqueous solution of polyethylene glycol modified with a methoxy group at one end and a carboxyl group at the other end with an acid value of 8.4. . The solvent of this aqueous solution of modified polyethylene glycol was replaced with ethylene glycol, and the nonvolatile content was adjusted to 33.3%. 300 parts of the ethylene glycol solution of polyethylene glycol modified with carboxyl at one end thus obtained was charged into the same flask used in Reference Example 1, heated to 50°C, and then poured into a dropping funnel at 91°C.
．． 70 parts of 2-(1-aziridinyl)-2-oxazoline were added dropwise over 30 minutes. After reacting for 5 hours, the mixture was cooled to obtain a solution (non-volatile content: 33.7%) containing a polymer having an oxazoline group as a reactive group at one end.

90 parts of a solution containing a polymer having an oxazoline group as a reactive group and 30 parts of CB 45 (manufactured by Mitsubishi Chemical Industries, Ltd.) were transferred to the flask shown in Reference Example 1, and reacted at 100°C for 5 hours to form a CB graft polymer. An ethylene glycol solution of (8) was obtained.

Examples 1 to 7 CB graft polymers (1) to (1) obtained in Reference Examples 1 to 7 were added to 100 parts of polyethylene terephthalate chips.
7) were added and mixed so that the CB content was 1 part, to obtain a polyester composition.

The obtained polyester was melt-extruded into a sheet at 290°C using an extruder, and then stretched at 90°C at a longitudinal stretching ratio of 3.5 times.
The film was biaxially stretched at a transverse stretching ratio of 4.0 times and further heat-set at 200°C to obtain a film with a thickness of 15 μm.

Example 8 100 parts of dimethyl terephthalate and 70 parts of ethylene glycol were added to a reactor, and further 0.035 parts of manganese acetate tetrahydrate was added, and while the temperature was raised, methanol was distilled off to complete the transesterification reaction. did.

Next, 0.03 part of 1 trimethyl phosphate and 0.03 part of antimony trioxide were added, and then the C prepared in Reference Example 8 was added.
Ethylene glycol solution 5 of B graft polymer (8)
After adding 50% of the mixture using a stirrer, polycondensation was carried out in a conventional manner to obtain a polyester composition.

The obtained polyester composition was formed into a film in the same manner as in Examples 1-7. Using these films, coarse particles and film surface roughness were evaluated according to the evaluation method described below, and the results are shown in Table 1.

Comparative Example 1 Untreated CB 45 was added to the ethylene glycol solution of 7tCB graft polymer (8) prepared in Reference Example 8.
Example 8 except that the ethylene glycol slurry of
A polyester film for comparison was obtained in the same manner as above.

The coarse particles and film surface roughness of the comparative film were evaluated, and the results are shown in Table 1.

Example 9 and Comparative Example 2 90B obtained in Reference Example 1 per 100 parts of U-polymer U-1060 (manufactured by Unitika), which is a polyarylate resin.
(1) and untreated CB MA-600, respectively.
A polyester composition was obtained by adding and mixing the mixture in a proportion of 2 parts per minute.

The obtained polyester was extrusion molded at a die temperature of 320° C. to obtain a film having a thickness of 50 μm.

These films were evaluated for coarse particles and film surface roughness, and the results are shown in Table 1.

<Film evaluation method> ■ Observe the film under polarized transmitted light using a coarse particle microscope to check for the presence of foreign matter. The maximum diameter that exists at the point where polarized light is applied is 5
The number of aggregated CB particles of μ or more was counted, and the following judgment was made.

Special grade: 10 aggregated particles less than 150 d.

First grade: 10 to 20 aggregated particles exist for 150 days.

Secondary: 20 to 50 aggregated particles exist for 150 days.

Grade 3: 50 aggregated particles of 150 cr1 or more are present.

Note that special grade and first grade are used for practical use.

(2) Film surface roughness Measured using a Sloan back surface roughness measuring machine at a stylus diameter of 12.5 μm and a stylus pressure of 50 m9.

Table 1 The following films obtained in Examples 1 to 9 all had a small amount of coarse particles and had smooth film surfaces and were good. On the other hand, in Comparative Examples 1 and 2, since the CBQ surface treatment had been carried out extensively, there were many coarse particles, and tearing occurred during film formation, resulting in poor workability.

Claims (1)

[Scope of Claims] 1. A polyester composition containing a carbon black graft polymer obtained by reacting carbon black and a polymer having reactivity with carbon black at a temperature of 0°C to 350°C. 2. The polymer having reactivity with carbon black has one or more reactive groups selected from aziridine group, oxazoline group, N-hydroxyalkylamide group, epoxy group, and isocyanate group in the molecule. The polyester composition according to claim 1, which is a polymer.