JPS63284255A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition high in a rate of crystallization and capable of keeping the crystalline state till a low temperature, by mixing a crystalline saturated polyester resin with two specified block copolymers. CONSTITUTION:An oligoester (a) of a degree of polymerization of 2-10 is reacted with an aliphatic oligoester or oligolactone (b) of a degree of polymerization of 5-30 to obtain a block copolymer (B) of a number-average MW of 1,000-20,000. Separately, an aliphatic oligoester of oligolactone (C) of a degree of polymerization of 2-6 is reacted with an oligoester (d) of a degree of polymerization of about 10-80 to obtain a block copolymer (C) of a number-average MW of 2,000-40,000. 100pts.wt. crystalline saturated polyester resin (A) optionally containing 0.1-10wt.% crystallization accelerator is mixed with 0.5-20pts. wt. component B and 0.5-100pts.wt. component C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyester resin composition with improved crystallization rate.

[Conventional technology]

Polyethylene terephthalate not only has a high softening point, but also has excellent chemical resistance, light resistance, and electrical, physical,
Due to its excellent mechanical properties, it is widely used in fibers, films, and molded products. however,
These excellent properties are largely dependent on the crystallinity of polyethylene terephthalate, and since the crystallization rate of polyethylene terephthalate is quite low compared to crystalline polymers such as nylon polyaceter μ, it is necessary to increase the crystallinity. It is necessary to process at a high temperature of 120° C. or higher over a long period of time.

Therefore, various methods have been proposed to improve the crystallization rate of polyethylene terephthalate. These methods can be roughly classified into the following two ways of thinking. One of them is that when polyethylene terephthalate is crystallized from a molten state, the supercooling state becomes long, so in order to shorten this time, the purpose is to promote the generation of crystal nuclei.
Inorganic additives such as silica, kaolin, alumina, etc.
6-38707, Japanese Patent Publication No. 47-27142, etc.), copolymers of α-olefins and salts of unsaturated μ-bony acids (Japanese Patent Publication No. 45-26225, etc.), sodium benzoate, etc. Organic carboxylic acid salt (Special Publication No. 46-2
9977, JP-A-54-158452, etc.)
An example of this method is to add .

Another method aims to improve the mobility of polyethylene terephthalate polymer chains at much lower temperatures. Examples include a method of adding a low polymerization product alone or as a block copolymer (Japanese Patent Publication No. 1987-
No. 87455, Japanese Patent Publication No. 57-I As145, Japanese Patent Application Publication No. 179259-1987, Japanese Patent Application Publication No. 58-21
0957, etc.).

Among these methods, the details of the mechanism of action of the additives that promote crystal nucleation are not known in many cases, but the power! When a basic compound such as a bonate salt is added, it is said that the effect is produced by lowering the molecular weight of polyethylene terephthalate, so such additives inevitably have disadvantages in terms of physical properties. In addition, when adding polycarbonate, polyalkylene sepacate, boriakylene adipate, etc., a plasticizer effect that helps the mobility of the polymer chains of polyethylene terephthalate at low temperatures can be expected, but at high temperatures Since these additives have little effect on generating crystal nuclei during crystallization, they must be used in combination with so-called nucleating agents.

[Problem that the invention seeks to solve]

The present inventors have made efforts to develop new additives that can accelerate the crystallization rate without sacrificing the physical properties of polyethylene (V-) and can sustain crystallization down to low temperatures. As a result, the present invention was completed.

[Means for solving problems]

That is, the gist of the present invention is that a block copolymer of a polyester oligomer with a degree of polymerization of 2 to 10 and an aliphatic polyester μ or polylactone oligomer with a degree of polymerization of 5 to 30 and CB) is used for crystalline saturated polyester resin. A polyester resin composition comprising a block copolymer of an aliphatic polyester or polylactone oligomer having a degree of polymerization of 2 to 6 and a polyester oligomer having a degree of polymerization of more than 10 to 80.

Copolymerized polyesters containing 70 or more repeating units of crystalline saturated polyester and polyethylene terephthalate used in the present invention may be mentioned. As the copolymerization component, known acid components or glyco-μ components can be used, such as isophthalic acid, naphthalene 1,4- or 2,6-dicarboxylic acid, diphenylμ ether 4,4'-cica μponic acid, etc. , adipic acid, sepacic acid and other acid components, propylene glycol, butylene glyco-y1 diethylene glycol, neopentyl glyco-μ, cyclohexane dimethanol-μ, 2.2-bis(4
-Hydroxyphenyl A/) Glyco components such as propane and oxyacids such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid are mentioned. In order to determine the effect of the additive, the rate of crystallization must be determined for each composition. Various methods are known for this measurement, such as measuring changes in density over time. Among these methods, the method using differential scanning calorimetry (hereinafter abbreviated as DEC) is the simplest.

This is because when an amorphous polymer created by heating and melting sump μ above the melting temperature of polyester and rapidly cooling it to room temperature is heated at a constant temperature from room temperature, the glass transition temperature (Tg) and low-temperature crystallization occur on the 080 curve. temperature (in Tc), the peak temperature of melting (Tm) is observed. When the molten sample is cooled at the same rate, an exothermic temperature (Tc-) due to crystallization is observed. Among these observed values, Tc and Tc- are known to be correlated with the half-crystallization time (τV2) in isothermal crystallization (Polymer 25 835
(1984)). That is, the lower the Tc, the smaller the τi (the higher the crystallization rate), and the higher the Tc-, the higher the crystallization rate. Therefore, Tc in DsC and Tc
By comparing -, it is possible to obtain knowledge about the crystallization rate.

The block copolymers blended into the polyester μ resin composition of the present invention include a polyester oligomer with a polymerization degree of 2 to 1o and an aliphatic polyester or polylactone oligomer block copolymer with a polymerization degree of 5 to 3o. Copolymer CB) is a block copolymer of an aliphatic polyester or polylactone oligomer having a degree of polymerization of 2 to 6 and a polyester oligomer having a degree of polymerization of more than 10 to 8 degrees.

In these block copolymers, substances that can be used as raw materials for polyester oligomers are aromatic carbonic acid such as terephthalic acid and isophthalic acid, and geo-μ such as ethylene glycol, propylene glycol, butisone glycol, and neopentyl glycol. . In addition, materials that can be used as raw materials for aliphatic polyester include aliphatic carbonic acids such as adipic acid and sepacic acid, and ethylene glycol.
〃, propylene glycol, butylene glycol-μ, neobenzi μ-glycol, etc.), and those that can be used as raw materials for aliphatic polylactones include lactic acid,
α- or β-hydroxyVbutyric acid, β-propiotuctone,
These are hydroquinone acids and lactones such as γ-parellofuctone and e-cablockone, and these may be used alone or in a copolymerized form.

The role of each block copolymer in the crystallization process of crystalline saturated polyester resin is considered as follows. In the block copolymer), a part of the ester oligomer is incorporated into the polyester μ crystal, and a part of the aliphatic polyester μ or polylactone oligomer is in the amorphous part, improving the mobility of polyester WG4 during the crystal growth process. As a result, it is thought to work to promote crystallization at low temperatures.

At this time, since a portion of the ester oligomer is incorporated into the crystal, elution after molding can be prevented. On the other hand, in the block copolymer (), a flexible aliphatic polyester μ or polyester moiety is introduced into a part of the polyester P main chain, so the flexibility of the polyester μ chain is improved, and nucleation occurs during crystallization. It is thought that it has the effect of promoting. Therefore, by simultaneously using CB) in these block copolymers, the nucleation rate and crystal growth rate are promoted, so the Tc content is significantly lower than when no addition is made, and the Tc- content is also lowered. It is thought that this increases the crystallization rate of the crystalline saturated polyester μ resin.

In addition, in the present invention, in order to efficiently express the functions of block copolymers (1) and CB), the number average molecular weight within the block copolymer is 1000 to 2000°0, and the number average molecular weight of block copolymer CB) is 2000 to 2000°0. Preferably, it is 40,000. Each block copolymer is composed of segments having various degrees of polymerization as described above, but if the degree of polymerization of the polyester oligomer constituting the block copolymer CB) exceeds 80, there is an effect of promoting nucleation. This is not preferable because it tends to become smaller.

In carrying out the present invention, within the block copolymer and proviso)
The amount of polyester/I/10 to be blended with the crystalline saturated polyester resin may be selected arbitrarily, but preferably polyester/I/10
0.031 parts by weight, the content of α in the block copolymer is about 5 to 20 parts by weight, and the content of α in the block copolymer is about 0.5 to 100 parts by weight.

If the amount incorporated in the block copolymer is less than 5 parts by weight, it is difficult to achieve the object of the present invention, and if it exceeds 2 parts by weight, the physical properties of the resulting polyester resin composition tend to deteriorate. So I don't like it very much. On the other hand, if the amount of the block copolymer blended is less than Q, 5 parts by weight, the blending effect will be small. Although there is no particular problem if the amount is 100 parts by weight or more, if the number average molecular weight is 10,000 or less, the physical properties of the resulting polyester resin composition are deteriorated, so in this case, it is preferably 100 parts by weight or less.

In the present invention, a crystalline saturated polyester μ resin to which a crystallization accelerator is added can be used depending on the purpose. Known crystallization promoters can be used,
For example, inorganic salts such as Yuuri, mica, clay, V-liquor, alumina, higher fatty acids (10 to 30 carbon atoms) such as sodium stearate and sodium benzoate, metal salts of aromatic carboxylic acids, α-olefins and α .

Examples include monovalent or divalent metal salts of ionic copolymers consisting of β-unsaturated carbonate salts, or mixtures thereof.

The amount of the accelerator added may be arbitrarily selected depending on the purpose, but is usually about 0.1 to 10 times the amount added to the polyester resin.

The polyester resin composition of the present invention may optionally contain fibrous fillers such as glass fibers and carbon fibers, fillers such as wotstonite, mica, glass foil, resin, and kaolin, light or Various fillers such as heat stabilizers, dyes or pigments can also be added.

The polyester/l/resin composition of the present invention can be produced by a commonly known method. For example, a crystalline saturated polyester, a block copolymer (T), (B), and a known crystallization accelerator are mixed as necessary, and then
, by melt-mixing in a Banbury mixer.

The present invention will be explained below using Examples.

Reference Example 1 Manufacture of Niblock Copolymer (1) Manufacture of Polyester Oligomer Purified dimethyl terephthalate) 19.49 and ethylene glycol/L/12.4 g with acetic acid strength y 0.0
4 g of antimony oxide 1089 were added thereto, and the mixture was heated to 180° C. in a reactor equipped with a distillation side tube and a condenser nitrogen introduction tube.

Next, when nitrogen gas is slowly passed through, the theoretical amount of methanol is distilled out within 2 hours and diethylene terephthalate is 25.4
g was produced. Then diethylene terephthasort 25.4
．． 9 was dissolved in pyridine 200-, and benzoyl chloride 149 was added dropwise while cooling on ice. After the addition, the layer was allowed to react at room temperature for 2 hours, and then poured gently into ice-cooled diluted hydrochloric acid. The precipitate was separated, washed with water, and dried to obtain 55 g of polyester oligomer with a degree of polymerization of 2.

Dissolve 8 g of diethylene terephthalate in 400 W of pyridine, and dissolve 20 g of terephthaloyl chloride.
30 (ld) of a chloroform solution in which 59 was dissolved was gently added dropwise. After stirring the finished layer at room temperature for 3 hours, 14 g of benzoyl chloride was added dropwise. After further stirring at room temperature for 2 hours, most of the chloroform was distilled off. The precipitate was poured into ice-cooled dilute hydrochloric acid to separate the P, washed with water, and dried to obtain polyester oligomer 759 with a degree of polymerization of 4.

(2) Production of polyester oligomer and block copolymer Polyester oligomer &5g of polymerization Kz and 5.79 g of ε-caproctone were mixed, sealed in a tube, and heated at 180°C for 1 hour.
The polymerization was allowed to stand for 0 hours.

When the product is dried in the washing layer with n-hexane, a polyvarnish 7-/I/oligomer with a degree of polymerization of 2 and a polylactone oligomer 〇 copolymer with a degree of polymerization of 5 are formed.9. OI was obtained. The number average molecular weight of the copolymer was about 1000. This block copolymer is designated as A-1.

Similarly, polyester oligomer 7, 59 with a degree of polymerization of 4
A polyester oligomer with a degree of polymerization of 4 and a polyester oligomer copolymer 118II with a degree of polymerization of 10 were obtained from 11.4 g of Droka Blockton. The number average molecular weight of the copolymer was approximately 1,800. This block copolymer is designated as A-2.

Reference Example 2 Manufacture of Niblock Copolymer (B) (1) Manufacture of Polycarbonate Oligomer Ethylene Glyco
A polycaprolactone oligomer having a polymerization degree of 4 was quantitatively obtained by static polymerization of 1, 49 and ε-cabroctone 459 at 180° C. for 10 hours in a sealed tube under a nitrogen atmosphere.

(2) Production of polyester oligomers and block copolymers 5 g of polycaprolactone oligomer with a degree of polymerization of 4, 12.8 g of ethylene glyco-A, and 4 g of terephthaloyl chloride
1 g was dissolved in 500 ml of a mixed solvent of trichloroethane and 0-dichlorobenzene, and the mixture was gradually heated and reacted.

When most of the hydrogen chloride gas was distilled off, a copolymerized polyester was precipitated, which was separated, washed with methanol, and dried. 50 g of the obtained copolymer was a block copolymer of polycablockone oligomer with a polymerization degree of 4 and polyester μ oligomer with a polymerization degree of 30. This block copolymer is designated as B-1.

A block copolymer of a polylactone oligomer with a polymerization degree of 4 and an ester oligomer with a polymerization degree of 15 was obtained using the same manufacturing method from 5 g of polycablockone oligomer with a polymerization degree of 4, 4 g of ethylene glycop&4, and 21 g of terephthaloyl chloride. This block copolymer is designated as B-2.

Examples 1 to 8, Comparative Examples 1 to 6 Polyethylene V-lid V-t (manufactured by Mitsubishi Rayon, Dyanite [F] MA-521) with an intrinsic viscosity of 1172 was
It was dried at 0° C. for 12 hours or more.

The inner and outer block copolymers produced in Reference Examples 1 and 2 above were also dried in the same manner. Next, Table 1
Mixtures of various compositions shown in are crushed and mixed in a freezer, dried for 12 hours at 110°C, and placed in a small extruder (CSI-MaxMixin) controlled at a rotor set temperature of 235°C and header general temperature of 265°C.
g Rxtruder C, 8, 194-A-104)
The mixture was put into a container, melted, kneaded, and extruded to obtain a ribbon-shaped sample. Samples 3 to 5119 were taken, melted and held at 280° C. for 10 minutes using a 20-type DSC manufactured by Seiko Electronics, and then rapidly cooled to room temperature to obtain amorphous samples. Set this to 0
The temperature was increased from 10°C to 270°C and a D8C curve was observed. The temperature was further maintained at 270° C. for 5 minutes, and then cooled at a rate of 15° C./min, and the DEIC curve was observed.

The low temperature crystallization temperature (Tc'') and the crystallization temperature from melting (Tc-) were determined from each DSC' curve, and the crystallization rate of each composition was compared.

〔Effect of the invention〕

As detailed above, since the polyester resin composition of the present invention has an excellent crystallization speed, it can be used as a film whose shape is fixed by crystallization after low-temperature mold molding or plastic processing in the field of composite materials. It can be applied to various fields such as short-time shaping of fibers, heat-resistant photoμ or crystallized unreinforced polyester products such as tubes and open-nap A/)v-.
The effect is extremely high.

Claims (1)

[Claims] 1. For crystalline saturated polyester resin, (A) a block copolymer of a polyester oligomer with a degree of polymerization of 2 to 10 and an aliphatic polyester or polylactone oligomer with a degree of polymerization of 5 to 30, and (B) polymerization. A polyester resin composition comprising a block copolymer of an aliphatic polyester or polylactone oligomer having a degree of polymerization of 2 to 6 and a polyester oligomer having a degree of polymerization of more than 10 to 80. 2. A patent in which 0.5 to 20 parts by weight of block copolymer (A) and 0.5 to 100 parts by weight of block copolymer (B) are blended with 100 parts by weight of crystalline saturated polyester resin. The polyester resin composition according to claim 1. 3. The polyester resin composition according to claim 1, wherein the crystalline saturated polyester resin contains a crystallization promoter.