JPS60170660A - Polyester block copolymer composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent thermal stability and mechanical properties, and giving a parison with excellent form-stability, by compounding the titled copolymer with an epoxy compound, a specific metallic salt compound and a phosphorus compound. CONSTITUTION:(A) 100pts.(wt.) of a polyester block copolymer obtained by the block-forming reaction of (i) an aromatic polyester containing aromatic dicarboxylic acid as main acid component with (ii) an aliphatic polyester containing aliphatic dicarboxylic acid as main acid component and/or an aliphatic hydroxycarboxylic acid as hydroxy acid component, is compounded with (B) 0.1- 40pts., preferably 1-30pts. of an epoxy compound and (C) <=10 pts., preferably 0.1-5pts. of a compound selected from organic sulfonic acid salt, sulfuric acid ester salt and trivalent organic phosphorus compound. The phosphorus compound of the component C is triphenyl phosphite, etc., and the merallic salt is preferably sodium dodecylbenzenesulfonate, sodium laurylsulfate, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyester block copolymer compositions. More specifically, the shape stability of the molded article precursor, so-called parison, in the molten state of the resin is good;
The present invention also relates to a polyester block copolymer composition having excellent thermal stability and mechanical properties.

Polyester block copolymers, which have aromatic polyester parts and aliphatic polyester parts in their molecular chains, are known as polymers with rubber-like elasticity, and can be processed into fibers and molded products by various molding methods such as injection molding, blow molding, and film molding. Used for products, films, etc. Among the various molding methods, especially when obtaining hollow molded products by blow molding or when extruding tubes, the molten parison during processing can be held in a fixed shape for a reasonable period of time, i.e. melting It is necessary that the shape stability in the state is good. Therefore, as a means to improve the shape stability in the molten state, a method has been proposed in which the molecular weight of the polymer is increased to increase the melt viscosity. Japanese Patent Application Publication No. 5
1-42797 discloses a method in which aromatic polyester and aliphatic polyester are melt-mixed to obtain a polyester block copolymer with an intermediate molecular weight, and then polymerized in a solid phase to increase the molecular weight. Polymerization rate is slow and productivity is low. Also, JP-A-51-111895, JP-A-Sho 5
2-29882 discloses a method of increasing the degree of polymerization by adding an acid lactam compound, a diaryl dicarboxylic acid ester, a carbonate ester, etc. However, when melt polymerization is performed with the addition of these compounds, the lactam compound is There are problems such as by-products such as phenol compounds contaminating the polymerization recovery system and discoloring the obtained polymer.

In JP-A-55-92723, a polyvalent isocyanate compound is added to aromatic polyester and aliphatic polyester to increase the degree of polymerization, but in this case as well, the resulting polymer is easily colored and has poor heat resistance. There are problems such as bad. Furthermore, JP-A-58-162654 proposes adding an epoxy compound to a polyester block copolymer obtained by reacting an aromatic polyester with a lactone in order to improve the hydrolysis resistance of the polymer. There are, but
To react lactones with aromatic polyester, as described in Japanese Patent Publication No. 48/4116, the reactivity of lactones is highly active toward the hydroxyl group of aromatic polyester, and therefore has a high blocking property. In order to obtain a polyester block copolymer with excellent elastic behavior, lactones are reacted with an aromatic polyester having a large number of hydroxyl end groups, so that the resulting polyester block polymer also has a large number of hydroxyl end groups. On the other hand, the reactivity of epoxy compounds is high with carboxyl terminal groups, and in polymers made by reacting lactones with aromatic polyesters, it is necessary to add a large amount of epoxy compounds to increase the viscosity, and therefore the required viscosity level It has drawbacks such as difficulty in obtaining it with good reproducibility and furthermore, gelation tends to occur in some areas.

As a result of intensive studies aimed at improving the shape stability of the parison during melting of the polyester block copolymer, the present inventors found that the polyester block copolymer was combined with an epoxy compound and a specific metal salt compound and/or a trivalent compound. The present invention has been accomplished by discovering that a composition containing a phosphorus compound has a stable high melt viscosity when melted and satisfies the above object.

That is, the present invention blocks (1) an aromatic polyester whose main acid component is an aromatic dicarboxylic acid and (2) an aliphatic polyester whose main acid component is an aliphatic BJ51M dicarboxylic acid and/or an aliphatic oxycarboxylic acid as an oxyacid component. 0.1 to 40 mm of epoxy compound alone to 100 parts by weight of the reacted polyester block copolymer
It has been found that the above object can be achieved by using a composition containing 1.95% of the above-mentioned composition.

The object of the present invention can be achieved even more effectively. That is, the present invention is characterized by the fact that the present invention combines aromatic polyesters whose main acid component is aliphatic dicarboxylic acids and/or aliphatic dicarboxylic acids and/or aliphatic dicarboxylic acids. ■0.1 to 40 parts by weight of an epoxy compound, ■organic sulfonate, sulfuric acid to 100 parts by weight of a polyester block copolymer obtained by blocking reaction of oxycarboxylic acid with an aliphatic polyester having an oxyacid component. A polyester block copolymer composition containing at least 10 parts by weight of at least one selected from ester salts and trivalent organic phosphorus compounds.

The manufacturing method and characteristics of the composition of the present invention will be explained in detail below.

The aromatic polyester containing aromatic dicarboxylic acid as the main acid component in the present invention refers to aromatic dicarboxylic acid or
It is a polymer or copolymer obtained by a condensation reaction containing the ester-forming derivative and a diol or the ester-forming derivative as main components. Note that "mainly" means that 6096 or more of the dicarboxylic acid components are aromatic dicarboxylic acids.

Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1.
5-naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4.4'
-diphenyl ether dicarboxylic acid or its ester-forming derivatives. Preferred aromatic dicarboxylic acids are terephthalic acid and 2,6-naphthalene dicarboxylic acid.

Diol components include aliphatic diols having 2 to 10 carbon atoms, ie, ethylene glycol, propylene glycol,
1.4-butanediol, neopentyl glycol, l
, 5-bentanediol, 1,6-hexanediol,
such as decamethylene glycol, cyclohexanediol and mixtures thereof. Preferred diols are ethylene glycol and 1,4-butanediol.

Specific examples of polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-naphthalate, and the like. Among these aromatic polyesters, highly crystalline polybutylene terephthalate is particularly preferred.

The aliphatic polyester used in the present invention includes an aliphatic dicarboxylic acid or an ester-forming derivative thereof, a diol or an ester-forming derivative thereof, and/or an acid component that is an aliphatic oxycarboxylic acid or a derivative thereof and/or
Alternatively, it is a polymer or copolymer obtained by a condensation reaction containing an oxyacid as a main component. The term "main acid component" means that the acid component contains -60% of the acid component.

Examples of aliphatic dicarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, -decanedicarboxylic acid, and ester-forming derivatives thereof. Specific examples of the glycol component are the same as those exemplified for the glycol component of the aromatic polyester.

Aliphatic oxycarboxylic acids include hydroxycaproic acid and hydroxycaproic acid, and their derivatives include ε-caprolactone. Particularly preferred aliphatic polyesters include polyethylene adipate, polybutylene adipate, polybutylene sebacate, and hypoly ε
-Caprolactone.

The aromatic and aliphatic polyesters may be polyesters copolymerized with a small amount of a trifunctional or higher functional compound such as trimellitic acid, trimesic acid, glycerin, melimethylolpropane, or pentae'2thritol.

In the present invention, as a method for forming blocks between an aromatic polyester and an aliphatic polyester, a method of melt-mixing an aromatic polyester and an aliphatic polyester and obtaining a polyester block copolymer through a transesterification reaction is preferably employed. At this time, it is possible to add a catalyst such as a titanium compound or a tin compound to shorten the transesterification reaction time, and it is also possible to remove the catalyst for the transesterification reaction after obtaining polyester block copolymerization by the transesterification reaction. It is also possible to add a phosphorus compound to activate or suppress it.

The epoxy compound which is an essential component of the composition according to the present invention is a compound having at least one epoxy group in the molecule, for example, a bisphenol type epoxy compound obtained by reacting bisphenol A and epichlorohydrin in various ratios. , novolac-type epoxy compounds obtained from Nophook resin and epichlorohydrin, polyglycidyl esters obtained from polycarboxylic acid and epichlorohydrin, alicyclic-type epoxy compounds obtained from alicyclic compounds (e.g. dicyclopentadiene), alcohols. consisting of an aliphatic compound having a functional hydroxyl group (e.g., bucundiol, glycerin, etc.), glycidyl ethers obtained from epichlorohydrin, epoxidized polybutadiene, and an unsaturated monomer having an epoxy group and other unsaturated monomers. Examples include epoxy group-containing copolymers. Preferred examples of these epoxy compounds include bisphenol A type epoxy compounds such as those shown below (where n is a number from 0 to 10), and glycidyl ester compounds such as diglycidyl hexahydrophthalate. ester,
Examples include tetrahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, and persatic acid glycidyl ester.

In addition, as the epoxy group-containing copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/
These include glycidyl methacrylate copolymer, ethylene/carbon oxide/grindyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, and among them, ethylene/glycidyl methacrylate copolymer is most preferred. Further, the epoxy compound used in the present invention may be substituted with a halogen atom such as chlorine or bromine, but containing a nitrogen atom forming an amino group is undesirable because it causes coloration.

The amount of the epoxy compound added in the present invention is suitably 0.1 to 40 parts by weight, more preferably 1 to 30 parts by weight, based on the polyester block copolymer lOO layer. If the amount added is less than 0.1 part by weight, the shape stability during melting will not be improved sufficiently, while if it exceeds 40 parts by weight, there is a drawback that the properties of the polyester block copolymer itself will be impaired.

The composition of the present invention may be composed of the above-mentioned epoxy compound and a polyester block copolymer, but preferably contains at least one selected from organic sulfonates, sulfate ester salts, and trivalent organic phosphorous compounds. shall be. Organic sulfonates and sulfate ester salts have the general formula %
It is expressed by the formula %() (). Here, in the formula, M represents a metal atom, R
represents an organic group, and n represents an integer of 1 or more. Preferred examples of M include alkali metals such as lithium, sodium, and potassium, alkaline earth metals such as magnesium, calcium, strontium, and barium, and zinc and aluminum. Preferred examples of R include phenyl, α-naphthyl, β-naphthyl, dodecylphenyl, dodecylnaphthyl, allyl, methacryl, and high molecular weight substances such as polystyrene and polyethylene glycol.

Preferred examples of organic sulfonates include the general formula (where M is lithium, sodium, potassium, calcium, R' and R// are methyl, ethyl, phenyl, 2-hydroxyethyl, 4-hydroxybutyl). ), sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate, sodium methallylsulfonate, potassium 1,5-naphthalenedisulfonate, formalin condensate of naphthalenesulfonate, sodium salt of sulfonated polystyrene, etc. . Preferred examples of sulfate ester salts include sodium lauryl sulfate, potassium lauryl sulfate, calcium stearyl sulfate-barium stearyl sulfate, sodium polyoxyethylene ethyl ether sulfate, and sodium polyoxyethylene dodecyl phenyl ether sulfate. Two or more of these organic sulfonate salts and sulfate ester salts may be used in combination.

Further, organic sulfonates and monosulfuric esters may be included as substituents in the polyester, but it is not preferable for them to be included in the epoxy compound.

The trivalent organic phosphorus compound, which is another component constituting the composition of the present invention, is represented by the general formula PR+ R2R3(d). Here, R and R2R3 represent an aliphatic group, an aromatic group, an alicyclic group, an alkoxy group, an alkylthio group, an amino group, etc., or a derivative thereof, and may be the same or different. Two or more of them may be connected by any chemical bond. Furthermore, R and R2R3 may contain a trivalent or pentavalent phosphorus atom. That is, two or more phosphorus atoms may be contained in the organic phosphorus compound. RIR2Rs include, for example, methyl, ethyl, propyl, butyl, octyl, denyl,
These include benzyl, phenyl, tolyl, naphthyl, cyclohexyl, ethoxy, isodekoxy, phenoxy, dimethylamino group, etc., and if only one of RIR2Rs is considered, it may be substituted with a halogen atom such as chlorine/bromine. Preferred examples of trivalent organic phosphorus compounds include triphenyl phosphite, tri'isodecyl phosphite,
Tris(nonylphenyl) phosphite and the like.

Addition of the compound selected from the above organic sulfonates, sulfuric ester salts, and trivalent organic phosphorus compounds is at a rate of 10 parts by weight or less, preferably 0.1 parts by weight, based on 100 parts by weight of the polyester block copolymer. ~5 parts by weight.

If it exceeds 10 parts by weight, it tends to lower the melt viscosity, making it difficult to achieve the object of the present invention and is not preferred.

The method of blending the composition of the present invention is not particularly limited, but after the blocking reaction of aromatic polyester and aliphatic polyester with a reaction source, the epoxy compound, organic sulfonate, sulfate ester salt, and trivalent phosphorus are combined. A method of blending one type of compound in a reaction source and discharging it, aromatic polyester and aliphatic polyester, epoxy compound and organic sulfonate, sulfuric ester salt, and one type of trivalent phosphorus compound of aromatic polyester. A method of melt-kneading a homogeneous mixture using an extruder at a temperature above the melting point, or a method of producing a polyester block copolymer using a reaction source of an aromatic polyester and an aliphatic polyester in advance and Examples include a method of melt-mixing an epoxy compound and one of an organic sulfonate, a sulfuric acid ester salt, and a trivalent phosphorus compound into a homogeneous mixture using an extruder at a temperature equal to or higher than the melting point.

The composition of the present invention includes, to the extent that the object of the present invention is not impaired,
Common additives such as antioxidants, UV absorbers, heat stabilizers, lubricants, mold release agents, colorants including dyes and pigments, fibrous and granular fillers and reinforcing agents, nucleating agents, flame retardants, etc. It may be modified with

In addition, a small amount of other thermoplastic resins (e.g., polyethylene, polypropylene, acrylic resin, fluororesin, polyamide, polyacetal, polycarbonate, polysulfone, polyphenylene oxide, etc.), thermosetting resin, within a range that does not deteriorate the original properties of the polyester block copolymer. (for example, phenol resin, melamine resin, polyester resin, silicone resin, epoxy resin, etc.), soft thermoplastic resin (for example, ethylene/vinyl acetate copolymer, -- ethylene/propylene terpolymer, etc.) may be added. These resins may be used alone or in combination of two or more.

The composition according to the present invention is characterized in that its shape is stable when it is extruded in a molten state to form a parison. Therefore, when molded into a molded product intended for a parison, the molded product is homogeneous in shape and size.

It also has good thermal stability. Therefore, a molded article can be obtained in which coloring is suppressed and deterioration in mechanical properties is suppressed.

Furthermore, since the polyester block copolymer is obtained by reacting aromatic polyester and aliphatic polyester, which have been previously formed as polymers, in block form, the desired composition can be obtained with a small amount of epoxy compound. . There are also fewer gelled substances.

The present invention will be explained below with reference to examples, and the properties of the resins in each example were measured according to the following methods.

Melt viscosity was measured at a temperature of 230°C using a flow tester.

Melt tension - A melt tension measurement device manufactured by Toyo Seiki was used. This measuring device consists of a 20 mm diameter extruder and a melt tension measuring device, and the temperature of the 20 mm diameter extruder is
At 30°C, the molten polymer was extruded with the screw rotation B set to 1Orpm, and the rotation speed of the melt tension measuring device was set to 3O.
rpm to determine the melt tension of the molten polymer.

In the examples, the relative viscosity is a value measured at a temperature of 25° C. of a 0.5% polymer solution using orthochlorophenol as a solvent. Furthermore, all items expressed in "parts" or "%" are expressed in weight ratios.

Reference Example I (Polymerization of polybutylene terephthalate) 75 parts of terephthalic acid, 74 parts of 1,4-butanediol, and 0.05 part of titanium tetrabutoxide as a catalyst were charged into a reaction vessel equipped with a rectification column, and the temperature was set at 220°C. The esterification reaction was carried out for 2 hours.

Next, the esterification reaction product was transferred to a polymerization iron equipped with a double helical ribbon stirrer, and then 0.05 parts of titanium tetrabutoxide was added as a polymerization catalyst, and the temperature was 250°C and the pressure was 0.
Polymerization was carried out under reduced pressure of 5 m*HI for 3 hours. The relative viscosity of the obtained polymer was 1.48, and the C0OH end group had a relative viscosity of 45 equivalents Q/
It was LO6f.

Reference Example 2 (Polymerization of polybutylene adipate) 87 parts of dimethyl adipate, 90 parts of 1,4-butanediol, and 0.05 part of titanium tetrabutoxide as a catalyst were charged into the reaction vessel used in Reference Example 1, and the temperature was increased from 100°C. The temperature was raised to 220°C over 2 hours to carry out transesterification. The obtained transesterification product was transferred to the polymerization iron used in Reference Example 1, and reacted for 2 hours at a temperature of 250°C and a reduced pressure of 0.5 silk Hf. The relative viscosity of the obtained polymer was l, 65, C0
The amount of OH terminal groups was 36 equivalents/106f.

Reference Example 3 (Polymerization of poly-ε-caprolactone) 100 parts of ε-caprolactone, 2 parts of 1,4-butanediol, and 0.5 part of titanium tetrabutoxide as a catalyst were charged into the polymerization iron used in Reference Example 1, and the temperature was 220. The reaction was carried out at ℃ for 2 hours at normal pressure under nitrogen atmosphere. The relative viscosity of the obtained polymer was 1.27, and the amount of COOH end groups was 0 equivalent/106. Met.

Examples 1 to 9, Comparative Examples 1 to 2 The polymers obtained in Reference Examples 1 to 3 above were mixed in the proportions shown on the front surface, reacted for 15 minutes at a temperature of 240°C under nitrogen atmosphere, and then cooled. A polyester block copolymer was obtained. The obtained polyester block copolymer was
It was vacuum dried at a temperature of c. The epoxy compound, sulfonate salt, sulfuric acid ester salt, and trivalent phosphorus compound shown in Table 1 were added to 100 parts by weight of this polyester block copolymer in the proportions shown in Table 1, and the temperature was set at 230°C after tri-blending. The mixture was melt-mixed and pelletized using an extruder equipped with a 4Qymφ screw.

Table 1 shows the values of melt viscosity and melt strength of the obtained resin composition.

The symbols or terms in Table 1 indicate the following descriptions.

PBT: Polybutylene terephthalate obtained in Reference Example 1 PBA: Polybutylene adipate obtained in Reference Example 2 PCL: Poly-ε-caprolactone obtained in Reference Example 3 a) "Epicote"': Yuka Shell Chemical Co., Ltd. Trade name (trade name) of bisphenol A-based epoxy compound manufactured by Yuka Shell Chemical Co., Ltd.: 1001, molecular weight: approximately 900 Structure;

191P: Hexahydrophthalic acid diglycidyl ester c) E/GMA (90/10): Ethylene/
Glycidyl methacrylate = 90/10 (weight ratio) polymer, 'MI: 3 repeating units d) BF-4ooo: Trade name of epoxidized polybutadiene manufactured by Adeka Argus Chemical Co., Ltd., molecular weight approximately 1000, Repeating unit; e) 5SIA: 3.5-dicarboxybenzenesulfonic acid sodium dimethyl ester f) TPT: Triphenyl phosphite g)'' Emalpa: Kao Atlas Co., Ltd. sodium polyoxyethylene alkyl ether sulfate (trade name) , 200 structure; R-() (CHz CH20)n 50s
As is clear from Table 1, the composition of the present invention has a melt viscosity,
It has a high melt tension and is an excellent material for extrusion molding and blow molding.

Example 11 64 parts of polybutylene terephthalate obtained in Reference Example 1, 27 parts of polybutylene adipate obtained in Reference Example 2, Example 7
After tri-blending 9 parts of E/GMA (90/10) and 0.05 part of Emar 200, 2 parts were used.
Melt mixing in a 40m11φ twin-screw extruder set at 50℃,
Pelletized. The melt viscosity of the obtained polymer is l 23
00 poise and a melt tension of 3° iF, indicating that it is an excellent extrusion molding material.

Comparative Example 3 50 parts of polybutylene terephthalate obtained in Reference Example I and ε
- Charge 50 parts of caprolactone into a reaction vessel at 230°C.
The mixture was reacted for 2 hours at normal pressure in a nitrogen atmosphere, discharged, and cooled to obtain a polyester block copolymer. 100 parts of dry product of this polyester block copolymer, Epikote fool
3 parts and 0.1 part of 5SIA at 230°C after tri-blending.
The mixture was melt-mixed and pelletized using an extruder equipped with a 40-jllφ screw. The obtained polymer had a melt viscosity of 3.8×I 03poise and a melt tension of 0.7f.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Scope of Claims] l ■ Aromatic polyester having an aromatic dicarboxylic acid as the main acid component; ■ Aliphatic polyester having an aliphatic dicarboxylic acid as the main acid component and/or an aliphatic oxycarboxylic acid as the oxyacid component A polyester block copolymer composition comprising 0.1 to 40 parts by weight of an epoxy compound based on 100 parts by weight of a polyester block copolymer which has been subjected to a blocking reaction. 2 Polyester obtained by blocking reaction of ■ aromatic polyester containing aromatic dicarboxylic acid as the main acid component and ■ aliphatic polyester containing aliphatic dicarboxylic acid as main acid component and/or aliphatic oxycarboxylic acid as oxy acid component For 100 parts by weight of the block copolymer: ■ 0.1 to 40 parts by weight of an epoxy compound; A polyester block copolymer composition containing each of the following parts by weight.