JPS6144947A - Polyester composition - Google Patents

Abstract

PURPOSE:A polyester composition having an excellent rate of crystallization, and good mechanical properties and heat resistance, made by incorporating a specified metal salt of a carboxylic acid into a linear polyester mainly consisting of ethylene terephthalate. CONSTITUTION:0.01-10pts.wt. alkali (earth) metal salt of an organic carboxylic acid having imide linkages and 50 or less carbon atoms (e.g. a compound of formula I, II or III) is added to 100pts.wt. linear polyester [of an intrinsic viscosity (a solution in p-chlorophenol at 50 deg.C) of about 0.45-2dl/g, a melting point of about 180-280 deg.C, and a glass transition temperature of about 40-140 deg.C] containing at least about 70mol% ethylene terephthalate units, and this mixture is melt- compounded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides ethylene terephthalate which has excellent mechanical properties such as tensile strength or bending rigidity, and heat resistance, and has an improved crystallization rate. It relates to polyester as a main structural unit.

[Conventional technology]

Conventionally, substantially linear polyesters containing ethylene terephthalate as the main constituent unit, such as polyethylene terephthalate, have excellent properties such as rigidity, heat resistance, and gas barrier properties, and can be used in various shapes such as films, sheets, laminates, and containers. Although it is used as a material for molded objects, it has the drawback that it has a slow crystallization rate and cannot be molded at high speed.

Therefore, in order to improve the crystallization rate of the polyester, measures such as increasing the temperature of the molding die have been adopted, but these methods have drawbacks such as thermal deterioration of the resin and warping of the molded product. Therefore, the crystallization rate of the polyester is improved,
For the purpose of improving mechanical properties such as bending rigidity and heat resistance, methods have been proposed in which various additives are blended into the polyester. These methods include a method of blending talc and other various inorganic compounds with the polyester;
A method of blending metal salts of aliphatic or aromatic carboxylic acids, blending various polymers such as polyalkylene glycol, alkoxypolyalkylene glycol-ethylene/(meth)acrylate copolymer, unsaturated polyester, polyamide, etc. Method 1 is also publicly known ◇ In particular, the evil fatigue technique that combines metal salts of carboxylic acid and I7,
JP 4B-4097, JP 51-148744, JP 56-145943, JP 57-38847, JP 57-1
45145, 58-63743, etc.

[Problem that the invention seeks to solve]

Although the crystallization rate of the polyester is considerably improved by the method of blending these conventionally proposed additives, a sufficient improvement in the crystallization rate to satisfy the current demand for high-speed moldability has not been achieved. The development of even better compounding agents is desired.

In addition, polyester containing ethylene terephthalate as its main constituent unit, such as polyethylene terephthalate, is a material with excellent mechanical properties, but with the diversification of molding applications, mechanical properties such as tensile strength, There is a need to further improve the physical characteristics.

[Means for solving problems]

The present inventors recognized the above-mentioned demand for a polyester having ethylene terephthalate as its main constituent unit, and developed a polyester composition having an excellent crystallization rate, mechanical properties such as flexural rigidity, and heat resistance. As a result of searching for a polyester composition with excellent mechanical properties such as physical properties and tensile strength, it was discovered that a polyester composition containing a specific carboxylic acid salt blended with the polynisder achieved the above object, and the present invention was achieved.

[Summary of the invention]

To summarize the present invention, the present invention relates to a substantially linear polyester CA) having ethylene terephthalate as a main constituent unit.
100 parts by weight of an alkali metal salt or alkaline earth metal salt of an organic carboxylic acid having 50 or less carbon atoms and having an imide bond (color) in a range of 0.01 to 10 parts by weight. The gist of this paper is as follows.

[Polyester (A)]

The polyester blended into the polyester composition of the present invention is a substantially linear polyester containing ethylene terephthalate as a main constituent unit. The content of ethylene terephthalate structural units in the polyester is 70 mol% or more, preferably 80 mol% or more. The dicarboxylic acid component units constituting the polyester may contain a small amount of other aromatic dicarboxylic acid component units in addition to the terephthalic acid component units. Specific examples of aromatic dicarboxylic acid component units other than terephthalic acid component units include isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid. The diol component units constituting the polyester may contain small amounts of other diol component units in addition to the ethylene glycol component units. ethylene glycol 51
Specifically, other diol component units other than the unit include propylene glycol, 1,3-propanediol, 1.
4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexane dimetatool, 1.
4-bis(β-hydroxyethoxy)benzene, ], 3
-bis(β-hydroxyethoxy)benzene, 2.2-
The number of carbon atoms such as bis(4-β-hydroxyethoxyphenyl)propane, bis(4-β-hydroxyethoxyphenyl)sulfone, bis(4-hydroxyphenylmethane, 2,2-bis(4-hydroxyphenyl)propane) 5 to 20 diol component units and a molecular weight of 3
00 to +0,000 polyethylene glycol,
Examples include polyalkylene glycol units such as polypropylene glycol and polytetramethylene glycol. In addition to the aromatic dicarboxylic acid component units and the diol component units, the polyester may also contain a small amount of a polyfunctional compound as required. Specifically, the polyfunctional compound component units include trimellitic acid, trimesic acid, pyromellitic acid,
Aromatic polybasic acids such as 3,3',5,5'-tetracarboxydiphenyl, aliphatic polybasic acids such as butanetetracarboxylic acid, phloroglucin, 1,2,4
, 5-tetrahydroxybenzene, aliphatic polyols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and oxypolycarboxylic acids such as tartaric acid and malic acid.

Further, the polyester may contain a small amount of an oxycarboxylic acid compound such as p-hydroxybenzoic acid in addition to the aromatic dicarboxylic acid component unit, the diol component unit, and the polyfunctional compound.

The composition of the constituent components of the polyalkylene terephthalate is:
The content of terephthalic acid component units is usually 40 to 51
mol%, preferably in the range of 43 to 50.5 mol%, and the content of aromatic dicarboxylic acid component units other than terephthalic acid component units is usually O to 10 mol%, preferably 0 to 7 mol%. range, the content of ethylene glycol component units is usually 35 to 51 mol%,
It is preferably in the range of 40 to 50.5 mol%, and the content of diol component units other than ethylene glycol component units is usually in the range of 0 to 15 mol%, preferably 0 to 10 mol%, and the polyfunctional compound component. The content of units is usually in the range of 0 to 10 mol%, preferably 0 to 8 mol%. In addition, the polyester (D intrinsic viscosity W
cη] (value measured at 50°C in p-chlorophenol solution) is usually 0.45 to 2.0 (l jl'/
g, preferably in the range of 0.50 to +8al/g, and the melting point is usually +80 to 280'C.

It is preferably in the range of 200 to 270°C, and the glass transition temperature is usually 40 to 140°C, preferably 5
It ranges from 0 to 120°C.

[Ingredients (B)]

The [ω] component blended into the polyester composition of the present invention is:
It is an alkali metal salt or alkaline earth metal salt of an organic carboxylic acid having an imide bond and having 50 or less carbon atoms.

The organic carboxylic acid having an imide bond and having 50 or less carbon atoms preferably has 6 to 45 carbon atoms, particularly preferably 6 to 40 carbon atoms. When the number of carbon atoms exceeds 50, the compatibility with the polyalkylene terephthalate generally deteriorates and a sufficient crystallization promoting effect cannot be obtained.
It must be within the above range.

The carboxylic acid is usually represented by the general formula (I) [wherein A1 and A2 (hereinafter, both are not abbreviated as A together. Note that A1 and A
2 includes a combination, and is preferably a combination. ) and B are an aliphatic group, an alicyclic group, an aromatic group, or a group containing a bond thereof; at least one of A and B contains a carboxyl group; (When A contains a carboxyl group, B may contain H.)
It is expressed as

Among the carboxylic acids represented by the general formula here:

Preferably, A is aliphatic, the general formula fl
) (In the formula, l is 2 to O, and m is an integer from 1 to 15.) Specifically, the following can be mentioned, and others can also be used. .

Further, among the carboxylic acids represented by the general formula (1), those in which A is an alicyclic type are preferably those represented by the general formula
Indicates an integer of 5. ), and particularly preferably n is 4. Specific examples include υ.

Further, among the carboxylic acids represented by the formula, those in which A is aromatic and preferably used in the composition of the present invention include general formula (g) or (V) (in both formulas, R1 to R6 is a group selected from the group consisting of hydrogen, a lower alkyl group, an aryl group, an aralkyl group, a halogen, a carboxyl group, a nitro group, and an amide group, and R7 to R9 have 20 carbon atoms.
Examples include phthalimide derivatives, trimellitimide derivatives, and virometdiimide derivatives represented by the following hydrocarbon groups.Specifically, examples thereof include the following.

As the salt of the above carboxylic acid (B> As the alkali metal or alkaline earth metal constituting the component, Ha, Oa
, Mg, Oa, Sr, Ba, etc., among which NIIL is preferable.

Particularly preferred constituting the composition of the present invention) 5! Specific examples of i and min include the following compounds.

mono- or disodium salt of mono- or disodium salt of.

The blending ratio of the carboxylic acid salt (B>) needs to be in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the polyester LA, and more preferably 0.01 to 10 parts by weight.
．． The range is from 0.6 to 5 parts by weight. The carboxylate salt [
If the blending ratio of B) is less than 0.01 parts by weight, a sufficient crystallization rate will not be obtained, and the effect of improving mechanical properties such as tensile strength will also be insufficient, and if it exceeds 10 parts by weight, bending strength etc. The effect of improving the mechanical properties of the material no longer appears. Note that for 031m, a single compound may be used in a proportion within the above range, or two or more types may be mixed and used in a proportion within the above range).

[Other ingredients]

The polyester composition of the present invention comprises the above-mentioned polyester composition.
and essential 2 of the above specific organic carboxylate (B)
Although it may consist of only the above ingredients, other ingredients such as plasticizers, other crystallization promoters, and various other compounding agents and additives may also be added as necessary.

Any known plasticizer may be used as the plasticizer that may be blended into the polyester composition of the present invention. For example, polyethylene glycol, polypropylene glycol, polythiogenol, or a copolymer thereof, or a divalent polymer thereof. Fe/-/I4, polyalkylene glycols such as copolymers with diols, dibenzoate of ethylene glycol, dibenzoate of diethylene glycol, dibenzoate of neopentyl glycol, dibenzoate of thioditanol, and polyalkylene gelylcols. Ester compounds such as dibenzoate, poly-
ε-caprolactone, aliphatic polyesters such as polyesters derived from aliphatic dicarboxylic acids and aliphatic diols, epoxidized polyalkylene gelylcols containing nivoxy groups, montan vinegar wax, polyolefin wax, modified polyolefin wax, etc. Examples include waxes, ether compounds such as trimethyl ether of thiodiphenol, diphenyl ether of diethylene glycol, and diphenyl ether of polyalkylene glycol. Of course, these may be used in combination. The plasticizer is 1
It is preferably added in an amount of 0.5 to 15 parts by weight, particularly preferably 1 to 10 parts by weight.

Any known crystallization promoter may be used as the crystallization promoter that may be incorporated into the polyester composition of the present invention. For example, solid inorganic compounds such as talc, clay, salts of organic carboxylic acids such as caproic acid, stearic acid, montanic acid, ammonium, *franic acid, terephthalic acid, etc., e.g. sodium, potassium salts, with pendant carboxyl groups. Mention may be made of the metal salts of organic polymers, for example copolymers of olefins or aromatic olefins with unsaturated carboxylic acid compounds such as acrylic acid or methacrylic acid or maleic anhydride. These are also suitable for use in a mixture. Among these crystallization promoters, metal salts of copolymers with aromatic olefins and β-unsaturated carboxylic acids are particularly preferred. Crystallization accelerator is polyester + Al
It is preferably added in an amount of 0.05 to 15 parts by weight, particularly preferably 0.1 to 10 parts by weight, per 00 parts by weight of shite.

In addition, other compounding agents or additives include reinforcing fillers such as diatomaceous earth, calcium carbonate, silica, silica alumina, alumina, carbon, mica, titanium oxide, carbon fiber, glass fiber, and aramid fiber, lubricants, surfactants,
Thickeners such as pentaerythritol, trimellitic acid, pyromellitic acid, flame retardants, UV stabilizers, antioxidants,
Examples include a mold release agent and a coloring agent. The blending ratio of these compounding agents or additives is appropriate.

Furthermore, various other polymers, such as polyolefins, olefin copolymers, or modified polymers thereof,
Polystyrene, polyamide, polycarbonate, polyacetal, polysulfone, polyphenylene oxide, fluororesin, silicone resin, epoxy resin, etc. may be blended.

The polyester composition of the present invention can be obtained by mixing a polymer mixture consisting of each essential component and, if necessary, compounding agents and additives, and melt-kneading the mixture according to a conventionally known method.

〔Example〕

Next, the present invention will be specifically explained using examples.

In addition, in the examples, molding and evaluation of the polyester compositions were performed in the following manner.

Press molding The dried polyester composition was molded using a press molding machine (molding temperature: 29 [1-C)] by 15 strokes x 10 cIn x 0.2α.
A rapidly cooled press sheet having the shape of was prepared.

Injection molding: Using an injection molding machine model 1S-35P manufactured by Toshiba Machinery Co., Ltd., a bending test sample with a thickness of 0.2 (W) was prepared at a mold temperature of 70°C.

Width 1.27G, length 6.65 cut from bending test press sheet
A strip-shaped test piece of bacteria or an injection molded test piece of the same shape was tested for 23 minutes using an Instron tensile tester model 1122.
The test was carried out at a temperature of 5 mm/min at a crosshead speed of 5 mm/min.

The crystallization rate was measured using a differential calorimeter (abbreviated as DSL, using a mold manufactured by PerkinElmer). In other words, the sample length is approximately 5 m.
g was placed in a sample pan and held at 290°C for 5 minutes, then the temperature was lowered to 2+0″C at a rate of 80″07 minutes and held at that temperature.

From the obtained crystallization curve, t1/2 (time until crystallization progresses to half the saturated crystallinity) was calculated.

Width L27 cut from heat-resistant press sheet or injection molded sample
z, using a strip-shaped test piece with a length of 2C1n, using a DuPont Dynamic Mechanical Analyzer Model 981.
- The temperature dependence of the elastic modulus was measured using a mold. The ratio of the elastic modulus (Eloo) at 100°C to the elastic modulus (IQ.) at 60°C, E 1o O/” 30, is used as an index to express heat resistance. Approximately 5 mg of quenched press sheet or injection sheet sample was measured.
Weigh it, raise the temperature at 20"C/min, 290°C
The DSO measurement was carried out under the condition that the temperature was lowered at 20"C/min after holding the temperature at 5 ml at The amount of heat △Ho obtained from the peak area at the crystallization temperature was measured. T.H obtained in this way is an index related to the low-temperature mobility of polyester molecules. The smoky △HH/△Ha indicates that it is easy to crystallize. A small value for both T(!H-ΔHH/ΔHc) indicates that the polyester is likely to crystallize.

Examples 1 to 17, Comparative Examples 1 to 2 Intrinsic viscosity 0.65 dJl'/g (o-chlor 7 min/g)
After tri-blending polyethylene terephthalate (25°C) with metal salts of various imide compounds (component B: see Table 2) and various additives (see Table 2) in the proportions shown in Table 1, 20 mmφ Melt mixing was performed using an extruder (Dulmage type screw, full flight type screw when glass fiber was blended, L/D = 28). Table 1 shows the results of examining the physical properties of the polyester composition thus obtained. In addition, in Table 2,
Metal salt B-2 of imide compound was synthesized as follows. A reactor was charged with 29.6 g of phthalic anhydride and 120 g of diphenyl ether, and the mixture was heated for 14 hours with stirring under a nitrogen atmosphere.
The temperature was raised to 0°C. Next, 26.2 g of aminocaprone was added, and the reaction was carried out for 1 hour while distilling water out of the system.

After further reaction at 170°C for 2 hours and 220°C for 3 hours, the product was precipitated in hexane and collected.

After dissolving 35 g of the thus obtained 5-(N-phthalimide)capron II in 400 ++ rjl', 5.36 g of IJium was dissolved
The aqueous solution containing the mixture was dropped to perform a neutralization reaction, and the precipitated white solid (B-2) was collected. Metal salts of various imide compounds were synthesized by conducting almost the same reactions as above.

Table 2. Additive list Table 2. ([tree)

Claims (1)

[Claims] (1) 100 parts by weight of a substantially linear polyester (A) whose main constituent unit is ethylene terephthalate and an alkali metal salt or alkaline earth metal salt of an organic carboxylic acid having an imide bond and having 50 or less carbon atoms (B) 0.01 to 10 parts by weight of a polyester composition.