JPS60130643A - Polyester composition - Google Patents

Abstract

PURPOSE:The titled composition having excellent mechanical properties such as tensile strength and flexural rigidity, excellent heat resistance, and increased rates of crystallization, made by incorporating a styrenic hydrocarbon copolymer into a polyester mainly composed of ethylene terephthalate. CONSTITUTION:A composition made by incorporating a styrenic hydrocarbon (e.g. styrene) and an unsaturated polycarboxylic acid derivative selected from among unsaturated polycarboxylic acids, and their anhydrides, salts, and esters [e.g. maleic acid (derviatives)] (A) in an amount of 0.1-50pts.wt. into 100pts.wt. linear polyester (B) mainly composed of ethylene terephthalate. The incorporation of component A into component B will increase the rate of crystallization, giving a resin composition with excellent mechanical properties such as tensile strength flexural rigidity, and improved heat resistance.

Description

Detailed Description of the Invention The present invention provides a polyester containing ethylene terephthalate as a main constituent unit, which has excellent mechanical properties such as tensile strength, bending rigidity, and heat resistance, and has improved crystallinity rate. Regarding.

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 an element +4 for molded bodies, it has the disadvantage that the crystallization rate is slow and high-speed formation is not possible. Therefore, measures such as lowering the temperature of the molding die have been adopted to improve the crystallization speed of the polyester, but this has drawbacks such as thermal deterioration of the resin and warping of the molded product. . Therefore, methods have been proposed in which various additives are added to the polyester for the purpose of increasing the crystallization rate of the polyester and improving mechanical properties such as bending III properties and heat resistance. These methods include methods of blending talc and other various inorganic compounds with the polyester, methods of blending metal salts of alicyclic or aromatic carbonic acids, methods of blending polyalkylene glycols, alkoxypolyalkylene glycols, ethylene, etc. Methods of blending various polymers such as meth)acrylate copolymers, unsaturated polyesters and polyamides are also known. However, although the method of blending these additives can considerably improve the crystallization rate of the polyester, 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.

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 polyester compositions with excellent mechanical properties such as physical properties and tensile strength, we found polyester compositions in which a specific styrenic hydrocarbon copolymer was blended with the polyester, It has been discovered that a polyester composition containing a hydroxyl group-containing copolymer, a styrenic hydrocarbon copolymer, a polyester composition containing a hydroxyl group-containing copolymer and a polyamide achieve the above object, and the present invention has been made based on the present invention. Reached.

To summarize the present invention, the present invention comprises: (A) a substantially linear polyester having ethylene terephthalate as a main constituent unit; A styrene-based hydrocarbon copolymer consisting of an unsaturated polycarboxylic acid derivative component unit (bl) selected from the group consisting of a compound, a salt thereof, and an ester thereof is added in an amount of 0. 1
The gist of the first invention is a polyester composition comprising: (A) a substantially linear polyester containing ethylene terephthalate as a main constituent unit; (B) a styrenic hydrocarbon; A styrenic hydrocarbon copolymer consisting of a component unit (al) and an unsaturated polycarboxylic acid derivative component unit (bl) selected from the group consisting of unsaturated polycarboxylic acids, their acid anhydrides, their salts and their esters, For 100 parts by weight of the polyester (A), 0.
and (C) a hydroxyl group-containing copolymer consisting of a partial hydrolyzate of an ethylene/lower fatty acid vinyl copolymer, based on 100 parts by weight of the polyester (A). The gist of the second invention is a polyester composition characterized by containing (A) a substantially linear polyester having ethylene terephthalate as a main constituent unit, (B) a styrenic hydrocarbon component unit (a) and a styrenic hydrocarbon copolymer consisting of an unsaturated polycarboxylic acid derivative component unit fbl selected from the group consisting of unsaturated polycarboxylic acids, acid anhydrides thereof, salts thereof and esters thereof,
0.1 to 50 parts by weight per 100 parts by weight of the polyester (A), (C) a hydroxyl-based copolymer consisting of a partial hydrolyzate of an ethylene/lower fatty acid vinyl copolymer, is added to the polyester (A). ) and 1 to 40 parts by weight of (D) polyamide per 100 parts by weight of the polyester (A), This is the gist of the third invention.

The polyester blended into the polyester composition of the present invention is a substantially linear polyester containing ethylene terephthalate as its main constituent level. The content of ethylene terephthalate structural units in the polyester is 70 mol% or more, preferably 80 mol% or more. In addition to the terephthalic acid component unit, the dicarboxylic acid component unit constituting the polyester may contain a small amount of other aromatic dicarboxylic acid component 1i. Specific examples of aromatic dicarboxylic acid component units other than terephthalic acid component units include isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid. The diol component units constituting the polyester may contain small amounts of other diol component units in addition to the 88th position of the ethylene glycol component. Specifically, other diol component units other than ethylene glycol component units include propylene glycol, 1.3-propanediol, 1.4-butanediol, neopentyl glycol, cyclohexane diol, cyclohexane dimetatool, 1 .4-bis(β-hydroxyethoxy)benzene, 1.3-bis(β-hydroxyethoxy)benzene,
2,2-bis(4-β-hydroxyethoxyphenyl)
Propane, His(4-β-hydroxyethoxyphenyl)sulfone, Bis(4-hydroxyphenylmethane, 2
, 2-bis(4-hydroxyphenyl)propane and other diol component units having 3 to 15 carbon atoms; and polyalkylene glycol units having a molecular weight of 300 to 10,000 such as polyethylene glycol, polypropylene glycol, and polytetramethylene. can do.

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, hemimellitic acid, 3,3'', 5
, 5″-tetracarboxydiphenyl and other aromatic polybasic acids, butanetetracarboxylic acid and other aliphatic polybasic acids, phloroglucin, L2,4.5-tetrahydroxybenzene and other aromatic polyols, beglycerin, Examples include aliphatic polyols such as trimethyl-1-luethane, trimethylolpropane, and pentaerythritol, and polycarboxylic 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 55.
The content of aromatic dicarboxylic acid component units other than terephthalic acid component units is usually O to 10 mol%, preferably 0 to 8 mol%. The content of ethylene glycol component units is usually in the range of 35 to 55 mol%, preferably 40 to 52 mol%, and the content of diol component units other than the 11th position of the ethylene glycol component is usually O to 15 mol. %, preferably in the range from 0 to 10 mol % and the content of polyfunctional compound component units is usually in the range from O to 10 mol %, preferably from 0 to 8 mol %. In addition, the intrinsic viscosity [η] of the polyester
(The value measured in p-chlorophenol solution at 50°C is usually 0.45 to 2.0 dl/g, preferably 0.
50 to 1.8 d1/g, and the melting point is usually 180 to 280°C, preferably 200 to 270°C.
℃ range, and the glass transition temperature is usually between 40 and 1
00°C1 is preferably in the range of 50 to 90°C.

The styrenic hydrocarbon copolymer (B) blended into the polyester composition of the present invention is a styrenic hydrocarbon component unit (a group consisting of al, an unsaturated polycarboxylic acid, an anhydride thereof, a salt thereof, and an ester thereof). It is a copolymer consisting of an unsaturated polycarboxylic acid derivative component unit (b) selected from Against 0.
It is necessary that the amount is in the range of 1 to 50 parts by weight, and more preferably in the range of 0.5 to 40 parts by weight.

If the blending ratio of the styrenic hydrocarbon copolymer is less than 0.1 part 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. Even if the amount exceeds 50%, the effect of improving the degree of crystallinity will not be seen, and the effect of improving mechanical properties such as tensile strength will not be seen either.

The styrenic hydrocarbon component unit (al content is 50 to 99%) constituting the styrenic hydrocarbon copolymer (B)
．． 8 mol%, preferably in the range of 60 to 99.5 mol%, unsaturated polycarphonic acid derivative component unit (b)
The content is usually in the range of 0.02 to 50 mol%, preferably 0.05 to 40 mol%. Further, the styrenic hydrocarbon copolymer may be a random copolymer, a graft copolymer, or a block copolymer. The number average molecular weight of the styrenic hydrocarbon copolymer (measured by GPC in a THF solvent at 0°C) is usually 3.000 to 500.000.
, preferably in the range of 5,000 to 300,000. The molecular weight distribution (Mw/Mn) is usually in the range of 1.1 to 20, preferably 1.2 to 15.

Specifically, as the styrenic hydrocarbon component unit (a) which is a constituent component of the styrenic hydrocarbon copolymer (B),
Styrene, α-methylstyrene, 0-vinyltoluene,
m-vinyltoluene, p-vinyltoluene, 0-isopropenyltoluene, m-isopropenyltoluene, p-
Examples include isopropenyltoluene, and a mixture of two or more of these may be used. Also,
The unsaturated polycarphonic acid derivative component unit (b) which is a component of the styrenic copolymer (B) includes maleic acid, citraconic acid, itaconic acid, bicyclo[2,2,1
) hept-2-ene-5,6-dicarboxylic acid, aliphatic or cycloaliphatic unsaturated polycarboxylic acids such as methylbicyclo(2,2,1)hept-2-ene-5,6-dicarboxylic acid, anhydrous Maleic acid, citraconic anhydride, itaconic anhydride, bicyclo(2,2,13hept-2-ene-5,6
- dicarboxylic acid anhydrides, aliphatic or alicyclic unsaturated polycarboxylic acid anhydrides such as disodium maleate, monosodium maleate, dipotassium maleate, monopotassium maleate, diammonium maleate, calcium maleate, Disodium citraconate, dipotassium citraconate, disodium itaconate, disodium bicyclo(2,2,1)hept-2-ene-5,6-dicarboxylate, methylbicyclo(2,2,i)hept-2-ene Aliphatic or alicyclic unsaturated polycarboxylic acid salts such as -5,6-dicarboxylic acid dipotassium, dimethyl maleate, diethyl maleate, diisopropyl maleate, monomethyl maleate, dimethyl citraconate, dimethyl itaconate, bicyclo( 2,2,1) dimethyl-2-2-cone-5,6-dicarboxylate, methylbicyclo(2,'2.1)hebdo-2-ene-5
For example, aliphatic or alicyclic unsaturated polycarboxylic acid esters such as dimethyl , 6-dicarboxylate may be used, and a mixture of two or more of these may be used.

Of the styrenic hydrocarbon copolymer (B), the styrenic hydrocarbon component unit (al and an unsaturated polycarboxylic acid selected from the group consisting of unsaturated polycarboxylic acids, acid anhydrides thereof, and esters thereof) When a copolymer consisting of the derivative component unit fbl is blended, the polyester composition of the present invention has particularly excellent mechanical properties such as tensile strength. When the styrenic hydrocarbon copolymer containing the acid salt component unit (b) is blended, the polyester composition of the present invention has particularly excellent mechanical properties such as flexural rigidity and heat resistance, and the crystallization rate is significantly improved. become.

The hydroxyl group-containing copolymer (C) blended into the polyester composition of the present invention is a partial hydrolyzate of ethylene glycol/lower aliphatic vinyl copolymer. It needs to be in the range of 1 to 40 parts by weight, more preferably 2 parts by weight, based on the proportion of the hydroxyl group-containing copolymer.
and 30 parts by weight. If the blending ratio of the hydroxyl group-containing copolymer is less than 1 part by weight, a sufficient crystallization rate will not be obtained (and the effect of improving mechanical properties such as flexural rigidity and flexural strength will not be observed).

The hydroxyl group-containing copolymer (C) is usually 10 to 400 parts by weight, preferably 20 to 3 parts by weight, per 100 parts by weight of the styrenic hydrocarbon copolymer (B).
00 parts by weight.

The hydroxyl group-containing copolymer (B) is a partial hydrolyzate of an ethylene/lower aliphatic vinyl copolymer, and is a copolymer consisting of ethylene component units, lower aliphatic vinyl component units, and vinyl alcohol component units. be. The content of ethylene component units in the hydroxyl group-containing copolymer is usually 10 to 60 mol%, preferably 20 to 50 mol%.
The content of lower fatty acid vinyl component units is usually in the range of O to 5 mol%, preferably 0 to 3 mol%, and the content of vinyl alcohol component units is usually 40 to 90 mol%. %, preferably in the range of 50 to 80 mol%. The hydrolysis rate of the hydroxyl group-containing copolymer is usually in the range of 88 to 100 mol%, preferably 93 to 99 mol%.

The melt flow rate and MFR (measured at 190° C.) of the hydroxyl group content copolymer are usually in the range of 0.05 to 30 g/10 m1n, preferably 0.1 to 20 g/10 m1n.

Specific examples of the lower fatty acid vinyl component unit constituting the hydroxyl group-containing copolymer include vinyl formate, vinyl acetate, vinyl propionate, and the like.

The polyamide (
The blending ratio of D) needs to be in the range of 1 to 40 parts by weight, and more preferably in the range of 2 to 30 parts by weight, per 100 parts by weight of the polyester (A). If the blending ratio of the polyamide (D) is less than 1 part by weight, a sufficient crystallization rate will not be obtained, and the effect of improving mechanical properties such as flexural rigidity and heat resistance will also be insufficient. Even if this happens, the effect of improving the crystallization rate will not be recognized, and the effect of improving the bending rigidity will also be insufficient.

Specifically, the polyamide includes polycaprolactam,
Examples include polyhexanothylene adibamide 1, poly-\gizamethylene sehamide, polyhexamethylene dodecylamide, polylaurin lactam, and poly-11-aminoundecanoic acid.

The intrinsic viscosity [η) (measured at 50°C in m-cresol solvent) of these polyamides is usually 0.6.
from 4.0 dl/g, preferably from 0.8 to 3.5
It is in the range of dl/g.

In the polyester composition of the present invention, in addition to the above-mentioned essential components, various compounding agents or additives conventionally blended into polyesters such as polyethylene terephthalate can be blended as needed. For example, fillers such as talc, diatomaceous earth, calcium carbonate, silica, silica aluminum, alumina, carbon, mica, carbonate fiber, glass fiber, various nucleating agents, lubricants, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetra Examples include surfactants such as methylene glycol, plasticizers such as dioctyl phthalate, neopentyl glycol, and Henshade, and thickeners such as bentaerythritol agents, trimellitic acid, and pyromellitic acid. The blending ratio of these compounding agents or additives is appropriate.

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-mixing the mixture according to a conventionally known method.

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

In addition, regarding the polymer, molding and evaluation of the polyester composition were performed by the following method.

Molding The dried polyester composition was molded using a press molding machine (molding temperature: 290°C) under a nitrogen atmosphere to form 15c+n
5cm X O, 05cm fa) and 15cn+
A sheet having a shape of X 15c+n X Q4c+n (b) was created.

5 cm long, parallel glS punched from the sheet of tensile test (a)
A dumbbell-shaped specimen with a width of 0,5 tm) was heated at 23°C using an Instron tensile tester model 1122.
The test was carried out under the conditions of a crosshead beat of 5 m/min.

Width 1.27 cm, length 6 cut from the sheet of bending test (b)
．． A strip test piece of 350I11 was tested using the above tensile tester at 23° C. and a crosshead speed of 5 mm/min.

Crystallization rate was measured using a Dsc model manufactured by PerkinElmer. That is, take about 5 mmg of sample in a sample pan,
After holding at 290°C for 5 minutes, the temperature was lowered to 190°C at a rate of 80°C/min and maintained at that temperature. From the obtained crystallization curve, t time (time until crystallization progresses to half of the saturated crystallinity) was calculated.

The temperature dependence of the elastic modulus was measured with a Dynamic Mechanical Analyzer Model 981 manufactured by DuPont, using a heat-resistant type (a short piece of 1 cm wide and 2 cm long cut from a BL sheet) 10-shaped test piece. Elastic modulus at 100°C (E+oo
) and the elastic modulus at 30°C (B-30) E100/
E-30 was used as an index representing heat resistance.

Example 1 Styrene 393g and toluene 4 were placed in a reactor equipped with a stirrer.
After 15 minutes of nitrogen bubbling, the reactor was sealed with nitrogen and the temperature was raised to 110°C. Add 1 g of benzoyl peroxide to the dropping funnel (i) and 3 Qn of toluene + 1. ? fE, put 7.5 g of maleic anhydride and 50 n+1 toluene into the lower funnel (ii),
After bubbling nitrogen for 15 minutes, the solution was added dropwise to the reactor over about 1 hour. After the dropwise addition was completed, the reaction was continued for the above period of time, and then the reaction product was precipitated in a large excess of hexane. The yield of the produced polymer was 171 g. Table 1 shows the results of analyzing the produced polymer (sample code: PSMi).

The number average molecular weight Mn measured by GPC (THF solvent, 40° C.) was 51,000, and the molecular distribution Mw/Mn was 2.1. Further, the maleic anhydride content in the produced polymer was determined by elemental analysis to be 4 mol %.

Polyethylene terephthalate resin [Kanehou Gosen Co., Ltd.]
Manufactured by Herpetsu I-E F G-7, intrinsic viscosity 0°80d
l/g] 2200 parts 20 parts of styrene/maleic anhydride copolymer (PSM-) synthesized by the above method
Melt blending was carried out using a mmφ extruder (L/D=28, Dalmage type screw) under conditions of an i11 fat temperature of 260° C. and a screw rotation speed of 3 Orρm. The results of examining its physical properties are shown in Table 2.

Examples 2 to 5 Various styrenic hydrocarbon polymers shown in Table 1 (sample code: PSM-2 to
4, PVM-1) was synthesized.

These polymers and polyethylene terephthalate resin (
EFG-7) according to the method of Example 1 to produce blend polymers having the compositions shown in Table 2. The results of measuring the physical properties are shown in Table 2.

Example 6 Polystyrene resin [manufactured by Mitsui Toatsu Co., Ltd., 1.-
100 g of Borex ap-525-51) and 500 ml of bala-xylene were charged, and the temperature was raised to 140°C.

Using a dropping funnel, add 1.3 dicumyl peroxide.
A solution containing 5 g of rosexylene and 30 g of maleic anhydride.
A paraxylene solution containing g was added dropwise over 4 hours. After the dropwise addition was completed, the reaction was further carried out at 140°C for 2 hours, and the resulting polymer was recovered by precipitating it into a large excess of methanol. Yield was 94g. Table 1 shows the analysis results of the produced polymer (sample code: STM-1). Table 2 shows the physical properties of a blend of 10 parts of this polymer (STM-1) and 100 parts of polyethylene terephthalate resin (EFG-7).

Example 7 After the styrene/maleic anhydride copolymer (sample code: PSM-2) used in Example 2 was melted into dots, water was added and a hydrolysis reaction was carried out at 90°C. Polyester 1 compositions having the compositions shown in Table 2 were produced under the same conditions as in Example 1, except that the styrene-maleic acid copolymer thus obtained was used. The results of measuring the physical properties were shown in the second experiment. -2) and 300ml of toluene were charged and the temperature was raised to 110°C. Using a dropping funnel, an aqueous solution containing 0.113g of NaOH was added dropwise over 5 minutes, and for 4 hours while distilled water was extracted from the system. Made it react.

After washing the reaction solution with water, the precipitated polymer was recovered by precipitating it in hexane. Produced polymer (sample code: PSM-
The results of the analysis of 5) are shown in Table 3. Reactions similar to those described above were carried out using various styrenic hydrocarbon copolymers as raw materials to synthesize copolymer salts as shown in Table 3. A polyester resin composition was produced in the same manner as in Example 1 using the styrenic hydrocarbon copolymer shown in Table 3. Table 4 shows the results of measuring the physical properties.

Example 16 Polyethylene terephthalate resin (EFG-7) 30
0 parts, 30 parts of Na salt of the styrene/maleic anhydride copolymer used in Example 8 (sample coat 2 PSM-5),
Force lath fiber ff411 with an average length of 6 mm (Nitto Boseki)
Co., Ltd., chip strand, C36PE-231314
One part was melted and mixed under the same conditions as in Example 1. Blend thus prepared, 151Jmer Q4A Examples 17 to 22, Comparative Examples 1 to 4 Polyethylene terephthalate resin [Kanebo Gosen Co., Ltd.
jlJ, EFG-7), styrene copolymer, hydrolyzate of ethylene/vinyl acetate copolymer [manufactured by Kuraray Co., Ltd., EVAL-EPF: ethylene-containing ML 30ml 1%, old 1
．． 5g/10m1n, EVAL-EP
B: Ethylene content 40m1%, MT5g/10m1n
), nylon resin [nylon 6, manufactured by Toshiku Co., Ltd.], Alamine CMto21XF, (77) 1.39 dl/
g, Nyl:):/6,6: DuPont, Seidel 101, [η) 1.55dl! /g using the fifth
Table (Examples 17-22) and Table 6 (Comparative Examples 1-4)
A blend sample with the composition shown in was prepared. The results of examining the physical properties are shown in Tables 5 and 6.

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi

Claims (1)

[Scope of Claims] (11(A) a substantially linear polyester having ethylene terephthalate as a main constituent unit, and (B) a styrenic hydrocarbon component unit ia+ and an unsaturated polycarboxylic acid, an acid anhydride thereof, a salt thereof and an unsaturated polycarboxylic acid derivative component unit (b) selected from the group consisting of 50 parts by weight of a polyester composition comprising: +21 (A) a substantially linear polyester having ethylene terephthalate as its main constituent unit; (B) a styrenic hydrocarbon component unit (al and unsaturated polycarbonate); A styrenic hydrocarbon copolymer consisting of an unsaturated polycarboxylic acid derivative component unit (b) selected from the group consisting of an acid, its acid anhydride, its salt and its ester is added to 100% of the polyester (A) by weight. 0.1 for part
and 50 parts by weight of a hydroxyl group-containing copolymer consisting of a partial hydrolyzate of (C)'I ethylene lower fatty acid vinyl copolymer, based on 100 parts by weight of the polyester (A).
0 parts by weight of a polyester composition. (31 (A) Substantially linear polyester having ethylene terephthalate as its main constituent unit, (B) Styrenic hydrocarbon component unit (from the group consisting of Al and unsaturated polycarphonic acid, its acid anhydride, its salt, and its ester) A styrenic hydrocarbon copolymer consisting of selected unsaturated polycarboxylic acid derivative component 11 (bl) was added at 0.1% per 100 parts by weight of the polyester (A).
(C) 1 to 40 parts by weight of a hydroxyl group-containing copolymer made of a partial hydrolyzate of an ethylene/lower fatty acid vinyl copolymer per 100 parts by weight of the polyester (A); D> A polyester composition containing 1 to 40 parts by weight of polyamide per 100 parts by weight of the polyester (A).