JPS6055055A - Polyester composition - Google Patents

Abstract

PURPOSE:To provide a polyester compsn. having improved adhesion to coating agents, consisting of a polyester type block copolymer contg. a polylactone segment and a specified copolyester. CONSTITUTION:A compsn. consists of 97-50wt% polyester type block copolymer ( I ) composed of a crystalline arom. polyester segment and a polylactone segment and having a polylactone segment content of 5-80wt%, and 3-50wt% polyester (II) which is a copolyester wherein the acid component consist of 50- 100mol% of arom. dicarboxylic acid and 0-50mol% of aliph. dicarboxylic acid and/or alicyclic dicarboxylic acid and the alcohol component consists of 2-20C glycol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester block copolymer composition having a rubber-like elastic body. More specifically, the present invention relates to coating agent 1, a polyester block copolymer composition with improved adhesion to, for example, a polyurethane adhesive.

Polyester block copolymer obtained by reacting aromatic polyester and lactones 1 So-called polyester elastomer is a material that has recently attracted interest in various uses due to 1 heat resistance 1 light resistance 1 good low temperature properties etc. be.

Methods for reacting aromatic polyester and lactone include a method for reacting crystalline aromatic polyester and lactone (Japanese Patent Publication No. 48-4116), a method for reacting crystalline aromatic polyester and lactone, and a block initial polymer obtained by reacting the crystalline aromatic polyester and lactone. A method in which one chain is extended by reacting a polyfunctional acylating agent with a polyfunctional acylating agent (Japanese Patent Publication No. 4B-4115) A method in which lactone is polymerized in the presence of a crystalline aromatic polyester while the former is in a solid phase (Japanese Patent Publication No. 4B-4115) 5ε-49037) is known.

However, even this excellent polymer has the following drawbacks. For example, it has poor adhesion with coating agents used for metal vapor deposition, sputtering, etc., and is unsuitable for applications using such coating agents (vapor deposited products 1 sputtered articles).

The inventor of the present invention has conducted intensive research in order to improve the drawbacks of polyester block copolymers consisting of aromatic polyester segments and polylacto segments, and as a result, has discovered that polyester can be blended into the copolymer and has arrived at the present invention. That is, the present invention consists of a polyester-type block copolymer (+) consisting of a crystalline aromatic polyester segment and a polylactone segment, and a polyester (1);
) The polyester type block copolymer (1) has a polylacto segment content of 5 to 80% by weight, and is a copolymerized polyester consisting mainly of glycol having 2 to 20 carbon atoms as an alcohol component. , and (1) A polyester composition characterized in that the polyester type block copolymer (1) is 97 to 50% by weight, and the polyester (1) is 3 to 50% by weight. It is.

Although the present invention has heat resistance and light resistance equivalent to those of polyester block copolymers, it also has excellent impact resistance and low-temperature properties, and also has good adhesion with coating agents, making it difficult to use for metal vapor deposition. It can be used for sputtering, etc., greatly expanding the uses of polyester block copolymers.

In the present invention, the compatibility between the polyester block copolymer (1) and the polyester (1) is extremely good, and the molded product does not peel off into layers.

The polyester block copolymer in the present invention consists of a crystalline aromatic polyester segment and a polylactone segment, and can be obtained, for example, by reacting a crystalline aromatic polyester with a lactone.

Crystalline aromatic polyester is a polymer mainly containing ester bonds or ester bonds and ether bonds, and therefore has at least one aromatic group as the main repeating unit and a hydroxyl group at the end of each molecule, and is used as a molding material. preferably has a molecular weight of 5,000 or more. The adhesive and coach ink material may be polyester having a molecular weight of 5000 or less.

Preferred specific examples include homopolyesters such as polyethylene terephthalate 1 polytetramethylene terephthalate 1 poly 1,4-cyclohexylene dimethylene tere 7 talate 1 polyethylene 2,6-naphthalate, polyethylene oxybenzoate, poly-p-phenylene bis Polyester ethers such as oxyethoxy terephthalate, consisting mainly of 1 tetramethylene terephthalate unit or ethylene terephthalate unit, in addition to 1 tetramethylene or ethylene isophthalate unit, 1 tetramethylene or ethylene adipate unit, 1 tetramethylene or ethylene sebacate unit, ．． ．． 4-cyclohexylene dimethylene ethylene terephthalate) unit.

These include copolymerized polyesters or copolymerized polyester ethers having copolymerized components such as 5-tetramethylene or ethylene-p-oxybenzoate units. The content of tetramethylene terephthalate units or ethylene terephthalate units is preferably 60 mol% or more.

As the lactone, 1ε-caprolactone is most preferable, and enantolactone A cabrylolactone F and the like can also be used, but two or more types of lactones can also be used at the same time.

In order to obtain the polyester elastomer used in the present invention, the crystalline polyester and lactones may be reacted without a catalyst, or even if a catalyst is used, the present invention will not be invalidated in any way. The content of lactone in the polyester flock copolymer is 5 to 80% by weight, preferably 20 to 70% by weight.

The copolymerized polyester used in the present invention consists of 50 to 100 mol% of aromatic dicarboxylic acid and 0 to 150 mol% of aliphatic dicarboxylic acid and/or alicyclic dicarboxylic acid as the acid component, and mainly as the alcohol component. Polyester consisting of glycol having 2 to 20 carbon atoms≠m.

Examples of aromatic dicarboxylic acids include terephthalic acid, 1-isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid. Particularly preferred is terephthalic acid or terephthalic acid and isophthalic acid.

Examples of the aliphatic dicarboxylic acids include polymethylene dicarboxylic acids (12-methylazide) such as sepatic acid (acid having 4 to 36 carbon atoms), and decamethylene dicarboxylic acid (acid having 4 to 36 carbon atoms).

Examples include aliphatic dicarboxylic acids having side chains such as 12-ethylsperic acid. Examples of alicyclic dicarboxylic acids include 1,4-cyclohexylene dicarboxylic acid.

Among these aliphatic dicarboxylic acids, adipic acid and cepatic acid are particularly preferred.

The acid component in polyester (1) consists of 50 to 100 mol% of aromatic dicarboxylic acid and 0 to 50 mol% of aliphatic dicarboxylic acid and/or alicyclic dicarboxylic acid. If the amount of aromatic dicarboxylic acid is less than 50 mol %, adhesive strength will decrease, hydrolyzability will be poor, and blocking will occur.

Glycols having 2 to 20 carbon atoms include 1-0 ethylene glycol, 1.3-i-ropylene glycol 1
1,4-butanediol, 1,5-bentanediol 1
Examples include neopentyl glycol, 16-hexanediol, 1 diethylene glycol, 1 dipropylene glycol, bisphenol AN, hydrogenated bisphenol, or ethylene oxide adducts or propylene oxide adducts thereof. Particularly preferred are ethylene glycol 9], 4-butanediol and neopentyl glycol.

Furthermore, ethylene glycol (A), 1 μm butane di-
(B) or neopentyl glycol (0) (
B) + (0) 2≧□ −〇4.5 It is desirable to satisfy the following relationship (A). When using ethylene glycol 11,4-butanediol or neopentyl glycol, other glycols having 2 to 20 carbon atoms may be used in an amount of 10 mol% or less of the total glycol component. The alcohol component of polyester (1) is 1
Polyhydric alcohols having a valence of 3 or more or glycols having 20 or more carbon atoms may be used.

The polyester used in the present invention can be produced by conventional production methods such as 1 transesterification method and 1 direct polymerization method. The reduced specific viscosity of the polyester (1) obtained by these methods is O05 to 2.5.

In the present invention, polyester block copolymer (1) 97-
Polyester lL/≠Tsumajingyu (1) consisting of 3 to 50 parts by weight and less than 3 parts by weight will not improve the adhesion of the coating agent of the product obtained from this composition. If the amount is less than 50 parts by weight, the melting point and crystallization rate of the composition obtained from the composition will be lowered, and the moldability will be lowered.

It is preferable to mix. In addition, because of the plasticizer, pigment 19- Fillers and the like can be added.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

In the Examples, each physical property of the rod was measured according to the following procedure. Furthermore, in the examples, parts simply refer to parts by weight.

(1) Solution viscosity The intrinsic viscosity of the saturated copolymerized polyester resin (1) is an extrapolated value.

(2) Melting point Fully automatic melting point measuring device (Mettler Model 1 Model F Knee 1)
This is the value measured at

(8) T-type peeling test Prene chips of polyester block copolymer Shugantsubaki (1) and saturated copolymer polyester (1) were peeled at 80°C.
After vacuum drying day and night, it was molded into a 0.15-sized sheet using an extruder. A urethane adhesive made of polytetramethylene adipate (MY-1000) and triphenylmethane triisocyanate was applied to the edge of this sheet, and the sheet was pressed under a pressure of 219/cd at 100°C for 70 minutes, and then the test piece was cut out and made into an XT type. A peel test was conducted to measure the normal liquid adhesion strength.

(4) Durability The T-peel resistance of the T-peel test piece was measured after it was treated with hot air at 140°C for 72,916 hours.

Established.

Production Example L 70 kg of polytetramethylene tereate and 3011 g of ε-cabrolactone were placed in a reactor, and after one nitrogen gas blow, the mixture was melted and reacted for 2 hours with stirring at 230°C.
Unreacted ε-caprolact strength 51sTq/cx under vacuum
The IS tensile elongation at break was 743%.

Production Example 2 Stirrer 1 Thirst degree iff, 10≠≠Full-tip stainless steel automatic δ resin, 680 parts of dimethyl tere 7 tallate, 78 parts of dimethyl isophthalate, 3 parts of ethylene glyfur, 1 part of Bθ], 4- After adding 236 parts of butanediol, 0.71 parts of potassium titanium oxalate and 0.65 parts of antimony trioxide, transesterification was carried out at 170°C to 220°C for 3 hours. 93 parts and 161 parts of adipic acid were added, and an esterification reaction was carried out at 5220°C to 250°C for 1.5 hours. Next, the pressure was gradually reduced at 266°C to remove excess glycol, and then a polycondensation reaction was carried out at 265°C under a reduced pressure of 0.1 to 0.3-H9 for 2.5 hours. The resulting copolymerized polyester resin body) had an intrinsic viscosity of 0.90 and a melting point of 13.
The temperature was 5°C. As a result of composition analysis by IMF, the composition of 1 copolymerized polyester resin (A) is 70 mol% of terephthalic acid.
, isophthalic acid 8 mol % 1 adipine l! 4!22 mol%
, 60 mol% of ethylene glycol) and 40 mol% of 1,4-butanediol.

Production Example & Copolymerized polyester resin (B, 0) shown in Table 1 was produced by the same method as Production Example 2.

Table 1 Example L 90 parts of the polyester block copolymer (1) obtained in Production Example 1 and 10 parts of the polyester copolymer (A) obtained in Production Example 2 were placed in a drum tumbler and heated at room temperature. Stirred for 10 minutes. The mixture was heated to 23 mm using a 40φ extruder.
It was extruded at 0° C. and formed into a sheet with a thickness of 0.5 mm and a width of 1 oc. The edges of the obtained sheet were coated with 7 parts of a 50% dispersion solution of urethane adhesive (polytetramethylene adipate (MY-1000) in toluene/M In K-50/50 solvent and triphenylmethane triisocyanate in toluene/M In K-50/50 solvent. M III K-5o/50 I in solvent
(mixed with 1 part of SO% dispersion solution), and the sheet obtained above was laminated together under a pressure of 21+97-100
After crimping for 70 minutes at °C, the test piece was cut out and subjected to a 1T peel test to measure the normal liquid adhesion strength. The results are shown in Table 2.

Example a The polyester block copolymer (1) obtained in Production Example 1 and the polyester copolymer obtained in Production Example 2 were placed in a predetermined one-drum tumbler, and 0.5-thickness was prepared in the same manner as in Example 1. A sheet was prepared, treated with a urethane adhesive, and then its normal adhesive strength was measured using a T-peel test.

Example & The degree was measured.

Further, 100 test pieces were heat-treated at 140°C for 16 hours.
The T-peel strength was measured after 45 hours of treatment in hot water at .degree. The results are shown in Table 2.

Table 2 15- 423-

Claims (1)

[Claims] A polyester block copolymer (1) consisting of a crystalline aromatic polyester segment and a polylactone segment
) and polyester (1) 1 (1) Polyester-type block copolymer 1) contains 5 to 80% by weight of polylactone segment and polyester (1) contains aromatic dicarboxylic acid as a brewing component. 50 to 100 mol% and 0 to 50 mol% of aliphatic dicarboxylic acid and/or alicyclic dicarboxylic acid, and mainly contains 2 to 0 carbon atoms as an alyol component.
It is a copolymerized polyester consisting of a glycol, and (1) the polyester type block copolymer (1) in the polyester composition is 97 to 50% polymerized, and the polyester (seal) is 3 to 5% polymerized. Special thing 1
- A polyester composition having the following characteristics.