JPS6353221B2 - - Google Patents

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 a polyester block copolymer composition that has improved adhesion to coating agents such as polyurethane adhesives. Polyester block copolymers obtained by reacting aromatic polyesters with lactones, so-called polyester elastomers, are materials that have recently become of interest for various uses due to their heat resistance, light resistance, and low-temperature properties. 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 a polyfunctional acylating agent is reacted with a polyfunctional acylating agent to extend the chain (Japanese Patent Publication No. 48-4115), 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. 52 -49037) is known. However, even such excellent polymers have the following drawbacks. For example, it has poor adhesion with coating agents used in metal vapor deposition, sputtering, etc., and is unsuitable for applications using such coating agents (vapor deposited products, sputtered articles). The inventor of the present invention has conducted extensive 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 thus 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 (), and (i) the content of the polylactone segment in the polyester type block copolymer () is (ii) The polyester () contains 50 to 100 mol% of aromatic dicarboxylic acid (however, terephthalic acid is 70 mol% or less) and aliphatic dicarboxylic acid and/or alicyclic dicarboxylic acid as acid components. It is a copolymerized polyester consisting of 0 to 50 mol% of acid and mainly consisting of glycol having 2 to 20 carbon atoms as an alcohol component, and (iii) the polyester type block copolymer () is 97 to 50% by mole in the polyester composition. % by weight, and is a polyester composition characterized in that the polyester () is 3 to 50% by weight. Although the present invention has heat resistance and light resistance equivalent to polyester block copolymers, it also has excellent impact resistance and low-temperature properties, and has good adhesion with coating agents, making it suitable for metal vapor deposition. It can be used for sputtering, etc., greatly expanding the applications of polyester block copolymers. In the present invention, the compatibility between the polyester block copolymer () and the polyester () is extremely good, and the molded product does not peel off into layers. The polyester block copolymer of the present invention consists of a crystalline aromatic polyester segment and a polylactone segment, and is obtained, for example, by reacting a crystalline aromatic polyester with a lactone. Crystalline aromatic polyester is a polymer that mainly contains ester bonds or ester bonds and ether bonds, has at least one type of aromatic group as the main repeating unit, and has a hydroxyl group at the end of the molecule, and is used as a molding material. preferably has a molecular weight of 5000 or more. Note that the adhesive and coating material may be polyester with a molecular weight of 5000 or less. Preferred specific examples include polyethylene terephthalate, polytetramethylene terephthalate,
Homopolyesters such as poly 1,4-cyclohexylene dimethylene terephthalate and polyethylene 2,6-naphthalate, polyester ethers such as polyethyleneoxybenzoate and poly-p-phenylene bisoxyethoxy terephthalate, mainly tetramethylene terephthalate units or Consists of ethylene terephthalate units, in addition to tetramethylene or ethylene isophthalate units, tetramethylene or ethylene adipate units, tetramethylene or ethylene sebacate units, 1,4-cyclohexylene dimethylene terephthalate units, tetramethylene or ethylene-p
- Copolymerized polyesters or copolymerized polyester ethers having copolymerized components such as -oxybenzoate units. The content of tetramethylene terephthalate units or ethylene terephthalate units is preferably 60 mol% or more. As the lactone, ε-caprolactone is most preferable, and enantolactone, caprylolactone, etc. can also be used, but two or more types of lactones can also be used at the same time. When reacting crystalline polyester and lactones to obtain the polyester elastomer used in the present invention, the present invention may be carried out without a catalyst or with the use of a catalyst. The lactone content in the polyester block copolymer is 5 to 80
% by weight, preferably 20-70% by weight. Copolymerized polyester used in the present invention ()
consists of 50 to 100 mol% of aromatic dicarboxylic acid (however, 70 mol% or less of terephthalic acid) as an acid component and 0 to 50 mol% of aliphatic dicarboxylic acid and/or alicyclic dicarboxylic acid, and mainly as an alcohol component. It is a polyester consisting of glycol having 2 to 20 carbon atoms. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid. Particularly preferred is terephthalic acid or terephthalic acid and isophthalic acid. Examples of aliphatic dicarboxylic acids include saturated aliphatic dicarboxylic acids having 4 to 36 carbon atoms. for example,
Examples include polymethylene dicarboxylic acids such as succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, and aliphatic dicarboxylic acids having side chains such as 2-methyladipic acid and 2-ethyl suberic acid. It will be done. Examples of alicyclic dicarboxylic acids include 1,4-cyclohexylene dicarboxylic acid. Among these aliphatic dicarboxylic acids, adipic acid and batic acid are particularly preferred. The acid component in polyester () is
It consists of 50 to 100 mol% of aromatic dicarboxylic acid (however, 70 mol% or less of terephthalic 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, hydrolysis resistance will be poor, and blocking will occur. Glycols having 2 to 20 carbon atoms include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, dipropylene Examples include glycol, bisphenol A, hydrogenated bisphenol A, ethylene oxide adducts, and propylene oxide adducts thereof. Especially ethylene glycol
1,4-butanediol or neopentyl glycol is preferred. Furthermore, ethylene glycol
(A), 1,4-butanediol (B) or neopentyl glycol (C) satisfies the relationship 2≧(B)+(C)/(A)≧0.5 to ensure adhesive durability. It is desirable in that it will most effectively demonstrate. When using ethylene glycol, 1,4-butanediol, or neopentyl glycol, the total glycol component
Other glycols having 2 to 20 carbon atoms may also be used in amounts up to 10 mol%. As the alcohol component of the polyester (), a small amount of trihydric or higher polyhydric alcohol, or glycol 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 transesterification and direct polymerization. The reduced specific viscosity of the polyester () obtained by these methods is 0.5
~2.5. In the present invention, 97 to 50 parts by weight of polyester block copolymer () and 3 to 50 parts by weight of polyester () are used.
If the amount of polyester () is less than 3 parts by weight, the effect of improving the adhesion of the coating agent of the product obtained from this composition will be small, and if it exceeds 50 parts by weight,
The melting point and crystallization rate of products obtained from this composition are lowered, and the moldability is lowered. It is preferable to incorporate antioxidants, weathering agents, etc. known for use in polyester block copolymers into the composition of the present invention. Also plasticizers, pigments,
Fillers and the like can be added. The present invention will be explained in detail below with reference to Examples, but the present invention is not limited thereto. In the Examples, each physical property 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 () is phenol/tetrachloroethane = 6/4
This is the zero extrapolated value of the relative viscosity measured at 30°C in a mixed solvent of (weight ratio). (2) Melting point Fully automatic melting point measuring device (manufactured by Mettler, model
This is the value measured with FP-1). (3) T-peel test A blend chip of polyester block copolymer () and saturated copolyester polyester () was tested.
After vacuum drying at 80℃ for 1 day and night, 0.5
It was formed into a sheet of mm. A urethane adhesive made of polytetramethylene adipate (MW = 1000) and triphenylmethane triisocyanate is applied to the edge of this sheet, and the bonding pressure is 2
After pressure bonding at 100° C. for 70 minutes under Kg/cm ² , the test piece was cut out and subjected to a T-peel test to measure the normal adhesive strength. (4) Durability T-shaped peel test piece was placed in a hot air oven at 140℃ for 16 days.
The T-peel strength after time treatment was measured. In addition, the test piece after heat treatment at 140°C for 16 hours was heated to 100°C.
The T-peel strength was measured after treatment in boiling water for 45 hours. Production example 1 Polytetramethylene terephthalate 70Kg, ε-
30 kg of caprolactone was placed in a reactor, and after purging with nitrogen gas, a melt reaction was carried out for 2 hours while stirring at 230°C, and unreacted ε-caprolactone was removed under vacuum. The resulting polyester block copolymer had a reduced specific viscosity of 1160. Tensile breaking strength 315
Kg/cm ² and tensile elongation at break was 743%. Production Example 2 680 parts of dimethyl terephthalate, 78 parts of dimethyl isophthalate, 380 parts of ethylene glycol, and 1,4-butanediol were placed in a stainless steel autoclave equipped with a stirrer, thermometer, and cooling tube.
236 parts, potassium oxalate titanate 0.71 part and antimony trioxide 0.55 part, and heated at 170℃ to 220℃.
After carrying out the transesterification reaction for an hour, 0.93 parts of triphenyl phosphorite and 161 parts of adipic acid were added, and the esterification reaction was carried out at 220 to 250°C for 1.5 hours. Then, after gradually reducing the pressure at 265℃ to remove excess glycol, at 265℃ under reduced pressure of 0.1 to 0.3 mmHg,
The polycondensation reaction was carried out for 2.5 hours. The resulting copolymerized polyester resin (A) has an intrinsic viscosity of 0.90 and a melting point of 135.
It was warm at ℃. As a result of compositional analysis by NMP, the composition of the copolymerized polyester resin (A) is 70 mol% terephthalic acid, 8 mol% isophthalic acid, 22 mol% adipic acid, 60 mol% ethylene glycol, and 40 mol% 1,4-butanediol. It was hot. Production Example 3 Copolymerized polyester resins (B, C) shown in Table 1 were produced in the same manner as in Production Example 2.

【table】

[Table] Example 1 90 parts of the polyester block copolymer () 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 for 10 minutes. Stirred. The mixture was extruded at 230°C using a 40φ extruder and formed into a sheet with a thickness of 0.5 mm and a width of 10 cm. A urethane adhesive (polytetramethylene adipate (MW)
= 1000) in toluene/MEK = 50/50 solvent 50%
7 parts of dispersion solution and triphenylmethane triisocyanate 50% in toluene/MEK = 50/50 solvent
1 part of the dispersion solution) was applied, and the sheet obtained above was pasted together under a pressure of 2 kg/cm ² at a pressure of 100 kg.
After curing for 70 minutes at ℃, the test piece was cut out and subjected to a T-peel test to measure the normal adhesive strength. The results are shown in Table 2. Example 2 A predetermined amount of the polyester block copolymer () obtained in Production Example 1 and the polyester copolymer obtained in Production Example 2 were placed in a drum tumbler, and a 0.5 mm thick sheet was prepared in the same manner as in Example 1. Making,
After treatment with a urethane adhesive, normal adhesive strength was measured using a T-peel test. Example 3 The T-shaped peel test piece obtained in Examples 1 and 2 was
The T-peel strength was measured after 16 hours of treatment in a hot air oven at .degree. In addition, 100 more test pieces were heat-treated at 140°C for 16 hours.
The T-peel strength was measured after treatment in boiling water at ℃ for 45 hours. The results are shown in Table 2.

【table】

Claims (1)

[Scope of Claims] 1 A polyester-type block copolymer () consisting of a crystalline aromatic polyester segment and a polylactone segment and a polyester (), (i) a polyester-type block copolymer () consisting of a polylactone segment in the polyester-type block copolymer (); Content is 5-80
(ii) Polyester () contains 50 to 100 mol% of aromatic dicarboxylic acid (however, 70 mol% or less of terephthalic acid) and 0 to 0 to aliphatic dicarboxylic acid and/or alicyclic dicarboxylic acid as acid components. A copolymerized polyester consisting of 50 mol% and mainly consisting of glycol having 2 to 20 carbon atoms as an alcohol component; A polyester composition characterized in that the content of polyester () is 3 to 50% by weight.