JPH04501277A - Blends of poly(ether ester) and polyester and molded products made therefrom - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Blend of Boi Neil Esseur and Boi Esseur and it 1 Noro Stand up! The present invention has the rigidity and notched isot impact strength of poly(ether ester) monomer. Flexible poly(ether ester) at an unexpected level compared to the German case The present invention further relates to blends of such blends with hard polyesters. Concerning molded products made from

L beans■! amount A particular advantage of the blends of the present invention is that they can be used in decorative coatings when used to form sheet materials. It can be used as a carrier for membranes and/or protective coatings.

According to the present invention, spraying is provided for applying the necessary protective and decorative coatings on automobile panels. The need for coloring can be avoided. Avoidance of spray coloring or substantial use of it The reduction is not only environmentally beneficial in terms of reducing air pollution, but also Coloring operations use so much paint that more than half of the paint can be wasted as scrap material. This is also beneficial from the point of view of cost savings. to achieve such objectives The means for forming may be glued or securely bonded to the panel to provide a protective and cosmetic coating. Through the use of thermoplastic sheet materials. Such techniques are well known and even For example, as described in U.S. Pat. No. 3,551,232, It has been used for such purposes.

A process of the type described in U.S. Pat. Using it in a standard environment poses a much greater challenge.

The surface appearance of such panels is of critical importance, so In addition to avoiding problems such as bubbling or blistering, to provide a protective and cosmetic coating equal to or superior to the quality of the spray-painted surface. is necessary. Furthermore, it is possible to slide flexible sheet materials onto supports that can have complex curvatures. It is very difficult to adhere to the surface of the panel, and the coating is visible on the entire surface of the panel. It is even more difficult to do so while maintaining homogeneous color purity, so automatic A special problem arises in the case of car panels.

The present invention securely attaches to a support panel to provide protection and protection as disclosed in the aforementioned patents. To provide a sheet material to which a decorative coating can be applied. However, the present invention Provides sheet materials with desirable physical properties, particularly improved stiffness and impact strength This is an improvement in this respect. In such applications, the sheet material is more suitable for supporting panels. It is desirable to have a certain degree of rigidity to ensure compatibility. processing (the sheet is first placed in a mold and pressed against its surface, then flowable material (injected into the mold and allowed to solidify), simply place it on the support panel. This also applies to the case of processing by placing sheets and gluing them between them.

Furthermore, it prevents permanent indentation and/or breakage during impact with hard objects. , in parts such as bumpers, sheet materials can have good impact strength. Obviously desirable.

The present invention improves the previously mentioned carriers due to their improved properties of stiffness and impact strength. The combination of poly(ether ester) and polyester is particularly useful in sheet formation. Offer a blend.

trans-1,4-cyclohexane dicarbon al, 1,4-cyclohexane dicarbon Metatool, poly(oxytetramethylene) glycol and branching agent poly(ether) Teresters) are disclosed in U.S. Pat. No. 4,349,469. related Other patents include U.S. Patent No. 4,003,882; No. 3.023.192; No. 4,221,703; No. 3.651,014 and No. 4.256.860. However, these patents In either case, the flexible polyester is one of the polyesters described herein. There is no suggestion that it exhibits improved physical properties when blended with other materials.

Mold plate ■Gori FIG. 1 shows a cross section of a finished structure using a carrier sheet of a blend according to the invention. It is a front view.

Light plate ■Sara ball The blend according to the invention can be prepared by first forming the blend into a sheet and then using the known A matured molding process in which the finished product is thermoformed by the application of heat and pressure using conventional methods. It is particularly useful in Also, relatively hard polyester (more condensed) is used in the blend. Blends are more easily thermoformed by the presence of non-crystalline polymers) be done. Blends are also useful in conventional injection molding and extrusion applications. .

According to the invention, (A) (1) essentially a 1,4-cycloisomer with a trans isomer content of at least 70%; A dicarboxylic acid component consisting of lohexanedicarboxylic acid, (2) Essentially (a) 95 to 65 mol% of 1,4-cyclohexane dimetatool, and (b) Poly(oxytetramethylene) glycol with a molecular weight of 500 to 1100 5 to 35 mol% a glycol component consisting of; (B) 80 to 100 mol% of terephthalic acid and at least one species having 2 to 12 carbon atoms 1. having repeating units from aliphatic or cycloaliphatic glycols; V, is 0.5~ 1.0 relatively hard polyester and has improved stiffness compared to poly(ether ester) alone. A flexible poly(ether ester) characterized by A blend of is offered.

Furthermore, the blend comprises 98-60% by weight of flexible poly(ester ether). polyester) and 2 to 40% by weight of relatively hard polyester. Teru Ester) Unpredictably Improved Notched Izots Compared to Alone It was found that the material had a high impact strength.

The dibasic acid component of the poly(ester ether) of the present invention is essentially at least 70 %, preferably at least 80%, most preferably at least 85% trans Consists of 1°4-cyclohexanedicarboxylic acid with isomeric content.

1,4-cyclohexane dicarboxylic acid and 1,4-cyclohexane dimetatool is well known and commercially available.

Interscience Publishers, Mark, At1a s and Cernia Akebono, “Man-Made Fibers: 5science” and Technology”, Vol, III is 1.4- on page 85 Production of cyclohexane dicarboxylic acid and 1゜4-cyclohexane dimetatool It is listed.

The poly(oxytetramethylene) glycol component of the present invention is commercially available and known manufactured by the method. Poly(oxytetramethylene) glycol has a molecular weight of 500 to 11oo1, preferably 1000 (weight average). poly(oxyte) Tramethylene) glycol is preferably 5 to 35 mol%, based on total glycol mol%. Preferably, it is used in an amount of 8 to 15%.

The poly(ester ether) of the present invention further comprises at least three C0OH or is a polybasic acid or polyhydric alcohol branching agent having 3 to 6 carbon atoms and having an OH functional group. based on the acid or glycol component.

Esters of many such acids or polyols can also be used.

Suitable branching agents include trimellitic acid or trimellitic anhydride, trimesic acid. , trimethylolethane, trimethylolpropane and trimer acids.

Total acid reactants should be 100 mole percent and total glycol reactants should be 100 mole percent. It should be understood that it should be in mole %.

The acid reactant is 1. when the branching agent is a polybasic acid or polybasic acid anhydride. a-sik Lohexanedicarboxylic acid "consists essentially of 1, but it is 100 It shall be calculated as part of mole % acid. Similarly, glycol reactants are When the branching agent is a polyol, 1,4-cyclohexane dimetatool It is calculated as part of 100 mol% glycol. shall be calculated.

The poly(ester ether) of the invention preferably comprises a phenolic antioxidant. The phenolic antioxidant is preferably sterically hindered and relatively non-volatile. stomach. Geigy Chemical as Irganox l0LO antioxidant Tetrakis [methylene-(3,5-di-t) commercially available from , ert-butyl-4-hydroxyhydrocinnamate)methane] is preferred.

Preferably, the antioxidant is O01-1. based on the weight of the copolyester ether. Use in an amount of 0.

The trans and cis isomer content of the final copolyester ether can be rapidly cured or Adjustments are made to produce a polymer that crystallizes. The cis and trans isomer content is Measure by a conventional method well known to those in the industry. For example, U.S. Patent No. 4,349.469 Please refer to the issue.

The polyester used in the present invention uses an acid component consisting essentially of terephthalic acid. It can be manufactured by conventional methods. Small amounts of other commonly used dicarboxylic acids (less than 10%), etc. For example, isophthalic acid, naphthalene dicarboxylic acid or aliphatic acids having 4 to 12 carbon atoms. Dicarboxylic acids can be used. Glyl for common copolymers with 2 to 12 carbon atoms or glycol combinations can be used. The preferred glycol is ethylene glycol. 1,4-butanediol and 1,4-cyclohexane dimetatool; It is a combination of them. Particularly preferred glycols are ethylene glycol and 1 , 4-cyclohexane dimetatool and combinations thereof. polyester Le I, V. is 0.5 to 1.0.

Flexible polyesters and rigid polyesters can be prepared using extruders, for example. 5. By conventional plastic melt mixing methods such as melt blending using mix can be done. Blends can be used for injection molded products such as facias and tubes as well as Useful in sheet materials for thermoformed articles.

Sheet materials made from said blends can be used as shown in FIG. . A carrier sheet is made from the blend. First, apply makeup and/or A protective coating is applied, which is a convenient point. If you wish, you can keep it! L coating film You can use any top plate that can be used to hold or serve glass. . Coatings can be applied by conventional means known to those skilled in the art. Shape of laminated sheet material applied to the support panel by full in-mold processing or simple gluing as described above. Can be used. If desired, depending on the composition of the support, an adhesive can be added to promote adhesion. Alternatively, a bonding layer (t, ie 1 ayer) can be used.

The following examples are included for a better understanding of the invention. In the example, the polymer “ "X" is 1. V, is 1.23 and 1,4-cyclohexanedicarboxylic acid (tran) (90%) 99.5 mol% Trimellitic anhydride 0.5 mol% 1.4-Cyclohexane dimetatool 91.1 mol% poly(ol) with a molecular weight of 1000 xytetramethylene) glycol 8.9 mol% It is described as having a repeating unit consisting of.

Polymer “Y” is 1. V is 0.75 and terephthalic acid is 100 mol% 1.4-Cyclohexane dimetatool 68 mol% ethylene glycol 32 mol% It is described as a polyester having repeating units consisting of

Bo! J? -rZJ is 1. V is 0.75 and terephthalic acid is 100 mol% Ethylene glycol 69 mol% 1. Described as a polyester consisting of 31 mol% of 4-cyclohexane dimetatool I will post it.

■ Example 1 Polymers are produced by mixing pellets and then partially compounding on a screw extruder. Blend polymer X with polymer Y in various ratios. Inject the resulting blend onto the specimen. Extrude and mold. Surprisingly, the bending elasticity of the blend measured according to ASTM D790 The sex rate was found to be higher than expected. The actual value obtained for the blend is It will be observed that the expected value is exceeded.

Another surprising result is the Notched Izot Impact Strength (ASTM) at 23°C. D256). As shown in Table 1 below, the impact strength of Polymer X is further It is substantially increased by the addition of small amounts of polymer Y.

19.000 1.336 9.6 51310 27.000 1.89B 11.0 58725 48.000 3,375 13.7 73235 9 2.000 6.468 22.6 1.207 Example 2 Similar blends were made from Polymer X and Polymer Z.

The flexural modulus is also unpredictably high. Table 2 shows notched Izotsu impact strength. We show that an unexpected increase in l- or 19.000 1.336 9.6 51310 28.000 1.969 10.3 55025 72.000 5,062 14.3 76435 1 10.000 7.734 16.3 870 Example 3 In this example, a flexible polyetherester is used as a relatively rigid polyester. Blend and measure flexural modulus.

The flexible polyetherester is Polymer X, and the relatively rigid polyester is 1. V, polyethylene terephthalate of 0.70.

100 0 20.000 1.40680 20 107.000 7.52 360 40 129.000 9,07040 60 1?6.000 12 ．． 37520 80 306.000 21.5150 100 390.00 0 27.420 example 4 Flexible polyether ester is a relatively rigid polyester as shown in the table below. and measure the flexural modulus.

The flexible polyetherester is Polymer X, and the relatively rigid polyester is 1. V, 0.75 terephthalic acid, 1,4-cyclohexane dimetatool 68 Polyester with mol% and 32 mol% ethylene glycol.

100 0 20.000 1.40680 20 46.000 3,234 60 40 100.000 7.03140 60 260.000 18. 28020 80 224.000 15.7500 100 269.000 18.913 example 5 Flexible polyether ester can be replaced with relatively rigid polyester as shown in the table below. and measure the properties. Flexible polyetherester It is the same as Polymer X except that the lithic acid is omitted. Relatively hard polyester Polymer Y. The data shown in parentheses are predicted values for comparison and are based on the present invention. The elasticity of the blends is shown to be higher than expected.

*On each side, the top number is in psi and the bottom number is in kg/C1a.

Example 6 Flexible polyetherester and relatively rigid polyester as shown in the table below and measure the properties. The flexible polyetherester is 1.4-cyc The concentration of lohexane dimetatool is 70 mol% and poly(oxytetramethyl) Polymer X is the same as Polymer ratio A relatively hard polyester is Polyester Y.

*On each side, the top number is in psi and the bottom number is in kg/d.

Example 7 1. The concentration of 4-cyclohexane dimetatool is 80 mol% and Repeat Example 6, except that the concentration of (cytetramethylene glycol) is 20 mol%. .

*On each side, the top number is in psi and the bottom number is in kg/d.

Example 8 Another blend is prepared similarly to the previous example using Polymer X and Polymer Z. . In this example, rather than using dimethyl terephthalate, the polyester , prepared by direct esterification of terephthalic acid (E, v, = 0.75).

100 0 19.000 (19,000) 9.6 5131.335 ( 1,335) 80 20 44.000 (34,000) 13.1 7003.094 (2,390) 60 40 120.000 (56,000) 17.5 9358.437 (3,937) *On each side, the top number is in psi and the bottom number is in kg/d.

Example 9 Relatively hard polyester was mixed with 100 mol% of terephthalic acid and 8% of 1°4-butanol. 0 mol% and 1,4-cyclohexane dimetatool 20 mol% repeat Example 8 (t, V, = 0.75).

100 0 19.000 (19,000) 9.6 5131.335 ( 1,335) 80 20 44.000 (34,100) 13.7 7323.094 (2,398) 60 40 122.000 (56,200) 18.2 9728.578 (3,951) *On each side, the top number is in psi and the bottom number is in kg/ci.

Example 10 Each of the polymer blends was extruded into a sheet and painted by roll coating. Apply a layer and dry. Next, apply adhesive to the opposite side of the sheet from the paint. The sheet is applied and adhered to the panel using the aged molding method. During the thermoforming operation, the The sheet is first heated to a soft state and then air pressure differential is used to support the polypropylene. Wrap it around the panel. Repeat these experiments using the above-mentioned all-in-mold processing method. In , the stiffness of the carrier sheet is matched to the stiffness of the support panel. Impact resistance ( The values are given in the example above) for cracking resistance, indentation resistance and energy absorption. It is suitable for applications such as automobile bumpers where cost is important.

Conventional additives can be used in the ingredients or blends. As such additives, Examples include coloring agents, stabilizers, plasticizers, flame retardants, adhesion promoters, and the like.

As used herein, the inherent viscosity (1,V,) is 60% by weight of phenol. and 40% by weight of tetrachloroethane per 100 d of solvent. The measurement is carried out at 25°C using 0.50 g of water.

The flexural modulus and notched Izot impact strength tests used herein are each According to ASTM 0790 and ASTM D256.

All parts, percentages, ratios, etc. are by weight unless otherwise specified.

Although the invention has been described with particular reference to its preferred embodiments, it is possible to It is to be understood that changes and improvements may be made therein.

Fig, 1 Submission of translation of written amendment (Article 184-8 of the Patent Law) August 3, 1990

Claims (1)

[Claims] 1. Blends of flexible poly(ether ester) and relatively rigid polyester A composition comprising: (A) (1) essentially a 1,4-cycloisomer having at least 70% trans isomer content; A dicarboxylic acid component consisting of lohexanedicarboxylic acid, (2) Essentially (a) 95 to 65 mol% 1,4-cyclohexanedimethanol, and (b) Poly(oxytetramethylene) glycol with a molecular weight of 500 to 1100 5 to 35 mol% A glycol component consisting of I. V. Flexible poly(ether ester) with 0.8 to 1.5 (B) 80 to 100 mol% of terephthalic acid and charcoal repeating unit from at least one aliphatic or cycloaliphatic glycol having a prime number of 2 to 12; I. V. 2-98 weight relatively hard polyester with a weight of 0.5-1.0 amount% characterized in that the blend comprises a Compositions with improved stiffness and notched Izod impact strength. 2. at least 3 carboxyl or hydroxy in an amount up to 1.5 mol% According to claim 1, the polyfunctional branching agent has a polyfunctional branching agent having a group. Composition. 3. The rigid polyester consists essentially of repeating units of terephthalic acid as well as ethylene. glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol consisting of repeating units from at least one glycol selected from A composition according to claim 1. 4. Blends of flexible poly(ether ester) and relatively rigid polyester A composition comprising: (A) (1) essentially a 1,4-cycloisomer having at least 70% trans isomer content; A dicarboxylic acid component consisting of lohexanedicarboxylic acid, (2) Essentially (a) 95 to 65 mol% 1,4-cyclohexanedimethanol, and (b) Poly(oxytetramethylene) glycol with a molecular weight of 900 to 1050 5 to 35 mol% A glycol component consisting of I. V. Flexible poly(ether ester) with 0.8 to 1.5 terephthalic acid) and (B) essentially repeating units of terephthalic acid. and ethylene glycol, 1,4-butanediol and 1,4-cyclohexane Consisting of repeating units from at least one glycol selected from dimethanol Relatively hard polyester 2-40% by weight characterized in that the blend comprises a Compositions with improved stiffness and notched Izod impact strength. 5. A thermoformed article comprising the composition according to claim 1. 6. A thermoformed article comprising the composition according to claim 4. 7. An injection molded article characterized by the composition of claim 1. 8. An injection molded article characterized as the composition of claim 4. 9. attached to a support panel comprising a carrier sheet having a coating on one side thereof. a sheet material modified so that the carrier sheet is A sheet material comprising the composition of item 1. 10. Blend of flexible poly(ether ester) and relatively hard polyester 1. A composition comprising a blend of (A) (1) essentially a 1,4-cycloisomer having at least 70% trans isomer content; A dicarboxylic acid component consisting of lohexanedicarboxylic acid, (2) Essentially (a) 95 to 65 mol% 1,4-cyclohexanedimethanol, and (b) Poly(oxytetramethylene) glycol with a molecular weight of 900 to 1050 5 to 35 mol% A glycol component consisting of I. V. Flexible poly(ether ester) with 0.8 to 1.5 terephthalic acid) and (B) essentially repeating units of terephthalic acid. and ethylene glycol, 1,4-butanediol and 1,4-cyclohexane Consisting of repeating units from at least one glycol selected from dimethanol Relatively hard polyester 2-40% by weight characterized in that the blend comprises a Compositions with improved stiffness and notched Izod impact strength. 11. A support characterized in that the sheet material according to claim 9 is adhered. Holding body. 12. Blend of flexible poly(ether ester) and relatively hard polyester 1. A composition comprising a blend of (A) (1) essentially a 1,4-cycloisomer having at least 70% trans isomer content; A dicarboxylic acid component consisting of lohexanedicarboxylic acid, (2) Essentially (a) 95 to 65 mol% 1,4-cyclohexanedimethanol, and (b) Poly(oxytetramethylene) glycol with a molecular weight of 900 to 1050 5 to 35 mol% A glycol component consisting of I. V. Flexible poly(ether ester) with 0.8 to 1.5 terephthalic acid) and (B) essentially repeating units of terephthalic acid. and ethylene glycol, 1,4-butanediol and 1,4-cyclohexane Consisting of repeating units from at least one glycol selected from dimethanol 2-40% by weight of relatively hard polyester characterized in that the blend comprises a Compositions with improved stiffness and notched Izod impact strength.