JPS61500667A - Color stabilizing composition and method of stabilizing polycarbonate-polyester compositions - 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] Aromatic properties based on the reaction of diols and dibasic acids in polycarbonate-polyester compositions Aromatic polycarbonate resins and polyester resins are processed by molding, extrusion, etc. Engineering thermoplastic plastics are each useful for producing molded convexes. They make up two classes of sticks. In recent years, these polymers have been blended into Unique properties that are not normally seen when each polymer is used alone in combination Interest in obtaining profiles is increasing.

However, a drawback often associated with such polymer blends is the development of yellow color. is.

There may be several reasons why this color, or yellowing, occurs. This is 1 Due to pyrolysis of more than one polymer at the high temperatures of its molding or processing Another possible reason for this is the presence of metal catalysts in this polymer, depending on how the polymer is produced. The presence of residue. Yet another possibility is that it causes a decomposition interaction. The fact is that it brings together two possible polymers.

These polymer blends are colored by the inclusion of certain phosphorus-containing compounds. It has been proposed in the patent literature that it can be stabilized against the occurrence of . These are US Pat. No. 4,954,539 (Kawase et al.) and British Pat. It is described in National Patent No. 1,545296. Also Saimer (8eymour) ) et al., US No. 4.08a 709, is also of interest. The stabilizing effects of trivalent phosphorus compounds are described without mentioning the beneficial effects of trivalent phosphorus compounds. Nowadays, certain phosphorus-containing compounds such as phosphorous acid, arylphosphones, and fluorocarbon-substituted conductor of phosphorous acid. can be added to blends of black and polyester to obtain better color stability. In fact, the results showed that using some phosphite esters What you can get is also good.

Therefore, the present invention includes the following two aspects. In other words, the above phosphorus compound stabilizes the color. A blend composition in which the phosphorus compound is Adding color stability to a thermoplastic molding composition by incorporating it into a blend of In its broadest aspect, the composition of the present invention comprises (a) an aromatic polycarbonate; aromatic poly(ester-carbonate), aromatic dihydric phenol sulfone carbonate, ma or mixtures of any of the foregoing and in combination therewith. υ) Aliphatic diols, aliphatic ether diols.

aliphatic diols or mixtures of these diols and aromatic and/or cycloaliphatic diols A polyester resin consisting of divalent acid units, (c) Formula (1) for color stabilization amount: %formula% (wherein Y is hydrogen or phenyl), or a phosphorus-containing compound of the formula ('+i) : [In the formula, Rf=F(CFICFritt, n and m are each independently 1 or 2. 2fi, t is an integer of 5 to 8], or a mixture of these 2fi and a thermoplastic mixture of In a preferred embodiment, the component axis) is an aromatic polycarbonate, especially poly(bis). phenolic carbonate) and poly(alkylene terephthalate) ) resin, especially poly(t4-butylene terephthalate). Another preferred state , component Gl) consists of poly(ester-carbonate) and component Φ) consists of I From copolyesters based on phthalic acid and terephthalic acid and aliphatic diols Become. In yet another preferred embodiment, the component (conversion) is an aromatic dihydric phenol. Sulfone resins, especially sulfones produced using phosgene and bisphenols It is a copolymer. These are all phosphorus compounds in the amounts listed above.

Preferably, by including phosphorous acid, the color development resistance is improved.

As for component (a), it can consist of an aromatic polycarbonate resin, which is They can be manufactured by those skilled in the art or obtained from a number of commercial sources. these To produce phosgene, dihydric phenol.

Reacts with carbonate precursors like haloformates or carbonate esters Typically, these will have repeating structural units of the following formula: cormorant.

Here, A is the divalent aromatic group of dihydric phenol used in polymer production. The aromatic carbonate polymer (measured in methylene chloride at 25°C) ) It is preferable that the intrinsic viscosity is in the range of (L50 to t o ttt / t. Bivalent Phenol has two hydrocarbon groups, each bonded to a carbon atom of the aromatic nucleus. means a mononuclear or polynuclear aromatic compound. Typical two g5:’2 for enol ．． 2-bis-(4-hydroxy-phenyl)propane, 2.2-bis-(翫5- dimethyl-4-hydroxyphenyl)furopane, 4,4'-dihydroac-diph phenyl ether, bis(2- and droxyphenyl)methane, mixtures thereof, etc. Included. Preferred aromatic carbonate polymers as component 6) are 2.2- Bis(4-hydroxy-phenyl)propane (bisphenol) to N4 It is a homopolymer.

The poly(ester-carbonates) used in this invention are known and commercially available. can. These generally consist of repeating carbonate groups in the linear polymer axis. : Carboxylate group di 〇 and aromatic carbon with a copolyester consisting of a formula group, but carboxylic At least some of the carbonate groups and at least some of the carbonate groups are aromatic carbons. Bonded directly to a ring carbon atom of an elementary group.

To prepare these poly(ester-carbonate) cobolimers, bifunctional functional carboxylic acids such as phthalic acid, inphthalic acid, terephthalda, homophthalate 乍, o-, m-, and p-phenylene acetic acid.

Polynuclear aromatics! y (e.g. diphene S e 1,4-naphthalic acid), 1 etc. of dihydric phenols of the type mentioned above and carbonate. react with a precursor. A particularly useful polyester carbonate is bisphenol Routines and isophthalic acid.

Terephthalic acid or a mixture of isophthalic acid and terephthalic acid, or Reactive derivatives (e.g. terephthaloyl dichloride, isophthaloyl dichloride) (or a mixture thereof) and phosgene. This preferred In class resins, dihydroxydiaryl units versus benzenedicarboxylate units The molar ratio of carbonate units is in the range of 1:CL30~α80:α70~α20 and the molar range of terephthalate units to inphthalate units is 9: It can be in the range of 1 to 2:8. The aromatic dihydric phenol sulfone resin used in component (a) can be manufactured by a person skilled in the art. It is a type of resin.

For example, as described in Schnell et al., U.S. No. 4271,367, According to Homopolymer of phenol, dihydroxydiphenyl sulfone and carbonate precursor can be manufactured. A preferred material is Fax US No. 3.75 7.409, bis-(muradimethyl-4-hydroxyphenyl) ) Sulfone j! iL Phosgene alone or especially in combination with bisphenols Alternatively, it is produced by polymerizing it together with a phosgene precursor. 40-99% sulfo and 1 to 60 weights! It is produced by reacting % bisphenol with phosgene. Particularly preferred are copolymers.

Polyesters suitable for use in the present invention with respect to aliphatic, aliphatic ether or alicyclic diol containing 10 or these and at least one aromatic dicarboxylic compound ν. Preferred poly Esters are derived from aliphatic diionyls and aromatic dicarboxylic acids and are repeated in the following general formula: It has a repeating unit.

Here, D is an integer from 2 to 4. The most preferred polyester is poly(ethylenetetra). (Leftalate).

The above item 1) is derived from ester and fatty acid and/or aliphatic polyol. Copolyesters formed from small amounts, such as from 115% to about 2% Included in invention. Aliphatic polyols include poly(ethylene 11 alcohol). Includes glycols. All such polyesters are covered by Tatoe's U.S. patents. Nos. 2,465,319 and 4047.539. I can do it.

derived from a cycloaliphatic diol and an aromatic and/or cycloaliphatic dicarboxylic acid To produce polyesters, for example, a polyester having a repeating unit of the following formula is used. For example, the synthesis of 1,4-cyclohexane dimetatool so that an ester is formed. Either the su- or trans-isomer (or a mixture of these) is Condenses with rubonic acid.

Here, the cyclohexane ring is selected from its cis and trans isomers. , R represents an aryl or aliphatic group containing 6 to 20 carbon atoms, which is It is a decarboxylated residue derived from aromatic dicarboxylic acids.

Examples of aromatic dicarboxylic acids represented by the decarboxylated residue R are ino7tal or are terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4'-di carboxydiphenyl ether, etc., and mixtures thereof. these awakenings all contain at least 41 aromatic nuclei. Acids containing fused rings, e.g. The existence of a ring as shown in 1.4- or 1.5-s7taledicarbonya You can also do it. Also included are cycloaliphatic dibasic acids such as cyclohexanedicarboxylic acid.

The preferred dicarboxylic acid is terephthalic acid or a mixture of terephthalic acid and isophthalic acid. It is a thing.

1゜Whether the cis- or trans-isomer of 4-cyclohexanedimethanol (1, mixture of these) and a mixture of isophthalic acid and terephthalic acid. Other preferred polyesters can be derived from the reaction of polyester like this would have a repeating unit of the formula:

Yet another preferred polyester is cyclohexane dimetatool, alkylene Made of copolyester derived from glycol and aromatic dicarboxylic acid. child In order to produce these copolyesters, a copolyester having units of the following formula is used. For example, 1,4-cyclohexane-dimetatool/su or is either the trans-isomer (or a mixture of these) and the alkylene glycerin. The kohl is condensed with an aromatic dicarboxylic acid.

wherein the cyclohexane ring is selected from its cis- and trans-isomers, R is as defined above, n is an integer from 2 to 4, D, x unit is about 10 to about At 90% by weight, the y units are about 90 to about 10% by weight.

Such preferred copolyesters include 1,4-cyclo to Φsandimetatool. Either the cis- or trans-isomer (or a mixture of these) It can be derived by reacting lene glycol and terephthalate in a molar ratio of 1:2:50.

These copolyesters have repeating units of the formula:

Here, I and y have already been defined.

Fatty ether diols derived from e.g. tetraethylene diol and dibasic acids Also included within the present invention are polyesters that are

The polyesters described herein are commercially available or analogous to by methods well known in the art, such as those described in U.S. Pat. No. 2,901,466. It can be manufactured.

The polyester used in the present invention is 60:40 phenol/tetrachloroethane. from about 0.04 to about 2.0 a/V measured at 25° to sO<0>C in a mixture or similar solvent. It has an inherent viscosity.

The relative amounts of components (a) and G) in the blends of the invention can vary widely. Ta For example, component (11) is in an amount of about 1 to about 99 parts by weight, and component (11) is in an amount of about 99 to about 1 part by weight. It can be present in quantities of parts.

As for component (C), it has been clarified that this material must be used in extremely small amounts. 101 to 1.0 per 100 total copies of (a) and (b). O0 The desired color stabilizing effect is achieved at a concentration of % by weight. As already pointed out, this cheap The stabilizer is phosphorous acid (Y = H in the above formula) or phenylphosphone 5v (Y = phenyl) or fluorocarbon-substituted derivatives of phosphorous e.g. It may be either an orocarbon-substituted phosphite or a mixture.

It is preferred to use the minimum amount necessary to achieve the desired result. That is, an excess amount would be wasted and could there be some negative impact on other properties? It is et al.

In embodiments where flame retardancy is a desired property, conventional additives may be included in conventional amounts.

For example, sulfonates such as benzenesulfonyapotassium, or aromatic halide rogen compounds such as tetrabromobisphenol A polymers or oligomers - alone or together with a suitable synergist such as at/temon oxide in the composition. It can be used at a concentration of about α05 to about 510 parts by weight per 100 parts of resin. .

The composition may contain effective amounts of other suitable additives such as dyes, pigments and other colorants. It can also contain additives, fillers, reinforcing agents, lubricants, etc.

The production of the composition and the processing of the finished article may be carried out using any suitable method. It may be applied. Ingredients include extruder, kneading mixer, Banbury. They may be mixed together using a mixer 1 or other mixing equipment. The resulting blend is , compression, injection, dispensing or extrusion techniques as desired and according to specific requirements. One preferred procedure involves pre-blending the ingredients. This pre-blend is heated to 520 to 570 Extrude under and cut the extrudate into small pieces, 525? (barrel) and 120-18 Injection molding with 0”F (mold).

The phosphorous acid or other phosphorus-containing compound or material of the present invention improves the color stability of the composition. or as an aqueous solution or dispersion without risk of adversely affecting other properties. or in the presence of moisture.

Moldings produced from the composition of the present invention exhibit color stability due to the presence of specified additives. When it gets better, when it is processed at high temperature, or when it comes into contact with metals involved in processing. , or in general, yellowing typically occurs in the case of the polymers described herein. When exposed to known substances, for example due to a lower yellow index number. It has higher resistance to yellowing as shown in the figure.

The invention is further illustrated by the following examples, but is not intended to be limited to these examples. There is no diagram.

Approximately αA dl/? at 25°C in chloroform bisphenol with an intrinsic viscosity of 50% by weight of Le A polycarbonate, copolyester (KopAp) A150゜East-z7 Kodak (Eastman Kodak), Tele 85 mol% phthalate, 15 mol% isophthalate and i,4-cyclohexane Contains 50 heavy weights (manufactured from Nzimetal Tools) and 07 weight x of arsenous acid A thermoplastic molding composition was prepared. Phosphorous acid is a blend of two polymers and The mixture was added by shaking in a paint shaker. The resulting mixture was K11lion single shaft type with diameter/diameter ratio of 24 and atmospheric exhaust type. Mixed by extruding through an extruder. The conditions of use are as follows 1.2 3 Die melt pressure Pressure V M■S setting, "F 52C15255255 355101,0OOpsi 76 4 Actual Si Ii,? 515 525 550 525---------The extrudate was cooled through a water bath and then pelletized. , followed by 1.3 oz. ry) Using a molding machine, the pellet was injection-modified into a test piece (dimensions: 2.5 inch). inch XZS inch Xα125 inch). The conditions used were as follows.

@@ (melt) temperature 520~55Q? Set degree 525? Mold @ degree 150? Injection speed: Medium to high speed (40 to 20 seconds) Part weight: 50 to 80 cm % of the yellow index of the molded piece is determined according to ASTM method D-1925. did. The results are shown in the table below.

This uses diphenylisodecyl phosphite (currently available technology) as a color stabilizer. Includes a comparison with a corresponding composition containing 107%

Phosphorous acid 4.4 Diphenylisodecyl phosphite 22.4 As you can see, it contains phosphorus ν. The blend has a very low yellow index.

Several additional compositions according to the invention were prepared using the ingredients and amounts shown below. here However, the color stabilizer is phosphorus/acid, which is added as a 70% aqueous solution at α1% by weight of the total composition. added. Other procedures were the same as described in Example 1. Yellow for each blend Color index and corresponding control (same blend but with addition of phosphorus/acid) Table 2 below shows the results.

Table 2 b = = r Dahl (KODAR) A 150 (actual 11a9'j I F reference).

The above data proves the color stabilizing effect of phosphorous acid and the procedure of Examples 2-5 can be repeated. , except that phenylphosphonic acid is used as a stabilizer instead of IJ phosphorous acid. result are shown in Table 5.

Table 3 7 Polyteto cod C reference--)/PBT 5α76 22.52 The data above is The color stabilizing effect of nylphosphonic acid has been demonstrated.

Repeat the above procedure again, but with the exception that fluorocarbon-substituted phosphites Neil (ZONYL”)tT’R, DuPont Nemours deNemcurs CO,) was used as a color stabilizer. The results are shown in Table 4. Table 4 1 kuru (Zonyl) /-=-ry (Zcr+yl) 11 nJ Zuto → Death --)/PBT 5U6 42. ．． The data above are based on fluorocarbon-substituted The color stabilizing effect of phosphoric acid esters has been demonstrated.

All patents cited above are incorporated herein by reference.

Other modifications and variations of the invention are possible and will occur to those skilled in the art in light of the above disclosure. It will float away.

Therefore, the scope of the invention as defined in the claims in the specific embodiments set forth above It is understood that internal changes can be made.

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Claims (1)

[Claims] 1. (a) Aromatic polycarbonate, aromatic poly(ester-carbonate), Aromatic dihydric phenol sulfone carbonates or mixtures of any of the foregoing , combined with this (b) Aliphatic diol, aliphatic ether diol, alicyclic diol, or this polyester containing a mixture of diols and aromatic or alicyclic dibasic acid units. resin and (c) Equation (i) of color stabilization amount: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (ii) a phosphorus-containing compound of formula (wherein Y is hydrogen or phenyl): ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Rf=F(CF2CH2)t, and n and m are each independently 1 or or 2, and t is an integer from 3 to 8). A thermoplastic composition consisting of. 2. Component (a) consists of an aromatic polycarbonate, and component (b) consists of a poly(alkyl) lenterephthalate) resin according to claim 1. Composition. 3. (a) consists of poly(hisphenol A carbonate), and (b) consists of poly(hisphenol A carbonate). 1,4-butylene terephthalate) The composition described in. 4. Component (a) consists of poly(ester-carbonate) and component (b) consists of copoly(ester-carbonate). The composition according to claim 1, characterized in that it consists of a realester. 5. Copolyesters derived from isophthalic acid, terephthalic acid and aliphatic diols 5. A composition according to claim 4, characterized in that it is 6. (a) consists of aromatic dihydric phenol sulfone and (b) copolyester The composition according to claim 1, characterized in that it consists of: 7. (a) is a copolymer of sulfone and pisphenol A and phosgene; , (b) is derived from isophthalic acid, terephthalic acid and aliphatic diols. The composition according to claim 6, characterized in that: 8. The aromatic polycarbonate in (a) has the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A is a divalent aromatic group of dihydric phenol.) The composition according to claim 1, characterized in that: 9. The poly(ester-carbonate) of (a) has repeated carbon atoms in the linear polymer chain. -ponate group, repeating carboxylate group and aromatic carbocyclic group, At least some of the carboxylate and carbonate groups are aromatic carbocyclic groups. The group according to claim 1, characterized in that the group is directly bonded to a ring carbon atom of A product. lO. The polyester of (b) has the formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is an integer of 2 to 4) A claim characterized in that it has a repeating unit of The composition according to item 1. 11. (b) is the formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein, R is aryl or alicyclic having 6 to 20 carbon atoms, aromatic repeating units of decarboxylated residues derived from dicarboxylic acids). The composition according to claim 1, characterized in that: 12. (b) is the formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The composition according to claim 1, characterized in that it has a repeating unit of. 13. (b) is the formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R is aryl or alicyclic having 6 to 20 carbon atoms, and is about 10 to about 90% by weight, and the y unit is about 90 to about 10% by weight. The copolyester according to claim 1, characterized in that it is a copolyester having a return unit. composition. 14. (b) is 1,4-cyclohexanedimethanol and ethylene glycol Claim 13, characterized in that it is derived from the reaction of and terephthalic acid. The composition described in . 15. 0.01 to 1.00 parts by weight of (c) per 100 parts of (a) and (b) ) The composition according to claim 1, characterized in that it contains the following. 16. For a total of 100 parts of (a) and (b), add (a) from 1 to 99 parts by weight, ( A composition according to claim 1, characterized in that it contains from 99 to 1 part by weight of b). 17. (a) Aromatic polycarbonate, aromatic poly(ester-carbonate) , aromatic dihydric phenol sulfone carbonate, or a mixture of any of the foregoing. combined with this thing (b) Aliphatic diol, aliphatic ether diol, alicyclic diol, or this Polyester containing a mixture of diols and units of aromatic or cycloaliphatic dibasic acids resin and A method for imparting color stability to a thermoplastic molding composition comprising: (c) Equation (i) of color stabilization amount: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (ii) a phosphorus-containing compound of formula (wherein Y is hydrogen or phenyl); : ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Rf=F(CF2CF2)t, and n and m are each independently 1 or 2 and t is an integer from 3 to 8) The method comprises incorporating into the composition. 18. The color stabilizer of component (c) as an aqueous dispersion or otherwise in the presence of moisture. 18. A method according to claim 17, characterized in that it is added to a composition. 19. Component (a) consists of aromatic polycarbonate, and component (b) consists of poly(alcohol). cylene terephthalate) according to claim 17. Method. 20. (a) is made of poly(pisphenol A carbonate), and (b) is made of poly(pisphenol A carbonate). (1,4-butylene terephthalate) Composition according to item 9. 21. Component (a) consists of poly(ester-carbonate) and component (b) consists of copoly(ester-carbonate). 18. A method according to claim 17, characterized in that it is made of polyester. 22. (b) is derived from isophthalic acid, terephthalic acid and aliphatic diols. 22. A method according to claim 21, characterized in that: 23. Component (a) consists of an aromatic dihydric phenol sulfone, and component (b) consists of a copolymer. 18. A method according to claim 17, characterized in that it consists of a lyester. 24. (a) is a copolymer of sulfone-pisphenol A and phosgene, and ( b) is derived from isophthalic acid, terephthalic acid and aliphatic diols. 24. The method of claim 23, characterized in: 25. The aromatic polycarbonate in (a) has the formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A is a divalent aromatic group of dihydric phenol.) 18. A method according to claim 17, characterized in that: 26. The poly(ester-carbonate) of (a) is repeated in a linear polymer chain. with carbonate groups, repeating carboxylate groups and aromatic carbocyclic groups and at least some of the carboxylate and carbonate groups are aromatic carbons. Claim 17, characterized in that it is directly bonded to a ring carbon atom of a cyclic group. Method described. 27. The polyester of (b) has the formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is an integer of 2 to 4) A claim characterized in that it has a repeating unit of The method according to item 17. 28. (b) is the formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein, R is aryl or alicyclic having 6 to 20 carbon atoms, aromatic repeating units of decarboxylated residues derived from dicarboxylic acids). 18. The method according to claim 17, characterized in that: 29. (b) is the formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The method according to claim 1, characterized in that it has a repeating unit of. 30. (b) is the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein R is aryl or alicyclic having 6 to 20 carbon atoms, x unit is about 10 to about 90% by weight, and the y unit is about 90 to about 10% by weight) Claim 17, characterized in that it is a copolyester having a return unit. Compositions as described. 31. (b) is 1,4-cyclohexanedimethanol and ethylene glycol. Claim 30, characterized in that it is derived from a reaction with phthalic acid. the method of. 32. Add (c) by 0.001 to 1.00 weight per 100 parts of (a) and (b) in total. 18. A method according to claim 17, characterized in that it is included in an amount of %.