JPH01500023A - Laminates containing scrap extruded together - 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] □ Field of invention: laminates containing co-extruded scrap This invention occurs during the manufacture of laminates and occurs at high operating temperatures of laminates. The present invention further provides for a laminate containing scrap to improve the stiffness of the laminate. products, especially cooking utensils made from improved scrap-containing laminates. do.

l1 standing 11 Adhesive layers of filled and unfilled polymeric materials can be used as electrical insulators to bank bullets. It has been used in a variety of applications ranging from protection and shielding. Especially for melt coextruders The resulting laminates have a wide range of uses as films and containers. Ru.

Melt coextrusion is a well-known and well-documented technique8. Goel Frados Van Nostrandrenhold ortrand Rehold) H, plastic engineering hand See also, among others, Koch et al. U.S. Patents 4,404,547 and 4,336,012, Ra5w1ssen See Nos. 4,403,934 and 4,426,451, given in .

The technique joins brides or layers of different polymers exhibiting different and advantageous properties used for. Thus, examples (Tg), oxygen permeability, impact resistance, flexural modulus, etc. Laminates with different polymer layers can be produced relatively easily. Ru.

Especially in March 1985 when laminates with 3 or more sheets have the same volume. The pending application No. 11Na710.126 filed on the 11th is made from thermoplastic resin. Discloses cooking utensils made from laminate made of at least three sheets. The inner sheet has a lower operating temperature than the thermoplastic from which the outer sheet is made. It is made of thermoplastic resin with Translated by the same person on March 19, 1984. Pending application No. 11590,791 is filed for Discloses cooking utensils made from a laminate consisting of three sheets. Has a higher service temperature than the thermoplastic resin from which the two outer sheets are made The inner sheet is made from a thermoplastic resin.

In laminates such as the laminate disclosed in the above-cited pending application, the individual sheets The thermoplastic polymer used to make it can withstand cooking temperatures; On the other hand, it is also generally chosen to provide a laminate that offers good economy. this For applications, high stiffness sufficient to retain dimensional stability while filling with food. Achieving stability at cooking temperature is a necessary criterion for acceptable performance. cooking 350-45o to completely make the tool article.

It has a Tg of the order of F (176.7 to 233.3). High service temperature thermoplastic Although using only synthetic polymers would of course provide useful cooking utensils, it would not be possible to do so at a prohibitive cost. That is. Cheaper, lower 7g polymers also make such articles perfectly possible. used to stabilize the polymer, but retains some stiffness if the polymer is crystalline. However, it may be used at high operating temperatures with considerable loss of stiffness. wax, such items may however be heated, such as when a container is filled with food. which will generally not retain sufficient dimensional stability under load-bearing conditions. Therefore, the solution also has a high In a laminate consisting of g-sheets – using low Tg materials as filler” sheets It is to be.

Thus useful items that can withstand cooking temperatures are g Polyethylene that retains some rigidity at cooking temperatures with an outer layer of polymer. Made by laminating low 7g polymers such as terephthalate. It will be done.

When making useful articles from such laminates, a significant amount of the laminate is Consumed in the form of nate scraps. This can be done, for example, by cutting from an article undergoing a thermoforming operation. It is something that can be done. As a reasonably accurate approximation, the cost of polymer is It tends to increase with the special transition temperature (Tg). So of laminate scraps The scrap contains high 7g sheets and is expensive if discarded.

Several attempts have been made to salvage scrap and cheaply produce useful items. It was British Patent No. 1,552,234 describes the individual particle size in the layers present. of granular plastic is thermally bonded and then sintered to reduce the existing layers to smaller With at least one additional layer having a large particle size, a sharp border between the eyebrows is avoided. Discloses a construction or insulating material made by compressing the material. Pons U.S. Pat. No. 4,402,889, issued to Bonis (i.e., virgin plastic with compositional limitations sufficient to provide moisture barrier) Creates a sheet with moisture barrier properties by extruding it together with a high-bore central layer. Discloses that.

If the layers melt without mixing, that is, the layers melt without substantially mixing and exist as separate molten phases. If there is a tendency to simply grind the scrap and turn it into a useful integral composite article, Any attempt to melt process the material will result in an article of poor quality. With this technology, products are often brittle, exhibit relatively low impact resistance, and have poor bonding properties. Peeling under relatively light loads such as cheesey and 5p1ity or under all conditions Applications exhibiting the property of releasing and releasing are often applied to such articles.

In other respects, much of the prior art simply abandons scrap altogether as an economical measure. Materials that can be used to avoid or replace virgin plastics The zero-order one containing the cheapness of is exemplary.

U.S. Patent No. 4,045.603, awarded to Ss.i.th. Shredded suspended U-type synthetic resin material (unspecified) discarded for making materials Strips of discarded and shredded cellulose fiber material used as a low cost source *U.S. patent 4 granted to Hungalford disclosing that , 287, 147 uses polyacrylate for reextrusion as separate layers in a multilayer fill. Ununiform material from rylonitrile film manufacturing operations or by utilizing scrap Discloses a method for generating this.

U.S. Patent 4, 234, 663 to Catte et al. U.S. Patents 4,476.080 and 4.410,602 issued to Oda et al. , even when the resin composition contains recovered synthetic resin with a relatively low thermal decomposition temperature. Forming film or sheet-like products from thermoplastic resins using conventional extruders Discloses methods and devices.

However, prior art of which the inventor is aware increases the stiffness of the laminate at service temperatures. In order to actually improve the laminates that generate scrap by None disclose the use of scrap laminate.

Kukan Yutaka 11 Each outer sheet is comprised of at least one thermoplastic polymer or blend of polymers. At least three melt-coextruded sheets with higher stiffness at service temperatures than the inner sheet The present invention provides a continuous plastic laminate comprising sheets of plastic.

where said continuous laminate is a laminate derived from the manufacture of said laminate. including scrap, said scrap having at least one additional separate internal layer therein; by melt-co-extruding the scrap or by melt-co-extruding the scrap. by melting and co-extruding the scrap as at least one part of the sheet. is included in it.

This reduces the stiffness of the scrap-containing laminate at service temperatures to that of the scrap. increased compared to an equivalent plastic laminate except for the incorporation of It's getting worse.

wherein the thermoplastic polymer or polymer blend is a polyaryl ether. lefone, poly(aryl ether), polyarylate, polyetherimide , polyester, aromatic, polycarbonate, styrene resin, poly(alkyl alkyl) acrylate) polyhydroxyether, polyamide, poly(arylene sulfur) Id) Crystalline polyolefin, polyphenylene oxide, or a blend thereof It will be.

Laminate scrap is excluded from articles made from thermoformable laminates. By-products include multi-layer ears, cuttings, cuttings, and discarded materials.

As will be discussed in more detail later, the operating temperature is a hot environment (home range, furnace, etc.) by using laminates inside or in contact with heated materials (such as hot food). Temperatures above room temperature imparted to the laminate by touching the laminate It is about.

Stiffness at service temperature means that the laminate resists deformation or distortion at the service temperature at which it is used. is the drag force of the laminate, the applied load, the flexural modulus of the laminate, and the flexural modulus of the laminate. Depends on thickness. Generally, stiffness is proportional to the product of the laminate's modulus of elasticity and three times its thickness. do.

Surprisingly, the present invention is capable of producing scrap-generated thermoplastic, thermoformable Improved lamination by scrap reinserting scrap during lamination Importantly for the purposes of the present invention, laminates with a high Tg The polymer or polymer blend used as sheet material also has a corresponding It has high stiffness and vice versa. Lower 7g indicating lower stiffness at service temperature The same relationship holds true for materials as well.

Scraps can be usefully reinserted into the laminate to make it easier to laminate. The improvement is that the scrap length has very low bond integrity. They are often of no use other than to make goods, and these goods generate scrap. This is surprising since it is inferior to the products made from the laminates. It is. Thus, scraps from laminates that would otherwise have been discarded Wraps are used in this invention to increase stiffness at the service temperature of the laminate. It is possible. Before incorporating the scrap into the laminate, It is processed by grinding and comminuting to the desired particle size.

In a preferred embodiment, the scrap is preferably at least one additional separate inner sheet. is preferably in contact with one of the two (higher Tg) outer sheets during lamination. is incorporated into.

In this example, there are two additional separate inner sheets, each in contact with an outer sheet. Most preferably, the separated scraps are hot extruded together.

The scrap can also be melted and used as at least one part of the sheet that is extruded together. , - can be extruded together. as part of one or both of the outer sheets or As part of more inner sheets or as part of outer and inner sheets It is extruded either way.

In yet another preferred embodiment, the scrap incorporated into the laminate is of low A substantially equal volume of material, preferably a laminate, from an inner sheet of 7g polymer. Replace the sheet with the lowest Tg polymer used to make the sheet.

As an example of the present invention, a three-layer ABA profile (!II high Tg polymer material A) The side sheet or layer is sandwiched with a third intermediate sheet of low Tg polymeric material B. For example, during melt extrusion of a laminate, scrap with It is poured into one or more layers of BA laminate.

In yet another preferred embodiment, laminate and scrubbed T, F Har The aforementioned U.S. patents 590,791 and 710,1 filed in the name of Tsing Found in 26. The entire disclosures of both applications are incorporated herein by reference. two Two immiscible polymers are blended together to form a scrubber. The resulting formulation when forming a laminate layer in the original structure prior to incorporation of the It is, of course, noted that exhibits two different Tg's. Generated from the resulting compound The scrap that is generated is either the inner layer or the outer layer of the laminate in which it was generated. It can have greater utility depending on what is inserted. And this is followed by It depends on the particular combination of polymers in the wrap.

An example of a preferred embodiment using the ABA laminate mentioned above is summarized as follows: It can be stated in detail. It is left out there. And there each person is 0.003 inches ( B has an overall predetermined thickness of 20 mils. The laminate has a predetermined thickness of 14 mils. child The laminate is abbreviated here as 3A/14B/3A. each number represents the thickness in mils for the individual layer named by the letter to its right. , Slack Of course, the ``sh'' represents the boundary of a layer, and the notation of similar territory is also used at the boundary of a layer.

A similar notation is also used in the examples that follow. 3 A / 14B / 3 A The stiffness of the laminate at the operating temperature is 3A/14B/3A scrap (e.g. 3A /14B/3　from the previous coextrusion of (e.g. during the next run) to accommodate the volume of scrap that is added to the enhanced by In this case relative to the volume % of scrap added to the laminate. The laminate is thicker than the 3A/14B/3B scrap (based on the total volume of all materials used to make) 3A/14B/3 The B die opening thickness is 20 mils total in the resulting scrap-containing laminate. Should be increased by 0.30X for the thickness of B by an amount equal to 26 mils or 6 mils It is.

Alternatively, the scrap may be distributed between the high Tg outer sheets and - They are melted together and coextruded.

In a preferred implementation for this example, the scrap is divided into equal parts, and each part is Outer sea) is melt coextruded as part A. As above, 30 volume% scrubber A total of 6 mils of scrap per each outer seam (if 3 mils of scrap per outer seam) is used. is added to the laminate to accommodate the drop volume. The resulting laminate consists of 3 sheets Motsu.

Alternatively, one or more additional inner sheets may be scraped mR. Can be coextruded. Preferred for this example using 30% scrap as above In a specific example, the scrap is divided into two equal parts, each with a separate value of 3 mil thickness. Melt coextruded as layers, each separate layer in contact with one of the two outer A layers . The result is a 5 layer laminate with two of the layers being scrap. Display introduced above This laminate is 3A/3 scrap/14B/3 scrap/ It will be named 3A.

Total thickness is 26 mils, of which 30% by volume (equal to 6 mils in thickness) is scrubber. It is a top.

If you want to maintain a consistent 20 mil laminate thickness, use a lower Tg point. Scrap is added as a replacement for a substantially equal volume of rimmer B. Ru. For example, the scrap can be mixed directly with B and co-extruded with it to form a three-layer sheet laminate. A laminate may also be produced. There the inner layer is still 14 mils and 6 mils of pure B. The equivalent has been replaced by scrap.

However, in the preferred embodiment the scraps are each in contact with the outer A sheet. melt coextruded as two separate 3 mil sheets with an amount of B equivalent to 6 mils. is removed from the B sheet. The resulting laminate was 20 mils thick and thus The overall thickness of the laminate is maintained. But the laminate has 5 sheets, It may be written as 3A/3 scrap/8B/3 scrap/3A.

The results of this preferred embodiment involve nothing more than coextruded scrap; Creates an improved laminate with enhanced stiffness at constant thickness at service temperature That's true. The scrap added to the laminate has a high Tg and high flexural modulus. The equivalent volume of B containing polymer A, while removed by reducing the thickness of the B layer. contains only low Tg, low flexural modulus polymer B. Thus the scrap The laminate containing the laminate is the original laminate 3A/14B/3 The stiffness of the laminate is therefore enhanced. It is.

Material cost savings not only come from using waste scrap, but also from scrap-containing laminate. Also led by the reduction in the amount of fresh B required to extrude the lower TgN in the Although the advantages afforded by the present invention are considerable, in addition to the substantial economic benefits. Even better (more rigid at operating temperatures)! ! Making products is the most important This is important.

The upper limit of scrap that can be incorporated into a laminate is determined by the weight of the laminate. About 50% by weight, preferably about 3% by weight. Adding scraps Overall lamination by eliminating the volume of lower 7g material to compensate for the added volume If the thickness of the layer should be kept constant, from any one lower 7g layer to the lower 7g layer. Preferably no more than about 75% by weight of the material is removed.

In the present invention, the temperature is generally between about 350 (176,7°C) and about 450＠F (233,7°C). 3°C) most preferably about 37 minutes (190,6°C) and about 425'F (2+8.3°C) Preference is given to using laminates with a temperature between

Examples of laminates made from 3-sheet and 2-sheet polymer sheet materials are shown. However, the present invention can be applied to laminates made of any large number of different sheets and different materials. It can be applied to The scrap is incorporated into the layers of the laminate during its melt extrusion. It will be done. and optionally the corresponding volume % of one or more lower 7g layer materials is excluded. It will be done. Thus, a laminate scrap with outline ABC has A and C as internal seals. ) Breaking in new extruded ABC laminates when having Tg higher than B Can be put in. Scrap may be assembled as one of one or more separate internal sheets. or may be melt-coextruded as part of A, B, and C. Or a combination thereof may be used. If you want to keep the laminate thickness constant, choose B. The volume % is the displacement corresponding to the volume % of the scrap added.

Detailed discussion The types of materials that have been used to make laminates vary widely, and all are compatible with the present invention. subject to the requirements set forth in the appended claims that are considered to fall within the scope of the claims. less The three melt coextruded layers can be made from any of the following exemplary layer materials with the least amount of coextrusion: May contain two.

Boriyal ether sulfone Poly(aryl ether) Polyarylate polyetherimide polyester Including polyester carbonate and polyaromatic sulfone carbonate Aromatic polycarbonate styrene resin Poly(allyl acrylate) polyhydroxy ether polyamide Poly(arylene sulfide) polyolefin polyphenylene oxide Laminates specifically contemplated for use in the present invention include those lacking.

Polyaryl ether sulfone/polycarbonate/boriyal ethers Lefon Boriyal ether sulfone/Boaryarylate/Boriaaryl ether sulfone phone Boaryl ether sulfone/Polyethylene terephthalate/Boaryl Ether sulfone polyaryl ether sulfone/polybutylene terephthalene Polyester/Boryaryl ether sulfone/Polyaryl ether sulfone Amide/boriyal ether sulfone Boria aryl ether sulfone/poly(arylene) sulfide/Boria aryl ether sulfone polyaryl ether sulfone/polypropylene/bolyaryl ether sulfone real ether sulfone Polyetherimide/Polycarbonate/Polyetherimide Polyetherimide/Polyethylene terephthalate/Polyetherimide Polyetherimide/Polyarylate/Polyetherimide Polyetherimide/Aryamide/Polyetherimide Polyetherimide/Polyetherimide arylene) sulfide/polyetherimide Polyetherimide/Polypropylene/Polyetherimide Polyetherimide/Polybutylene terephthalate/Polyetherimide The laminates named above contain three layers, which are indicated on each laminate. Laminates containing additional alternating layers of the same polymeric material are also specifically contemplated. .

The laminate included in the present invention has an important feature of dimensional stability in high operating temperature environments. Applications such as hot food containers and cooking utensil articles such as sual ovens. specifically for thermoformed laminate applications used as sterile containers for medical devices. It has the usability.

The present invention relates to a true oven cooking utensil, that is, a conventional heat range oven and a microwave oven. It has particular applicability in the area of cooking utensils that can be heated in microwave ovens. It is intended that Such cooking utensils include heating frozen food (TV) meals. Disposable ovenable containers as well as reusable containers of the type used for Includes cooking utensil containers.

As previously noted, service temperatures are temperatures above room temperature that are applied to the laminate, e.g. Contact with heated air in a domestic range oven or microwave Hot food that has been processed, steamed or otherwise heated (or damage caused to the laminate by contact with other objects (such as medical instruments). temperature above room temperature. Relatively low stiffness at operating temperatures at such temperatures Laminate layers made from low Tg polymers with may otherwise impart less stiffness and strength to the laminate. Therefore high stiffness at operating temperature A laminate layer that maintains the stiffness of a laminate formed on a hot food container, for example Primarily responsible for maintaining dimensional stability. Stiffness at operating temperature of laminate Of course, one approach to improving the original laminate is to Simply incorporate a polymer of Tg. But this is expensive 7g virgin material is expensive and easily increases manufacturing costs, making it cost-prohibitive. The laminate is more practical than the original laminate, which can serve the same purpose, i.e. for the utilization of scrap. Making cheaper, better and higher stiffness laminates.

thermoplastic polymer A. Boriyal ether sulfone The poly(aryl ether sulfone) used in the present invention (special lath poly(aryl ether) ether) is an amorphous thermoplastic polymer containing units of formula.

In the formula, R is independently hydrogen, C1 to C6 alkyl, C4 to C8 cycloalkyl. and X' are independently, where R1 and R2 are independently hydrogen or atom of CICG. Lukiru or Here, R3 and R4 are independently hydrogen or C1 to C8 alkyl, and al is 3 to An integer of 8, -5-1-〇-1 or'! yoa is an integer from O to 4, and n is independently from 1 to 4. where the ratio of unit (1) to unit (Il) and/or (m) is greater than 1. The units are connected to each other by 10-bonds.

In a preferred specific example, the unit (1) is the formula The expression ■ is the expression 1◎− or −◎−◎− have The formula m is the formula Preferred polymers of the invention have the formula %formula% 1◎− or −◎−◎− contains units of Other preferred boaryarylether sulfones of the present invention are Formula −◎ −5O2−〇　− as well as Contains units of

These units are interconnected by 10-bonds.

Boaryl ether sulfones can have a random or ordered structure.

The polyaryl ether sulfone of the present invention is N-methylpyrrolidone or other suitable has a reduced viscosity of greater than about 0.4 to about 2.5 at 25°C as measured in a suitable solvent. Ru.

The polyaryl ether sulfone of the present invention reacts with a monomer represented by the following formula. It is made by letting people.

(V) (■) and or where RHa IX' and n are defined above. Then, X and Y are independently cl, B' , F, NO2 or OH, and at least 50% of Y' is OH.

Cl, B'' of the OH group used to generate the polyaryl ether sulfone The ratio of concentration to F and/or NO2 groups is preferably about 0.90 to about 1.10. is about 0.98 to about 1.02.

The monomers represented by (rV) (V) (Vl) and ■ include the following: ing.

2.2-bis(4-hydroxyphenyl)propane 2.2-bis(3,5-dimethyl) thyl-4-hydroxyphenyl)propane Bis(-4-hydroxyphenyl)methane 4,4'-dihydroxyphenyl sal Phidobis-(3,5-dimethyl-4-hydroxyphenyl)sulfone 4.4'-dihydroxydiphenyl ether 4.4'-hydroxyphenyl sulfur Phone 2.4'-Dihydroxydiphenylsulfone 4.4'-Dichlorodiphe Nilsulfone 4.4'-dinitrodiphenylsulfone 4-chloro-4'-di Hydroxydiphenylsulfone 4,4'-bisphenol, hydroquinone Preferred monomers include hydroquinone, 4-4-bisphenol, 2.2-bis(4-hydroxyphenyl)propane (bisphenol A) 2.2-bis(3,5-dimethyl-4-hydroxyphenol)propane (TM BA), Bis-(3,5-dimeta-4-hydroxyphenyl)sulfone (TMBS ), 4.4'-dichlorodiphenylsulfone and 4.4'-dihydroxydipheny Contains lusulfone or 4chloro-4'-hydroxydiphenylsulfone .

The polymers of this invention contain substantially equal molar amounts of hydroxy-containing compounds ((I) V) to (■)) and 8-day and nitro-containing compounds (depicted in the above formula (m) V) and (V)) from about 0°5 to about 1.0 per mole of hydroxy group. mol of alkali metal carbonate and maintain the reaction medium in virtually anhydrous conditions during the polymerization. In order to It is created by.

The temperature of the reaction mixture is maintained at about 120 to about 180°C for about 1 to about 5 hours, and then about 200 to about 250°C, preferably about 210 to about 230°C and about 1 to 0 hours. held for a while.

The reaction is carried out at atmospheric pressure in an inert atmosphere such as nitrogen. most expensive Higher or lower pressures may also be used.

The polyaryl ether sulfone is then processed by conventional techniques such as coagulation and solvent evaporation. will be collected.

The solvent mixture consists of a solvent that forms an azeotrope with water and a polar/neutral solvent. water and Solvents that form azeotropes include benzene, toluene, xylene, and ethylbenzene. , chlorobenzene, and other aromatic hydrocarbons.

The polar neutral solvent used in the present invention is used in this technique to produce polyarylsulfones. It is generally known and has the formula R5-5(0) b-Rs Contains sulfur-containing solvents such as those of In the formula, each R5 has no aliphatic unsaturation, low a class hydrocarbon group which preferably contains a carbon atom at about the 8-position and which is attached to the is an integer from 1 to 2 (including 2) and represents a divalent alkylene group. vinegar. Thus in all of these solvents all oxygen and two carbon atoms are sulfur It is bound to the yellow atom. The following are intended for use with this invention: Solvents such as those having the formula

where the R8 groups are independently groups such as methyl, ethyl, propyl, butyl and similar groups. Lower alkyl, aryl groups such as phenyl, and alkylphenyl groups such as tolyl group group, as well as in tetrahydrothiophene oxide and dioxide. This is the case when the R6 group is internally bonded as in the divalent alkylene width. Ru.

Specifically, these solvents include dimethyl sulfoxide and dimethyl sulfone. , diphenyl sulfone, dimethyl sulfoxide, diethyl sulfone, di- Sopropylsulfone, tetrahydrothiophene 1,1-dioxide (usually tet ramethylene sulfone or sulfone) and tetrahydrothiophene -1 monooxide is included.

Additionally, nitrogenous solvents may also be used. These include dimethylacetamide , dimethylformamide and N-methylpyrrolidone.

The ratio of the solvent forming the azeotrope to the polar neutral solvent is about 10=1 to about 1:1, preferably are used in a weight ratio of about 7:1 to 5:1.

During the reaction, the hydroxy-containing compound is reacted with the alkali metal carbonate in situ. By doing so, its alkali salts are gradually converted. Alkali metal carbonate Potassium carbonate is preferred. of carbonates, such as potassium and sodium carbonates. Mixtures can also be used.

Water forms an azeotrope with the solvent so that substantially anhydrous conditions are maintained during the polymerization. and continuously removed from the reaction mass.

It is essential that the reaction medium remain substantially anhydrous during polycondensation. be. Amounts of water up to about 1 percent are acceptable. and fluorinated dihalogenzee Although there are some advantages when used with noid compounds, substantially larger water The amount of reaction of water with halo and/or nitro compounds leads to the formation of phenolic species. It is preferable to avoid this since only products with low molecular weights are ensured. So high poly Preferably during the reaction 0.5 wt. % or less.

Preferably the polymer is treated with methyl chloride or benzene after the desired molecular weight is achieved. Treatment with activated aromatic or aliphatic halides such as chloride be done. Such treatment of the polymer converts the terminal hydroxy groups into ether groups, This stabilizes the polymer. Such treated polymers have good melting and and oxidative stability.

B, polyaryl ether resin Poly(aryleethers) suitable for blending with polyarylether sulfones The resin is a linear suspended polyarylene polyether with a repeating unit of the following formula. In the formula, E' is the residue of a divalent phenol, and E' is the ortho and distal position with respect to the valence bond. It is a residue of a benzenoid compound that has an inert electron-withdrawing group in one of its positions. , both of the above residues are valently bonded to the ether oxygen via an aromatic carbon atom. It is. Such aromatic polyethers are described, for example, in U.S. Pat. No. 3,264,536. 4,175,175. Categories of polyaryl polyester resins contained within. The phenol of 215 is, for example, dihydroxydiphenyl alkali Weakly acidic dinuclear phenols such as propane, 1,1-bis(4-hydroxyphenyl)2-phenyletha , its nuclear halogenated derivatives such as bis(4-hydroxyphenyl)methane or These are chlorinated derivatives containing one or two chlorines in each aromatic ring.

Other materials, also appropriately called bisphenols, are also very valuable and preferred. These materials include, for example, ether oxygen (-0-), or two phenolic nuclei within it. are attached to the same or different carbon atoms of the residue Bisphenols with symmetrical or asymmetrical bonding groups such as Such a two-core fue Nols are characterized as having a structure.

In the formula, A is an aromatic group and preferably a phenylene group, and R?S and R'v are from 1 to 4. Alkyl, aryl, halogen atoms with 5 carbon atoms, i.e., fluorine, chlorine , bromine, or iodine or alkoxyl groups having 1 to 4 carbon atoms. or a different inert substituent, where C independently has a value from 0 to 4 (inclusive). and R8 is an aromatic carbon atom as in dihydroxy-diphenyl. It represents a bond between, and is a divalent radical such as -s　2- Radicals such as arekylene, alkylyzo, cycloalkylene, cycloalkyly Divalent hydrocarbon radicals such as dene or halogen, alkyl, aryl, or the like Similar substituted alkylene, alkylidene and cycloalifutic radicals as well as It contains a ring fused to both aromatic radicals and aromatic radicals.

An example of a special divalent polynuclear phenol is 2,2-bis-(4-hydrophenol), among others. (roxyphenol)propane 2,2-bis-(3,5-dimethyl-4-hydroxy Cyphenyl) propane 2.4-dihydroxydiphenylmethane bis-(2-hydroxyphenyl)meth bis(4-hydroxyphenyl)methane bis(4-hydroxy-2,6-cy Methyl-3-methoxyphenyl)methane 1.1-bis-(4-hydroxyphenyl)ethane 1.2-bis-(4-hydro xyphenyl)ethane 1,1-bis-(4-hydroxy-2-chlorophenyl) ethane 1.1-bis-(3-methyl-4-hydroxyphenyl)propane 1.3-bis-(3-methyl-4-hydroxyphenyl)propane 2.2-bis-(3-phenyl-4-hydroxyphenyl)propane 2,2-bis-(3-isopropyl-4-hydroxyphenyl)propane 2.2-bis-(2-isopropyl-4-hydroxyphenyl)propane 2.2-His-(4-hydroxy-naphthyl)propane 2.2-bis-(4- Hydroxyphenyl)pentane 3.3-bis-(4-hydroxyphenyl)pen Tan2.2-His-(4-hydroxyphenyl)heptane bis-(4-hydro xyphenyl)phenylmethane 2.2-bis-(4-hydroxyphenyl)-1 -phenyl-propane 2.2-bis-(4-hydroxyphenyl)1,1.1,3.3,3-hexaf Luolopropane Bis-(hydroxyphenyl) alkanes such as bis-(4-hydroxyphenyl) sulfonebis-(3,5-dimetal-4-hydroxyphenyl)sulfonyl) On 2.4'-dihydroxydiphenylsulfone 5-chloro-2,4'-dihydro Xydiphenylsulfone 5-chloro-4,4'-dihydroxydiphenylsulfone di(hydroxyphenyl)sulfone bis-(4-hydroxy phenyl)etherza 4,3'-4,2'-2,2°-2,3''-dihydroxy Phenyl ethers 4.4'-dihydroxy-2,6-dimethyldiphenyl ether Bis-(4-hydroxy-3-isobutylphenyl)ether Bis-(4-hydroxy-3-isopropylphenyl) ether Bis-(4-hydroxy-3-chlorophenyl)ether Bis-(4-hydroxy-3-fluorophenyl)ether Bis-(4-hydroxy-3-bromophenyl) ether Bis-(4-hydroxy-naphthyl) ether bis-(4-hydroxy-3-k) loronaphthyl) ether and 4,4'-dihydroxy-3,6-simethoxidof Di(hydroxyphenyl) ethers such as enyl ether are included.

As used herein, the E term, defined as a dihydric phenol residue, has two refers to the remainder of the dihydric phenol after removal of the aromatic hydroxyl group, thus As can be easily seen, these polyarylene polyethers are composed of residual dihydric phenols. and the remainder of the benzenoid bonded via the aromatic ether oxygen atom.

Any dihalobenzenoid or dinitrobenzenoid compound or mixture thereof is E 'The compound or compounds are used to provide the residue, and the compound or compounds are However, two molecules bonded to a benzene ring having an electron-withdrawing group at at least one position It has a halogen or nitro group.

Dihalobenzenoid or dinitrobenzenoid compounds are As long as there is an activated electron-withdrawing group in the When attached to a benzenoid ring, it is attached to a mononuclear or different benzenoid ring. It can be either multi-nucleated if

Substituted benzenoid reactants of fluorine and base are preferred; fluorine compounds are preferred due to their fast reactivity. This is because of their low cost. Fluorine-substituted benzenoid compounds are the most Also preferred is particularly preferred when trace water is present in the polymerization reaction system. But this water The content is kept below about 1% and preferably below 0.5% for best results. Should.

The base of useful E' residues contributing to poly(arylether) resins. Examples of zenoid compounds are as follows.

4.4'-dichlorodiphenylsulfone 4.4'-difluorosyphenylsulfone Fon 4.4'-bis(4-chlorophenylsulfonyl)bisphenyl 4.4'-bis(4-fluorophenylsulfonyl)bisphenyl 4.4-difluorobenzophenone 4.4'-dichlorobenzophenone 4.4'-bis(4-fluorobenzoyl)benzene4.4'-bis(4-chlorobenzoyl) lobenzoyl)benzene 2,6-dichlorobenzonitrile their isomers etc. In these compounds, electron-withdrawing groups are used as activating side groups. Of course reaction conditions should be inert under the Preferred are 4,4'-dichlorodiphenylsulfone and 4,4'-diflu Two halogen- or nitro-substituted benzenes such as in orodiphenylsulfone It is a strong activating group like a dolphin attached to the noid ring. Besides, as mentioned below, Strongly attractive groups of are also used in equal cases.

Stronger electron withdrawing groups give the fastest reaction and are therefore preferred. the same benzenoid It is further preferred that the nucleus does not contain an electron donating group such as halogen or nitro. However, the presence of other groups on the nucleus or in the residues of the compound is acceptable.

Activating groups can basically be of either of two types.

(L) Other nitro or hero phenyl sulfones, or alkyl sulfones, Multiple cysts such as ano, trifluoromethyl, nitroso, and pyridine a monovalent group that activates one or more halogen or nido groups on the same ring. (b) divalent groups capable of activating halogen rearrangement on two different rings, e.g. group Organic phosphine oxyto O H9 (In the formula, R9 is a hydrocarbon group and an ethylidene group -C-A C- (In the formula, A is hydrogen or halogen).

Dihalobenzenoids or dinitrobenzes with two or more polymers optionally E of benzenoid compounds in the polymer structure. 'The remainders may be the same or different.

The E′ term, defined as the residue of a benzenoid compound, is the halogen on the benzenoid nucleus. of the aromatic or benzenoid residue of the compound after removal of the rogene atom or nitro group. That's true.

The polyarylene polyethers of this invention are made by methods well known in the art. It will be done. For example, double alkali metal salts of dihydric phenols and dihalobenzenoid compounds certain liquid organic sulfoxides or sulfones under substantially anhydrous conditions with It is produced by a general substantially equimolar reaction in the presence of a solvent. This reaction requires a catalyst. Not necessary.

Polymers also contain dihydric phenols, alkali metals, alkali metal hydrides, alkaline Potash metal hydroxide, alkali metal alkoxide or alkali metal alkyl compound A two-step process that is first converted in situ in a primary reaction solvent to an alkali metal salt in reaction with A law will be created.

Preferably, alkali metal hydroxides are used. water present or produced To ensure anhydrous conditions, the dialkali metal salt of dihydric phenol is mixed with the dihydric phenol. Reacts with approximately stoichiometric amounts of dihalobenzenoid or dinitrobenzenoid compounds let

Additionally, polyethers are described, for example, in U.S. Pat. It can be made using the procedure described. In that case, at least one phenol and at least one A substantially equimolar mixture of one dihalobenzenoid at about 100°C to about 400°C higher than the atomic number of sodium carbonate or sodium bicarbonate and sodium at a temperature of heated with a mixture of a second alkali metal carbonate or bicarbonate having a higher atomic number. .

Additionally, polyethers can be made using the procedure described in Canadian Patent 847,963. It can be done. In that case, bisphenols and dihalobenzenoid compounds are It is heated in the presence of potassium carbonate using a high boiling solvent such as Fon.

Preferred polyarylene polyethers of the present invention are those substituted with inert substituents. Products made using the following four types of divalent polynuclear phenols, including derivatives of It is.

(a) R1[1 In the formula RID groups are independently hydrogen, lower alkyl, aryl and the same or different represents those halogen substituents which may also be

HO-◎　-0-◎　-OH and substituted derivatives thereof.

As mentioned above, two or more different divalent phenols can be used to accomplish the same purpose. It is also contemplated in this invention to use a mixture of 1, 2, and 3. Thus mentioned above The -E- residues in the polymer structure may actually be the same or different aromatic residues when sell.

Poly(aryl ether) is a special polyether in methylene chloride at 25°C. from about 0.35 to about 1.5, as measured by a method in a suitable solvent at a suitable temperature. It has original viscosity.

Preferred poly(aryl ether)s have the formula %) It has a repeating unit of

C, polyarylate Polyarylates suitable for use in the present invention include dihydric phenols and Both are derived from one aromatic dicarboxylic acid and chloroform (0.5 g /100s+l chloroform) or other suitable solvent. 4 to about 1.0, preferably about 0.6 to about 0.8 dl/g+n. have

Particularly preferred dihydric phenols have the following formula [where Y is independently hydrogen, 1 to 4 carbon atoms] selected from an alkyl group of elementary atoms, chlorine, or bromine, and each d is independently the value of O-4 and R1+ is a divalent saturated or unsaturated aliphatic hydrocarbon group, especially 1 to 6 carbon atoms. an alkylene or alkylidene group having atoms, or a silyl group having up to 9 carbon atoms; Chloalkylidene or cyclokylene group, -0-1-CO-1-502- or -S -, dihydric phenols can be used independently or in combination. Ru.

Dihydric phenols that can be used in the present invention include the following.

2.2-bis-(4-hydroxyphenyl)propane, 2.2-bis-(3,5 -dimethyl-4-hydroxyphenyl)propane, Bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl) Methane, bis-(4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane, 1.1-bis-(4-hydroxyphenyl)ethane, 1.2-bis-(4-hydro roxyphenyl)ethane, ], 1-bis-(4-hydroxy-2-chlorophenylene) ) ethane, 1,3-bis-(3-methyl-4-hydroxyphenyl)ethane, ], 3-bis-(3-methyltohydroxyphenyl)propane, 2,2-bis -(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis-(3- isopropyl-4-hydroxyphenyl)propane, 2.2-bis-(2-isopropyl-4-hydroxyphenyl)propane, 2.2-bis-(4-hydroxyphenyl)pentane, 3.3-bis-(4-hydroxyphenyl) Droxyphenyl)pentane, 2,2-bis-(4-hydroxyphenyl)heb Tan, 1,2-bis-(4-hydroxyphenyl)-1,2-bis-phenyl) propane, 4.4'-(dihydroxyphenyl) ether, 4.4'-(dihydroxyphenyl) nil) sulfide, 4.4'-(dihydroxyphenyl)sulfone, 4.4'- (dihydroxyphenyl) sulfoxide, 4,4'-(dihydroxybenzophene) non) and naphthalene diols.

Aromatic dicarboxylic acids that can be used in the present invention include terephthalic acid, isophthalic acid, and any naphthalene dicarboxylic acids and mixtures thereof, and those having 1 to 4 alkyl groups. Alkyl-substituted congeners of these carboxylic acids with carbon atoms, and other inert substitutions. Substituents such as acids containing halides, alkyl or aryl ethers are included. . Acetoxybenzoic acid can also be used. Preferably isophthalic acid and terephthalic acid A mixture of is used. The ratio of isophthalic acid to terephthalic acid in the mixture is from about 0:100 to about 100:0, while the most preferred acid ratio is about 75:25. ~about 50:50. It also has about 0.5 to about 20% of 2 to about 10 carbon atoms. Aliphatic diacids such as adipic acid and cepatic acid can also be used additionally during polymerization repulsion. can be used.

The polyarylates of the present invention may be any of the well known prior art polyester forming reactants. reactions, e.g. reaction of acid chlorides of aromatic dicarboxylic acids with dihydric phenols, Reaction of diaryl esters of dicarboxylic acids with dihydric phenols or aromatic diaryl esters. It can be produced by reacting an acid with a diester derivative of a dihydric phenol. I can do it. These methods are described, for example, in U.S. Pat. 6.3°780, 148.3,824,213 and 3,133,898 has been done.

The polyarylate is preferably prepared according to the method described in U.S. Pat. No. 4,321,355. Therefore, it can be manufactured. The method consists of the following steps.

(a) at least an acid anhydride derived from an acid containing 2 to 8 carbon atoms; is also reacted with one dihydric phenol to form the corresponding diester, and ( b) The above diester is combined with at least one aromatic dicarboxylic acid and a polyarylate. The reaction is carried out at a temperature sufficient to form Here, after dihydric phenol diester formation, the remaining acid anhydride is reduced to a concentration of ca. 1500pp-Un^; The improvement is to remove this part.

Suitable acid anhydrides are derived from organic acids containing 2 to 8 carbon atoms. preferable The acid anhydride is acetic anhydride. Dihydric phenols are described above.

Generally, divalent phenols are reacted with acid anhydrides under conventional esterification conditions to form divalent phenols. Phenol diester. This reaction takes place in the presence of a solvent or in the absence of a solvent. Ru.

Furthermore, the reaction can be carried out in the presence or absence of conventional esterification catalysts.

D. polyetherimide Polyetherimides suitable for use in the present invention are well known in the art, such as U.S. Pat. No. 3,847,867, 3,838.

097 and 4,107,147).

The polyetherimide is of the formula:

where e is an integer greater than l, preferably from about lO to about 10,000 or more and -0-R1t-0- is bonded to the 3 or 4 and 3' or 4' positions Ori, RI2 is (a) a substituted or unsubstituted aromatic group, for example (b) a divalent group of the following formula, In the formula, R+< is independently 01-C6 alkyl, aryl, or s! ;t-0-, -S-, -CO-, -SO2-, -SO-, 1 to 6@ carbon atoms child fullkylene, cycloalkylene of 4 to 8 carbon atoms, 1 to 6 carbon atoms alkylidene of 4 to 8 carbon atoms, or cycloalkylidene of 4 to 8 carbon atoms, R+s is an aromatic hydrocarbon group having 6 to 20 carbon atoms and its halogenated derivative; conductor, or an alkyl-substituted derivative thereof having an alkyl group of 1 to 6 carbon atoms, Alkylene and cycloalkylene groups having 2 to 20 carbon atoms and 02 to C 8 alkylene terminated polydiorganosiloxane or formula (R14 and R15 are as defined above).

The polyetherimide may also be of the formula:

In the formula, -〇-2 is (wherein R+e is independently halogen, lower alkyl, or lower alkoxy), as well as (In the formula, oxygen: i can be bonded to any ring, and to one of the bonds of the imido carbonyl group RI2, RI3 and e is as defined above.

These polyetherimides can be prepared using methods well known in the art, such as U.S. Pat. ,833,544,3,887,588,4.017.

Those described in 511, 3,965, 125 and 4,024,110 Manufactured by law.

The polyetherimide of formula (■) can be prepared according to any of the methods well known to those skilled in the art, including, for example: can be obtained in any way.

The method uses the following formula (where RI2 is as defined above) and any aromatic bis(ether anhydride) of formula (XI) H2N-R+3- NH2 (RI3 as defined above) This includes reactions with diamino compounds. The reaction is generally carried out in a well-known solvent, e.g. Chlorobenzene, metacresol/toluene, N,N-dimethylacetamide, etc. in which the interaction between the dianhydride and the diamine is controlled at about 20 to about 250°C. This can be advantageously carried out at a temperature of . Alternatively, you can Etherimide can be any dianhydride of formula (X) and any diamino of formula (XI). Do not heat the mixture of ingredients at high temperatures while simultaneously stirring the compound and the mixture. They can be made by melting and polymerizing them. Generally about 200℃ Melt polymerization temperatures between ~400°C and preferably between 230°C and 300°C are used. It will be done. Addition of any chain terminator commonly used in melt polymerization Ru. Reaction conditions and nature of components depend on desired molecular weight, intrinsic viscosity, and solvent resistance It can make a big difference. Generally equimolar amounts of diamine and dianhydride S high molecular weight polymers are used. There may be a slight molar excess (approximately 1 to 5 Mol % ) diamine using the formula! The force S that causes the formation of polyetherimide of , which is greater than the Q measured in metacresol at 25°C, 2 dl/g. having a viscosity η, preferably 0.35 to 0.60 or 0.7 dl/g or more do.

For example, the aromatic bis(ether anhydride) of formula (X) has ζf2.2-bis-[4-( 2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 4.4″-bis(2,3-dicarboxyphenoxy)diphenyl)ether di anhydride, 1.3-bis(2,3-dicarboxyphenoxy)benzene dianhydride Do, 4.4'-bis(2,3-dicarboxyphenoxy)diphenyl)sulfide dianhydride, 1. Tobis(2,3-dicarboxyphenoxy)benzene dianhydride , 4.4'-bis(2,3-dicarboxyphenoxy)benzophenone dianha Idride, 4.4'-bis(2,3-dicarboxyphenoxy)diphenylsulfone dia hydride, 2.2-bis-[4-(3,4-dicarboxyphenoxy)phenyl]propane 　Gianhydride, 4.4”-bis(3,4-dicarboxyphenoxy)diphenyl ether dia hydride, 4.4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide anhydride, 1.3-bis(3,4-dicarboxyphenoxy)benzene dianhydride Do, 1.4-bis(3,4-dicarboxyphenoxy)benzene dianhydride Do, 4.4'-bis(3,4-dicarboxyphenoxy)benzophenone dianha Idride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-carboxyphenoxy) xy) diphenyl-2,2-propane dianhydride, etc., and these di- Contains a mixture of anhydrides.

Organic amines of formula (XI) include, for example, p-phenylene diamine, p-phenylene Diamine, 2,2-bis(p-aminophenyl)propane, 4,4'-diamino diphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'-dia Minodiphenylsulfone, 4,4'-diaminodiphenyl ether, 1,5-di Aminonaphthalene, 3,3'-dimethylbenzidine, 3,31-dimethoxyben Contains zidine.

The polyetherimide of formula (IX) can be prepared, for example, by the general formula (1) [wherein R13 is defined above] (as per the definition), and (2) general formula %formula% an alkali metal salt of an organic compound (the middle part of the formula is an alkali metal, RI2 is defined above) reaction of a mixture of components (as defined in the definition) in the presence of a dipolar neutral solvent It is created by doing.

The bis-trophthalimide used to make the polymer is the diamine described above. Reacting N　Ht　-R1s　-N　H2 with a nitro-substituted aromatic anhydride of the formula Manufactured by. Ideally, the molar ratio of diamine to anhydride is Approximately 1=2. The first reaction product is bis(amic acid), which is then dehydrated. trophthalimide) to the corresponding bis.

Diamines are described above.

Nitrophthalic anhydrides useful in the present invention include 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, phthalic acid, and mixtures thereof. These reactants are commercially available in reagent grade. ing.

These are also Organic 5ynthesee, Co11active V anhydrous film using the procedure described in Ol. I., Wiley (1984), page 40B. It can also be produced by nitration of tarric acid. other closely related species of Nitroaromatic anhydrides can also be used in the reaction, e.g. anhydrous 2-nitrophthal acid, l-nitro-2,3-naphthalenedicarboxylic anhydride, and 3-methoxy anhydride An example is -6-nitrophthal.

Among the divalent carboxylic acid aromatic groups that R12 can represent, a of formula (Xm) In connection with alkali metal salts (including mixtures of such groups), for example 6 to 20 divalent aromatic hydrocarbon radicals of carbon atoms, such as phenylene, biphenylene, and There are phthalenes. Examples include hydroquinone, resorcinol There are residues such as chlorine and chlorohydroquinone. Furthermore, the aryl nucleus of R12 is an aliphatic group. , sulfoxide group, sulfonyl group, sulfur, carbonyl group, oxygen, etc. It may be the residue of a dihydroxydiarylene compound that has been combined. Such a di Typical arylene compounds are as follows.

2.4-dihydroxydiphenylmethane, bis(2-hydroxyphenyl)methane 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl) phenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, bis (4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, 1.1-bis(4-hydroxyphenyl)ethane, 1.2-bis(4-hydroxyphenyl)ethane Cyphenyl)ethane, 1,1-bis(4-hydroxy-2-chlorophenyl)ethane Tan, 1,1-bis(2,5-dimethyl4-hydroxyphenyl)ethane, 1 ．． 3-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis( 3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropane) lopyl-4-hydroxyphenyl)propane, 2.2-bis(4-hydroxynaphthyl)propane, hydroquinone, naphthalene diols, Bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)s lufit, bis(4-hydroxyphenyl)sulfone, and the like.

Alkali metal salts of formula (Xm) along with compounds exemplified by formula (XII) When used, these components should be equal for optimum molecular weight and properties of the polymer. Advantageously, a different molar ratio is present. a slight molar excess, e.g. about 0.001 ~0.10 molar excess of dithio-substituted organic compound or alkali metal salt of formula (Xm) When the molar ratios that can be used are approximately equal, the polymer has substantially one end. is terminated by a=Z-NO2 at and terminated by a phenol group at the other end.

If there is a molar excess of one compound, that particular end group will predominate.

An alkali metal salt of formula (Xm) is reacted with a dinitro-substituted organic compound of formula (XII). The reaction conditions used can vary widely. Generally temperatures on the order of about 25°C to about 150°C are present. However, the components used, the reaction products to be determined, the reaction time, the solvent used, etc. It is also possible to use lower or higher temperature conditions depending on the temperature. Other reaction conditions at atmospheric pressure, depending on the conditions, the components used, the rate at which it is desired to carry out the reaction, External pressures above atmospheric pressure and below atmospheric pressure can be used.

Reaction times can also vary widely depending on the components used, temperature, and desired yield. Approximately 5 minutes varying times from 30 to 40 hours to obtain maximum yield and desired molecular weight. It turns out that it can be used for. Thereafter, the reaction product is converted into the desired polymerization reaction by a suitable method. It can be processed to precipitate and/or separate the reaction products. generally normal Solvents, such as alcohols (methanol, ethanol, isopropyl alcohol, etc.) ) and aliphatic hydrocarbons (e.g. pentane, hexane, octane, cyclohexane) etc.) can be used as precipitants for this purpose.

Dinitro-substituted organic compounds of formula ■ and alkali metal salts of formula ■ (such alkali (mixtures of metal salts can also be used) are carried out in the presence of dipolar neutral solvents. It is very important to.

The polymerization is carried out under anhydrous conditions, usually in a dipolar neutral solvent, e.g. It is carried out using dimethyl sulfoxide added at . 10-20% by weight A total amount of solvent sufficient to give a final solution containing the polymer, a dipolar neutral solvent or Preferably, mixtures of such solvents and aromatic solvents are used.

Preferred polyetherimides include those having repeating units of the following formula.

E. Polyesters Polyesters suitable for use herein include polymers containing from 2 to 10 carbon atoms. aliphatic or cycloaliphatic diol or mixtures thereof and at least one aromatic Derived from dicarboxylic acids. Derived from aliphatic diols and aromatic dicarboxylic acids The polyester has repeating units of the following general formula.

In the formula, n is an integer of 2 to 10.

A preferred polyester is poly(ethylene terephthalate).

Also contemplated herein are the polyesters and copolyesters mentioned above. A small amount, e.g. 0.5 to about 2% by weight, of aliphatic acids and/or aliphatic polyols to form It has a unit derived from a molecule. Glycol for aliphatic polyol , for example poly(ethylene glycol). These include, for example, US Patent 2, It can be made according to the teachings of 465, 319 and 3,047°539.

Polyesters derived from cycloaliphatic diols and aromatic dicarboxylic acids are examples. For example, either the cis or trans isomer of 1,4-cyclohexane dimetatool ( or a mixture thereof) with an aromatic dicarboxylic acid and a polymer having a repeating unit of the following formula. It is produced by condensation to produce a realester.

In the formula, the cyclohexane ring is selected from their cis and trans isomers, and R17 is There are aryl groups containing 6 to 20 carbon atoms, which are aromatic dicarboxylic groups. It is a decarboxylated residue derived from phosphoric acid.

Examples of aromatic dicarboxylic acids represented by R17 in formula (IX) are isophtha acid or terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4 ゛-Dicarboxydiphenyl ether, etc., and mixtures thereof. these All of the acids have at least one aromatic nucleus. Fused rings, e.g. 1,4- or ], 5-naphthalene dicarboxylic acid can also be present. Preferred dicarbo The acid is terephthalic acid or a mixture of terephthalic acid and isophthalic acid.

A preferred polyester is cis or trans of 1,4-cyclohexane dimetatool. Reaction of isophthalic acid and terephthalic acid mixtures with isomers (or mixtures thereof) derived from. These polyesters have repeating units of the following formula: .

Another preferred polyester is cyclohexane dimetatool, alkylene glycol and aromatic dicarboxylic acids. These common Polyesters include, for example, cis and trans 1,4-cyclohexane dimetatool. any of the isomers (or mixtures thereof) and alkylene glycols and aromatic di-isomers. The carboxylic acid is condensed to produce a copolyester with repeating units of the following formula: Manufactured by combining.

where the cyclohexane ring is selected from cis and trans isomers and R17 is defined above. As above, n is an integer from 2 to 1O, and f units are about 10 to 90! Quantity% Me, the g unit is about 10-90! % of the total amount.

A preferred copolyester is cis or trans of 1,4-cyclohexane dimetatool. any of the isomers (or mixtures thereof), and ethylene glycol, terephthalate It is derived from reacting tarric acid in a molar ratio of 1:2:3.

These copolyesters have 10 to 10,000 repeating units of the following formula. It is. Block as well as random copolymers are possible.

The polyesters described herein are commercially available or well known in the art. 2,901,466, such as the method described in U.S. Pat. It can be manufactured by

The polyester used herein is a 60:40 phenol/tetrachloro about 0.4 to 2.0 when measured at 23 to 30°C in an ethane mixture or similar solvent It has an intrinsic viscosity of dl/g.

F, aromatic polycarbonate Thermoplastic aromatic polycarbonates that can be used herein include chlorinated carbonates. having an intrinsic viscosity of about 0.4 to about 1.0 dl/g when measured in tyrene at 25°C , homopolymers and copolymers, and mixtures thereof. polycarbonate is made by reacting a dihydric phenol with a carbonate precursor.

Typical of some of the dihydric phenols that can be used are bisphenols. A, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl) -3-methylphenyl)propane, 4,4-bis(4-hydroxyphenyl) Butane, 2,2-(3,5,3",5'-tetrabromo-4,4"-dihydroxy cydiphenyl)propane, (3,3'-dichloro-4,4"-dihydroxydif) (phenyl)methane, etc. Other bisphenol-type dihydric phenols are Permit No. 2,999,835, No. 3,028,365, and No. 3,334,15 It is described in No. 4.

Naturally, two or more different dihydric phenols, or dihydric phenols and glycols Copolymers with or with hydroxy or acid-terminated polyesters can be used. .

The carbonate precursor is a carbonyl halide, carbonate ester or halofluoride. It could be Lemate. The carbonyl halide that can be used in the present invention is carbonyl bromide. , carbonyl chloride and mixtures thereof, which can be used in the present invention Typical examples are diphenyl carbonate and di(chlorophenyl) carbon. di-(halophenyl) carbonate or di-(bromophenyl) carbonate, etc. ) carbonates, di(tolyl) carbonate, di(naphthyl) carbonate , di(chloronaphthyl) carbonate, etc., or mixtures thereof. (rukylphenyl) carbonates. Haloforms suitable for use in the present invention The compounds include dihydric phenols and subhaloformates, such as bisphenols. A bischloroformate, hydroquinone, etc., or glycol, For example, ethylene glycol bishaloformate, neopentyl glycol This includes polyethylene glycol and polyethylene glycol. Other carbonate precursors As will be clear to those skilled in the art, carbonyl chloride, also known as phosgene, is preferred. Delicious.

Aromatic polycarbonate polymers are prepared using phosgene or haloformates. , and using molecular weight modifiers, acid acceptors and catalysts, by methods well known in the art. Molecular weight modifiers that can be used to carry out the method include monohydric compounds such as phenol, para-tert-butylphenol, and para-bromophenol. As a zero molecular weight U4 stabilizer, including phenols, primary and secondary amines, etc. Preference is given to using phenols.

Suitable acid acceptors may be organic or inorganic acid acceptors.

Suitable organic acid acceptors are tertiary amines, such as pyridine, triethylamine, dimethylamine, etc. Includes materials such as tylaniline, tributylamine, and the like. Inorganic acid receptor is water oxides, carbonates, bicarbonates, or alkali or alkaline earth metal phosphates. I can do it.

Catalysts that can be used in the present invention include, for example, promoting the polymerization of bisphenol-A and phosgene. The catalyst may be any suitable catalyst. A suitable catalyst is triethylamine , tripropylamine, N,N-dimethylaniline; Tetraethylammonium chloride, Cetyltriethylammonium bromide, Tet iodide Quaternary ammonium compounds such as ra-n-heptyl ammonium; and bromide Robe-tilttriphenyl-phosphonium and methyl-triphenylphosphonium bromide Quaternary phosphonium compounds such as

When using phosgene or haloformates, the polycarbonate is one-phase (homogeneous) (solution) or two-phase (interfacial) systems. Diaryl carbonate precursor When using , bulk reactions are possible.

Aromatic polyester carbonates can also be used; these are called "polycarbonates". It is included within the scope of "polyarylate" and "polyarylate." These are e.g. as described in U.S. Pat. No. 3,169,121, which is incorporated herein. ing. Such copolymers contain repeated carbonate groups in the linear polymer chain. carboxylate group and aromatic carboxylic acid groups, of which at least some of the carboxylate groups At least some of the carbonate groups are attached to the ring carbon atoms of the aromatic carboxylic acid group. Directly connected. Copolymers contain difunctional carboxylic acids and difunctional carboxylic acids as essential components. It is made by reacting a functional phenol and a carbonate precursor.

Processes for making copolymers are well known, particularly as described in U.S. Pat. 169.121. These copolymers have the following in their linear chains: at least two of the repeating units.

In the formula, A is an aromatic such as phenylene, biphenylene, naphthylene, anthrylene, etc. It is a family group.

F is methylene, ethylene, propylene, propylidene, isopropylidene, butylene Ren, butylidene, amylene, isoamylene, amylidene, isoamylidene, etc. It is an alkylene or alkylidene group such as.

R is hydrogen, alkyl, cycloalkyl, aryl, etc.

Y is an inorganic atom such as chlorine, bromine or fluorine, an inorganic group such as nitro, R or any oxy group such as OR, where Y is the reactant and reactant. It only needs to be inert to and unaffected by the conditions.

■ is an integer from zero to the number of positions available for substitution on A.

p is an integer from zero to the number of positions available on F.

t is an integer at least equal to l.

S is zero or l.

Further, U is any integer including zero.

Examples of dihydric phenols useful in making polyester carbonates include It includes all of those mentioned in connection with polyarylethers.

Carboxylic acids useful in making polyester carbonates include: .

Oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pime Straight paraffin charcoals such as phosphoric acid, sheric acid, azelaic acid, and sebacic acid Saturated aliphatic dibases M derived from hydrogen hydrides and their halogen-substituted derivatives : of thio-diglycolic acid or diglycolic acid containing beta atoms in the aliphatic chain aliphatic carboxylic acids such as; unsaturated acids such as maleic acid and fumaric acid; fluoric acid, isophthalic acid, terephthalic acid, homophthalic acid, 0-5 m- and p-phenylic acid Aromatics such as renniacetic acid and polynuclear aromatic diacids (e.g. 1,4-naphthalic acid) aromatic and aliphatic-aromatic dicarboxylic acids; Aliphatic hydroxy acids such as hydroxybutyrate, glycolic acid and lactic acid; manzo Phosphoric acid and fatty-aromatic hydroxyl such as o-, m- and p-hydroxybenzoic acid sialic acids; and hydric acids, including long chain fatty acids such as 12-hydroxystearic acid. Roxy acids; Tetrahydrophthalic acid, Tetrahydroterephthalic acid, Tetrahydroisophthalic acid Cycloaliphatic Vl including etc.

Preferred polyester carbonates include phosgene, terephthaloyl chloride, and ionic chloride. Condensation of softaloyl with bisphenol-A and a small amount of p-tert-butylphenol It comes from letting things happen.

In a preferred embodiment, the polycarbonate is, for example, a composite of Keifer. US Pat. No. 4.404.35+, Fox (Fax) No. 3,737,40 No. 9, or Fox No. 4,510,289, and published on July 2, 1979. Described in Baron European Patent Application No. 78100447.8 It is a polyaromatic sulfone carbonate. These polymers are It is made by conventional methods and generally contains aromatic diphenols and aromatic sulfonyl diphenols. by reacting the polymers together with a carbonate precursor such as phosgene. can get. The preparation of sulfone-containing polycarbonates is well known and is cited above. It has been described in many patent documents. Diphenol generally has the following formula: I have it.

In the formula, Z is a bond, Cl-C8 alkylene, C2-C8 alkylidene, cyclohexy Ren, cyclohexylidene, S, 0 or CO, and Rag is hydrogen, chlorine, or Alkyl substituents having 1-3 carbon atoms, ■ is 0, 1 or 2.

Aromatic sulfonyl diphenol has the following formula.

Rag　R19 RHI is hydrogen, Cl-C5 alkyl, preferably methyl.

The above phenols are reacted with a carbonate precursor to form a polymer. In the formula R +8, Ras, 2 and V have the meanings given above, and X and y are the relative amounts of reactants. is a positive number that varies by , and j typically has a value of 5-160.

G, styrene resin Styrenic resins suitable for use in the present invention include ABS-type heavy polymers, the molecules of which are Contains two or more polymeric moieties of different composition that are chemically combined. Polymers are good Preferably a conjugated diene such as butadiene, or a monomer copolymerizable therewith, e.g. is made by polymerizing a conjugated diene with styrene. A chain is provided. After the formation of the main chain, at least one reaction in the presence of the prepolymerized main chain A graft polymer is obtained by polymerizing one, preferably two graft monomers. Ru. These resins are made by methods well known in the art.

As mentioned above, the backbone polymer is a conjugated diene such as polybutadiene or polyisoprene. polymers such as butadiene-styrene, butadiene-acrylonitrile, etc. Copolymers are preferred.

The specific conjugated diene monomer utilized to create the backbone of the graft polymer is Generally, it is described by the following formula.

In the formula, A is hydrogen, an alkyl group containing 1-5 carbon atoms, chlorine or bromine. selected from the group. Examples of dienes that can be used are butadiene, isoprene, 1, 3-hebutadiene, methyl-1,3-pentadiene, 2,3-dimethyl-1,3 -butadiene, 2-ethyl-1,3-pentadiene, 1.3= and 2,4-hex Sadien; like dichlorobutadiene, bromobutadiene, dibromobutadiene rolo- and bromo-substituted butadienes; mixtures thereof, and the like. preferred conjugate The diene is butadiene.

A monomer or group of monomers that can be polymerized in the presence of a prepolymerized backbone is Novinyl aromatic hydrocarbons. The monovinyl aromatic monomers utilized are Generally, it is described by the following formula.

where A is as defined above. Monovinyl aromatic compounds and alkyl -, cycloalkyl-, aryl-, alkaryl-, aralkyl-, alkoxy Examples of C-, aryloxy- and other substituted vinyl aromatic compounds include styrene, 3 -Methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene, α -bromostyrene, dichlorostyrene, dipromostyrene, tetrachlorostyrene and mixtures thereof. Preferred monovinyl aromatic hydrocarbons used The base material is styrene and/or α-methylstyrene.

The second group of monomers that can be polymerized in the presence of a prepolymerized backbone is acrylonitrile. Acrylic monomers such as lyl, substituted acrylonitriles and/or acrylic esters good examples are acrylonitrile, ethyl acrylate, and methacrylate. Alkyl acrylates such as methyl lylate.

Acrylonitrile, substituted acrylonitrile, or acturic acid esters are generally is described by the following equation.

In the formula, A is as defined above, and B is a group consisting of cyano and carbalkoxy. where the alkoxy group of carbalkoxy has 1 to about 12 carbon atoms. Contains atoms. Examples of such monomers are 7-crylonitrile, ethacrylonitrile. methacrylonitrile, α-chloroacrylonitrile, β-chloroacryloni Tolyl, α-bromoacrylonitrile, and β-bromoacrylonitrile, meth acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate salt, propyl acrylate, isopropyl acrylate, and mixtures thereof includes. Preferred acrylic monomer is acrylonitrile, preferred acrylic acid The esters are ethyl acrylate and methyl methacrylate.

For making graft polymers, 1,3-butadiene polymers or copolymers are a good example. The conjugated diolefin polymer or copolymer makes up about 50% of the total graft polymer composition. It accounts for 2 in weight. Styrene and 7-crylonitrile are polymerized in the presence of the main chain. Exemplary monomers account for about 40 to about 95 parts by weight of the total graft polymer composition. occupies

Good examples are acrylonitrile, ethyl acrylate or methyl methacrylate The second group of graft monomers of the Graph 1 polymer composition preferably comprises all graft monomers. It accounts for about 10 to about 4011 of the polymer composition. Monobi with styrene as a good example The aromatic hydrocarbon comprises about 30 to about 70% by weight2 of the total graft polymer composition. occupy

When making a polymer, a certain proportion of the polymerized monomers grafted onto the main chain are attached to each other. It is normal for the copolymer to appear as a free copolymer. Styrene graph Acrylonitrile is used as one of the grafted monomers, and acrylonitrile is used as the second grafted monomer. When a certain proportion of the composition is free styrene-acrylonitrile When copolymerizing, styrene is present in the composition used to make the graft polymer. If α-methylstyrene (or other monomer) is used instead, some of the compositions The ratio may be alpha-methylstyrene-acrylonitrile copolymer. Also, α− Graft polymer-copolymerization of copolymer such as methylstyrene-7crylonitrile May be added to body formulations.

When we refer to graft polymer-copolymer blends herein, we are referring to graft polymer-copolymer blends. at least one copolymer incorporated into the copolymer composition; It is optionally contemplated that the composition may contain up to 0% free copolymer.

Optionally, the elastomer backbone includes n-butyl acrylate, ethyl acrylate, It can be an acrylate rubber such as 2-ethylhexyl acrylate and the like. Furthermore When a small amount of diene is copolymerized into the acrylate rubber backbone, the matrix backbone and resulting in improved grafting.

These resins are well known in the art and many are commercially available.

H, poly(alkyl acrylate) resin The poly(alkyl acrylate) resin that can be used in the present invention methyl methacrylate) resins are homologous polymers of methyl methacrylate (i.e. polymethyl methacrylate). acrylate), or methyl methacrylate and vinyl monomer (e.g. acrylonitrile) tolyl, N-allylmaleimide, vinyl chloride or N-vinylmaleimide) polymers or alkyl acrylates where the alkyl group contains 1-8 carbon atoms esters or methacrylates, such as methyl acrylate, ethyl acrylate, Including butyl acrylate, ethyl methacrylate and butyl methacrylate Ru. The amount of methyl methacrylate is greater than about 70% by weight of the copolymer resin.

Alkyl acrylate resins include polybutadiene, polyisoprene and/or butane. can be grafted onto unsaturated elastomer backbones such as gen-isoprene copolymers. Wear.

In the case of graft copolymers, the alkyl acrylate resin accounts for about 50% of the graft copolymer. A proportion greater than 0 weight X.

These resins are well known in the art and are commercially available.

Methyl methacrylate tree N class is 0.1% in 11 chloroform solution at 25°C. It has a reduced viscosity of approximately 2.0 dl/g.

■, polyhydroxyethers Thermoplastic polyhydroxy ethers that can be used in the present invention have the following general formula: Ru.

-[H-0-H'-0]j・1 In the formula, H is a residue of a dihydric phenol, and H" is selected from mono- and dieboxides. residue of an epoxide containing 1-2 hydroxyl groups, ゛ is an integer indicating the degree of polymerization, and is at least about 30, preferably above about 80. be.

Generally, thermoplastic polyhydroxy ethers are prepared by methods well known in the art. Under polymerization conditions, an epoxide containing 1 or 2 epoxide groups and a dihydric phenol is produced by contacting the compound in substantially equimolar amounts with

Any dihydric phenol can be used to form polyhydroxy ethers. Ru. Exemplary binary phenols are mononuclear such as hydroquinone, resorcinol, etc. These are dihydric phenols and polynuclear phenols. Divalent polynuclear phenols are It has the following general formula:

In the formula, R20 independently represents a divalent group such as naphthylene and phenylene (phenylene is preferred). It is an aromatic hydrocarbon group. 6 is the same or different, and methyl n- Alkyl groups, such as propyl, n-butyl, n-hexyl, n-octyl, etc. Preferably an alkyl group of 1-4 carbon atoms; a halogen atom, i.e. salt, bromine; , iodine, or fluorine; or methoxy, methoxymethyl, ethoxy, ethoxyer Alkoxy groups such as thyl, n-butyroxy, amyloxy, etc., preferably 1-4 selected from alkoxy groups of 5 carbon atoms. are independently integers from zero to 4. Ru. R21 independently represents a divalent saturated aliphatic hydrocarbon group, especially one having 18 carbon atoms. alkylene or alkylidene groups, especially C(CH3)2, cycloalkylene, Chloalkylidene or other such as 0.5SSO1SO2, CO1 chemical bond etc. Any divalent group. Particularly preferred are divalent polynuclear phenolic bodies with the following general formula: G and k are as defined above and R22 is preferably 1-3 carbons. alkylene or alkylidene with atoms, cycloa with 6-12 carbon atoms alkylene or cycloalkylidene.

Dieboxides useful in the preparation of polyhydroxyethers are repeating units of the formula can be expressed.

In the formula, R23 is a bond between adjacent carbon atoms, or an aliphatic, aromatic, alicyclic, heterocyclic or represents a divalent organic radical such as an acyclic atomic arrangement.

Other diebogiesides that may be mentioned are those in which the two oxirane groups are aromatic ethers. In other words, compounds with the following atomic groups are included.

-C-0-J-0-(R240)--C- In the formula, R24 is a divalent organic group, J is a divalent aromatic residue of a dihydric phenol, e.g. m is an integer from zero to l.

Still other dieboxides have an oxirane group attached to a nearby carbon atom; includes ethers in which at least one pair of is part of an alicyclic hydrocarbon.

These polyhydroxy ethers are described, for example, in U.S. Pat. No. 3,238,087. No. 3,305,528; No. 3,924,747; and No. 2,777.0 No. 51 herein described and is made by methods well known in the art.

J, polyamides Polyamide polymers that can be used in the present invention are well known in the art. Types of polyamides suitable for use include amorphous and semi-crystalline materials.

Polyamide polymers include homologous polymers as well as copolymers. These polymers are diamines by conventional methods such as condensation of diamines and dibasic acids and addition polymerization. It can be produced from the condensation of functional monomers. diacids, such as carbonic acid, oxalic acid, glutaric acid, Adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, dodecane di diamines such as dionic acid, isophthalic acid, terephthalic acid, etc., such as hydrazine, ethyl Diamine, hexamethylene diamine, 1,8-octanediamine, piperazine and many combinations of amino acids are possible. Chain of functional interludes of reactants contains straight or branched aliphatic hydrocarbons, or cycloaliphatic or aromatic rings; Heteroatoms such as nitrogen, sulfur, and nitrogen can also be included. Secondary diamines leading to the formation of a monosubstituted polyamide.

In addition, aromatic polyamide polymerization in which both the diamine and the dibasic acid are aromatic Also included in the present invention are the following.

Dibasic acids include terephthalic acid, isophthalic acid, phthalic acid, and the like. Aromatic diami 0-phenylenediamine, 2,4-diaminotoluene, 4,4'-methylene including dianiline and the like.

Polyamide polymers undergo water removal following reaction of amine groups with carboxyls. Direct amidation, low-temperature polycondensation of diamines and diacid chlorides, ring-opening polymerization, activated double bonds Addition of amines to polymerization, isocyanate polymerization, and formaldehyde and dinitrile This reaction is produced by a method well known in this technology.

Polyamide polymers include:

Polyhexamethylene-adipamide, i.e. nylon-6°6; Poly(ε-caprolactam), nylon-6; polypropiolactam, Mari nylon-3; poly(pyrrolidin-2-one), i.e. nylon-4; poly (ω-enantamide), i.e., nylon-7; polycapryllactam, i.e., nylon-7; nylon-8; poly(ω-belargonamito), i.e. nylon-9; poly(11- aminodecanoic acid), i.e. nylon-10; poly(ω-undecanoic acid), Mari nylon-11; polyhexamethylene terephthalamide, or nylon 6,T; Nylon-6, 10, etc.

K, poly(arylene sulfide) The poly(arylene sulfides) suitable for use in the present invention are solids and have at least Both have a melting point of about 150'F (65.6°C) and are insoluble in Kayadori's solvent.

Such resins are disclosed, for example, in U.S. Pat. No. 3,354,129. Conveniently created by a method. In summary, this method uses suitable polar organic compounds. Alkali metal sulfides and polyhalo ring-substituted aromatic compounds in the presence of For example, the reaction of sodium sulfide with dichloride in the presence of N-methyl-2-pyrrolidine Involves the formation of poly(phenylene sulfide) by reaction with lobenzene.

The resulting polymer consists of polymers coupled to repeating units predominantly via the sulfur atom. Contains an aromatic nucleus of a substituted monomer. Polymers suitable for use according to the invention are , a polymer neck with repeating units -R25-5-, where R25 is phenyl , biphenylene, naphthylene or their lower alkyl-substituted derivatives.

Lower alkyls include methyl, ethyl, propyl, isobutyl, n-hexyl, etc. una] - means an alkyl group having 6 carbon atoms.

Preferred poly(arylene sulfides) are poly(phenylene sulfides), That is, the following equation %formula%] [where p has a value of at least about 50] It is a crystalline polymer with repeating structural units containing sulfur atoms. Appropriate poly ( phenylene sulfide) compositions are trademarks of Rydon, a Phillips Oil Company. It is marketed under the name The poly(phenylene sulfide) component Measured at 600°F (315,6°C) using a standard orifice The root flow index is in the range of about 10 to about 7000 d$ per minute. is preferable.

The term poly(arylene sulfide) refers not only to homologous polymers but also to arylene sulfides. It is also intended to include ruphide copolymers, terpolymers, and the like.

[Polyolefins Melt coextruded polyolefins useful in the present invention include low, medium, and high density coextrusions. Includes crystalline polypropylene and crystalline polyethylene. High density polyethylene is preferred Delicious. Crystalline polypropylene is particularly preferred due to its high service temperature, Ren-propylene copolymers can also be used.

containing polyolefin layers, including those used to make various types of containers. Multilayer laminates having 0.0000000000000000000000000000000000000000000000000000000000000000000000000000000 than Examples of polyolefins of the type described in Iwasawa et al., U.S. Pat. No. 4,497,856, U.S. Pat. No. 4, Castelein. , 464,439, U.S. Pat. No. 4,440,824 to Bonis. No. 4,430,288 to Bonis.

[Polyphenylene oxides] Polyphenylene oxides suitable for use in the present invention are well known in the art and include Specifically, U.S. Pat. No. 7.662, No. 4,345,050, No. 4.340,696, No. 4, 3 34, No. 050, No. 4,238,584, No. 4,156゜772, No. 4, No. 156,771, No. 4,154,771 and No. 4,140,675 There is a rough description. Polyphenylene oxides generally contain the following repeating units: Homologous polymers, copolymers (including block copolymers) and blends with polymer components It includes things.

Here, the above repeating units may be substituted with various inert groups, as described below. It is possible.

Suitable polyphenylene oxides (P P C1) are described in U.S. Pat. No. 918, and has the following formula (XX).

R25R25R25R25R25R25(XX) The groups represented by R25 in the formula are the same or different, and each hydrogen atom or represents an alkyl group containing 1-4 carbon atoms, preferably hydrogen or a methyl group. vinegar.

× is l R26-C-R26 , where R2B represents hydrogen or an alkyl group containing 1-4 carbon atoms. vinegar.

m' and n' represent integers from 0-200, preferably from 5-60. these compounds The class is the formula (XXI) Polyphenylene corresponding to [wherein R11 and n' have the same meanings as in formula (XX)] Ren ethers can be expressed by the following formula [wherein R26 is the same or different, and the formula (XX ) has the same meaning as inside] and the presence of a catalyst in an organic solvent. reaction at a temperature of -30 to 200"C and optionally under high pressure. It is characterized by

Suitable carbonyl compounds corresponding to general formula (XXn) are aldehydes, such as lumaldehyde (e.g., even in its trimeric form, trioxane or baraphor) (as maldehyde), acetaldehyde, butyraldehyde, and acetone Ketones such as methyl ethyl ketone. Preference is given to using aldehydes. Of these, formaldehyde (preferably in the form of trioxane) is particularly preferable.

Suitable polyphenylene oxides may further include polyphenylene oxides greater than zero, which are well known to those skilled in the art. "Monofunctional polyphenylene" with an average hydroxyl group value per molecule of 1.0 or less This includes oxidants. These polyphenylene oxides are manufactured using prior art methods. It can be exemplified by the following formula (XXm).

R27 In the formula, each R27 independently represents hydrogen, a hydrocarbon group, a halohydrocarbon group, or a hydrocarboxylic group. group or halohydrocarboxy group, the number of groups is at least 1, preferably 10, More preferably, the number is 40 to +70. Block polymer monofunctional polyphenyl The phenylene oxyto unit can be conceptualized with the structure of the above formula (XXm). In that case , the hydrogen atom is a monohydroxy group of polyphenylene oxide, i.e., a -valent phenylene group. Dissociates from phenoxy group, which can be called noxy group.

The expression "phenylene oxide" is defined as per molecule greater than zero and less than or equal to 2.0. "Multifunctional polyphenylene oxide" well known to those skilled in the art with a low average hydroxyl group ”. These polyphenylene oxides are described in U.S. Pat. No. 4,234. , No. 706, and can be exemplified by the following formula (XXIV). Ru.

In the formula, -(OGO)- is a divalent quinone residue, and G is a divalent arene. e) group, where b' or C' is at least equal to 1, and the sum of b' and cl is preferably is at least equal to 10, more preferably 40-170 and R27 is at least equal to 10, more preferably 40-170; It is the same as in the formula (XXm). Multifunctional polyphenylene block polymer The oxide unit can be conceptualized by the structure of the above formula (XXIV); in that case, water The elementary atoms are the hydroxy group of polyphenylene oxide coupled with quinone, all In other words, is it a quinone-coupled polyphenoxy group that can be called a divalent phenoxy group? dissociate from

Suitable polyphenylene oxides include polyphenylene blocks and as listed above. When blocks with similar structures are coupled by reaction with a specific compound, For example, formal (forn + al ) coupled with polyphenylene oxides are disclosed in U.S. Pat. No. 4,340,6. No. 96, by the reaction of methylene halide and polyphenylene oxide. It is made by Linear and fractional polyphenylene oxides coupled with quinones Calibrated and/or crosslinked acyl-coupled polymers are described in U.S. Pat. No. 4,156,772, the molecular equivalent is greater than zero and less than or equal to 2.0. di- and/or trifunctional polyphenylene oxide with low average hydroxyl groups. It can be formed by contacting a valent acyl halide. polyphenyleneoxy Linear, branched, and/or crosslinked polymers coupled with a heterocycle of As described in National Patent No. 4,156,771, (a) thicker than zero; polyphenylene oxide with an average hydroxyl group per molecule of 1.0 or less; or (b) a low average hydroxyl group per polymer molecule of greater than zero and less than or equal to 2.0. or (a) and (b) can be produced by contacting a mixture of with phosphoryl halide. like this Quinone-coupled polyphenylene oxides used in For example, it is described in US Pat. No. 4,140,675.

Suitable polyphenylene oxides are further described in U.S. Pat. No. 4,334,050. Arene boris sulfonate with described polyphenylene oxide and aromatic formal block copolymers, such as halide-cut block copolymers; on the unhindered dihydric phenol described in U.S. Patent No. 4,345,050. Block copolymers of polyphenylene oxide and polyformal, and Polyphenylene oxide and sterically hindered polyphenylene oxide described in Patent No. 4.377.662 block copolymers with aromatic polycarbonate.

Formulations containing polyphenylene oxide, such as (1) polyphenylene oxide and Block copolymers with sterically hindered aromatic polycarbonates, and (11) Contains the vinyl aromatic resins described in U.S. Pat. No. 4,446,278. Formulations are also useful. Suitable formulations are available from General Electric Co.) IO It is commercially available under the registered trademark RVL.

[Second processing] Fillers, pigments, stabilizers, etc. can be used in the layer materials, provided that such additives Non-melt coextrusion of the specific layer materials in which they are used to significantly increase the melt viscosity If fillers are used, they should not have any effect on the core layer. less than about 501 x based on the weight of each such layer using It is preferable to set the amount to .

Laminates (including scrap as part of the original layer or as separate internal layers) using the procedure and apparatus described, for example, in U.S. Pat. No. 3,557.265. You can make it. The patented method uses films or sheets with multiple layers. In order to create reduce the flow magnitude in a direction generally perpendicular to the interface between the different flows, and Multiple flow cross-sectional structures by increasing flow magnitude in generally parallel directions A sheet with a laminated structure is provided.

Different laminated systems are easier to co-extrude using certain co-extrusion dies. For example, in a preferred embodiment, the inventors Realyl ether sulfone/polyethylene terephthalate l-boaryaryl ether C1 oere is used to re-inject scrap into the telsulfone laminate. n) advantageous die (available from Cloeren Die Company, Osinge, Texas). I found out that it can be used.

The laminate is generally about 15 to about 40 mils thick, preferably about 30 mils thick. . The inner layer is generally about 3 to about 15 mils thick.

The laminate is thermoformed into the shape of the desired article. Thermoforming is used for example in engineering ・Polymer Science Ant Fist Technology (Engineering P olymer 5science and Technology) Volume 13 (19 71 > pages 832-843, by methods well known in the art. can be achieved. Generally, the laminate is vacuum formed into a female mold. With this method, the laminate is fixed to the mold frame only around that area, heated to a predetermined temperature for a predetermined time, and then removed from the mold. is brought into contact with the end of the

This contact creates a seal and allows air to be removed between the hot laminate and the mold. The pressure forces the hot laminate against the mold. It is also possible to seal The laminate can be draped by hand over the required contour of the female mould, so that . As an alternative to vacuum forming, positive air pressure can also be applied to force the laminate into the female mold. Can be used repeatedly on the upper part of layered products.

Promotes uniform distribution in products with specific shapes such as box shapes (cooking utensils) A plug aid can be used to do this. This should be done in areas where it would become too thin. The plug can be any form of mechanical aid for delivering the material in minutes. Made of metal, this is heated to avoid cooling the laminate before it reaches its final shape. It is heated to a temperature slightly lower than that of plastic. instead of metal, smooth Can be used with granular wood or thermosetting plastics such as phenolics and epoxies. Wear. These materials do not conduct heat easily, so they are suitable for plastics that do not remove much heat from the sheet. The lug aid is compatible with both vacuum forming and pressure forming techniques.

Another technique that can be used to thermoform laminates is matt molding. child In this method, the laminate is fixed in a clamping form and heated to a suitable forming temperature.

The male mold is placed on the top or bottom platen and the female mold is placed on the other platen. The attached mold is closed and the laminate is pressed against the contours of the male and female molds. male and female The gap between the molds determines the wall thickness. Trapped air escapes from both mold surfaces Do it like this. Keep the mold closed until the laminate cools.

In a useful U configuration, the laminate is fixed to the formwork only at its periphery. Next, laminate products In a furnace, the temperature is increased to a temperature higher than the glass transition temperature of the polymer in the laminate for about 15 to 20 seconds. Heat and allow the laminate to flex at its own length. The laminate is then brought into contact with the female mold end. to create a seal between the hot plastic and the mold. R type is on the upper platen It is located in

Activate the vacuum and pull the laminate into the area of the female mold. The molding temperature is generally around 240. The temperature is approximately 380″F (193.3°C).

The material is left in the mold for about 30 seconds, and the material typically rises from its initial temperature to about 240°C. Allow the mold to cool to a temperature of approximately 380”F (193.3℃). At this point, the molded laminate is rigid and can be removed from the mold. preferred molding The procedure results in a better distribution of material thickness in the molded part, and also using this method. When used, molded articles generally do not develop pinholes. A preferred modification of the procedure is to The laminate is pressed into the female mold by means of a plug aid. The plug feeds the laminate into the female mold. into the mold, but in a position where it does not touch any part of the mold. Then turn on the vacuum , allowing the laminate to be molded to the female profile. The molded laminate as shown above. Leave to cool and remove from the mold.

[Cooking utensils] As previously mentioned, it is possible to fabricate cooking utensils from the improved laminates of the present invention. is specifically intended.

Cooking utensils are any shaped containers or containers used for heating or cooking food. - can be. Cooking utensils can be of any shape with dimensions depending on the desired end use. Representative cooking utensils, which may be of any shape or design, are disclosed, for example, in U.S. Pat. ．． No. 938,730, No. 3,743,077, and No. 3°955.170. be discovered. In addition, typical designs of cooking utensils include, for example, Design Patent No. 236. , No. 574, No. 194, No. 277, and No. 236, No. 182. Ru. Cooking utensils can be used to cook all kinds of foods, including frozen foods, in conventional or micro Can be used for heating and baking in a wave oven.

[Example] The invention is further disclosed and illustrated by the following examples.

Example 1 Points obtained from Union Carbide Corporation under the RADEL registered trademark. MERLON from Mobay Chemical with an outer layer of aryl ether sulfone 8MS3] Bisphenol-A polycarbonate obtained under the registered trademark of 18 A 24 mil thick ABA mold is made by melt coextruding the laminate with an inner layer. I made a laminated product. ABA laminate layer 12.5$/75X/12.5$ Coextrusion was carried out at a thickness ratio of . The coextruder is 3.5 inches, 30:IL/ 1 D Brodex main extruder and 2.5 inch, 30: ] L/D Prodex It consisted of an auxiliary extrusion auxiliary furnace. The operating conditions were as follows.

Finishing roll speed FRM 19 = (1, 7) dynamic crab knitting speed 2 Daili pu = 25 mil rubber roll speed FRM 16 = (3, 30) (measurement) 11 trap Upper roll temperature ”F (’C) 300 (149) 302 (+50) 29 8 (148) Central roll temperature 370 (188) 347 (+75) 362 (183) Bottom roll temperature 360 (+82) 360 (182 ) 357 (181) Head pressure LS I 795 2075 Adapter pressure LB 205 1950 die band temperature Band ill @F 675 (357) Band $t2” F 675 (357) Band #3 @F 675 (357) screen chain Jar temperature 550 (288) 675 (357) Band #1 6F 2 0-60-40-20 675 (357) Band #2 °F 550 (288) 　20 mesh barrel zone temperature Band #1 °F 525 (274) 640 (338) Band #2 °F 540 (282) 660 (349) Band #3 6F 550 (288) 675 (3 57) Band 114’ F 550 (288) Too (371) Band #5 ° 　F　550(288)　7rift0ter 675(357) Melting temperature　”　F　 559 (293) 703 (373) Screw speed RPM 25 44 = ( 3,23) Screw Amperage AMPS 186 65 Dryer temperature ”F 230 (110)-6HR, 275 (135)-6HR .

-’　X　X　7　3　6 While the polycarbonate pellets are placed in the main extruder hopper, the poly(aryl ether sulfone) was placed in an auxiliary coextrusion device. Suitable for forming frozen food packaging materials We produce high-quality sheets with Ta.

By using higher quality (i.e. higher glass transition temperature) sheets and packaging materials. The scraps from the original co-extrusion and thermoforming were combined into Add to the main extruder instead of the Scrap is made of high T8, high flexural modulus poly (aryl ether sulfone) and polycarbonate with low Tg and low flexural modulus Because its average T8 is higher than that of polycarbonate alone, the produced sheet The laminate and packaging material have an overall higher Tg and flexural modulus than the original laminate at service temperature. ing. Scrap has a lower value (if any) than polycarbonate. packaging materials and sheets made from scrap are cheaper than the original laminates. Ru.

Although only a few exemplary embodiments of the invention have been described in detail, the novel teachings and advantages of the invention have been described. It is understood that many changes to the exemplary embodiments ζ are possible without materially departing from the point Those skilled in the art will readily recognize this. Accordingly, all such changes are subject to the following requests: It is intended to be included within the scope of the invention as defined in the claims.

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Claims (29)

[Claims] 1. Continuous plastic comprising at least three melt-coextruded sheets A laminate, each layer consisting of a thermoplastic polymer or thermoplastic polymer blend; the side sheets have higher stiffness at operating temperatures than at least one inner sheet; In that case, the continuous laminate contains laminate scrap resulting from laminate manufacturing; Scrap is included in an upper limit of approximately 50% by weight based on the laminate weight; Claps are simultaneously melted and pressed together with at least one additional separate inner layer of scrap. or as part of at least one melt-coextruded sheet. Incorporated by subjecting the wrap to melt coextrusion, thereby eliminating scrap The stiffness of the laminates containing plastic at the operating temperature is the same as that of the laminates except for the inclusion of scrap. Enhanced compared to tick laminates, Also in that case, the thermoplastic polymer or thermoplastic blend is a polyarylether Sulfone, poly(arylether), polyarylate, polyetherimide , polyester, aromatic polycarbonate, styrene resin, poly(alkyl lacquer) rylate), polyhydroxyether, polyamide, poly(arylene sulfur) crystalline polyolefin, polyphenylene oxide, or blends thereof A continuous plastic laminate selected from the group consisting of: 2. Temperatures between about 350°F and about 450°F (176.7-233.3°C) A continuous plastic laminate as defined in claim 1, suitable for use in Goods. 3. If the laminate scrap is adjacent to at least one of the two outer sheets, Claim no. Continuous plastic laminate as defined in paragraph 1. 4. The scrap has at least one inner sheet that has a lower service temperature than the outer sheet. Substituting substantially the same amount of thermoplastic material from Continuous plastic laminate as defined in paragraph 1. 5. Polyarylether sulfone has the following formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and/or ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ in which R is independently hydrogen, C1-C6 alkyl or C4-C8 cyclo It is loalkyl, and X′ independently has ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [Here, R1 and R2 are independently hydrogen or C1-C9 alkyl] or ▲ mathematical formula, chemical There are formulas, tables, etc.▼ [Here, R3 and R4 are independently hydrogen or C1-C8 alkyl, and a1 is 3-8 ], -S-, -O-, or ▲Mathematical formulas, chemical formulas, tables, etc.▼ , a is an integer from 0 to 4, n is independently an integer from 1 to 3, and the unit is (1). The ratio to the sum of (II) and/or (III) is greater than 1, and the unit is -O - successive pluses as defined in claim 1, connected to each other by a combination; Chick laminate product. 6. Polyarylether sulfone has the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Contains repeating units, and these units are connected to each other by -O- bonds. A continuous plastic laminate as defined in claim 5. 7. Poly(aryl ether) has the following formula -O-E-O-E'- contains repeating units of, where E is the residue of a dihydric phenol and E' is an atom. having an inert electron-withdrawing group in at least one of the ortho and para positions with respect to the valence bond; are the residues of benzenoid compounds, both of which have aromatic carbon atoms. a continuous polymer as defined in claim 1, which is valently bonded to the Plastic laminate. 8. Claim 7, wherein the poly(aryl ether) contains units of the formula: Continuous plastic laminate defined in . ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 9. The polyarylate comprises a dihydric phenol and at least one aromatic dicarboxylic acid. A continuous plastic laminate as defined in claim 1, derived from. 10. Polyarylate is bisphenol A and terephthalic acid or isophthalic acid The linkage defined in claim 9 derived from an acid or a mixture thereof. Continuing plastic laminate products. 11. The polyether amide polymer has the following formula (VIII) ▲ Numerical formula, chemical formula, table, etc. ▼▲There are mathematical formulas, chemical formulas, tables, etc.▼. Continuous plastic laminates as defined in Section 1, where e is greater than 1, preferably about is an integer from 10 to about 10,000 or more, and -O-R12-O- is 3 or 4, and is bonded to the 3' or 4' position, and R12 is (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ a substituted or unsubstituted aromatic group, (b) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ selected from the group consisting of divalent groups, where R14 is independently C1-C6 alkyl , aryl, or halogen, and R15 is -O-, -S-, -C-, -SO2 -, -SO-, alkylene of 1-6 carbon atoms, cyclo of 4-8 carbon atoms alkylene, alkylidene of 1-6 carbon atoms, or silyl of 4-8 carbon atoms selected from chloroalkylidene, and R13 is an aromatic carbide of 6-20 carbon atoms. Hydrogen groups and their halogenated derivatives or their alkyl-substituted derivatives (a alkyl contains 1-6 carbon atoms), alkyl contains 2-20 carbon atoms alkylene and cycloalkylene groups, and C2-C8 alkylene-terminated polydiorgano Siloxane or formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where R14 and R15 are as previously defined)]. 12. Polyetherimide has the following formula (IX) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ Claim 1 Continuous plastic laminates defined in paragraph [where -O-Z is ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (where R16 is independently hydrogen, lower alkyl or lower alkoxy); ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ is a member selected from the group consisting of, and oxygen may be bonded to any ring, located ortho or distal to one of the bonds of the imidocarbonyl group, and also R12 and R13 and e are as defined in claim 11]. 13. Polyetherimide has the following formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ continuous plastic as defined in claim 1, having repeating units of Laminated products. 14. Polyester is the general formula XV▲There are mathematical formulas, chemical formulas, tables, etc.▼Repetition of [in the formula, n is an integer from 2-10] A continuous plastic laminate as defined in claim 1 having units. 15. Claims where the polyester is poly(ethylene terephthalate) Continuous plastic laminates as defined in paragraph 1. 16. Aromatic polycarbonate reacts with dihydric phenol and carbonate precursor. A continuous plastic laminate as defined in claim 1 which is a reaction product. 17. The dihydric phenol is bisphenol-A, and the carbonate precursor is a salt. continuous plastic volume as defined in claim 27, which is carbonyl Layered goods. 18. Claims where the polycarbonate is poly(ester carbonate) Continuous plastic laminates as defined in paragraph 1. 19. The styrene polymer is a conjugated diene monomer, or a conjugated diene monomer and Monomers that can be copolymerized together or acrylic esters can be polymerized to create elastomers. After obtaining the main chain, grafting at least one grafting monomer onto this main chain. a continuous plastic as defined in claim 1 made by Laminated products. 20. The styrene resin is a butadiene/styrene/acrylonitrile resin. A continuous plastic laminate as defined in claim 19. 21. poly(alkyl acrylate) is poly(methyl methacrylate), A continuous plastic laminate as defined in claim 1. 22. Polyhydroxyether has the following formula -H-O-H'-O- , where H is the residue of dihydric phenol and H' is the residue of mono- and diepoxyphenol. a residue of an epoxide selected from sido containing 1-2 hydroxyl groups and wherein j' is an integer representing the degree of polymerization and is at least about 30. Continuous plastic laminates as defined in item 1 of the scope of the request. 23. The polyamide is made of nylon 6,6, nylon 6, or nylon 6,10. A continuous plastic laminate as defined in claim 1, selected from the group consisting of: . 24. Poly(arylene sulfide) has the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Claim 1, wherein p has a value of at least about 50. Continuous plastic laminate defined in . 25. Polyolefins include crystalline polyethylene, crystalline polypropylene, and ethylene. A compound defined in claim 1 selected from the group consisting of lene-propylene copolymers. defined continuous plastic laminates. 26. Polyphenylene oxide has the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼(XX) [Each group represented by R25 in the formula is the same the same or different, each containing a hydrogen atom or 1-4 carbon atoms; represents an alkyl group containing ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ , where R26 is hydrogen or an alkyl group containing 1-4 carbon atoms. and m and n represent integers from 0 to 200]. Continuous plastic laminates as defined in item 1 of the scope of the request. 27. A laminate as defined in claim 1 in the form of a cooking utensil. 28. A laminate as defined in claim 1 in the form of a heated food container. 29. A laminate as defined in claim 1 in the form of a sterilizable container.