FR2477170A1 - MOLDED ARTICLE BASED ON POLYESTER OR SATURATED POLYAMIDE HAVING IMPROVED PROPERTIES AND PROCESS FOR PRODUCING THE SAME - Google Patents

Abstract

PROCESS FOR IMPROVING THE PHYSICAL AND CHEMICAL PROPERTIES OF ARTICLES MADE FROM POLYESTER OR SATURATED POLYAMIDE, AND ARTICLES OBTAINED BY THIS PROCESS. AN ARTICLE SHAPED INTO A POLYMER COMPOSITION OF WHICH THE ESSENTIAL COMPONENT IS A SATURATED LINEAR POLYESTER OR POLYAMIDE INCLUDING A PATTERN OF STRUCTURE OF FORMULA: (CF DRAWING IN BOPI) IN WHICH R AND R, IDENTICAL OR DIFFERENT, EACH REPRESENT A MONO ORGANIC GROUP AND M AND N ARE NUMBERS FROM 0 TO 3, IN THE PROPORTION OF 0.01 TO 50 MOLES PER 100 MOLES OF THE TOTAL ESTER OR AMIDE STRINGS OF THE POLYESTER OR POLYAMIDE MOLECULE, AND THE FORMED ARTICLE IS EXPOSED TO ACTIVE RADIATION, FOR EXAMPLE ULTRAVIOLET RADIATION.

Description

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  Molded article based on polyester or saturated polyamide having

  improved properties and its production process.

  The present invention relates to a saturated linear polyamide or polyamide molded article containing certain specific structural patterns and having various physical and

  improved chemicals, and its production process.

  The saturated polyesters and polyamides can be easily melt-molded and the molded products obtained have excellent mechanical properties, heat resistance, chemical resistance, etc. For this reason, they are

  used in various fields, for example in the form of fibers, pel-

  winglets, etc. Depending on their use, however, their physical or chemical properties are not yet satisfactory and their

improvement is desired.

  For example, among saturated linear polyesters, polyethylene terephthalate has mechanical properties,

  resistance to heat, dimensional stability, resistance

  excellent chemistry and analogues, and is used as a

  starting material for molded articles such as fibers and films.

  However, when heated in the air for a long time,

  mechanical properties are deteriorated; this is disadvantageous for use as electrical insulation material, wired for tires, etc. When treated at elevated temperatures in various stages, the dimensions are more or less modified; this is unfavorable for use as films, fibers, fabrics, etc. The Young's modulus is still not high enough for use as a magnetic recording tape, wired for tires, etc. The pinhole resistance is poor, so it is not suitable for use as a wrapping film. In the case of a biaxially stretched film, the resistance in the direction of the thickness is small and it is easily broken when it is used as packaging material,

  magnetic recording card holder, etc. In the use

  as a support for magnetic recording tape, film

  metallized, etc., oligomers tend to migrate to the surface.

  These defects are also observed more or less in other poly-

  Saturated linear esters and polyamides.

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  To overcome these disadvantages, various proposals have been made including copolymerization of suitable monomer components and incorporation of resinous materials and / or

  appropriate additives. However, the improvement of some

  defective property usually leads to the loss of certain

  favorable intrinsic properties. Thus, the improvement of

  lower properties with maintenance of the intrinsic properties

  taggers is usually difficult.

  Following extensive research, the demand for

  discovered in accordance with the invention that, when irradiating with

  active radiation of molded articles of polyesters and polyesters

  saturated linear amides having certain structural motifs, there is areticulation between or among the molecules, so that the physical and chemical properties (for example resistance to

  heat, resistance to thermal deterioration, dimensional stability

  mechanical properties, chemical resistance, resistance to migration of oligomers) molded articles are favorably

  improved without significant deterioration of their intrinsic properties.

  advantageous claims. The invention is based on this discovery.

  According to the invention, irradiation with radia-

  active compositions a molded article made of a polymer composition comprising as essential component a saturated linear polyester or polyamide containing structural units of the general formula

0

-N-

  wherein R 2 and R 2 are the same or different and each represents a monovalent organic group such as a monovalent aliphatic, alicyclic or aromatic group having one or more carbon atoms (preferably 1 to 20, more particularly 1 to 10 carbon atoms) and m and n are each an integer of 0 to 3, in an amount of from 0.01 to 50 moles of the total of the ester or amide groups

  of the polyester or polyamide molecule, so that there is

  between or among the molecules of the polyester or polyamide,

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  the physical and chemical properties of the molded article being

favorably improved.

  As typical examples of organic groups represented by R 1 or R 2, there may be mentioned methyl, ethyl, propyl, phenyl, cyclohexyl, etc. groups. In the most common case

rant, m and na are equal to 0.

  The polymeric composition for the manufacture of the molded article comprises as essential component the saturated linear polyester or polyamide containing the units of formula (). So,

  therefore, the polymer composition may ordinarily contain the poly-

  saturated linear ester or polyamide containing the pattern (in

  not less than 0.1% by weight (weight of the structural

  mule (1)) relative to the weight of the polymer composition.

  In the case of saturated linear polyester,

  can be used for the introduction of the structure structure

  mule (I) the monomeric compound of the general formula

2X-R-N N-R-Y (II)

(R)

  Wherein R3 and R4 are each a divalent aliphatic, alicyclic or aromatic group having one or more carbon atoms, preferably 1 to 20 carbon atoms (especially 1 to 10 carbon atoms), and optionally containing one or more carbon atoms; ether group, an ester group, an amide group, an imide group or the like, and X and Y each represents a hydroxy group in free or activated form (for example, an esterified hydroxy group) or a carboxy group in free or activated form (For example, an esterified carboxy group or a halocarbonyl group), and R2, m and n are as defined above, or its precursor. Specific examples of the divalent group represented by R or R are methylene, ethylene, phenylene, cyclohexylene, and the like. This monomeric compound (II) or its precursor can

  be prepared by reaction between (A) a benzophenonetetracarbic acid

  optionally substituted for the nucleus (x), or derivative thereof

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  functional (preferably acid anhydride) and () a compound

  containing a primary amino group and at least one functional group

  forming an ester. In the present description, the term

  "ester-forming functional group" means a group that reacts with an alcoholic OH group in free or activated form or a COOH group

  carboxylic acid in free or activated form to form an ester group.

  Examples of compounds (B) are C 2 -C 10 alkanolamines, for example ethanolamine, propanolamine, butanolamine, C 2 -C 10 amino acids, for example glycine, P-alanine, γ-amino-n-butyric acid, paminobenzoic acid, m-aminobenzoic acid, etc. For the production of saturated linear polyester,

  (C) dicarboxylic acids or their functional derivatives are

  (D) diols or their functional derivatives, (E) lactones or hydroxycarboxylic acids or their functional derivatives, etc.,

  in addition to said monomer compound (II). Examples of carboxylic acids

  (C) are terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyledicarboxylic acid, diphenoxyethanedicarboxylic acid, (5-sodium sulfo) isophthalic acid, succinic acid, adipic acid , sebacic acid, dodecanedioic acid, dicarboxylic acids having an imide group,

  etc. Examples of diols (D) are ethylene glycol, trimethyl-

  glycol, 1,2-propylene glycol, tetramethylene glycol, hexamethylene

  methylene glycol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-

  cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyethylene glycols (having a molecular weight of not more than 000), polytetramethylene glycols (having a molecular weight

  not more than 10,000), resorcinol, hydroquinone, 2,2-bis-

  (4-hydroxyphenyl) propane, etc. Examples of the lactones or hydroxycarboxylic acids (E) are p-propiolactone, 1 -caprolactone,

  m-hydroxybenzoic acid, p-hydroxybenzoic acid, N-hydroxy-

  ethylimide of trimellitic acid.

  In addition, the saturated linear polyester may contain units derived from trifunctional compounds such as

  glycerol, pentaerythritol, trimellitic acid and pyro acid

  mellitic, provided that the polyester can be substantially

molded in the molten state.

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  The saturated linear polyester may be produced from said monomers comprising the monomeric compound (II) by a conventional technique. For example, an alkyl ester is heated

  dicarboxylic acid and an alkylene glycol in the presence of a

  A catalyst is used to give a glycol ester, which is then heated to a temperature above the melting point under a greatly reduced pressure. At any stage in this process, the monomer (II) can be added to the reaction system. However, when it contains a carboxyl group, it is preferably added to the system.

  after the end of transesterification between the dicarboxylic acid

  alkyl boxylate and alkylene glycol. In the case where the monomer (II) added to the polyester has an intrinsic viscosity of more than 0.3, it heats sufficiently above the melting point of the polyester to effect the transesterification and then the heating is continued.

  at elevated temperature under reduced pressure for the repolymerization

  tion. Instead of the monomer (II) itself, one can submit to the

  reaction at the polymerization stage benzophenonetetracarboxylic acid

  optionally substituted (A) and the compound (B) or their adduct (i.e., amidic acid). In addition, the product may

  removed from the reactor after polycondensation in the molten state and

  in the form of flakes or powder to the polymerization in

  solid phase by a known conventional technique.

  In the production of saturated linear polyester, a catalyst is usually used, for example metal elements and their compounds, such as oxides, hydroxides, carboxylates, alkoxides, halides, complexes and double salts. As catalysts for transesterification, carboxylates (for example acetate, butyrate), complex alkoxides, double salts,

  etc., metals (eg Ca, Sr, Ba, Zn, Mn, Pb, Ti). Among them-

  ci, the use of calcium acetate, zinc acetate, acetate

  manganese, potassium titanyloxalate, etc., is favorable.

  Examples of catalysts for polycondensation are trioxide

  antimony, ammonium dioxide, lead dioxide, titanyl-

  potassium oxalate, etc. In addition, it is possible to use amines, for example triethylamine, pyridine, morpholine and alkaline salts of carboxylic acids (for example potassium terephthalate,

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  sodium acetate, lithium acetate, as inhibitors for the formation of an ether group and phosphoric acid, phosphorous acid, phosphonic acids, their esters, etc., as stabilizers. The amount of catalyst to be introduced into the reaction system is usually 0.001 to 0.1 mol%, preferably

  from 0.005 to 0.05 moles E relative to the total of the acid components.

  It is necessary that the saturated linear polyester thus prepared contains 0.01 to 50 mole% of units of structure (I), based on the total of the ester groups. When the amount is below the lower limit, the crosslinking almost does not occur by irradiation. A higher quantity is

  better, but an excess beyond the upper limit is useless.

  A preferred amount is from 0.1 to 20 mole percent of the total groups

  ester and, more particularly, from 0.5 to 10 mol%.

  Among various saturated linear polyesters, those in which not less than 50 mole% of the dicarboxylic acid units are benzenedicarboxylic acid units and not less than mole% of the diol units are C 2 -C 10 alkylene glycol units are favorable. In addition, those containing 0.01 to 50 mole% are preferred.

  relative to the total ester groups, repeating units repre-

  by one of the following formulas "o

-OCH2) d N0- N- (CH2 4-o-

2d 1 '2 e oC CO R2m) no

OC

(R (R)

n and "l CO

s OC C -

(2 t i '1_ 4- 2 t

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  where d and e are each an integer of 2 to 6 and f and g are each an integer of 1 to 6 and R, R, m and n are such that

defined above.

  More particularly preferred is a saturated linear polyester, containing terephthalic acid units as the dicarboxylic acid component and C 2 -C 10 alkylene glycol units as the diol component, in molar proportions of 99.9: 0.1 to 80. : 20, and of following formula o il / 2 c Co

N- (Cl2) e-O-

-O- (CH) -N 2 (C2) e-

2 d \ 70 oc i Co

  wherein R1, R2, m, n. d and e are as defined above.

  The saturated linear polyester obtained above generally has an intrinsic viscosity of 0.3-1.5 dl / g, determined at 30 ° C. in a symmetrical phenol-tetrachloroethane mixture in a

molar ratio of 60:40.

  In the case of the saturated linear polyamide, it is possible to use the monomeric compound of the general formula ## STR4 ## in order to introduce the units of structure (I).

X'-R -N C N-R-Y (III)

  M (R) no wherein R5 and R6 each represents a divalent aliphatic, alicyclic or aromatic group having one or more carbon atoms, preferably 1 to 20 carbon atoms (more particularly, 1 to 10 carbon atoms), and containing optionally a group

  ether, an ester group, an amide group, an imide group or

  and X 'and Y' each represents a primary or secondary amino group in free or activated form (for example amide) or a carboxy group in free or activated form (for example carboxy).

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  esterified, halocarbonyl), and R 1 R 2 m and n are as defined above, or its precursor. Typical examples of the divalent R 6 group represented by R 5 or R 5 are methylene, ethylene, hexamethylene, phenylen, cyclohexylene, and the like. This monomer (III) or its precursor can be prepared by reaction between (A) benzophenonetetracarboxylic acid optionally substituted for the ring (s) or its functional derivative (preferably acid anhydride) and (F) ) a compound having a group

  primary amino and at least one functional group forming an amide.

  In the present description, the term "functional group forming

  an amide, a group which reacts with a free or activated COOH carboxylic group or an amino group NH 2 in free or activated form to give an amide group Examples of the compound (F)

  are C2-C101 diamines, for example ethylenediamine, propylene-

  diamine, tetramethylenediamine, hexamethylenediamine, C 2 -C 10 amino acids, for example glycine, P-alanine, 7-amino-n-butyric acid, p-aminobenzoic acid, m-aminobenzoic acid, etc. For the production of saturated linear polyamide,

  (G) dicarboxylic acids or their functional derivatives are

  (H) diamines or their functional derivatives, (J) lac-

  amino acids or their functional derivatives, etc. Examples of dicarboxylic acids (G) are terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid,

  diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid,

  lactic acid, 5-sodium sulpho-isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, dicarboxylic acids having an imide group, and the like. Examples of diamines (H) are ethylenediamine, propylenediamine,

  tetramethylenediamine, hexamethylenediamine, polyoxyethylene

  diamine, polyoxytetramethylenediamine, p-xylylenediamine, oxylylenediamine, m-xylylenediamine, p-phenylenediamine,

  o-phenylenediamine, m-phenylenediamine, 4,4'-diaminodine

  phenylmethane, etc. Examples of lactams or amino acids (J)

  are -caprolactam, glycine, P-alanine, Y-amino acid,

  n-butyric acid, p-aminobenzoic acid, m-aminobenzoic acid, etc.

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  The saturated linear polyamide can be produced from said monomers containing the monomer compound (III) by a conventional technique. For example, the "nylon salt" formed from a dicarboxylic acid and a diamine is heated in the presence of water under high pressure to give a lower polymer and then>

  after progressive relaxation of the pressure, the polycondensation

  tion. Since the monomer (III) has an amino group and / or a

  terminal carboxy group, it can be subjected to the sensitive reaction

  in the same way as the amino and carboxylic acid compounds

  ordinary. In the case of a lactam, the polymerization can be carried out

  cycle opening in the presence of water, if desired, in

  presence of an alkali metal or alkaline earth metal. It is usually performed

  narily by heating under atmospheric pressure. In an optional stage, the monomer (III) can be added as a salt

  of amine to the reaction system for copolymerization.

  The saturated linear polyamide contains 0.01 to 7 moles of structure units (1) relative to the total of

  amide groups. When the quantity is below the lower limit

  However, cross-linking does not occur almost by irradiation.

  A higher quantity gives a better result. But the excess beyond the upper limit is not necessary. The preferred amount is from 0.1 to 20 mol%, in particular from 1 to 10 mol%,

  compared to the total amide groups.

  Among various linear saturated polyamides, those in which not less than 50 moles are preferred. The structural units are units corresponding to one or the other of the formulas

- (CH2) a-Com-

  and -NH- (CH2) b -NHOO- (CH2) c CO wherein a is an integer of 5 to 11, b is an integer of 2 to 6, c is an integer of 2 to 10. In addition, preferred are those containing 0> 01 to 50 mol%, based on the total amide groups, of structural units represented by any of the following formulas: ## STR2 ##

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he co c

-OC (CH2) f - N- (CH2) g-CO-

and O o

HN (CH2) h \ 4 <\ N- (CH2) 11-

OC COl2 o

R (R)

  1) m1 2 in which h and j are each an integer of 2 to 6 and R, R2,

  m, n, f and g are as defined above.

  Particularly preferred is a saturated linear polyamide containing units of the general formula: ## STR2 ## wherein R 1, R 2, m, n, h and j are as defined above, and patterns corresponding to one or other of the formulas

- (CH2) has CONH-

and

-NH- (CH2) b- NHCo- (cH) c-cO-

  in which a, b and c are as defined above, in a

  molar proportion of 0.1: 99.9 to 20:80.

  The saturated linear polyamide thus prepared usually has a relative viscosity of 2.0 to 3.0, measured at 20 ° C.

  in 1% by weight solution in concentrated sulfuric acid.

  The polymer composition for the production of the molded article of the invention may contain, in addition to the polyester

  saturated linear polyamide having the structure structure

  mule (I), any polyester or polyamide that has or is not

  the structural units of formula (I) in its molecule.

  In addition, the polymer composition may contain other resins, such as polyolefins, for example polyethylene, polypropylene, rubbery polymers, for example

  polyisoprene, polyacrylonitrile, butadiene, polybutadiene, poly (sty)

  rene-butadiene), polyamides, for example "nylon 6", "nylon 6,6", "nylon 11", "nylon 12", thermoplastic polyester elastomers%

  by way of example polyethylene terephthalate-polyethylene block copolymer

  ethylene glycol, copolymer: sequenced polyethylene terephthalate-poly-

  butylene glycol, block copolymer polybutylene terephthalate-poly-

  ethylene glycol, block copolymer polybutylene terephthalate-poly-

  butylene glycol, thermoplastic polyurethane elastomers, polyoxypropylenes, polycarbonates, polyorganosiloxanes and fluoropolymers, etc. In addition, the polymer composition can

  contain lubricants, ultraviolet absorbers,

  oxidizing agents, antistatic agents, glass fibers, carbon fibers, foaming agents, other resins, pigments,

  dyes, flame retardants, etc., depending on use.

  For the preparation of a molded article, the polymer composition can be shaped by a process

  conventional molding such as extrusion, injection, compression,

  flage or inflation. For example, it can be shaped in the molten state to give a molded article such as fibers, films or bottles. If desired, it can be applied after forming a drawing, a heat treatment, etc. In addition, any secondary treatment, such as printing, plating, metallization or lamination can be applied with any film

or leaf.

  The molded article thus obtained is then

  irradiated with active radiation so as to crosslink the poly-

  saturated linear ester or polyamide containing the structural units

  of formula I. The mechanism of the cross-linking of polyester or poly-

  saturated linear amide containing the structural units of formula (I), under the effect of irradiation with active radiation, is not yet cleared. Probably, the ketone group present in the

  pattern (I) absorbs a photon and is excited and sets a hydrogen atom

  gene of another molecular chain, and a new chemical bond

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  is formed between the molecular chains due to the chemical reaction of the radical type. In these reactions, an imide group in the unit (1) acts efficiently and improves the activity of the

  photochemical reaction. Thus, therefore, the term "stricture" or

  "used in this description means to designate

  a state in which two or more molecules are linked by one or more chains and the resulting product may vary from a solvent-soluble product to a non-soluble product (i.e.

gelled product).

  The irradiation can be carried out by a conventional technique. As a light source, it is possible to use a high pressure or low pressure mercury lamp, a xenon lamp, a boosted lamp, etc. In general, ultraviolet rays having a wavelength of 200 to 200.degree.

  400 m / u, preferably 310 to 400 np. Other electromagnetic radiation

  Magnetics are also usable. There is no limitation

  particular to irradiation conditions such as irradiation duration

  and irradiation atmosphere. Ordinarily, the duration of irradiation

  can vary from 0.1 s to 30 min depending on the physical properties

  or desired chemicals. Even if the irradiation is carried out in

  With oxygen, the crosslinking is not substantially inhibited. From the point of view of the irradiation efficiency, the irradiation is carried out at a temperature above the glass transition temperature of the molded article before irradiation and below the melting point of this article. Ordinarily, the irradiation intensity is not less than 1 W / m; preferably, it is -about 10 to 1000 W / m 2

  more particularly from about 50 to 300 Wn.

  The post-crosslinking molded article has excellent heat resistance, such as dimensional stability and thermal degradation resistance, excellent mechanical properties such as strength and elongation, bending resistance and pin resistance, excellent chemical resistance, such as that solvent resistance, property of. slip, adhesiveness, printability, gas-tightness property, etc., and is useful as an electrical insulation material, as a support for

  magnetic recording tape, packaging material.

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  As a characteristic illustration of the use of the molded article after crosslinking, a stretched or unstretched film of polyethylene terephthalate or polybutylene containing 0.5 to 5 mole% of units (I) relative to the total ester groups , provided with a metal layer (for example copper, aluminum, silver),

  is useful as a support for a printed circuit board. In part-

  a non-stretched film of polyethylene terephthalate or poly-

  Butylene containing 2 to 5 mole% of units (1), based on the total ester groups, can advantageously retain after irradiation its initial shape even after immersion in a solder bath at a temperature of 260 to 300 ° C. In addition, the unstretched film can be lined with a glass cloth to give a support ribbon of

integrated circuit.

  A biaxially stretched polyethylene terephthalate film containing 0.1 to 2 mole% of units (1), relative to

  total ester groups, possesses after irradiation

  favored ticks as a medium for magnetic recording tape.

  tick. This film has excellent dimensional stability to

  such as coating and "slitting". In addition, migration of the oligomer through the surface is avoided and the elasticity is

Good.

  A biaxially stretched polyethylene terephthalate film containing 0.1 to 2 mole% of units (1) relative to the total ester groups after irradiation is particularly

  useful as an electrical insulation material, because the deterioration

* thermal ration hardly occurs, even when used at high temperature for a long time, so that the permissible temperature limit can be higher. Thus, it serves for the miniaturization of mechanical or electrical instruments and

  increases the reliability of mechanical and electrical instruments.

  When the irradiation is sufficient, the resulting film becomes virtually infusible and serves to reduce accidents due to

over-amperage.

  A biaxially stretched polyethylene terephthalate film containing 0.1 to 1 mole% of units I relative to the total ester groups after proper irradiation has a resistance of

  excellent bend resistance, impact resistance and pinhole resistance, and is therefore

magnetic or packaging film.

  The following examples illustrate the invention without, however, limiting its scope. In these examples, percentages are by weight unless otherwise indicated.

EXAMPLE 1

  In a 4-liter autoclave equipped with a

  1144 g (5.89 moles) of dimethyl terephthalate, 720 ml (13 moles) of ethylene glycol, 418 mg of zinc acetate dihydrate and 358 mg of antifoam trioxide were introduced into the mixture and a stirrer. and the mixture is heated at a temperature of 145 to 215 C for 2 h

  eliminating the methanol formed by distillation; there is transesterism

  fication. After addition of 126.6 g of benzophenonetetracarboxylic acid N, N'-bis (5-hydroxyethyl) imide, the mixture is heated at 215 ° C. with stirring at atmospheric pressure for 15 minutes, and the temperature is then increased by lowering the temperature. pressure so

  reach after 50 min a temperature of 275 C and a pressure of

  0.04 mmHlg. These temperature and pressure conditions are maintained for 30 minutes during which there is polycondensation and formation of a polymer whose intrinsic viscosity is 0.637 dl / g. The melting point (determined by the temperature of the melting peak obtained at the thermogram plotted using the calorimeter

  differential, at the heating rate of 20 C / min, is 252 C.

  For the sake of comparison, polyethylene terephthalate, which is not copolymerized with N, N'bis (β-hydroxyethyl) imide, is prepared by a substantially analogous procedure using benzophenonetetracarboxylic acid. There is an intrinsic viscosity

  0.520 dl / g and a melting point of 260 ° C.

  After drying, the polymer prepared above

  sus was melt extruded at a temperature of 285 ° C to 290 ° C,

  with the formation of an undrawn film of 300 microns thick

  sor. The film was then stretched at the ratio of 3.5 in the machine direction and the ratio of 3.6 in the transverse direction; it was followed by a heat treatment at 200 ° C. and thus

  obtained a biaxially stretched film 24 microns thick.

  This biaxially stretched film was heated to 120 C and exposed

  to a 450 W high-pressure mercury lamp maintained

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  top of the film at a distance of 10 cm for 10 s or 10 min. In the case of the polymer of Example 1, the film, after exposure for 10 min, no longer melts on a

  plate heated to 265 C and it contains 86% gel. After exposure

  for 10 s. the film has an intrinsic viscosity of 0.669, higher than the intrinsic viscosity (0.609) before exposure, and contains 2% gel. The film of the polymer of Example 1, before irradiation, and the films of the comparative polymer, before and after exposure, melt on the plate heated to 265 ° C. and

contain no gel.

  The term "gel" as used herein refers to the insoluble materials remaining after heating 1 g of the film for 2 hours at 120 ° C. in 250 ml of a symmetrical phenol tetrachloroethane mixture, 60:40 by weight. . The gel fraction is deduced by calculating the weight of the insoluble matter collected on a glass filter n0 2 after washing by the same

  solvent mixture, then with chloroform in order, and drying.

EXAMPLE 2

  11.05 parts are introduced into an autoclave

  adipate of N, N'-bis (β-aminoethyl) imide of benzophenonetetraacetic acid.

  110.7 parts of ε-caprolactam, 34 parts of water and 0.24 parts of silica (commercial product ("Syloid No. 150", from Fuji Devison Co., Japan) and an atmosphere of Nitrogen in the autoclave is closed and heated for 3 hours at 180 ° C., then it is allowed to relax at atmospheric pressure for 1 hour during which the temperature is raised to 260 ° C. The reaction is continued for another 7 hours at room temperature. The polymer is discharged from the autoclave by discharging with nitrogen, washed with hot water at 80 ° C. for 16 hours and then dried at 90 ° C. under vacuum for 24 hours. C and having a relative viscosity of 2.45 (measured in 96% sulfuric acid at a concentration of 1 g / dl at 20 ° C.) By means of a heating press, the polymer is put in

  at 2700C in the unstretched film of about 100 microns thick.

  sor. The biaxially stretched film is simultaneously coated in a "TM Long" stretching machine, the drawing speed is 30,000% / min and the draw ratio is 3 in the direction

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  machine and 3 in the transverse direction. The stretched film was fixed in both directions on a metal frame and treated with hot air at 200 ° C for 30 seconds. This heat-hardened film

has good transparency.

  The stretched film is held with the unstretched film at 1250C under exposure to a high-pressure mercury lamp (from Nippon Battery Co., Ltd., Japan) with

  a luminous intensity of 170 W / m or 225 W / m (as measured by

  JV-365 ultraviolet meter from Ushio Electric Co., Ltd.).

  By way of comparison, an undrawn film and a stretched "nylon 6" (ie, polycaprolactam) film are prepared under the same conditions and displayed as

described above.

  The properties of the various films are reported in Table I below; Examination of the results reported in this table shows that on exposure, the undrawn and drawn films of Example 2 have an increasing viscosity and become practically insoluble in the solvents. Dandruff

  Comparative of nylon 6, stretched or not, have a viscosity which decreases.

  The viscosity in question is the relative viscosity measured on a solution of 200 mg of the film in 20 ml

  of 96% sulfuric acid at 250 ° C, Ostwald viscometer.

  The insoluble content is determined by the following procedure. 1 g of the film is dissolved in 100 ml of 96% sulfuric acid at room temperature with stirring overnight; the solution was filtered through a No. 2 sintered glass under vacuum, the insolubles were washed with water, dried at 120 ° C. under vacuum for 2 h, cooled to room temperature and weighed; from the result obtained, by calculation, the percentage of insoluble

  relative to the initial weight of the film.

EXAMPLE 3

  42.8 kg of terephthalic acid, 32.0 kg of ethylene glycol, 18.8 g of antimony trioxide, 78.3 g of triethylamine, 4.7 g of trimethyl phosphate and 25 g are introduced into an autoclave. of

  silica "Syloid No. 150" and the mixture is heated to 24,000 under a pressure of

  3.5 kg / cm 2 for 105 min, then relax at atmospheric pressure.

  pheric. 415.4 g of acid dianhydride are heated separately

2477 1 7 0

  benzophenonetetracarboxylic acid, 158.3 g of monoethanolamine and 1289 ml of ethylene glycol at 140 ° C. under a nitrogen atmosphere for 3 hours; the reaction mixture is introduced into the first autoclave and then heated at 240 ° C. at atmospheric pressure for 15 minutes. The reaction mixture is transferred to a 150 l reactor for polycondensation,

  the temperature is raised from 240 to 280 C in 75 min by lowering

  pressure up to 0.1 mmHg and polycondensa-

  at 280 ° C., 1 mmHg for 70 minutes; a polymer with a melting point of 260 ° C. and a reduced specific viscosity of 0.652 dl / g are obtained (measured by dissolving 100 mg of the polymer in 25 ml of a 6: 4 mixture by weight of phenol and symmetrical tetrachloroethane).

measured at 30 C).

EXAMPLE 4

  A mixture of 41.7 kg of terephthalic acid, 31.2 kg of ethylene glycol, 18.3 g of antimony trioxide, 76.2 g of triethylamine, 4.6 g of sodium phosphate, is heated in an autoclave.

  trimethyl and 25 g of "Syloid n 150" silica at 240 ° C under

  3.5 kg / cm for 105 min, then relax at atmospheric pressure.

  pheric. After the addition of 2051 g of benzophenonetetracarboxylic acid N, N'-bis (β-hydroxyethyl) imide, heating was continued at 240 ° C. at atmospheric pressure for 15 minutes. The reaction mixture is transferred to another polycondensation reactor and the polycondensation proceeds substantially as described in Example 3; a polymer with a melting point of 255 ° C. and a reduced specific viscosity of 0.674 dl / g are obtained (measured on a solution of 100 mg of the polymer in 25 ml of a 6: 4 mixture in pids).

  of phenol and symmetrical tetrachloroethane at 30 ° C).

EXAMPLE 5

  The polymer of Example 3 was dried at 1400C under vacuum overnight and then extruded at 285 C through a 500 mm wide T-die and cooled on a cylinder.

  the surface of which is at a temperature of 30 C and

  takes at a speed of 15 m / min; we get an unstretched film

  0.2 mm thick and 420 mm wide.

  The sequential biaxial stretch film is subjected to the roll / roll technique. We stretch

  in the machine direction at 80 C at a ratio of 3.5 and then in the direction

  cross section at 115 C at a ratio of 3.8; we end with a

  heat setting at 205 C with a relaxation of 5%. Film

  obtained biaxially stretched film has a thickness of 15 microns and

has good transparency.

  This biaxially stretched film is subjected to exposure to a high-pressure mercury lamp (80 W / cm) of the

  firm Toshiba Denzai K.K. After exposure, the viscosity of the

  petticule has increased to a significant extent.

  For comparison, we prepare a

  biaxially stretched polyethylene terephthalate film

  in the same way and this 15 micron film is

  a thickness of exposure under the same conditions; the opinion-

  cosity tends to decrease.

  The results obtained are reported in Table II below. The reduced specific viscosity (C sp / c) was measured by dissolving 100 mg of the film in 25 ml of a 6: 4 mixture by weight of phenol and symmetrical tetrachloroethane,

  at 30 C, Ostwald viscometer.

EXAMPLE 6

  Extrude with the aid of a device identical to that used in Example 5, in the form of a film

  stretched, the polymer containing N, N'-bis (β-hydroxyethyl) -

  imide of benzophenonetetracarboxylic acid, in an amount of 2 mol% (relative to the ester chain members: a structural unit I for 100-membered ester) obtained in Example 4 and a mixture of the same polymer and a polyethylene terephthalate having a specific reduced viscosity of 0.660 dl / g, in relative proportions by weight of 1: 3, a mixture obtained using a V-blender and which contains N, N'-bis (β-hydroxyethyl) units; of benzophenonetetracarboxylic acid in a proportion of 0.5 mole% (based on the total ester chain contained in the polymer and polyethylene terephthalate, ie 0.25 structural unit I per 100 total ester linkages). The films are then subjected to

  sequential biaxial stretching; after biaxial stretching, a pel-

  thin, 15 microns thick. This film is exposed for 2 seconds to a mercury lamp at high pressure. We study the variation of

2477 1 70

  the viscosity with the variation of the distance between the lamp and the film. The results of these tests are reported in Table III below. Examination of the results reported in this table shows that the films of the polymer containing 2 mole%

  N, N'-bis (β-hydroxyethyl) imide of benzophenonetetracarboxylic acid

  and a polymer mixture containing 0.5 mol% of the same imide give rise to a notable increase in viscosity, whereas the comparative film of polyethylene terephthalate gives rise to

a decrease in viscosity.

EXAMPLE 7

  The folding strength of the film of Example 5 at 20 ° C and 65% moisture was determined using the Japanese type JIS P-8115 MIT folding tester. The film according to the invention, the viscosity of which

  increased with exposure to the high-pressure mercury lamp

  feels a significantly improved resistance to folding. The polyethylene terephthalate film and the unexposed film have low bending resistance. The bending strength measurement was made on a sample of the film in the form of a 1 cm wide strip which was subjected to a load of 1 kg. The results of the measurements are reported in Table IV below.

EXAMPLE 8

  Mixed in a V 100 mixer,

  of the polymer of Example 4 (2 mol% bis-imide), 15 parts of a commercial flame retardant (AFR-3001X, chromium aromatic compound from Asahi Glass Co., Ltd.) and 5 parts of antimony trioxide, auxiliary flame retardant, and the mixture is extruded at 2900C. The extrudate is cooled and granulated and ground and dried at 140 ° C. under vacuum overnight. The ground product and a copper foil "T5A" from Fukuda Metal Foil and Powder Ind. Co. and / or a "EPC 070" glass cloth from the firm Arisawa Mfg. Co., in the form of laminated sheet usable as a circuit support ribbon

  integrated by passing to the hydraulic press at 290'C.

24,771 7 0

  The laminated sheet is heat-treated at 180C in the hydraulic press and exposed to the lamp.

  high pressure mercury already used in Example 5, a

  10 cm, and moving at a speed of 0.7 m / min.

  By way of comparison, similar laminated sheets in which the resin is polyethylene terephthalate or the 2 mol% bis-imide polymer are prepared.

  containing no flame retardant or flame retardant auxiliary

  giant. Commercial triazine resin is also used

reinforced by glass fabric.

  These laminated sheets are subjected to various tests, including flame resistance, heat resistance and bending resistance tests, including

  procedures are described below.

  Incombustibility A test tube is suspended vertically

  the laminated sheet of 1 x 10 cm which is brought into contact with its

  lower half with the flame of a match for 3 s and the possible combustion of the test piece is observed. For a specimen that ignites, the result X is given; for a specimen that does not

  not ignite, we give the result 0.

Heat resistance

  A test piece of the stratum leaf is immersed

  in silicone oil maintained at 280 ° C. for 10 seconds and the possible deformations are observed. When there is deformation,

  we denote X; when there is no deformation, we write 0.

  Resistance to folding Onplia at an angle of 1800 and a possible breakage is observed. When there is a break, we write X; when there

has not break, we note 0.

  The results of these tests are reported

in Table V below.

EXAMPLE 9

  A film of the 2 mol% bis-imide polymer of Example 6, after biaxial stretching, is exposed to the

  mercury lamp of high pressure of Example 5 and the

  physical properties of the exposed test piece.

24 77 1 7 0

  The results of these studies are reported in Table VI below; determination of physical properties

was done as follows.

  Melt breaking temperature It is determined in the following manner: on a specimen of the film 1 mm wide and 25 mm long, a charge of 0.1 g is applied and heated to air by heating to the speed of 4 C / min; the temperature at which the test piece is observed

breaks.

  Heat resistance A specimen of the film is immersed in silicone oil maintained at 280 ° C. for 10 seconds and the

possible deformations.

  Insoluble 1 g of the film is placed in 250 ml of a 6: 4 mixture of phenol and symmetrical tetrachloroethane in a 300 ml flask and the flask is kept in an oil bath at 1200 ° C. for 2 hours with stirring for 1 hour. other. After 2 hours. the flask is removed from the oil bath and cooled. The contents are filtered through a No. 2 sintered glass under vacuum. The insolubles are washed on a chloroform filter and then with acetone, dried at 120 ° C. under vacuum for 2 hours, cooled and weighed. From the results obtained,

  the insoluble content% is determined by calculation.

  The results obtained are reported in the

Table VI below.

EXAMPLE 10

  The procedure is as in Example 5, but is treated with heat at 23 ° C. under a relaxation of 10%, and then

  subjecting the polymer to 0.5 mol% bis-imide with biaxial stretching

  tial. After biaxial stretching, the film is exposed as described in Example 5 and subjected to heat shrinkage test according to

  the procedure of Japanese standard JIS C-2318. As a comparison

  the same test, a film of terephthalate

  polyethylene subjected to biaxial stretching.

  The results of these tests are reported

in Table VII below.

24 7 71 70

EXAMPLE 11

  The film of Example 5 was subjected to biaxial stretch-strength testing at high temperature. The

  film is degraded using the aging tester

  Gear type 104 HG2 from Negoro Mfg. Co., Ltd., at 1800C for 21 days; after the test, the variations in strength and elongation of the film are determined according to the procedure of Japanese JIS C-2318. The

  The results obtained are reported in Table VIII below.

TABLE I

  Conditions Example 2 Irradiation comparison Temp-Intensity Time e Temp- Intensity Time Unstretched Biaxial stretch Unstretched Biaxial stretching light raster (min) (OC) (W / m2) t Insoluble Visco- Insoluble Visco- Insoluble Visco- Insoluble Visco- Insoluble sity (%) sity () sit (%) sity Before exposure 2.42 O 2.29 0 2 59 0 2.41 O

1.25 170 0.15 2d85 O 2.77 O - - -

170 0> 3 3.21 O 3.06 O 2.43 0 2.32.0

225 5 - 64 - 75 - - -

  225 0X1 3.42 0 3.54 0 2.41 0 12.26 O

_...__. |

225 1 - 32 - 38 - - _ _

225 5 - 63 - 70 2.07 0: 2; 03 0

225 10 - 81 - 89

225 -y, O1 -_ -

w w -4,

TABLE II

  Conditions Example S Irradiation comparison Lamp distance Irradiation time Specific viscosity Specific viscosity (cm) (s) reduced (dl / g) (dl / g) Before exposure 0 0.621 0.662

1 0.704 -

2 0.841 0.649

3 0,952 -

4 1,053 0.643

3 0.762 0.656

6 0.919 0.652

3 0.713 -

6 0.826 0.657

9 0.931 -

12 1.025 0.654

rg) -Ij

II-'J,

  III flv'Inv 1r- c - r <w C% 89 '0 ZLL'o L

690 SL'O 01

  8990 TLO 910! 95 O - g99ó0 Z9L 0 Oz 099'0 Z9'O TtO '0 Z Z99 0 LT9'0 999' 0 UOTTsodxa 3UeAv aulTúiqlpxTod Z o ap a4lellqd99zgL saeamXiod ap agueTg X saoom ZV a02m; TO JFlezedmoO 9 aodumaxa (2 /, p) Dwnppa anbTgTopds 94TsoasTA adoule el ap (mDus) (U / Ip) a2TnPp} anblTods 3TsoasTA odmeI eIoap aaue2sTH

TABLE IV

  Viscosity Folding strength, specific film number of folds reduced _ _ _ _ ___ I (dl / g) unexposed polyethylene terephthalate 0, 662 24.5 x 10 Polymer 0.5 mol% unexposed 0.621 21.3 x 104 Polymer at 0.5 mol% exposed for 2 s at 0.841 86.8 x 104 distance at 10 cm Polymer at 0.5 mol% exposed for 3 s at 0.952 114.8 x 104 distance of 10 cm O rgQ - J -Jb

TABLE V

  Thickness Irradiation Resistance to Resistance Stratified product (/ u) Incombustibility heat at bending Glass fabric / terephthalate of 150 non XX 0 polyethylene Glass / polymer fabric at 2 moles% 150 no XX 0 without flame retardants Glass fabric / polymer at 2 moles% 150 yes OO 0 with flameproofing agents Glass / polymer fabric at 2 mole% 150 non 0 XO with flame retardants Glass / polymer fabric at 2 mole% / 150 yes 0 0 0 copper with flame retardants Glass fabric / polymer with 2 mole% / 150 non OX 0 copper with flame retardants Copper / polymer & 2 mole% 7. 100 yes O 0 O with flame retardants Copper / polymer at 2 mole% 100 non O x 0 with flame retardants

. j ................_.....

  I Copper / polyethylene terephthalate 100 non X x O Triazine resin reinforced by 110 non x 0 x commercial glass fabric

.t .0.

-J NI -PJ

TABLE VI

MB

TABLE VII

  -gb. cj Radiation conditions Temperature of rupture resistance by Insoluble heat fusion (%) Distance from Duration () lamp (s) (cm) Polyethylene terephthalate - O 239 X 0 Polymer 2 mole% - 0 231 X 0 Polymer at 2 moles 7. 25 300 285 0 79 Radiation conditions Heat shrinkage (%) Distance of the duration Example 10 Comparative lamp (cm) (s)

0 1.10 1.10

3 0.75 1.15

6 0.15 0.35

9 0 0.20

TABLE VIII

  ra c-J C4 Before degradation After degradation PolymerIrradiation Thickness Viscosity Resistance Elongation% of the% of

  (/ u) specific (kg / mm2) resistance elongation

  initial initial reduction (dl / g) Polymer yes 0.998 18.3 26 68 91 0.5 mole% Polymer to non 0.618 25.5 46 45 17 0.5 mole% Terephthalate yes 15 0.584 26.6 50 48 14 polyethylene

2477 1 70

Claims (28)

R E V E N D I C A T I 0 N S ___________________________   1. Method for improving physical properties   chemical composition of a shaped article consisting of a poly-   This process is characterized in that a polymeric composition comprising as its essential component a saturated linear polyester or polyamide containing a structural unit having the formula Oc CO is formed as a shaped article. -N N- (I) (R (R) M n   wherein R1 and R, having identical or different meanings,   each represents a monovalent organic group, m and n each being a number of 0 to 3, in an amount of from 0.01 to 50 moles per mole of total ester or amide linkages present in the molecule of the polyester or polyamide, and the article shaped to active radiation ..   2. Method according to claim 1, characterized   in that m and n are both equal to 0.   3. Process according to claim 1, characterized in that the monovalent organic group is an aliphatic group,   alicyclic or aromatic C1-ClO.   4. Method according to claim 1, characterized in that the essential component is a polyester of which at least 50 mole% of the dicarboxylic acid units are units of a benzenedicarboxylic acid and at least 50 mole% of the units of   dioI are units of a C2-C10 alkylene glycol.   5. Method according to claim 1, characterized in that the essential component is a polyester containing a structural unit corresponding to one of the formulas Oc-1Co O (CH2) d Ns / cifioaN- (CH2) e-O- 24 7 7 1 7 0 oo -OC.} OCN1 O and o CO ## STR5 ## 10.OC- (cC) f-N.:x o .j- (ll>. (R) (R2)   in which d and e are numbers from 2 to 6, f and g are numbers from 1 to 6 and R1 R2, m and n have the meanings indicated in claim 1.   6. Process according to claim 1,   characterized in that the essential component is a polyester comprising   terephthalic acid units as dicarboxylic acid units;   and C2-C10 alkylene glycol units as the units   of diols, in molar proportions of 99.9: 0.1 to 80:20, and laying on the iCO formula. oc C N- (CH2-O- -O- (CH2) d-N2CeCO (R) (R)   in which d and e are numbers from 2 to 6, R, R, m and n having   the meanings given in claim 1.   7. The process according to claim 1, wherein   characterized in that the essential component is a polyamide of which at least 30.50 mole% of the structural units are units corresponding to one of the formulas - (CH2) has CONH- and -NH- (CH 2) bNHCO- (CH 2) -CO-   where a is a number from 5 to 11, b is a number from 2 to 6 and c a number from 2 to 10.- 2477 1 70   8. Process according to claim 1, characterized   in that the essential component is a polyamide containing a structural unit corresponding to one of the formulas wherein Oc O 0) N OC N: OC. oc -. CO i. -HN- / - CO N- (CH2) j-NH   where f and g are numbers from 1 to 6, h and j are numbers from 2 to 6, and R1, R, m and n have the meanings indicated in claim 1.   9. Process according to claim 1, characterized   in that the essential component is a polyamide comprising units having the formula CO \ S N- (CH) .- NH-   wherein h and j are numbers 2 to 6, R 1, R 2, m and n have the meanings given in claim 1, and units corresponding to one of the formulas and - (CH2) a-CONH- and -NH- (CH2) b-NHCO- (CH2) c -C0-   in which a is a number from 5 to 11, b is a number from 2 to 6 and c is a number from 2 to 10, in molar proportions of 0.1: 99.9 at 20:80.   10. Process according to claim 1, characterized   in that the shaped article is an unstretched film.   11. The method of claim 1, characterized   It is understood that the shaped article is a stretched film.   12. The method of claim 1, characterized   in that the shaped article is a fiber.   13. The method of claim 1, characterized   in that the shaped article is a fabric.   14. The process according to claim 1, characterized   in that the active radiation is ultraviolet radiation   at a wavelength of 200 to 400 m.   15. A shaped article, characterized in that   consists of a polymer composition comprising as essential component   a linear saturated polyester or polyamide containing a structural unit of the formula wherein R1 and R, which may be identical or different, each represent a monovalent organic group and m and n are numbers of O at 3, in a proportion of from 0.01 to 50 mol% per 100 mol of total ester or amide catnones contained in the polyester or polyamide molecule,   and who has been exposed to active radiation.   16. Shaped article according to claim 15,   characterized in that m and n are both equal to 0.   Shaped article according to claim 15, characterized in that the monovalent organic group is a group   aliphatic, alicyclic or aromatic C1-Co10. 2 4 7 7 1 7 0   Shaped article according to claim 15, characterized in that the essential component is a polyester of which at least 50 mole% of the carboxylic acid units are benzenedicarboxylic acid units and at least 50 mole% of the diol units are units of a C2-C10 alkylene glycol. 19. Shaped article according to claim 15,   the essential component is a polyester containing   a structural unit corresponding to one of the formulas -O (CH 2) n -N 2 / e o C o C C Go -oc NC N X NCO-   (R) (R) n {oc (43 oc aR1) 4,, CO v O (R n and 0 he oc c. Co -OC- (CH2) -N / N- (CH2) g-CO-   where n and e are numbers from 2 to 6 and f and g are numbers from 1 to 6, R, m and n having the meanings indicated in claim 1.   20. Shaped article according to claim 15,   characterized in that the essential component is a polyester containing   terephthalic acid units as dicarboxylic acid units and C 2 -C 10 alkylene glycol units and units of the formula below in molar proportions of 99.9: 0.1 to 80: 20 ,. as diol motifs: 2477 1 70   in which d and e are numbers from 2 to 6 and R 1, R 2, n   having the meanings indicated in claim 1.   21. A shaped article according to claim 15, characterized in that the essential component is a polyamide of which at least 50 mol% of the structural units are units corresponding to one of the formulas! - (CH2) -CONH- and -NH- (CH2) b-NHCO- (CH2) c-CO-   in which a-is a number from 5 to 11, b a number from 2 to 6 and c a number from 2 to 10.   22. A shaped article according to claim 15, characterized in that the essential component is a polyamide containing a structural unit corresponding to one of the formulas 20 ,, .0 Oc c -OC eOC \ -r- CO- C (R) R)   CO 4230)) X (n) - and o C HN (CH2)) -NC 2 g 0o (R) m nR) n 24 7170   in which f and g are numbers from 1 to 6, h and j are numbers 2 to 6 and R 1, R, m and n have the meanings indicated in claim 1.   23. A shaped article according to claim 15, characterized in that the essential component is a polyamide containing units of formula mn in which h and j are numbers from 2 to 6 and R1, R2, m and n have the meanings indicated in claim 1, and the patterns corresponding to one of the formulas - (CH2) a-CONH and -NH- (CH2) b-NHCO- (CH2) c-CO-   in which a is a number from 5 to 11, b is a number from 2 to 6 and c is a number from 2 to 10, in molar proportions of from 0.1: 99.9 to 20:80.   24. Shaped article according to the claim   in that it consists of an unstretched film.   25. Shaped article according to the claim   in that it consists of a stretched film.   26. Shaped article according to the claim in that it consists of a fiber.   27. Shaped article according to the claim   in that it consists of a fabric.   Shaped article according to the claim, characterized, characterized, characterized, characterized in that the active radiation is ultraviolet radiation.   at a wavelength of 200 to 400 m / u.