TWI292448B - Process for the manufacture of nonwoven surfaces - Google Patents

Description

129. The invention relates to a novel method for producing a non-woven surface. More particularly, the present invention relates to a method of making a non-woven surface by a method of directly melt spinning into continuous filaments in the form of flakes. [Prior Art] Non-woven surfaces are widely used in the preparation of many applications such as surface coatings. Such surfaces are obtained according to a number of processes, such as a wet process, in which the fibers are suspended in a liquid that advantageously comprises a product that makes the bond possible. These fibers are gathered on the agglomerated surface to produce a sheet which is stoned and formed to form a non-woven surface. The other-process that is also used is called "Dry Path Process". This process is in which the cut and carded fibers formed into a web form a sheet, and then the sheet is treated to impart adhesion thereto. In this dry path it is also possible to make sheets from filaments. Green, however, in the case of continuous strands or filaments, the most widely used is the dazzling spinning process, which is called the "direct spinning" process. = = squeezing one or more polymers through a Or a plurality of spinnerets, which are drawn by a pneumatic member and deposited on the agglomerated surface sheet. The sheet may be rendered viscous, resin impregnated or bonded by heat according to various processes. It has a higher refining polymer than other spinning points or softening points, and then obtains the adhesion by heat-treating the sheet. The 3 points are the sheets which are not good in characteristics and good uniformity, and the first is obtained. .doc 1292448 The uniform distribution of filaments on the agglomerated surface and the subsequent deposition of filaments exhibits uniform characteristics and characteristics. It is difficult to produce uniform continuous filaments or strands and lengths in a continuous spinning process. Uniform distribution of filaments or strands. This is due to the fact that individual filaments exiting from each spinneret orifice are gathered together into a multifilament strand. This filament is agglomerated pneumatically. However, as illustrated in U.S. Patent 4,758,134, In the long An electrostatic charge is generated which causes the filament to disperse and prevents the process from being painful. This patent provides for operation in a humid atmosphere. This solution also shows disadvantages, especially when the polymer pair is used. When the moisture is sensitive, for example, polyamine. [Invention] One of the objects of the present invention is particularly to overcome the disadvantages caused by the use of a composition based on thermoplastic polymerization, which exhibits prevention of static interference The effect becomes a possible conductive property. To this end, the present invention provides a method for producing a non-woven surface by directly melt spinning a filament based on a composition of a thermoplastic Φ polymer, comprising: feeding the composition In a plurality of spinning heads, each of the spinning heads comprises if = spinning holes; then the obtained filaments are fed into a pneumatic drafting device and a flattened filament, and the drawn continuous filaments are formed into sheets therein. The method 2 is characterized in that the thermoplastic polymer-based composition fed to the spinneret comprises a human matrix and/or a modified polymerizable additive, and the modified polymerizable additive package Corresponds to the following general formula of repeating units ·· 3 99007.doc 1292448

Yu Yu

Wherein: the same or different Ri, R2, R3 and R4 represent an aliphatic, cycloaliphatic or aromatic hydrocarbon chain containing from 2 to 18 carbon atoms, and R5 represents a polyether group having a molecular weight between 400 and 200,000, A and B represents a CO, NH or hydrazine group; when A represents CO, B represents NH or hydrazine and vice versa, and when the upgrading additive does not exist or does not contain the repeating unit of formula (1) or IV, the polymeric matrix comprises At least one of the units 1 or 11 and at least one of the repeating units III or IV are repeated. Advantageously, such compositions exhibit a volumetric conductivity greater than or equal to 1 < 10·9 s/cm, preferably between 5X10-9 S/cm and 5X10-8 S/cm. However, compositions exhibiting a volumetric conductivity other than the above range (e.g., less than 1 x 10-9 s/cm) may also be suitable for use in the present invention. The filaments are gathered to form a plurality of multifilament strands, and then positioned on the receiving surface to produce a filament process which may include feeding each filament into a pneumatic drafting device or feeding it into a pneumatic drafting device to form Sheet. 99007.doc 1292448 Fish: The y system is made of a conductive polymerizable composition, so that the static charge generated on the surface of the filament between the stages of the spinneret into a sheet can be removed only. Therefore, the filaments remain parallel to each other, and the filaments can be transported through the apparatus before being formed into a sheet without being deviated from its advancement path. The compositions of the present invention also make it possible to limit the formation of such electrostatic charges and thereby limit the dispersion effect of the filaments or the adhesion of the filaments to the metal walls of the device used for spinning. The term "electrically conductive poly = or electrically conductive composition" is understood to mean a polymer or composition that directly exhibits a structure or group that imparts a higher electrical conductivity than an unconditioned polymer or composition. Share. However, the level of conductivity is still low and in particular makes it possible to remove static which may form during the formation of such polymers or compositions. The thermoplastic polymer used in the present invention is advantageously a thermoplastic polymer belonging to the group of (iv) amines and polythene. As a polymer brewing method suitable for use in the method of the present invention, there may be mentioned a conductive polycondensation obtained by polymerizing a diacid and a diol, which comprises a morphological diol (such as B-butanol, butylene glycol or a mixture of propylene glycol) and polyoxyalkylene diol. Particularly suitable for use in the thermoplastic polyamines of the first to the present invention, mention may be made of "copolyamines obtained by "one of the acids, diamines or endoamines." However, a special structure will be shown. Monomers are added to the conventional monomers. These monomers advantageously exhibit a bond bridge in their structure and preferably contain a poly-dish chain and exhibit a reaction before the functional groups of other monomers. a compound of the base, such as an amine, acid or hydroxy-functional group of the ruins of the ancient temple. Workshop 99007.doc • 9- 1292448 These compounds containing an amine g-energy are sold, in particular, by Huntsman under the name Jeffamines. In a first preferred embodiment of the invention, the thermoplastic polymer is advantageously a copolymerized guanamine of the S repeating unit, which is shown to provide conductivity of a conventional polyamine such as polyamine 6,6 or polyamine 6. The polyoxyalkylene chain is made possible. Thus, the thermoplastic polymer of the first embodiment of the invention is a copolymerized decylamine comprising a repeating unit corresponding to formula I or II and III or IV. Corresponding to the polymerization of diacids and diamines a reaction product, the diacid being selected from the group consisting of succinic acid, adipic acid, terephthalic acid, isophthalic acid, phthalic acid, undecanoic acid, and mixtures thereof, and the diamine is selected from the group consisting of a group consisting of diamines, 2-methylpentanediamine, m-xylylenediamine, and mixtures thereof. This list is not exhaustive and other diacids or diamines may also be used. The repeating unit of formula II corresponds to the lactam. Or a polycondensation product of an amino acid selected from the group consisting of caprolactam, aminoundecanoic acid, aminododecanoic acid, and mixtures thereof. Again, this list does not have Excessive and other internal guanamine or amino acid can also be used. Advantageously, the weight concentration of the repeating unit of formula III and / or IV is between 5 5 and 5% by weight of all repeating units or polymers Conductive polyamines corresponding to the above definitions are disclosed, for example, in the patent application WO 94/23101. These polyamines are by virtue of the use of intrinsic amines or amino acids such as caprolactam and amine groups. Monoacid or aminododecanoic acid is obtained as a primary and conventional monomer. It can also be used for manufacturing ( For example, the conventional polymerization process of polyamine 6,6, in the presence or absence of a catalyst, the conductivity is obtained by polymerizing a diamine such as hexamethylenediamine and diacid adipic acid. Thermoplastic polyamines. According to the tree: to obtain the desired degree of polymerization, initially add polyoxymethylene diamine monomer with diamine or diacid monomer or salt formed by diacid and diamine monomer The polyoxyalkylene diamine is added to the polymerization medium either into the polymerization medium or during the polymerization process (for example, before or during the stage in which the polymer is placed in a vacuum). In this first embodiment, the composition Contains conductive thermoplastic polymer as a main component or a single part. Of course: there may be common additives, such as heat stabilizers, additives for improving the aging resistance of polymers (such as w-transition), pigments, dyes, matting Agents, nucleating agents and the like. In a second embodiment of the invention, the thermoplastic polymer is included based on the thermoplastic polymer and the conductivity of the improved composition is made: a modified polymeric additive. This additive contains an alkyl chain in its structure. For the sake of clarity and conciseness, the following conductive additives ". This additive is referred to as "addition, and another feature of the first example of the first modification is the modification of the polymerization property; the degree is between the core and the 3% by weight relative to the total 'weight of the composition' According to still another feature of the present invention, the ground system is at a weight % and 15% by weight of the bismuth, and the additive is lower than the feed 1:1 viscosity of the additive to exhibit a favorable melt viscosity of the human melt viscosity. Therefore, in the process of m ▲δ (detailed in (4) 'green 矣 and W A J)' additive migration to the stock, "the surface characteristics (detailed for its conductivity characteristics) can be adjusted 99007.doc • 11 - 1292448

According to a first alternative form, the modified polymerizable additive according to the present invention advantageously comprises a thermoplastic structure preferably having a property similar to that of the thermoplastic polymer of the composition and a structure comprising a polyoxyalkylene chain. Thermoplastic Junction The composition of this second embodiment of the invention is advantageously obtained by blending a thermoplastic polymer with a modified polymeric additive and optionally other additives such as those listed above. This blending can be carried out by any conventional process. One of the preferred processes is to blend the components into an endless screw comprising one or more screws and extrude through the spinneret to form a strip. This strip is then chopped to produce particles of the desired size and desired weight. After drying as appropriate, the granules are used and fed into equipment for spinning and making non-woven surfaces. However, it is also possible to add a modified polymerizable additive to the molten thermoplastic polymer before being fed into the spinneret to spin the nonwoven fabric without departing from the scope of the present invention. Pure or in the form of a concentrated solution (parent mixture) in the host polymer. The structure can be a polyester or polyamine structure. As the polyester which is suitable as the polymerization additive of the method of the present invention, a copolymerized vinegar obtained by polymerizing a diacid and a diol monomer, such as a glycol, may be mentioned. A mixture of a tri-m-alcohol and a polyoxygen-extension base. / 乍 (4) The polyamine which is a modified polymeric additive of the present invention may be mentioned by copolymerizing a decylamine obtained by hydrating a conventional diacid, diamine or decylamine monomer. However, monomers showing a particular structure are added to the conventional monomers. 99007 d〇c -12- 1292448 These monomers advantageously exhibit an ether bridge in their structure and are preferably compounds containing a polyoxyalkylene chain and exhibiting terminal functional groups which react before the functional groups of other monomers These terminal functional groups are, for example, amine, acid or hydroxy functional groups. Such compounds containing amine functional groups are especially sold under the name Jeffamines by Huntsman. The conductive or modified polymerizable additive is obtained by polymerizing a monomer of the formula in the presence of a monofunctional chain-limiting compound:

H〇一C—Rrg —OH (V) 0 〇 H2N——R—NH2

(VI) (VII) B——R—B (VIII) wherein: the same or different Ri, R 2 and R 3 represent an aliphatic, cycloaliphatic or aromatic hydrocarbon chain containing from 2 to 18 carbon atoms, indicating a molecular weight at A polyether group between 400 and 200,000, and B represents a COOH, NH2 or OH functional group. In order to control the melt viscosity of the additive and limit its reactivity upon blending with the thermoplastic polymer, the polymerization is carried out in the presence of a monofunctional compound of a chain-limiting length according to a known process for producing a polymer. As the monofunctional compound, monofunctional acids and monofunctional amines can be mentioned. Therefore, acetic acid, propionic acid 990G7.doc • 13-1292448 and decylamine are preferred compounds. Advantageously, the weight concentration of the monomer of the formula 111 in the monomer mixture is between 1% and 20%, advantageously between 1% and 1% by weight of all monomers. Polyamines corresponding to the above definitions are disclosed, for example, in the patent application WO 94/23101. Such polyamines are obtained by using, inter alia, mesalamine or an amino acid such as caprolactam, amidodecanoic acid or aminododecanoic acid as the main and conventional monomers. In a second alternative form of the second embodiment of the invention, the modified polymerizable or electrically conductive additive is advantageously a compound comprising: > at least one thermoplastic block and > at least one polyoxyalkylene Base block. More specifically, the compound comprises: > to y thermoplastic polymer block formed by: a green or braided macromolecular chain comprising at least one multifunctional core and at least one attached to the core a thermoplastic polymer branch or fragment comprising at least three identical reactive functional groups, and/or a straight bond macromolecular chain comprising a bifunctional core and at least one thermoplastic polymer segment attached to the core, And > at least one polyoxyalkylene block, which is attached to at least a portion of the reactive end of the thermoplastic polymer block. This conductive compound is especially disclosed in International Patent Application No. 03/002668. Thus the compound comprises a thermoplastic polymer block and at least one polyoxyalkylene 99007.doc -14 - 1292448 alkyl block: - the thermoplastic polymer block comprises: > a star or braided macromolecular chain comprising At least one polyfunctional core and at least one thermoplastic polymer branch or fragment attached to the core, the core comprising at least three identical reactive functional groups, and/or > linear macromolecular chains comprising difunctional And a thermoplastic polymer segment attached to the core, at least a portion of the free end of the polyoxyalkylene block and the thermoplastic polymer block are attached in the following manner: > star or At least one free end of the braided macromolecular chain is attached to a polyoxyalkylene block selected from a thermoplastic polymer branch or fragment end and a polyfunctional core end, and/or > large linear At least one free end of the molecular chain is linked to the polyoxyalkylene block, the free end being selected from the end of the thermoplastic polymer segment and the polyfunctional core end; when the thermoplastic polymer block comprises only a large linear type Chain, when the two free ends of the macromolecular chains and linear polyoxy alkylene block is connected. In a preferred embodiment, the compound has a stellar polyamine structure. The stellate polyamine is obtained by copolymerizing a monomer mixture comprising: a) a polyfunctional compound comprising at least three identical reactive functional groups selected from the group consisting of an amine functional group and a carboxylic acid functional group , b) monomer of the following formula (Xa) and / or (Xb): 99007.doc -15- 1292448 χ—«Γγ (Xa) y (Xb)

NH c) When appropriate, a monomer of the following formula (IX): Z-R6-Z (IX) wherein: >z represents the same functional group as the reactive functional group of the polyfunctional compound, # >r12 and R6 represents the same or different, substituted or unsubstituted, aliphatic, cycloaliphatic or aromatic hydrocarbon group containing 2 to 20 carbon atoms and which may contain a hetero atom, > when referring to a carboxylic acid functional group , Y is a primary amine functional group, or > when X represents a primary amine functional group, Y is a carboxylic acid functional group. The term "carboxylic acid" is understood to mean a carboxylic acid and derivatives thereof, such as anhydrides, acid chlorides, esters and the like. The term "amine" is to be understood to mean an amine and its derivatives. The process for producing such star-shaped polyamines is disclosed in the patents FR 2 743 077 and FR 2 779 730. These processes result in the formation of star-shaped a molecular chain, which may act as a mixture with a linear macromolecular chain. The stellar polyamine can also be obtained by, for example, in an infinite torsion blending system • melt blending from a polymerized decylamine and/or an amine group. Acetate and polyfunctional compounds obtained by the same type of polyamines obtained, the polyfunctional compound comprising at least three identical reactive functional groups selected from amine or carboxylic acid functional groups. For example, decylamine is醯 6 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The polyfunctional compound of the early form may be selected from the group consisting of a compound exhibiting a dendritic or dendritic structure. It may also be a compound represented by a free formula (χι):

Rtt^QZ, ]m (χΐ) where: • Ru is an aromatic or aliphatic straight or cyclic nicotine containing at least 2 carbon atoms and may contain heteroatoms, • Q is a covalent bond or contains 1 to 6 An aliphatic hydrocarbon group of one carbon atom, • Z1 represents a primary amine group or a carboxylic acid group, and • m is an integer between 3 and 8. According to a particular feature of the invention, the Rn group is a cycloaliphatic group such as a tetravalent cyclohexyl group or a 1,1,1-propane triyl or H3.propane triyl. As other Rii groups suitable for use in the present invention, mention may be made, by way of example, of substituted or unsubstituted trivalent phenyl and cyclohexyl groups having a plurality (advantageously between 2 and 12). a mercapto tetravalent diamine polyarylene group (such as a group derived from EDTA (ethylenediaminetetraacetic acid)), an octavalent cyclohexanone group or a cyclohexanedione group, and a source free polyol (such as B) a group of compounds produced by the reaction of a diol, pentaerythritol, sorbitol or mannitol with acrylonitrile. The Q group is preferably an anthracene group or a polymethylene group such as an ethyl group, a propyl group or a butyl group or a polyoxyalkylene group such as a polyoxyalkylene group. According to a particular embodiment of the invention, the number m is greater than or equal to 3 and advantageously the temple is at 3 or 4. 99007.doc -17-1292448 The reactive functional group of the polyfunctional compound represented by the symbol ζ! is a functional group capable of forming a guanamine functional group. As an example of the polyfunctional compound, there may be mentioned 2,2,6,6-tetra(azepine ethyl)cyclohexanone, a diaminopropane-oxime of the following formula, ruthenium, osmium, Ν'-tetraacetic acid :

HO-C - H2C\ CHfC —OH /N-ch2-h?c-n[

CHr〇-〇H o 或 or a compound derived from the reaction of trimethylolpropane or glycerol with ethylene oxide and the amination of terminal hydroxyl groups. The latter compound is sold by Huntsman under the trademark Jeffamines T® and has the general formula: Q - nh2 r^-q-nh2 q - nh2 where: -Ru represents propane triyl or 1,2,3-propane triyl, -Q Indicates polyoxyalkylene. Examples of potentially suitable polyfunctional compounds are specifically mentioned in the patents US 5 346 984, US Pat. No. 5,959, 069, the patent application WO 96/3 5739, and the patent EP 672 703. More specifically, mention is made of a nitrogen trialkylamine (especially nitrogen triethylamine), an alkyl diamine (especially diethyltriamine), a trialkylene tetraamine and a tetraalkylene group. Pentaamine (alkylene is preferably ethyl), and 4-aminoethylamine, 8-octanediamine 099007.doc -18- 1292448 A dendrimer of the formula: (R1) 〇2 N-(CH2)n)2-N-(CH2)xN.((CH2)n-NR102)2 where:

R1G is a halogen atom or a -(CH2)n-NR72 group, wherein R7 is a hydrogen atom or a -(CH2)n-NR82 group, wherein R8 is a hydrogen atom or a _(CH2)n-NR92 group, wherein R9 is A hydrogen atom or a _(CH2)n-NH2 group, η is an integer between 2 and 6, and X is an integer between 2 and 14. η is preferably equal to an integer of 3 or 4, especially 3, and χ is preferably an integer (including a limit) between 2 and 6, preferably between 2 and 4 (including limits), especially equal to 2. Each R10 group can be selected independently of the other groups. The R1 group is preferably a hydrogen atom or a -(CH2)n-NH2 group. ^

Mention may also be made of polyfunctional compounds which exhibit 3 to - tare acid groups, preferably 3 or 4 acid groups. Among them, preferred are aromatic rings and/or heterocyclic rings, compounds, aromatic rings and/or heterocyclic rings such as a benzyl group, a naphthyl group, a fluorenyl group, a biphenyl group and a triphenyl group, or a heterocyclic ring such as _, a hydrazine group. (4) " Billi, ten, ^ Nansai is 吟, 噎琳, Philippine, foreign Lin, turnip and naphthalene ugly. Particularly preferred are 3,5,3',5' nonylphenyltetracarboxylic acids, acids derived from phthalocyanines and naphthalocyanines: naphthalenetetracarboxylic acid, 2,4,6-pyridinetricarboxylic acid, 3,5, 3,,5,_bipyridyltetrakis(4)'3'5'3',5'-dibenzimidine, acid, ^8· 十定四赖, more specifically 1'3,5- stupid Tricarboxylic acid and benzoic acid. Also mentioned are the polyfunctional compounds di-, melamine, derived from 2,3,5,6-tetra 99007, whose core is a heterocyclic ring such as 1,3,5-triazine and 1,4_ethyl. Doc -19- 1292448 Compound of carbazine, 1,4-pilin or tetrathiafulvalate. More specifically, 2,4,6-tris(aminohexanoic acid)_1,3,5-triazine (TACT) is mentioned. According to a preferred embodiment, the polyfunctional compound is selected from the group consisting of 2,2,6,6-tetrakis(/?-carboxyethyl)cyclohexanone, 1,3,5-benzenetricarboxylic acid, 2,4,6_ Tris(aminohexanoic acid) β1,3,5-triazine and 4-aminoethyl-1,8-octanediamine. The monomer mixture derived from the star-shaped or braided macromolecular chain of the present invention may contain other compounds such as chain-limiting agents, catalysts or additives such as light stabilizers, heat stabilizers or matting agents.

In this second embodiment of the invention, the composition comprises as a basic component a conventional thermoplastic polymer such as polyamine or polyester and the above-mentioned conductive additive. As suitable thermoplastic polymers, mention may be made of polyamides 6, polyamines 6,6, blends thereof and copolymerized decylamines, polyamines 12, polyethylene glycols, polypropylene glycols, propylene glycols, Its blend and copolymerized vinegar. As described in the above embodiments, the composition may comprise other components conventionally used in the manufacture of strands or fibers, such as heat stabilizers, additives to improve polymer ageing resistance (such as υν stabilizers), pigments, A colorant, matting agent or nucleating agent. The process of producing a nonwoven article formed from a composition of a thermoplastic polymer by the process of extruding the melt polymerizable composition through one or more spinnerets to form a bundle of filaments. Especially in U.S. Patents 3,968,307, 4,052,146, 4,406,850, 4,424,257, 4,424,258, 4,830,904, 5,534,339, 5,783,503, 5,895,710, 6,074,590, and 6,207,276 These processes. To form a sheet, the filaments are pneumatically drawn and deposited on the surface of a collection of 99007.doc -20-1292448. Then, the known method is to bond the filaments of the sheet. The filaments exiting the spinneret formed by the composition of the present invention remain parallel to each other and can be deposited on the surface in a uniform manner and evenly distributed after the coating. This is because no repulsion between the filaments is observed, so it is observed that the filament does not deviate in the advancing direction. According to the present invention, the filaments can exhibit a highly variable cross-sectional shape. In addition, it is possible to produce filaments made of different thermoplastic polymers, especially two-component filaments, without departing from the scope of the invention. In this case, there must be a polymer in the thermoplastic polymer which is a conductive property according to the present invention. Further advantages and details of the present invention will become more apparent from the following illustrations that are illustrative only and not limiting in any way and according to the single-present representation of the bulk conductivity for determining the volume conductivity of the strands. Clearly understand. [Examples] Example 1 By adding 3149 g of anhydrous nylon salt (salt obtained by stoichiometric reaction between one molecule of hexamethylenediamine and one molecule of hexamethylenediamine) to 2941 g by means of a polymerization reactor Polyacrylamide PA 6,6 was produced from 21 g of pure copper acetate monohydrate powder, 7.56 g of potassium bromide powder having a purity of 99.5% by weight, and 3.96 g of phenylphosphonic acid having a purity of 98% by weight. The reaction mixture was heated to 112.自; then the autogenous pressure to adjust the absolute value of 1.2 bar by distilling water in the concentration step is maintained at this value until a temperature of 12 (TC is obtained. The reaction mixture is then heated to 215 〇c without distilled water. At 99007. Doc -21 - 1292448 At this temperature, the autogenous pressure reaches the absolute value and the hydrous water is adjusted by the step of steaming the crane under pressure to maintain the autogenous pressure at this value until the temperature reaches 230 ° C. Under this pressure In the step of distilling, when the temperature of the reaction mixture reaches a value of 220 C, 13.6 g of a 5% by weight aqueous suspension of titanium dioxide is added. When the temperature of 230 C is reached, the pressure is lowered to atmospheric pressure in the depressurization step. At the end of the step, the temperature of the reaction mixture reached a value of 275. The reaction mixture was held at 275 for 1 minute in the finishing step; the polymer was then cast into strip form, cooled and granulated by cutting strips. The particle was determined to have a viscosity value of 丨4〇mi/g of the obtained polymer A. This value was determined by using the ISO EN 307 standard method. Potentiometric analysis in difluoroethanol/gasoline (50/50) The amine end group and the acid end group were determined to be 43 and 76 meq/kg, respectively. Example 2 The procedure of Example 1 was used, when the temperature of the reaction mixture reached a value of 260 C in the depressurization step. 3.57 g of pure adipic acid powder was additionally added to an initial mixture of 77.59 g of 70% by weight of jeffamine ED 2〇〇3 or XTJ_5〇2 aqueous solution to prepare a conductive copolymerized copolymer according to the first embodiment of the present invention. Further, the duration of the finishing step was 45 minutes. The viscosity of the obtained copolymer determined according to the method described in Example 1 was 139 ml/g. Potentiometric analysis in a trifluoroethanol/chloroform solvent medium The amine end group and the acid end group were respectively determined to be 43 and 77 meq/kg. The obtained copolymer B contained 2% by weight of a repeating unit corresponding to the formula m, that is, a Jeffamine monomer. 99007.doc -22- 1292448 Example 3 The manufacturing process was repeated in the same manner as in Example 2, in which 8.93 g of pure adipic acid powder and 193.98 g of a 20% by weight aqueous solution of tJeffamine ED 2003 or XTJ_502 were introduced. The viscosity of the polymer was 125 ml/g. Potential The copolymer C obtained by the method for determining the amine end group and the acid end group in the trifluoroethanol/chloroform solvent medium is 50 and 85 meq/kg, respectively. The copolymer C obtained contains 5% by weight of the repeating unit corresponding to the formula III. Jeffamine monomer.

Example 4: Production of modified polymeric additive I The reaction was carried out in a 7.5 liter autoclave. 1116.0 g e-caprolactam (9.86 mol), 57.6 g 1,3,5-benzenetricarboxylic acid (0.27 mol), 1826.4 g Jeffamine® M2070 (0.82 mol), 1·9 g Ultranox 8 236 and 3.5 g A 50% by weight aqueous solution of hypophosphorous acid was introduced into the reactor. The autoclave was purged with dry nitrogen. The reactor was maintained in a dry nitrogen buffer wash. The reaction mass was gradually heated from 20 ° C to 200 ° C. The temperature of the reaction medium was then raised to 250 °C. This temperature is then maintained until the reaction is terminated. After a standing period of 1 hour under these conditions, the system was gradually placed under vacuum to reach a pressure of 5 mbar and then maintained for an additional hour under vacuum. All of the polymer in the reactor was transferred to the mold. Differential thermal analysis indicated that the polymer obtained showed a melting peak at 205 °C. Characterization by space exclusion chromatography (solvent: dimethyl acetamide / 0.1% LiBr) can determine the weight average molecular mass Mw and the number average molecular mass Μη of the polymer (relative to the polystyrene standard Quality of expression): 99007.doc -23- 1292448

Mw = 15,520 g/mol Μη = 10,960 g/mol 定量 The quantitative determination of the terminal group indicated a residual acid functional group content of 16.8 meq/kg and a residual amine functional group content of 1.9 meq/kg. 1H NMR (Brukei* 300 MHz) of a solution in a 1/1 by weight mixture of deuterated trifluoroacetic acid and deuterated chloroform indicated that the content of residual caprolactam was zero (undetectable) and each astral fraction The average degree of polycondensation of the pA6 block in the shoot was 8.4. This additive is referred to as additive I. I Example 5: Production of the composition d according to the invention The procedure described in Example 2 was repeated. However, pure adipic acid powder is not introduced. Further, under this condition, 271.2 g of a 20% by weight aqueous solution of the conductive additive I prepared according to Example 4 was introduced in place of the Jeffamine Ed 2003 solution. The finishing time is 15 minutes. The composition thus obtained had a viscosity value of 149 ml/g as determined by the above method and thus the viscosity value φ of the thermoplastic polymer present in the composition was 149 ml/g. The amine end groups and acid end groups were determined to be 39 and 71 meq/kg by potentiometric analysis in a trifluoroethanol/gas-like solvent medium. The composition thus prepared contains 2% by weight of a conductive additive. Example 6: Production of the composition ε according to the present invention A re-replication procedure was carried out in the same manner as in Example 5, in which 678 g of a 20% by weight aqueous solution of the conductive additive 1 produced according to Example 4 was introduced. The finishing time is limited to 10 minutes. The viscosity of the composition thus obtained was determined to be 152 ml/g according to the above method, and thus the viscosity of the thermoplastic polymer present in the composition was 99007.doc -24-1292448 of 152 ml/g. The amine end groups and acid end groups were determined by potentiometric analysis in a trifluoroethanol/chloroform solvent medium to be 40 and 71 meq/kg, respectively. The composition E thus prepared contained 5% by weight of a conductive additive. Example 7: The compositions or polymers A, B, c, d and E produced in the above examples were dried and re-smelted at 295 C and at a rate of 450 in/min and 430 g/h. The weight was extruded through the spinneret to form filaments of 12 dtex and gathered together to form a strand comprising 14 filaments. The strands are drawn on the drafting members according to a draft ratio equal to 3.5 to produce strands recorded as 7a, 7b, 7c and 7d, respectively. The volumetric conductivity of these strands was measured according to the following scheme: The volumetric conductivity of the textile strands was measured according to the '2 point' measurement method. Several strands were positioned to be electrically conductive according to the scheme not shown in FIG. The lengths of the contact points are parallel. The measurement is made between two steel contact points with a spacing of 20 mm. The reciprocating value of the strands is usually 5, meaning a total of 1 strand of strands (which is accurate) Corresponding to 100 lengths, filaments, 1 strand containing 10 individual filaments.) Use a binocular magnifying glass to pre-measure the diameter of the strands studied by J., and measure the exact length of the strands with a gauge. At 20 c The conditions and 50% relative humidity were measured on a Keithley 617 conductivity meter with an applied voltage of volts. The volume resistance was obtained by a direct reading device. The volume resistivity p (unit: acm) was determined by applying the following relationship. Previous measurements are derived: 99007.doc -25- 1292448 R.TT.d2·!! p = 4.e where: R = volume resistance (Ω) strand diameter (cm) total number of strands contact point (cni Finally, the volume conductivity (single or in view 'just happens to be the volume resistivity) Composition 13⁄4 " 伯电 ▼ 千理蹩下下录-- A 7a ^οΤ^Γιο19 - -- B 7b ~~' 1.6 χ 1〇^ c 7c 19.5 χ 1〇'9 D 7d ΎΙ^Γιο19 ---- E 7e 1.8 χ ι〇^ Medium: 1 / 1 叼 罜 罜 罜 吸入 吸入 直接 直接 直接 直接 直接 直接 直接 直接 直接 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The deposition of the flakes on the surface of the load-bearing surface makes it possible to obtain a satisfactory performance of the filaments compared to the repulsion of the filaments known by the sharp object "A." Example 8 - Manufacturing according to the present invention Additive Η From 240·2 g 64 景景0, 曲I? 疋/chen bismuth ammonium salt aqueous solution is based on the copolymer of Juyi Cong 6,6, which is added with: 6 mg defoamer 12-945 gjeffamine ED 600 (φ Huntsmanf t ) 3.453 g adipic acid 99007.doc -26- 1292448 〇·345 g acetic acid. Polyamine is produced according to a standard polymerization process, which involves the stage of concentrating the solution in a stirred high pressure dad reactor. In the polycondensation stage, which has a step of about 47 minutes of distillation at a fixed pressure of 17.5 bar at a final temperature of 250 C. a step of decomposing from about 1 minute at 172.5 bar} at a final temperature of 273 ° C and a finishing step at a final temperature of about 272 ° C for about 2 minutes. Obtaining a copolymer based on PA6,6, The viscosity value was 73 ml/g. > Example 9: Production of additive m according to the present invention A copolymer based on polyamidamine 6,6 was prepared from 240.2 g of a 64% by weight aqueous solution of concentrated hexamethylene diammonium salt. : 5 mg defoamer 0.6962 g hexamethylenediamine (32.4% by weight aqueous solution) 0.9216 g Adipic acid 0.345 g 100% acetic acid. The polyamine is produced in a scrambled high pressure dad reactor according to the following process: the stage of concentrating the solution is followed by a polycondensation stage in which it is steamed in the stationary phase for about 47 minutes under a pressure of 17·5 bar. The final step is a temperature of 250 °C. The polymerization was continued with a depressurization step from 17.5 bar to 1 bar, and the depressurization step was interrupted at 1 bar to introduce 18.5 g of a 70% aqueous solution of jeffamine ED 2003 (sold by Huntsman); the overall temperature was maintained at: (9). After this addition, the decompression step was completed and the depressurization step was continued for about 50 minutes, and the final temperature was 272 C. The finishing step lasted about 20 minutes and the final temperature was 272.4 〇C. 99007 doc -27- 1292448 A copolymer based on PA6,6 was obtained with a viscosity of 72 nil/g. Example 10 Fiber or strand fabrication was tested using the additive-free polymer A according to the examples of the present invention and at various concentrations of the additives and oxime described in Examples 8 and 9, as described in Table 1 below. In these examples, the additive is added to the polymer crucible in a single screw extruder and extruded into a strip form to form particles by shredded strips according to known techniques. The composition or polymer thus obtained is dried separately, followed by 295. The crucible is remelted and extruded through a spinning machine containing 34 holes of 〇·23 mm in diameter.

head. The composition rate in the spinneret orifice was 19.4 m/min. Cool the filaments with a cold air blower at the outlet of the spinneret. The filaments are drawn into an inhalation system containing a spray gun that is typically used in a spinning process. The filaments are discharged from the spray gun at a rate of 4 〇〇〇m/min. The filaments were subjected to a draw ratio of about 2 Torr. To monitor and determine if the filament exiting the gun has an electrostatic charge, the filament flow is directly oriented to approximately 45 relative to the vertical. Tilt on the target surface. Attachment of the filament to the target surface indicates the presence of an electrostatic charge. Hunting is placed about 3 cm (1 inch) from the axis of the filament flow. Electrometer 〇E1(10)ro-Tech Systems sells 2 j at the name μ^γ心心(7)2)) also judges the existence of the filament flow near the jet The electrostatic field device is grounded or ungrounded. Measurements are made in both configurations. A nearby electrostatic field of zero reflects the absence of static charge. The results of the neoprene of the present invention are shown in the following table: , mouth ', '" orally obtained from polyamines 4 99007.doc -28-1292448 test composition electrometer results kV / inch matrix polymer modified Polymerizable Additive (% by weight) 10A Control Example 1 Polymer A 6/10 10B Example 1 Polymer A 5% Example 8 Additive II 2/4 10C Example 1 Polymer A 2% Example 9 Additive III 1/3 10D Polymer A of Example 1 5% Additive of Example 9 III -1/1.5 10E Polymer A of Example 1 8% Additive of Example 9 III - 1.5/0.5 In addition, compared with the control test 10A, Adhesion to the metal wall or target surface was not observed in the inventive test. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a scheme for positioning a plurality of strands in parallel over a given length between conductive contact points.

99007.doc -29-

Claims (1)

Π9 Jinzan m patent application declaration patent scope replacement (August 95) X. Patent application scope: j year month} original L private"«*>»*»*" ., ___________Hum, by direct Melt spinning is based on the length of a thermoplastic polymer composition: a method of making a non-woven surface comprising: feeding the composition into a plurality of spinnerets each comprising a plurality of spinning orifices; The filaments are fed into the pneumatic drafting device and the platform, and the obtained filaments are formed into: a sheet in the W. The method is characterized in that the thermoplastic polymer-based composition comprises a polymerizable matrix and/or a modified polymerizable property. Additives: The modified polymerizable additive contains repeating units corresponding to the following formula: Ten f~Rr1~~nt 1 Ten-R "K~l·· 丨丨0 HJ Ten A-R4-A-B-R5 —B at III XB-RrA —B———R—B—A—R3-]- IV wherein: R1, R2, R3 and R4, which are the same or different, represent a 9-sided, cycloaliphatic or aromatic group containing 2 to 18 carbon atoms. a hydrocarbon chain having a molecular weight of 4 Å and 2 Å, a polyether group between 〇〇〇, A', B, or a C 〇, \ 或 〇 group; when a represents c ,, b represents NH or 0 and vice versa, when the field additive does not exist or does not comprise a repeating unit of the formula πι or ..., 99007-950807.doc 1292448 The polymerizable matrix comprises at least one of the repeating unit or the III or IV . At least one of them and a repeating unit 2. The method of claim 1 is in the total composition 1. /〇 and medium. The feature is that the modified polymerizable additive is 30/. The weight concentration between them is present in the composition. 3. The method of claim 2 is in the total composition 1% and medium. It is intended that the modified polymeric additive is present in the composition at a concentration of between 15% by weight. 4. The method according to any one of claims 1 to 3, wherein the additive is obtained by a monomer of the formula: wherein the polymerization is carried out in the presence of the modified polymerizable b-bonding compound in the presence of H0&quot ;~^~RrC—〇H 〇0 (V) (VI) H2n-R-nh2 〇(VII) B——Rg—B (VIII) wherein: the same or different represents an aliphatic, cycloaliphatic or aromatic hydrocarbon chain containing from 2 to 18 carbon atoms, and Rs represents a molecular weight between 400 and 200,000. Polyether group, B represents COOH, title 2 or OH functional group. The method of claim 4, wherein the chain limiting agent is selected from the group consisting of a monofunctional acid and a monofunctional amine. 6. The method of claim 5, wherein the monofunctional compounds are selected from the group consisting of acetic acid, propionic acid and benzylamine. 7. The method of claim 4, characterized in that the single system is present in a weight concentration between the monomer of the formula v and/or vi and/or VII and the monomer mixture 1 〇 〇 . 8. The method according to any one of the preceding claims, wherein the modified polymerizable additive comprises: > at least one thermoplastic block and > at least one polyoxyalkylene blocking block. The method of any one of items 1 to 3, characterized in that the modified polymerizable additive comprises: > an eve & plastic polymer block, which is formed by: a macromolecular chain comprising at least a polyfunctional core and at least one thermoplastic polymer branch or sheet I attached to the core, the core comprising at least three identical reactive functional groups, and/or linear macromolecules a chain comprising a bifunctional core and at least one thermoplastic polymer segment attached to the core, and > at least a polyoxyalkylene block, at least a portion of a reactive end of the thermoplastic polymer block connection. 10. The method of claim 9, wherein the bond between the thermoplastic polymer blocks is: 99007-950807.doc -3 - 1292448 > at least one free end of the star or braided macromolecular chain Attached to the polyalkylene oxide block, the free end is selected from a thermoplastic polymer branch or fragment end and a polyfunctional core end, and/or > at least one free end of the linear macromolecular chain and poly The alkylene oxide block is bonded, the free end is selected from the end of the thermoplastic polymer segment and the bifunctional core end; when the thermoplastic polymer block comprises only a linear type of macromolecular chain, the linear macromolecular chain The two free ends are connected to a polyalkylene oxide block. 11. The method of claim 10, wherein the star-shaped macromolecular chain is a stellate polyamine obtained by copolymerizing a monomer mixture, the monomer mixture comprising a > polyfunctional compound comprising at least Three identical reactive functional groups selected from amine functional groups and carboxylic acid functional groups, > monomers of the following general formula (Xa) and/or (Xb): (Xa) (Xb) NH > If appropriate, the monomer of the following formula (IX): Z-R6-Z (IX) wherein: Z represents the same group as the reactive functional group of the polyfunctional compound, and is identical to R6 or Different, substituted or unsubstituted aliphatic, cycloaliphatic or aryl containing from 2 to 20 carbon atoms and containing heteroatoms = 99007-950807.doc -4- 1292448 hydrocarbyl, when X represents a carboxylic acid function When π is a primary amine functional group, or when X represents a primary amine functional group, hydrazine is a carboxylic acid functional group. 12. The method of any one of claims 3 to 3, wherein when the polymeric matrix comprises repeating units of formula III and/or IV, the weight concentration of the repeating unit of formula (1) and/or 1 is in the matrix Then between 5 and 5% by weight. 13·If requested! The method according to any one of the preceding claims, wherein the repeating unit of the formula (1) and/or IV is derived from a polyoxyalkylene monomer having two reactive terminal functional groups and a diacid monomer or an indoleamine The reaction between. The method of any one of claims 3 to 3, wherein the repeating unit of the formula is obtained by a reaction between a diacid and a diamine selected from the group consisting of succinic acid and a group consisting of diacid, terephthalic acid, isophthalic acid, dodecane monoacid, and mixtures thereof, the diamine being selected from the group consisting of hexamethylenediamine, 2-methylpentylamine, and m-xylylenediamine . 15. The method of any one of claims 1 to 3, characterized in that the repetition of the formula π is carried out by polycondensation of an indoleamine or an amino acid, such an indoleamine or amino acid. It is a group of endogenous amines, aminoundecanoic acid and aminododecanoic acid. 99007-950807.doc 5-