CA1246787A - Composition and process for preadherising polyester filaments - Google Patents
Composition and process for preadherising polyester filamentsInfo
- Publication number
- CA1246787A CA1246787A CA000449296A CA449296A CA1246787A CA 1246787 A CA1246787 A CA 1246787A CA 000449296 A CA000449296 A CA 000449296A CA 449296 A CA449296 A CA 449296A CA 1246787 A CA1246787 A CA 1246787A
- Authority
- CA
- Canada
- Prior art keywords
- polyepoxide
- composition
- water
- alcohol
- tertiary amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
Abstract
Abstract The invention relates to a composition and a pro-cess for preadherising polyester filaments.
This composition consists of a polyepoxide and a tertiary amine having the following general formula:
This composition consists of a polyepoxide and a tertiary amine having the following general formula:
Description
Z9~6787 Composition and process for preadherising polyester filaments The ;nvention relates to a compos;t;on of a poly-epox;de and an amine for preadherising polyester fila-ments w;th good adhes;ve propert;es towards rubber. The;nvention further relates to a process for preadher;sing polyester filaments.
To improve the adhes;ve propert;es of synthetic f;laments towards rubber ;t ;s conventional to treat them with a composit;on which is a mixture of latex and resor-cinol-formaldehyde res;n (an RFL bath). This conpos;tion is then hardened on the filaments by means of a thermal treatment.
~he presently frequently used filaments for rein-forcing tyres, flexible tubes, V-belts and conveyor belts are polyester filaments. The d;sadvantage in using poly-ester filaments is that they have an insufficient number of reactive end groups, so that the filamenttRFL bond is poor. It is therefore necessary to subject the polyester filaments to a pretreatment. Th;s pretreatment, also referred to as preadherisat;on, is very often carr;ed out by the fibre manufacturer himself, so that the consumer can carry out the adherisation with RFL before vulcanising the filament with rubber.
There are numerous existing processes for pread-herising polyester. U.S. Patents 3,383,242 and 3,297,468,
To improve the adhes;ve propert;es of synthetic f;laments towards rubber ;t ;s conventional to treat them with a composit;on which is a mixture of latex and resor-cinol-formaldehyde res;n (an RFL bath). This conpos;tion is then hardened on the filaments by means of a thermal treatment.
~he presently frequently used filaments for rein-forcing tyres, flexible tubes, V-belts and conveyor belts are polyester filaments. The d;sadvantage in using poly-ester filaments is that they have an insufficient number of reactive end groups, so that the filamenttRFL bond is poor. It is therefore necessary to subject the polyester filaments to a pretreatment. Th;s pretreatment, also referred to as preadherisat;on, is very often carr;ed out by the fibre manufacturer himself, so that the consumer can carry out the adherisation with RFL before vulcanising the filament with rubber.
There are numerous existing processes for pread-herising polyester. U.S. Patents 3,383,242 and 3,297,468,
- 2 ~ ~246787 for example, relate to a prosess for pretreatin0 poly-ethylene terephthalate filaments by applying to said fi~aments (A) a dispersion of a hardenable combination of a diepoxide and a diamine having primary or sccondary functions (harden;ng agent) and (O) a ~ater-dispersible filament finish. This application takes place onto an undra~n filament, ~hich is ~ound up and subsequently con-ventionally stretched in a second operation. The disad-vantage of this process is that it is necessary to use a composition ~hich solidifies into a gellike mass after a fe~ hours at room temperature. The stability of the solution is thus poor. In addition, the filament cannot be drawn using heated rollers, but can only be dra~n in ovens, i.e. even at slo~ take-off speeds. Excess pread-herising solution would harden on the rollers and ~ouldquickly build up into a crust. Moreover, the filaments tre-ated in this process have impaired mechanical properties.
In U.S. Patent 3,962,011 nylon cord yarns, i.e.
already plied yarns, are impregnated ~ith a comb;nation of a polyepoxide and a tertiary amine and the combination is thermally hardened.
U.S. Patent 3,793,425 and German Offenlegungs-schrift 2,056,707 relate to an integrated sp;n-stretch process for producing polyester filament yarns by apply-ing a composition containing a polyepox;de res;n buffered at alkal;ne pH to the freshly spun and l;ke~;se st;ll ~`` lZ9L~787 un6tretched polyester filament, and then hot-~tretching and winding-up the filament thus treated.
The present invention provides a composition for S preadherising polyester filaments which contains a polyepoxide and a tertiary amine, a~ well as a process for preadherising polyester filaments ~y applying the composition according to the invention to the ~tretched filament.
The invention therefore relates to a process for preadherising polye~ter filaments to ameliorate their adhesive properties towards rubber, wherein the polyester filaments after stretching are treated with a composition consisting of a : polyepoxide and a tertiary amine having the following general ; formula ~Rl X (CH2) ~ \ (I) \ R2 where 1~ n~ 6, R1 and R2, are identical or different, each alkyl having C1_~, hydroxyalkyl having C1_6, alkylaryl or aryl, and X
i~ H, OH, NH2, NH3, NR~R5 or R6, where R3, R~, R, and R6 are each al~yl having C1_6 or aryl groups.
The invention further relates to a composition of a polyepoxide and an amine for preadherising polyester filaments, which i6 characterised in that the amine is a tertiary amine having the following general formula:
`:
~C
~- ~29L~787 - 3a -X ~CHZ)~ - N / (I) \ R2 where 1~ n ~ 6, Rl and R2, identical or different, are each alkyl having C1-61 hydroxyalkyl having Cl_6, alkylaryl or aryl, and X
i5 H, OH, NH2, NHR3, NR~R5 or R6, where R3, R4, Rs and R6 are each alkyl having C1-6 or aryl groups.
This composition is more stable than tha~ described in U.S. Patents 3,383,242 and 3,297,468. Compound (I) is an amine having at least one tertiary function. It is assumed that the tertiary amine has a catalytic action on the reaction between the polyepoxide and the polymer. The group X can also be a primary, secondary or ~2~787 tertiarj amine. ~n that case the second am;ne function ;ncreases the catalyt;c activ;ty. By v;rtue of compound (I) an adhes;ve layer is formed and, alone or together w;th an RFL treatment, confers good adhes;on to the fila-ment on vulcanisation into rubber.
Compound (I) is preferably N,N-dimethylbenzyl-am;ne~ 3-diethylamino-1-propylam;ne, 3-dimethylamino-1-propylamine, tribenzylamine, triethanolamine or triethyl-am;ne. The type of polyepoxide in the composition according to the invention is not critical. The speci-fically preferred type is that of the glycidyl ethers which are generally prepared by reacting epichlorohydr;n with an alkanol or a phenol. The polyepox;de can be saturated, unsaturated, aliphatic, cycloaliphatic, aro-matic, heterocyclic or substituted. The compounds aree;ther monomers or polymers having at least two epoxy groups per molecule.
Examples of such compounds are the epoxy deriva-t;ves of bisphenol A or of phthalic acid, the epoxyphenol novolac, the epoxycresol novolac, the glycidyl isocyanur-ates, the epoxy-containing derivatives of hydantoin, such as hydantoin triglycidyl ether, the aliphatic glycidyl ethers, such as butanediol diglycidyl ether, ethylene-glycol diglycidyl ether or glycerol triglycidyl ether, and the glycidyl der;vatives of triaz;ne, such as tris-t2,3-epoxypropoxy)-3-propionyl-1,3,5-hexahydro-s-triaz;ne (TEPS).
~ ` lZ~787 - 5 ~
Because the abovementioned TEPS is read;ly sol-uble in water it was already used ;n the compos;t;on des-c;ibed ;n U.S. Patent 4,121,901. The composition accord-;ng to the ;nvent;on is ;n solut;on ;n water, alcohol, a water-alcohol mixture or a f;bre finish. For the pur-poses of th;s ;nvent;on a f;bre f;nish ;s ch;efly a pro-duct wh;ch ;mproves the fr;ctionaL, antistatic and wet-t;ng propert;es of the synthet;c f;lament.
This composition can be used either on its own or together ~;th aux;l;ar;es. For the purposes of th;s invention auxiliaries are products which are capable of ;mprov;ng st;lL further the adhes;on of the f;lament to rubber, for example carr;er or swell;ng agents, such as ethylene glycol, caprolactam or polyvinyl or benzyl alco-hol, or solvents which permit more efficient d;ffus;on ofthe epoxide into the polymer. Wetting agents or surface-active agents, such as the commercial products QZ 13 from CI3A-GEIGY and TW 1196*from ZSCHIMMER ~ SCHWARZ, which are solutions w;th s;licones or ethoxylated compounds, can also be used. Secondary preadherising agents can also be applied ;n add;t;on, for example those based on silanes tepoxysilanes), polychlorophenols tVulcabond E*
from VULNAX) or those hav;ng free or blocked ;socyanate groups, or urethanes, poly;m;nes, polyacrylates and poly-am;des. It ;s likew;se possible to subject the filamentpreadherised according to the invention to a treatment r~ w;th the conventional pretreatment agent compris;ng a . 1 * Trade Mark ~Z4 Ei787 polyepox;de and a blocked poly;socyanate before the RFL
treatment.
The amount of polyepoxide ;n the composition according to the invention is 5 to 99% by weight and that of compound ~I) is 0.01 to 6.0, preferably 0.05 to 3, X
by weight. The remainder comprises wat~r, alcohol, water-alcohol mixture or fibre finish.
The invention further relates to a process for preadherising polyester filaments which is characterised in that the abovementioned composition of polyepoxide and tertiary amine is applied to the stretched filament. In this process, unlike in the process descr;bed ;n U.S.
Patent 3,793,425 and German Offenlegungsschrift Z,û56,707, the stretch rollers do not become encrusted, and the filaments have good mechanical properties.
The type of polyepoxide and of compound (I) is the same as in the composition accord;ng to the inven-tion, as is the nature of the solut;on.
The amount of polyepox;de and espec;ally of com-pound (I) appl;ed to the filament is fa;rly critical,according to the invention. As regards the polyepoxide, a level below O.O5X g;ves r;se to the problems of ;nade-quate adhesion and irregular distribution of the poly-epoxide along the filament, and a level greater than O.SX
does not give better adhesion. Compound (I) gives maxi-mum adhesion of the filament to the rubber when applied in an amount of 2 to 300 ppm, preferably 5 to 100 ppm.
~%4~i787 All the abovement;oned levels of polyepoxide and eompound (I) are relative to the treated polyester filament.
For the purposes of the present invention poly-esters are linear polycondensed esters prepared by react-ing one or more diols of the HO(CH2)nOH series ~here 1 ~ n C 10 ~ith a dicarboxylic acid, preferably tere-phthal;c acid, or a corresponding diester, such as dime-thyl terephthalate. The polyesters can also be modified uith organic or inorganic additives. The polyester used for reinforcing elastomers has been or;ented and stretched in order to obtain reinforcing filaments hav-ing satisfactory mechan;cal properties for their use.
The preferred polyester is polyethylene tere-phthalate without restriction as regards the terminal carboxyl group or diethylene glycol content.
The stretched filament is produced in an integ-rated spin-stretch process in which the filament is ~ound up at take-up speeds of 2,000 to 6,000 m/m;n. The com-position according to the invention ;s applied by means of one or t~o metering PinS between the final duo and the ~inding apparatus or subsequently during the rebind;ng of the stretched filament.
It may be necessary to do further treatments on the stretched filament in order to improve its running perfor-2S mance or fatigue level, for example by applying polysiloxanes,silanes, polyethylene glycols or ester or mineral oils.
The process according to the invention makes it - 124~787 possible to produce a polyester filament having very good mechan;ca~ properties and an ;mproved adhcsion to rub-ber. This process is also very simple and very econom;-cal, since the stretching is not adversely affected. The linear density of the polyester filament yarn thus pro-duced is not critical. It 1s preferably between 500 and 2,50û dtex, and the number of individuaL filaments is between 8û and SûO. This filament yarn is particularly suitable for reinforcing rubber articles, such as car tyres, conveyor belts, V-belts and flexible tubes. It can also be used for articles which are coated with polyvinyl chloride.
The filament yarn thus obta;ned is then ready for a conventional treatment with an RFL bath prior to the vulcanisation with rubber. For certa;n uses it is even vulcanised into the rubber without RFL impregnation.
The filament yarn preadherised according to the invention can also be subjected to a secondary treatment in a conventional polyepoxide bath mixed w;th an aqueous dispersion~of a blocked poly;socyanate before it is imp-regnated with the RfL and/or vulcanised into the rubber.
The invention finally relates to the polyester f;lament yarns thus produced w;thout restriction as regards the terminal carboxyl group content. It is of course also possible to apply the composition to the un-stretched filaments separately from or together with the spin finish in a separate spinning and stretching process ~2~787 _ 9 _ or in a spin-stretch process.
The polyepox;de, ~hich ;s advantageously soluble in uater, is dissolved in a concentration of 5 to 99X in a presubmitted amount of water, water-ethanol m;xture or solvent, such às polyglycols, ben2yl alcohol or ester o;ls. Afterwards, but before the composition ;s used, compound ~I) is added in a concentrat;on of 0.01 to 6.0, preferably 0.05 to 3.0, X by we;ght.
Production of cord yarn A polyester filament yarn hav;ng a linear density of 1,100 dtex and comprising 192 high-modu~us, high-strength monofilaments ;s produced as follows using a spin-strech process:
The highly viscous polymer is melted at a tempe-rature of 280 to 330C in an extruder, and the melt isextruded through a sp;nneret. After cooling down in an quenching stag the filaments are drawn off at normal speed and are guided over a fin;sh application roller, where a sp;n finish is applied, and over a plurality of pairs of rollers which are operated at different tempera-tures and speeds, where the filaments are stretched and heat-set. Depending on the desired mechanical yarn pro-perties the rollers can have temperatures between 70 and 245C. The roller speeds are such that the spun f;~a-ments can be stretched up to six times their originallength. The filaments are directly wound up at a take-up speed of 3,000 m/min.
- 12~787 - lo -A number of these filament yarns, for example 2, are t~isted together in conventional manner to form a gr age cord yarn. This yarn is then impregnated on a treatment machine ~;th an RFL solution consist;ng of 20X of a resorc;nol-formaldehyde resin and of a latex and is then thermally treated ;n convent;onal manner at 150C
for 30 seconds and then at 235C for 1 minute. This ;mpregnated cord ;s then vulcanised ;nto the rubber.
The adhesive properties of the cord vulcanised into the rubber are tested using UNIROYAL's A-300 strip test, in ~hich the variable measured is the force ~hich is necessary to separate t~o layers of rubber from a cord fabric vulcanised into the rubber. A pull force of less than 10 daN ind;cates poor adhesion, and a pull force greater than 15 or 20 daN indicates good to very good adhes;on to the rubber.
The appearance value indicates ho~ ~ell the rub-ber adheres to the cord layer. The highest value of S
characterises an adhesive bond ~here the crack appears in 2û the rubber and no cord is visible at the crack surface.
The poorest value of O characterises an adhesive bond ~here the crack takes place at the rubber-cord ;nterface, so that no rubber remains stuck to the cord layer. The values from 0.5 to 4.5 are ;ntermed;ate levels. In the present case the cord has a pull force of 7 daN and an appearance value of 0.
` ` 12~787 Examples 1 to 11 The yarn ;s produced ;n accordance w;th the invention as mentioned above, except that the f;laments are guided at a po;nt between the f;nal duo and w;nd;ng apparatus over a preadher;s;ng dev;ce ;n the form of a meter;ng pin ~here the compos;tion ;s appl;ed.
The compos;t;on cons;sts of a polyepox;de~ a ter-t;ary am;ne and a solvent. The concentration of the poly-epox;de ;n our examples ;s 35X by we;ght, wh;le that of the tert;ary am;ne accord;ng to the ;nvent;on ;s given in the table~ The level on the fibre ;n the examples ;s 0.2X of epoxy resin. The yarn thus produced ;s ;mpreg-nated w;th RFL and then vulcan;sed ;nto the rubber.
The table below shows the str;p test results obtained on apply;ng d;fferent compos;t;ons.
Example 1 shows how poor the adhes;on ;s ~hen the compos;t;on does not conta;n compound ~I) accord;ng to the ;nvent;on ;n add;t;on to the polyepox;de.
In Examples 2 to 4 the catalyt;c effect of the tert;ary amine accord;ng to the ;nvent;on comes ;nto play. Example 3 represents an opt;mal am;ne concentra-t;on at wh;ch the pull force value ;s at a max;mum.
In Example 5 only 0.05X of polyepox;de, and not 0.2X, were appl;ed to the yarn. The pull force ;s lower, although ;t ;s still h;gher than ;n Example 1, where the polyepox;de level ;s four t;mes as h;gh but no compound (I) ;s present.
12~787 Examples 6 to 10 l;kew;se form part of the subject-matter of our invent;on. As can be seen, the nature of the polyepoxide tdiepox;de or tr;epoxide having different structures) is of not ins;gnificant ;mportance) ~Examples 6 and 8). The solvent, by contrast, is not cr;tical (Examples 8 and 9). In Examples 7, 8 and 10 different am;nes are used together with the same epoxide.
In Example 11, the polymer used and ethylene ox;de are added before be;ng melted in the extruder. The resulting f;~ament only has a term;nal carboxyl group content of 5 mol/t. The f;lament yarn produced ;n accor-dance w;th the invention as regards its compos;t;on and the process used ;n mak;ng ;t has fa;rly good adhes;ve propert;es. The adhes;ve properties are only ins;gn;fi-cantly worse than those ;n Example 8, where the yarn con-ta;ns a term;nal carboxyl group content of 20 mol/t.
The f;laments of Examples 2 to 11, wh;ch were obtained ;n accordance w;th the ;nvention, are d;st;n-gu;shed by good process;ng properties, for example the absence of depos;ts at the twist;ng stage. Although the ;ndividual filaments are treated, the fatigue level of the tyre cord produced is not ;mpa;red.
~ 12~6787 T~ble ~r-pl-~olyepolide Solvent j~o~pound ~1) StriP t st I ,, lSEPS ~1 ll2 none lO l 0 _ _ _ 2~ ~ O S ~ DPA ~9~16 0 3 0
In U.S. Patent 3,962,011 nylon cord yarns, i.e.
already plied yarns, are impregnated ~ith a comb;nation of a polyepoxide and a tertiary amine and the combination is thermally hardened.
U.S. Patent 3,793,425 and German Offenlegungs-schrift 2,056,707 relate to an integrated sp;n-stretch process for producing polyester filament yarns by apply-ing a composition containing a polyepox;de res;n buffered at alkal;ne pH to the freshly spun and l;ke~;se st;ll ~`` lZ9L~787 un6tretched polyester filament, and then hot-~tretching and winding-up the filament thus treated.
The present invention provides a composition for S preadherising polyester filaments which contains a polyepoxide and a tertiary amine, a~ well as a process for preadherising polyester filaments ~y applying the composition according to the invention to the ~tretched filament.
The invention therefore relates to a process for preadherising polye~ter filaments to ameliorate their adhesive properties towards rubber, wherein the polyester filaments after stretching are treated with a composition consisting of a : polyepoxide and a tertiary amine having the following general ; formula ~Rl X (CH2) ~ \ (I) \ R2 where 1~ n~ 6, R1 and R2, are identical or different, each alkyl having C1_~, hydroxyalkyl having C1_6, alkylaryl or aryl, and X
i~ H, OH, NH2, NH3, NR~R5 or R6, where R3, R~, R, and R6 are each al~yl having C1_6 or aryl groups.
The invention further relates to a composition of a polyepoxide and an amine for preadherising polyester filaments, which i6 characterised in that the amine is a tertiary amine having the following general formula:
`:
~C
~- ~29L~787 - 3a -X ~CHZ)~ - N / (I) \ R2 where 1~ n ~ 6, Rl and R2, identical or different, are each alkyl having C1-61 hydroxyalkyl having Cl_6, alkylaryl or aryl, and X
i5 H, OH, NH2, NHR3, NR~R5 or R6, where R3, R4, Rs and R6 are each alkyl having C1-6 or aryl groups.
This composition is more stable than tha~ described in U.S. Patents 3,383,242 and 3,297,468. Compound (I) is an amine having at least one tertiary function. It is assumed that the tertiary amine has a catalytic action on the reaction between the polyepoxide and the polymer. The group X can also be a primary, secondary or ~2~787 tertiarj amine. ~n that case the second am;ne function ;ncreases the catalyt;c activ;ty. By v;rtue of compound (I) an adhes;ve layer is formed and, alone or together w;th an RFL treatment, confers good adhes;on to the fila-ment on vulcanisation into rubber.
Compound (I) is preferably N,N-dimethylbenzyl-am;ne~ 3-diethylamino-1-propylam;ne, 3-dimethylamino-1-propylamine, tribenzylamine, triethanolamine or triethyl-am;ne. The type of polyepoxide in the composition according to the invention is not critical. The speci-fically preferred type is that of the glycidyl ethers which are generally prepared by reacting epichlorohydr;n with an alkanol or a phenol. The polyepox;de can be saturated, unsaturated, aliphatic, cycloaliphatic, aro-matic, heterocyclic or substituted. The compounds aree;ther monomers or polymers having at least two epoxy groups per molecule.
Examples of such compounds are the epoxy deriva-t;ves of bisphenol A or of phthalic acid, the epoxyphenol novolac, the epoxycresol novolac, the glycidyl isocyanur-ates, the epoxy-containing derivatives of hydantoin, such as hydantoin triglycidyl ether, the aliphatic glycidyl ethers, such as butanediol diglycidyl ether, ethylene-glycol diglycidyl ether or glycerol triglycidyl ether, and the glycidyl der;vatives of triaz;ne, such as tris-t2,3-epoxypropoxy)-3-propionyl-1,3,5-hexahydro-s-triaz;ne (TEPS).
~ ` lZ~787 - 5 ~
Because the abovementioned TEPS is read;ly sol-uble in water it was already used ;n the compos;t;on des-c;ibed ;n U.S. Patent 4,121,901. The composition accord-;ng to the ;nvent;on is ;n solut;on ;n water, alcohol, a water-alcohol mixture or a f;bre finish. For the pur-poses of th;s ;nvent;on a f;bre f;nish ;s ch;efly a pro-duct wh;ch ;mproves the fr;ctionaL, antistatic and wet-t;ng propert;es of the synthet;c f;lament.
This composition can be used either on its own or together ~;th aux;l;ar;es. For the purposes of th;s invention auxiliaries are products which are capable of ;mprov;ng st;lL further the adhes;on of the f;lament to rubber, for example carr;er or swell;ng agents, such as ethylene glycol, caprolactam or polyvinyl or benzyl alco-hol, or solvents which permit more efficient d;ffus;on ofthe epoxide into the polymer. Wetting agents or surface-active agents, such as the commercial products QZ 13 from CI3A-GEIGY and TW 1196*from ZSCHIMMER ~ SCHWARZ, which are solutions w;th s;licones or ethoxylated compounds, can also be used. Secondary preadherising agents can also be applied ;n add;t;on, for example those based on silanes tepoxysilanes), polychlorophenols tVulcabond E*
from VULNAX) or those hav;ng free or blocked ;socyanate groups, or urethanes, poly;m;nes, polyacrylates and poly-am;des. It ;s likew;se possible to subject the filamentpreadherised according to the invention to a treatment r~ w;th the conventional pretreatment agent compris;ng a . 1 * Trade Mark ~Z4 Ei787 polyepox;de and a blocked poly;socyanate before the RFL
treatment.
The amount of polyepoxide ;n the composition according to the invention is 5 to 99% by weight and that of compound ~I) is 0.01 to 6.0, preferably 0.05 to 3, X
by weight. The remainder comprises wat~r, alcohol, water-alcohol mixture or fibre finish.
The invention further relates to a process for preadherising polyester filaments which is characterised in that the abovementioned composition of polyepoxide and tertiary amine is applied to the stretched filament. In this process, unlike in the process descr;bed ;n U.S.
Patent 3,793,425 and German Offenlegungsschrift Z,û56,707, the stretch rollers do not become encrusted, and the filaments have good mechanical properties.
The type of polyepoxide and of compound (I) is the same as in the composition accord;ng to the inven-tion, as is the nature of the solut;on.
The amount of polyepox;de and espec;ally of com-pound (I) appl;ed to the filament is fa;rly critical,according to the invention. As regards the polyepoxide, a level below O.O5X g;ves r;se to the problems of ;nade-quate adhesion and irregular distribution of the poly-epoxide along the filament, and a level greater than O.SX
does not give better adhesion. Compound (I) gives maxi-mum adhesion of the filament to the rubber when applied in an amount of 2 to 300 ppm, preferably 5 to 100 ppm.
~%4~i787 All the abovement;oned levels of polyepoxide and eompound (I) are relative to the treated polyester filament.
For the purposes of the present invention poly-esters are linear polycondensed esters prepared by react-ing one or more diols of the HO(CH2)nOH series ~here 1 ~ n C 10 ~ith a dicarboxylic acid, preferably tere-phthal;c acid, or a corresponding diester, such as dime-thyl terephthalate. The polyesters can also be modified uith organic or inorganic additives. The polyester used for reinforcing elastomers has been or;ented and stretched in order to obtain reinforcing filaments hav-ing satisfactory mechan;cal properties for their use.
The preferred polyester is polyethylene tere-phthalate without restriction as regards the terminal carboxyl group or diethylene glycol content.
The stretched filament is produced in an integ-rated spin-stretch process in which the filament is ~ound up at take-up speeds of 2,000 to 6,000 m/m;n. The com-position according to the invention ;s applied by means of one or t~o metering PinS between the final duo and the ~inding apparatus or subsequently during the rebind;ng of the stretched filament.
It may be necessary to do further treatments on the stretched filament in order to improve its running perfor-2S mance or fatigue level, for example by applying polysiloxanes,silanes, polyethylene glycols or ester or mineral oils.
The process according to the invention makes it - 124~787 possible to produce a polyester filament having very good mechan;ca~ properties and an ;mproved adhcsion to rub-ber. This process is also very simple and very econom;-cal, since the stretching is not adversely affected. The linear density of the polyester filament yarn thus pro-duced is not critical. It 1s preferably between 500 and 2,50û dtex, and the number of individuaL filaments is between 8û and SûO. This filament yarn is particularly suitable for reinforcing rubber articles, such as car tyres, conveyor belts, V-belts and flexible tubes. It can also be used for articles which are coated with polyvinyl chloride.
The filament yarn thus obta;ned is then ready for a conventional treatment with an RFL bath prior to the vulcanisation with rubber. For certa;n uses it is even vulcanised into the rubber without RFL impregnation.
The filament yarn preadherised according to the invention can also be subjected to a secondary treatment in a conventional polyepoxide bath mixed w;th an aqueous dispersion~of a blocked poly;socyanate before it is imp-regnated with the RfL and/or vulcanised into the rubber.
The invention finally relates to the polyester f;lament yarns thus produced w;thout restriction as regards the terminal carboxyl group content. It is of course also possible to apply the composition to the un-stretched filaments separately from or together with the spin finish in a separate spinning and stretching process ~2~787 _ 9 _ or in a spin-stretch process.
The polyepox;de, ~hich ;s advantageously soluble in uater, is dissolved in a concentration of 5 to 99X in a presubmitted amount of water, water-ethanol m;xture or solvent, such às polyglycols, ben2yl alcohol or ester o;ls. Afterwards, but before the composition ;s used, compound ~I) is added in a concentrat;on of 0.01 to 6.0, preferably 0.05 to 3.0, X by we;ght.
Production of cord yarn A polyester filament yarn hav;ng a linear density of 1,100 dtex and comprising 192 high-modu~us, high-strength monofilaments ;s produced as follows using a spin-strech process:
The highly viscous polymer is melted at a tempe-rature of 280 to 330C in an extruder, and the melt isextruded through a sp;nneret. After cooling down in an quenching stag the filaments are drawn off at normal speed and are guided over a fin;sh application roller, where a sp;n finish is applied, and over a plurality of pairs of rollers which are operated at different tempera-tures and speeds, where the filaments are stretched and heat-set. Depending on the desired mechanical yarn pro-perties the rollers can have temperatures between 70 and 245C. The roller speeds are such that the spun f;~a-ments can be stretched up to six times their originallength. The filaments are directly wound up at a take-up speed of 3,000 m/min.
- 12~787 - lo -A number of these filament yarns, for example 2, are t~isted together in conventional manner to form a gr age cord yarn. This yarn is then impregnated on a treatment machine ~;th an RFL solution consist;ng of 20X of a resorc;nol-formaldehyde resin and of a latex and is then thermally treated ;n convent;onal manner at 150C
for 30 seconds and then at 235C for 1 minute. This ;mpregnated cord ;s then vulcanised ;nto the rubber.
The adhesive properties of the cord vulcanised into the rubber are tested using UNIROYAL's A-300 strip test, in ~hich the variable measured is the force ~hich is necessary to separate t~o layers of rubber from a cord fabric vulcanised into the rubber. A pull force of less than 10 daN ind;cates poor adhesion, and a pull force greater than 15 or 20 daN indicates good to very good adhes;on to the rubber.
The appearance value indicates ho~ ~ell the rub-ber adheres to the cord layer. The highest value of S
characterises an adhesive bond ~here the crack appears in 2û the rubber and no cord is visible at the crack surface.
The poorest value of O characterises an adhesive bond ~here the crack takes place at the rubber-cord ;nterface, so that no rubber remains stuck to the cord layer. The values from 0.5 to 4.5 are ;ntermed;ate levels. In the present case the cord has a pull force of 7 daN and an appearance value of 0.
` ` 12~787 Examples 1 to 11 The yarn ;s produced ;n accordance w;th the invention as mentioned above, except that the f;laments are guided at a po;nt between the f;nal duo and w;nd;ng apparatus over a preadher;s;ng dev;ce ;n the form of a meter;ng pin ~here the compos;tion ;s appl;ed.
The compos;t;on cons;sts of a polyepox;de~ a ter-t;ary am;ne and a solvent. The concentration of the poly-epox;de ;n our examples ;s 35X by we;ght, wh;le that of the tert;ary am;ne accord;ng to the ;nvent;on ;s given in the table~ The level on the fibre ;n the examples ;s 0.2X of epoxy resin. The yarn thus produced ;s ;mpreg-nated w;th RFL and then vulcan;sed ;nto the rubber.
The table below shows the str;p test results obtained on apply;ng d;fferent compos;t;ons.
Example 1 shows how poor the adhes;on ;s ~hen the compos;t;on does not conta;n compound ~I) accord;ng to the ;nvent;on ;n add;t;on to the polyepox;de.
In Examples 2 to 4 the catalyt;c effect of the tert;ary amine accord;ng to the ;nvent;on comes ;nto play. Example 3 represents an opt;mal am;ne concentra-t;on at wh;ch the pull force value ;s at a max;mum.
In Example 5 only 0.05X of polyepox;de, and not 0.2X, were appl;ed to the yarn. The pull force ;s lower, although ;t ;s still h;gher than ;n Example 1, where the polyepox;de level ;s four t;mes as h;gh but no compound (I) ;s present.
12~787 Examples 6 to 10 l;kew;se form part of the subject-matter of our invent;on. As can be seen, the nature of the polyepoxide tdiepox;de or tr;epoxide having different structures) is of not ins;gnificant ;mportance) ~Examples 6 and 8). The solvent, by contrast, is not cr;tical (Examples 8 and 9). In Examples 7, 8 and 10 different am;nes are used together with the same epoxide.
In Example 11, the polymer used and ethylene ox;de are added before be;ng melted in the extruder. The resulting f;~ament only has a term;nal carboxyl group content of 5 mol/t. The f;lament yarn produced ;n accor-dance w;th the invention as regards its compos;t;on and the process used ;n mak;ng ;t has fa;rly good adhes;ve propert;es. The adhes;ve properties are only ins;gn;fi-cantly worse than those ;n Example 8, where the yarn con-ta;ns a term;nal carboxyl group content of 20 mol/t.
The f;laments of Examples 2 to 11, wh;ch were obtained ;n accordance w;th the ;nvention, are d;st;n-gu;shed by good process;ng properties, for example the absence of depos;ts at the twist;ng stage. Although the ;ndividual filaments are treated, the fatigue level of the tyre cord produced is not ;mpa;red.
~ 12~6787 T~ble ~r-pl-~olyepolide Solvent j~o~pound ~1) StriP t st I ,, lSEPS ~1 ll2 none lO l 0 _ _ _ 2~ ~ O S ~ DPA ~9~16 0 3 0
3~ ~ l 0 ~ ~ 20 5 3 5 2 0 ~ ~ l8 0 3 5 5~ ~ 1 0 ~ ~ 16 0 3 0 6BD W (b) ~ O S t DMD ~fl l~ 0 3 0 7 GSG ~e) ~ I 0 t DMPA le~ l6 3 3 0 - 3 5 8 ~ ~ O S ~ DMB If ~ lô 0 3 5 9 ~ R20/ethanol 2 l0 5 ~ ~ 19 0 3 0 - 3 5 0 6 t TEA Id~ 20 0 3 5 ll ~ 1l20 5 ~ DMB lf~ 15.0 1.0 ~-) TEPS - tris(2,3-epo~ypropoly)-3- Id) SEA - triethrnolrn1ne propionyl-1,3,5-he~hydro- ~e~ DMPA ~ 3-dinethyl~eino-1-s-tr1e21ne propyl~ine Ib) BDDG - butrnediol diglycidyl ether ~f ) DMB - di~ethylben2ylanine Ic~ GTG - 91ycerol triglyc1dyl ether 191 DPA r 3-diethyl~ ino-1-
Claims (15)
1. A process for preadherizing polyester filaments to ameliorate their adhesive properties towards rubber, wherein the polyester filaments after stretching are treated with a composition consisting of a polyepoxide and a tertiary amine having the following general formula (I) where 1<n< 6, R1 and R2 are identical or different, each alkyl having C1-6, hydroxyalkyl having C1-6, alkylaryl or aryl, and X is H, OH, NH2, NH3, NR4R5 or R6, where R3, R4, R5 and R6 are each alkyl having C1-6 or aryl groups.
2. A process as claimed in claim 1, wherein compound (I) is N, N-dimethylbenzylamine, 3-diethylamino-1-propylamine, 3-dimethylamino-1-propylamine, triethylamine, tribenzylamine or triethanolamine.
3. A process as claimed in claim 1, wherein the polyepoxide is tris(2,3-epoxypropoxy)-3-propionyl-1,3,5-hexahydro-s-triazine, butanediol diglycidyl ether, hydantoin triglycidyl ether, ethylene glycol diglycidyl ether or glycerol triglycidyl ether.
4. A process as claimed in claims 1 to 3, wherein the composition is soluble in water, alcohol, a water-alcohol mixture or a fiber finish.
5. A process as claimed in claims 1 to 3, wherein the composition consists of 5 to 99% by weight of polyepoxide, 0.01 to 6.0% by weight, of a tertiary amine, the remainder being water, alcohol or fiber finish.
6. A process as claimed in claims 1 to 3, wherein 0.05 to 0.5% of polyepoxide and 2 to 300 ppm of tertiary amine, relative to the filament, is applied to the polyester filament.
7. A process as claimed in claim 1, wherein the stretched filament is produced at a take-up speed between 2,000 and 6,000 m/min using an integrated spin-stretch process.
8. The process as claimed in claim 7, wherein the composition is applied by means of a metering peg between stretching and winding or subsequently on re-winding.
9. Polyester filaments produced as claimed in claims 1 to 3.
10. A composition of a polyepoxide and an amine for preadherising polyester filaments to ameliorate their adhesive properties towardsrubber, characterized in that the amine is a tertiary amine as defined in claim 1.
11. The composition according to claim 10, characterized in that compound (I) is N,N-dimethylbenzyl-amine, 3-diethylamino-1-propylamine, 3-dimethylamino-1-propylamine, triethylamine, tribenzylamine or triethanolamine.
12. The composition according to claim 10, characterized in that the polyepoxide is tris(2,3-epoxy-propoxy)-3-propionyl-1,3,5-hexahydro-s-triazine, butanediol diglycidyl ether, hydantoin triglycidyl ether, ethylene glycol diglycidyl ether or glycerol triglycidyl ether.
13. The composition according to claims 10 to 12, characterized in that it is in solution in water, alcohol, a water-alcohol mixture or a fibre finish.
14. The composition according to claims 10 to 12, characterized in that it consists of 5 to 99% by weight of polyepoxide, 0.01 to 6.0% by weight of a tertiary amine, the remainder being water, alcohol or fibre finish.
15. The composition according to claims 10 to 12, characterized in that it consists of 5 to 29% by weight of polyepoxide, 0.05 to 3% by weight of a tertiary amine, the remainder being water, alcohol or fibre finish.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH161483A CH654585A5 (en) | 1983-03-24 | 1983-03-24 | COMPOSITION AND METHOD OF PREADHAERIZATION OF SYNTHETIC FEDES. |
| CH1614/83 | 1983-03-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1246787A true CA1246787A (en) | 1988-12-13 |
Family
ID=4214555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000449296A Expired CA1246787A (en) | 1983-03-24 | 1984-03-09 | Composition and process for preadherising polyester filaments |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0139667B2 (en) |
| BR (1) | BR8406457A (en) |
| CA (1) | CA1246787A (en) |
| CH (1) | CH654585A5 (en) |
| DE (1) | DE3476213D1 (en) |
| ES (1) | ES8700681A1 (en) |
| WO (1) | WO1984003707A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547755A (en) * | 1988-11-24 | 1996-08-20 | Rhone-Poulenc Viscosuisse Sa | Pre-adherized polyester filament yarn for tire cord |
| US5576105A (en) * | 1992-09-14 | 1996-11-19 | Rhone - Poulenc Viscosuisse S.A. | Tire core made from an improved polyester filament yarn |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH677499A5 (en) * | 1988-11-24 | 1991-05-31 | Schweizerische Viscose | Polyester tyre cord filaments - are impregnated with adhesive to bond to rubber before hot air treatment and single-stage drawing |
| EP0519927B1 (en) * | 1991-01-14 | 1998-04-01 | Rhone-Poulenc Filtec Ag | Method of producing a pre-adhered polyester filament, and tyre-ply cord made from this filament |
| CA2082127A1 (en) * | 1991-11-06 | 1993-05-07 | William L. Hergenrother | Ultraviolet light curable adhesive active finish for reinforcing members and related methods |
| ES2119008T3 (en) * | 1993-04-30 | 1998-10-01 | Bridgestone Corp | INITIATORS OF ANIONIC POLYMERIZATION AND PRODUCTS OF REDUCED HYSTERESIS THEREOF. |
| TW363989B (en) * | 1997-04-07 | 1999-07-11 | Rhodia Industrial Yarns Ag | Process for pre-adhering polyester filaments |
| US9484123B2 (en) | 2011-09-16 | 2016-11-01 | Prc-Desoto International, Inc. | Conductive sealant compositions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793425A (en) * | 1971-12-27 | 1974-02-19 | R Arrowsmith | Coating process for polyester substrates |
| US3962011A (en) * | 1972-12-18 | 1976-06-08 | The General Tire & Rubber Company | Composite of polyamine bonded to rubber and method for making the same |
| AR208219A1 (en) * | 1975-01-27 | 1976-12-09 | Rhone Poulenc Sa | NEW PRE-ADHERIZING ENSIMAJE COMPOSITION FOR POLYESTER-BASED FILAMENTS |
-
1983
- 1983-03-24 CH CH161483A patent/CH654585A5/en not_active IP Right Cessation
-
1984
- 1984-03-09 CA CA000449296A patent/CA1246787A/en not_active Expired
- 1984-03-13 ES ES530532A patent/ES8700681A1/en not_active Expired
- 1984-03-15 BR BR8406457A patent/BR8406457A/en not_active IP Right Cessation
- 1984-03-15 EP EP84900966A patent/EP0139667B2/en not_active Expired - Lifetime
- 1984-03-15 DE DE8484900966T patent/DE3476213D1/en not_active Expired
- 1984-03-15 WO PCT/CH1984/000042 patent/WO1984003707A1/en active IP Right Grant
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547755A (en) * | 1988-11-24 | 1996-08-20 | Rhone-Poulenc Viscosuisse Sa | Pre-adherized polyester filament yarn for tire cord |
| US5693275A (en) * | 1988-11-24 | 1997-12-02 | Rhone-Poulenc Viscosuisse | Method of making an improved pre-adherized polyester filament yarn |
| US5576105A (en) * | 1992-09-14 | 1996-11-19 | Rhone - Poulenc Viscosuisse S.A. | Tire core made from an improved polyester filament yarn |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3476213D1 (en) | 1989-02-23 |
| CH654585A5 (en) | 1986-02-28 |
| BR8406457A (en) | 1985-03-12 |
| WO1984003707A1 (en) | 1984-09-27 |
| ES8700681A1 (en) | 1986-11-16 |
| EP0139667A1 (en) | 1985-05-08 |
| ES530532A0 (en) | 1986-11-16 |
| EP0139667B2 (en) | 1996-05-15 |
| EP0139667B1 (en) | 1989-01-18 |
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