DE2336158A1 - BINDING AGENT FOR BONDING REINFORCEMENT MATERIALS WITH VULCANIZABLE NATURAL OR SYNTHETIC RUBBER - Google Patents

Description

PATENT LAWYERS '
D R. ■ IN GH FlNCKE
DIPL. - Ir-JP ₁ . H. DOHR
DlPL-IHQ. 3. STAEQER

8 MUNICH 5
MÜLLERSTRASSE 31

Folder 23257 - Dr Λ.
OIL oasis 5O9

CANADIAN INDUSTRIES LBlITED

and
ICI AMERICA INC.

Binding agent for joining reinforcement materials, with vulcanizable natural or synthetic rubber ~ "

PRIORITY: 07/14/1972 - Great Britain

The invention relates to a binder for binding reinforcing materials with vulkanisierbareci, natural or synthetic rubber, to a process for coating of the V _e rstärkungsmaterials with the binder on the coated reinforcing materials, to a method for connecting the treated reinforcing materials with vulcanizable rubber and Vulcanizing the rubber and finally onto the vulcanized reinforced rubber articles obtained.

Numerous binders are already known for joining reinforcing materials, such as cotton, rayon, nylon, silk, polyester, steel and glass in the form of threads, fibers, yarns (cords), textiles and the like, with natural or synthetic rubber. Such reinforced rubbers have found wide use in articles such as 3. ± _n

Tires, conveyor belts,! Drive belts, hoses, balloons and other similar items, which "in use are exposed to more or less severe conditions. Because of the harsh conditions these. Objects are subject to high demands on the binder posed. It often occurs that when the object is stressed, the reinforcing material becomes detached from the rubber separates that heat is generated, that cracks propagate and that the product collapses at all. It is clear that this adhesion is extremely important in the manufacture of rubber tires.

In CA-PS 652 487 there is a two-layer binder system with each covering of the system being applied to the reinforcing fibers. A topping consists of a composition containing triallyl cyanurate and optionally Contains vinyl chloride, and the other covering consists of a composition that a latex consists of a vinyl pyridine -miso hpolymer and a latex made of a resorcinol / Contains formaldehyde condensate. One difficulty encountered with this binder system resides in FIG weak adhesion between the two pads.

In CA-PS 78O 935 a binder composition is described which consists of an aqueous solution of the reaction products of an aliphatic aldehyde, such as formaldehyde, with the reaction product of an unsaturated aliphatic triester of cyanuric acid and an excess of a polyhydric phenol, such as resorcinol, and of a rubber-like mixed polymer latex or a styrene / butadiene mixed polymer latex, such as, for example, a styrene / butadiene / vinylpyridine mixed polymer latex or a styrene / butadiene mixed polymer latex or a mixture of these two la

According to the invention, a binder is now created, which is an improved method j, m \ connecting V _e r-

Strengthening materials with vulcanizable rubber results and has specific uses as a binder for glass or steel tire cords ".

Thus, according to a first feature of the invention, a binder for connecting reinforcing materials with vulcanizable rubber is proposed, which contains the following: as the first component (i) a thermally curable copolymer of at least one non-functional c-, ethylenically unsaturated main monomer, at least one carboxyl group containing G ^ ß-ethylenically unsaturated monomer and at least one epoxide group-containing CKy ß-ethylenically unsaturated monomer or (2) a thermally curable mixture of a copolymer of at least one non-functional main monomer and at least one carboxyl group-containing α, ß-ethylenic unsaturated monomer with an epoxy resin, and as the second component a resorcinol / eorraaldehyde latex mixture.

According to the invention there is also a method for treatment proposed by reinforcement materials with a binder described above, which thereby it is carried out that the first component of the binder is applied to the reinforcing material, the one obtained The coating is heated in order to remove at least the liquid medium and preferably also the complementary one to crosslink reactive carboxyl groups and epoxy groups, the second component of the binder applies and finally the second coating obtained is heated to it to harden. If only that at the first heating stage liquid medium is removed, then both components are hardened in the last stage.

According to the invention, reinforcement materials are also proposed that use the binding agent described above are coated.

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Finally, according to the invention, a method for producing reinforced vulcanized rubber is also proposed, which is carried out by placing the above coated reinforcing material in vulcanizable Embeds rubber and then vulcanizes the rubber.

Finally, the invention also relates to reinforced, vulcanized rubber and objects made from it, such as p.3. Hoists, conveyor belts, drive belts, hoses, balloons, etc. like

The thermosetting material that is used for the first & oraponente of the binder according to the invention is used, can be selected from the two alternatives described above to be selected. In each pail the carboxyl group-containing, ß-ethylenically unsaturated monomer of the Lischpolynier is preferably a tv, ß-ethylenically unsaturated Carboxylic acid Examples of suitable acids are acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid. Methacrylic acid is preferred. The Spoxydgruppers containing monomers of the mixed polymer can be, for example, glycidyl methacrylate or glycidyl acrylate. The epoxy resin can be selected from commercially available spoxy resins, such as 3. VCardura "3 (Trademark), which is a Glycidyl ester, which is produced by reacting epichlorohydrin with a mixture of saturated, highly branched, mainly tertiary monocarboxylic acids with a chain length is obtained from Cq, Cq and 0. ("Versatic acid"), "Genepoxy" Sl 205 (trademark), which is a modified diglycidyl ether of bisphenol-A, "Epon" 812 (Trade Mark), which is a diglycidyl ether of glycerin, "Epon" 826 (Trade Mark), which is an essentially pure diglycidyl ether of bisphenol-A, "Epon" 828 (trademark), which is a slightly resinified porn from "Epon" 526

309886 / 0S73 _BAD oRiGJNAL

acts, and other diglycidyl ethers of polyhydric alcohols or phenols or diglycidyl esters of polycarboxylic acids etc.

The mixed polymers of the first component contain at least one non-functional, X, ß-ethylenically unsaturated monomer included, which forms the main monomer component of the interpolymer. Suitable monomers these 2ype are styrene, alkylstyrenes, alkyl methacrylates and -acrylates, itaconates, maleates, fumarates, vinyl acetate, other similar vinyl esters and vinyl chloride. Preferred monomers are styrene, butyl acrylate, methyl methacrylate and 2-ethyl exyl rylate.

The first component of the binder described above may contain one or more plasticizers, i.e. modifiers that change the glass transition temperature (Tg) of the Affect mixed polymer. Examples of such modifiers are low molecular weight polymeric esters, monomers Esters and polyalkylene glycols.

Suitable polymeric esters are e.g. butyl- and benzyl-ab-, closed diet ethylene glycol adipates, maleates and phthalates, and benzyl closed diet ethylene glycol / epoxy resin adipates. Examples of monomeric esters are dibutyl hydroxyether succinate, dibenzyl adipate, dibenzyl phthalate and reopen tylglycol dibenζoate. Polypropylene glycol with a molecular weight for example 1025 is a suitable polyalkylene glycol.

The calibrators are preferably grounded into the first component incorporated in an amount ranging from 1 to 30% by weight, preferably 5 to 25 weight percent based on total solids weight is sufficient. These amounts represent the total amount ε, η represent plasticizers if more than one plasticizer is used.

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Other thermally curable polymeric materials that are suitable for use as the first component of the binder suitable for the invention can be found in U.S. Patents 2,604,464,

2 604 457, 2 798 861, 2 964 492, 3 179 714, 3 222 418 and

3 222 420.

Particularly useful compositions for the first component of the binder contain copolymers of 85 to 97 wt .- ^ of a non-functional 0, ß-ethylenically unsaturated monomer and from 15 to 3 wt .- $ of a carboxyl group-containing #, ß-ethylenically unsaturated monomer in Mixture with an epoxy resin in a weight ratio of 100: 10 to 100: 5 (mixed polymer: resin).

Preferred copolymer compositions are latex preparations which contain styrene in an amount from 30 to 65 % by weight, alkyl acrylate in an amount in the range from 60 to 30% by weight and a carboxyl group-containing / χ, β-ethylenically unsaturated monomer in an amount in the range from 5 to 10 wt .- ^ included. Styrene can preferably also be used in an amount of 15 to 80% by weight together with a monomer containing 3 to 20% by weight of carboxyl groups. If the latex is used for the first component, it is important to select a latex with a film-forming temperature in the working range of the immersion bath temperature, ie 5 to 10 ° on both sides of the working temperature.

The percentage of solids that are thermally curable Mixed polymer solution is determined by application discussions, such as the desired take-up weight and the intended drying time of the fiber bobbin, and not through technological considerations of the reaction taking place. Preferably, a suitable range of solids is between 1 and 50 percent by weight, in particular 3 to 10 wt .- ^.

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The thermally curable first component of the preparation can be in the form of a solution, an emulsion, or a Have dispersion. The emulsion and the dispersion can be aqueous or organic in nature. "An aqueous copolymer dispersion is preferably used. When they are in the form of an aqueous dispersion, the interpolymers can be made up of any one of them of the procedures set out in the UK filings 33O84- / 72, 33O85 / 72, 33O86 / 72 and '33088/72 are. Other conventional techniques, as described for example in the CA-! PSen mentioned above can be used to prepare the interpolymer of the first component.

In order to promote the curing or thermosetting reaction between the carboxyl groups and epoxy groups of the component, it has been found useful to incorporate a catalyst in the binder formulation. Suitable catalysts are, for example, tertiary amines, especially dimethylethanolamine. Usually 1 to 2% by weight of amine, based on the weight of the total solids, has a favorable effect on curing. Transition metal salts have also proven to be particularly effective in the thermal hardenable material. Zinc salts are preferred. Better stability can be achieved in the case in which the material is an aqueous latex _, if the cation is treated with ammonium hydroxide or an equivalent organic base, such as, for example, thylethanolamine, One of the best catalysts is the zinc ammonium acetate complex. This catalyst can be used with great advantage especially when the reinforcing material is a tire rim. Usually a lot of a complex results from 0.1 to 4 wt .- ^, calculated as ^ metal ion, based on the thermally curable solids, a favorable curing effect.

3 0988B / G873

The curing times and temperatures of the first component of the binder of the invention can vary widely, but generally in the range of I9O to 260 ⁰ C or in the range of 1 to 3O min.

Any conventional resorcinol / iOrmaldehyde latex mixture can be used can be used as the second component of the binder according to the invention. Examples of latex are terpolymers of butadiene, vinyl pyridine and styrene; Mixed polymers of styrene and butadiene; Mixtures of the terpolymers and the copolymers; natural rubber; and butyl rubber. Usually the mixture is aqueous in nature and contains the Reaction product of resorcinol with formaldehyde together with a dispersed rubbery copolymer. An example of such a rubbery copolymer latex is a Vinyl pyridine copolymer latex sold under the trademark "Gentac" is marketed. This is a Aqueous dispersion of a terpolymer obtained by copolymerizing 70 parts by weight of butadiene and 15 parts by weight Vinyl pyridine and 15 parts by weight of styrene is produced. This dispersion usually contains about 4-0 ^ elast omerfe fabrics. Another suitable interpolymer latex is "Pliolite" 2108. This name is a trademark for a styrene / butadiene rubber latex produced by interpolymerization from 29 parts by weight of styrene and 71 parts by weight of butadiene is obtained. Mixtures of "Gentac" and "Pliolite" 2108 can also be used. Other latices, such as natural rubber and butyl rubber latices, can also be used be used. The resorcinol / iormaldehyde-guiniiii copolymer latex mixture can alternatively be modified with "H-7", which designation is a Trademark for a chlorophenol adduct, i.e., um the reaction product of a chlorophenol, resorcinol and formaldehyde. Other common known variations of the Resorcinol / formaldehyde latex can also be used

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In general, the particular selection of this component will be determined by the type of rubber base material "in which the reinforcement cord is to be embedded. With a combination of RPV ¹¹ HT" it has been found useful to keep the two components in the range of 90/10 to 40/60 parts by weight and preferably in the range from 80/20 to 50/5 parts by weight.

The curing times and curing temperatures for the Eesorcin / Formaldehyde Iiat ex component are roughly the same Same order of magnitude as for the thermally curable first component.

In general, the. two components of the invention Binder can be applied by any of the conventionally known methods, for example Dipping, spraying, painting and the like.

In the binders according to the invention, the main mass of the composition consists preferably of the resorcinol / formaldehyde Iiatex mixture. For example, the first component can thermally curable 3 "make up to 20 wt .- ^, in particular 7 to 12 wt. -4>, wherein the RPL mixture from the remainder consisting, and 97 to 80 wt .- ^ and in particular 93-88 wt .- ^ matters.

The type of reinforcement materials upon which the inventive Binders that can be applied are e.g. cotton, rayon, silk, nylon, polyester, steel and glass, which can be in the form of threads, fibers, yarns (cords), fabrics and the like. Preferably consist these materials made of steel threads and glass threads, which for example have the shape of a tire cord.

The rubbers in which the reinforcing materials coated with the binders according to the invention are incorporated

30 9 886/087 3

can be absorbed are, for example, vulcanizable natural ones and synthetic rubbers. Examples of synthetic rubbers are butadiene polymers, i.e. those polymers which Have rubber-like properties and the polymerization of butadiene alone or with one or more arene other polymerizable ethylenically unsaturated compounds, such as styrene, methyl styrene, methyl isoprcpenyl ketone and acrylonitrile can be produced, the butadiene in the mixtures preferably in one Amount of at least 40 wt .- ^, based on the total polymerizable material. Commercially available rubbers of this type are G-R-S 1000, GR-S 15ΟΟ, GR-S 1600, GR-S 2000 etc.

Other suitable synthetic materials are the neoprene guinmis and the isobutylene rubbers ("ButyV rubber).

If necessary, conventional vulcanization can be applied to the rubber additives, accelerators and accelerator activators be admitted.

The vulcanization conditions used in accordance with the invention are those conventionally used for natural rubber and synthetic rubber can be used.

The following examples illustrate the invention. All parts and percentages are by weight unless nothing other is indicated.

example 1

A woven glass ribbon with a width of 12.7 nua (heat-cleaned "Hesgon" A) was placed in a 5 % solids solution of Binder A, the solvent being

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0.5 ° / o of zinc metal complex, based on solids, contained, soaked, and then 9 ° lake to 24O ⁰ C heated. The tape was then immersed in a 20 ⁰ Jo Peststoffe containing aqueous RFL mixture (abbreviation of resorcinol / formaldehyde latex) and 90 ⁰ C lake heated to 24-O.

The treated tape was then placed on a 19 mm wide unvulcanized rubber strip for tires (Goodrich No. SX 288). The tape and rubber were then placed in a compression molding press at 56 kg / cm and 149 ⁰ G 3P min, whereby the bond and rubber vulcanization took place. The bond strength of the vulcanized, reinforced rubber strip was then tested as in the example below 3 is described. '

The binder A used in this example was a solution of a thermally curable mixture of 59 parts of a styrene / butyl acrylate / acrylic acid mixed polymer. (in a weight ratio of 43.5 files styrene, 50.0 Parts of butyl acrylate and 6.5 parts of acrylic acid) and 10 parts "Epon" 826 in a 4M mixture of xylene / ButanoX. The binder can be prepared in the same manner as described in Example 5 of CA-PS 534,261. It can can also be obtained as a dispersion in water according to the methods which fertilize in GB notes 33084/72 and 33085/72 are described.

The here used RPL system was a mixture of resorcinol / formaldehyde resin and "Gentac" (vinylpyridine / butadiene / styrene Datex) _f as is commonly used in the art (see for example US-PS 3 24O 251 and 2 99O 313 ).

The zinc metal complex was zinc acetate complexed with ammonium hydroxide.

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Example 2

Example 1 was repeated, except that the RFL solution was modified in such a way that a reaction product of p-chlorophenol, formaldehyde and resorcinol (77 parts of Ri ¹ L to 23 parts of reaction product) was incorporated. The bonding strength of the obtained reinforced vulcanized rubber strip was determined in the same manner as in Example 3.

The reaction product of p-chlorophenol, formaldehyde and resorcinol used herein was prepared as follows :

Formaldehyde solution, p-chlorophenol and sodium hydroxide were ^{mixed together at 80 °} C. in water. After cooling, the strong alkalinity was reduced to pH 8.5 to 9.5 with 5N sulfuric acid, and the precipitated 4-chloro-2,6-dihydroxymethylphenol (compound A) was removed by filtration, washed with water, slurried twice with water , filtered again and dried at 70 to 75 ⁰ C.

The solid was then ground and the powder dispersed in water. This dispersion was added to a solution of resorcinol in water at 100 ⁰ C. After cooling, the precipitated was "H-7 trimer" filtered off and washed with water, and then the filtrates were again heated to 100 ⁰ C and then abgekiib.lt again. The second batch thus obtained was combined with the first filter cake, and the whole was again slurried in water, filtered again, and then at 75 ⁰ C dried.

The dry solid was then dissolved in 3N ammonia to make a 20 # solution.

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The reactions that take place in this production process are represented as followsϊ

II + 2 CH ₂ O + NaOH -

■ OH ■ "■

OHCH ₂ - ^^ 'V' CH ₂ OH

The reinforced, vulcanized rubber strips of the Bei ~ Games 1 and 2 were made to bond by peeling the glass tape from the rubber strip at an angle of 180 ° examined using a Scott tester at a pull rate of 30.5 cm / min; Was used. In the' force measured in all cases represents the raft that it is necessary to tear the rubber, whereby part of the rubber remains firmly attached to the tape. The test results were as follows:

Glass reinforced vulcanized

Rubber strips

Example 1 Example 2

Bond strength (kg / cm)

13.6 16.5

These results demonstrate the exceptional bond strengths obtained using the stated system can be, whereby the system, which the chloro-

3098 86/087 3

H -

phenyl / resorcinol / formaldehyde reaction product with the RPL mix contains, shows a particularly exceptional strength.

Example 4

A piece (5 strands of 0.221 mm) of braided steel wire cord (Bekaert Glear Bright Wire) was immersed in a mixture containing 20% pesticides, which RPL, which had been modified according to Example 2, and the reaction product of chlorophene oil, resorcinol and formaldehyde (77 parts of Ri ¹ L, 23 parts of reaction product) contained. Drahtcord was then 90 see at 24O ⁰ C cured.

The bohandslte in this way was Cord (vulcanized Goodrich no. 1920 at 149 ⁰ C and 56 kg / cm ² for 30 minutes) then in two rubber strips embedded, said strip having a width of 6.3 mm. The strips formed the vertical parts in an "H" and the wire formed the horizontal part in the "H". The bond strength was then determined as shown in Example 6.

Example 5

A piece of braided steel wire cord (Bekaert Clean Bright Wire) was poured into a dispersion containing 5 pesticides. Binder B in water containing 0.5 # zinc as Aamoniumacetatkomplex, based on Peststoffe, dipped and then 90 see cured at 24O ⁰ C. Wax were the treated Drahtcord was then jn a $ 20 Pest materials containing solution of the RPL mixture which gemäj3 Example 4 modified '(HPI 77 parts, 23 parts Reaktionsprodu ^ t) is immersed and then 9O see cured at 24O ⁰ C.

303886/0873

The binder B used here was an aqueous dispersion of a styrene / butyl aylate / methacrylic acid mixed polymer (42 / 51.8 / 6.2) mixed with "Epon" in a ratio of 9.6: 1. The making of this latex was like followsϊ

Batch beatand parts quantity

Cin share)

A Sodium dodecyl diphenyl ether- 20
disulfonate (45 &)

Nonyl-phenoxypoly- (ethyleneoxy

15) ethanol 0.7

Water (distilled) 100.0

ITa ₂ S ₂ Og · '1.0

HaHCO 1.0

B styrene 202.5

Butyl acrylate 250.0

-Methacrylic acid. "■ 30.0

"Epon" 826 '"50.0

Water (distilled),. 480.0

Sodium dodecyl diphenyl ether

disulfonate (45 1 ») 9.3

Nonylphen oxy-poly- (ethylene oxy

i5) ethanol 2.8

Ha ₂ S ₂ Og 1.0

Charge A was ^{heated to 80 °} C. and charge B was added over a period of 3 hours. The reaction mixture was left to stand for 1 st, and then 0.5 g of Ka ₂ S ₂ Og was added as a solution in 10 g of water (freshly prepared). The reaction mixture was a further 1/2 st

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dissolve themselves and then cooled and filtered. The I <atex obtained had a theoretical pesticide content of 47 1 ".

In an alternative method to the above method, a solution of 0.5 g Hydrosulfite AWC (trademark) in 5 g V / water (freshly made) and then 2.0 ml of t-butyl hydroperoxide were used instead of the final addition of ^ ^a p ^ 2 ^ 8 added.

The wire cord was then embedded in a rubber strip and the strip was vulcanized according to Example 4. The bond strength was then determined as in the following example β .

Example 6

The reinforced vulcanized rubber strips that are in shape of the letter "H" in Examples 4 and 5 were vulcanized at a speed of 3 °, 5 cm / min pulled apart on a Scott tester, and the time needed to pull the rubber strip and wire apart Force was measured in each example and taken as a measure of the bond strength. The results were as follows:

Wire reinforced bond strength vulcanized (kg / cm) rubber strips _____

Example 4 17.7

Example 5 22.7

The above results show the extraordinary improvement in bond strength that can be achieved using the combination

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of the binder B with the modified HFL-Gemisah according to of the invention, in contrast to the bond strength obtained with the modified RE1-Gemiseh alone is obtained.

Examples 7 to 14 describe the preparation of various other thermally curable materials which can form the first component of a binder according to the invention. As described in the preceding Examples 1 to 6, each of these materials can be used as a first coating on a. Reinforcing material can be applied ¹ , the second component being ^aes - ^ i * ¹ ^ "* by means of one of the conventionally known resorcinol / iOrmaldehyde- ^ atex mixtures.

Example 7

A thermally curable latex that is made from a copolymer 39.3 parts of styrene, 4-5.2 parts of butyl aorylate and 5.8 parts Methacrylic acid and 9.7 parts of "Epon" 826 contained was as produced in the Polge, being a "process with emulsified Charge was used.

Batch ingredients quantity

(in pieces)

A sodium dodecyl diphenyl ether

disulfonate ( $ 45) 2.0

Nonylphenoxypoly (ethyleneoxy 15)

ethanol 0.7

Water (distilled), 100.0

g ■ -1.0

1.0

B styrene 202.5

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Batch components; __ Men ^ e

(in pieces)

B butyl acrylate 232.5

Methacrylic acid 30.0

"Epon" 826 50.0

Water (distilled) 480.0

Sodium dodecyl diphenyl ether

disulfonate (45 1 °) 9.3

Nonylphenoxypoly (ethyleneoxy 15) "

ethanol 2.8

Na ₉ S ₉ O, 1.0

C.

The Charge A was heated to 85 "to 9O ⁰ C, and the batch was then B during a period of 3 st added. Das'.Reaktion sg emi son was held for 15 min at 9O ⁰ C. Then a solution of 0, 5 g of NapSpOn in 10 g of water (freshly prepared) were added. The reaction mixture was then left to stand for a further 30 minutes and then cooled and filtered. A latex with a solids content of 47% (theory) was obtained. The method of this example is comparable to the procedure of Example 5, except that Example 5 describes a low temperature version of the procedure of this example.

Example 8

A thermally curable latex, which consists of a mixed polymer of 37.4 parts of styrene, 46.3 parts of butyl acrylate and 6.9 parts of methacrylic acid and 9.3 parts of ^l! Epon "826 was prepared using a unulsion feed oplite process as follows.

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Batch
Δ

Components

Sodium alkyl aryl polyether sulfonate (28 # Containing pesticides Solution)

Water (distilled)

NaHCO.

Quantity (in ¹ jl rush)

: 3.6

100.0

1.0 1.0

B styrene

Butyl acrylate methacrylic acid

Sodium alkylaryl polyäthersulfonat (28 i "Pe st materials containing i)

1-octane thiol

water

135.0

167.5

37.5

15.0 0.25 ml 1.0 369.0

Styrene

Butyl acrylate "Epon"

Sodium dodecyl diphenyl ether disulfonate (45 f>)

Nonylphenoxy ~ poly (ethyleneoxy 15) ethanol

Water (distilled)

1-octane thiol

Na ₂ S ₂ O ₈

55.8

• 69.2

50.0

3.0

0.5 150.0

0.25 ml 0.25

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Batch ingredients men ^ e

(in pieces)

D styrene 11.2

Butyl acrylate 13.8

Sodium dodecyl diphenyl ether

disulfonate (45 1 ") 1.0

Water (distilled) 30.0

Na ₂ S ₂ O ₈ 0.1

Charge A was ^{heated to 85 °} C. and Charge B was then added over a period of 2 to 3 hours. The reaction mixture was then kept at the above temperature for 1/2 hour. The reaction mixture was then ^{cooled to 80 °} C. and then Charge C was added over a period of 1 to 2 hours. The reaction mixture was ^{kept at 80 °} C. for a further 15 min. Next, Charge D was added over a period of 10 minutes, and the reaction mixture was then ^{held at 80 °} C. for a further half an hour. A freshly prepared solution of 0.25 g of ^Na p ^ 2 ^ 8 ⁱⁿ ^ ^{ml water} was added. Alternatively, a freshly prepared solution of 0.5 g Hydrosulfite A'.YC in 5.0 g of water are added and then 2.0 ml of t-butyl hydroperoxide, in order to bring the conversion to an end. the reaction mixture was The latex obtained had a solids content of 45.4 ° (theory).

Example 9

A thermally curable latex made from a mixed polymer 42.3 parts of styrene, 42.3 parts of butyl acrylate and 5.8 parts of methacrylic acid and 9.6 parts of "Epon" 826 contained

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according to the following information according to the "procedure of Example 8 made.

Batch ingredients lot

(in pieces)

A sodium alcylaryl polyether

sulfonate (28 solution containing solids i °) · 3> 6

Water (distilled) η00.0

8 ¹ > °

1.0

B styrene 170.0

Butyl acrylate 170.0 methacrylic acid - 33.0

Sodium alkylaryl polyether sulfonate ($ 28 solids solution) 12.0

Water (distilled) 362.0

Na ₂ S ₂ Og 1.0

1-Oetan-thiol 0.5 ml

Styrene 60.0

■ butyl acrylate 60.0

"Epon" 826 55.0

Sodium dodecyl diphenyl ether

disulfonate (45 1 °) 3.0

Nonylphenoxy-poly- (ethyleneoxy 15) -

ethanol 0.5

Water (distilled) 180.0

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Batch components Quantity-e

(in pieces)

^ s ₂ O ₈ ο, ι

1-octane thiol 0.25 ml

D styrene '12.5

Butyl acrylate .12.5

Sodium dodecyl diphenyl ether

disulfonate ( $ 45) 1.0

Water (distilled) 25.0

Na ₂ S ₂ Og 0.1

The Charge A was heated to 9O ⁰ to 95 C, and then the batch B was added over a period of 2 to 3 hours. The reaction mixture was i / 2 hour at 90 to 95 ⁰ C and then cooled to 80 ⁰ C. Charge C was then added over a period of 1 to 2 hours. The reaction mixture was held at 80 ° C for an additional 10 minutes and then Charge D was added over a period of 15 minutes. A freshly prepared solution of 0.5 g of Hydrosulfite AWC in 5.0 g of water was added, followed by the addition of 2.0 ml of t-butyl hydroperoxide. The reaction mixture was ^{kept at 80 °} C. for a further half hour and then closed3. cooled and filtered.

Example 10

A thermally curable latex that is a mixed polymer of 22.3 parts of diethyl methacrylate, 22.3 parts of styrene, 44.3 Parts of butyl acrylate and 5.3 parts of methacrylic acid sov / ie

0 3806/0873 B ^ ORiQINAL

Containing 5.3 parts of "Epon" 826 was added according to the monomer addition procedure en manufactured as indicated in the pole. -

Batch ingredients quantity

(in pieces)

A sodium dodecyl diphenyl ether

disulfonate (45 #) 6.0

Nonylphenoxy-poly- (ethyleneoxy 15) -

ethanol 1.5

«. _fc 8 ¹ '°

Water (distilled) 500.0

B methyl methacrylate 100.0

Styrene 100.0

Butyl acrylics; 200.0

Methacrylic acid 24.0

"Epon" 826 24.0

Sodium dodecyl diphenyl ether

disulfonate (i00 ^) 2.5

lfonylphenoxy-poly- (ethyleneoxy 15) -

ethane oil 1.5

Charge A was ^{heated to 80 °} C. and then 10% of charge B were added. The reaction mixture was held at 80 ° C. for 1/2 hour and then the remainder of Charge B was added over a period of 5 to 6 hours. During the last 3 hours of this addition, a freshly prepared solution of 1.0 g of H & ^ SJ ^ q in 50.0 g of water was added. The Heaktionsgemisch was kept for another hour at 80 ⁰ C, after which the addition was over and what
Finally the latex was cooled and filtered.

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Example 11

A thermally curable latex, which is a copolymer of 39.3 parts of styrene, 45.2 parts of butyl acrylate and 5.8 parts len methacrylic acid and 9.7 parts of "Genepoxy" M205 was prepared as indicated below by the modifier inoculation method manufactured.

Batch ingredients quantity

(in pieces)

A sodium dodecyl diphenyl ether

disulfonate (45 fi) 2.0

Nonylphenoxy-poly- (ethyleneoxy 15) -

ethanol. '0.66

Water (distilled) 100.0

Na ₂ S ₂ Og 1.0

NaBDO 1.0

"Genepoxy" M205 60.0

B styrene 202.5

Butyl acrylate 232.5

Methacrylic acid 3 °, °

Water (distilled) 480.0

Sodium dodecyl diphenyl ether

disulfonate (45 1 °) ■ 9.3

Nonylphenoxy-poly- (ethyleneoxy 15) -

ethanol 2.8

Na ₂ S ₂ Og 1.0

All ingredients except the last of Batch A were combined and completely dissolved, with the

"Genepoxy ¹ , ¹ M205 is added to this solution and

309886/0873

using a Cowles mixer. The Charge A was heated in a flask ^to ^ O "to 85 ° C. The batch B wurde'während a period of 15 min added to the flask, the addition was stopped., And the temperature of the reaction mixture was raised to 95 ⁰ C and 15 held min at this temperature. then, the addition of charge B was added again for a further 3 i / 2 st. the Beaktionsgemisch was 1 st to 95 ⁰ C maintained, the reaction to environmentally, to bring the end, after which the latex obtained was then cooled and was filtered.

Example 12

A thermally curable latex which is a copolymer of 39.3 parts of styrene, 45.2 parts of butyl acrylate and 5.8 parts Methacrylic acid containing 9.7 parts of "Epon" 826 was made according to the modifier inoculation process, as indicated below.

Batch Ingredients Quantity

(in pieces)

A sodium dodecyl diphenyl ether

disulfonate (45 &) 2.0

Nonylphenoxy-poly- (ethyleneoxy 15) -

athanol 0.66 Water (distilled) 100.0 Fa ₂ S ₂ O ₈ 1.0 NaHGO ₃ 1.0 Polyvinyl alcohol (pre-dissolved) 3.0 Water (distilled) 50.0 "Epon" 826 50.0

309886/0873

Batch beatand parts ^

(in pieces)

B styrene 202.5

Butyl rylate 23 2.5

Methacrylic acid 30.0

Water (distilled) 4-30.0

Sodium dodecyl diphenyl ether

disulfonate (45 f ») 9.3

Nonyl-phenoxy ~ poly- (ethyleneoxy 15) -

ethanol 2.8

Na ₂ S ₂ Og 1.0

All ingredients except the last of Batch A were combined and completely dissolved with the addition of the "Epon" 826 sur solution. The mixture was emulsified on a Cowles mixer for 10 minutes. Charge A was ^{heated to 90 °} C. and charge B was added over a period of 4 hours. The temperature of the reaction mixture changed from 90 to 95 ^° C. during the addition. A freshly prepared solution of 0.5 g of Na ₂ S ₂ Og in 5.0 g of water was then added. The reaction mixture was left to stand for a further 2 l / 2 st, counted off and filtered.

Example 13

A thermally curable latex, which auc 64.4 parts of styrene, 27.6 parts of butylate and 3.0 parts: Methacrylic acid and 6.2 'parts of "Epon" 826 and 6.0 parts of a plasticizer made from a polyester of adipic acid / Containing diethylene glycol / bensyl alcohol, according to the Emulsion process with actual feeding and non-

Codifier

more reactive / charged as described below " is.

309886 / 0B73 bad ORIGINAL

Components

Sodium alfcylaryl polyether sulfonate (28 ^ solution containing pesticides) V / ater Sodium persulfate Sodium biearb onate Amount (in parts)

3.6 100.0

1.0 1.0 '

B styrene

Butyl acrylate Methacrylic acid Polye st er-Weio hmac her Sodium-alteylaryl-polyether sulfonate (28 % solids solution) Water 1-Octan-thiol Sodium persulfate 258.0 110.0

4-0.0

30.0

15.0 400.0

2.0 (0.25 ml) 1.0

Styrene butyl acrylate "Epon" sodium dodecyl diphenyl ether disulfonate (45 1 °)

Honyl-phenoxy-poly- (ethyleneoxy 15) ethanol

Water 1 - Oc t an - t hi oil Sodium persulfate 51.5 22.1 31.0 ■

3.0

0.5 155.0

0.5 (0.1 ml) 0.25

309886/0873

Char / ye constituents Me η ^ e

(in pieces)

D styrene 12.9

Butyl rylate 5.5

Sodium dodecyl diphenyl ether

disulfonate ( $ 45) 1.0

Water 32.0

Sodium persulfate 0.1

Charge A was ^{heated to 92 °} C. and then Charge B was added over a period of 3 hours. The temperature of the Reaktionsgemisehs was raised to 95 ° C and maintained for 30 min, after which the mixture was cooled to 8O ⁰ C. Charge C was then added over a 40 minute period. The reaction mixture was then ^{kept at 80 °} C. for a further 20 min. Charge D was added over a period of 10 to 15 minutes, and the reaction mixture was again ^{held at 80 °} C. for a further 2 hours. The resulting latex was cooled and filtered.

The polyester plasticizer used in the above latex was manufactured as follows:

Ingredients quantity

(in pieces)

Adipic acid 1 752

Diethylene glycol 636

Toluene 177

Dibutyl tin diacetate 10.75

Benzyl alcohol 1,296.0 (1O ■ £ over

shot)

The first three ingredients were melted together, and then the dibutyl tin diacetate was melted

309886/0873

given. The reaction mixture was heated to reflux and held at this value for 2 hours. Water (the theoretical amount is 216 g) was removed at 15O ⁰ C, until the acid number was 310 (actually 215 g water were removed). The above amount of benzyl alcohol was then added and reflux was maintained until the acid number was 5.0. The temperature of the reaction mixture rose to 180 ^° C. over a period of 5 hours, during which time 207 g of water of condensation were removed and the acid number reached 23.5. A further 140 parts of benzyl alcohol were then added to raise the acid number to 50. Care was taken that the temperature did not rise above 200 ° C. during the additions.

Example 14

A thermally curable latex, which is a copolymer of 75.0 parts of methyl methacrylate, 8.5 parts of butyl acrylate, 2.2 parts of glycidyl methacrylate and 3.3 parts of methacrylic acid and 11.0 parts polyester plasticizer from adipic acid / diethylene glycol / benzyl alcohol was prepared by a method similar to that in the preceding Example was used.

Patent claims

309886/087 3

Claims (28)

PATENT CLAIMS 1. Binding agent for bonding a reinforcing material with vulcanizable rubber, characterized in that e3 ″ contains the following: as the first component (i) a thermally curable copolymer of at least one non-functional, α, ß-ethylenically unsaturated main monomer, at least one carboxyl group-containing, ex, ß-ethylenically unsaturated monomer and at least one Epoxy-containing, ex, ß-ethylenically unsaturated Monomer or (2) a thermally curable mixture of a mixed polymer of at least one non-functional Main monomer and at least one carboxyl group-containing, cc, ß-ethylenically unsaturated monomer and of an epoxy resin, and as the second component a resorcinol / formaldehyde latex mixture. 2. Binder according to claim 1, characterized in that the ex, ß-ethylenically unsaturated monomer in (Ό or (2) containing ^{carbox3 r l groups is an ex, ß-ethylenically unsaturated carboxylic acid.} 3. Binder according to claim 2, characterized in that the «, ß-ethylenically unsaturated carboxylic acid from Acrylic acid, methacrylic acid, itaconic acid, maleic acid and Fumaric acid is selected. 4. Binder according to claim 1, characterized in that the epoxy-containing monomer des Mixed polymer of glycidyl methacrylate and glycidyl acrylate is selected. 5. Binder according to claim 1, characterized in that one of the following is used as the epoxy resin: 309886/0873 a glycidyl ester made by reacting Epichlorohydrin and a mixture of saturated, strong branched, mainly tertiary monocarboxylic acids with a chain length of C, CLq and CL .., a modified one Diglycidyl ether of 3isphenol-A, a diglyeidyl ether of Glycerin, a largely pure diglycidyl ether of bisphenol-A, a slightly resinified form of an essentially pure diglycidyl ether of bisphenol-A or other diglycidyl ethers of polyhydric alcohols or phenols or diglycidyl esters of polycarboxylic acids. 6. Binder according to claim 1, characterized in that the non-functional, oc, ß-ethylenically unsaturated main monomer is styrene, an alkyl styrene, an alkyl methacrylate or acrylate, an itaconate, a maleate, a pumparate, vinyl acetate or vinyl chloride. 7. Binder according to claim 1, characterized in that it contains at least one plasticizer. 8. Binder according to Anapruch 7, characterized in that the plasticizer is a low molecular weight polymer Ester, a monomeric ester or a polyalkylene glycol is used. 9. Binder according to claim 1, characterized in that the first component is the Porm of a solution, emulsion or dispersion. 10. Binder according to claim 1, characterized in that the first component is the Porm of an aqueous dispersion having. 11. Binder according to claim 1, characterized in that a tertiary amine, a salt of a catalyst 309886/0873 Transition metal, a complex of a salt of a transition metal with ammonium hydroxide or a complex of a salt a transition metal with an equivalent organic base is present in the first component. 12. Binder according to claim 11, characterized in that that the catalyst consists of 1 to 2 wt .- $ of a tertiary amine based on the weight of the total solids in the first component. 13. Binder according to claim 11, characterized in that the catalyst from 0.1 to 4 wt .- ^, calculated as the metal ion, based on the total solids of the first component, of a salt of a transition metal complex consists. 14. Binder according to claim 11 or 12, characterized in that that the catalyst consists of Hirnethyläthanolamin. 15. A binder according to claim 11 or 13, characterized in that the catalyst consists ^z inkammoniumacetatkomplex from the. 16. Binder according to claim 1, characterized in that the latex of the resorcinol / iOrmaldehyde-latex mixture from a terpolymer of butadiene, vinyl pyridine and styrene, a mixed polymer of styrene and butadiene, a mixture of the terpolymer and the mixed polymer, ITatura rubber or Butyl rubber. 17. Binder according to one of claims 1 or 16, characterized in that the resorcinol / formaldehyde latex is modified with a chlorophenol adduct, which is the reaction product of chlorophenol resorcinol and formaldehyde. 309886/0873 18. Binder according to claim 1, characterized in that the first component 85 to 97 Sew .- / ^{0 of} a non-functional α, ß-ethylenically unsaturated monomer and 15 to 3 wt .-? & A carboxyl group-containing (X, ßäthylenisch unsaturated monomer in Mixture with an epoxy resin in a weight ratio of 100: 10 to 100: 5 (mixed polymer: resin) contains. 19. Binder according to claim 18, characterized in that the first component is styrene in an amount of 30 to 65 wt .- $, alkyl acrylate in an amount in the range of 60 to 30 wt. -I * and carboxyl groups-containing oc, ß-ethylenic contains unsaturated monomer in a range from 5 to 10 wt .- #. 20. Binder according to claim 19, characterized in that the copolymer of the first component is styrene in in an amount from 15 to 80% by weight and carboxyl group-containing monomer in an amount in the range from 3 to 20 Contains weight-f °. 21. A binder according to claim 1, characterized in that the first component is 3 to 20 wt .- $, and the second component of 97-80 wt. ° -f makes the approach. 22. A binder according to claim 21, characterized in that the first component 7 to 12 wt. ~ F ° and the second component from 93 to 88 wt. -I "constitutes the Ansatz.es. 23 «A method for treating reinforcing materials with a binder according to claim 1, characterized in, that one applies the first component to the reinforcing material ", the resulting covering is heated to liquid Remove medium and to crosslink the reactive carboxyl and epoxy groups, apply the second coating and then heated it to harden. 30988 6/0873 7336158 24. The method according to claim 23, characterized in that the heating after the application of the first component and the second component is carried out "at a temperature in the range from 190" to 260 ^° C. for a time in the range from 1 to 30 minutes. 25. The method according to claim 23 or 24, characterized in that that as reinforcement material cotton, rayon, silk, nylon, polyester, steel or glass in the form of threads, Pasern, yarn or '.Textile fabric is used. 26. The method according to claim 23 or 24, characterized in that that the reinforcement material consists of glass or steel thread tire cord. 27. The method according to claim 23, characterized in that in addition, the coated reinforcement material is embedded in vulcanizable rubber and the rubber then vulcanized. 28. The method according to claim 27, characterized in that the rubber is natural rubber or a synthetic rubber selected from butadiene polymers, neoprene gourami and isobutylene rubber is used. .H.f I; C <3. D'.PL-U'lG.H.β · * « S. ΜΑΕβ » 3 09886/0873