JPS5953779A - Treating agent for thermoplastic synthetic fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a treatment agent for thermoplastic synthetic fibers, and its purpose is to have an adhesive function when the fibers are made into a composite with rubber, and to streamline the production process. The present invention relates to an extremely effective treatment agent for electrical contact.

Conventionally, thermoplastic synthetic fibers such as power running aliphatic polyamide fibers, aromatic polyamide fibers, and polyester fibers have been widely used in the field of industrial materials due to their excellent physical properties.

For example, rubber reinforcement applications are mainly used for tires, conveyor belts, hoses, rubberized composite membranes, etc., but especially in rubber products reinforced with fibers such as tires, the most important requirements for reinforcing fibers are The characteristic is the adhesion between the cord and the rubber after being embedded in the ear and undergoing the vulcanization process.
Strong retention and two-dimensional stability. In particular, with regard to adhesiveness, various improvements have been made depending on the physicochemical surface characteristics of each fiber material.

Existing bonding techniques for representative fibers are described below.

For aliphatic polyamide adhesives, RFL (resorcinol, formalin,
The main component is rubber latex). There are two factors between this RFL and aliphatic polyamide: 1) the physical factor that their solubility parameters are almost the same, 11) the active hydrogen atoms in the 7-mid groups distributed in the main chain of aliphatic polyamide, and the low resorcinol/formalin Due to the above two factors, such as the strong primary bond with the condensate and the strong hydrogen bond between the felt hydroxyl group of resorcinol and the amide bond, a single immersion treatment in RFL liquid is sufficient. This makes it possible to develop strong adhesive strength.

On the other hand, polyester fibers have only a few terminal hydroxyl and carboxyl groups as functional groups in their molecular structure, so their adhesion to rubber is not as good as that of aliphatic polyamides (one-step treatment with RFL liquid is not sufficient). It was difficult to provide sufficient adhesive force.However, after several years of research,
2. Advances are rapidly progressing, and currently, as a method that can be carried out technically, glycerol diglycidyl ether is added to the undrawn yarn before it is treated with the upper WU 'l't FL liquid. A method of treating with a pre-treatment agent mainly containing an epoxy compound such as
A two-stage treatment method, or RFL, in which a pretreatment agent such as a monoocyanate compound or an ethylene urea compound is used before treatment.

Practical adhesion of IIF'4 between polyester fibers and rubber has been achieved for the first time by methods such as mixing these compounds into a liquid and applying them.

Furthermore, in the case of aromatic polyamide, aliphatic polyamide t
It has the disadvantage that it has inferior adhesion to rubber compared to a4ij+, and only extremely insufficient adhesion can be obtained when treated with a normal RFL liquid. Currently, epoxy compounds are used to treat polyester fibers, or acidic polymers obtained by polycondensation reactions of hydroxybenzoic acid, halogenated phenols, and aldehydes are used. A method has been adopted in which a polymer obtained by reacting with a phosphor is preliminarily illuminated.

As mentioned above, by accumulating technology over many years, each IN
Adhesion processing techniques have been developed depending on the surface chemical structure of the 1tii&, but in each case, the stage of the twisted hood or the cord is woven into a sudare weave. ! At the stage after m,
The method of immersion application of RFL aqueous dispersion, which is an adhesive between rubber and fibers, is the mainstream method and is recognized as the most common and established adhesive technology. In this RFL adhesive layer, a resorcinol/formalin low condensate that contributes to bonding with fibers and a latex component that has an affinity for rubber form a reciprocal polymer network structure, and during rubber vulcanization, the rubber molecular chains and latex They become entangled with the molecular chains, and in this entangled state, a crosslinking reaction proceeds between both double bond molecular chains by the sulfur compound blended into the unvulcanized rubber. Through the above mechanism, sufficient adhesion can be imparted between the fiber 1L and the rubber through the RFL.

Because of the above effects, the RFL liquid immersion process for cords or cord fabrics is widely practiced as an essential process for bonding.

- The present inventors have arrived at the present invention as a result of intensive research into an innovative adhesive technology that can omit such an RFL dipping step.

That is, the present invention provides an adhesive comprising rubber, a resorcinol-aldehyde compound, and an aldehyde compound, and a thermoplastic synthetic fiber whose main component is a rubber swelling compound having a rubber swelling ratio of 20 or more with respect to unvulcanized rubber. It is a processing agent.

In the present invention, thermoplastic synthetic fibers are fibers made of aliphatic polyamide, polyesophore, chill, or aromatic polyamide. As aliphatic polyamide Saikai,
Nylon6. Nine 66, nylon 8. nylon 11
Examples include synthetic fibers such as ordinary polyamides such as polyamides, polyamides having hetero elements, polyamides having ether bonds, and the like. In addition, polyester fibers are mainly made of polyethylene terephthalate and polyethylene naphthalate, but some or all of the acid components or diol components can be replaced with inctaric acid, β-hydroxyethoxybenzoic acid, naphthalene dicarboxylic acid, or diphenyldicarboxylic acid. , bifunctional acids such as cepatic acid, and trimethylene glycol, neopentyl glycol.

hexamethylene glycol, polyethylene glycol,
■ 60 or more moles of repeating units in the main chain are aromatic, replaced with one or more compounds of aliphatic, alicyclic, and aromatic dihydroxy compounds such as 4-bishydroxyethoxybenzene and bisphenol A. It also includes fibers made of polyester having the following.

Furthermore, aromatic polyamide fibers (~) are polymers in which repeating co-positions are bonded by carboxylic acid amide groups (-N) (co-), and the imino and carbonyl groups are each directly bonded to the aromatic group. The fiber is made of a polymer obtained using an aromatic dicarboxylic acid, an aromatic diamine, and/or an aromatic aminocarboxylic acid as a starting material.

The fiber form of such thermoplastic synthetic fibers may be multifilament yarn, spun yarn, coated or woven fabric, but cord or cord woven fabric is most suitable for use as a rubber compensator.

According to in-depth research conducted by the present inventors, by attaching the adhesive and the processing agent containing the rubber swelling compound to the thermoplastic synthetic fiber, 1) the rubber swelling compound is Since it also functions as a lubricant, it can provide appropriate frictional surface characteristics for yarn twisting and weaving processes.

When conventional RFL liquid is applied to fibers and the fibers are wound up, adhesion occurs due to the adhesive between the fibers, which not only causes noticeable fluffing during unwinding, but also creates adhesive residue on the guide of the running yarn. High scum accumulates and the coefficient of friction decreases, further promoting brushing and loops.

1i) The adhesive is dissolved or emulsified in a rubber swelling compound that is advantageous for uniform adhesion to the ffl fibers, thereby promoting diffusion of the adhesive onto the fiber surface and promoting uniform adhesion of the adhesive. , which is highly effective in improving adhesion.

111) A rubber swelling compound having a rubber swelling rate of 2° or more does not inhibit the strong adhesion function of the rubber/fiber interface of the adhesive. Rather, it improves the "wetting" of the unvulcanized rubber used as the adherend to the fibers and promotes the adhesive function.

iv) When applied in the form of dissolved, emulsified, or dispersed water, the viscosity can be reduced to a particularly low level, which is advantageous for uniform adhesion to the fiber surface, and since no organic solvent is used, safety is improved. It is advantageous in terms of TIL environment and economy.

We have come to discover that it has a special combined effect.

In the present invention, when processing in a system in which each component described in detail later is dissolved, emulsified, or dispersed in water, the emulsifier used is an anionic surfactant.

Either a cationic surfactant or a nonionic surfactant may be used. In addition, in order to prevent precipitation and coagulation of emulsion particles during emulsification, demelting, and concentration, and further improve the mechanical stability of emulsion particles, anionic surfactants and nonionic surfactants or cationic interfaces are used. It can also be achieved by using a mixed emulsifier of an active agent and a nonionic surfactant.

As an example of the anionic surfactant, at least one of higher fatty acid salts (eg, potassium laurate, sodium oleate, etc.), rosinate salts, and disproportionated rosinate salts is suitable. In addition to using this higher fatty acid salt, rosinate salt, or disproportionated rosinate salt, these may be used by directly dissolving them in water (or, higher fatty acid salts may be added to the mixture of the adhesive and rubber swelling agent compound). Dissolve p-zic acid or disproportionated rosin acid, use an alkaline aqueous solution (for example, aqueous sodium hydroxide solution, etc.) as a dispersion medium, and mix and emulsify it in the aqueous solution to dissolve the higher fatty acid salt, p-sic acid salt, or disproportionated rosin acid. A salt may be formed and used. Examples of cationic surfactants include furkyldimethylpendylammonium coulide, polyoxyethylene alkylamine, octadecyltrimethylammonium, octadecyltrimethylammonium chloride or octadecylamine acetate. Examples of nonionic surfactants include the general formula R(-()-R
r-KomaH8-24 alkyl group, alkenyl group or furkylphenyl group having 8-16 carbon atoms, R1 is a fulkylene group having 2-5 carbon atoms, n is a number of 3-50) Examples of such compounds include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether phosphate, and polyoxyethylene propylene nonylphenyl ether phosphate.

The amount of emulsifier used is 0.5 to 15 parts by weight, preferably 1 to 8 parts by weight, per 100 parts by weight of the mixture of the adhesive and rubber swelling compound. The amount of emulsifier is 0.5ffiLt
If it is less than s, the emulsification will be poor, and if it exceeds 15 parts by weight, the adhesiveness will be poor.

In the present invention, the emulsifying device 11 for mixing and emulsifying each component includes, for example, a homomixer, a homogenizer, a disper mill, a colloid mill, etc., and if necessary, two types of emulsifying devices may be used in combination.・You can also do it. If desired, water can be added in addition to the organic solvent μ.

In this case, the concentration of the adhesive components (rubbers, resorcinol/aldehyde-based initial condensates, and aldehyde compounds) in the solution or dispersion is 1 to 90% by weight, preferably 5 to 50% by weight. be.

If the concentration is below the above range, the effective amount of adhesive for the contact layer will decrease, so the amount of non-aqueous adhesive solution applied must be increased by that amount. Scattering during the yarn twisting process becomes a problem. On the other hand, if the concentration falls within the above range, the viscosity of the non-aqueous adhesive solution increases, which is detrimental in terms of uniform application. However, even if the upper limit of the above range is exceeded, the objective can be sufficiently achieved by optimizing the molecule 1k and the molecular structure of the rubber, and the above upper limit does not limit the present invention.

Furthermore, the processing agent of the present invention can also be used in a state in which the adhesive is dissolved or dispersed in a rubber swelling compound. The rubber swelling compound is one or two organic solvents such as esters, ketos, alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, and chlorinated hydrocarbons that promote the dissolution of rubber. Examples of rubber swelling compounds used in the present invention include butyl stearate, octyl stearate, and ester compounds of monohydric alcohol and monobasic fatty acid. rate, inoctyl stearate, octyl isostearate, oleyl laurate, lauryl oleate,
There are oleyl oleate, insude 7lyluoleate, etc.
Dibasic fatty acids, which are one of the f14 components of ester compounds of monohydric alcohols and polybasic fatty acids of dibasic or more, include mapric acid, succinic fermentation, glutaric acid, adipic acid, and pimeline. acid, speric acid, azelain tjl
, aliphatic dicarboxylic acids such as cepatic acid and maleic acid,
Examples include alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid and cyclooctane dicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid. Examples of these esters include diisooctyl semecate, diisostearyl sebacate, diisotridecyl azide, dioctyl azelate, dioleyl adipate, monooleyl adipate, dioleyl phthalate, and the like. Furthermore, as esters of monohydric alcohol and tribasic fatty acids, there are Trimerit 7, Trimerit, and Trimerit. Examples include geographies, etc.

Ichinoj, as ester compounds of polyhydric alcohol and monobasic fatty acid, neopentyl glycol dioleate,
Ethylene glycol diolate, glycerin triolate, trimethyp-propane triolate, nrubitan trioleate, pentaerythritol tetraolate, etc.
), and esters of polyhydric alcohols and dibasic or higher polybasic fatty acids include ester compounds obtained by reacting oleyl alcohol with ethylene glycol-trimellitic acid monoester, and trimethylolbutane-mono-trimellitic acid. Examples include ester compounds obtained by reacting monoester with oleyl alcohol.

Other rubber-swelling compounds include higher fatty acids such as lauric acid, oleic acid, isostearic acid, and caprylic acid, and (2) higher alcohols such as octyl alcohol, lauryl alcohol, oleyl alcohol, and isocetyl alcohol. (3) Mineral oils include Redwood 80 seconds mineral oil and Redwood 240 seconds mineral oil.

At 500 seconds, naphthenic mineral oil, etc. is crushed.

For the rubber swelling compound used in the present invention as exemplified above, esters, ketones, alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, etc., which promote the dissolution of rubber, are added. A small amount of one or a mixture of two or more organic solvents such as logenated hydrocarbons and sulfur-containing hydrocarbons may be added. Furthermore, if desired, water can be added in addition to the above organic solvent.

Note that the "rubber swelling rate" defined in the present invention is
Unvulcanized rubber with a natural rubber/styrene-butadiene copolymer (styrene rate = 25%) ratio of 70/30 was heated at 80°C.
It was determined by the weight increase rate after being immersed in a rubber swelling compound for 6 hours. The rubber swelling compound applied to the fibers in the present invention must have a rubber swelling rate of 20 inches or more, but the compounds exemplified above all have a rubber swelling rate of 20 inches or more.
It has a rubber swelling rate of at least 1.

Note that if the swelling ratio of the rubber swelling compound is less than about 20%, the adhesive strength between the fiber and the rubber will not be sufficient.

The molecular chain of the rubber swelling compound is approximately 100 to 1000.
If the molecular weight is less than ioo, it is likely to volatilize during heat setting, resulting in a poor working environment and reduced lubricity during the twisting process, resulting in fuzzing of the cord.

On the other hand, if it exceeds 1,000, the molecular weight is too high, resulting in a high coefficient of friction, which deteriorates the quality of the twisting process, and the rubber swelling rate becomes less than about 20 inches, which is undesirable because the adhesiveness decreases.

The reason why the compound used in roof tiles must be rubber-resistant is that when the unvulcanized rubber is molded and vulcanized after applying an adhesive and heat-treated, the rubber swelling compound is It promotes the adhesion of the rubber to the treated cord, expands the substantial adhesion area between the unvulcanized rubber and the cord, and improves the molecular chain between the unvulcanized rubber and the rubbers that are the constituent components of the adhesive described below. This is because it promotes entanglement and greatly contributes to improving adhesion through co-vulcanization.

Examples of rubbers that are one component of the adhesive include natural rubber, cyclized rubber, natural rubber derivatives such as chlorinated rubber, resin, styrene-butadiene rubber, styrene-butadiene-vinylpyridine terpolymer, and urethane rubber. , acrylic rubber, polyurethane rubber, polybutadiene rubber,
General rubbers such as in-butylene rubber, in-prene-in-butylene rubber, acrylonitrile-butadiene rubber, zutadiene low polymer, styrene-butadiene low polymer, styrene-butadiene-vinylpyridine low polymer, or α, β
Rubbers that are liquid at room temperature, such as low copolymers of ethylenically unsaturated dicarboxylic acid and butadiene, or rubbers that have functional groups such as carboxyl groups, hydroxyl groups, amino groups, amide groups, methylol groups, and epoxy groups in the rubber molecules. 1 or 2 of
It is a mixture of more than one species.

In addition, since the solubility parameter value differs depending on the rubber composition, it is necessary to select and use a rubber swelling agent depending on the rubber composition.

In addition, as a resorcinol-fuldehyde initial condensate,
is an initial condensation reaction product made by reacting resorcinols and aldehydes as main components, usually in the presence of an alkali catalyst or an acidic catalyst. , 2 dioxybenzene.

1.4 Dioxybenzene, resoacetophenone.

α-resorcyl aldehyde, β-resorcyl aldehyde, r-resorcyl aldehyde, α-resorcic acid, β-
resorcinic acid, r-resorcinic acid, resorcin dialdehyde, resorcinol 2.5-carboxylic acid, bipgal,
Polyvalent hydroxylbenzene such as gallic acid and its derivatives 4
body 41 is included. Note that if an alkylresorcinol/aldehyde-based initial condensate in which at least a part of the resorcinol (.) is replaced with furkylresorcinol, the lipophilicity will increase and the compatibility with the rubber swelling compound will improve, so the concentration of the condensate can be reduced. It is now possible to increase the adhesive strength even further. L:i remarkable.

In addition, even if a shell oil resorcinol/aldehyde initial composite containing a small amount of alkylresorcinol (one part of which is replaced with shell oil resorcinol) is used, good effects can be obtained and it is economically advantageous.

Furthermore, the alkylresorcinol constituting the contact agent refers to one or more alkyl substituted products of resorcinol. The number of carbon atoms in the alkyl group is preferably 1 to 4. Examples of such furkyl groups include methyl and ethyl groups.
Propyl group.

There are 1Ro-propyl group, n-butyl group, 1io-butyl group, and tart-butyl group. However, carbon number is 5
The objects of the present invention can also be achieved with alkyresorcinols having the above alkylyl groups.

Note that two or more kinds of the above-mentioned furkylresorcinols may be mixed together.

In addition, 1. used in the present invention. The shell oil resorcinol is a tosulfur z/-ol mixture mainly containing furkyresorcinol obtained by dry distillation of shale, etc.
-methylresorcinol, 5-ethylresorcinol,
4,5-dimethylresorcinol, 2,5-dimethylresorcinol + 21'! 5') ') Methyl resorcinol, etc. If desired, shell oil resorcinol may be fractionally distilled and only a specific fraction used. It refers to aldehyde compounds such as , acetaldehyde, n-, butyraldehyde, and aquine furfural, or compounds that generate aldehydes by decomposition such as parapormaldehyde, para-acetaldehyde, hexamethylene tetrami/, and α-polyoxymethylene.

FA L for the reaction between resorcinols and aldehydes
, f (eg, phenol, alkylphenol,
Parachlorophenol, m-cresol.

Aniline, urea, catefol, hydroquinone.

bipcalol, tannic acid, gallic acid,) r2p glycine, toluene, xylem/, coumarin, cyclohexane,
Cashew oil, shellac, dammar, rosin or rosin derivative 2-right oil resin.

Amino-based trees, methanol, ethanol, n-
Zutanol, ethylene glycol, glycerinase.

Polyhydric alcohols such as polyethylene glycol.

A co-condensing agent such as furfuryl alcohol or a modifying agent may be added.

The amount of aldehyde to be reacted with the resorcinols of alkyresorcinolli (or sierol oilnsorcinol) is 1 mol or less, preferably 0.5 mol or less, when the aldehyde is converted to formaldehyde per 1 mol of the resorcinol. The amount is 95 mol or less, more preferably 0.80 mol or less.A condensate in which 11 of the aldehydes exceeds the above range becomes unstable and tends to gel even in rubber swelling compounds.

PH is 1.0 to 5.0, more preferably 1.5 to 4.0
It is. This can improve the solubility of the condensate in the rubber swelling compound.

In particular, a high level of adhesive strength can be obtained by improving the cohesive strength of the adhesive layer, but for this purpose it is preferable that the chain length of the alkyl group to which resorcinol is added is relatively short. However, if the alkyl group chain length is short, the compatibility with the rubber swelling compound decreases, but by bringing the pH of the acetone solution of the resorcinol aldehyde-based initial condensate to the acidic side, the compatibility of the condensate decreases. The present inventor has revealed that it is possible to prevent this and obtain high adhesive strength.

Further, the solubility of the resorcinol aldehyde-based primary metal compound in the rubber swelling compound is 3y/(xoor rubber swelling compound) or more, preferably 5 or more, and more preferably io? It is good if it is above. When the solubility is less than 32, the formation of an interpenetrating network structure between the resorcinol-aldehyde-based initial condensate and the rubber is not sufficiently achieved, and as a result, satisfactory adhesion between the fiber and the rubber cannot be obtained. do not have. In particular, the solubility in the rubber swelling compound is sufficiently satisfactory due to the fact that a small amount of the resorcinols constituting the resorcinol/aldehyde initial condensate (at least some of them are furkylresorcinol).

Furthermore, the aldehyde compounds constituting the adhesive other than rubbers and resorcinol/aldehyde-based initial condensates are i which rotate with the above-mentioned aldehydes constituting the condensates.

Here, the blending ratio of the rubber and the resorcinol aldehyde-based initial condensate is from 9515 to 5/95 in terms of weight ratio, preferably from 7 o/a o to 10/90. If the amount of rubber used exceeds the above range, the adhesion at the interface between the adhesive and the fibers formed by heat treatment will be insufficient, and generally speaking, as the dissolution rate of the rubber increases in the solvent, The viscosity of the non-aqueous adhesive solution increases, making it difficult to maintain uniform adhesion. Therefore, when the concentration is lowered, the amount of active ingredients on the fibers decreases, making it impossible to exhibit sufficient adhesive strength.

On the other hand, if the blending ratio of rubber is below the above range, the interfacial adhesion between the vulcanized adhesive layer and the adhered rubber will be insufficient.

In addition, the amount of the aldehyde compound added is 100% of the condensate
It is desirable that the aldehyde compound is present in an amount of 5 to 100 parts by weight based on the heavy background area.

If the amount of aldehyde compound added is below the above range, the formation of an interpenetrating polymer network structure incorporating rubber molecular chains by the above condensate and aldehyde compound will be insufficient, resulting in satisfactory adhesion. I can't get power. On the other hand, if the amount of the aldehyde compound added exceeds the above range, the amount will be an order of magnitude higher than that required to form the network structure, and the negative aspects of shortening the pot life of the water-based adhesive composition will become apparent. Furthermore, depending on the type of aldehyde compound, especially formaldehyde.

This is because when acetaldehyde is used, aldehyde odor increases, which is undesirable in terms of work space. However, the object of the present invention can be achieved even if the upper limit of the above range is exceeded, and this upper limit is not intended to limit the present invention. In addition to rubbers, the above-mentioned condensates, and aldehyde compounds, the composition of the present invention contains stabilizers for preventing the aging of rubbers, antioxidants, preservatives, insect repellents, plasticizers, and 1nV retardant. It may be added as a component.

The mixing ratio of the rubber swelling compound and the adhesive (rubber, resorcinol aldehyde initial condensate, and aldehyde compound) is 5/95 to 9515 by weight, preferably 25/75 to 90/10. be. 951
5 is superior in terms of emulsion stability,
Since the amount of adhesive 11t effective for adhesion is small, the amount of the water curable composition (treatment agent) applied to the fibers must be increased accordingly. Splashing of the agent during the process is a problem.

On the other hand, when it is less than 5/95, the stability of emulsification and dispersion decreases, and the friction coefficient of the yarn increases significantly, resulting in frequent fuzz and loops during the yarn twisting process due to the decrease in lubricity. However, even below the lower limit of the above range, the object of the present invention can be achieved by optimizing the molecular weight and molecular structure of the rubber, and this lower limit does not limit the present invention.

The amount of the treatment agent containing the combs, resorcinol-based initial condensate, and aldehyde compound attached to the fibers is 0.1 to 30% by weight, preferably 1 to 20% by weight. The amount of adhesion is about o. xfifi
If the amount is less than about 30% by weight, the resulting reinforcing material will not have sufficient adhesion to the rubber, while if it exceeds about 30% by weight, the adhesion to the rubber may be further improved, but not significantly (and rather uneconomical). Incidentally, it is sufficient if the amount of the adhesive component excluding the rubber swelling compound is 0.01 to 5% by weight based on the fiber.

According to the research conducted by the present inventors, the most preferable results can be obtained when the ratio of each component (J) +- is adjusted within the following range.

) Rubber 2-24 (weight) ←)
Resorcinol aldehyde initial condensate 1.5-18
(Weight) Chiso → Aldehyde compound 1.5 to 18 (weight) circulation)
Rubber swelling monovalent compound 95-40% (by weight) [However,
(c) + ←> 10 + → 10 G # = xoo (weight) Chi] Also,
When dissolving, emulsifying, or dispersing these in water, the concentration, i.e., the total weight of (a) to (b) in the entire aqueous composition, is preferably from 3 to 50 (by weight), particularly from 10 to 35
(Weight) Chi is optimal.

In order to apply a treatment agent containing such an adhesive to thermoplastic synthetic fibers, there are the following steps: i) Applying it during the spinning process; 11) Applying it during stretching or immediately after stretching and before winding; 111) Twisted cord or twisted yarn. Added during the process, iv) Added during the warping or weaving process, ■) #@
give something to something.

It can be applied in any one or more of the above steps.

In the case of aliphatic polyamide fibers, the treatment agent of the present invention may be directly applied by the above method, but in the case of polyester fibers or aromatic polyamide fibers, before applying the treatment agent, for example, unstretched The effects of the present invention can be more effectively exhibited by treating the yarn with a pretreatment agent mainly containing an epoxy compound such as glycerol diglycidyl ether to activate the fiber surface in advance.

Preferred application steps for industrially implementing the present invention are:
1) to 111), with 11) being particularly preferred.

The fibers to which the treatment agent has been attached as described above are then heat-treated before being vulcanized with the adhered rubber, thereby allowing the rubber and fibers to adhere to each other and forming a strong adhesive film on the fiber surface. . The heat treatment temperature is the same as that of conventional RFL.
Although it shows excellent adhesion even under heat treatment at 180 to 240°C in liquid processing, for example, after-oiling is applied to the yarn just before winding after stretching, and after making it into a twisted cord, it can be woven into a sudare weave. The processing temperature when heat-treating the prepared material may be 100° C. or higher. The heat treatment temperature may be increased as the process speed increases, and the object of the present invention can be achieved quickly by this, and the temperature range is not intended to limit the present invention. On the other hand, it is important to note that fibers coated with the above-mentioned treatment agent will be exposed to these rays during the process leading to vulcanization, as the three-prong bonds of the rubber they contain will disappear due to radioactivity at the ultraviolet edge. Consideration must be given to taking the necessary measures to block this as much as possible.

The product obtained as described above is vulcanized by a rubber vulcanization method commonly used in the industry.
Synthetic fibers and rubber can obtain excellent adhesion.

The adhesive in the treatment agent adheres to the fibers for the first time through heat treatment, forming the adhesive layer necessary for bonding between the rubber and the tX fibers. Until then, it is oily and also functions as a lubricant. A major feature of the present invention lies in the fact that even when the fibers are rubbed by various guides, they do not fall off, but rather spread and move up the surface of the fibers to promote adhesion.

On the other hand, when the conventional RF L liquid is applied in the above step instead of the treatment agent of the present invention, the RFL solidifies and the R
Since the FL dry coating becomes sticky and solid, this causes the generation of guide scum or significant P-Ra staining, and the coefficient of friction against metal increases significantly, and furthermore, yarn comrades or The cords become stuck together, making it impossible to unravel them. Furthermore, due to the above reasons, the RFL coating peels off and falls off from the fibers, making it impossible to fully exhibit its adhesive function.

According to the present invention, the RFL can be used without using the normally used RFL.
A satisfactory adhesion force between the fiber and the rubber can be obtained by applying, for example, after-oiling with an adhesive containing an oily rubber-swelling compound as a treatment agent in a step prior to treatment, and passing through a vulcanization step.

1i) The RFt liquid dipping step can be omitted, allowing rationalization of equipment processes.

This large jL advantage can be obtained, and its industrial significance is extremely large.

The present invention will be explained in more detail with reference to Examples below. Note that 1% of the middle part of the example is a heavy M;: standard.

In addition, in the examples, CRA adhesive strength indicates the adhesive strength between treated cords and rubber, and three treated cords were embedded near the surface layer of a rubber sheet and vulcanized at 150°C for 30 minutes under pressure, and then the three treated cords were 200 processing code from rubber sheet
It is peeled off at a rate of 1/min ('), and the load detected at that time is kyg/3 pieces.

The bending hardness of the cord is measured using the Gurley method, and the larger the measured value, the harder it is.

Example 1 To prepare an adhesive emulsion, 2/o of oleic acid (emulsion stabilizer)/polyoxyethylene-adducted sorbitan monooleate (emulsifier) was added to the adhesive solution shown in Table 1.
, s was gradually added to an aqueous solution of caustic soda containing undiluted potassium p-zinate while stirring with a homomixer to form an emulsion with a concentration of 15%. The resulting emulsion had a pH of 10.

On the other hand, nylon 6 filament, which was melt-spun from a nozzle with a hole diameter of 0.3a and a number of holes of 204, was spun at 300 m/jt.
A specific rubber swelling compound, oleyl adipate, was deposited by conventional p-to oiling method (Appendix 2 & 1t = 1.2%) before winding onto a bobbin at a speed of h. The undrawn yarn thus obtained was heated to 190°C using a hot drawing machine.
The obtained ts+6ods/2o4fil
The drawn yarn has the composition shown in Table 1 before winding up.
.

An adhesive emulsion consisting of an adhesive solution (non-aqueous component)
The adhesion was carried out by the p-two oiling method so that the adhesion as shown in Table 1 was as shown in Table 1.

In addition, the resorcinol aldehyde type used here is the first +
1JI condensates are shown in Table 2.

The drawn yarn thus obtained was first twisted 40 times/10α, and then two yarns were twisted 40 times/10 crn to make a tire cord.

The composition of the initial condensate A-)I of resorcinols and aldehydes used in this case is shown in Table 2.

This tire cord yarn was heat-treated at 210°C for 3 minutes, omitting the immersion treatment in the RFL liquid and the drying process. The treated cord was embedded in unvulcanized rubber for tire carcass made by mixing natural rubber and styrene-butadiene copolymer rubber, and vulcanized and cured at 150°C for 30 minutes. The hardness was measured.

As shown in Table 1, the level of adhesion for the present invention is significantly maintained in terms of uniformity of the adhesive J6 compared to that obtained with the conventional RFL liquid treatment. In terms of adhesion, rubber adhesion, and bending hardness, we have obtained data with no color loss compared to conventional products, and we have also repeatedly conducted actual vehicle driving tests. It has been proven that there are no particular problems in terms of physical properties and other durability compared to 1.

Only 1. Therefore, the level exceeding the range shown in the present invention, for example, Jikkenya 9 (low aldehyde content) B, r) JP'
A level of 1% A10 (low addition of resorcinol-aldehyde-based initial condensate) shows a significantly low value of adhesive strength. This is interesting data in the sense that it proves the adhesion mechanism mentioned above.

Example 2 Pore diameter 0.3I! J, 300 m/TI of nylon 6 fiber yarn melt-spun into yarn from a nozzle with 204 holes.
The specific rubber swelling compounds shown in Table 1 were deposited by conventional roller oiling method before winding onto a bobbin at a speed of 100 s. The undrawn yarn obtained in this way was drawn by M at 190°C using a hot drawing machine to obtain] 260de,
The adhesive solution shown in Table 3 was applied to the drawn yarn of 0.1 to 30% by weight by a roller lubricating method before winding it up. The drawn yarn thus obtained was first twisted 40 times/10 m, and then twisted twice for 40 times/10 d to make a tire cord. The compositions of the initial condensates A and -H of resorcinols and aldehydes used in this case are shown in Table 2.

Next, this tire cord yarn was heat-treated at 210° C. for 3 minutes, omitting the immersion treatment in the RF'4 liquid and the drying step.

The treated cord was embedded in an unvulcanized rubber for tire carcass made by mixing natural rubber and stainless steel-butadiene copolymer rubber, and vulcanized and bonded at 150°C for 30 minutes. We measured the

As shown in Table 3, the level of adhesion for the present invention is significantly superior in terms of adhesive layer uniformity compared to that obtained by conventional RFL# processing. Power,
In terms of rubber adhesion and bending hardness, data with no color loss was obtained compared to conventional products, and as a result of repeated vehicle driving tests, physical properties and other durability performance, including physical properties, were improved compared to conventional RFL liquid treatment. It has been proven that there is no problem when .

However, levels below the range shown in the present invention, such as a 19 (low amount of fulldehydes) and 420 (
When the amount of the resorcinol/aldehyde yarn initial barring condensate added is small, the adhesive strength shows a significantly low value. This is interesting data in the sense that it proves the adhesion mechanism mentioned above.

Claims (1)

[Scope of Claims] 1.9 Mui A, an adhesive consisting of a resorcinol/aldehyde-based initial fastener and an aldehyde compound, and a rubber swelling compound having a rubber swelling ratio of 20% or more with respect to unvulcanized rubber as one component. A processing agent for thermoplastic synthetic fibers characterized by: 2 The thermoplastic synthetic fiber is aliphatic polyamide. 3 Rubbers include natural rubber, cyclized rubber, cyprene chloride, styrene/butadiene vinylpyridine turbopolymer, urethane rubber, acrylic rubber, polyisoprene, polybutadiene rubber, imbutylene rubber, Inbrene isoptylene rubber, 7-crynitrile butadiene rubber, butadiene low M [combination, styrene butadiene low polymer, styrene-butadiene vinylpyridine low polymer, α. It is excluded from the group consisting of low copolymers of β-ethylenically unsaturated dicarboxylic acid and butadiene and rubbers having carboxyl, hydroxyl, amino, amide, meth-q-zlz or epoxy groups in the rubber molecule. The treatment agent for thermoplastic synthetic fibers according to claim 1, which contains at least one type of treatment agent that exhibits less fragility. 4. PH of resorcinol aldehyde-based initial condensate
7 or less, the processing agent for thermoplastic synthetic fibers according to claim 1. 5. PI of resorcinol-based aldehyde-based initial shrinkage products
The treatment agent for thermoplastic synthetic fibers according to claim 4, wherein ( is 1.θ to 5.0. Thermoplastic synthetic ta according to claim 1, which is furkyl resorcinol, and a textile treatment agent. B. Claims r, l' in which at least a part of the alkyl resorcinol is sierre oil resorcinol.
, The treatment agent for thermoplastic synthetic fibers according to item 6. 8. In the resorcinol/aldehyde-based initial condensate, the thermoplastic according to claim 1, 6, or 7, wherein the amount of aldehyde is 1 mole or less per 1 mole of resorcinol constituting the 3B condensate. Treatment agent for synthetic fibers. 9. The aldehydes and/or aldehyde compounds constituting the resorcinol/aldehyde-based initial condensate are formaldehyde, acetaldehyde, n-butyraldehyde, aquerein, furfural, and paraformaldehyde. 2. The treatment agent for thermoplastic synthetic fibers according to claim 1, which is at least one member selected from the group consisting of cetalsuhydride, hexamethylenetetramine, and σ-polyoxymethine. 10. A rubber swelling compound is an ester of a monobasic or dibasic polysalt with a molecular length of 100 to 1000: a #5 fatty acid and a polyhydric alcohol with a monohydric content of 211 il 1 or more. Thermoplastic synthesis j according to item 41,
A drug used as a medicine. 11. The treatment agent for thermoplastic synthetic fibers according to claim 1, wherein the weight ratio of the rubber and the initial condensate of resorcinol/aldehyde is 9515 to 5/95. 12, resorcinol aldehyde initial condensate is 10
The aldehyde compound is 5 parts (,;゛ parts or more per 0 parts). The composition of the resorcinol/aldehyde initial condensate, the aldehyde compound, and the rubber swelling compound is (a) Rubbers 2 to 24 weights) i) H←) Resorcinol aldehyde initial condensate 1.5 to 24 weight ratio f→ Aldehyde Compound: 1.5 to 18 weight percent Rubber swelling compound: 95 to 40 weight percent Thermoplastic synthesis (A-miscellaneous treatment agent) according to claim 1. 14. Rubbers, resorcinol aldehyde-based compound ill
Claim 1: A product obtained by dissolving, dispersing or emulsifying a condensate, an aldehyde compound and a rubber swelling compound 1 in water.
Thermoplastic synthetic preparation I/1 preparation preparation as described in Section 1. 15. The thermoplastic synthetic fiber treatment agent according to claim 1, which is obtained by dissolving or dispersing rubber, a resorcinol/aldehyde-based initial condensate, and an aldehyde compound in a rubber swelling compound.