JPS6249396B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a treatment agent for thermoplastic synthetic fibers,
The purpose of this invention is to provide an adhesive treatment agent which has an adhesive function when the fiber is formed into a composite with rubber, and which is extremely effective in streamlining the production process. Conventionally, thermoplastic synthetic fibers such as 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 membrane materials, etc., but especially in rubber products reinforced with fibers such as tires, the most important requirements for reinforcing fibers are Characteristics include adhesion between the cord and rubber after being embedded in a tire and undergoing a vulcanization process, strong retention, and 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. Regarding aliphatic polyamides, RFL (mainly composed of resorcinol, formalin, and rubber latex) is an adhesive commonly used in the industry. There are physical factors between RFL and aliphatic polyamide, such as the fact that their solubility parameters are almost the same, and active hydrogen atoms in the amide groups distributed in the main chain of aliphatic polyamide and the resorcinol/formalin low condensate. Chemical factors such as a strong primary bond between them and a strong hydrogen bond between the felt hydroxyl group of resorcinol and the amide bond, etc. Due to the above two factors, sufficient adhesive strength can be achieved with just one step of immersion treatment in RFL liquid. It makes it possible to perform. On the other hand, since polyester fiber has only a few terminal hydroxyl and carboxyl groups as functional groups in its molecular structure, its adhesion to rubber is not as good as that of aliphatic polyamide, and one-step treatment with RFL liquid is sufficient. It was difficult to provide sufficient adhesive strength. However, research has progressed rapidly over the past few years, and currently, as an industrially viable method, prior to processing the RFL liquid, an epoxy compound such as glycerol diglycidyl ether is used in the undrawn yarn stage. A two-stage treatment method in which a water-inert isocyanate compound or an ethylene urea compound is used as a pretreatment agent before dipping the RFL, or a two-step treatment method in which a water-inert isocyanate compound or an ethylene urea compound is used as a pretreatment agent before the RFL is immersed, or the RFL liquid contains these compounds. Practically satisfactory adhesion between polyester fibers and rubber can be obtained for the first time by methods such as mixing and applying compounds such as the above. Furthermore, aromatic polyamide fibers also have the disadvantage that their adhesion to rubber is inferior to that of aliphatic polyamide fibers, and extremely insufficient adhesion strength can be obtained when treated with a normal RFL liquid. Currently, the method using an epoxy compound similar to that used for treating polyester fibers, or the reaction of epichlorohydrin with an acidic polymer obtained by a polycondensation reaction of hydroxybenzoic acid, a halogenated phenol, and an aldehyde, is currently available. Methods such as pre-adhering a polymer have been adopted. As described above, through the accumulation of technology over many years, adhesive processing techniques have been developed that are tailored to the surface chemical structure of each fiber, but in all cases, the process involves the step of twisted cords or the weaving of cords into a sudare weave. At a later stage, the mainstream method is to apply an aqueous dispersion of RFL, which is an adhesive between rubber and fibers, by dipping, and is recognized as the most common and established adhesive technology. This RFL adhesive layer consists of a low condensate of resorcinol/formalin that contributes to bonding with fibers, and a latex component that has an affinity for rubber, forming an interpenetrating polymer network structure, and during rubber vulcanization, the rubber molecular chains and latex molecules form an interpenetrating polymer network structure. The sulfur compound blended into the unvulcanized rubber causes a crosslinking reaction between both double bond molecular chains in this entangled state. Through the above mechanism, sufficient adhesion can be imparted between the fiber and the rubber through the interposition of RFL. From the above effects, cord or cord fabric
The RFL liquid immersion process is widely and generally practiced as an important process indispensable for bonding. The inventors of the present invention have arrived at the present invention as a result of extensive research into an innovative adhesive technology that can omit such an RFL dipping step. That is, the present invention provides an adhesive comprising a rubber, a resorcinol aldehyde compound, and an aldehyde compound, and a rubber swelling ratio with respect to unvulcanized rubber.
A treatment agent for thermoplastic synthetic fibers whose main component is 20% or more of a rubber-swelling compound. In the present invention, thermoplastic synthetic fibers are fibers made of aliphatic polyamide, polyester, or aromatic polyamide. Examples of aliphatic polyamide fibers include common polyamides such as nylon 6, nylon 66, nylon 8, and nylon 11, synthetic fibers such as polyamides having hetero elements, and polyamides having ether bonds. 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 isophthalic acid, β-hydroxyethoxybenzoic acid, naphthalene dicarboxylic acid,
Difunctional acids such as diphenyldicarboxylic acid and sebacic acid, and aliphatic and alicyclic acids such as trimethylene glycol, neopentyl glycol, hexamethylene glycol, polyethylene glycol, 1,4-bishydroxyethoxybenzene, and bisphenol A. It also includes fibers made of polyester in which 60 mol% or more of the repeating units in the main chain have aromatic groups, each of which is replaced with one or more types of aromatic dihydroxy compounds. Furthermore, aromatic polyamide fibers include polymers in which repeating units are bonded with carboxylic acid amide groups (-NHCO-), and the imino groups and carbonyl groups are each bonded directly to the aromatic group;
That is, it is a fiber 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 is as follows:
Any of multifilament yarns, spun yarns, cords, or woven fabrics may be used, but cords or cord woven fabrics are most suitable for rubber reinforcement. According to the inventors' intensive research,
By attaching the above-mentioned adhesive and the above-mentioned processing agent containing a rubber-swelling compound to the above-mentioned thermoplastic synthetic fiber, the rubber-swelling compound also functions as a lubricant, so that it is resistant to yarn twisting and weaving processes. Appropriate friction surface properties can be imparted even when When conventional RFL liquid is applied to fibers and the fibers are wound, the adhesive between the fibers causes close contact between the fibers, which not only causes noticeable fuzz when unwinding, but also creates adhesive residue on the guide of the running yarn. High scum accumulates and the coefficient of friction is high, further promoting fuzz and loops. The adhesive is dissolved or emulsified in a rubber swelling compound that is advantageous for uniform adhesion to fibers, thereby promoting diffusion of the adhesive to the fiber surface and promoting uniform adhesion of the adhesive, Great for improving adhesion. A rubber swelling compound with a rubber swelling rate of 20% or more does not inhibit the strong adhesive 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. 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, there are safety and work environment issues. and economically advantageous. We have discovered that it has a special combined effect. In the present invention, when processing with a system in which each component described in detail later is dissolved, emulsified, or dispersed in water, the emulsifier to be used may be an anionic surfactant, a cationic surfactant, or a nonionic surfactant. But that's fine. In addition, in order to prevent precipitation and coagulation of emulsion particles during emulsification, desolvation, and concentration, and further improve the mechanical stability of emulsion particles,
A mixed emulsifier of an anionic surfactant and a nonionic surfactant or a cationic surfactant and a nonionic surfactant can also be used. 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. This higher fatty acid salt,
When using a rosin acid salt or a disproportionated rosin acid salt, these may be directly dissolved in water and used, or the mixture of the adhesive and rubber swelling agent compound may be added with a higher fatty acid, rosin acid or disproportionated rosin acid. may be dissolved, and an alkaline aqueous solution (for example, an aqueous sodium hydroxide solution, etc.) is used as a dispersion medium, and upon mixing and emulsification in the aqueous solution, a higher fatty acid salt, a rosinate salt, or a disproportionated rosinate salt may be produced and used. Examples of cationic surfactants include alkyldimethylbenzylammonium chloride, polyoxyethylenealkylamine, octadecyltrimethylammonium, octadecyltrimethylammonium chloride or octadecylamine acetate. Examples of nonionic surfactants include the general formula
R ₁ (-O-R ₂ -)nOH or

[Formula] (In the formula, R ₁ is an alkyl group having 8 to 24 carbon atoms, an alkenyl group, or an alkyl phenyl group having 8 to 16 carbon atoms in an alkyl group, R ₂
is an alkylene group having 2 to 5 carbon atoms, n is an integer of 3 to 50), such as polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether phosphate ester, Examples include oxyethylene propylene nonyl phenyl ether phosphate. The amount of emulsifier used is 0.5 to 15 parts by weight, preferably 1 to 8 parts by weight, based on 100 parts by weight of the mixture of adhesive and rubber swelling compound. The amount of emulsifier is 0.5
If it is less than 15 parts by weight, it will be difficult to form an emulsifier, and if it exceeds 15 parts by weight, the adhesiveness will be poor. In the present invention, as an emulsifying device for mixing and emulsifying each component, for example, a homo mixer,
There are homogenizers, disper mills, colloid mills, etc., and two types of emulsifying devices can be used in combination if necessary. If desired, water can be added in addition to the above organic solvent. in this case,
The concentration of 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. If the concentration is below the above range, the amount of adhesive effective for bonding will decrease, so the amount of non-aqueous adhesive solution applied must be increased accordingly, but this will also prevent contamination of the rollers and guides and twisting yarns. Scattering during the process becomes a problem. On the other hand, if the concentration exceeds the above range, the viscosity of the non-aqueous adhesive solution will increase, which will be 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 molecular weight and molecular structure of the rubber, and the above upper limit does not limit the present invention. Furthermore, the treatment 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 more organic solvents such as esters, ketones, alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, and chlorinated hydrocarbons that promote the dissolution of rubber. may be dissolved in a mixture of Examples of the rubber swelling compound used in the present invention include butyl stearate, an ester compound of a monohydric alcohol and a monobasic fatty acid,
These include octyl stearate, isooctyl stearate, octyl isostearate, oleyl laurate, lauryl oleate, oleyl oleate, isostearyl oleate, and ester compounds of monohydric alcohols and polybasic fatty acids of dibasicity or more. Dibasic fatty acids, which are one of the constituent components, include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, and cyclohexanedicarboxylic acid. , cycloaliphatic dicarboxylic acids such as cyclooctanedicarboxylic acid,
Examples include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid. For example, these esters include diisooctyl sebacate, diisostearyl sebacate, diisotridecyl adipate, dioctyl azelate, dioleyl adipate, monooleyl adipate, dioleyl phthalate, and the like. Furthermore, examples of esters of monohydric alcohols and tribasic fatty acids include trimellitic acid triolate and trimellitic acid dioleate. On the other hand, examples of ester compounds of polyhydric alcohols and monobasic fatty acids include neopentyl glycol diolate, ethylene glycol diolate, glycerin trioleate, trimethylolpropane trioleate, sorbitan trioleate, and pentaerythritol tetraoleate. In addition, as esters of polyhydric alcohols and polybasic fatty acids having dibasic or higher properties, ester compounds obtained by reacting ethylene glycol-trimellitic acid monoester with oleyl alcohol, and oleyl alcohol reacting with trimethylolpropane-trimellitic acid monoester Examples thereof include ester compounds. Other rubber-swelling compounds include (1) 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. Can be mentioned. (3) Examples of the mineral oil include 80-second mineral oil, 240-second mineral oil, and 500-second naphthenic mineral oil. For the rubber swelling compounds used in the present invention as exemplified above, esters, ketones, alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons that promote the dissolution of rubber are used. A small amount of one or a mixture of two or more organic solvents such as hydrogen and sulfur-containing hydrocarbons may be added. Furthermore, if desired, water can be added in addition to the above organic solvent. The "rubber swelling rate" defined in the present invention refers to the rate at which a 2 mm thick unvulcanized rubber with a natural rubber/styrene-butadiene copolymer (styrene rate = 25%) ratio of 70/30 is 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 added to the fibers in the present invention must exhibit a rubber swelling rate of 20% or more, but
All of the compounds exemplified above have a rubber swelling rate of 20% or more. Note that if the swelling rate 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 weight of the above rubber swelling compound is approximately 100~
Preferably 1000. When the molecular weight is less than 100, it tends to volatilize during heat setting, and the cord tends to become fluffy due to a reduced working environment and reduced lubricity during the twisting process. On the other hand, if it exceeds 1000, the molecular weight is too high, resulting in a high coefficient of friction, which worsens the twisting process, and also causes a rubber swelling rate of less than about 20%, resulting in a decrease in adhesive properties, which is undesirable. The reason why the compound used here must be rubber-swellable is that when the unvulcanized rubber is molded and vulcanized after applying the adhesive and heat-treating, the rubber-swelling compound has a rubber-swelling property. Promotes adhesion to the treated cord, expands the substantial adhesion area between the unvulcanized rubber and the cord, and entangles molecular chains between the unvulcanized rubber and the rubbers that are constituent components of the adhesive described below. This is because co-vulcanization greatly contributes to improving adhesion. Rubbers that are one component of the adhesive include, for example, natural rubber, cyclized rubber, natural rubber derivatives such as chlorinated rubber, chloroprene, styrene-butadiene rubber, styrene-butadiene-vinylpyridine terpolymer, urethane rubber, acrylic rubber, General rubbers such as polyisoprene, polybutadiene rubber, isobutylene rubber, isoprene-isobutylene rubber, acrylonitrile butadiene rubber, butadiene 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. It is one type or a mixture of two or more types. 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. Further, the resorcinol/aldehyde-based initial condensation product refers to an initial condensation reaction product in which a resorcinol and an aldehyde are reacted as main components, usually in the presence of an alkali catalyst or an acidic catalyst. The resorcinols mentioned here include 1,3 dioxybenzene, 1,2 dioxybenzene, and 1.4 dioxybenzene.
Dioxybenzene, resoacetophenone, α-resorcyl aldehyde, β-resorcyl aldehyde, γ-resorcyl aldehyde, α-resorcinic acid, β-resorcinic acid, γ-resorcinic acid, resorcin dialdehyde, resorcin 2,5 Contains polyhydric hydroxybenzenes such as dicarboxylic acids, pyrogallol, and gallic acid, and derivatives thereof. In addition, if an alkylresorcinol/aldehyde initial condensate in which at least a portion of the resorcinol is replaced with an alkylresorcinol is used, the lipophilicity increases and the compatibility with the rubber swelling compound improves, making it possible to increase the concentration of the condensate. Therefore, the increase in adhesive strength is even more remarkable. Also, at least one of the alkylresorcinols
The use of an initial condensate of cheloylresorcinol/aldehyde in which part of the product is replaced with cheloylresorcinol also provides good effects and is economically advantageous. Further, the alkylresorcinol constituting the adhesive refers to one or more alkyl substituted products of resorcinol. The number of carbon atoms in the alkyl group is preferably 1 to 4. Such alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, and tert-butyl. However, the object of the present invention can also be achieved with an alkylresorcinol having an alkyl group having 5 or more carbon atoms. Note that two or more types of the above-mentioned alkylresorcinols may be mixed together. Furthermore, the siel oil resorcinol used in the present invention is a phenol mixture mainly composed of alkylresorcinol obtained by dry distillation of shale, etc., and includes 5-methylresorcinol, 5-methylresorcinol,
Ethylresorcinol, 4,5-dimethylresorcinol, 2,5-dimethylresorcinol,
It consists of 2,4,5-trimethylresorcinol and the like, and if desired, shell oil resorcinol may be fractionally distilled to use only a specific fraction. The aldehydes constituting the condensate include formaldehyde, acetaldehyde, n-butyraldehyde, aldehyde compounds such as acroleinfurfural, paraformaldehyde, paraacetaldehyde, hexamethylenetetramine,
Refers to compounds that decompose to produce aldehydes, such as α-polyoxymethylene. In the reaction of resorcinols and aldehydes, if desired, phenol, alkylphenol, valachlorphenol, m-cresol, aniline, urea, catechol, hydroquinone, pyrocalol, tannic acid, gallic acid, phloroglycine, toluene, xylene, coumaron , cyclohexane, cashew oil, shellac, dammar,
Rosin or rosin derivatives, petroleum resins, amino resins, methanol, ethanol, n-butanol,
Polyhydric alcohols such as ethylene glycol, glycerinase and polyethylene glycol, co-condensing agents or modifiers such as furfuryl alcohol may be added. The amount of aldehyde to be reacted with resorcinols such as resorcinols, alkylresorcinols, or sieroil resorcinols is 1 mol or less, preferably 0.95 mol of aldehyde converted to formaldehyde, per 1 mol of resorcinol.
It is less than 1 mol, more preferably less than 0.80 mol.
A condensate in which the amount of aldehydes exceeds the above range becomes unstable and tends to gel even in rubber swelling compounds. Note that the pH of the resorcinol/aldehyde-based initial condensate is preferably acidic, that is, 7 or less.
In particular, the pH is 1.0 to 5.0, more preferably 1.5 to 4.0. Thereby, the solubility of the condensate in the rubber swelling compound can be improved. In particular, a high level of adhesive force can be obtained by improving the cohesive force 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 increasing the pH of the acetone solution of the resorcinol/aldehyde initial condensate to the acidic side, the compatibility of the condensate decreases. The present inventor has revealed that this method prevents the occurrence of oxidation and obtains high adhesive strength. In addition, the solubility of the resorcinol/aldehyde initial condensate in the rubber swelling compound is 3 g/
(100g of rubber swelling compound) or more preferably 5g
The amount is more preferably 10 g or more. If the solubility is less than 3 g, the formation of an interpenetrating network structure between the resorcinol-aldehyde-based initial condensate and the rubber will not be sufficiently achieved, and as a result, satisfactory adhesion between the fiber and the rubber will not be obtained. In particular, by at least a part of the resorcinols constituting the resorcinol/aldehyde initial condensate being alkylresorcinol, the solubility in the rubber swelling compound becomes sufficiently satisfactory. Furthermore, the aldehyde compounds constituting the adhesive other than the rubbers and the resorcinol/aldehyde-based initial condensate are the same as the above-mentioned aldehydes constituting the condensate. Here, the weight ratio of rubber and resorcinol/aldehyde-based initial condensate is 95/5 to/
95, preferably 70/30 to 10/90. If rubber is used in excess of the above range,
The adhesion at the interface between the adhesive and the fibers formed by heat treatment becomes insufficient, and generally speaking, as the dissolution ratio of rubber increases in the solvent, the viscosity of the non-aqueous adhesive solution increases and becomes more uniform. Adhesion becomes difficult to manage.
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. The amount of the aldehyde compound added is 5 parts by weight per 100 parts by weight of the condensate.
~1000 parts by weight is desirable. If the amount of the aldehyde compound added is less than the above range, the formation of an interpenetrating polymer network structure that incorporates rubber molecular chains by the condensate and the aldehyde compound will be insufficient, resulting in an unsatisfactory result. Adhesive strength cannot be obtained. On the other hand, if the amount of the aldehyde compound added exceeds the above range, the amount will be more than necessary 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 when formaldehyde or acetaldehyde is used, the odor of aldehyde increases, which is undesirable in terms of the working environment. 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 does not 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 aging of rubbers, antioxidants, preservatives, insect repellents, plasticizers,
A flame retardant or the like may be added as a third component. The mixing ratio of the rubber swelling compound and the adhesive (rubber, resorcinol/aldehyde initial condensate, and aldehyde compound) is 5/95 to 5/95 by weight.
The ratio is 95/5, preferably 25/75 to 90/10. If it exceeds 95/5, it is excellent in terms of emulsion stability, but on the other hand, the amount of adhesive effective for adhesion decreases, so the amount of the hydrogen composition (treatment agent) applied to the fibers is increased accordingly. There must be. This causes problems such as contamination of rollers and guides and scattering of agents during the yarn twisting process. 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, the object of the present invention can be achieved even below the lower limit of the above range 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 rubber, resorcinol/aldehyde-based initial condensate, and aldehyde compound attached to the fibers is 0.1 to 30% by weight, preferably 1 to 20% by weight. If the adhesion amount is less than about 0.1% by weight, the resulting reinforcing material will not have sufficient adhesion to rubber, while if it exceeds about 30% by weight, the adhesion to rubber will further improve, but not significantly.
Rather, it is 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 subcombination ratio of each component is adjusted within the following range. (a) Rubbers 2-24% (by weight) (b) Resorcinol/aldehyde-based initial condensate 1.5-18% (by weight) (c) Aldehyde compound 1.5-18% (by weight) (d) Rubber swelling compound 95-18% (by weight) 40 (weight)% [However, (a) + (b) + (c) + (d) = 100 (wt)%] In addition, when dissolving, emulsifying or dispersing these in water, the concentration, i.e. The above in an all-aqueous composition
The total weight of (a) to (d) is preferably 3 to 50% (by weight),
In particular, 10 to 35% (by weight) is optimal. Treatment agents including such adhesives can be applied to thermoplastic synthetic fibers by: applying them during the spinning process; applying them during or immediately after stretching and before winding; applying them to twisted cords or during the twisting process. , Applied during warping or weaving process, Applied to textiles. 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. In carrying out the present invention industrially, preferred application steps are ) to), with ) being particularly preferred. The fibers to which the treatment agent has been attached as described above are then heat-treated to bond the rubber and fibers to form a strong adhesive film on the fiber surface before vulcanization with the adhered rubber. I can do it. The heat treatment temperature is the same as that of conventional RFL liquid treatment.
It shows excellent adhesion even under the same conditions of 180 to 240℃, but
For example, the treatment temperature may be 100° C. or higher when the treatment agent is applied to the yarn after stretching and immediately before winding, and then the yarn is subjected to after-oiling to form a twisted cord and then heat-treated to form a sudare weave. The heat treatment temperature may be increased as the process speed increases, and the object of the present invention is thereby fully achieved, and the temperature range is not intended to limit the present invention. On the other hand, it is important to note that the double bonds of the rubbers contained in fibers coated with the treatment agent are destroyed by radiation such as ultraviolet rays, so during the process leading to vulcanization, these Consideration must be given to taking necessary measures to block the rays of light as much as possible. By vulcanizing the product thus obtained using a rubber vulcanization method commonly employed in the industry, excellent adhesive strength between synthetic fiber and rubber can be obtained. The adhesive in the treatment agent adheres to the fibers for the first time through heat treatment, forming the adhesive layer necessary for adhesion between the rubber and the fibers. A major feature of the present invention is that the fibers do not fall off even when rubbed by various guides, but rather spread, promoting the adhesive function on the fiber surface. On the other hand, if a conventional RFL liquid is applied in the above step instead of the treatment agent of the present invention, the RFL will solidify and the RFL dry film on the fiber will become sticky and solid, which will lead to the generation of guide scum. Otherwise, it causes significant roller staining, and furthermore, the coefficient of friction against metal increases significantly, and the yarns or cords stick together, making it impossible to unwind. 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. Thus, according to the present invention, even if the normally used RFL is not used,
Satisfactory adhesive strength can be obtained between the fibers and the rubber by performing, for example, after-oiling with an adhesive containing an oily rubber-swelling compound as a treatment agent in a step before the RFL treatment, and then going through a vulcanization step. The RFL liquid immersion process can be omitted, making it possible to streamline the equipment process. This has great advantages, and its industrial significance is extremely large. Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, in the middle part of the example, % is based on weight. 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 the rubber sheet under pressure.
Vulcanize at 150℃ for 30 minutes, then peel the three treated cords from the rubber sheet at a speed of 200mm/min.
The load detected at that time is expressed in kg/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, a stock solution obtained by mixing the adhesive solution shown in Table 1 with oleic acid (emulsion stabilizer)/polyoxyethylene-adducted sorbitan monooleate (emulsifier) in a ratio of 2/0.5 was added to rosin. The mixture was gradually added to an aqueous solution of caustic soda containing potassium acid while stirring with a homomixer to form an emulsion with a concentration of 15%. The emulsion obtained has a pH=
10 hot. On the other hand, nylon 6 fiber yarn was melt-spun from a nozzle with a hole diameter of 0.3 mm and a number of holes of 204.
Before winding onto a bobbin at a speed of 300 m/min, a specific rubber swelling compound dioleyl adipate was deposited (deposition amount = 1.2%) by a conventional roller oiling method. The undrawn yarn thus obtained was hot-stretched at 190°C using a hot-stretching machine, and the obtained
Before winding up the drawn yarn of 1260de/204fil, a roller is oiled with an adhesive emulsion having the composition shown in Table 1 so that the adhesion amount as an adhesive solution (non-aqueous component) becomes the value shown in Table 1. It was attached by law. The resorcinol/aldehyde initial condensate used here is shown in Table 2. The drawn yarn thus obtained was first drawn 40 times/10 times.
The first twist of 10 cm was applied, and then the second strand was twisted 40 times/10 cm to make a tire cord. The compositions of the initial condensates A-H of resorcinols and aldehydes used at this time 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 RFL liquid and the drying process. The treatment code is natural rubber and styrene.
Embedded in unvulcanized rubber for tire carcass mixed with butadiene copolymer rubber, 150℃, 30
After vulcanization and adhesion for minutes, the CRA adhesive strength and bending hardness of the obtained product were measured. As shown in Table 1, the level of adhesion for the present invention is significantly superior in terms of uniformity of the adhesive layer compared to that obtained with conventional RFL liquid processing. Furthermore, data on adhesive strength, rubber adhesion, and bending hardness were obtained that showed no color loss compared to conventional methods, and as a result of repeated actual vehicle driving tests, physical properties and other properties were improved compared to conventional RFL liquid treatment. It was proven that there were no particular problems in terms of durability and performance. However, at levels exceeding the range shown in the present invention, such as Experiment No. 9 (low amount of aldehydes) and Experiment No. 10 (low amount of resorcinol/aldehyde-based initial condensate added), the adhesive strength is significantly reduced. shows a low value. This is interesting data in the sense that it proves the adhesion mechanism mentioned above.

【table】

【table】

【table】

【table】

[Table] Example 2 Nylon 6 fiber yarn, which was melt-spun into yarn from a nozzle with a hole diameter of 0.3 mm and a number of holes of 204, was spun into yarn at a speed of 300 m/mm by a normal roller oiling method before being wound onto a bobbin. Specific rubber swelling compounds shown in Table 1 were deposited. The undrawn yarn thus obtained was hot-stretched at 190°C using a hot-stretching machine, and the obtained
Apply the adhesive solution shown in Table 3 to the drawn yarn of 1260de/204fil in an amount of 0.1 to 30% by weight before winding it up.
It was attached by roller oiling method so that The drawn yarn thus obtained was first drawn 40 times/
A 10cm first twist was applied, and then two strands were twisted 40 times/10cm to make a tire cord. The compositions of the initial condensates A-H of resorcinols and aldehydes used at this time 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 RFL liquid and the drying process. The treatment code is natural rubber and styrene.
Embedded in unvulcanized rubber for tire carcass mixed with butadiene copolymer rubber, 150℃, 30
After vulcanization and adhesion for minutes, the CRA adhesive strength and bending hardness of the obtained product were measured. As shown in Table 3, the level of adhesion associated with the present invention is significantly superior in terms of uniformity of the adhesive layer compared to that obtained by conventional RFL liquid processing; In terms of force, rubber adhesion, and bending hardness, data with no color loss was obtained compared to conventional ones.Furthermore, as a result of repeated vehicle driving tests, physical properties and other durability performance were improved compared to conventional RFL liquid treatment. It has been proven that there are no particular problems. However, levels below the range shown in the present invention, such as No. 19 (low aldehydes) and No.
At a level of 20 (low amount of resorcinol/aldehyde yarn initial condensate added), the adhesive strength shows a significantly low value. This is interesting data in the sense that it proves the adhesion mechanism mentioned above.

【table】

【table】

Claims (1)

[Scope of Claims] 1. An adhesive consisting of rubber, a resorcinol/aldehyde-based initial condensate, and an aldehyde compound, and a rubber swelling compound having a rubber swelling ratio of 20% or more relative to unvulcanized rubber as the main components. Characteristic treatment agent for thermoplastic synthetic fibers. 2. The processing agent for thermoplastic synthetic fibers according to claim 1, wherein the thermoplastic synthetic fibers are aliphatic polyamide, polyester, or aromatic polyamide. 3 Rubbers include natural rubber, cyclized rubber, chlorinated rubber,
Chloroprene, styrene-butadiene rubber, styrene-butadiene vinylpyridine terpolymer, urethane rubber, acrylic rubber, polyisoprene, polybutadiene rubber, isobutylene rubber, isoprene-isobutylene rubber, acrylonitrile-butadiene rubber, butadiene low polymer, styrene-butadiene low polymer, styrene-butadiene Consisting of a vinylpyridine low polymer, a low copolymer of α,β-ethylenically unsaturated dicarboxylic acid and butadiene, and a rubber having a carboxyl group, hydroxyl group, amino group, amide group, methylol group, or epoxy group in the rubber molecule. The treatment agent for thermoplastic synthetic fibers according to claim 1, which is at least one selected from the group consisting of: 4 Resorcinol/aldehyde-based initial condensate
The treatment agent for thermoplastic synthetic fibers according to claim 1, which has a pH of 7 or less. 5 Resorcinol/aldehyde-based initial condensate
The treatment agent for thermoplastic synthetic fibers according to claim 4, which has a pH of 1.0 to 5.0. 6 Claim 1, wherein at least a portion of the resorcinols constituting the resorcinol/aldehyde-based initial condensate is an alkylresorcinol.
Thermoplastic synthetic fiber treatment agent as described in . 7. The processing agent for thermoplastic synthetic fibers according to claim 6, wherein at least a part of the alkylresorcinol is sierre oil resorcinol. 8 In the resorcinol/aldehyde-based initial condensate, resorcinols constituting the condensate 1
The treatment agent for thermoplastic synthetic fibers according to claim 1, 6, or 7, wherein the amount of aldehydes is 1 mole or less per mole. 9 The aldehydes and/or aldehyde compounds constituting the resorcinol/aldehyde-based initial condensate are formaldehyde, acetaldehyde, n
- The treatment agent for thermoplastic synthetic fibers according to claim 1, which is at least one member selected from the group of butyraldehyde, acrolein, furfural, paraformaldehyde, paraacetaldehyde, hexamethylenetetramine, and α-polyoxymethylene. . 10 The rubber swelling compound is a monobasic or dibasic or more polybasic fatty acid with a molecular weight of 100 to 1000 and 1
The treatment agent for thermoplastic synthetic fibers according to claim 1, which is an ester with a polyhydric alcohol having a valence or a valence of two or more. 11. The processing agent for thermoplastic synthetic fibers according to claim 1, wherein the weight ratio of the rubber and the resorcinol aldehyde-based initial condensate is from 95/5 to 5/95. 12. The treatment agent for thermoplastic synthetic fibers according to claim 1, wherein the aldehyde compound is present in an amount of 5 parts by weight or more based on 100 parts by weight of the resorcinol/aldehyde-based initial condensate. 13 The composition of rubbers, resorcinol/aldehyde-based initial condensates, aldehyde compounds, and rubber swelling compounds is (a) Rubbers 2 to 24% by weight (b) Resorcinol/aldehyde initial condensates
1.5 to 24% by weight (iii) aldehyde compound 1.5 to 18% by weight (d) rubber swelling compound 95 to 40% by weight The processing agent for thermoplastic synthetic fibers according to claim 1. 14. The processing agent for thermoplastic synthetic fibers according to claim 1, which is obtained by dissolving, dispersing, or emulsifying rubbers, resorcinol/aldehyde-based initial condensates, aldehyde compounds, and rubber swelling compounds in water. 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.