JPH0216769B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a rubber reinforcing material that has an adhesive function as a composite with rubber and is extremely effective in streamlining production processes. 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, it is mainly used for reinforcing rubber products such as tires, Kumbeyer belts, hoses, and rubberized composite membrane materials.In particular, for products such as tires, the most important properties required of the fiber side are These are the adhesion, strong retention, and dimensional stability of the cord and rubber after being embedded in a tire and undergoing a vulcanization process. Regarding adhesiveness, various efforts have been made depending on the physicochemical surface characteristics of each fiber material. For aliphatic polyamides, RFL (Resorcinol,
The main ingredients are formalin and rubber latex).
The relationship between this RFL and the aliphatic polyamide is (i) the physical factor that their solubility parameters are almost the same, (ii) the active hydrogen atoms in the amide groups distributed in the main chain of the aliphatic polyamide, and the presence of resorcinol. Due to two factors, such as the primary bond with the formalin low condensate and the strong hydrogen bond between the phenolic hydroxyl group of resircin and the amide bond, it can be cured by just one step of immersion in RFL solution. It has become possible to exhibit sufficient adhesive strength. On the other hand, polyester fibers contain only a small number of 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, and it cannot be treated in one step with RFL liquid. It was difficult to provide sufficient adhesive force. However, research on this topic has progressed rapidly over the past few years. Currently, as an industrially practicable method, prior to processing the above RFL liquid,
A method of treating the undrawn yarn with a pretreatment agent containing an epoxy compound such as glycerol diglycidyl ether, or treatment with a water-inert isocyanate compound or an ethylene urea compound as a pretreatment agent before dipping and attaching RFL2. There are step-treatment methods and methods of adding these compounds by mixing them into the RFL liquid, and only by these methods can a practically satisfactory adhesion between polyester fiber and rubber be obtained. . Furthermore, aromatic polyamide fibers also have inferior adhesion to rubber compared to aliphatic polyamide fibers, and
RFL liquid treatment has the disadvantage that extremely insufficient adhesive strength can be obtained. 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. Means such as pre-adhering a polymer to be used is provided. As mentioned above, through many years of technological accumulation, adhesive processing techniques have been established that suit the surface chemical structure of each fiber, but in both cases, the rubber and fiber The mainstream method is to apply an aqueous dispersion of RFL, which is an adhesive, by immersion, and this is recognized as the most common and established adhesive technology. This RFL
In the adhesive layer, a low condensate of resorcinol/formalin that contributes to bonding with fibers and a latex component with rubber affinity form an interpenetrating polymer network structure, and during rubber vulcanization, the rubber molecular chains and the latex molecular chains are bonded together. are intertwined with each other, 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 this mechanism, sufficient adhesion can be imparted between the fiber and rubber through the intervention of RFL. Due to the above effects, the RFL liquid immersion process is an indispensable and important process commonly employed in this industry. The present inventors have arrived at the present invention as a result of intensive research aimed at providing an epoch-making adhesive technology that can omit the RFL dipping step as described above. That is, the present invention provides (A) on the surface of a thermoplastic synthetic fiber to which a rubber swelling compound having a rubber swelling rate of 20% or more with respect to unvulcanized rubber used as an adherend is adhered in advance; (B) rubber. , a rubber reinforcing material characterized in that an adhesive comprising a resorcinol/aldehyde-based initial condensate and an aldehyde compound in a specific proportion is attached in a state dissolved or dispersed in the 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, i.e., It is a fiber made of a polymer obtained using aromatic dicarboxylic acid, aromatic diamine and/or aromatic aminocarboxylic acid as starting materials. The fiber form of such thermoplastic synthetic fibers is as follows:
It may be multifilament yarn, spun yarn, cord, or woven fabric. According to the inventors' intensive research,
By attaching a rubber swelling compound to the above-mentioned thermoplastic synthetic fiber in advance, the compound can (1) double as a lubricant and can therefore be used as a spinning oil in the yarn manufacturing process; can. Furthermore, appropriate frictional surface characteristics can be imparted to yarn twisting and weaving processes. (2) Furthermore, an adhesive consisting of a rubber, a resorcinol/aldehyde-based initial condensate, and an aldehyde compound is dissolved or dispersed in a rubber swelling compound and then adhered to the rubber/
The rubber swelling compound does not inhibit the strong adhesion function of the fiber interface. We have discovered that it has a special effect. When an oil agent containing a surfactant, which is commonly used in the conventional art, is applied to the fibers instead of the rubber swelling compound, the adhesive function of the adhesive is expressed, but
The adhesion level is inferior to the treated yarn according to the present invention. Examples of rubber swelling compounds used in the present invention include butyl stearate, ester compounds of monohydric alcohols and monobasic fatty acids,
These include octyl stearate, isooctyl stearate, octyl isostearate, oleyl laurate, lauryl oleate, oleyl oleate, isostearyloleate, and ester compounds of monohydric alcohols and polybasic fatty acids of dibasicity or more. Dichlorinated fatty acids, which are one of the constituents, include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid,
Examples include aliphatic dicarboxylic acids such as sebacic acid and maleic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and cyclooctanedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. For example, these esters include diisooctyl sepacate,
These include diisostearyl sepacate, diisotridecyl adipate, dioctyl azelate, dioleyl adipate, monooleyl adipate, dieleyl phthalate, and the like. Further monohydric alcohol and 3
Examples of esters of basic fatty acids include trimellitic acid triolate and trimellitic acid dioleate. On the other hand, ester compounds of polyhydric alcohols and monobasic fatty acids include neopentyl glycol diolate, ethylene glycol diolate, glycerin trioleate, trimethylolpropane trioleate, sorbitan trioleate, pentaerythritol tetraolate, etc. Examples of esters of alcohols and polybasic fatty acids having dibasic or higher polybasic fatty acids include ester compounds obtained by reacting oleyl alcohol with ethylene glycol trimellitate monoester, and ester compounds obtained by reacting oleyl alcohol with trimethylolpropane trimellitate monoester. can be mentioned. 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. In addition, the "rubber swelling rate" defined in the present invention refers to unvulcanized rubber with a 2 mm thick natural rubber/styrene-butadiene copolymer (styrene-butadiene copolymer (styrene rate = 25%) ratio of 70/30) heated to 80℃. It was determined by the weight increase rate after being immersed in a 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 200~
Preferably 1000. If it is less than 200, for example, when used in place of a spinning oil, it will easily volatilize on the heating roller or heater plate during the drawing process, have insufficient lubricating ability and tend to generate fluff during the drawing process, and may easily cause fuzz during the twisting process. Fuzz is likely to occur on the cord. On the other hand, if it exceeds about 1000, the molecular weight will be too high and the coefficient of friction will increase, making the twisting process worse.
Furthermore, the rubber swelling rate tends to be less than about 20%. In addition, the amount of the rubber swelling compound attached to the fiber is 0.1
-10% by weight, preferably 0.5-4.0% by weight.
If the adhesion amount is less than 0.1% by weight, the production yield in the drawing process and yarn twisting process will be poor. Meanwhile, 10% by weight
Exceeding this is not preferable because the manufacturing cost increases. In order to attach the rubber swelling compound to fibers, it is used as it is without being diluted, or it is diluted with an organic solvent that is compatible with the compound, but in order to attach it to fibers, (a) spinning step; It is applied as a spinning oil to undrawn yarn. (b) Apply after removing adhesion-inhibiting components in the oil agent that had previously adhered to the drawn thread, the yarn just after being drawn, the twisted cord, or the fabric with water or an organic solvent. Methods such as the following can be adopted. Note that the rubber swelling compound needs to be applied in a step before applying the adhesive described below. The reason for this is that by applying it in advance before the adhesive treatment, it is possible to promote wetting (uniform adhesion effect) and adsorption effect of the adhesive dissolved or dispersed in the rubber swelling compound to the surface of the yarn. . Also,
The reason why the compound applied 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 becomes unvulcanized. 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. In the present invention, as mentioned above, a rubber swelling compound is attached to the surface of the thermoplastic synthetic fiber in advance,
Next, an adhesive composition in which an adhesive is dissolved or dispersed in a rubber swelling compound is applied. Examples of rubbers that are one component of the adhesive include natural rubber, cyclized rubber, natural rubber derivatives such as chlorinated rubber, chloroprene, styrene-butadiene rubber, styrene-butadiene-vinylpyridine terpolymer, urethane rubber, and acrylic rubber. Common rubbers such as polyisoprene, polybutadiene rubber, isobutylene rubber, isoprene-isobutylene rubber, acrylonitrile butadiene rubber, butane diene low polymer, styrene/butadiene/vinylpyridine low polymer are α,β-ethylenically unsaturated dicarboxylic acids. One or two types of rubbers that are liquid at room temperature, such as low copolymers of 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 a mixture of the above. In addition, since the solubility parameter value differs depending on the rubber composition,
It is necessary to select and use an appropriate rubber swelling agent. 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, 1,
4 dioxybenzene, resoacetophenone, α-
Polyhydric compounds such as resorcyl aldehyde, β-resorcyl aldehyde, γ-resorcyl aldehyde, α-resorcinic acid, β-resorcinic acid, γ-resorcinic acid, resorcin dialdehyde, resorcin 2,5 dicarboxylic acid, pyrogallol, gallic acid, etc. Contains hydroxylbenzene and its derivatives. Note that when an alkylresorcinol/aldehyde initial condensate in which at least a part of the resorcinol is replaced with an alkylresorcinol is used, the lipophilicity increases and the compatibility with the rubber swelling compound improves, so the concentration of the condensate can be increased. 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, which is another component constituting the adhesive, refers to one or more alkyl substituted products of resorcinol. The alkyl group preferably has 1 to 4 carbon atoms. 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 alkyresorcinol 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. The shale oil resorcinol used in the present invention is a phenol mixture mainly composed of alkyl resorcinol obtained by dry distillation of oil shale, and includes 5-methylresorcinol, 5-
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, parachlorophenol, m-cresol, aniline, urea, catechol, hydroquinone, pyrogallol, 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, glycerin 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-swellable products. 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 blending ratio of rubber and resorcinol/aldehyde-based initial condensate is 95/5 to 95/5 by weight.
5/95, preferably 70/30 to 10/90. If the amount of rubber exceeds the above range, the adhesion between the adhesive and the fibers formed by heat treatment will be insufficient, and the dissolution rate of the rubber in the solvent will generally increase. As the adhesive increases, the viscosity of the non-large adhesive solution increases, making it difficult to control 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. The amount of the aldehyde compound added is 5 parts by weight per 100 parts by weight of the condensate.
~100 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 required to form the network structure will be greater than the amount necessary, and the negative aspects of shortening the pot life of the non-aqueous adhesive solution 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, even if the upper limit of the above range is exceeded, the object of the present invention can be sufficiently achieved, and the upper limit does not limit the present invention.
In addition to rubbers, the above-mentioned condensates, and aldehyde compounds, the adhesive 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 amount of the adhesive composition containing rubber, resorcinol/aldehyde-based initial condensate, and aldehyde compound adhered to the fibers is 0.1 to 30% by weight, preferably 1 to 20% by weight. The amount of adhesion is approx.
If it is less than 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 and is rather uneconomical. Incidentally, it is sufficient if the amount of the adhesive component excluding the rubber swelling compound serving as a solvent or dispersant is 0.01 to 5% by weight based on the fiber. In order to attach the adhesive to the surface of the thermoplastic synthetic fiber, the adhesive is dissolved or dispersed in a rubber swelling compound and then applied. The rubber swelling compound is a compound similar to the rubber swelling compound attached to the thermoplastic synthetic fiber in advance, but it also contains esters, ketones, alcohols, aromatic hydrocarbons, etc. that promote the dissolution of rubber. It may be dissolved in one or a mixture of two or more organic solvents such as aliphatic hydrocarbons and chlorinated hydrocarbons. If desired, it is also possible to use a compound with a molecular weight lower than that of the rubber swelling compound shown above. Furthermore, if desired, water can be added in addition to the above organic solvent. 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 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. The adhesive solution can be applied to thermoplastic synthetic fibers by (i) applying it during the spinning process, (ii) applying it to the drawn yarn or immediately after drawing before winding up, or (iii) applying it to the twisted cord or during the twisting process. (iv) Applied during the warping or weaving process; (v) Applied to the fabric; It can be applied in any one or more of the above steps. In the case of aliphatic polyamide fibers, the adhesive solution of the present invention may be directly applied by the above method, but in the case of polyester fibers or aromatic polyamide fibers, for example, before applying the adhesive solution, The effects of the present invention can be more effectively exhibited by treating the fiber surface with a pretreatment agent mainly containing an epoxy compound such as glycerol diglycidyl ether at the drawing stage to activate the fiber surface in advance. The most preferred application steps are (i) to (iii). The fibers to which the adhesive has been attached as described above are then heat-treated to bond the rubber and fibers and form a strong adhesive film on the fiber surface before vulcanization with the adhered rubber. I can do it. Although the heat treatment temperature is the same as the conventional heat treatment condition of 180 to 240℃ after RFL liquid treatment, it shows excellent adhesion. When heat-treating the cord, which is made into a twisted cord and then made into a sudare weave, the treatment temperature 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 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 in the rubber contained in fibers coated with the above-mentioned adhesive will be destroyed by radiation such as ultraviolet rays, so these should not be used during the process leading to vulcanization. Care must be taken to take necessary measures to block the light rays 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. Adhesives only adhere to the fibers through heat treatment, forming the adhesive layer necessary for adhesion between the rubber and the fibers. Until then, the adhesive is oily and has the function of a lubricant. However, a major feature of the present invention is that even when the fibers are rubbed by various guides, they do not fall off, but rather spread, promoting the adhesive function on the fiber surface. On the other hand, if a conventional RFL liquid containing water is applied in the above process instead of the adhesive of the present invention,
RFL solidifies and the RFL dry film on the fiber becomes sticky, which causes guide scum to occur or significant roller fouling, and the coefficient of friction against metal to increase significantly. Close stacking occurs, making it impossible to unwrap. 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, (i) an oily adhesive solution can be subjected to, for example, after-oiling and a vulcanization process in a step before RFL treatment, without using RFL, which is commonly used in the industry; (ii) The RFL liquid immersion process and drying process can be omitted, streamlining the equipment process and eliminating drying energy costs. This is a great advantage, 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: Before winding the nylon 6 fiber yarn melt-spun into yarn from a nozzle with a hole diameter of 0.3 mm and a hole number of 204 into a yarn at a speed of 300 m/min with a bobbin, the yarns shown in Table 1 were prepared using a normal roller oiling method. A specific rubber-swelling compound was 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 2 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/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
The adhesive was vulcanized for minutes, and the CRA adhesive strength and bending hardness of the resulting 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 processing. Furthermore, in terms of adhesion, rubber adhesion, and bending hardness, data with no color buildup was obtained compared to conventional products, and as a result of repeated actual vehicle driving tests,
It has been proven that there are no particular problems with physical properties or other durability compared to conventional RFL liquid treatment. However, if the level exceeds the range shown in the present invention, for example, Experiment No. 9 (low amount of aldehydes) and Experiment No. 10 (low amount of resorcinol/aldehyde-based initial condensate added), the adhesive strength will be large. shows a low value. This is interesting data in the sense that it proves the adhesion mechanism mentioned above.

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Claims (1)

[Scope of Claims] 1. Rubber, resorcinol, An adhesive comprising an aldehyde-based initial condensate and an aldehyde compound, wherein the weight ratio of the rubber and the resorcinol-aldehyde-based initial condensate is 95/5 to 5/95, and 100 parts by weight of the resorcinol-aldehyde-based initial condensate. 1. A rubber reinforcing material comprising a composition in which an adhesive containing 5 parts by weight or more of an aldehyde compound is dissolved or dispersed in a rubber swelling compound. 2. The rubber reinforcing material according to claim 1, wherein the amount of the rubber swelling compound that is attached to the thermoplastic synthetic fibers in advance is 0.1 to 10% by weight based on the thermoplastic synthetic fibers. 3. The rubber reinforcing material according to claim 1, wherein the thermoplastic synthetic fiber is aliphatic polyamide, polyester, or aromatic polyamide. 4. The rubber reinforcing material according to claim 1, wherein the rubber swelling compound is an ester of a monobasic or polybasic fatty acid with a molecular weight of 200 to 1000 and a monohydric or polyhydric alcohol. 5 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, Butane diene low polymer, styrene butadiene low polymer, styrene/butadiene vinylpyridine low polymer, low copolymer of α, β-ethylenically unsaturated dicarboxylic acid and butadiene, and carboxyl, hydroxyl, and amino groups in the rubber molecule. The rubber reinforcing material according to claim 1, which is at least one selected from the group consisting of rubbers having , amide groups, methylol groups, or epoxy groups. 6 Claim 1, wherein at least a portion of the resorcinols constituting the resorcinol/aldehyde-based initial condensate is an alkylresorcinol.
Rubber reinforcing material as described in section. 7. The rubber reinforcing material according to claim 6, wherein at least a part of the alkylresorcinol is shell oil resorcinol. 8 In the resorcinol/aldehyde-based initial condensate, resorcinols constituting the condensate 1
The rubber reinforcing material 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 rubber reinforcing material according to claim 1, which is at least one member selected from the group of -butyraltehyde, acrolein, furfural, paraformaldehyde, paraacetaldehyde, hexamethylenetetramine, and α-polyoxymethylene. 10 The adhesive composition is applied to thermoplastic synthetic fibers.
The rubber reinforcing material according to claim 1, wherein 0.1 to 30% by weight is attached.