JP2693592B2 - Impregnating agent for glass fiber - Google Patents

Description

TECHNICAL FIELD The present invention relates to an impregnating agent for glass fibers and a glass fiber cord having a coating derived from the impregnating agent. More specifically, it has an impregnating agent for glass fibers and a film derived therefrom, which is suitable as an impregnating agent for glass fiber cords or the like used as a reinforcing material for products that receive both heat and external force during running, such as a timing belt. Regarding glass fiber cord.

<Prior Art> Conventionally, a glass fiber cord as a core wire (reinforcing material) for a timing belt has a resorcin formalin latex (RF) before being embedded in a base rubber of a timing belt.
L) Processing is usually done.

JP-A-50-3184 discloses that resorcinol-formaldehyde resin 2 to 10 parts by weight, butadiene-styrene-
An impregnating agent for glass fibers is disclosed which comprises 20-60 parts by weight of vinyl pyridine terpolymer, 15-40 parts by weight of carboxylated butadiene styrene resin and 3-30 parts by weight of an incompatible wax (eg paraffin wax).

Further, JP-B-47-37513, JP-A-53-70196 or JP-A-54-69192 discloses that adhesion with a base rubber, flexibility, heat resistance, water resistance, etc. should be improved. As such, an impregnating agent using a rubber component in the impregnating agent latex, such as natural rubber latex, neoprene latex, polybutadiene latex or polyacrylonitrile latex, has been proposed.

However, the treatment method using these impregnating agents has a drawback that it is difficult to obtain a rubber product excellent in heat resistance and bending fatigue due to insufficient heat resistance of the impregnating agent itself.

In recent years, when it is used as a reinforcing material for a timing belt due to a temperature rise in the vicinity of an automobile engine, this defect tends to be more serious, and no industrially satisfactory treating agent has been known.

<Problems to be Solved by the Invention> An object of the present invention is to provide a novel impregnating agent for glass fiber having a composition.

Another object of the present invention is to provide an impregnating agent for glass fiber having a novel composition, which contains an isobutylene-isoprene copolymer as one of rubber components as an impregnating agent.

Still another object of the present invention is to provide a glass fiber cord used in a product which is subjected to both heat and external force together, to give the product excellent heat resistance, flex fatigue resistance and flexibility. It is an object of the present invention to provide an impregnating agent for glass fiber cords.

Still other objects and advantages of the present invention will become apparent from the following description.

<Means for Solving the Problems> According to the present invention, the above objects and advantages of the present invention are represented by (1) resorcin-formaldehyde resin 2 to 15% by weight (2) butadiene-styrene It is achieved by an impregnating agent for glass fibers, which comprises 15 to 80% by weight of vinylpyridine-terpolymer and (3) 15 to 70% by weight of isobutylene-isoprene copolymer.

The impregnating agent of the present invention is characterized by containing the above-mentioned three components (1), (2) and (3) as essential components.

In a preferred embodiment of the impregnating agent of the present invention, the resorcinol-chlorophenol-formaldehyde resin (5) is used as a part of the resorcinol-formaldehyde resin of the above component (1) in order to further increase the adhesive force between the reinforcing material and the rubber. It is used instead. That is, (1) resorcinol-formaldehyde resin 1 to 15% by weight, more preferably 3 to 12% by weight, (5) resorcinol-chlorophenol-formaldehyde resin 0 to 14% by weight, preferably 1 to 14% by weight, Ingredient (1)
And the total amount of the above component (5) is 3 to 12% by weight. Similarly, dicarboxylated butadiene-styrene resin (4)
Is used in place of a part of the terpolymer of the above component (2). That is, (2) butadiene-styrene-vinylpyridine-terpolymer 2 to 80% by weight, more preferably
20 to 70% by weight, (4) dicarboxylated butadiene-styrene resin 0 to 72% by weight, more preferably 10 to 30% by weight, and the total of the above components (2) and (4) is 15 to 80% by weight. , And more preferably 40 to 70% by weight.

 Next, the present invention will be described more specifically.

As the resorcin-formalin resin of the component (1),
A resole-type water-soluble addition condensate obtained by reacting resorcin with formalin in the presence of an alkaline catalyst such as an alkali hydroxide or an amine can be preferably used. Particularly preferably, the reaction molar ratio of resorcin and formalin is 1: 1.
~ 3. For example, it is preferably used as an aqueous solution having a solid content of 5 to 10% by weight, for example, a solid content of 8% by weight.

As the butadiene-styrene-vinyl pyridine terpolymer of component (2) (hereinafter referred to as VP), a number of such VPs well known to those skilled in the art can be used. Such VPs are about 60-80% by weight of butadiene, 10-
Particularly suitable are those containing 20% by weight styrene, 10 to 20% by weight vinylpyridine. VPs are preferably used, for example, as a latex having a solid content of about 40% by weight.
Representative suitable VPs are Nipol 2518FS (trade name, manufactured by Zeon Corporation), JSR0650 (trade name, manufactured by Japan Synthetic Rubber Co., Ltd.),
And Pyratex J-1904 (trade name, manufactured by Sumitomo Nogatak Co., Ltd.).

The isobutylene-isoprene copolymer of the component (3) is
A product obtained by mixing isoprene with isoprene in a proportion of 1.5 to 4.5% and polymerized, and is suitably used, for example, as a latex having a solid content of about 40% by weight. Among them, a halogenated isobutylene-isoprene copolymer is particularly preferable. This halogenated isobutylene-isoprene copolymer is obtained by halogenating an isobutylene-isoprene copolymer with chlorine or bromine, and has a halogen content of 1.1 to 2.4% by weight. The halogenated isobutylene-isoprene copolymer is
For example, it is preferably used as a latex having a solid content of about 40% by weight. The component (3) can be obtained as a butyl rubber latex and a halogenated butyl rubber latex from Steel Manufacturing Co., Ltd.

The dicarboxylated butadiene-styrene resin as the component (4) is produced by copolymerizing butadiene and styrene in the presence of a small amount of an ethylenically unsaturated dicarboxylic acid such as maleic acid. As the dicarboxylated butadiene-styrene resin, those containing, for example, 20 to 80% by weight of butadiene, 5 to 70% by weight of styrene and 1 to 10% by weight of ethylenically unsaturated dicarboxylic acid are advantageously used.

The dicarboxylated butadiene-styrene resin as the component (4) has a solid content of, for example, 30 to 60% by weight, for example, a solid content of about 40.
It is preferably used as a latex of weight%. A typical suitable dicarboxylated butadiene-styrene resin is
Nipol 2570X5 (trade name, made by Zeon Corporation), JSR 066
8, JSR 0691 or JSR 0697 (trade name, manufactured by Japan Synthetic Rubber Co., Ltd.) and the like.

Component (5), resorcinol-chlorophenol-formaldehyde resin, is a water-soluble addition condensate obtained by reacting resorcinol, chlorophenol and formaldehyde in an aqueous solution, and is a trademark of VALCABOND E as an aqueous solution having a solid content of about 20% by weight. It is available from ICI under the name.

The latex as described above for components (2)-(5) may contain emulsifiers well known to those skilled in the art.

The glass fiber impregnating agent of the present invention comprises the above-mentioned component (1),
(2) and (3) or (4), based on the total weight of the solid contents of these three components, the component (1) is 2 to 15% by weight, the component (2) is 15 to 80% by weight, and the component It contains 15 to 70% by weight of (3) or component (4). If the amount of the component (1) is less than 2% by weight, the adhesion to the matrix rubber will be insufficient, and if it exceeds 15% by weight, the coating film of the impregnating agent will become hard and the bending fatigue property will decrease. When the amount of the component (2) is less than 15% by weight, the adhesion with the matrix rubber becomes insufficient as in the case of the component (1), and when it exceeds 80% by weight, the film of the impregnating agent becomes too soft to protect the glass fiber filament. The function to perform is not fully performed, and bending fatigue easily occurs. Ingredient (3)
Alternatively, if the amount of the component (4) is less than 15% by weight, the heat resistance, bending fatigue resistance and flexibility, which are the objects of the present invention, cannot be obtained.
If the content is more than wt%, the adhesion to the matrix rubber will be significantly reduced. The more preferable range of the above weight ratio is 5 to 10% by weight for the component (1) and for the component (2).
About 35-65% by weight and component (3) or (4)
20 to 50% by weight. Securing the above-mentioned weight ratio of the three components is important for achieving the above object of the present invention.

The preferred impregnating agent of the present invention containing the component (4) can replace 10 to 90%, preferably 20 to 50% of the weight ratio of the component (2) in the above weight range of the component (2). .

The preferred impregnating agent of the present invention containing the component (5) can replace 20 to 80%, preferably 20 to 50% of the weight ratio of the component (1) in the above weight range of the component (1). .

The impregnating agent for glass fibers of the present invention may contain a base such as ammonia for adjusting the pH, if necessary, and may further contain an antioxidant and the like. The impregnating agent for glass fibers of the present invention usually has a solid content of 15 to 30% by weight.
Can be suitably used as the aqueous latex.
If the concentration is too low, the adhesion to the glass fiber will be insufficient, and if the concentration is too high, the stability of the impregnating agent will deteriorate and gelation will tend to occur. The impregnating agent for glass fibers of the present invention is applied to the glass fiber strands by immersing the glass fiber strands therein, removing the excess, and then optionally drying. At that time, the glass fiber strand may or may not be provided with a sizing agent which is applied when the glass fiber is spun. The desired number of glass fiber strands are then collected and usually twisted to obtain glass fiber cords. The glass fiber cord is embedded in an unvulcanized rubber base material by a method known per se, and heat-vulcanized under pressure.

In the above method, the impregnating agent of the present invention is applied to the glass fiber cord in an amount generally corresponding to 10 to 30% by weight in terms of solid content to give a coating of the impregnating agent on the glass fiber cord.

The impregnant coating is usually heat treated to give a solid coating prior to being embedded in the rubber substrate. The solid coating preferably accounts for 10 to 30% by weight of the glass fiber in terms of solid content.

The glass fiber cord treated with the impregnating material of the present invention exhibits particularly excellent adhesion to various rubbers, especially chloroprene rubber. Rubber for automotive timing belts
Chloroprene rubber is common, but in recent years, with the rise in temperature near the engine of automobiles, heat-resistant rubbers such as chlorosulfonated polyethylene and hydrogenated nitrile rubber have been used as rubber for timing belts. Was. Although the adhesion to such heat-resistant rubber is sufficient, it is more preferable that the glass fiber cord provided with the impregnating composition of the present invention is further treated with a treatment liquid containing a halogen-containing polymer and an isocyanate compound.

Further, the obtained rubber products are excellent in heat resistance, bending fatigue resistance and flexibility. Therefore, the impregnating agent of the present invention can be very suitably used as an impregnating agent for glass fiber cords which are subjected to both heat and external force together, for example, used in timing belts.

 Hereinafter, the present invention will be described in more detail by way of examples.

Example 1 (1) A filament of non-alkali glass having a diameter of 9 μm was spun, and this was bundled with a sizing agent to obtain a glass strand of 33.7 tex, and three strands of this were combined to have the following composition: * Resorcin-formaldehyde resin Aqueous solution (Resorcin and formalin reaction molar ratio 1: 2, solid content 8% by weight) ...... 30 parts by weight * Butadiene-styrene-vinylpyridine terpolymer latex (about 70% by weight butadiene, 15% by weight styrene, Contains 15% by weight vinyl pyridine, solid content 40
% By weight, JSR 0650) ...... 45 parts by weight * Butyl rubber latex (isobutylene-isoprene copolymer, which is obtained by mixing isoprene with isoprene at a ratio of about 3% and polymerized, solid content 40% by weight). 20 parts by weight * 25% ammonia water ...... 1 part by weight * Water ...... 4 parts by weight Immerse and pass through the impregnating agent, and then the excess impregnating agent has a solid content of about 20% by weight with respect to the glass cord. The glass fiber bundle was impregnated with the impregnating agent, and the glass fiber bundle was heat treated at a temperature of about 250 ° C. for 2 minutes. The glass fiber bundle was then subjected to 2.1 twists in the Z direction (S direction) per inch.

(2) The 13 twisted glass fiber bundles were combined and twisted 2.1 times per inch in the S direction (Z direction) to obtain a cord of ECG150 3/13 2.1S (Z). This cord was cut to a length of 120 mm, and 20 cords were arranged in parallel on an unvulcanized chloroprene rubber sheet with the composition shown in Table 1 (total width).
This was pressed and vulcanized at 150 ° C. for 25 minutes from above and below.

After vulcanization, the tip of the cord and the tip of the rubber were firmly gripped and pulled in opposite directions, the cord was peeled from the rubber, and the adhesiveness was examined.

⊚: Rubber fracture, ∘: 3/4 or more rubber fracture, Δ: 1/2 or more rubber fracture, ×: No rubber fracture, and the adhesive strength is maximum at ⊚, and decreases in order of ○, Δ and ×.

In addition, nylon canvas is wrapped around a cylindrical drum, and the treated cord is spun on the S twisted product and the Z twisted product alternately, and the unvulcanized sheet of the rubber compound shown in Table 1 is laminated thereon, It was vulcanized under the conditions. Next, the cylindrical material was cut into an inch width to manufacture a timing belt. Attach the timing belt between two pulleys with a diameter of 40 mm,
After running for 1000 hours in an atmosphere of ° C, the belt was cut along the cord, the state of the cord on the cut surface was observed with an electron microscope, and the state of the impregnating agent (RFL) was judged according to the following criteria.

◎: unchanged, not running ○: RFL hardened and cohesive failure started, △: cohesive failure progressed and broken into stones, ×: cohesive failure further progressed and became sandy, and after running Of the belt was examined by the method described below.

That is, the present timing belt was attached to a tensile tester having pulleys on the upper and lower clamps, and the tensile strength at the time of breaking the timing belt was measured. Next, the following formula was used to determine the strength retention after the timing belt running test.

The results are shown in Table-3.

Example (2) * Resorcin-formaldehyde resin aqueous solution (solid content 8% by weight) ...... 30 parts by weight * Butadiene-styrene-vinylpyridine terpolymer latex (solid content 40% by weight, JSR 0650) ...... 30 parts by weight * Butyl rubber latex (solid content 40% by weight) ... 20 parts by weight * Dicarboxylated butadiene-styrene resin latex (containing 50% by weight butadiene, 45% by weight styrene and 5% by weight ethylenically unsaturated dicarboxylic acid,
(Solid content 40% by weight, Nipol 2570X5) …… 15 parts by weight
* 25% ammonia water ... 1 part by weight * Water ... 4 parts by weight was used and treated in the same manner as in Example (1). The results are shown in Table-3.

Example (3) * Resorcin-formaldehyde resin latex (solid content 8% by weight) 22.5 parts by weight * Resorcin-chlorophenol-formaldehyde resin aqueous solution (Valka Bond E solid content 20% by weight) 3 parts by weight * Butadiene -Styrene-vinyl pyridine terpolymer latex (solid content 40% by weight, JSR 0650) ...... 30 parts by weight * Butyl rubber latex (solid content 40% by weight) ...... 20 parts by weight * Dicarboxylated butadiene-styrene resin latex ( Solid content 40% by weight, Nipol 2570X5) ...... 15 parts by weight * 25% ammonia water ...... 1 part by weight * Water ...... 8.5 parts by weight The same treatment as in Example (1) was performed using an impregnating agent. Was done. The results are shown in Table-3.

Example (4) * Resorcin-formaldehyde resin aqueous solution (solid content 8% by weight) ...... 30 parts by weight * Butadiene-styrene-vinylpyridine terpolymer latex (solid content 40% by weight, JSR 0650) ...... 30 parts by weight * Chlorobutyl rubber latex (isobutylene-isoprene copolymer halogenated with chlorine, chlorine content 1.8% by weight, solid content 40% by weight) ...... 20 parts by weight * Dicarboxylated butadiene-styrene resin latex (Solid content 40% by weight, Nipol 2570X5) ...... 15 parts by weight * 25% ammonia water ...... 1 part by weight * Water ...... 4 parts by weight An impregnating agent consisting of 4 parts by weight was used in the same manner as in Example (1). Processed. The results are shown in Table-3.

Example (5) The ECG150 3/13 2.1S (Z) cord obtained in Example (2) was treated with a treating solution having the following composition, and the non-volatile content was 2.5 to 3.5.
The coating was performed so that the weight percentage became, and the organic solvent was evaporated and removed to obtain a glass fiber cord having a secondary coating layer.

* Chlorosulfonated polyethylene TS-340 (TOSO
Co., Ltd.) 5.25 parts by weight * Methylenebis (4-phenylisocyanate) ...... 4.5 parts by weight * P-dinitrosobenzene ...... 2.25 parts by weight * Carbon black ...... 3.0 parts by weight * Xylene 51.0 parts by weight * Trichloroethylene 34.0 Parts by weight This glass fiber cord was tested in the same manner as in Example (1) except that an unvulcanized hydrogenated nitrile rubber sheet having a rubber composition shown in Table 2 was used. However, the ambient temperature of the timing belt running test was 120 ° C. Table-Results
3 is shown.

Comparative Example (1) * Resorcin-formaldehyde resin aqueous solution (solid content 8% by weight) ...... 30 parts by weight * Butadiene-styrene-vinyl pyridine terpolymer latex (solid content 40% by weight, JSR 0650) ...... 30 parts by weight * Dicarboxylated butadiene-styrene resin latex (solid content 40% by weight, Nipol 2570X5) ...... 35 parts by weight * 25% ammonia water ...... 1 part by weight * Water ...... 4 parts by weight The treatment was carried out in the same manner as in Example (1). The results are shown in Table-3.

Comparative Example (2) * Resorcin-formaldehyde resin aqueous solution (solid content 8% by weight) ...... 30 parts by weight * Butyl rubber latex (solid content 40% by weight) ...... 65 parts by weight * 25% ammonia water ...... 1 part by weight * Water: Treatment was carried out in the same manner as in Example (1) using an impregnating agent consisting of 4 parts by weight. The results are shown in Table-3.

Comparative Example (3) Except that the glass fiber cord obtained in Comparative Example (1) was used, the operation was performed in exactly the same manner as in Example (5). The results are shown in Table-3.

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Claims (8)

(57) [Claims] 1. A solid content% by weight, (1) resorcin-formaldehyde resin 2 to 15% by weight, (2) butadiene-styrene-vinylpyridine-terpolymer 15 to 80% by weight, and (3) isobutylene-isoprene. An impregnating agent for glass fiber containing 15 to 70% by weight of a copolymer. (2) Resorcin-formaldehyde resin (1-15% by weight) (2) Butadiene-styrene-vinylpyridine-terpolymer (2-80% by weight) (3) Isobutylene-isoprene Polymer 15 to 70% by weight (4) Dicarboxylated butadiene-styrene resin 0 to 72% by weight, and (5) Resorcinol-chlorophenol-formaldehyde resin 0 to 14% by weight, provided that the above component (1) and the above component ( 5) total is 2-15
The glass fiber impregnating agent contains the component (2) and the component (4) in an amount of 15 to 80% by weight. 3. The impregnating agent according to claim 1 or 2, wherein the component (3) is a halogenated isobutylene-isoprene copolymer. 4. The impregnating agent according to claim 1, which is an aqueous latex mixture having a solid content of 15 to 30%. 5. The component (1) is 3 to 12%, the component (2) is 20 to 70%, and the component (3) is 20 to 40%.
The impregnating agent according to claim 1, which is 6. The component (1) is 3 to 12%, the component (2) is 20 to 70%, and the component (3) is 20 to 40%.
The above component (4) is 10 to 30%, the above component (5) is 0 to 5%, provided that the total of the above component (1) and the above component (5) is 3 to 12% by weight. And the total of the above component (2) and the above component (4) is 30 to 70% by weight,
The impregnating agent according to claim 2. 7. A glass fiber cord having a coating of the impregnating agent according to claim 1 or 2. 8. The glass fiber cord according to claim 7, wherein the solid film is coated in an amount of 10 to 30% by weight based on the solid content of the glass fiber.