ADHESIVE COMPOSITION, ORGANIC FIBER AND TREATING METHOD THEREOF, AND METHOD OF FORMING ORGANIC FIBER/RUBBER COMPOSITE

Abstract

The invention provides an adhesive composition. The adhesive composition includes a halohydrin compound, a blocked isocyanate compound and latex, in which the adhesive composition does not include resorcinol, formaldehyde and epoxy compound. The invention also provides a method for treating organic fiber. The method includes impregnating an organic fiber or a fabric with the abovementioned adhesive composition; and drying the organic fiber or the fabric.

Claims

1. An adhesive composition for bonding an organic fiber to rubber, comprising 10.0 to 30.0 parts of weight of a halohydrin compound, 10.0 to 30.0 parts of weight of a blocked isocyanate compound and 80.0 to 240.0 parts of weight of latex, wherein the adhesive composition does not include resorcinol, formaldehyde, and epoxy compound.

2. The adhesive composition of claim 1, wherein the halohydrin compound is a chlorohydrin compound.

3. The adhesive composition of claim 1, wherein the halohydrin compound is halogen-substituted sorbitol, halogen-substituted glycerol, or a combination thereof.

4. The adhesive composition of claim 3, wherein the halogen-substituted sorbitol is chloro-substituted sorbitol.

5. The adhesive composition of claim 3, wherein the halogen-substituted glycerol is chloro-substituted glycerol.

6. The adhesive composition of claim 1, wherein the latex is a copolymer of butadiene and vinyl pyridine.

7. A method for treating organic fiber, comprising: impregnating an organic fiber or a fabric with the adhesive composition of claim 1; and drying the organic fiber or the fabric.

8. The method of claim 7, wherein the organic fiber is selected from the group consisting of polyester fiber, nylon fiber, aromatic polyamide fiber, or a combination thereof.

9. The method of claim 8, wherein the polyester fiber is polyethylene terephthalate fiber.

10. The method of claim 8, wherein the nylon fiber is nylon 66 fiber.

11. The method of claim 8, wherein the aromatic polyamide fiber is poly(m-phenylene isophthalamide) fiber.

12. An organic fiber, wherein the organic fiber is prepared by the method of claim 7.

13. The organic fiber of claim 12, wherein the organic fiber is used in tires, hoses, conveyor belts or belts.

14. A method of forming organic fiber/rubber composite, comprising: providing an impregnated organic fiber cord fabric having the adhesive composition of claim 1 thereon; and adhering the impregnated organic fiber cord fabric to rubber.

Description

EXAMPLE 1-1

[0039] 91.0 g (0.5 mol) of sorbitol (available from Alfa-Aesar Co.) was dispersed in 100 g of toluene (available from Sigma-Aldrich Co.) with the addition of 1.42 g (0.01 mol) of boron trifluoride diethyl etherate (available from Sigma-Aldrich Co.). Next, 109.20 g (1.18 mol) of epichlorohydrin (available from Alfa-Aesar Co.) was slowly added and reacted at a constant temperature of 60 C. After the complete reaction of epichlorohydrin, which was tracked by JIS method K7236, toluene was removed by concentration under reduced pressure to obtain chloro-substituted sorbitol.

EXAMPLE 1-2

[0040] 46.05 g (0.5 mol) of glycerol (available from Alfa-Aesar Co.) was added to 1.42g (0.01 mol) of boron trifluoride diethyl etherate (available from Sigma-Aldrich Co.). Next, 109.20 g (1.18 mol) of epichlorohydrin (available from Alfa-Aesar Co.) was slowly added and reacted at a constant temperature of 60 C. After the complete reaction of epichlorohydrin, which was tracked by JIS method K7236, chloro-substituted glycerol was obtained.

[0041] Preparation of adhesive compositions

EXAMPLE 2-1

[0042] 20.0 g of chloro-substituted sorbitol, 33.0 g of isocyanate compound IL-6 (available from EMS-GRIVORY Co.; solid content=60%), 390.0 g of copolymer of butadiene and vinyl pyridine VPL0653 (available from Croslene Chemical Industries. Ltd., solid content=41%), and 557.0 g of deionized water were mixed to form an adhesive composition T1.

EXAMPLE 2-2

[0043] 20.0 g of chloro-substituted glycerol, 33.0 g of isocyanate compound IL-6, 390.0 g of copolymer of butadiene and vinyl pyridine VPL0653, and 557.0 g of deionized water were mixed to form an adhesive composition T2.

Preparation of Conventional Pre-Impregnation Liquid

COMPARATIVE EXAMPLE 1-1

[0044] 9.0 g of sorbitol-type epoxy resin EX-614B (available from Nagase ChemteX Co.), 31.0 g of isocyanate compound IL-6, 0.4 g of surfactant OT-75 (available from Cytec Solvay Co.; concentration=75%), and 959.6 g of deionized water were mixed to form a conventional pre-impregnation liquid pre-impregnation liquid P1.

COMPARATIVE EXAMPLE 1-2

[0045] 9.0 g of glycerin-type epoxy resin EX-313 (available from Nagase ChemteX Co.), 31.0 g of isocyanate compound IL-6, 0.4 g of surfactant OT-75, and 959.6 g of deionized water were mixed to form a conventional pre-impregnation liquid pre-impregnation liquid P2.

Preparation of an Impregnated Organic Fiber Cord Fabric

EXAMPLE 3-1

[0046] Polyester yarn (available from Oriental Industries (Suzhou) Ltd.; content: polyethylene terephthalate (PET); 1500 d/2-ply, twist=370370 TPM) were woven into a cord-like structure. Next, an impregnation machine (available from BENNINGER as Pilot Machine CPM4H-2D-V40-1E) was adopted, such that the cord-like structure was impregnated with the adhesive composition T1, and was then dried at 170 C. for 90 seconds and baked at 245 C. for 60 seconds to form an impregnated organic fiber cord fabric.

EXAMPLE 3-2

[0047] In the present example, an impregnated organic fiber cord fabric was formed in the same manner with Example 3-1, except that the adhesive composition T1 was replaced by the adhesive composition T2.

COMPARATIVE EXAMPLE 2-1

[0048] Two impregnation stages were carried out using the same impregnation machine. First, polyester yarn (available from Oriental Industries (Suzhou) Ltd.; content: polyethylene terephthalate (PET); 1500 d/2-ply, twist=370370 TPM) were woven into a cord-like structure. Next, in the first impregnation stage, the cord-like structure was impregnated with the conventional pre-impregnation liquid P1, and was then dried at 170 C. for 90 seconds and baked at 245 C. for 60 seconds.

[0049] Subsequently, in the second impregnation stage, the baked cord-like structure was impregnated with a conventional RFL adhesive composition, and was then dried at 170 C. for 90 seconds and baked at 245 C. for 60 seconds to form an adhesive layer on the yarn surface, thereby obtaining the impregnated organic fiber cord fabric.

[0050] Subsequently, an organic fiber/rubber composite was formed by hot pressing rubber (the rubber composition is listed in Table 1 and is available from Kuo Chi Trading Co., Ltd.).

COMPARATIVE EXAMPLE 2-2

[0051] In the present example, an impregnated organic fiber cord fabric was formed in the same manner with Comparative Example 2-1, except that in the first impregnation stage, the conventional pre-impregnation liquid P1 was replaced by the conventional pre-impregnation liquid P2.

COMPARATIVE EXAMPLE 2-3

[0052] In the present example, an impregnated organic fiber cord fabric was formed in the same manner with Comparative Example 2-1, except that in the first impregnation stage, the conventional pre-impregnation liquid P1 was replaced by the adhesive composition T1.

COMPARATIVE EXAMPLE 2-4

[0053] In the present example, an impregnated organic fiber cord fabric was formed in the same manner with Comparative Example 2-1, except that in the first impregnation stage, the conventional pre-impregnation liquid P1 was replaced by the adhesive composition T2.

[0054] Next, after hot-pressing of rubber to the impregnated organic fiber cord fabrics of Examples 3-1 to 3-2 and Comparative Examples 2-1 to 2-4 to form composites of organic fiber and rubber, the composites were subjected to an adhesion test, a heat resistance test and a fatigue resistance test. Specifically, ASTM method D4393 was adopted to perform a peeling test. ASTM method D6588 was adopted to perform the fatigue resistance test (testing conditions: compression ratio=20%; elongation ratio=6.5%; fatigue time=24 hrs; rotational speed=1800 rpm). The heat resistant test refers to a vulcanization treatment at 170 C. for 60 minutes and a following adhesion performance testing in accordance with ASTM method D4393. The test results are listed in Table 2.

TABLE-US-00001 TABLE 1 Component Parts by mass Natural rubber (1# Natural rubber) 90.0 Styrene-Butadiene Rubber (1500) 10.0 Stearic acid (200-type, First Grade) 2.0 Promoter DM 1.2 Promoter TT 0.03 zinc oxide 8.0 carbon black (N330) 35.0 brimstone 2.5 Adhesive A 0.8 Adhesive RS 0.96 Total 150.49

TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Comparative Example 3-1 Example 3-2 Example 2-1 Example 2-2 Example 2-3 Example 2-4 adhesion test 220N, 100% 213N, 100% 245N, 100% 228N, 100% 229N, 100% 210N, 80% (peeling force, rubber coverage) heat resistance 173N, 100% 167N, 80% 183N, 100% 168N, 70% 135N, 20% 120N, 5% (peeling force, rubber coverage) fatigue resistance 90.1% 92.3% 89.5% 90.7% 82.1% 83.0% (breaking strength retention rate)

[0055] As can be seen from the testing results in Table 2, the adhesion, heat resistance, and fatigue resistance of the impregnated organic fiber cord fabric, which is impregnated with the adhesive composition of the present disclosure by one single impregnation stage, are similar to those of the conventional impregnated organic fiber cord fabric, which is formed by two impregnation stages (see the testing results of Examples 3-1 to 3-2 and Comparative Examples 2-1 to 2-2).

[0056] In addition, compared with the impregnated organic fiber cord fabrics formed by using conventional RFL adhesive composition in the second impregnation stage (see Comparative Examples 2-3 to 2-4), the impregnated organic fiber cord fabrics formed by using the adhesive composition of the present disclosure (see Examples 3-1 to 3-2) have significantly improved heat resistance and fatigue resistance. This is due to poor compatibility between halohydrin compound and blocked isocyanate compound, which are used to activate the organic fiber, and the conventional RFL adhesive composition. Therefore, the adhesive composition of the present disclosure not only poses no hazard to operators and the environment as it does not contain resorcinol and formaldehyde, but also increases the heat resistance and fatigue resistance of the organic fiber/rubber composite.

Experiments on Different Yarn Types

EXAMPLE 4-1

[0057] In the present example, an impregnated organic fiber cord fabric was formed in the same manner with Example 3-1, except that the polyester yarn was replaced by Nylon 66 yarn (1260d/2-ply, twist=350350 TPM).

EXAMPLE 4-2

[0058] In the present example, an impregnated organic fiber cord fabric was formed in the same manner with Example 3-2, except that the polyester yarn was replaced by poly(m-phenylene isophthalamide) fiber yarn (1500d/2-ply, twist=325325 TPM).

COMPARATIVE EXAMPLE 3-1

[0059] In the present example, an impregnated organic fiber cord fabric was formed in the same manner with Example 4-1, except that the adhesive composition T1 was replaced by the conventional RFL adhesive composition.

COMPARATIVE EXAMPLE 3-2

[0060] In the present example, two impregnation stages were carried out using the same impregnation machine. First, poly(m-phenylene isophthalamide) fiber yarn (1500 d/2-ply, twist=325325 TPM) were woven into a cord-like structure. Next, in the first impregnation stage, the cord-like structure was impregnated with the conventional pre-impregnation liquid P1, and was then dried at 170 C. for 90 seconds and baked at 245 C. for 60 seconds.

[0061] Subsequently, in the second impregnation stage, the baked cord-like structure was impregnated with a conventional RFL adhesive composition, and was then dried at 170 C. for 90 seconds and baked at 245 C. for 60 seconds to form an adhesive layer on the yarn surface, thereby obtaining the impregnated organic fiber cord fabric.

[0062] Subsequently, the impregnated organic fiber cord fabric is adhered to rubber by a hot pressing process to form an organic fiber/rubber composite (the rubber composition is listed in Table 1).

[0063] Next, each of the organic fiber/rubber composite of Examples 4-1 to 4-2 and Comparative Examples 3-1 to 3-2 was subjected to an adhesion test. Specifically, ASTM method D4393 was adopted to perform a peeling test. The test results are listed in Table 3.

TABLE-US-00003 TABLE 3 Comparative Example Comparative Example 4-1 Example 4-2 Example 3-1 3-2 Yarn Nylon 66 poly(m- Nylon 66 poly(m- material (1260d/ phenylene (1260d/ phenylene 2-ply) isophthalamide) 2-ply) isophthalamide) fiber fiber (1500d/2-ply) (1500d/2ply) adhesion 207N, 217N, 193N, 205N, test 90% 80% 85% 85% (peeling force, rubber coverage)

[0064] As can be seen from the testing results in Table 3, the adhesive composition of the present disclosure is suitable for yarn materials such as polyester, nylon or aromatic polyamide, and the adhesion performance thereof is similar to that of the conventional RFL adhesive composition.

[0065] In summary, the present disclosure provides an adhesive composition. Since the adhesive composition of the present disclosure does not contain resorcinol and formaldehyde, thereby posing no hazard to operators and the environment, as compared with the conventional RFL adhesive composition. Moreover, the adhesive composition of the present disclosure contains a halohydrin compound and a blocked isocyanate compound, and is capable of achieving excellent adhesion performance using one single impregnation stage. Compared to the conventional technique of using two impregnation stages, the adhesive composition of the present disclosure is cost-effective. Furthermore, the halohydrin compound and the blocked isocyanate compound, which are used to activate the organic fiber, have excellent compatibility with latex. Accordingly, the organic fiber/rubber composite impregnated with the adhesive composition of the present disclosure has excellent physical and mechanical properties, dry heat shrinkage, heat resistance, and fatigue resistance. Therefore, the adhesive composition of the present disclosure is suitable for use in a variety of organic fiber/rubber composite products.

[0066] Although the present invention has been described in considerable detail with reference to certain embodiments thereof, other embodiments are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the embodiments contained herein.

[0067] It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the present invention cover modifications and variations of this invention provided they fall within the scope of the following claims.