TW555803B - Resin cross-linking agent and cross-linked rubber obtained from the same - Google Patents

Abstract

Disclosed is a resin cross-linking agent which effects faster cross-linking reaction than the conventional one without using a cross-linking promoter that may cause corrossion. The invention provides a resin cross-linking agent obtained from the mixture of a resol type phenol/formaldehyde cocondensed resin and a novolac type phenol/formaldehyde cocondensed resin, or composed of the cocondensed resol resin of a para-alkylphenols, a phonole unsubstitnted in the para-positions and a formaldehyde. The invention further provides a cross-linked rubber obtained by using the above-mentioned resin cross-linking agent.

Description

555803 V. Description of the invention (1) [Technical field of the invention] The present invention relates to a resin crosslinking agent and a rubber crosslinked by the resin crosslinking agent. More specifically, it relates to a resin cross-linking agent made of a soluble phenol-type phenol-formaldehyde co-condensation resin and a rubber cross-linked by the resin cross-linking agent. [Prior art] Phenolic resin crosslinking agent has always been used as a crosslinking agent for rubber crosslinking. As a phenol resin crosslinking agent, a soluble phenolic alkylphenol-formaldehyde co-condensation resin is used. The crosslinking accelerator is usually an i-containing elastomer using an inorganic S compound such as tin chloride, ferric chloride, chloroprene rubber, chlorosulfonated polyethylene, or an organic acid. In some cases, a co-condensation resin using an alkylated phenol and methyl formaldehyde is also used. However, when using an i-containing compound or an organic acid as a crosslinking accelerator, there are disadvantages such as corrosion of metal molds during cross-linking molding and corrosion of metal parts when used in electrical products, which are very disadvantageous in rubber cross-linking. Big question. Therefore, even if a cross-linking accelerator that causes metal corrosion is not used, a resin cross-linking agent that can obtain cross-linking quickly has its strong demand. The object of the present invention is to provide a resin cross-linking agent that can obtain rapid cross-linking without using a cross-linking accelerator that causes metal corrosion. The present invention also provides a cross-linked rubber that can be obtained by using the resin cross-linking agent. In order to solve this problem, as a result of an intensive review by the present inventors, it was found that by using a mixture of a soluble phenolic phenol-formaldehyde co-condensation resin and a phenolic phenolic-formaldehyde co-condensation resin for paint, a resin cross-linking agent for rubber is used. ,

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Or, by co-condensing a para-alkylphenol, a phenol without a substituent at the para-position, and a soluble phenolic resin as a resin cross-linking agent, Nenshi [Summary of the Invention] The present invention provides a A cross-linking agent made of a mixture of a soluble phenol-formaldehyde-formaldehyde co-condensation tree and a phenolic-type phenol-formaldehyde co-condensation resin for paint. The present invention further provides a tree cross-linking agent formed from a para-alkylphenol, a co-condensation of a phenol having no substituent at the para-position and a formaldehyde-soluble resin. 9 The present invention further provides a rubber crosslinked by using the resin crosslinking agent. [Embodiments of the Invention] ^ The following is a detailed description of the present invention. As the rubber suitable for the resin crosslinking agent of the present invention, natural rubber, SBR, isoprene rubber, BR, butyl rubber, EPDM, other ethylene propylene rubber, etc. are suitable, among which butyl rubber, EPDM, Other ethylene-propylene rubbers are preferred. Specific examples include SBR 1 500 (SBR manufactured by JSR Corporation), Polysa-Buty 1 3 65 (Polysa Corporation, butadiene rubber), EP33 (EPDM manufactured by JSR Corporation), and the like. The soluble phenol-formaldehyde phenol-formaldehyde co-condensation resin used in the present invention may be synthesized by a known method. The soluble phenol-formaldehyde phenol-formaldehyde co-condensation resin is co-condensed with a soluble phenol-form alkylphenol and formaldehyde. Resin is preferred. The alkyl carbon number of the alkylphenol is preferably from 1 to 20. As soluble acid

313394.ptd Page 6 555803 V. Description of the invention (3) For those alkylphenols whose raw materials are constricted, such as o-cresol, m-cresol, p-cresol, o-n-butylphenol, O-iso-butylphenol, o-second butylphenol, m-n-butylphenol, m-iso-butylphenol, m-third: base phenol, p-n-butylphenol, p-one Iso-butylphenol, p-tert-butylphenol, o-n-hexylphenol, o-iso-hexylphenol, o-third-hexylphenol m-n-hexylphenol, m-iso-hexylphenol, m-one Third hexylphenol, p-n-hexylphenol, p-iso-hexylphenol, p-third hexylphenol, o-n-octylphenol, o-iso-octylphenol, o-third octyl group One-n-octyl age, m-iso-octyl group, m-third-octylphenol, p-n-octylphenol, p-iso-octylphenol, p-third-octylphenol, o-n-decyl Phenol, o-iso-decylphenol, o-third decylphenol, m-n-decylphenol, m-iso-decylphenol, m-third-decylphenol, p-n-decylphenol , P-iso-decylphenol Decyl Fun a cresol. Examples of phenols other than novolac include unsubstituted phenol and m-diphenol. The GPC measurement value of the soluble phenolic phenol-acetaldehyde co-condensation resin converted to polystyrene is calculated. The calculated degree of polymerization is preferably in the range of 4 to 50. Specific commercial products include Takata Chemical. Industrial Takirol 201, Hitachi Chemical Industrial Hitanol 2501, Schenectady

International Inc. SP — 1044, SP — 1045, etc. For the lacquer used in the present invention, the acid-type co-condensation resins can be used as long as they have good dispersibility to rubber, and there are no particular restrictions on the specific compounds such as co-condensation resins. Age · Condensation resins, alkyl phenols, acetaldehyde co-condensation resins, etc.

555803 V. Description of the invention (4) Resin, resorcinol • phenol • formaldehyde co-condensation resin, resorcinol • methylphenol • formaldehyde co-condensation resin, etc. As the base group of the alkylphenol-formaldehyde co-condensation resin, alkyl groups having 1 to 20 carbon atoms are preferred. Specific commercially available products such as Tamanol 759 manufactured by Arakawa Chemical Industries, manufactured by Showa Polymer Chemical Industries, Sumicanol 610 and 620 manufactured by Sumitomo Chemical Industries. The content of the phenolic phenol-formaldehyde co-condensation resin for paint in the resin crosslinking agent of the present invention is preferably 0.1 to 70% by weight, more preferably 1 to 50% by weight, and most preferably 5 to 50% by weight. If the content of the phenolic resin for lacquer is less than 0.1% by weight / 0, the effect of the present invention cannot be seen, and when it exceeds 70% by weight, the tensile strength of the crosslinked rubber is reduced. The co-condensed soluble phenolic resins of the para-based radicals of the present invention, the para-non-substituted ages, and formic acid are based on the plastic materials lecture 15 "Resins" (published by Nikkan Kogyo Shimbun). Synthesis by the well-known methods described. The alkyl group in the para-alkyl phenols used in the present invention preferably has a carbon number of 1 to 20, and a carbon number of 4 to 10 is preferred. Specific compounds include, for example, p-phenol, p-n-butylphenol, p-iso-butylphenol, p-third-butylphenol, p-n-hexylphenol, p-iso-hexylphenol, For one third one hexyl group, for one positive one octyl group, for one different one octyl group, for one third one octyl group, etc. Specific examples of the phenolic compound without a para-position used in the present invention are phenol, o-cresol, m-cresol, m-ethylphenol and the like. The amount of para-unsubstituted phenols used in the present invention is preferably in the range of 0.1 to 50% by weight of all phenols contained in para-based phenols, and 1 to 40% by weight Better, more preferably in the range of 5 to 40% by weight, if it is in the range of 0.1% by weight

313394.ptd Page 8 ’The intersection of inorganic fillers in rubber, with temperature. If it is an agent, a fast rubber such as an organic acid can be obtained in the same manner as the required agent. V. Description of the invention (5) If the following is not used, the effect of the present invention will be reduced. The resin cross-linking agent of the present invention makes the rubber 100 parts by weight, usually 1 to 1 part by weight. In the various crosslinking rubber stoppers, carbon black, quicklime, etc. of the present invention, the same temperature as the conventional resin crosslinking agent using the resin crosslinking of the present invention, the resin crosslinking metal suitable for the present invention is selected according to the type of rubber Causes of corrosion_Compounds or resin cross-linking agents that perform more than conventional resin cross-linking agents. If used and metal corrosion occurs, it can reach :: m 'and rubber with conventional resin cross-linking and cross-linking agents. Crosslinked, crosslinked rubber. In addition, when using a soluble phenolic south: type phenol-acetaldehyde co-condensation tree W, a crosslinked rubber having a small permanent compression deformation and a combination of strengths using a para-alkylphenol-based phenolic resin can be obtained. . When it exceeds weight%, the degree of cross-linking 2 f is not particularly limited, but it is preferably 3 to 2 5 with respect to S > '. In general, an aging preventive agent, zinc powder, etc. can be blended.

The cross-linking temperature is suitable for the range of 130 to 230 ° C. It can be cross-linked by gel without using a cross-linking accelerator that will be generated. That is, if the cross-linking agent of the present invention has the same amount, the degree of parental connection is shortened. Under the conditions of the present invention, a resin-crosslinked crosslinked rubber using a mixture of a cross-linked formaldehyde-formaldehyde co-condensation resin and a paint fat of higher hardness than the past in the present invention is used. When para-unsubstituted phenols and formaldehyde are used as resin cross-linking agents, tearing can be obtained.

IM Page 9 555803 V. Description of the Invention (6) The following examples illustrate the present invention in more detail. Example 1 15 weights were divided into 80 weights. / ◦ Takirol 201 (a soluble phenol-formaldehyde-formaldehyde co-condensation resin manufactured by Taoka Chemical Industry Co., Ltd.) and 20% by weight Sumicanol 610 (a phenol-formaldehyde-formaldehyde co-condensation resin manufactured by Sumitomo Chemical Industries, for paint) Resin Crosslinking Agent A, formulated with ο 1 ysa — Buty 1 3 6 5 (^ 01 ^ 8 manufactured by Yaba Corporation, butyl rubber) 100 parts by weight, 81 ^ carbon black 50 parts by weight, and stearic acid 1 part by weight After 5 minutes by weight of zinc powder and 200 ° C. extrusion cross-linking at 35 ° C., the following rubber physical properties were measured. The results are shown in Table 1. Hardness: Measured according to J I S K6 2 5 3 using a type A durum. Compression set (%) Measured after 125 hours at 125 ° C in accordance with JIS K62 62. Cross-linking speed: The rubber complex was measured at 180 ° C in an oscillating ammeter, and evaluated according to the cross-linking curve. The cross-linking curve is shown in Figure 1. Example 2 A resin crosslinker B made of 18% by weight of 8% by weight of Takirol 201 and 15% by weight of Tamanol 759 (manufactured by Arakawa Chemical Industry Co., Ltd., and a formaldehyde co-condensation resin for paints) was formulated. Into 100% by weight Pol ysa — Butyl 36 5, 50% by weight SRF carbon black, 1% by weight stearic acid and 5% by weight zinc powder, and subjected to extrusion and crosslinking at 2000 ° C for 3 to 5 minutes The hardness and compression set were measured in the same manner as in Example 1. The results are shown in Table 1. The cross-linking speed was measured in the same manner as in Example 1.

313394.ptd Page 10 555803 V. Description of the invention (7) The figure shows. Comparative Example 1 Will Takirol 201 be divided into 18 parts by weight and 100 parts by weight? 〇43 &But; 3 Butyl 3 6 5, 50 parts by weight of SRF carbon black, 1 part by weight of stearic acid, and 5 parts by weight of zinc powder, after extruding and crosslinking at 2000 ° C for 3 to 5 minutes, and the examples 1 The hardness and compression set were measured in the same manner. The results are shown in Table 1. The crosslinking rate was measured in the same manner as in Example 1. This crosslinking curve is shown in FIG. 1. Table 1 Example 1 Example 2 Comparative Example 1 Resin crosslinking agent AB Takirol 20 1 Crosslinking agent blending amount 15 18 18 Hardness 67 77 Compression set 33 33 36 Example [Synthesis of resin crosslinking agent A] 1 liter After the triangle glass bottle was replaced with nitrogen, 315 g of tertiary octylphenol, 35 g of cresol, and 275 g of 37% formalin aqueous solution were put in, and the internal temperature was raised to about 40 while slowly stirring. Up to ° C, followed by dripping 1 3-8 g of 4 7% caustic soda aqueous solution into the reaction, and reacted at 90 to 95 ° C for 1 hour, and then added 6 7 m of pure water, 2 7 5 m The toluene of 1 was cooled, and the reaction solution was neutralized with hydrochloric acid, followed by oil-water separation. The condensation resin in the oil layer was recovered with a rotary evaporator, and about 3 50 g of a co-condensation resin (resin crosslinking agent A) was obtained.

313394.ptd Page 11 555803 V. Description of the invention (8) [Crosslinking of butyl rubber with resin crosslinker A] The compound composition shown in Table 2 was cross-linked by extrusion at 200 ° C for 35 minutes. A crosslinked rubber was obtained, and the physical properties of the crosslinked rubber were measured by the following methods. The results are shown in Table 2 and Figure 2. Hardness: Measured according to J I S K6 2 5 3 using a type A durum. Tear strength (N / mm): According to JIS K62 52, the shape of the test piece is notched with an angle. Cross-linking speed: The rubber complex was measured at 180 ° C in an oscillating ammeter, and evaluated according to the cross-linking curve. The cross-linking curve is shown in Figure 2. Example 4 [Synthesis of Resin Crosslinker B] In the synthesis of the resin crosslinker A for rubber in Example 3, the amount of the third octylphenol was changed to 326g, or m-cresol was changed to 24g of phenol. The same operation as in Example 3 can obtain about 35 Og of co-condensation resin (resin crosslinker B for rubber) ° [crosslinking butyl rubber with resin crosslinker B] In the compound composition shown in Table 2, in 20 A crosslinked rubber was obtained after extrusion crosslinking at 0 ° C for 3 to 5 minutes. The crosslinked rubber was measured in the same manner as in Example 3, and the results are shown in Table 2 and Figure 2. Comparative Example 2 Using the well-known resin cross-linking agent Takirol 201, the compounded composition shown in Table 2 was subjected to compression-extrusion cross-linking at 2000 ° C for 35 minutes to obtain a cross-linked rubber. The measurement was performed in the same manner as in Example 3. The results are shown in Table 2 and Figure 2.

313394.ptd Page 12 555803 V. Description of the invention (9) Main 9 (parts by weight) Example 3 Example 4 Comparative Example 2 Polysubutyl 365 100 100 100 Carbon black 50 50 50 Stearic acid 1 1 1 Zinc powder 5 5 5 Resin crosslinker A 18 0 0 Resin crosslinker B 0 18 0 Takirol 20 1 0 0 18 Table 3 Example 3 Example 4 Comparative example 2 Hardness 76 77 55 Tear strength (N / mm) 29 3 1 25

IIH 313394.ptd Page 13 555803 Brief Description of Drawings [Simplified Description of Drawings] Figure 1 is the intersection of Example 1, Example 2 and Comparative Example 1 measured at 180 ° C by Oscillating rheometer联 平面。 Curve. Fig. 2 is a cross-linking curve measured in Example 3, Example 4 and Comparative Example 2 by an oscillating ammeter at 180 ° C. [Description of Element Symbols] (1) shows a crosslinking curve obtained in Example 1. (2) shows the cross-linking curve obtained in Example 2. (3) shows the cross-linking curve obtained in Comparative Example 1. (4) shows the crosslinking curve obtained in Example 3. (5) shows the crosslinking curve obtained in Example 4. (6) shows the crosslinking curve obtained in Comparative Example 2.

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Claims (1)

555803 Revised ^ ^? 4 nose 4—335 report ΐ ΐ ΐττ ^ ·-~ amended ί Niu VI, [Xin please patent Faner-1. A resin cross-linking agent for fat and lacquer phenolic type. 2. Such as the scope of patent application Type phenol-formaldehyde co-condensation resin. 3. Such as the scope of patent application Phenolic-type phenol • 曱 condensation resin. 4. Such as applying for a patent range of phenolic phenols • methyl% 〇 5. As applying for a patent range of phenolic • formaldehyde altogether 6. A resin crosslinker phenol and formaldehyde total 7. Such as applying for a patent range of substituted phenols Content 8. If the scope of the patent application is unsubstituted phenols 9. One crosslinked rubber, one resin crosslinked rubber is butyl rubber, which is composed of soluble novolac phenol • formaldehyde co-condensation phenols • formaldehyde The resin cross-linking agent of item 1 formed by a mixture of condensation resins, wherein the soluble phenol-formaldehyde resin is a resin cross-linking agent of item 1 or 2 of soluble phenol-type alkylphenols and aldehydes, among which aldehydes for lacquers The co-condensation resin is a resin cross-linking agent of the m-cresol or phenol-acetaldehyde co-item 1 or 2, wherein the content of the aldehyde co-condensation resin for lacquer is 0.1 to 70 weight of the resin cross-linking agent of the 3 item , Wherein the content of the phenolic resin for lacquer is 0.1 to 70% by weight. It is made by condensing soluble phenol-type resin with parabens and no substituent at the para position. The resin cross-linking agent according to item 6, wherein the para position is not 0.1 to 50% by weight of the total phenols. The resin cross-linking agent according to item 6 or 7, wherein para-phenol, o-cresol, or m-cresol. It is crosslinked by using any of the agents in the scope of claims 1 to 8 of the patent application, in which the crosslinked, EPDM or ethylene propylene rubber is used. 313394.ptc Page 1 2003. 02.12.015