JP2009001714A - Rubber composition for diaphragm and diaphragm obtained therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber composition for diaphragms which gives a vulcanizate equivalent to a vulcanizate of a chloroprene rubber-containing rubber composition compounded with a lead compound such as lead oxide in water resistance and still retains requirements, such as flex fatigue resistance, tensile strength, and compression set, for a diaphragm and to provide a diaphragm obtained by vulcanizing and molding a composition at least partially consisting of the rubber composition. <P>SOLUTION: The rubber composition for diaphragms contains a rubber component based on chloroprene rubber, zinc oxide, hydrotalcite, carbon black, and silica. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a rubber composition for a diaphragm and a diaphragm obtained by vulcanization and molding using at least a part of the composition.

Conventionally, as a rubber composition containing chloroprene rubber (hereinafter abbreviated as “CR”), an acid generated using a metal oxide vulcanizing agent due to the special property that an acid is generated during vulcanization of CR. Vulcanization is carried out while absorbing water, and specifically, a technique in which magnesium oxide and zinc oxide are used in combination as a metal oxide vulcanizing agent is used. However, according to the CR-containing rubber composition, since the inorganic component derived from magnesium oxide (for example, MgCl ₂ ) has a property of having high water absorption, it is used in an environment where it comes into contact with moisture, for example, As a diaphragm application, there is a problem that it cannot withstand practical use in terms of water resistance. Therefore, when the CR-containing rubber composition is used for an application requiring water resistance, a technique using a lead compound such as lead oxide as a vulcanizing agent (Patent Document 1), or zinc oxide and hydrotalcite or A technique (Patent Document 2) has been proposed in which the fired product is used in combination as a metal oxide vulcanizing agent.
JP-A-5-86229 Japanese Patent Laid-Open No. 11-12392

  However, when a lead compound such as lead oxide is used as the metal oxide vulcanizing agent, lead is highly toxic and it is desirable to avoid the use of lead in consideration of recent environmental problems. Also, when zinc oxide and hydrotalcite are used in combination as a metal oxide vulcanizing agent, they are non-toxic, and the water resistance of rubber after vulcanization is when magnesium oxide and zinc oxide are used in combination. However, when used as a diaphragm application requiring water resistance, further improvement in water resistance is required.

  The present invention is a CR-containing rubber composition containing a lead compound such as lead oxide (hereinafter, referred to as “diaphragm”) while ensuring the required properties as a diaphragm such as flexural fatigue resistance, tensile strength and compression set of vulcanized rubber. A rubber composition for diaphragms having water resistance equivalent to that of rubber after vulcanization of “lead-based CR-containing rubber composition” and obtained by vulcanizing and molding at least a part of the composition. It aims at providing the diaphragm which can be used.

  As a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved by the rubber composition shown below, and have completed the present invention.

  That is, the rubber composition for a diaphragm of the present invention is characterized by containing a rubber component mainly composed of CR, zinc oxide, hydrotalcite, carbon black and silica.

  The vulcanized rubber of such a rubber composition has water resistance equivalent to that of the vulcanized rubber of the lead-based CR-containing rubber composition even if it is a non-lead type, and further has bending fatigue resistance, tensile strength, and compression set. It satisfies the required characteristics as a diaphragm.

  The rubber composition for a diaphragm of the present invention contains a rubber component mainly composed of CR, zinc oxide, hydrotalcite, carbon black and silica.

  The rubber component refers to a rubber component mainly containing CR, that is, a rubber component containing 50% or more of CR in the rubber component. If the rubber component is composed mainly of CR, the vulcanized rubber can be suitably used as a diaphragm.

  As the zinc oxide, zinc oxide (zinc white) generally used as a rubber vulcanization accelerating aid can be used. The blending amount of zinc oxide is preferably 2 to 10 parts by weight and more preferably 4 to 6 parts by weight with respect to 100 parts by weight of the rubber component. When zinc oxide is less than 2 parts by weight, the vulcanization reaction is delayed, and when it exceeds 10 parts by weight, the vulcanization reaction is accelerated and the scorch resistance is lowered.

Hydrotalcite falls under the category of metal oxide vulcanizing agent. In the narrow sense, it refers to magnesium, aluminum, hydroxide, carbonate, hydrate as naturally occurring minerals. And a synthetic product of metal oxide having a composition similar to that of hydrotalcite. Typically, the main component is the following general formula:
Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O (natural product)
_{Mg 4.5 Al 2 (OH) 13} CO 3 · 3.5H 2 O ( an example of a synthetic)
Is given by As for compounds having metal hydroxides, metal carbonates and the like in the main skeleton, those that can form metal oxides by heat dehydration and the like are broadly included in metal oxide compounds. The amount of hydrotalcite is preferably 4 to 20 parts by weight and more preferably 6 to 10 parts by weight with respect to 100 parts by weight of the rubber component. When the hydrotalcite is less than 4 parts by weight, the scorch resistance is lowered, and when it exceeds 20 parts by weight, the vulcanization reaction is delayed.

  As the carbon black, known carbon black having reinforcing properties, specifically, for example, SAF, ISAF, HAF, FEF, GPF and the like are used. The compounding amount of the carbon black is preferably 20 to 70 parts by weight, more preferably 30 to 60 parts by weight with respect to 100 parts by weight of the rubber component. Carbon black can be used as long as the hardness, water resistance and durability of the vulcanized rubber can be adjusted. If the blending amount of carbon black is less than 20 parts by weight, the reinforcing effect of carbon black cannot be obtained sufficiently, and if it exceeds 70 parts by weight, rubber mixing properties, workability during processing, and the like deteriorate.

  As the silica used as a reinforcing agent in the present invention, a known silica can be used as a rubber reinforcing agent. Since silica easily aggregates when the moisture content becomes high, drying and kneading is also a preferable embodiment as necessary. The amount of silica is preferably 3 to 18 parts by weight and more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the rubber component. Silica can be used as long as the hardness, water resistance and durability of the rubber after vulcanization can be adjusted. If the blending amount is less than 3 parts by weight, the reinforcing effect of silica cannot be sufficiently obtained, and if it exceeds 18 parts by weight, the water resistance of the rubber after vulcanization is deteriorated.

  It is also a preferred embodiment of the present invention to use a silane coupling agent when adding silica. A well-known silane coupling agent can be used without limitation, and the amount of the silane coupling agent can be used as long as the dispersibility of silica can be adjusted.

  The rubber composition of the present invention may contain sulfur which is usually used in the rubber industry as a vulcanizing agent, and the blending amount thereof is 0.2 to 1.5 parts by weight with respect to 100 parts by weight of the rubber component. preferable. If the amount of sulfur is within the above range, a rubber having excellent water resistance and reinforcing properties can be obtained as a vulcanized rubber.

  In addition, the diaphragm composition of the present invention includes known vulcanization accelerators, vulcanization acceleration assistants, vulcanization retarders, colorants, reinforcing agents, anti-aging agents, fillers, softeners, plasticizers, lubricants. Various additives such as can be added.

  For example, examples of the filler include clay, talc, mica, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, and various natural or artificial fibers.

  Examples of the softener include plant softeners such as tall oil mainly composed of linoleic acid, oleic acid, and abietic acid, pine tar, rapeseed oil, cottonseed oil, peanut oil, castor oil, palm oil, fuactis, paraffinic oil, and naphthenic oil. Examples thereof include mineral softeners such as oil or aromatic oil.

  Examples of the plasticizer include phthalic acid-based, sebacic acid-based, adipic acid-based, phosphate ester-based, epoxy-based, chlorinated paraffin-based, ether-based, thioether-based, polyester-based, and polyether-based plasticizers.

  Examples of the lubricant include stearic acid, metal soap of stearic acid, high melting point wax, low molecular weight polyethylene, polyethylene glycol, or octadecylamine.

  The rubber composition for a diaphragm of the present invention comprises a rubber component, zinc oxide, hydrotalcite, carbon black and silica, and if necessary, a silane coupling agent, a vulcanization accelerator and other various compounding agents described above, a Banbury mixer, It can be obtained by kneading using a kneader used in a normal rubber industry such as a kneader or a roll.

  In addition, the blending method of each of the above components is not particularly limited, and blending components other than vulcanized components such as zinc oxide, hydrotalcite, sulfur and vulcanization accelerator are kneaded in advance to obtain a master batch, and the remaining components Any of a method for adding and kneading the components, a method for adding and kneading each component in an arbitrary order, a method for adding all components simultaneously and kneading may be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the following, “parts” means parts by weight.

Example 1
(Preparation of rubber composition)
100 parts CR (manufactured by Tosoh Corporation, trade name: Skyprene B-5A), 1 part stearic acid, 55 parts carbon black (manufactured by Tokai Carbon Co., Ltd., trade name: Seast S (SRF)), silica (manufactured by Tosoh Silica Corporation) , Trade name: nip seal AQ) 5 parts, silane coupling agent (manufactured by Dow Corning Toray, trade name: SH-6062) 0.15 parts and oil 15 parts are kneaded using a normal Banbury mixer, master batch Adjusted. Next, 5 parts of zinc oxide (2 types), 8 parts of hydrotalcite (trade name: Hydrotalcite KW2100), 0.5 parts of sulfur, vulcanization accelerator (2 types) were added to this master batch. Each 1.0 parts of Ouchi Shinsei Chemical Co., Ltd., trade names: Noxeller DT and Noxeller TS) were added and kneaded again using a kneader to prepare a rubber composition.

Examples 2-3 and Comparative Examples 1-3
A rubber composition was prepared in the same manner as in Example 1 except that the amount of each component used for preparation of the rubber composition in Example 1 was changed as shown in Table 1. In Comparative Example 1, lead oxide (manufactured by Reinchem, trade name: Renogran PbO-80) and carbon black (trade name: Seast SO (FEF), manufactured by Tokai Carbon Co., Ltd.) were used.

About each rubber composition, each vulcanized rubber was produced and the characteristic evaluation was performed.
(Evaluation)
The evaluation was performed on vulcanized rubber obtained by heating and vulcanizing each rubber at 160 ° C. for 20 minutes using a predetermined mold.
<Hardness (A)>
Based on JIS-K 6253, the hardness was measured with a type A durometer.
<Tensile properties>
About 100% elongation modulus (M ₁₀₀ (MPa)), tensile strength (T _B (MPa)) and elongation (E _B (%)), JIS-K 6251 Measured according to
<Viscoelastic properties>
(S′Max (dNm)), (t _c (10) (min)) and (t _c (90) (min)) were measured with a rheometer (manufactured by Monsanto, apparatus name: MDR-2000).
<Tear Strength (TR)>
In accordance with JIS-K 6252, the tear strength (TR (N / mm)) was measured with an angle-shaped test piece without cutting.
<Compression set>
Based on JIS-K 6262, the value after being allowed to stand at 100 ° C. for 24 hours was measured.
<Water resistance>
A test piece having a width of 20 mm, a length of 50 mm, and a thickness of 2 mm was immersed in water at 70 ° C., and the hardness change and volume change rate of the rubber after standing for 7 days or 14 days were measured. The volume change rate is given by volume change rate (%) = 100 × (W2−W1) / W1, where W1 is the volume of the test piece before the test and W2 is the volume after the test. The change in hardness was evaluated by the number of change points.
<Durability>
Based on JIS-K 6260, the bending crack generation test was done at 40 degreeC, and the frequency | count when the crack generate | occur | produced in the sample was measured. The evaluation results are shown in Table 1.

  From the results of Table 1, the vulcanized rubber of the diaphragm rubber composition of Example 1 has the same hardness change and volume change rate after the water resistance test as the vulcanized rubber of the lead-based CR-containing rubber composition. And showed excellent water resistance equivalent to that of lead. Regarding the durability, the number of times at the time when the crack was generated in the bending crack generation test was 150,000 times, but the result was sufficiently within the practical range as a diaphragm. In the vulcanized rubber of the CR-containing rubber composition of Example 3, the hardness change and volume change rate after the water resistance test are the same values as the vulcanized rubber of the lead-based CR-containing rubber composition. The same excellent water resistance was exhibited. Further, regarding the durability, cracks did not occur even after 200,000 times in the bending crack generation test, and excellent durability equivalent to that of the lead type was shown. In addition, the vulcanized rubbers of the CR-containing rubber compositions of Examples 1 to 3 exhibited values that satisfactorily satisfied the required characteristics as a diaphragm in terms of tensile strength, tear strength, and compression set. On the other hand, since the vulcanized rubber of the CR-containing rubber composition of Comparative Example 3 has a silica compounding amount exceeding 18 parts by weight, the volume change rate after the water resistance test is vulcanized rubber of the lead-based CR-containing rubber composition. However, the change in hardness was large and the water resistance deteriorated. Moreover, the vulcanized rubber of the CR-containing rubber composition in which carbon black is blended with zinc oxide and hydrotalcite of Comparative Example 2 and silica is not blended is the CR-containing rubber composition of Examples 1-3. Compared with vulcanized rubber, both the hardness change and the volume change rate after the water resistance test deteriorated.

Claims (4)

A rubber composition for a diaphragm comprising a rubber component mainly composed of chloroprene rubber, zinc oxide, hydrotalcite, carbon black and silica. 2. The rubber composition for a diaphragm according to claim 1, wherein a blending amount of the silica is 3 to 18 parts by weight with respect to 100 parts by weight of a rubber component mainly composed of the chloroprene rubber. 2. 100 parts by weight of a rubber component mainly composed of the chloroprene rubber is blended with 2 to 10 parts by weight of the zinc oxide, 4 to 20 parts by weight of hydrotalcite and 20 to 70 parts by weight of carbon black. Or the rubber composition for diaphragms of 2. A diaphragm obtained by vulcanizing and molding at least a part of the rubber composition for a diaphragm according to any one of claims 1 to 3.