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WO2019203015A1 - Composition de caoutchouc contenant du caoutchouc butyle, une résine co-condensée de phénol-formaldéhyde de type résol et du phénol - Google Patents

Composition de caoutchouc contenant du caoutchouc butyle, une résine co-condensée de phénol-formaldéhyde de type résol et du phénol Download PDF

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Publication number
WO2019203015A1
WO2019203015A1 PCT/JP2019/015058 JP2019015058W WO2019203015A1 WO 2019203015 A1 WO2019203015 A1 WO 2019203015A1 JP 2019015058 W JP2019015058 W JP 2019015058W WO 2019203015 A1 WO2019203015 A1 WO 2019203015A1
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WIPO (PCT)
Prior art keywords
general formula
rubber composition
resin
phenol
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/015058
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English (en)
Japanese (ja)
Inventor
文哉 尾崎
伸行 佐藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taoka Chemical Co Ltd
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Taoka Chemical Co Ltd
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Filing date
Publication date
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Priority to KR1020207029082A priority Critical patent/KR102614843B1/ko
Priority to CN201980025887.0A priority patent/CN111989365B/zh
Publication of WO2019203015A1 publication Critical patent/WO2019203015A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the present invention relates to a rubber composition containing butyl rubber, a resol-type phenol formaldehyde cocondensation resin and a phenol having a specific structure.
  • butyl rubber is excellent in environmental resistance and electrical properties such as heat aging resistance, chemical resistance and weather resistance, and is suitably used in various rubber products.
  • butyl rubber is a copolymer of isobutylene and a small amount of isoprene, and since there are few unsaturated bonds serving as cross-linking points, the cross-linking rate is slow, and the applicable cross-linking methods are also limited.
  • butyl rubber is crosslinked by a method using a resol type phenol formaldehyde cocondensation resin as a crosslinking agent
  • the crosslinking rate is slow only with the resin. Therefore, especially when industrially implemented, it is usually an inorganic halogen compound such as tin chloride or ferric chloride, a halogen-containing elastomer such as chloroprene rubber or chlorosulfonated polyethylene, an organic acid, or a halogenated alkylphenol-formaldehyde co-condensation.
  • a crosslinking accelerator such as a resin is used in combination.
  • Patent Document 1 proposes a method in which a mixture of a resol type phenolic formaldehyde cocondensation resin and a novolac type phenolic formaldehyde cocondensation resin is used as a resin crosslinking agent. According to the method, it is described that the crosslinking rate is improved without using a compound or resin having a halogen atom, or an organic acid as a crosslinking accelerator.
  • the inventors of the present application made a trial addition to the method described in Patent Document 1, and although the crosslinking rate was improved, the resin crosslinking agent described in the Patent Document or a rubber composition containing the resin crosslinking agent (not yet described).
  • the adhesive property of the crosslinked rubber composition is very high, and it is found that it is difficult to industrially use the resin crosslinking agent due to occurrence of sticking or contamination to the production apparatus in the kneading process or molding process. did.
  • An object of the present invention is to provide a rubber having an excellent crosslinking rate without using a compound or resin having a halogen atom which may cause metal corrosion or an organic acid as a crosslinking accelerator when butyl rubber is crosslinked using a resin crosslinking agent. It is to provide a composition (uncrosslinked rubber composition).
  • the present invention includes the following inventions.
  • a rubber composition comprising butyl rubber, a resol type phenol formaldehyde cocondensation resin, and a phenol, As the phenols, the following general formula (1):
  • R 1 and R 2 represent a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, a phenyl group, or a 4-hydroxyphenyl group.
  • R 3 and R 4 represent a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms or a 4-hydroxyphenyl group.
  • a rubber composition comprising at least one phenol selected from the group consisting of bis (4-hydroxyphenyl) sulfone.
  • R 1 and R 2 represent a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, a phenyl group, or a 4-hydroxyphenyl group.
  • R 3 and R 4 represent a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms or a 4-hydroxyphenyl group.
  • at least one phenol selected from the group consisting of bis (4-hydroxyphenyl) sulfone are mixed in advance to obtain a resin mixture, and the resin mixture and butyl rubber are mixed [1. ]
  • a resol type phenolic formaldehyde co-condensation resin The following general formula (1): (In the above general formula (1), R 1 and R 2 represent a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, a phenyl group, or a 4-hydroxyphenyl group.) A compound represented by The following general formula (2): (In the general formula (2), n represents an integer of 1 to 9) A compound represented by The following general formula (3): (In the general formula (3), R 3 and R 4 represent a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms or a 4-hydroxyphenyl group.) A compound represented by And at least one phenol selected from the group consisting of bis (4-hydroxyphenyl) sulfone.
  • the present invention when a butyl rubber is cross-linked using a resin cross-linking agent, a rubber composition having excellent cross-linking speed without using a compound or resin having a halogen atom that may cause metal corrosion, or an organic acid as a cross-linking accelerator. It becomes possible to provide a product (uncrosslinked rubber composition).
  • the rubber composition of the present invention has moderately controlled adhesiveness, and it is possible to avoid sticking to a manufacturing apparatus and contamination in the molding process.
  • the crosslinked rubber composition obtained by crosslinking the rubber composition of the present invention has improved crosslink density, processability and moldability as compared with a rubber composition crosslinked by a known method.
  • a crosslinked rubber composition excellent in swelling resistance and solvent resistance can be provided.
  • the rubber composition of the present invention includes butyl rubber, a resol-type phenol formaldehyde cocondensation resin, a compound represented by the above general formula (1), a compound represented by the above general formula (2), and the above general formula (3). And a rubber composition comprising at least one phenol selected from the group consisting of bis (4-hydroxyphenyl) sulfone.
  • the butyl rubber used in the rubber composition of the present invention is a synthetic rubber produced by copolymerization of isobutylene and isoprene and generally having a degree of unsaturation of 0.6 mol% to 2.8 mol% and a Mooney viscosity of 20 to 90M.
  • Examples of the resol type phenolic formaldehyde cocondensation resin contained in the rubber composition of the present invention include, for example, a resol type phenol / formaldehyde cocondensation resin, a resole type alkylphenol / formaldehyde cocondensation resin, a resole type resorcinol / phenol / formaldehyde cocondensation resin, and a resole.
  • Type resorcinol / cresol / formaldehyde co-condensation resin include, for example, a resol type phenol / formaldehyde cocondensation resin, a resole type alkylphenol / formaldehyde cocondensation resin, a resole type resorcinol / phenol / formaldehyde cocondensation resin, and a resole.
  • a resol-type alkylphenol / formaldehyde cocondensation resin is preferable from the viewpoint of compatibility with rubber, and a resole in which the alkyl group of the alkylphenol may have a branch having 1 to 20 carbon atoms.
  • Type alkylphenol-formaldehyde cocondensation resin is more preferable, and resol-type alkylphenol-formaldehyde cocondensation resin in which the alkyl group of the alkylphenol may be an alkyl group having 4 to 12 carbon atoms is particularly preferable.
  • the rubber composition of the present invention can contain one or more resol type phenolic formaldehyde cocondensation resins.
  • the softening point of the resol-type phenol formaldehyde cocondensation resin contained in the rubber composition of the present invention is usually 120 ° C. or less, preferably 80 to 110 ° C.
  • the use of a resin with a softening point of 120 ° C. or lower improves the dispersibility when preparing the rubber composition, thus reducing the temperature during rubber kneading.
  • the rubber composition of the present invention can be prepared more easily.
  • resol-type phenol formaldehyde cocondensation resin contained in the rubber composition of the present invention include the resins produced in the Examples section described later, Takuro Chemical 201 Co., Ltd. HITanol 2501, manufactured by Kasei Kogyo Co., Ltd. Examples thereof include SP-1044 and SP-1045.
  • the rubber composition of the present invention preferably contains 8 to 20 parts by weight, more preferably 10 to 18 parts by weight of a resol type phenol formaldehyde cocondensation resin with respect to 100 parts by weight of butyl rubber.
  • a resol type phenol formaldehyde cocondensation resin By setting the content of the resol-type phenolic formaldehyde cocondensation resin to 8 parts by weight or more, the crosslinking rate can be further improved, and by setting the content to 20 parts by weight or less, unreacted (participating in crosslinking) It is possible to reduce the co-condensation resin.
  • the compound represented by the general formula (1), the compound represented by the general formula (2), the compound represented by the general formula (3), and the bis (4- Specific examples of phenols represented by the above general formula (1) among at least one phenol selected from the group consisting of (hydroxyphenyl) sulfone (hereinafter sometimes referred to as specific phenols) include, for example, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol F (4,4′-dihydroxydiphenylmethane), bisphenol B (2,2-bis (4-hydroxyphenyl) butane), bisphenol E (1, 1-bis (4-hydroxyphenyl) ethane), bisphenol AP (1,1-bis (4-hydroxyphenyl) -1-phenyl ), Bisphenol BP (bis (4-hydroxyphenyl) diphenylmethane), and the like.
  • specific phenols include, for example, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol F (4,4′-dihydroxydiphenylmethane
  • phenols represented by the general formula (2) include bisphenol Z (1,1-bis (4-hydroxy). Phenyl) cyclohexane), 1,1-bis (4-hydroxyphenyl) cyclododecane and the like.
  • phenols represented by the above general formula (3) include 1,2-bis (4-hydroxy). Phenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and the like.
  • the rubber composition of the present invention can contain one or more specific phenols.
  • the specific phenols are preferably 0.01 to 2.0 parts by weight, more preferably 0.01 to 1.5 parts by weight, still more preferably 0.03 parts per 100 parts by weight of butyl rubber. Contains ⁇ 1.5 parts by weight.
  • the crosslinking rate can be further improved, and by making the content 2.0 parts by weight or less, the dispersibility of the specific phenols in the rubber Can be improved.
  • the crosslinking rate is improved without using a crosslinking accelerator containing a halogen atom, so the halogen content in the rubber composition of the present invention is 0.1% by weight or less.
  • the halogen content contained in the rubber composition of the present invention is obtained by burning and decomposing the rubber composition in a flask filled with oxygen, and absorbing the inorganic halogen content in the generated gas in the absorbent in the flask to obtain an analysis sample.
  • the sample can be quantified by silver nitrate titration, potentiometric titration, ion chromatography or the like.
  • the rubber composition of the present invention can contain additives usually blended with rubber in addition to butyl rubber, resol type phenolic formaldehyde cocondensation resin, and specific phenols.
  • the additive include anti-aging agents, fillers such as carbon black, various inorganic fillers such as baked clay, zinc white, stearic acid, and oils.
  • the rubber composition of the present invention can contain one or more additives.
  • the method for producing the rubber composition of the present invention may be a method for producing a rubber composition by mixing a resol-type phenol formaldehyde cocondensation resin and a specific phenol with butyl rubber, or a resol-type phenol.
  • a method may be used in which a formaldehyde co-condensation resin and a specific phenol are mixed in advance to obtain a resin mixture, and then the resin mixture is mixed with butyl rubber to produce a rubber composition.
  • a method in which a condensation resin and a specific phenol are mixed in advance to obtain a resin mixture, and then the resin mixture and butyl rubber are mixed is preferable because each component is easily dispersed uniformly in butyl rubber.
  • the content ratio of the resol type phenolic formaldehyde cocondensation resin and the specific phenol in the resin mixture is the same as that of the resol type phenolic formaldehyde.
  • the specific phenols are usually 0.05 to 25 parts by weight, preferably 0.05 to 19 parts by weight, more preferably 0.15 to 19 parts by weight with respect to 100 parts by weight of the condensation resin.
  • the crosslinked rubber composition obtained by crosslinking the rubber composition of the present invention can be obtained by crosslinking the rubber composition of the present invention described above.
  • a method for crosslinking the rubber composition of the present invention for example, a method in which the process from the molding process to the end of crosslinking is performed by a pressure press or the like, the molding process and primary crosslinking are performed in the pressure press, for example, for 5 to 15 minutes, and then The method of performing secondary crosslinking in an oven or an electric furnace, for example, for 30 minutes to 4 hours can be mentioned. From the viewpoint of productivity of the crosslinked rubber composition, the method of performing primary crosslinking and secondary crosslinking separately. Is preferred.
  • the cross-linking temperature of the rubber composition of the present invention can be applied in the same temperature range as when a conventional resin cross-linking agent is used. Specifically, it is, for example, 130 to 230 ° C, preferably 160 to 210 ° C, more preferably 180 to 200 ° C.
  • the crosslinked rubber composition obtained by crosslinking the rubber composition of the present invention can be used as various rubber products, and can be suitably used as packings, O-rings and the like.
  • the softening point of the resol type phenol formaldehyde cocondensation resin described below is a value measured by a method based on JIS K2207.
  • the mixture was cooled to 65 ° C., added with 84 g of water, 90 g of toluene and 16.4 g of 30% by weight sulfuric acid, stirred, allowed to stand, and separated to obtain a toluene layer. Thereafter, washing of the toluene layer with water was repeated three times. Subsequently, the toluene layer containing the resin is concentrated for 1 hour under normal pressure until the internal temperature reaches 118 ° C., and then is concentrated under reduced pressure for 90 hours and the internal temperature reaches 121 ° C. for 1 hour. -368 g of butylphenol / formaldehyde co-condensation resin (resin-1) was obtained. The softening point of the obtained cocondensation resin was 110 ° C.
  • Example 1 Preparation of resin mixture A-1> Resol-type p-tert-octylphenol-formaldehyde cocondensation resin Tacrol 201 (softening point: 88 ° C., manufactured by Taoka Chemical Co., Ltd., hereinafter may be referred to as resin 201) 50 g and 1,1,2,2- 4.0 g of tetrakis (4-hydroxyphenyl) ethane (hereinafter sometimes referred to as THPE) is placed in a mortar and mixed at 25 ° C. while crushing with a pestle to obtain a resin mixture A-1 containing THPE (THPE). 54 g) was obtained.
  • resin 201 Resol-type p-tert-octylphenol-formaldehyde cocondensation resin
  • resin 201 softening point: 88 ° C., manufactured by Taoka Chemical Co., Ltd., hereinafter may be referred to as resin 201)
  • Example 2 Preparation of resin mixture A-2>
  • Resin mixture A-2 containing Bis-A (Bis-A) was operated in the same manner as in Example 1 except that 0.33 g of bisphenol A (hereinafter sometimes referred to as Bis-A) was used instead of 4.0 g of THPE. 50.3 g of A content 0.66% by weight) was obtained.
  • Example 3 Preparation of resin mixture A-3> The same operation as in Example 1 was carried out except that 4.0 g of Bis-A was used instead of 4.0 g of THPE to obtain 54 g of a resin mixture A-2 containing Bis-A (Bis-A content 7.4% by weight). It was.
  • Example 5 Preparation of resin mixture A-5> A resin mixture A-5 containing Bis-F (Bis-F content 0.66% by weight) 50.3 g was operated in the same manner as in Example 1 except that 0.33 g of Bis-F was used instead of 4.0 g of THPE. Got.
  • Example 6 Preparation of resin mixture A-6> The same operation as in Example 1 was carried out except that 4.0 g of Bis-F was used instead of 4.0 g of THPE to obtain 54 g of a resin mixture A-6 containing Bis-F (Bis-F content 7.4% by weight). It was.
  • Example 7 Preparation of resin mixture A-7> BIS-Z was operated in the same manner as in Example 1 except that 0.17 g of 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter sometimes referred to as BIS-Z) was used instead of 4.0 g of THPE. 50.2 g of a resin mixture A-7 containing BIS (BIS-Z content of 0.33% by weight) was obtained.
  • BIS-Z 1,1-bis (4-hydroxyphenyl) cyclohexane
  • Example 8 Preparation of resin mixture A-8> A resin mixture A-8 containing BIS-Z (BIS-Z content 0.66 wt%) 50.3 g was operated in the same manner as in Example 1 except that 0.33 g of BIS-Z was used instead of 4.0 g of THPE. Got.
  • Example 9 Preparation of resin mixture A-9> The same operation as in Example 1 was conducted except that 4.0 g of BIS-Z was used instead of 4.0 g of THPE, to obtain 54 g of a resin mixture A-9 containing BIS-Z (BIS-Z content 7.4% by weight). It was.
  • Example 10 Preparation of resin mixture A-10> Resin mixture A-10 containing TPM was operated in the same manner as in Example 1 except that 0.17 g of tris (4-hydroxyphenyl) methane (hereinafter sometimes referred to as TPM) was used instead of 4.0 g of THPE. 50.2 g) was obtained.
  • TPM tris (4-hydroxyphenyl) methane
  • Example 11 Preparation of resin mixture A-11> The same operation as in Example 1 was carried out except that 0.33 g of TPM was used instead of 4.0 g of THPE, to obtain 50.3 g of a resin mixture A-11 (TPM content 0.66% by weight) containing TPM.
  • Example 12 Preparation of resin mixture A-12> The same operation as in Example 1 was carried out except that 4.0 g of TPM was used instead of 4.0 g of THPE, to obtain 54 g of a resin mixture A-12 containing TPM (TPM content: 7.4% by weight).
  • Example 14 Preparation of resin mixture B-2> The same operation as in Example 13 was carried out except that the amount of THPE used was 2.5 g, to obtain 53 g of a resin mixture B-2 containing THPE (THPE content 4.8% by weight).
  • Example 15 Preparation of resin mixture B-3> The same operation as in Example 13 was carried out except that 2.5 g of bis (4-hydroxyphenyl) sulfone ⁇ bisphenol S (hereinafter sometimes referred to as Bis-S) ⁇ was used instead of THPE, and Bis-S was contained. 53 g of resin mixture B-3 (Bis-S content 4.8% by weight) was obtained.
  • Bis-S bis (4-hydroxyphenyl) sulfone ⁇ bisphenol S
  • Example 16 100 parts by weight of butyl rubber (Polycer butyl 402), 50 parts by weight of carbon black (“Seast S” (SRF grade) manufactured by Tokai Carbon Co., Ltd.), 5 parts by weight of zinc flower (Zohua Chemical Industry Co., Ltd., Zinc Flower 2)
  • Example 16 the resin mixture used was the resin mixture shown in Tables 1 to 3 below, and the amount used was also changed to the blending amount of the co-condensation resin and additives shown in Tables 1 to 3. Except for the above, a rubber composition and a crosslinked rubber composition were prepared in the same manner as in Example 16, and the following evaluation measurement was performed. The results are shown in Tables 1 to 3. In Tables 1 to 3, the amount of each component represents the amount (parts by weight) based on 100 parts by weight of butyl rubber. In Reference Examples 1 and 2, only the resin 201 (Reference Example 1) and the resin-1 (Reference Example 2) obtained in Production Example 1 were used in place of the resin mixture.
  • the vulcanization speeds t (10) and t (90) for Examples 16 to 27 and Comparative Examples 5 to 8 were 10% of the maximum torque value obtained in Reference Example 1, and 90%.
  • the vulcanization speeds t (10) and t (90) of Reference Example 2 and Examples 28 to 30 the time to reach 10% of the maximum torque value obtained in Reference Example 2 and 90% are reached. It was time.
  • (2) Handleability (appearance) The rubber composition after kneading with the roll, the crosslinked rubber sheet after press molding, and the roll and mold surfaces are free of rubber agglomerates, foaming, deformation (thinning, etc.), and contamination of the roll and mold. The presence or absence was visually observed.
  • the rubber composition of the present invention containing a resol-type alkylphenol / formaldehyde cocondensation resin and specific phenols is a case where only a resol-type alkylphenol / formaldehyde cocondensation resin is used as a crosslinking agent (Reference Example).
  • Reference Example 2 As compared with 1, Reference Example 2), it was found that the above-mentioned physical properties were improved.
  • the rubber composition containing phenols other than the specific phenols has the above-described physical properties as compared with the case where only the resol type alkylphenol / formaldehyde cocondensation resin is used as a crosslinking agent (Reference Example 1 and Reference Example 2). It turned out to be worse (Comparative Examples 5 to 8).

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Abstract

La présente invention concerne une composition de caoutchouc contenant un caoutchouc butyle, une résine co-condensée phénol-formaldéhyde de type résol et un phénol, la composition de caoutchouc contenant, en tant que phénol, au moins un phénol choisi dans le groupe constitué de phénols représentés par les formules générales (1), (2), (3) et (4 ); son procédé de production ; et un mélange de résine contenant une résine co-condensée de phénol-formaldéhyde de type résol et au moins un phénol choisi dans le groupe constitué des phénols représentés par les formules générales (1), (2), (3) et (4).
PCT/JP2019/015058 2018-04-16 2019-04-05 Composition de caoutchouc contenant du caoutchouc butyle, une résine co-condensée de phénol-formaldéhyde de type résol et du phénol Ceased WO2019203015A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020207029082A KR102614843B1 (ko) 2018-04-16 2019-04-05 부틸 고무, 레졸형 페놀류 포름알데히드 공축합 수지, 및 페놀류를 포함하는 고무 조성물
CN201980025887.0A CN111989365B (zh) 2018-04-16 2019-04-05 丁基橡胶、甲阶型酚类甲醛共缩聚树脂及包含酚类的橡胶组合物

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JP2018078339 2018-04-16
JP2018-078339 2018-04-16

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JP (1) JP6611144B2 (fr)
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CN (1) CN111989365B (fr)
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WO (1) WO2019203015A1 (fr)

Citations (4)

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