JP4385831B2 - Phenol resin mixture for rubber composition addition - Google Patents
Phenol resin mixture for rubber composition addition Download PDFInfo
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- JP4385831B2 JP4385831B2 JP2004111058A JP2004111058A JP4385831B2 JP 4385831 B2 JP4385831 B2 JP 4385831B2 JP 2004111058 A JP2004111058 A JP 2004111058A JP 2004111058 A JP2004111058 A JP 2004111058A JP 4385831 B2 JP4385831 B2 JP 4385831B2
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- rubber composition
- phenol resin
- resin mixture
- phenol
- Prior art date
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- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 87
- 239000005011 phenolic resin Substances 0.000 title claims description 84
- 229920001971 elastomer Polymers 0.000 title claims description 81
- 239000005060 rubber Substances 0.000 title claims description 81
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 32
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 27
- 235000010290 biphenyl Nutrition 0.000 claims description 16
- -1 methylol group Chemical group 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000004132 cross linking Methods 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 229920003986 novolac Polymers 0.000 claims description 15
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 9
- 125000006839 xylylene group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 5
- 125000005724 cycloalkenylene group Chemical group 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical group COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 5
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- HCJMNOSIAGSZBM-UHFFFAOYSA-N 6-methylsalicylic acid Chemical compound CC1=CC=CC(O)=C1C(O)=O HCJMNOSIAGSZBM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000004849 alkoxymethyl group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000005172 methylbenzenes Chemical class 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- NSENZNPLAVRFMJ-UHFFFAOYSA-N 2,3-dibutylphenol Chemical compound CCCCC1=CC=CC(O)=C1CCCC NSENZNPLAVRFMJ-UHFFFAOYSA-N 0.000 description 1
- HRQPPTDGMMGDKC-UHFFFAOYSA-N 2,3-dipropylphenol Chemical compound CCCC1=CC=CC(O)=C1CCC HRQPPTDGMMGDKC-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- FCUBUGPGVCEURB-UHFFFAOYSA-N 3-methyl-2-propylphenol Chemical compound CCCC1=C(C)C=CC=C1O FCUBUGPGVCEURB-UHFFFAOYSA-N 0.000 description 1
- WRFWTYGMKIUAKL-UHFFFAOYSA-N 3-methylphenol Chemical compound CC1=CC=CC(O)=C1.CC1=CC=CC(O)=C1 WRFWTYGMKIUAKL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PLKZZSKEJCNYEQ-UHFFFAOYSA-N 4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=C(O)C=C1 PLKZZSKEJCNYEQ-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 235000019492 Cashew oil Nutrition 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940059459 cashew oil Drugs 0.000 description 1
- 239000010467 cashew oil Substances 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000013191 viscoelastic testing Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
本発明は、ゴム組成物添加用フェノール樹脂混合物、特にタイヤのカーカス部材、コンベヤベルト及びホース等に用いられるゴム組成物に添加される特定構造のフェノール樹脂混合物に関するものである。 The present invention relates to a phenol resin mixture for adding a rubber composition, and more particularly to a phenol resin mixture having a specific structure which is added to a rubber composition used for tire carcass members, conveyor belts, hoses and the like.
従来、ゴムを高弾性化する手段としては、カーボンブラック等の充填剤を増量したり、加硫剤の硫黄を増量して架橋点を増やす等の手法が知られているが、かかる手法を採るとゴム組成物の耐破壊性等の物性が著しく低下するという問題があった。 Conventionally, as means for increasing the elasticity of rubber, methods such as increasing the filler such as carbon black or increasing the crosslinking point by increasing the sulfur of the vulcanizing agent are employed. In addition, there is a problem that physical properties such as fracture resistance of the rubber composition are remarkably lowered.
これに対し、ゴムの耐破壊性の低下を抑えながらゴムを高弾性化する手段として、ノボラック型又はレゾール型の未変性フェノール樹脂を添加する方法や、トールオイル又はカシューオィル等の不飽和油、或いはキシレン又はメシチレン等の芳香族炭化水素で変性したフェノール樹脂を添加する方法が提案されており、耐破壊性の低下を抑えながらゴム組成物を高弾性化するために広く用いられている(例えば、特許文献1及び2参照)。 On the other hand, as a means to increase the elasticity of rubber while suppressing a decrease in the fracture resistance of rubber, a method of adding a novolak-type or resol-type unmodified phenol resin, an unsaturated oil such as tall oil or cashew oil, or A method of adding a phenol resin modified with an aromatic hydrocarbon such as xylene or mesitylene has been proposed, and is widely used to increase the elasticity of a rubber composition while suppressing a decrease in fracture resistance (for example, (See Patent Documents 1 and 2).
しかしながら、昨今のゴムに対する性能要求は非常に厳しいものがあり、ゴムの耐破壊性の低下を抑えながらゴムを更に高弾性化する必要がある。これに対し、上述の未変性フェノール樹脂や変性フェノール樹脂を添加する方法では、耐破壊性の低下を抑えながらゴムを更に高弾性化するという意味では不充分であり、依然として改良の余地があった。 However, recent performance requirements for rubber are very severe, and it is necessary to further increase the elasticity of rubber while suppressing a decrease in the fracture resistance of the rubber. On the other hand, the above-mentioned method of adding the unmodified phenol resin or the modified phenol resin is insufficient in terms of further increasing the elasticity of the rubber while suppressing a decrease in fracture resistance, and there is still room for improvement. .
そこで、本発明の目的は、ゴム組成物の耐破壊性の低下を防止しながらゴム組成物の高弾性化が可能なゴム組成物添加用フェノール樹脂混合物を提供することにある。 Accordingly, an object of the present invention is to provide a phenol resin mixture for adding a rubber composition capable of increasing the elasticity of the rubber composition while preventing a decrease in the fracture resistance of the rubber composition.
本発明者は、上記目的を達成するために鋭意検討した結果、特定構造のフェノール樹脂をゴム組成物に添加することにより、ゴム組成物の耐破壊性の低下を防止しながら、ゴム組成物を著しく高弾性化できることを見出し、本発明を完成させるに至った。 As a result of intensive investigations to achieve the above object, the present inventor has added a phenol resin having a specific structure to the rubber composition, thereby preventing the rubber composition from being deteriorated in breakage resistance. It has been found that the elasticity can be remarkably increased, and the present invention has been completed.
即ち、本発明のゴム組成物添加用フェノール樹脂混合物は、下記式(I):
本発明のゴム組成物添加用フェノール樹脂混合物の好適例においては、前記R1及びR2の少なくとも一部がアラルキレン基である。ここで、該アラルキレン基としては、キシリレン基及びビフェニルジメチレン基が好ましく、p-キシリレン基及び[1,1'-ビフェニル]-4,4'-ジメチレン基が更に好ましい。前記R1及びR2の少なくとも一部がp-キシリレン基である場合、該p-キシリレン基の含有量は、全R1及びR2の5モル%以上であるのがより一層好ましい。また、前記R1及びR2の少なくとも一部が[1,1'-ビフェニル]-4,4'-ジメチレン基である場合、該[1,1'-ビフェニル]-4,4'-ジメチレン基の含有量は、全R1及びR2の5モル%以上であるのがより一層好ましい。 In a preferred example of the phenol resin mixture for adding a rubber composition of the present invention, at least a part of the R 1 and R 2 is an aralkylene group. Here, as the aralkylene group, a xylylene group and a biphenyldimethylene group are preferable, and a p-xylylene group and [1,1′-biphenyl] -4,4′-dimethylene group are more preferable. When at least a part of R 1 and R 2 is a p-xylylene group, the content of the p-xylylene group is more preferably 5 mol% or more of the total R 1 and R 2 . When at least a part of R 1 and R 2 is a [1,1′-biphenyl] -4,4′-dimethylene group, the [1,1′-biphenyl] -4,4′-dimethylene group The content of is more preferably 5 mol% or more of the total R 1 and R 2 .
本発明のゴム組成物添加用フェノール樹脂混合物の他の好適例においては、前記式(I)中のR0が、水素又は炭素数1〜8のアルキル基であり、pが0である。ここで、前記式(I)中のR0がメチル基であるのが更に好ましく、前記式(I)中のR0がメチル基で、mが1であるのがより一層好ましく、前記式(I)中のR0がメチル基で、該メチル基がヒドロキシル基に対して3位又は4位に結合しているのが特に好ましい。 In another preferable example of the phenol resin mixture for adding a rubber composition of the present invention, R 0 in the formula (I) is hydrogen or an alkyl group having 1 to 8 carbon atoms, and p is 0. Here, R 0 in the formula (I) is more preferably a methyl group, R 0 in the formula (I) is more preferably a methyl group, and m is more preferably 1. It is particularly preferable that R 0 in I) is a methyl group, and the methyl group is bonded to the hydroxyl group at the 3-position or the 4-position.
本発明のゴム組成物添加用フェノール樹脂混合物は、メチレン供与体である硬化剤を前記フェノール樹脂の1〜30質量%含むのが好ましい。ここで、該硬化剤としては、ヘキサメチルメチロールメラミンが好ましい。 The phenol resin mixture for adding a rubber composition of the present invention preferably contains 1-30% by mass of the phenol resin with a curing agent which is a methylene donor. Here, as the curing agent, hexamethylmethylol melamine is preferable.
本発明によれば、特定構造で表され、ゴム組成物に添加することで、ゴム組成物の耐破壊性の低下を防止しながらゴム組成物の高弾性化が可能なフェノール樹脂とメチレン架橋フェノールノボラック樹脂とを含むゴム組成物添加用フェノール樹脂混合物を提供することができる。 According to the present invention, a phenol resin and a methylene-crosslinked phenol , which are represented by a specific structure and can be added to a rubber composition, can increase the elasticity of the rubber composition while preventing deterioration of the fracture resistance of the rubber composition. A phenol resin mixture for adding a rubber composition containing a novolac resin can be provided.
以下に、本発明を詳細に説明する。本発明に用いるフェノール樹脂は、上記式(I)で表される。一方、従来のゴム組成物に用いられている下記式(IV):
また、変性フェノール樹脂は、フェノール樹脂を重合した後、該重合体を変性するので、構造的に分子の未端のみが変性され、中央部は未変性のフェノール樹脂と同じである。そのため、分子末端のゴム成分への相溶性は改善されるものの、中央部の相溶性が低いので、充分なゴム物性が得られない。 Further, since the modified phenolic resin is polymerized after the phenolic resin is polymerized, only the molecular end is structurally modified, and the central part is the same as the unmodified phenolic resin. Therefore, although the compatibility of the molecular terminal with the rubber component is improved, the compatibility of the central portion is low, so that sufficient rubber physical properties cannot be obtained.
これに対して、式(I)で表されるフェノール樹脂は、複数のフェノール類がメチレン基より大きな2価の基を介して結合した部分を含むため、分子の未端及び中央の双方のゴム成分に対する相溶性が改善されている。一例として、下記式(V):
より詳しくは、上記フェノール樹脂は、複数のフェノール類がメチレン基より大きな2価の基を介して結合した部分を含むため、ゴム組成物に従来用いられていた未変性又は変性フェノール樹脂よりも、極性の官能基であるフェノール基とフェノール基との距離が長い部分を含む。そのため、上記フェノール樹脂は、上記未変性及び変性フェノール樹脂よりも極性が低く、(1)ゴム成分中での分散性が改善され、ゴム組成物を大幅に高弾性化することができる。また、上記フェノール樹脂は、ゴム成分中での分散性が良好なため、該フェノール樹脂をゴム組成物に添加しても、ゴム組成物の均一性が維持され、ゴム組成物中に破壊の起点となる部分がなく、そのため、(2)該フェノール樹脂が添加されたゴム組成物は、硬化後の形態が応力に対しより強く、耐破壊性の低下が最小限に抑制されている。 More specifically, since the phenol resin includes a portion in which a plurality of phenols are bonded via a divalent group larger than a methylene group, it is more preferable than an unmodified or modified phenol resin conventionally used in rubber compositions. It includes a portion where the distance between the phenol group and the phenol group which is a polar functional group is long. Therefore, the phenol resin has a lower polarity than the unmodified and modified phenol resins, (1) dispersibility in the rubber component is improved, and the rubber composition can be made highly elastic. In addition, since the phenol resin has good dispersibility in the rubber component, even when the phenol resin is added to the rubber composition, the uniformity of the rubber composition is maintained, and the starting point of destruction in the rubber composition. Therefore, (2) the rubber composition to which the phenol resin is added has a form after curing that is stronger against stress, and a decrease in fracture resistance is minimized.
本発明に用いるフェノール樹脂は、上記式(I)で表される。式(I)において、繰り返し単位数nは、0〜10である。また、式(I)においてR0は、水素、炭素数1〜10のアルキル基、炭素数1〜4のアルコキシ基、フェニル基及びメチロール基からなる群から選ばれる少なくともひとつの官能基であり、好ましくは、水素又は炭素数1〜8のアルキル基であり、同一でも異なっていてもよい。ここで、炭素数1〜10のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられ、これらの中でも、メチル基及びエチル基が好ましく、メチル基が更に好ましい。また、炭素数1〜4のアルコキシ基としては、メトキシ基及びエトキシ基が好ましい。なお、R0がメチル基の場合、該メチル基がヒドロキシル基に対して3位又は4位に結合しているのが特に好ましい。 The phenol resin used in the present invention is represented by the above formula (I) . In the formula (I) , the number of repeating units n is 0-10. In Formula (I) , R 0 is at least one functional group selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and a methylol group, Preferably, they are hydrogen or a C1-C8 alkyl group, and may be the same or different. Here, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. Moreover, as a C1-C4 alkoxy group, a methoxy group and an ethoxy group are preferable. When R 0 is a methyl group, it is particularly preferable that the methyl group is bonded to the hydroxyl group at the 3-position or the 4-position.
式(I)において、pは0又は1の整数で、0であるのが好ましく、mは1〜3の整数で、1であるのが好ましい。なお、OH、R0、R1及びR2のいずれも結合していない位置には水素が結合している。 In the formula (I), p is an integer of 0 or 1, preferably 0, and m is an integer of 1 to 3, and is preferably 1. Note that hydrogen is bonded to a position where none of OH, R 0 , R 1 and R 2 is bonded.
式(I)において、R1及びR2は、架橋基で、但し、R1及びR2の少なくとも一部は、アリーレン基、炭素数2〜l0のアルキレン基、アラルキレン基、シクロアルケニレン基及びシクロアルカジエニレン基からなる群から選ばれる少なくとも一種の架橋基であり、互いに同一でも異なってもよい。従来、高弾性化を目的としてゴム組成物に添加されていたフェノール樹脂は、R1及びR2の総てがメチレン基であるが、本発明に用いるフェノール樹脂は、R1及びR2としてメチレン基より大きな2価の基を含むため、フェノール基同士の距離が長い部分が存在し、前述のような作用を発揮する。 In the formula (I) , R 1 and R 2 are bridging groups, provided that at least part of R 1 and R 2 is an arylene group, an alkylene group having 2 to 10 carbon atoms, an aralkylene group, a cycloalkenylene group and a cyclo group. At least one bridging group selected from the group consisting of alkadienylene groups, which may be the same or different. Conventionally, phenolic resins added to rubber compositions for the purpose of increasing elasticity are all methylene groups for R 1 and R 2 , but the phenolic resin used in the present invention is methylene as R 1 and R 2. Since a divalent group larger than the group is included, there is a portion where the distance between the phenol groups is long, and the above-described action is exhibited.
ここで、上記アリーレン基としては、フェニレン基等が挙げられ、炭素数2〜l0のアルキレン基としては、エチレン基、プロピレン基等が挙げられ、アラルキレン基としては、キシリレン基、ビフェニルジメチレン基(−CH2−C6H4−C6H4−CH2−)等が挙げられ、シクロアルケニレン基としては、シクロヘキシレン基、ジシクロデシレン基、トリシクロデシレン基等が挙げられ、シクロアルカジエニレン基としては、シクロペンタジエニレン基等が挙げられる。R1及びR2は、その少なくとも一部が、上記架橋基の中でもキシリレン基又はビフェニルジメチレン基であるのが好ましい。なお、キシリレン基には、構造異性体、即ち、o-キシリレン基、m-キシリレン基、p-キシリレン基が存在し、また、ビフェニルジメチレン基にも、構造異性体、即ち、[1,1'-ビフェニル]-4,4'-ジメチレン基、[1,1'-ビフェニル]-2,2'-ジメチレン基、[1,1'-ビフェニル]-2,3'-ジメチレン基、[1,1'-ビフェニル]-2,4'-ジメチレン基、[1,1'-ビフェニル]-3,3'-ジメチレン基、[1,1'-ビフェニル]-3,4'-ジメチレン基が存在するが、架橋基がこれら構造異性体の一種単独から構成されていてもよいし、架橋基中に複数の構造異性体が混在していてもよい。上記架橋基の中でも、R1及びR2としては、p-キシリレン基及び[1,1'-ビフェニル]-4,4'-ジメチレン基が好ましく、これら架橋基の割合は、全R1及びR2の5モル%以上(即ち、R1及びR2の総数の5%以上)であるのが好ましく、10モル%以上であるのが更に好ましく、15モル%〜100モル%であるのがより一層好ましい。なお、R1及びR2がp-キシリレン基であるフェノール樹脂としは、上記式(V)で表されるフェノール樹脂が挙げられ、R1及びR2が[1,1'-ビフェニル]-4,4'-ジメチレン基であるフェノール樹脂としては、下記式(VI):
で表されるフェノール樹脂が挙げられる。
Here, examples of the arylene group include a phenylene group, examples of the alkylene group having 2 to 10 carbon atoms include an ethylene group and a propylene group, and examples of the aralkylene group include a xylylene group and a biphenyldimethylene group ( —CH 2 —C 6 H 4 —C 6 H 4 —CH 2 —) and the like, and examples of the cycloalkenylene group include a cyclohexylene group, a dicyclodecylene group, a tricyclodecylene group and the like, and a cycloalkadienylene. Examples of the group include a cyclopentadienylene group. It is preferable that at least a part of R 1 and R 2 is a xylylene group or a biphenyldimethylene group among the crosslinking groups. The xylylene group includes structural isomers, that is, o-xylylene group, m-xylylene group, and p-xylylene group, and the biphenyldimethylene group also has a structural isomer, that is, [1,1. '-Biphenyl] -4,4'-dimethylene group, [1,1'-biphenyl] -2,2'-dimethylene group, [1,1'-biphenyl] -2,3'-dimethylene group, [1, 1'-biphenyl] -2,4'-dimethylene group, [1,1'-biphenyl] -3,3'-dimethylene group, [1,1'-biphenyl] -3,4'-dimethylene group However, the crosslinking group may be composed of one of these structural isomers alone, or a plurality of structural isomers may be mixed in the crosslinking group. Among the above crosslinking group, the R 1 and R 2, p-xylylene group and a [1,1'-biphenyl] -4,4'-dimethylene group is preferable, the proportion of these crosslinking groups, all R 1 and R Is preferably 5 mol% or more of 2 (that is, 5% or more of the total number of R 1 and R 2 ), more preferably 10 mol% or more, and more preferably 15 mol% to 100 mol%. Even more preferred. The phenol resin in which R 1 and R 2 are p-xylylene groups includes a phenol resin represented by the above formula (V), and R 1 and R 2 are [1,1′-biphenyl] -4. As a phenol resin which is a 4,4'-dimethylene group, the following formula (VI):
The phenol resin represented by these is mentioned.
なお、本発明に用いるフェノール樹脂において、R1及びR2の一部がメチレン基で構成される場合、好ましくは全R1及びR2の5モル%以上が、より好ましくは10モル%以上が、さらに好ましくは20モル%以上が、最も好ましくは50モル%以上が、アリーレン基、炭素数2〜l0のアルキレン基、アラルキレン基、シクロアルケニレン基又はシクロアルカジエニレン基からなる群から選ばれる少なくとも一種の架橋基である。 In the phenol resin used in the present invention, when a part of R 1 and R 2 is composed of a methylene group, preferably 5 mol% or more, more preferably 10 mol% or more of all R 1 and R 2 are present. More preferably, 20 mol% or more, and most preferably 50 mol% or more is at least selected from the group consisting of an arylene group, an alkylene group having 2 to 10 carbon atoms, an aralkylene group, a cycloalkenylene group, or a cycloalkadienylene group. It is a kind of crosslinking group.
また、上記式(I)で示されるフェノール樹脂に対し、メチレン架橋したフェノールノボラック樹脂を混合して使用する。ここで、メチレン架橋したフェノールノボラック樹脂としては、例えば、上記式(IV)で示される構造の樹脂、及び下記式(VII):
本発明に用いるフェノール樹脂としては、市販のフェノール樹脂、例えば、明和化成社のMEH-7800、MEH-7851等が使用できる。また、本発明に用いるフェノール樹脂は、以下の方法で合成することもできる。 As the phenol resin used in the present invention, commercially available phenol resins such as MEH-7800 and MEH-7851 manufactured by Meiwa Kasei Co., Ltd. can be used. Moreover, the phenol resin used for this invention is also compoundable with the following method.
上記式(I)で表されるフェノール樹脂は、フェノール類(A)と、例えば、1,4-ジアルコキシメチルベンゼン、4,4'-ビス(アルコキシメチル)ビフェニル等の分子中にアルコキシ基を2つ有する化合物、並びに1,4-ジハロゲン化メチルベンゼン、4,4'-ビス(ハロゲン化メチル)ビフェニル等の分子中にハロゲンを2つ有する化合物等の上記架橋基を形成する化合物(B)とを、例えば酸触媒の存在下で縮重合させて合成することができる。ここで、架橋基を形成する化合物(B)において、アルコキシ基としては、炭素数1〜4のアルコキシ基が好ましく、具体的には、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられ、これらの中でも、メトキシ基が好ましい。また、ハロゲンとしては、フッ素、塩素、臭素、ヨウ素が挙げられ、これらの中でも塩素が好ましい。また、通常、フェノール類(A)の使用量は、架橋基を形成する化合物(B)の8倍モル以上であればよく、好ましくは9〜50倍モルで、より好ましくは10〜30倍モルである。フェノール類(A)の使用量が架橋基を形成する化合物(B)の8倍モルより少ないと、架橋が過度に進み、目的のフェノール樹脂を安定的に得ることができない。また、フェノール類(A)の使用量が多過ぎると、未反応の原料が多くなり経済的でない。 The phenol resin represented by the above formula (I) includes phenols (A) and an alkoxy group in the molecule such as 1,4-dialkoxymethylbenzene, 4,4′-bis (alkoxymethyl) biphenyl, and the like. Compound having two crosslinkable groups, such as a compound having two halogens in a molecule such as a compound having two, and 1,4-dihalogenated methylbenzene, 4,4′-bis (halogenated methyl) biphenyl, etc. Can be synthesized by, for example, condensation polymerization in the presence of an acid catalyst. Here, in the compound (B) that forms a crosslinking group, the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, specifically, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Among these, a methoxy group is preferable. In addition, examples of the halogen include fluorine, chlorine, bromine, and iodine. Among these, chlorine is preferable. In general, the amount of the phenols (A) used may be 8 times mol or more, preferably 9 to 50 times mol, more preferably 10 to 30 times mol of the compound (B) forming the crosslinking group. It is. When the amount of the phenols (A) used is less than 8 moles of the compound (B) that forms a crosslinking group, the crosslinking proceeds excessively and the desired phenol resin cannot be stably obtained. Moreover, when there is too much usage-amount of phenols (A), an unreacted raw material increases and it is not economical.
上記式(I)のフェノール樹脂の製造に用いることができるフェノール類(A)としては、フェノール、m-クレゾール(3-メチルフェノール)p-クレゾール(4-メチルフェノール)、エチルフェノール、n-プロピルフェノール、t-ブチルフェノール、オクチルフェノール、ノニルフェノール、フェニルフェノール、キシレノール、メチルプロピルフェノール、ジプロピルフェノール、ジブチルフェノール、グアヤコール、グエトール、トリメチルフェノール、4-ヒドロキシビフェニル、メチロールフェノール、カテコール、レゾルシン、ハイドロキノン等が挙げられる。これらフェノール類には、構造異性体も存在するが、いずれも使用することができる。また、これらフェノール類は、一種単独で用いても、二種以上を混合して用いてもよい。上記フェノール類の中でも、フェノール、クレゾール、キシレノール、4-ヒドロキシビフェニル、メチロールフェノールが好ましく、硬化反応の点から、フェノール及びクレゾールが更に好ましい。 Examples of the phenols (A) that can be used for the production of the phenol resin of the formula (I) include phenol, m-cresol (3-methylphenol), p-cresol (4-methylphenol), ethylphenol, and n-propyl. Examples include phenol, t-butylphenol, octylphenol, nonylphenol, phenylphenol, xylenol, methylpropylphenol, dipropylphenol, dibutylphenol, guaiacol, guetol, trimethylphenol, 4-hydroxybiphenyl, methylolphenol, catechol, resorcin, hydroquinone, etc. . These phenols also have structural isomers, any of which can be used. Moreover, these phenols may be used individually by 1 type, or 2 or more types may be mixed and used for them. Among the above phenols, phenol, cresol, xylenol, 4-hydroxybiphenyl, and methylolphenol are preferable, and phenol and cresol are more preferable from the viewpoint of curing reaction.
上記フェノール樹脂の製造に使用する酸触媒としては、シュウ酸、ギ酸、酢酸、パラトルエンスルホン酸、ジメチル硫酸等の有機酸、塩酸、硫酸等の無機酸が挙げられる。触媒の使用量は、使用するフェノール類の0.01〜1質量%の範囲が好ましい。触媒の使用量が使用するフェノール類の0.01質量%未満では、反応速度が遅く、1質量%を超えると、反応が急激に進行して反応を制御することが困難となる場合がある。 Examples of the acid catalyst used for the production of the phenol resin include organic acids such as oxalic acid, formic acid, acetic acid, p-toluenesulfonic acid and dimethylsulfuric acid, and inorganic acids such as hydrochloric acid and sulfuric acid. The amount of the catalyst used is preferably in the range of 0.01 to 1% by mass of the phenols used. If the amount of the catalyst used is less than 0.01% by mass of the phenols used, the reaction rate is slow, and if it exceeds 1% by mass, the reaction may proceed rapidly and it may be difficult to control the reaction.
反応温度は、使用するフェノール類及び架橋基を形成する化合物の配合割合にもよるが、通常50〜200℃、好ましくは70〜180℃、より好ましくは80〜180℃である。反応温度が低過ぎると重合が進まず、反応温度が高過ぎると反応の制御が難しくなり、目的のフェノールノボラック樹脂を安定的に得ることが困難となる。 The reaction temperature is usually 50 to 200 ° C., preferably 70 to 180 ° C., more preferably 80 to 180 ° C., although it depends on the blending ratio of the phenols to be used and the compound that forms a crosslinking group. If the reaction temperature is too low, the polymerization does not proceed. If the reaction temperature is too high, it becomes difficult to control the reaction, and it becomes difficult to stably obtain the target phenol novolac resin.
また、反応時間は、上記反応温度にもよるが、通常は10時間以内であり、反応圧力に関しては、通常は常圧で行うが、若干の加圧ないし減圧下で反応を行ってもよい。 Although the reaction time depends on the reaction temperature, it is usually within 10 hours, and the reaction pressure is usually normal pressure, but the reaction may be performed under slight pressure or reduced pressure.
具体的に、上記式(V)のフェノール樹脂は、フェノールと1,4-ジアルコキシメチルベンゼン又は1,4-ジハロゲン化メチルベンゼンとを、上記酸触媒の存在下で縮重合させて合成することができ、上記式(VI)で表されるフェノール樹脂は、フェノールと4,4'-ビス(アルコキシメチル)ビフェニル又は4,4'-ビス(ハロゲン化メチル)ビフェニルを、上記酸触媒の存在下で縮重合させて合成することができる。 Specifically, the phenol resin of the formula (V) is synthesized by polycondensation of phenol and 1,4-dialkoxymethylbenzene or 1,4-dihalogenated methylbenzene in the presence of the acid catalyst. The phenol resin represented by the above formula (VI) is obtained by mixing phenol and 4,4′-bis (alkoxymethyl) biphenyl or 4,4′-bis (halogenated methyl) biphenyl in the presence of the acid catalyst. And can be synthesized by condensation polymerization.
本発明のゴム組成物添加用フェノール樹脂の物性については、特に制限はないが、取り扱いの面から、ポリスチレン換算での数平均分子量が800〜5000であるのが好ましく、1000〜3000であるのが更に好ましく、また、軟化点が80℃以上であるのが好ましく、90℃〜140℃であるのが更に好ましい。 The physical properties of the phenol resin for rubber composition addition of the present invention are not particularly limited, but from the viewpoint of handling, the number average molecular weight in terms of polystyrene is preferably 800 to 5000, and preferably 1000 to 3000. Further, the softening point is preferably 80 ° C. or higher, and more preferably 90 ° C. to 140 ° C.
ゴム成分に対し、上記フェノール樹脂を配合することで、高弾性なゴム組成物が得られる。ここで、ゴム成分としては、天然ゴム(NR);ポリイソプレンゴム(IR)、ブチルゴム(IIR)、ポリブタジエンゴム(BR)及びスチレン-ブタジエン共重合体ゴム(SBR)等の合成ジエン系ゴムが挙げられる。これらゴム成分は、一種単独でも、ブレンドでもよい。上記ゴム組成物における、上記式(I)のフェノール樹脂の添加量は、上記ゴム成分100質量部に対して1〜30質量部であり、1〜10質量部の範囲が好ましい。該フェノール樹脂の添加量がゴム成分100質量部に対して1質量部未満では、硬化性能が不充分となる場合があり、30質量部を超えると、ゴム組成物の柔軟性が損なわれる場合がある。 By blending the above phenol resin with the rubber component, a highly elastic rubber composition can be obtained. Here, examples of the rubber component include natural rubber (NR); synthetic diene rubbers such as polyisoprene rubber (IR), butyl rubber (IIR), polybutadiene rubber (BR), and styrene-butadiene copolymer rubber (SBR). It is done. These rubber components may be used alone or in a blend. The addition amount of the phenol resin of the formula (I) in the rubber composition is 1 to 30 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the rubber component. If the addition amount of the phenol resin is less than 1 part by mass relative to 100 parts by mass of the rubber component, the curing performance may be insufficient, and if it exceeds 30 parts by mass, the flexibility of the rubber composition may be impaired. is there.
上記フェノール樹脂をゴム成分に配合する際は、更にメチレン供与体である硬化剤を配合するのが好ましい。但し、前記R0がメチロール基の場合、該フェノール樹脂は自己硬化性なので、硬化剤は不要である。該硬化剤としては、ヘキサメチレンテトラミン、ヘキサメチルメチロールメラミン等が挙げられる。ここで、硬化剤の配合量は、前述した式(I)のフェノール樹脂の1〜30質量%の範囲が好ましい。硬化剤の配合量が1質量%未満では、フェノール樹脂の硬化が充分進まず、30質量%を超えると、ゴムの架橋系に悪影響を与える場合がある。 When blending the phenol resin into the rubber component, it is preferable to blend a curing agent which is a methylene donor. However, when the R 0 is a methylol group, the phenol resin is self-curing, so that no curing agent is required. Examples of the curing agent include hexamethylenetetramine and hexamethylmethylolmelamine. Here, the compounding amount of the curing agent is preferably in the range of 1 to 30% by mass of the above-described phenol resin of the formula (I) . When the blending amount of the curing agent is less than 1% by mass, the curing of the phenol resin does not proceed sufficiently, and when it exceeds 30% by mass, the rubber crosslinking system may be adversely affected.
また、上記ゴム成分には、上記ゴム組成物添加用フェノール樹脂及び硬化剤の他に、ゴム業界で通常使用される配合剤、例えば、充填剤、軟化剤、老化防止剤、加硫剤、加硫促進剤等を用途に応じて適宜配合することができる。上記ゴム組成物は、ロール等の開放式混練機、バンバリーミキサー等の密閉式混練機等の混練り機を用いて混練りすることによって得られ、成形加工後に加硫を行い、各種ゴム製品に適用可能である。例えば、該ゴム組成物は、タイヤ、特にタイヤのカーカス部材、コンベヤベルト及びホース等に用いることができる。 In addition to the above-mentioned phenol resin for adding a rubber composition and a curing agent, the rubber component includes compounding agents usually used in the rubber industry, such as fillers, softeners, anti-aging agents, vulcanizing agents, additives. A sulfur accelerator or the like can be appropriately blended depending on the application. The rubber composition is obtained by kneading using an open kneader such as a roll or a kneader such as a closed kneader such as a Banbury mixer, and vulcanized after molding to produce various rubber products. Applicable. For example, the rubber composition can be used for tires, particularly carcass members of tires, conveyor belts, hoses and the like.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
(合成例1:明和化成製、品名BCrF−2−5)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量2000容量部のガラス製4つ口フラスコに、m-クレゾール酸841質量部(7.787モル:m-クレゾール65モル%及びp-クレゾール35モル%含有)、4,4'-ビスメトキシメチルビフェニル63.9質量部(0.264モル)、42%のホルマリン336.3質量部(4.75モル)及びシュウ酸2.8質量部を加え、内温97℃で15時間反応させた。その後、25%の硫酸0.4質量部を添加し、100℃にて脱水し、170℃まで4時間かけて昇温することで脱メタノール反応させ、その後、減圧40torr−スチーミング処理で未反応成分を除去した。得られた樹脂の軟化点は130℃で、GPCによるポリスチレン換算数平均分子量(Mn)は1237で、重量平均分子量(Mw)は2057であった。
(Synthesis Example 1: Meiwa Kasei Co., Ltd., product name BCrF-2-5)
To a glass 4-neck flask with a capacity of 2000 parts by volume equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 841 parts by mass of m-cresolic acid (7.787 mol: 65 mol% of m-cresol and p-cresol) 35 mol% content) 4,4'-bismethoxymethylbiphenyl 63.9 parts by mass (0.264 mol), 42% formalin 336.3 parts by mass (4.75 mol) and oxalic acid 2.8 parts by mass were added, and the internal temperature was 97 ° C for 15 hours. Reacted. Thereafter, 0.4 parts by mass of 25% sulfuric acid was added, dehydrated at 100 ° C., and subjected to demethanol reaction by raising the temperature to 170 ° C. over 4 hours, and then the unreacted components were removed by reduced pressure 40 torr-steaming treatment. Removed. The resulting resin had a softening point of 130 ° C., a polystyrene-reduced number average molecular weight (Mn) by GPC of 1237, and a weight average molecular weight (Mw) of 2057.
(合成例2:明和化成製、品名XCrF−11)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量1000容量部のガラス製4つ口フラスコに、m-クレゾール酸324質量部(3モル)、p-キシレンジメチルエーテル81質量部(0.488モル)、42%のホルマリン118質量部(1.65モル)及び25%の硫酸0.2質量部を加え、内温97℃で13時間反応させた。その後、100℃にて脱水し、内温を170℃まで4時間かけて昇温することで脱メタノール反応させ、その後、減圧40torr−スチーミング処理で未反応成分を除去した。得られた樹脂の軟化点は129℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は1041で、重量平均分子量(Mw)は2523であった。
(Synthesis Example 2: Meiwa Kasei Co., Ltd., product name XCrF-11)
To a 1000-volume glass four-necked flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 324 parts by mass (3 mol) of m-cresolic acid, 81 parts by mass of p-xylene dimethyl ether (0.488) Mol), 118 parts by mass of formalin (42%) (1.65 mol) and 0.2 part by mass of 25% sulfuric acid were added and reacted at an internal temperature of 97 ° C. for 13 hours. Thereafter, dehydration was performed at 100 ° C., and the internal temperature was raised to 170 ° C. over 4 hours to cause demethanol reaction, and then unreacted components were removed by reduced pressure 40 torr-steaming treatment. The softening point of the obtained resin was 129 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 1041, and the weight average molecular weight (Mw) was 2523.
(合成例3:明和化成製、品名XBCrF−4)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量2000容量部のガラス製4つ口フラスコに、m-クレゾール酸968質量部(8.962モル)、4,4'-ビスメトキシメチルビフェニル63.9質量部(0.264モル)、p-キシレンジメチルエーテル50.8質量部(0.306モル)、42%のホルマリン339.3質量部(4.75モル)及びシュウ酸2.8質量部を加え、内温97℃で15時間反応させた。その後、50%の硫酸0.6質量部を添加し、100℃にて脱水し、内温を170℃まで6時間かけて昇温することで脱メタノール反応させ、その後、減圧40torr−スチーミング処理で未反応成分を除去した。得られた樹脂の軟化点は130℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は1234で、重量平均分子量(Mw)は2005であった。
(Synthesis Example 3: Meiwa Kasei Co., Ltd., product name XBCrF-4)
To a glass 4-necked flask with a capacity of 2000 parts by volume equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 968 parts by mass of m-cresolic acid (8.962 mol), 4,4′-bismethoxymethylbiphenyl 63.9 parts by mass (0.264 mol), p-xylene dimethyl ether 50.8 parts by mass (0.306 mol), 42% formalin 339.3 parts by mass (4.75 mol) and 2.8 parts by mass of oxalic acid were added and reacted at an internal temperature of 97 ° C. for 15 hours. . Thereafter, 0.6 parts by mass of 50% sulfuric acid was added, dehydrated at 100 ° C., the internal temperature was raised to 170 ° C. over 6 hours to cause a demethanol reaction, and then the pressure was reduced by 40 torr-steaming treatment under reduced pressure. The reaction component was removed. The softening point of the obtained resin was 130 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 1234, and the weight average molecular weight (Mw) was 2005.
(合成例4:明和化成製、品名XHF−3M)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量1000容量部のガラス製4つ口フラスコに上記式(IV)で表されるノボラック型フェノール樹脂(軟化点94℃、遊離フェノール0.03%)375質量部、4,4'-ビスメトキシメチルビフェニル41.7質量部(0.172モル)を加え、内温120℃で溶解混合させた。その後、10%の硫酸0.4質量部を添加し、内温を175℃まで3時間かけて昇温することで反応させ、その後、減圧下(40torr)で水分を除去した。得られた樹脂の軟化点は124℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は2032で、重量平均分子量(Mw)は8861であった。
(Synthesis example 4: Meiwa Kasei Co., Ltd., product name XHF-3M)
A novolac type phenol resin represented by the above formula (IV) (softening point 94 ° C., free phenol 0.03) on a 1000-volume glass four-necked flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer %) 375 parts by mass, 41.7 parts by mass of 4,4′-bismethoxymethylbiphenyl (0.172 mol) was added and dissolved and mixed at an internal temperature of 120 ° C. Thereafter, 0.4 part by mass of 10% sulfuric acid was added, the reaction was carried out by raising the internal temperature to 175 ° C. over 3 hours, and then water was removed under reduced pressure (40 torr). The softening point of the obtained resin was 124 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 2032 and the weight average molecular weight (Mw) was 8861.
(合成例5:明和化成製、品名BHF−3M)
合成例4において、4,4'-ビスメトキシメチルビフェニルに代えてp-キシレンジメチルエーテル41.7質量部(0.251モル)を使用した以外は同様にして反応を行った。得られた樹脂の軟化点は132℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は1648で、重量平均分子量(Mw)は27968であった。
(Synthesis Example 5: Meiwa Kasei Co., Ltd., product name BHF-3M)
The reaction was conducted in the same manner as in Synthesis Example 4 except that 41.7 parts by mass (0.251 mol) of p-xylene dimethyl ether was used instead of 4,4′-bismethoxymethylbiphenyl. The softening point of the obtained resin was 132 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 1648, and the weight average molecular weight (Mw) was 27968.
(合成例6:明和化成製、品名MEH−7851−4H)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量1000容量部の4つ口ガラス製フラスコに、フェノール188質量部(2モル)、4,4'-ビスメトキシメチルビフェニル331.5質量部(1.37モル)及び50%の硫酸0.23質量部を加え、窒素気流下、内温110℃〜130℃にて3.5時間、さらに165℃にて3時間反応させ、95℃まで冷却した。冷却後、90℃以上の純水500質量部を投入して電気伝導度が50μS/cm以下になるまで水洗した。その後、内温を160℃まで昇温し、減圧−スチーミング処理にて未反応成分を除去した。得られた樹脂の軟化点は130℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は1400で、重量平均分子量(Mw)は9178であった。
(Synthesis Example 6: Meiwa Kasei Co., Ltd., product name MEH-7851-4H)
In a four-necked glass flask with a capacity of 1000 parts by volume equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 188 parts by mass of phenol (2 moles) and 331.5 parts by mass of 4,4′-bismethoxymethylbiphenyl (1.37 mol) and 0.23 part by mass of 50% sulfuric acid were added, and the mixture was reacted at an internal temperature of 110 ° C. to 130 ° C. for 3.5 hours and further at 165 ° C. for 3 hours under a nitrogen stream, and cooled to 95 ° C. After cooling, 500 parts by mass of pure water at 90 ° C. or higher was added and washed with water until the electric conductivity reached 50 μS / cm or lower. Thereafter, the internal temperature was raised to 160 ° C., and unreacted components were removed by a reduced pressure-steaming treatment. The softening point of the obtained resin was 130 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 1400, and the weight average molecular weight (Mw) was 9178.
(合成例7:明和化成製、品名MEH−7800−3H)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量1000容量部のガラス製4つ口フラスコに、フェノール188質量部(2モル)、p-キシレンジメチルエーテル229.08質量部(1.38モル)、及び50%の硫酸0.16質量部を加え、窒素気流下、内温135℃にて3.5時間、さらに160℃にて1.5時間反応させ、95℃まで冷却した。冷却後、90℃以上の純水500質量部を投入して電気伝導度が30μS/cm以下になるまで水洗した。その後、内温を160℃まで昇温し、減圧−スチーミング処理にて未反応成分を除去した。得られた樹脂の軟化点は95℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は2185で、重量平均分子量(Mw)は20746であった。
(Synthesis Example 7: Meiwa Kasei Co., Ltd., product name MEH-7800-3H)
In a 1000-volume glass four-necked flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 188 parts by mass of phenol (2 mol), 229.08 parts by mass of p-xylene dimethyl ether (1.38 mol), Then, 0.16 parts by mass of 50% sulfuric acid was added, and the mixture was reacted under a nitrogen stream at an internal temperature of 135 ° C. for 3.5 hours and further at 160 ° C. for 1.5 hours, and cooled to 95 ° C. After cooling, 500 parts by mass of pure water at 90 ° C. or higher was added and washed with water until the electric conductivity reached 30 μS / cm or lower. Thereafter, the internal temperature was raised to 160 ° C., and unreacted components were removed by a reduced pressure-steaming treatment. The softening point of the obtained resin was 95 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 2185, and the weight average molecular weight (Mw) was 20,746.
(合成例8:明和化成製、品名MEH−X−5H)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量1000容量部のガラス製4つ口フラスコに、上記式(V)で表されるキシリレン架橋ノボラック樹脂(軟化点87℃、遊離フェノール0.2%)200質量部に対し、上記式(VII)で表されるノボラック型クレゾール樹脂(軟化点155℃、遊離クレゾール1.5%)300質量部を加え、窒素気流下、内温190℃にて溶解混合させた。得られた樹脂の軟化点は133℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は1908で、重量平均分子量(Mw)は13782であった。
(Synthesis Example 8: Meiwa Kasei Co., Ltd., product name MEH-X-5H)
A xylylene cross-linked novolak resin represented by the above formula (V) (softening point 87 ° C., free phenol) was added to a 1000-volume glass four-necked flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer. 0.2%) To 200 parts by mass, add 300 parts by mass of the novolak-type cresol resin (softening point 155 ° C, free cresol 1.5%) represented by the above formula (VII), and dissolve at an internal temperature of 190 ° C under a nitrogen stream. Mixed. The softening point of the obtained resin was 133 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 1908, and the weight average molecular weight (Mw) was 13782.
(参考例1)
表1に示す配合処方に従い、天然ゴム100質量部に対し、HAF級カーボンブラック50質量部、アロマオイル5質量部、ステアリン酸3質量部、亜鉛華4質量部、老化防止剤6PPD[N-(1,3-ジメチルブチル)-N'-フェニル-p-フェニレンジアミン]1質量部、加硫促進剤TBBS[N-t-ブチル-2-ベンゾチアゾールスルフェンアミド]2.2質量部、硫黄5質量部と共に、合成例1で得られたフェノール樹脂を10質量部使用し、更に、ヘキサメチルメチロールメラミン1質量部も併せて混合してゴム組成物を調製した。
( Reference Example 1 )
According to the formulation shown in Table 1, for 100 parts by mass of natural rubber, 50 parts by mass of HAF grade carbon black, 5 parts by mass of aroma oil, 3 parts by mass of stearic acid, 4 parts by mass of zinc oxide, anti-aging agent 6PPD [N- ( 1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine] 1 part by mass, vulcanization accelerator TBBS [N-t-butyl-2-benzothiazolesulfenamide] 2.2 parts by mass, sulfur 5 parts by mass At the same time, 10 parts by mass of the phenol resin obtained in Synthesis Example 1 was used, and 1 part by mass of hexamethylmethylolmelamine was further mixed to prepare a rubber composition.
(参考例2〜7、実施例8及び比較例1〜2)
参考例1において、合成例1で得られたフェノール樹脂に代えて、合成例2〜8で得られた樹脂を使用する以外は、参考例1と同様にしてゴム組成物を調製した。なお、比較例1で用いたフェノール樹脂は、上記式(IV)で表されるノボラック型フェノール樹脂(品名580、軟化点129℃)であり、比較例2で用いたフェノール樹脂は、上記式(VII)で表されるノボラック型クレゾール樹脂(品名MER−130、軟化点129℃)である。
( Reference Examples 2-7, Example 8 and Comparative Examples 1-2)
In Reference Example 1 , a rubber composition was prepared in the same manner as in Reference Example 1 except that the resins obtained in Synthesis Examples 2 to 8 were used in place of the phenol resin obtained in Synthesis Example 1. The phenol resin used in Comparative Example 1 is a novolak type phenol resin (product name 580, softening point 129 ° C.) represented by the above formula (IV), and the phenol resin used in Comparative Example 2 is the above formula ( VII) is a novolac cresol resin (product name MER-130, softening point 129 ° C.).
次に、参考例1〜7、実施例8及び比較例1〜2で得られたゴム組成物を145℃で30分間加硫して物性測定用のサンプルを作製し、下記に示す方法で硬度試験、引張試験及び動的粘弾性試験を行った。得られた結果を、比較例1を100として指数表示し、表1に併せて示した。 Next, the rubber compositions obtained in Reference Examples 1 to 7, Example 8 and Comparative Examples 1 and 2 were vulcanized at 145 ° C. for 30 minutes to prepare samples for measuring physical properties. Tests, tensile tests and dynamic viscoelastic tests were performed. The obtained results are shown as an index with Comparative Example 1 being 100, and are also shown in Table 1.
[硬度測定]
上記加硫ゴム組成物について、JIS K6253に準拠してJIS A硬度を測定した。
[Hardness measurement]
The vulcanized rubber composition was measured for JIS A hardness according to JIS K6253.
[引張試験]
上記加硫ゴム組成物からなるJISダンベル状3号形サンプルを用意し、JIS K6251に準拠して25℃で引張試験を行い、切断時伸び、引張強さ、50%伸張時の引張応力を測定した。
[Tensile test]
Prepare a JIS dumbbell-shaped No. 3 sample consisting of the above vulcanized rubber composition, and perform a tensile test at 25 ° C in accordance with JIS K6251 to measure elongation at break, tensile strength, and tensile stress at 50% elongation. did.
[動的粘弾性試験]
上記加硫ゴム組成物について、東洋精機社製スペクトロメーターを用い、歪1%、測定温度25℃にて動的貯蔵弾性率(E’)を測定した。
[Dynamic viscoelasticity test]
About the said vulcanized rubber composition, the dynamic storage elastic modulus (E ') was measured at 1% of distortion, and the measurement temperature of 25 degreeC using the Toyo Seiki spectrometer.
本発明のフェノール樹脂とメチレン架橋フェノールノボラック樹脂とを含むゴム組成物添加用フェノール樹脂混合物をゴム組成物に添加することで、切断時伸び、引張強さ及び50%伸長時の引張応力の低下を抑制してゴム組成物の耐破壊性の低下を防止しつつ、動的貯蔵弾性率を向上させ、ゴム組成物を著しく高弾性化できる。 By adding a phenol resin mixture for rubber composition addition containing the phenol resin of the present invention and a methylene-crosslinked phenol novolac resin to the rubber composition, elongation at break, tensile strength and tensile stress at 50% elongation can be reduced. While suppressing the deterioration of the fracture resistance of the rubber composition, the dynamic storage elastic modulus can be improved and the rubber composition can be made highly elastic.
Claims (13)
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JP4511231B2 (en) * | 2004-04-05 | 2010-07-28 | 株式会社ブリヂストン | Pneumatic tire |
TWI415911B (en) * | 2005-07-13 | 2013-11-21 | Ube Industries | Biphenylene cross-linked phenol novolac resin and the use thereof |
WO2007026553A1 (en) * | 2005-08-31 | 2007-03-08 | Ube Industries, Ltd. | Low softening point phenol novolac resin, method for producing same, and epoxy resin cured product using same |
JP4716845B2 (en) * | 2005-10-24 | 2011-07-06 | 日本化薬株式会社 | Phenol resin, its production method, epoxy resin and its use |
JP5228328B2 (en) * | 2007-02-01 | 2013-07-03 | 宇部興産株式会社 | Low melt viscosity phenol novolac resin, process for producing the same, and cured epoxy resin using the same |
JP5446319B2 (en) * | 2009-02-27 | 2014-03-19 | 宇部興産株式会社 | Cresol resin for photoresist, method for producing the same, and photoresist composition containing the resin |
JP5854351B2 (en) * | 2011-12-26 | 2016-02-09 | 明和化成株式会社 | Photoresist composition |
JP6406537B2 (en) * | 2014-05-22 | 2018-10-17 | 日立化成株式会社 | Method for producing phenol novolac resin, method for producing insulating cured product, and method for producing resist material |
CN113121768B (en) * | 2019-12-31 | 2023-05-05 | 华奇(中国)化工有限公司 | Long-chain phenolic resin and preparation method and application thereof |
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