JP2007291332A - Method for producing adhesive composition - Google Patents
Method for producing adhesive composition Download PDFInfo
- Publication number
- JP2007291332A JP2007291332A JP2007004659A JP2007004659A JP2007291332A JP 2007291332 A JP2007291332 A JP 2007291332A JP 2007004659 A JP2007004659 A JP 2007004659A JP 2007004659 A JP2007004659 A JP 2007004659A JP 2007291332 A JP2007291332 A JP 2007291332A
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- JP
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- Prior art keywords
- adhesive composition
- phenols
- weight
- formaldehyde
- formaldehyde condensate
- 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.)
- Granted
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 60
- 239000000853 adhesive Substances 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229920001971 elastomer Polymers 0.000 claims abstract description 51
- 239000005060 rubber Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920000126 latex Polymers 0.000 claims abstract description 30
- -1 amine compound Chemical class 0.000 claims abstract description 29
- 239000004816 latex Substances 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 230000005540 biological transmission Effects 0.000 claims abstract description 18
- 238000006482 condensation reaction Methods 0.000 claims abstract description 18
- 150000002989 phenols Chemical class 0.000 claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 17
- 230000002787 reinforcement Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000003365 glass fiber Substances 0.000 claims description 42
- 239000000839 emulsion Substances 0.000 claims description 31
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 22
- 229960001755 resorcinol Drugs 0.000 claims description 17
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 15
- 229920002681 hypalon Polymers 0.000 claims description 13
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 12
- 230000003014 reinforcing effect Effects 0.000 claims description 10
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical group C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 claims description 9
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 7
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 claims description 6
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 claims description 6
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 6
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 claims description 6
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 6
- GHVHDYYKJYXFGU-UHFFFAOYSA-N Beta-Orcinol Chemical compound CC1=CC(O)=C(C)C(O)=C1 GHVHDYYKJYXFGU-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 6
- FRNQLQRBNSSJBK-UHFFFAOYSA-N divarinol Natural products CCCC1=CC(O)=CC(O)=C1 FRNQLQRBNSSJBK-UHFFFAOYSA-N 0.000 claims description 6
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 6
- KRIDOPOPBBSDNT-UHFFFAOYSA-N 2,4,5-trimethyl-1,3-benzenediol Natural products CC1=CC(O)=C(C)C(O)=C1C KRIDOPOPBBSDNT-UHFFFAOYSA-N 0.000 claims description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 5
- OTJFQRMIRKXXRS-UHFFFAOYSA-N (hydroxymethylamino)methanol Chemical compound OCNCO OTJFQRMIRKXXRS-UHFFFAOYSA-N 0.000 claims description 4
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 4
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 claims description 4
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 claims description 3
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 claims description 3
- KQDJTBPASNJQFQ-UHFFFAOYSA-N 2-iodophenol Chemical compound OC1=CC=CC=C1I KQDJTBPASNJQFQ-UHFFFAOYSA-N 0.000 claims description 3
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 claims description 3
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 3
- 229940018563 3-aminophenol Drugs 0.000 claims description 3
- MNOJRWOWILAHAV-UHFFFAOYSA-N 3-bromophenol Chemical compound OC1=CC=CC(Br)=C1 MNOJRWOWILAHAV-UHFFFAOYSA-N 0.000 claims description 3
- SJTBRFHBXDZMPS-UHFFFAOYSA-N 3-fluorophenol Chemical compound OC1=CC=CC(F)=C1 SJTBRFHBXDZMPS-UHFFFAOYSA-N 0.000 claims description 3
- FXTKWBZFNQHAAO-UHFFFAOYSA-N 3-iodophenol Chemical compound OC1=CC=CC(I)=C1 FXTKWBZFNQHAAO-UHFFFAOYSA-N 0.000 claims description 3
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 claims description 3
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 claims description 3
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 claims description 3
- VSMDINRNYYEDRN-UHFFFAOYSA-N 4-iodophenol Chemical compound OC1=CC=C(I)C=C1 VSMDINRNYYEDRN-UHFFFAOYSA-N 0.000 claims description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 3
- MSFGJICDOLGZQK-UHFFFAOYSA-N 5-ethylbenzene-1,3-diol Chemical compound CCC1=CC(O)=CC(O)=C1 MSFGJICDOLGZQK-UHFFFAOYSA-N 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 3
- 229940087646 methanolamine Drugs 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- 150000003739 xylenols Chemical class 0.000 claims description 3
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 claims description 2
- RHJZBSMDVJWBSO-UHFFFAOYSA-N 4,5-diethylbenzene-1,3-diol Chemical compound CCC1=CC(O)=CC(O)=C1CC RHJZBSMDVJWBSO-UHFFFAOYSA-N 0.000 claims description 2
- RCNCKKACINZDOI-UHFFFAOYSA-N 4,5-dimethylbenzene-1,3-diol Chemical compound CC1=CC(O)=CC(O)=C1C RCNCKKACINZDOI-UHFFFAOYSA-N 0.000 claims description 2
- JOZMGUQZTOWLAS-UHFFFAOYSA-N 5-butylbenzene-1,3-diol Chemical compound CCCCC1=CC(O)=CC(O)=C1 JOZMGUQZTOWLAS-UHFFFAOYSA-N 0.000 claims description 2
- PQZOMNGGAHDSEH-UHFFFAOYSA-N 2,5-diethylbenzene-1,3-diol Chemical compound CCC1=CC(O)=C(CC)C(O)=C1 PQZOMNGGAHDSEH-UHFFFAOYSA-N 0.000 claims 1
- JODLJSZXZPDONB-UHFFFAOYSA-N C(C)C1(O)CC(O)=C(C(=C1)CC)CC Chemical compound C(C)C1(O)CC(O)=C(C(=C1)CC)CC JODLJSZXZPDONB-UHFFFAOYSA-N 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 abstract description 14
- 229920001568 phenolic resin Polymers 0.000 abstract description 14
- 238000001556 precipitation Methods 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 6
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 2
- 239000007859 condensation product Substances 0.000 abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- DEXXACGTZUBAMY-UHFFFAOYSA-N 4-chlorophenol;formaldehyde Chemical compound O=C.OC1=CC=C(Cl)C=C1 DEXXACGTZUBAMY-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 239000002585 base Substances 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000012783 reinforcing fiber Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZRUOTKQBVMWMDK-UHFFFAOYSA-N 2-hydroxy-6-methylbenzaldehyde Chemical compound CC1=CC=CC(O)=C1C=O ZRUOTKQBVMWMDK-UHFFFAOYSA-N 0.000 description 6
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KNAJYSZHBGJAHK-UHFFFAOYSA-N 2-chlorophenol;formaldehyde Chemical compound O=C.OC1=CC=CC=C1Cl KNAJYSZHBGJAHK-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WNYHOOQHJMHHQW-UHFFFAOYSA-N 1-chloropyrene Chemical compound C1=C2C(Cl)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 WNYHOOQHJMHHQW-UHFFFAOYSA-N 0.000 description 2
- KWLKAVNWFAWQRC-UHFFFAOYSA-N 2,4,5-triethylbenzene-1,3-diol Chemical compound CCC1=CC(O)=C(CC)C(O)=C1CC KWLKAVNWFAWQRC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 1
- NDPQQOZDGOFANP-UHFFFAOYSA-N 2-methyl-5-propylbenzene-1,3-diol Chemical compound CCCC1=CC(O)=C(C)C(O)=C1 NDPQQOZDGOFANP-UHFFFAOYSA-N 0.000 description 1
- CUEMVIJZQVZJRC-UHFFFAOYSA-N 5-ethyl-2-methylbenzene-1,3-diol Chemical compound CCC1=CC(O)=C(C)C(O)=C1 CUEMVIJZQVZJRC-UHFFFAOYSA-N 0.000 description 1
- GSMQBBTWVGEFGD-UHFFFAOYSA-N 5-ethyl-4-methylbenzene-1,3-diol Chemical compound CCC1=CC(O)=CC(O)=C1C GSMQBBTWVGEFGD-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は、ゴムと繊維を接着するための接着性組成物に関する。ゴム製の伝動ベルトにおいて、補強のための繊維コ−ドをベルト内部に埋設させる際に母材ゴムとの接着を高めるために繊維コ−ドに被覆して用いる接着性組成物に関し、特に、補強のためのガラス繊維コ−ドをベルト内部に埋設させる際に母材ゴムとの接着を高めるためにガラス繊維コ−ドに被覆して用いる接着性組成物の製造方法に関する。 The present invention relates to an adhesive composition for bonding rubber and fiber. In a rubber transmission belt, an adhesive composition used by coating a fiber cord to enhance adhesion to a base rubber when a reinforcing fiber cord is embedded in the belt. The present invention relates to a method for producing an adhesive composition used by coating a glass fiber cord in order to enhance adhesion to a base rubber when a reinforcing glass fiber cord is embedded in a belt.
フェノール類−ホルムアルデヒド縮合物は、ベンゼン環にＯＨ基が付加したフェノール類とホルムアルデヒドを縮合反応させて得られる。フェノール類−ホルムアルデヒド縮合物は、種々の充填材との組み合わせによって、電子、電気、機械等の耐熱部品、耐磨耗部品等広範囲な用途に使用される。 The phenols-formaldehyde condensate is obtained by a condensation reaction of phenols having an OH group added to a benzene ring and formaldehyde. Phenols-formaldehyde condensates are used in a wide range of applications such as heat-resistant parts such as electronics, electricity, and machines, and wear-resistant parts, in combination with various fillers.
例えば、ゴム製の伝動ベルトにおいては、補強のためにガラス繊維コ−ドをベルト内部に埋設させる際に、ガラス繊維コードと母材ゴムとの接着性を高める目的でガラス繊維コ−ドに被覆して用いる接着性組成物には、水に易溶であるためレゾルシン−ホルムアルデヒド縮合物が、ビニルピリジン−スチレン−ブタジエン重合体のエマルジョン、スチレン−ブタジエン重合体のエマルジョン、クロロスルホン化ポリエチレンのエマルジョンとともに用いられる。これら、高分子物質のエマルジョンは、水の中に高分子物質が安定して存在しているもの、いわゆるラテックスである。 For example, in a rubber transmission belt, when the glass fiber cord is embedded in the belt for reinforcement, the glass fiber cord is coated for the purpose of improving the adhesion between the glass fiber cord and the base rubber. In the adhesive composition used, the resorcin-formaldehyde condensate is easily dissolved in water, together with an emulsion of vinylpyridine-styrene-butadiene polymer, an emulsion of styrene-butadiene polymer, and an emulsion of chlorosulfonated polyethylene. Used. These emulsions of a polymer substance are so-called latex in which the polymer substance is stably present in water.
特許文献１および特許文献２において、補強のための繊維コ−ドをベルト内部に埋設させる際に、母材ゴムとガラス繊維の接着性を向上させて界面の剥離を防止する目的で、フィラメントを束ねたガラス繊維コ−ドに、レゾルシン−ホルムアルデヒド縮合物と各種ラテックスとを水に分散させたガラス繊維被覆用塗布液を塗布した後、乾燥させ接着性被覆層としたゴム補強用ガラス繊維が開示されている。 In Patent Document 1 and Patent Document 2, when the reinforcing fiber cord is embedded in the belt, the filament is formed for the purpose of improving the adhesion between the base rubber and the glass fiber and preventing the separation of the interface. Disclosed is a glass fiber for reinforcing rubber that is coated with a glass fiber coating solution in which a resorcin-formaldehyde condensate and various latexes are dispersed in water and then dried to form an adhesive coating layer. Has been.
一方、レゾルシン−ホルムアルデヒド縮合物を除くフェノール類−ホルムアルデヒド縮合物は水に溶解し難く、溶解したとしても析出し易い。 On the other hand, phenols-formaldehyde condensates other than resorcin-formaldehyde condensate are difficult to dissolve in water and are likely to precipitate even if dissolved.
そこで、特許文献３においては、水に溶解させるために、スルホメチル基もしくは、スルフィメチル基をフェノール類−ホルムアルデヒド縮合物に付加させる方法が開示されている。しかし、スルホメチル基もしくは、スルフィメチル基を付加させる際の、フェノール−ホルムアルデヒド縮合物を作製後、スルホメチル化剤およびスルフィメチル化剤を添加した後の付加反応は複雑であり、時間と手間を要する。
フェノール類−ホルムアルデヒド縮合物は、フェノール類とホルムアルデヒドを縮合反応させて得られる。フェノール類は比較的安価で入手し易いものが多く、フェノール類−ホルムアルデヒド縮合物は種々の充填材との組み合わせによって優れた物性が得られる等の利点を有しているが、フェノール類−ホルムアルデヒド縮合物は、レゾルシン−ホルムアルデヒド縮合物を除いて水に溶解しにくく溶解したとしても液安定性が悪く、即ち、レゾルシン−ホルムアルデヒド縮合物が析出しやすく接着性組成物として使用し難い。 The phenols-formaldehyde condensate is obtained by a condensation reaction of phenols and formaldehyde. Phenols are relatively inexpensive and easy to obtain, and phenols-formaldehyde condensates have the advantage that excellent physical properties can be obtained by combining with various fillers. Even if the product is difficult to dissolve in water except for the resorcin-formaldehyde condensate, the liquid stability is poor, that is, the resorcin-formaldehyde condensate easily precipitates and is difficult to use as an adhesive composition.
仮に、水溶性のレゾルシン−ホルムアルデヒド縮合物と同様に、他のフェノール類−ホルムアルデヒド縮合物が易溶であり析出し難ければ、接着性組成物として、前述の伝動ベルトに埋設して使用するゴム補強用繊維の被覆材として使用可能である。しかしながら、レゾルシン−ホルムアルデヒド縮合物を除いたフェノール類−ホルムアルデヒド縮合物は水に溶解し難く溶解したとしても析出し易く、ゴム製の伝動ベルトにおいて補強のための繊維コ−ドをベルト内部に埋設させる際に母材ゴムとの接着を高めるために繊維コ−ドに被覆して用いる接着性組成物には使用され得ないという問題があった。 If the other phenols-formaldehyde condensates are easily soluble and difficult to precipitate, as in the case of the water-soluble resorcin-formaldehyde condensate, the rubber used as an adhesive composition embedded in the aforementioned transmission belt It can be used as a covering material for reinforcing fibers. However, phenols-formaldehyde condensates excluding resorcin-formaldehyde condensate are difficult to dissolve in water and are likely to precipitate even when dissolved, and a reinforcing fiber cord is embedded in the belt in a rubber transmission belt. In this case, there is a problem that it cannot be used for an adhesive composition used by coating a fiber cord in order to enhance the adhesion to the base rubber.
レゾルシン−ホルムアルデヒド縮合物を除いた水に溶解し難いフェノール類−ホルムアルデヒド縮合物を水に溶かす手段として、アルカリ添加を行う方法が挙げられる。しかしながら、水酸化ナトリウム等の強アルカリを用いた場合、繊維コードを侵し引張り強度を弱めてしまうという問題があった。また、フェノール類−ホルムアルデヒド縮合物をアンモニア等の弱アルカリにより溶解したとしても、水に分散したラテックスとに混合し接着性組成物溶液を調製するとフェノール類−アルデヒド縮合物が析出しゲル化し易いという問題があった。 As a means for dissolving the phenols-formaldehyde condensate which is difficult to dissolve in water excluding the resorcinol-formaldehyde condensate, a method of adding an alkali can be mentioned. However, when a strong alkali such as sodium hydroxide is used, there is a problem that the fiber cord is eroded and the tensile strength is weakened. Moreover, even if the phenols-formaldehyde condensate is dissolved by a weak alkali such as ammonia, it is said that when the adhesive composition solution is prepared by mixing with a latex dispersed in water, the phenols-aldehyde condensate precipitates and easily gels. There was a problem.
また、レゾルシン−ホルムアルデヒド縮合物を除いた水に溶解し難いフェノール類−ホルムアルデヒド縮合物をアルカリ添加により溶解した後、析出することなきよう、水中で安定させる手段としては、界面活性剤を添加して分散させる方法があるが、接着性組成物として用いた際に、界面活性剤の添加により、接着力が低下する傾向がある。特に、伝動ベルト等において、高温化で接着力の維持が求められる場合、接着力の経時による低下により使用され得ないという問題があった。 As a means of stabilizing in water so that the phenols-formaldehyde condensates that are difficult to dissolve in water excluding the resorcinol-formaldehyde condensate are dissolved by alkali addition and do not precipitate, a surfactant is added. Although there is a method of dispersing, when used as an adhesive composition, the adhesive force tends to be reduced by the addition of a surfactant. In particular, in a transmission belt or the like, when maintenance of adhesive force is required at high temperatures, there is a problem that it cannot be used due to a decrease in adhesive force over time.
本発明は、レゾルシン−ホルムアルデヒド縮合物を除いた水に溶解し難いフェノール類−ホルムアルデヒド縮合物とラテックスを水に溶解分散させた接着性組成物、特にゴム製の伝動ベルトに繊維コードを補強のため母材ゴムに埋設させる際に、母材ゴムとの接着を高めるために繊維コ−ドに被覆して用いるに良好な接着性組成物の製造方法を提供することを目的とする。 The present invention relates to an adhesive composition in which a phenols-formaldehyde condensate that is difficult to dissolve in water excluding resorcin-formaldehyde condensate and a latex are dissolved and dispersed in water, particularly for reinforcing a fiber cord on a rubber transmission belt. It is an object of the present invention to provide a method for producing an adhesive composition that is suitable for use by being coated on a fiber cord in order to enhance adhesion to the base rubber when embedded in the base rubber.
レゾルシン−ホルムアルデヒド縮合物を除いた水に溶解し難いフェノール類−ホルムアルデヒド縮合物を溶解し、更にラテックスと混合後も析出することなきよう水に安定に溶解させるためには、フェノール類とホルムアルデヒドを水中で縮合反応させて得られたフェノール類−ホルムアルデヒド縮合物の沈殿を、水溶液中での塩基性度定数（Ｋｂ）が５×１０−５以上、１×１０−３以下であるアミン化合物を加えて溶解させた後、ラテックスとともに混合する。塩基性度定数（Ｋｂ）が５×１０−５のより大きい範囲であれは、フェノール類−ホルムアルデヒド縮合物の水溶液にラテックスを混合した場合も、フェノール類−ホルムアルデヒド縮合物の析出が起こり難い。また、ガラス繊維またはポリエステル繊維等からなる繊維コードに被覆した際、塩基性度定数（Ｋｂ）が１×１０−３未満であれば、アルカリにより繊維コードが変質し引っ張り強さが低下する等の懸念がない
このように、フェノール類をホルムアルデヒドと反応させてなるフェノール類−ホルムアルデヒド縮合物の沈殿が生成した反応液に塩基性度定数（Ｋｂ）、５×１０−５以上、１．０×１０−３以下であるアミン化合物を加え溶解させたフェノール類−ホルムアルデヒド縮合物の水溶液に、ラテックス加え混合させた接着性組成物をガラス繊維またはポリエステル繊維コード等に被覆したゴム補強用繊維を母材ゴムに埋設して伝動ベルトを作成すれば、ゴム補強用繊維と母材ゴムとの長時間使用後の引っ張り強度の低下が見られない。
In order to dissolve phenols-formaldehyde condensates that are difficult to dissolve in water excluding resorcin-formaldehyde condensate, and to dissolve stably in water without precipitation even after mixing with latex, phenols and formaldehyde must be dissolved in water. The amine compound having a basicity constant (Kb) in the aqueous solution of 5 × 10 −5 or more and 1 × 10 −3 or less is added to the precipitate of the phenol-formaldehyde condensate obtained by the condensation reaction in After dissolving, mix with latex. When the basicity constant (Kb) is in a larger range of 5 × 10 −5 , the precipitation of the phenols-formaldehyde condensate hardly occurs even when the latex is mixed with the aqueous solution of the phenols-formaldehyde condensate. Further, when the fiber cord made of glass fiber or polyester fiber is coated, if the basicity constant (Kb) is less than 1 × 10 −3 , the fiber cord is altered by alkali and the tensile strength is reduced. There is no concern In this way, the basicity constant (Kb), 5 × 10 −5 or more, 1.0 × 10 5 is added to the reaction solution in which a phenol-formaldehyde condensate precipitate formed by reacting phenol with formaldehyde is generated. -3 or less, a rubber reinforcing fiber in which an adhesive composition obtained by adding a latex and mixing with an aqueous solution of a phenols-formaldehyde condensate dissolved by adding an amine compound equal to or less than 3 is coated with glass fiber or polyester fiber cord is a base rubber. If a transmission belt is created by embedding it in a cable, there will be no decrease in tensile strength after long-term use of rubber reinforcing fibers and base rubber. .
特に、前記接着性組成物をガラス繊維コードに塗布被覆したゴム補強用ガラス繊維を水素添加アクリロニトリルゴムまたはクロロピレンゴムに埋設し作製した伝動ベルトを長時間使用した後の引っ張り強さの低下が抑制される。 In particular, reduction of tensile strength after long-time use of a transmission belt made by embedding rubber reinforcing glass fiber coated with glass fiber cord with the adhesive composition in hydrogenated acrylonitrile rubber or chloropyrene rubber is suppressed. Is done.
即ち、本発明は、フェノール類をホルムアルデヒドと水中で縮合反応させて生成したフェノール類−ホルムアルデヒド縮合物の沈殿を、塩基性度定数（Ｋｂ）が５×１０−５以上、１×１０−３以下であるアミン化合物を加えて溶解させた後、ラテックスと混合させることを特徴とする接着性組成物の製造方法である。 That is, in the present invention, the precipitation of phenol-formaldehyde condensate formed by condensation reaction of phenols with formaldehyde in water has a basicity constant (Kb) of 5 × 10 −5 or more and 1 × 10 −3 or less. An amine compound is added and dissolved, and then mixed with latex.
本発明の接着性組成物の製造方法は、フェノール類をホルムアルデヒドと水中で縮合反応させて生成したフェノール類−ホルムアルデヒド縮合沈殿物に塩基性度定数（Ｋｂ）が５×１０−５以上、１×１０−３以下であるアミン化合物を加え溶解させた後、ラテックスのエマルジョンとともに混合させて調製する。 In the method for producing an adhesive composition of the present invention, a basicity constant (Kb) of 5 × 10 −5 or more is applied to a phenol-formaldehyde condensation precipitate formed by a condensation reaction of phenols with formaldehyde in water. An amine compound of 10 −3 or less is added and dissolved, and then mixed with a latex emulsion to prepare.
さらに、本発明は、アミン化合物を加える量が、フェノール類−ホルムアルデヒド縮合物の重量に対して、言い換えれば、フェノール類−ホルムアルデヒド縮合物の重量を１００％基準とする重量百分率で表して、５０．０重量％以上、５００．０重量％以下であることを特徴とする上記の接着性組成物の製造方法である。即ち、フェノール類−ホルムアルデヒド縮合物の重量に対して、重量比で０．５倍以上、５倍以下のアミン化合物を加える。 Further, according to the present invention, the amount of the amine compound added is expressed in terms of 50% by weight based on the weight of the phenols-formaldehyde condensate, in other words, 100% based on the weight of the phenols-formaldehyde condensate. It is a manufacturing method of said adhesive composition characterized by being 0 weight% or more and 500.0 weight% or less. That is, the amine compound is added in a weight ratio of 0.5 to 5 times the weight of the phenol-formaldehyde condensate.
さらに、本発明は、アミン化合物が、メチルアミン、エチルアミン、ｔ−ブチルアミン、ジメチルアミン、ジエチルアミン、トリエチルアミン、トリ−ｎ−ブチルアミン、メタノ−ルアミン、ジメタノ−ルアミン、ジエタノ−ルアミンから選ばれることを特徴とする上記の接着性組成物の製造方法である。 Furthermore, the present invention is characterized in that the amine compound is selected from methylamine, ethylamine, t-butylamine, dimethylamine, diethylamine, triethylamine, tri-n-butylamine, methanolamine, dimethanolamine, and diethanolamine. It is a manufacturing method of said adhesive composition.
さらに、本発明は、フェノール類がｏ−クレゾ−ル、ｍ−クレゾ−ル、ｐ−クレゾ−ル、エチルフェノール、ｉｓｏ−プロピルフェノール、キシレノ−ル、３，５−キシレノ−ル、ブチルフェノール、ｔ−ブチルフェノール、ノニルフェノール、ｏ−フルオロフェノール、ｍ−フルオロフェノール、ｐ−フルオロフェノール、ｏ−クロロフェノール、ｍ−クロロフェノール、ｐ−クロロフェノール、ｏ−ブロモフェノール、ｍ−ブロモフェノール、ｐ−ブロモフェノール、ｏ−ヨ−ドフェノール、ｍ−ヨ−ドフェノール、ｐ−ヨ−ドフェノール、ｏ−アミノフェノール、ｍ−アミノフェノール、ｐ−アミノフェノール、ニトロフェノールであるｏ−ニトロフェノール、ｍ−ニトロフェノール、ｐ−ニトロフェノール、２，４−ジニトロフェノール、ｍ−メトキシフェノール、５−メチルレゾルシン、５−エチルレゾルシン、５−プロピルレゾルシン、５−ｎ−ブチルレゾルシン、４，５−ジメチルレゾルシン、２，５−ジメチルレゾルシン、４，５−ジエチルレゾルシン、２，５−ジエチルレゾルシン、４，５−ジプロピルレゾルシン、２，５−ジプロピルレゾルシン、４−メチル−５−エチルレゾルシン、２−メチル−５−エチルレゾルシン、２−メチル−５−プロピルレゾルシン、２，４，５−トリメチルレゾルシン、２，４，５−トリエチルレゾルシンから選ばれることを特徴とする上記の接着性組成物の製造方法である。 Furthermore, the present invention is such that the phenols are o-cresol, m-cresol, p-cresol, ethylphenol, iso-propylphenol, xylenol, 3,5-xylenol, butylphenol, t -Butylphenol, nonylphenol, o-fluorophenol, m-fluorophenol, p-fluorophenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-iodophenol, m-iodophenol, p-iodophenol, o-aminophenol, m-aminophenol, p-aminophenol, o-nitrophenol which is nitrophenol, m-nitrophenol, p-nitrophenol, 2,4-dinitropheno M-methoxyphenol, 5-methylresorcin, 5-ethylresorcin, 5-propylresorcin, 5-n-butylresorcin, 4,5-dimethylresorcin, 2,5-dimethylresorcin, 4,5-diethylresorcin, 2,5-diethyl resorcin, 4,5-dipropyl resorcin, 2,5-dipropyl resorcin, 4-methyl-5-ethyl resorcin, 2-methyl-5-ethyl resorcin, 2-methyl-5-propyl resorcin, 2. The method for producing an adhesive composition as described above, which is selected from 2,4,5-trimethylresorcin and 2,4,5-triethylresorcin.
さらに、本発明は、ラテックスが、ビニルピリジン−スチレン−ブタジエン共重合体のエマルジョン、スチレン−ブタジエン共重合体のエマルジョンおよび／またはクロロスルホン化ポリエチレンのエマルジョンであることを特徴とする上記の接着性組成物の製造方法である。 Furthermore, the present invention provides the above adhesive composition, wherein the latex is an emulsion of vinylpyridine-styrene-butadiene copolymer, an emulsion of styrene-butadiene copolymer and / or an emulsion of chlorosulfonated polyethylene. It is a manufacturing method of a thing.
さらに、本発明は、上記の接着性組成物の製造方法により得られた接着性組成物を、ガラス繊維コードに塗布被覆してなることを特徴とするゴム補強用ガラス繊維である。 Furthermore, the present invention is a glass fiber for rubber reinforcement, wherein the glass fiber cord is coated and coated with the adhesive composition obtained by the above-described method for producing an adhesive composition.
さらに、本発明は、上記のゴム補強用ガラス繊維を母材ゴムに埋設させてなる伝動ベルトである。 Furthermore, the present invention is a transmission belt in which the rubber reinforcing glass fiber is embedded in a base rubber.
本発明の接着性組成物の製造方法において、水に溶解し難いフェノール類−ホルムアルデヒド縮合物の沈殿物に塩基性度定数（Ｋｂ）が５×１０−５以上、１×１０−３以下であるアミン化合物を加え溶解させた後、ラテックスと混合させることで、フェノール類−ホルムアルデヒド縮合物が析出することを抑制した。 In the method for producing an adhesive composition of the present invention, the basicity constant (Kb) is 5 × 10 −5 or more and 1 × 10 −3 or less in the precipitate of phenols-formaldehyde condensate that is difficult to dissolve in water. The amine compound was added and dissolved, and then mixed with latex to suppress precipitation of phenols-formaldehyde condensate.
本発明の接着性組成物の製造方法によって、ゴム製の伝動ベルトにおいて、繊維コードを補強のため母材ゴムに埋設させる際に、母材ゴムとの接着を高めるために繊維コ−ドに被覆して用いる接着性組成物に、レゾルシン−ホルムアルデヒド縮合物を除く水に溶解し難いフェノール類−ホルムアルデヒド縮合物を使用することを可能とした。特にガラス繊維コードを母材ゴムに埋設させ伝動ベルトに成形する際の接着性組成物の製造方法として有効であった。 When the fiber cord is embedded in the base rubber for reinforcement in a rubber transmission belt by the method for producing an adhesive composition of the present invention, the fiber cord is coated to enhance adhesion to the base rubber. It was possible to use phenols-formaldehyde condensates that are difficult to dissolve in water, excluding resorcin-formaldehyde condensates, in the adhesive composition used. In particular, it was effective as a method for producing an adhesive composition when a glass fiber cord was embedded in a base rubber and molded into a transmission belt.
本発明の接着性組成物の製造方法は、フェノール類をホルムアルデヒドと水中で縮合反応させてフェノール類−ホルムアルデヒド縮合物の沈殿が生成した液に塩基性度定数（Ｋｂ）が５×１０−５以上、１×１０−３以下であるアミン化合物を加え、フェノール類−ホルムアルデヒド縮合物の沈殿を溶解させて溶液とした後、ラテックスと混合させて調製する。 In the method for producing an adhesive composition of the present invention, the basicity constant (Kb) is 5 × 10 −5 or more in a liquid in which phenols are condensed with formaldehyde in water to form a precipitate of phenols-formaldehyde condensate. An amine compound that is 1 × 10 −3 or less is added to dissolve the precipitate of the phenols-formaldehyde condensate to form a solution, which is then mixed with the latex.
塩基性度定数（Ｋｂ）とは、アルカリが水素イオンを溶液から受け入れる度合いを測定し、塩基性度として表したものであり、数１の式の平衡定数である。 The basicity constant (Kb) is a measure of the degree of alkali's acceptance of hydrogen ions from a solution and is expressed as basicity, and is an equilibrium constant of the equation (1).
例えば、レゾルシン−ホルムアルデヒド樹脂を除く水に溶解し難いフェノール類−ホルムアルデヒド縮合物を水に溶解させる場合には、通常、フェノール類−ホルムアルデヒド縮合物にアンモニアまたは水酸化ナトリウム等のアルカリを加える。 For example, when a phenols-formaldehyde condensate that is difficult to dissolve in water excluding resorcin-formaldehyde resin is dissolved in water, an alkali such as ammonia or sodium hydroxide is usually added to the phenols-formaldehyde condensate.
しかしながら、アンモニアのように塩基性度定数（Ｋｂ）が小さいアルカリを加えることで、レゾルシン−ホルムアルデヒド樹脂を除く水に溶解し難いフェノール類−ホルムアルデヒド縮合物を水に溶解させられるが、溶解したものを接着性組成物とするために、ラテックスと混合するとフェノール類−ホルムアルデヒド縮合物が析出する。 However, by adding an alkali having a small basicity constant (Kb) such as ammonia, phenols-formaldehyde condensates that are difficult to dissolve in water other than resorcin-formaldehyde resin can be dissolved in water. When mixed with latex to form an adhesive composition, a phenol-formaldehyde condensate precipitates.
また、水酸化ナトリウムのように塩基性度定数（Ｋｂ）が大きいアルカリを加えることで、レゾルシン−ホルムアルデヒド樹脂を除く水に溶解し難いフェノール類−ホルムアルデヒド縮合物を水に溶解させたものを接着性組成物とするためにラテックスと混合すると、フェノール類−ホルムアルデヒド縮合物の析出が抑制される。しかしながら、強アルカリであるため、ガラス繊維やポリエステル繊維等の繊維材料を劣化させて、繊維材料の引っ張り強さを弱めてしまい使用され難い。 Also, by adding an alkali having a large basicity constant (Kb) such as sodium hydroxide, it is possible to adhere a phenol-formaldehyde condensate that is difficult to dissolve in water except for resorcinol-formaldehyde resin. When mixed with latex to form a composition, precipitation of phenols-formaldehyde condensate is suppressed. However, since it is a strong alkali, fiber materials such as glass fiber and polyester fiber are deteriorated, and the tensile strength of the fiber material is weakened.
ところが、フェノール類をホルムアルデヒドと水中で縮合反応させた、レゾルシン−ホルムアルデヒド樹脂を除く水に溶解し難いフェノール類−ホルムアルデヒド縮合物の沈殿が生成した液に塩基性度定数（Ｋｂ）に５×１０−５以上、１×１０−３以下であるアミン化合物を加え、前記の水に溶解し難いフェノール類−ホルムアルデヒド縮合物の沈殿溶解させた後、ラテックスとともに水に混合させると、該フェノール類−ホルムアルデヒド縮合物をラテックスと混合後も、フェノール類−ホルムアルデヒド縮合物の析出が起こり難いことがわかった。 However, phenols were condensation reaction with formaldehyde and water, resorcin - hardly phenols dissolved in water except formaldehyde resin - in liquid precipitate formed formaldehyde condensate in basicity constant (Kb) 5 × 10 - When an amine compound of 5 or more and 1 × 10 −3 or less is added, the phenols-formaldehyde condensate that is difficult to dissolve in water is precipitated and dissolved, and then mixed with water together with latex, the phenols-formaldehyde condensation It was found that precipitation of phenols-formaldehyde condensate hardly occurs even after mixing the product with latex.
このように、本発明の接着性組成物の製造方法において、レゾルシン−ホルムアルデヒド樹脂を除く水に溶解し難いフェノール−ホルムアルデヒド縮合物を溶解後も析出なきよう安定させるためにアミン化合物を加えて溶解させた後、ラテックスと混合する。この場合のアミン化合物の塩基性度定数（Ｋｂ）が５×１０−５以上、１×１０−３以下ある。 Thus, in the method for producing an adhesive composition of the present invention, an amine compound is added and dissolved in order to stabilize the phenol-formaldehyde condensate that is difficult to dissolve in water excluding resorcin-formaldehyde resin so that it does not precipitate even after dissolution. And then mix with latex. In this case, the basicity constant (Kb) of the amine compound is 5 × 10 −5 or more and 1 × 10 −3 or less.
加えるアミン化合物の塩基性度定数（Ｋｂ）が５×１０−５より小さいと、フェノール類−ホルムアルデヒド縮合物が溶解せず溶解したとしても経時により析出する、１×１０−３より大きいと接着性組成物とした際に接着力が低下する。 A basicity constant of the amine compound (Kb) is 5 × 10 -5 smaller addition, phenol - also precipitated over time as formaldehyde condensate is dissolved without dissolution, 1 × 10 -3 greater and the adhesive Adhesive strength decreases when a composition is formed.
アミン化合物を加えることでフェノール類−ホルムアルデヒド縮合物の沈殿を溶解させる際の、アミン化合物を加える量は、フェノール類−ホルムアルデヒド縮合物の重量に対して５０．０重量％以上、５００．０重量％以下である。言い換えれば、フェノール類−ホルムアルデヒド縮合物の重量を１００％基準とする重量百分率で表して、５０．０重量％以上、５００．０重量％以下である。即ち、加えるアミン化合物の重量は、クロロフェノール−ホルムアルデヒド縮合物（Ａ）の重量に対して、重量比で、１／２以上、５倍以下である。 The amount of the amine compound added when dissolving the precipitate of the phenols-formaldehyde condensate by adding the amine compound is 50.0% by weight or more and 500.0% by weight with respect to the weight of the phenols-formaldehyde condensate. It is as follows. In other words, the weight of the phenol-formaldehyde condensate is expressed as a percentage by weight based on 100%, and is 50.0% by weight or more and 500.0% by weight or less. That is, the weight of the amine compound to be added is 1/2 or more and 5 times or less by weight with respect to the weight of the chlorophenol-formaldehyde condensate (A).
尚、フェノール類−ホルムアルデヒド縮合物の重量は、フェノール類をホルムアルデヒドと水中で縮合反応させて生成したフェノール類−ホルムアルデヒド縮合物の沈殿を擁する液を加熱して蒸発させて得られる固形分濃度として求められる。この際、未反応のフェノール類およびホルムアルデヒドは揮発除去される。 The weight of the phenol-formaldehyde condensate is determined as the solid content concentration obtained by heating and evaporating the liquid containing the phenol-formaldehyde condensate precipitate formed by the condensation reaction of phenols with formaldehyde in water. It is done. At this time, unreacted phenols and formaldehyde are volatilized and removed.
アミン化合物を加える量が５０．０重量％より少ないと、レゾルシン−ホルムアルデヒド樹脂を除く水に溶解し難いフェノール類−ホルムアルデヒド縮合物の沈殿を溶解させる効果がなく、５００．０重量％より多く含有させる必要はない。アミン化合物の量が５００．０重量％より多くなると、接着性組成物におけるフェノール類−ホルムアルデヒド縮合物およびラテックスの含有割合が低下し、繊維コードに塗布したゴム補強用繊維が柔軟でなくなる、特に、接着性組成物をガラス繊維コードに塗布したゴム補強用ガラス繊維は柔軟でなくなる。 When the amount of the amine compound added is less than 50.0% by weight, there is no effect of dissolving the precipitate of phenols-formaldehyde condensate which is difficult to dissolve in water except for resorcinol-formaldehyde resin, and more than 500.0% by weight is contained. There is no need. When the amount of the amine compound is more than 500.0% by weight, the content ratio of the phenols-formaldehyde condensate and latex in the adhesive composition decreases, and the rubber reinforcing fiber applied to the fiber cord becomes inflexible. The glass fiber for rubber reinforcement in which the adhesive composition is applied to the glass fiber cord becomes inflexible.
本発明の接着性組成物の製造方法に使用されるアミン化合物には、メチルアミン、エチルアミン、ｔ−ブチルアミン、ジメチルアミン、ジエチルアミン、トリエチルアミン、トリ−ｎ−ブチルアミン、メタノ−ルアミン、ジメタノ−ルアミン、ジエタノ−ルアミンが挙げられる。好ましくは、ジメチルアミン、ジエチルアミン、ジメタノ−ルアミン、ジエタノ−ルアミンである。更に、好ましくは、ジメチルアミン、ジエタノ−ルアミンである。ジメチルアミンは価格が安く、ジエタノールアミンはアミン特有のにおいがなく取り扱いが容易である。 Examples of the amine compound used in the method for producing the adhesive composition of the present invention include methylamine, ethylamine, t-butylamine, dimethylamine, diethylamine, triethylamine, tri-n-butylamine, methanolamine, dimethanolamine, and diethanol. -Luamine. Preferred are dimethylamine, diethylamine, dimethanolamine, and diethanolamine. More preferred are dimethylamine and diethylamine. Dimethylamine is inexpensive, and diethanolamine is easy to handle because it has no amine-specific odor.
これらアミン化合物の塩基性度定数（Ｋｂ）は、有機化学（中）第３版（東京化学同人）および有機化学用語辞典（第２刷）朝倉書店、１６７頁〜１７５頁等に示されており、ジメチルアミンの塩基性度定数（Ｋｂ）は５．４×１０−４、ジエタノールアミンの塩基性度定数（Ｋｂ）は１．０×１０−４．５である。 The basicity constants (Kb) of these amine compounds are shown in Organic Chemistry (Middle) 3rd Edition (Tokyo Kagaku Dojin) and Organic Chemistry Glossary (Second Printing) Asakura Shoten, pages 167-175, etc. The basicity constant (Kb) of dimethylamine is 5.4 × 10 −4 , and the basicity constant (Kb) of diethanolamine is 1.0 × 10 −4.5 .
本発明の接着性組成物の製造方法に使用されるフェノール類には、アルキルフェノールであるｏ−クレゾ−ル、ｍ−クレゾ−ル、ｐ−クレゾ−ル、エチルフェノール、ｉｓｏ−プロピルフェノール、キシレノ−ル、３，５−キシレノ−ル、ブチルフェノール、ｔ−ブチルフェノール、ノニルフェノール、またはハロフェノールであるｏ−フルオロフェノール、ｍ−フルオロフェノール、ｐ−フルオロフェノール、ｏ−クロロフェノール、ｍ−クロロフェノール、ｐ−クロロフェノール、ｏ−ブロモフェノール、ｍ−ブロモフェノール、ｐ−ブロモフェノール、ｏ−ヨ−ドフェノール、ｍ−ヨ−ドフェノール、ｐ−ヨ−ドフェノール、またはアミノフェノールであるｏ−アミノフェノール、ｍ−アミノフェノール、ｐ−アミノフェノール、ニトロフェノールであるｏ−ニトロフェノール、ｍ−ニトロフェノール、ｐ−ニトロフェノール、２，４−ジニトロフェノール、またはｍ−メトキシフェノール、５−メチルレゾルシン、５−エチルレゾルシン、５−プロピルレゾルシン、５−ｎ−ブチルレゾルシン、４，５−ジメチルレゾルシン、２，５−ジメチルレゾルシン、４，５−ジエチルレゾルシン、２，５−ジエチルレゾルシン、４，５−ジプロピルレゾルシン、２，５−ジプロピルレゾルシン、４−メチル−５−エチルレゾルシン、２−メチル−５−エチルレゾルシン、２−メチル−５−プロピルレゾルシン、２，４，５−トリメチルレゾルシン、２，４，５−トリエチルレゾルシンが挙げられ、ホルムアルデヒドと縮合反応させてフェノール類−ホルムアルデヒド縮合物とする。これらフェノール類は水中でホルムアルデヒドと縮合反応させると、水に難溶なフェノール類−ホルムアルデヒド縮合物として沈殿物として析出する。 The phenols used in the method for producing the adhesive composition of the present invention include alkylphenols such as o-cresol, m-cresol, p-cresol, ethylphenol, iso-propylphenol, and xylenol. O-fluorophenol, m-fluorophenol, p-fluorophenol, o-chlorophenol, m-chlorophenol, p-, which are chlorophenol, 3,5-xylenol, butylphenol, t-butylphenol, nonylphenol, or halophenol O-aminophenol which is chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-iodophenol, m-iodophenol, p-iodophenol, or aminophenol, m -Aminophenol, p-aminophenol, nito The phenols o-nitrophenol, m-nitrophenol, p-nitrophenol, 2,4-dinitrophenol, or m-methoxyphenol, 5-methylresorcin, 5-ethylresorcin, 5-propylresorcin, 5-n- Butyl resorcin, 4,5-dimethyl resorcin, 2,5-dimethyl resorcin, 4,5-diethyl resorcin, 2,5-diethyl resorcin, 4,5-dipropyl resorcin, 2,5-dipropyl resorcin, 4-methyl -5-ethylresorcin, 2-methyl-5-ethylresorcin, 2-methyl-5-propylresorcin, 2,4,5-trimethylresorcin, 2,4,5-triethylresorcin, and condensation reaction with formaldehyde To make phenols-formaldehyde condensate. When these phenols are subjected to a condensation reaction with formaldehyde in water, they are deposited as precipitates as water-insoluble phenols-formaldehyde condensates.
ホルムアルデヒドと縮合反応させてフェノール類−ホルムアルデヒド縮合物を得る際に、ホルムアルデヒドとの反応性が高く、反応時間が短いことより、好ましくは、ｍ−クレゾール、ｍ−クロロフェノール、ｐ−クロロフェノールである。更に、好ましくは、ｐ−クロロフェノールである。ｐ−クロロフノールは、特にホルムアルデヒドとの反応性が良く、ｐ−クロロフノール−ホルムアルデヒド縮合物を得るまでの反応時間が短い。 When a phenol-formaldehyde condensate is obtained by a condensation reaction with formaldehyde, m-cresol, m-chlorophenol, and p-chlorophenol are preferred because of high reactivity with formaldehyde and a short reaction time. . Furthermore, p-chlorophenol is preferable. p-Chlorofunol has particularly good reactivity with formaldehyde, and the reaction time until obtaining the p-chlorofunol-formaldehyde condensate is short.
本発明の接着性組成物の製造方法において、使用されるラテックスには、ビニルピリジン−スチレン−ブタジエン共重合体のエマルジョン、スチレン−ブタジエン共重合体のエマルジョン、クロロスルホン化ポリエチレンのエマルジョンが挙げられる。尚、本発明において、ラテックスとは、水の中に高分子物質が安定して存在しているものであり、高分子物質のエマルジョンはいわゆるラテックスである。 In the method for producing an adhesive composition of the present invention, examples of latex used include vinylpyridine-styrene-butadiene copolymer emulsion, styrene-butadiene copolymer emulsion, and chlorosulfonated polyethylene emulsion. In the present invention, latex means a polymer substance stably present in water, and an emulsion of the polymer substance is a so-called latex.
これらのラテックスは、ゴム製の伝動ベルトにおいて、補強のためのガラス繊維コ−ドをベルト内部に埋設させる際に母材ゴムとの接着を高めるためにガラス繊維コ−ドに被覆して用いる接着性組成物に用いられる。母材ゴムとしては、水素添加アクリロニトリルゴム、クロロピレンゴム等が挙げられる。 These latexes are used in rubber transmission belts by coating glass fiber cords to enhance adhesion to the base rubber when embedding reinforcing glass fiber cords in the belt. Used in sex compositions. Examples of the base rubber include hydrogenated acrylonitrile rubber and chloropyrene rubber.
本発明の接着性組成物の製造方法による接着性組成物をガラス繊維コードに塗布被覆してなるゴム補強用ガラス繊維は、母材ゴムに埋設させて伝動ベルトとした際に、母材ゴムとの接着力を高め、引張り強さに優れる伝動ベルトを与える。本発明の伝動ベルトは、初期の接着強さが持続され、引っ張り強さを持続し寸法安定性に優れており、耐水性、耐熱性を併せ持つ。 A glass fiber for rubber reinforcement formed by coating and coating a glass fiber cord with an adhesive composition according to the method for producing an adhesive composition of the present invention is embedded in a base rubber and used as a power transmission belt. Increases the adhesive strength of the belt and gives a transmission belt with excellent tensile strength. The transmission belt of the present invention maintains the initial adhesive strength, maintains the tensile strength and has excellent dimensional stability, and has both water resistance and heat resistance.
例えば、前記ゴム補強用ガラス繊維の上層に、更にクロロスルホン化ポリエチレンと有機ジイソシアネートとメタクリル酸亜鉛とを有機溶剤に分散させた２次被覆液を塗布後乾燥させて更なる２次被覆層を形成させた後に、このゴム補強用ガラス繊維を補強材として、母材ゴムに水素化ニトリルゴムを用いて伝動ベルトを作製する。このようにして作製した歯付きベルトは自動車用のタイミングベルト等に使用し得る。 For example, a secondary coating solution in which chlorosulfonated polyethylene, organic diisocyanate, and zinc methacrylate are dispersed in an organic solvent is applied to the upper layer of the rubber reinforcing glass fiber and then dried to form a further secondary coating layer. Then, using the rubber reinforcing glass fiber as a reinforcing material, a power transmission belt is manufactured using hydrogenated nitrile rubber as a base rubber. The toothed belt thus produced can be used as a timing belt for automobiles.
以下、具体的に実施例を示し、本発明の接着性組成物の製造方法を詳細に説明する。
実施例１
（被覆液の調製）
還流冷却器、温度計、攪拌機をつけた三つ口セパラブルフラスコに、ｐ−クロロフェノール、１３０重量部、濃度、３７．０重量％のホルムアルデヒド水溶液、８０重量部（モル比で表せば、１．０）、濃度、１．０重量％の水酸化ナトリウム水溶液、２０重量部を仕込み、８０℃に加熱した状態で３時間攪拌し、ｐ−クロロフェノール−ホルムアルデヒド縮合物の沈殿を得た。冷却した後、攪拌しつつジメチルアミンを１０重量部加えて、ｐ−クロロフェノール−ホルムアルデヒド縮合物を溶解させて水溶液とした。尚、ジメチルアミンの塩基性度定数（Ｋｂ）は５．４×１０−４である。この際、ｐ−クロロフェノール−ホルムアルデヒド縮合物の重量に対して、加えたジメチルアミンの重量は２００．０重量％であった。即ち、ｐ−クロロフェノール−ホルムアルデヒド縮合物の重量を１００％基準とする重量百分率で表して、加えたジメチルアミンの重量は２００．０重量％であった。尚、濃度、１．０重量％の水酸化ナトリウム水溶液の前記添加は、ｐ−クロロフェノールとホルムアルデヒドを縮合反応させてｐ−クロロフェノール−ホルムアルデヒド縮合物とするための触媒として縮合反応に必要な量以上に加えてはいない。
Hereinafter, a specific example is shown and the manufacturing method of the adhesive composition of this invention is demonstrated in detail.
Example 1
(Preparation of coating solution)
In a three-necked separable flask equipped with a reflux condenser, a thermometer and a stirrer, p-chlorophenol, 130 parts by weight, concentration, 37.0% by weight formaldehyde aqueous solution, 80 parts by weight (in terms of molar ratio, 1 0.0), a 1.0 wt% aqueous sodium hydroxide solution and 20 parts by weight, and the mixture was stirred for 3 hours while heated to 80 ° C. to obtain a p-chlorophenol-formaldehyde condensate precipitate. After cooling, 10 parts by weight of dimethylamine was added with stirring to dissolve the p-chlorophenol-formaldehyde condensate to obtain an aqueous solution. The basicity constant (Kb) of dimethylamine is 5.4 × 10 −4 . At this time, the weight of the added dimethylamine was 200.0% by weight with respect to the weight of the p-chlorophenol-formaldehyde condensate. That is, the weight of p-chlorophenol-formaldehyde condensate was expressed as a percentage by weight based on 100%, and the weight of added dimethylamine was 200.0% by weight. In addition, the above-mentioned addition of a 1.0 wt% sodium hydroxide aqueous solution is an amount necessary for the condensation reaction as a catalyst for the condensation reaction of p-chlorophenol and formaldehyde to form a p-chlorophenol-formaldehyde condensate. No addition to the above.
次いで、上記のように合成し、水に溶解しているｐ−クロロフェノール−ホルムアルデヒド縮合物に、ラテックスとして、市販のビニルピリジン−スチレン−ブタジエン共重合体のエマルジョン、クロロスルホン化ポリエチレンエマルジョンおよびアンモニア水を加え攪拌し完全に溶解させた。 Next, a p-chlorophenol-formaldehyde condensate synthesized as described above and dissolved in water was used as a latex as a commercially available emulsion of vinylpyridine-styrene-butadiene copolymer, chlorosulfonated polyethylene emulsion and aqueous ammonia. Was stirred and completely dissolved.
詳しくは、溶解させたｐ−クロロフェノール−ホルムアルデヒド縮合物水溶液、２８０重量部、ビニルピリジン、スチレン、ブタジエンを、ビニルピリジン：スチレン：ブタジエン＝１５：１５：７０重量比となるように重合したビニルピリジン−スチレン−ブタジエン共重合体のエマルジョンとしての日本エイアンドエル株式会社製、商品名、ピラテックス（固形分濃度、４１．０重量％）４４０重量部、クロロスルホン化ポリエチレンエマルジョンとしての住友精化株式会社製、商品名、ＣＳＭ４５０（固形分濃度、４０．０重量％）２１０重量部、ｐＨ調整剤としてのアンモニア水（濃度、２５．０重量％）２２重量部とに、全体として１０００重量部になるように水を加えて、被覆液を調製した。ラテックス混合後もｐ−クロロフェノール−ホルムアルデヒド縮合物の析出は起こらず、被覆液が得られた。 Specifically, a dissolved p-chlorophenol-formaldehyde condensate aqueous solution, 280 parts by weight, vinylpyridine, styrene, butadiene, polymerized to a vinylpyridine: styrene: butadiene = 15: 15: 70 weight ratio. -Nippon A & L Co., Ltd. as an emulsion of styrene-butadiene copolymer, trade name, 440 parts by weight of pilatex (solid content concentration, 41.0 wt%), manufactured by Sumitomo Seika Co., Ltd. as a chlorosulfonated polyethylene emulsion The product name, 210 parts by weight of CSM450 (solid content concentration, 40.0% by weight), 22 parts by weight of ammonia water (concentration, 25.0% by weight) as a pH adjuster, and 1000 parts by weight as a whole Water was added to prepare a coating solution. Even after the latex was mixed, precipitation of the p-chlorophenol-formaldehyde condensate did not occur, and a coating solution was obtained.
径９μｍのガラス繊維フィラメントを２００本集束したガラス繊維コ−ド６本を引き揃えた後、前記被覆液を塗布し、その後、温度、２８０℃下で、２２秒間乾燥させて本発明の接着性組成物の製造方法による接着性組成物としての被覆層を設けゴム補強用ガラス繊維とした。 After arranging 6 glass fiber cords of 200 glass fiber filaments having a diameter of 9 μm bundled together, the coating liquid is applied, and then dried at a temperature of 280 ° C. for 22 seconds, thereby providing the adhesive property of the present invention. A glass fiber for rubber reinforcement was provided by providing a coating layer as an adhesive composition by the method for producing the composition.
このゴム補強用ガラス繊維コ−ドの引っ張り強さは、１９６Ｎであった。
実施例２
ジメチルアミンに替えて、ジエタノールアミンを用いて、実施例１と同様にゴム補強用ガラス繊維を作製した。
（被覆液の調製）
還流冷却器、温度計、攪拌機をつけた三つ口セパラブルフラスコに、ｐ−クロロフェノール、１３０重量部、濃度、３７．０重量％のホルムアルデヒド水溶液、８０重量部（モル比で表せば、１．０）、濃度、１．０重量％の水酸化ナトリウム水溶液、２０重量部を仕込み、８０℃に加熱した状態で３時間攪拌し、ｐ−クロロフェノール−ホルムアルデヒド縮合物の沈殿を得た。冷却した後、攪拌しつつジエタノールアミンを１０重量部加えて、ｐ−クロロフェノール−ホルムアルデヒド縮合物を溶解させて水溶液とした。尚、ジエタノールアミンの塩基性度定数（Ｋｂ）は１．０×１０−４．５である。
The tensile strength of the rubber-reinforced glass fiber cord was 196N.
Example 2
Glass fibers for rubber reinforcement were produced in the same manner as in Example 1 using diethanolamine instead of dimethylamine.
(Preparation of coating solution)
In a three-necked separable flask equipped with a reflux condenser, a thermometer and a stirrer, p-chlorophenol, 130 parts by weight, concentration, 37.0% by weight formaldehyde aqueous solution, 80 parts by weight (in terms of molar ratio, 1 0.0), a 1.0 wt% aqueous sodium hydroxide solution and 20 parts by weight, and the mixture was stirred for 3 hours while heated to 80 ° C. to obtain a p-chlorophenol-formaldehyde condensate precipitate. After cooling, 10 parts by weight of diethanolamine was added with stirring to dissolve the p-chlorophenol-formaldehyde condensate to obtain an aqueous solution. The basicity constant (Kb) of diethanolamine is 1.0 × 10 −4.5 .
この際、ｐ−クロロフェノール−ホルムアルデヒド縮合物の重量に対して、加えたジエタノールアミンの重量は２００．０重量％であった。即ち、ｐ−クロロフェノール−ホルムアルデヒド縮合物の重量を１００％基準とする重量百分率で表して、加えたジエタノールアミンの重量は２００．０重量％であった。尚、１．０重量％濃度の水酸化ナトリウム水溶液の前記添加は、ｐ−クロロフェノールとホルムアルデヒドを縮合反応させてｐ−クロロフェノール−ホルムアルデヒド縮合物とするための触媒として縮合反応に必要な量以上に加えてはいない。 Under the present circumstances, the weight of the added diethanolamine was 200.0 weight% with respect to the weight of a p-chlorophenol-formaldehyde condensate. That is, the weight of p-chlorophenol-formaldehyde condensate was expressed as a percentage by weight based on 100%, and the weight of added diethanolamine was 200.0% by weight. The addition of the 1.0% by weight aqueous sodium hydroxide solution is more than the amount necessary for the condensation reaction as a catalyst for the condensation reaction of p-chlorophenol and formaldehyde to form a p-chlorophenol-formaldehyde condensate. In addition to that.
次いで、上記のように合成し、水に溶解しているｐ−クロロフェノール−ホルムアルデヒド縮合物に、ラテックスとして、市販のビニルピリジン−スチレン−ブタジエン共重合体のエマルジョン、クロロスルホン化ポリエチレンエマルジョンおよびアンモニア水を加え攪拌し完全に溶解させた。 Next, a p-chlorophenol-formaldehyde condensate synthesized as described above and dissolved in water was used as a latex as a commercially available emulsion of vinylpyridine-styrene-butadiene copolymer, chlorosulfonated polyethylene emulsion and aqueous ammonia. Was stirred and completely dissolved.
詳しくは、溶解させたｐ−クロロフェノール−ホルムアルデヒド縮合物水溶液、２８０重量部、ビニルピリジン、スチレン、ブタジエンを、ビニルピリジン：スチレン：ブタジエン＝１５：１５：７０重量比となるように重合したビニルピリジン−スチレン−ブタジエン共重合体のエマルジョンとしての日本エイアンドエル株式会社製、商品名、ピラテックス（固形分濃度、４１．０重量％）４４０重量部、クロロスルホン化ポリエチレンエマルジョンとしての住友精化株式会社製、商品名、ＣＳＭ４５０（固形分濃度、４０．０重量％）２１０重量部、ｐＨ調整剤としてのアンモニア水（濃度、２５．０重量％）２２重量部とに、全体として１０００重量部になるように水を加えて、被覆液を調製した。尚、実施例１と同様にラテックス混合後もｐ−クロロフェノール−ホルムアルデヒド縮合物の析出は起こらず、被覆液が得られた。 Specifically, a dissolved p-chlorophenol-formaldehyde condensate aqueous solution, 280 parts by weight, vinylpyridine, styrene, butadiene, polymerized to a vinylpyridine: styrene: butadiene = 15: 15: 70 weight ratio. -Nippon A & L Co., Ltd. as an emulsion of styrene-butadiene copolymer, trade name, 440 parts by weight of pilatex (solid content concentration, 41.0 wt%), manufactured by Sumitomo Seika Co., Ltd. as a chlorosulfonated polyethylene emulsion The product name, 210 parts by weight of CSM450 (solid content concentration, 40.0% by weight), 22 parts by weight of ammonia water (concentration, 25.0% by weight) as a pH adjuster, and 1000 parts by weight as a whole Water was added to prepare a coating solution. In addition, like Example 1, precipitation of p-chlorophenol-formaldehyde condensate did not occur after latex mixing, and a coating solution was obtained.
径９μｍのガラス繊維フィラメントを２００本集束したガラス繊維コ−ド６本を引き揃えた後、前記被覆液を塗布し、その後、温度、２８０℃下で、２２秒間乾燥させて、本発明の接着性組成物の製造方法による接着性組生物としての被覆層を設けゴム補強用ガラス繊維とした。ゴム補強用ガラス繊維の引っ張り強さは、１７３Ｎであった。
実施例３
（被覆液の調整）
還流冷却器、温度計、攪拌機をつけた三つ口セパラブルフラスコに、ｍ−クレゾール、１０８重量部、濃度、３７．０重量％のホルムアルデヒド水溶液、８０重量部（モル比で表せば、１．０）、濃度、１．０重量％の水酸化ナトリウム水溶液、２０重量部を仕込み、８０℃に加熱した状態で７時間攪拌し、ｍ−クレゾール−ホルムアルデヒド縮合物の沈殿物を得た。冷却した後、攪拌しつつジメチルアミンを加えて、ｍ−クレゾール−ホルムアルデヒド縮合物の沈殿を溶解させて水溶液とした。尚、ジメチルアミンの塩基性度定数（Ｋｂ）は５．４×１０−４である。ｍ−クレゾール−ホルムアルデヒド縮合物の重量に対してジメチルアミンの重量は２００．０重量％となるように溶解した。尚、１．０重量％濃度の水酸化ナトリウム水溶液の前記添加は、ｍ−クレゾールとホルムアルデヒドを縮合反応させてｍ−クレゾール−ホルムアルデヒド縮合物とするための触媒として縮合反応に必要な量にとどめ、必要以上に加えてはいない。
After arranging 6 glass fiber cords, each of which 200 glass fiber filaments having a diameter of 9 μm are bundled, the coating liquid is applied, and then dried at a temperature of 280 ° C. for 22 seconds to bond the present invention. A glass fiber for rubber reinforcement was provided by providing a coating layer as an adhesive assemblage by the method for producing an adhesive composition. The tensile strength of the glass fiber for rubber reinforcement was 173N.
Example 3
(Adjustment of coating liquid)
In a three-necked separable flask equipped with a reflux condenser, a thermometer, and a stirrer, m-cresol, 108 parts by weight, concentration, 37.0% by weight formaldehyde aqueous solution, 80 parts by weight (1. 0), an aqueous solution of sodium hydroxide having a concentration of 1.0% by weight, and 20 parts by weight, were stirred for 7 hours while heated to 80 ° C. to obtain a precipitate of m-cresol-formaldehyde condensate. After cooling, dimethylamine was added with stirring to dissolve the precipitate of the m-cresol-formaldehyde condensate to obtain an aqueous solution. The basicity constant (Kb) of dimethylamine is 5.4 × 10 −4 . The weight of dimethylamine was 200.0% by weight with respect to the weight of the m-cresol-formaldehyde condensate. The addition of the 1.0% by weight aqueous sodium hydroxide solution is limited to the amount required for the condensation reaction as a catalyst for the condensation reaction of m-cresol and formaldehyde to form an m-cresol-formaldehyde condensate. It is not added more than necessary.
次いで、上記のように合成し、水に溶解しているｍ−クレゾール−ホルムアルデヒド縮合物に、ラテックスとして、市販のビニルピリジン−スチレン−ブタジエン共重合体のエマルジョン、クロロスルホン化ポリエチレンエマルジョンおよびアンモニア水を加え攪拌し完全に溶解させた。 Next, a commercially available vinylpyridine-styrene-butadiene copolymer emulsion, chlorosulfonated polyethylene emulsion and aqueous ammonia are added as latex to the m-cresol-formaldehyde condensate synthesized as described above and dissolved in water. The mixture was stirred and completely dissolved.
詳しくは、溶解させたｍ−クレゾール−ホルムアルデヒド縮合物水溶液、２４０重量部、ビニルピリジン、スチレン、ブタジエンを、ビニルピリジン：スチレン：ブタジエン＝１５：１５：７０重量比となるように重合したビニルピリジン−スチレン−ブタジエン共重合体のエマルジョンとしての日本エイアンドエル株式会社製、商品名、ピラテックス（固形分濃度、４１．０重量％）４４０重量部、クロロスルホン化ポリエチレンエマルジョンとしての住友精化株式会社製、商品名、ＣＳＭ４５０（固形分濃度、４０．０重量％）２１０重量部、ｐＨ調整剤としてのアンモニア水（濃度、２５．０重量％）２２重量部とに、全体として１０００重量部になるように水を加えて、被覆液を調製した。 Specifically, a dissolved m-cresol-formaldehyde condensate aqueous solution, 240 parts by weight, vinylpyridine, styrene, and butadiene, polymerized to a vinylpyridine: styrene: butadiene = 15: 15: 70 weight ratio— Made by Nippon A & L Co., Ltd. as an emulsion of styrene-butadiene copolymer, trade name, 440 parts by weight of pilatex (solid content concentration, 41.0% by weight), manufactured by Sumitomo Seika Co., Ltd. as a chlorosulfonated polyethylene emulsion, The product name, 210 parts by weight of CSM450 (solid content concentration, 40.0% by weight), and 22 parts by weight of aqueous ammonia (concentration, 25.0% by weight) as a pH adjuster so as to be 1000 parts by weight as a whole. Water was added to prepare a coating solution.
実施例１と同様の手順で、前記被覆液をガラス繊維コードに塗布し本発明の接着性組成物の製造方法による接着性組成物としての被覆層としたところ、ゴム補強用ガラス繊維の引っ張り強さは、１８５Ｎであった。
比較例１
ｐ−クロロフェノール−ホルムアルデヒド縮合物の重量に対して、濃度、２５重量％のアンモニア水を４００重量％加えて溶解させる以外は実施例１と同様の手順でｐ−クロロフェノールホルムアルデヒド縮合物の水溶液を調製した。次いで、このｐ−クロロフェノールホルムアルデヒド縮合物の水溶液を用い、前述した市販のビニルピリジン−スチレン−ブタジエン共重合体のエマルジョンと、クロロスルホン化ポリエチレンエマルジョンとにアンモニア水と水を添加したところ、ｐ−クロロフェノールホルムアルデヒド縮合物の析出が起こり使用できなかった。
比較例２
ｐ−クロロフェノール−ホルムアルデヒド縮合物の重量に対して水酸化ナトリウムを２００重量％加えて、ｐ−クロロフェノール−ホルムアルデヒド縮合物の沈殿を溶解させる以外は実施例１と同様の手順でｐ−クロロフェノール−ホルムアルデヒド縮合物水溶液を調製した。次いで、このｐ−クロロフェノール−ホルムアルデヒド縮合物水溶液を用い、前述した市販のビニルピリジン−スチレン−ブタジエン共重合体のエマルジョンと、クロロスルホン化ポリエチレンエマルジョンとにアンモニア水と水を添加したところ、ｐ−クロロフェノールホルムアルデヒド縮合物の析出は起こらず、被覆液を得た。
In the same procedure as in Example 1, the coating liquid was applied to a glass fiber cord to form a coating layer as an adhesive composition according to the method for producing an adhesive composition of the present invention. The height was 185N.
Comparative Example 1
An aqueous solution of p-chlorophenol formaldehyde condensate was prepared in the same manner as in Example 1 except that 400% by weight of ammonia water having a concentration of 25% by weight was dissolved with respect to the weight of the p-chlorophenol-formaldehyde condensate. Prepared. Next, using this aqueous solution of p-chlorophenol formaldehyde condensate, ammonia water and water were added to the above-mentioned commercially available vinylpyridine-styrene-butadiene copolymer emulsion and chlorosulfonated polyethylene emulsion. Precipitation of chlorophenol formaldehyde condensate occurred and could not be used.
Comparative Example 2
p-Chlorophenol was prepared in the same manner as in Example 1 except that 200% by weight of sodium hydroxide was added to the weight of the p-chlorophenol-formaldehyde condensate to dissolve the precipitate of the p-chlorophenol-formaldehyde condensate. -An aqueous formaldehyde condensate solution was prepared. Then, using this aqueous p-chlorophenol-formaldehyde condensate solution, ammonia water and water were added to the above-mentioned commercially available vinylpyridine-styrene-butadiene copolymer emulsion and chlorosulfonated polyethylene emulsion. Precipitation of chlorophenol formaldehyde condensate did not occur and a coating solution was obtained.
径９μｍのガラス繊維フィラメントを２００本集束したガラス繊維コ−ド６本を引き揃えた後、前記被覆液を塗布し、その後、温度、２８０℃下で、２２秒間乾燥させて被覆層を設けゴム補強用ガラス繊維した。 After arranging 6 glass fiber cords of 200 glass fiber filaments having a diameter of 9 μm bundled together, the coating solution is applied, and then dried at a temperature of 280 ° C. for 22 seconds to provide a coating layer. Reinforcing glass fiber.
このゴム補強用ガラス繊維の引っ張り強さは、ガラス繊維コードの本来の引っ張り強さより低い１１８Ｎになった。 The tensile strength of the glass fiber for rubber reinforcement was 118 N, which is lower than the original tensile strength of the glass fiber cord.
以上、実施例１、２、比較例１、２の結果を表１に纏めた。 The results of Examples 1 and 2 and Comparative Examples 1 and 2 are summarized in Table 1 above.
Claims (7)
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