JP5157747B2 - Resin composition for screw - Google Patents
Resin composition for screw Download PDFInfo
- Publication number
- JP5157747B2 JP5157747B2 JP2008214771A JP2008214771A JP5157747B2 JP 5157747 B2 JP5157747 B2 JP 5157747B2 JP 2008214771 A JP2008214771 A JP 2008214771A JP 2008214771 A JP2008214771 A JP 2008214771A JP 5157747 B2 JP5157747 B2 JP 5157747B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- parts
- adhesive polymer
- screw
- adhesive
- 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.)
- Active
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- 239000011342 resin composition Substances 0.000 title claims description 24
- 239000000178 monomer Substances 0.000 claims description 66
- 229920000642 polymer Polymers 0.000 claims description 65
- 239000002998 adhesive polymer Substances 0.000 claims description 54
- 239000000839 emulsion Substances 0.000 claims description 49
- 229920001577 copolymer Polymers 0.000 claims description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000001735 carboxylic acids Chemical group 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 description 33
- 239000000853 adhesive Substances 0.000 description 28
- 230000001070 adhesive effect Effects 0.000 description 28
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- 229940048053 acrylate Drugs 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 16
- 238000010079 rubber tapping Methods 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- 229920006267 polyester film Polymers 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 229910000861 Mg alloy Inorganic materials 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 10
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000002699 waste material Substances 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 239000003094 microcapsule Substances 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 8
- -1 2-ethylhexyl Chemical group 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 7
- 239000012986 chain transfer agent Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229940114077 acrylic acid Drugs 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- IZUVGRMMRWJVKU-UHFFFAOYSA-N 3-ethoxycarbonylbut-3-enoic acid Chemical compound CCOC(=O)C(=C)CC(O)=O IZUVGRMMRWJVKU-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- UAYKGOMDUQLCJS-UHFFFAOYSA-N ethylsulfanyl acetate Chemical compound CCSOC(C)=O UAYKGOMDUQLCJS-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、各種の部品を組み立てるのに使用されるねじに塗布する樹脂組成物に関する。さらに詳しくは、ねじの少なくとも一部に塗布され、ねじの締め込み時や抜き取り時に発生する成形屑を補足するのに効果的なねじ用樹脂組成物に関するものである。 The present invention relates to a resin composition applied to a screw used for assembling various parts. More specifically, the present invention relates to a resin composition for a screw which is applied to at least a part of a screw and is effective for supplementing molding waste generated when the screw is tightened or removed.
パソコン、携帯電話及びデジタルカメラ等の電子機器のおいては、機器の内部部品やハウジング等の基材としてアルミニウム合金やマグネシウム合金等が使用されている。これは、軽量化とリサイクル性が考慮されているからである。また、当該部品の固定には、ねじが多く使用されている。２つの部品の固定方法は、一方の部品に溝なしの素通し貫通の下穴を予め開孔した後、部品を重ね合わせてねじを下穴にねじ込み、下穴壁面に雌ねじ溝を切削形成しながらねじ込むことにより行われるのが一般的である。 In electronic devices such as personal computers, mobile phones, and digital cameras, aluminum alloys, magnesium alloys, and the like are used as base materials for internal parts and housings of devices. This is because weight reduction and recyclability are considered. Further, many screws are used to fix the parts. Two parts can be fixed by pre-opening a through hole without a groove in one of the parts in advance, then superimposing the parts, screwing the screw into the pilot hole, and cutting the female screw groove on the wall surface of the pilot hole. This is generally done by screwing.
前記の部品の固定方法では、ねじ込み作業中における雌ねじ成形時の摩擦力や、雌ねじが形成される基材の降伏点を越えて下穴周壁を変形させることにより、下穴で雌ねじ溝の切削形成が行われる。このため、基材の下穴の周壁から摩擦粉や剥離片が成形屑となって発生し、この成形屑が落下したり、飛散したりして電子機器の作動部内に入り込む。また、一旦締め込んだねじを取り外す時には、ねじ溝やねじ山に付着して残った成形屑が飛散することがある。これら成形屑が電子回路のプリント基板上に落下すると電子回路がショートすることになり、電子機器の故障の原因となる。 In the fixing method of the above-mentioned parts, the frictional force at the time of female thread forming during screwing work and the peripheral wall of the pilot hole are deformed beyond the yield point of the base material on which the female screw is formed, so that the female thread groove is cut by the pilot hole. Is done. For this reason, friction powder and peeling pieces are generated as molding waste from the peripheral wall of the base hole of the base material, and the molding waste falls or scatters and enters the operating portion of the electronic device. Moreover, when removing the screw once tightened, the molding waste remaining after adhering to the screw groove or the thread may be scattered. If these molding scraps fall on the printed circuit board of the electronic circuit, the electronic circuit will be short-circuited, causing a failure of the electronic device.
前記のような基材の成形屑が落下するのを防止するため、ねじに塗布する材料が提案されている。例えば、特許文献１には、ねじ脚部の先端から少なくとも６０％以上の部分にマイクロカプセルにエポキシ樹脂系接着剤を封入した樹脂接着剤を塗布することにより、雌ねじ成型時における成形粉の発生が少なくなることが記載されている。また、特許文献２には、油性あるいは水性の潤滑成分を主剤とし、この主剤を接合するバインダとを封入したマイクロカプセルを含有した被覆材が記載されている。特許文献３には、弾性体を含有する有機溶剤又は含水エマルション液中に、液状潤滑剤だけを内包するマイクロカプセルを分散させて作られる粘着性分散液が記載されている。更に、特許文献４には、粘着剤とエポキシ樹脂用の硬化剤とを含有するか、もしくは粘着剤として作用でき且つエポキシ樹脂系接着剤用の硬化剤としても作用できるポリアミドと粘着付与剤とを含有するエマルジョン液中に、液状潤滑剤のみを内包するマイクロカプセルとエポキシ樹脂系接着剤を内包するマイクロカプセルとを分散させて作られる粘着性分散液の形の液状組成物である。 In order to prevent the molding waste of the base material from falling, a material applied to the screw has been proposed. For example, in Patent Document 1, by applying a resin adhesive in which an epoxy resin adhesive is encapsulated in a microcapsule to at least 60% or more from the tip of a screw leg, generation of molding powder at the time of female screw molding is generated. It is described that it becomes less. Patent Document 2 describes a coating material containing microcapsules containing an oily or aqueous lubricating component as a main component and a binder to which the main component is bonded. Patent Document 3 describes an adhesive dispersion prepared by dispersing microcapsules containing only a liquid lubricant in an organic solvent or an aqueous emulsion containing an elastic body. Furthermore, Patent Document 4 includes a polyamide and a tackifier that contain an adhesive and a curing agent for an epoxy resin, or that can act as an adhesive and also act as a curing agent for an epoxy resin adhesive. It is a liquid composition in the form of an adhesive dispersion prepared by dispersing microcapsules enclosing only a liquid lubricant and microcapsules encapsulating an epoxy resin adhesive in an emulsion liquid.
しかしながら、特許文献１及び２の発明では、切削屑を捕捉するための主剤をマイクロカプセル化しなければならないこと、またマイクロカプセルが破壊される前の状態では、潤滑性がなく、ねじ込みに大きなトルクが必要であるという問題がある。特許文献３及び４の発明においても同様に、液状潤滑剤を内包するマイクロカプセルを作製しなければならない。更にいずれの発明もマイクロカプセルを使用しているため、マイクロカプセルに内包する成分が瞬時に浸透することは期待できず、潤滑効果や成形屑の補足が不十分であるという問題もある。 However, in the inventions of Patent Documents 1 and 2, the main agent for capturing cutting waste must be microencapsulated, and in a state before the microcapsule is broken, there is no lubricity and a large torque is applied to screwing. There is a problem that it is necessary. Similarly, in the inventions of Patent Documents 3 and 4, a microcapsule containing a liquid lubricant must be prepared. Furthermore, since any invention uses a microcapsule, it cannot be expected that the components contained in the microcapsule will permeate instantaneously, and there is a problem that the lubrication effect and supplementation of molding waste are insufficient.
本発明は、前記課題に鑑みなされたものであって、その目的は、ねじに塗布された状態では非粘着性であるものの、ねじの締め込みと同時に粘着性を発現し、成形屑の補足に有効なねじ用樹脂組成物を提供することである。 The present invention has been made in view of the above problems, and its purpose is to be non-adhesive when applied to a screw, but to exhibit adhesiveness at the same time as the screw is tightened, and to supplement molding waste. It is to provide an effective resin composition for screws.
本発明者は鋭意検討した結果、ねじの締め付け前後において粘着力が変化する樹脂組成物を用いた場合に前記課題を解決することができ、特に非粘着性重合体と粘着性重合体とを特定割合で含む水性重合体エマルションが好ましいことを見出し、本発明を完成させるに至った。 As a result of intensive studies, the present inventor can solve the above problems when using a resin composition whose adhesive strength changes before and after screw tightening, and particularly identifies a non-adhesive polymer and an adhesive polymer. The present inventors have found that an aqueous polymer emulsion contained in a proportion is preferable and have completed the present invention.
すなわち、本発明は以下の通りである。
１．ねじ溝に塗布される樹脂組成物であって、ねじの締め付け前は非粘着性重合体（Ａ）が連続相であり、粘着性重合体（Ｂ）が島状となる海島構造を有し、ねじの締め付けと同時に粘着性重合体（Ｂ）が連続相であり、非粘着性重合体（Ａ）が島状となる海島構造に変化するねじ用樹脂組成物であり、
上記非粘着性重合体（Ａ）がα、β−エチレン性不飽和カルボン酸単位及び水１００ｇに対する溶解度が２ｇ以下である疎水性のラジカル重合性単量体単位を主構成単位とし、共重合体におけるカルボキシル基の一部又は全量が沸点１１０℃以下の塩基で中和されている水溶性又は水分散性の共重合体であり、上記粘着性重合体（Ｂ）として、（メタ）アクリル酸アルキルエステルを主成分とするガラス転移温度が−３０℃以下の重合体を与えるラジカル重合性単量体を乳化重合することによって得られる水性重合体エマルションからなり、かつ、非粘着性重合体（Ａ）：粘着性重合体（Ｂ）の重量割合が、固形分の重量比で、２０：８０〜３５：６５であることを特徴とするねじ用樹脂組成物。
２．上記非粘着性重合体（Ａ）のガラス転移温度（Ｔｇ）が２０℃以上であることを特徴とするねじ用樹脂組成物。
That is, the present invention is as follows.
1. It is a resin composition applied to a thread groove, and has a sea-island structure in which the non-adhesive polymer (A) is a continuous phase before the screw is tightened, and the adhesive polymer (B) is island-shaped, the continuous phase is tightened at the same time as adhesive polymer of the screw (B), a non-tacky polymer (a) is Rene Ji resin composition to change the island structure comprising an island-shaped,
The non-adhesive polymer (A) is composed mainly of an α, β-ethylenically unsaturated carboxylic acid unit and a hydrophobic radical polymerizable monomer unit having a solubility in 100 g of water of 2 g or less as a main constituent unit. Is a water-soluble or water-dispersible copolymer in which a part or all of the carboxyl groups in the base is neutralized with a base having a boiling point of 110 ° C. or lower. As the adhesive polymer (B), an alkyl (meth) acrylate A non-adhesive polymer (A) comprising an aqueous polymer emulsion obtained by emulsion polymerization of a radical polymerizable monomer that gives a polymer having an ester as a main component and a glass transition temperature of -30 ° C or lower. : The resin composition for screws, wherein the weight ratio of the adhesive polymer (B) is 20:80 to 35:65 by weight ratio of the solid content.
2. The screw resin composition, wherein the non-adhesive polymer (A) has a glass transition temperature (Tg) of 20 ° C or higher.
なお、本発明における非粘着性とは、ＪＩＳ Ｚ ０２３７に準じて測定した１８０度ひきはがし法（ただし、加圧ローラーの重量は１００ｇとする。）による粘着力が、１０ｇ／２５ｍｍ以下であることをいう。 In addition, the non-adhesiveness in this invention means that the adhesive force by 180 degree | times peeling method (however, the weight of a pressure roller shall be 100 g) measured according to JISZ0237 is 10 g / 25mm or less. Say.
本発明に係るねじ用樹脂組成物は、加圧前後において粘着性が変化する組成物である。本発明の組成物をねじに塗布した場合、ねじの締め付け前は非粘着であるため、べたつくことはなく、作業時や保管時に異物が付着することはない。一方、ねじの締め付け時には、潤滑効果を発揮するために大きなトルクを必要とすることなくねじを締め付けることができ、またねじの締め付けと同時に加圧により粘着性を発現するため、部品の基材から発生する成形屑を十分に捕捉することができる。更に、ねじ抜き取り時にねじ山等に付着した成形屑が落下することもない。 The resin composition for screws according to the present invention is a composition whose adhesiveness changes before and after pressing. When the composition of the present invention is applied to a screw, it is non-adhesive before tightening the screw, so that it does not become sticky, and no foreign matter adheres during operation or storage. On the other hand, at the time of screw tightening, the screw can be tightened without requiring a large torque in order to exert a lubricating effect. The generated molding waste can be sufficiently captured. Further, the molding waste adhering to the screw thread or the like does not fall when the screw is removed.
本発明のねじ用樹脂組成物は、粘着性ポリマーが島で非粘着ポリマーが海となる海島構造を有するのであれば、いずれの樹脂組成物も使用することができるが、粘着性を制御する観点から水性重合体エマルションが好ましい。以下、水性重合体エマルションについて説明する。 As long as the resin composition for screws of the present invention has a sea-island structure in which the adhesive polymer is an island and the non-adhesive polymer is the sea, any resin composition can be used. To aqueous polymer emulsions are preferred. Hereinafter, described aqueous polymer emulsion.
本発明の水性重合体エマルションとしては、例えば、特許３４３１７６８号公報、ないしは特開平１１−５９５９号公報に記載されているような、初期状態では非粘着性かまたは粘着性がきわめて低いが、加温した場合や加圧した場合により強い粘着性を発現する感熱粘着剤組成物を使用することができる。
本発明における重合体のガラス転移温度（以下「Ｔｇ」と略記することがある）は、以下の計算式（１）から求められる値をいう。
As the aqueous polymer emulsion of the present invention, for example, as described in Japanese Patent No. 3431768 or Japanese Patent Application Laid-Open No. 11-5959, the initial state is non-adhesive or extremely low in adhesiveness. A heat-sensitive adhesive composition that expresses stronger tackiness when applied or pressurized can be used.
The glass transition temperature (hereinafter sometimes abbreviated as “Tg”) of the polymer in the present invention refers to a value obtained from the following calculation formula (1).
Ｔｇ＝重合体のＴｇ
Ｗ（ａ）＝重合体における単量体（ａ）からなる構造単位の重量分率
Ｗ（ｂ）＝重合体における単量体（ｂ）からなる構造単位の重量分率
Ｗ（ｃ）＝重合体における単量体（ｃ）からなる構造単位の重量分率
Ｔｇ（ａ）＝単量体（ａ）の単独重合体のガラス転移温度
Ｔｇ（ｂ）＝単量体（ｂ）の単独重合体のガラス転移温度
Ｔｇ（ｃ）＝単量体（ｃ）の単独重合体のガラス転移温度
Tg = Tg of polymer
W (a) = weight fraction of structural unit consisting of monomer (a) in polymer W (b) = weight fraction of structural unit consisting of monomer (b) in polymer W (c) = heavy Weight fraction of structural unit consisting of monomer (c) in coalescence Tg (a) = Glass transition temperature of homopolymer of monomer (a) Tg (b) = Homopolymer of monomer (b) Glass transition temperature of Tg (c) = monomer (c) homopolymer glass transition temperature
本発明のねじ用樹脂組成物を構成する非粘着性重合体（Ａ）について、以下に説明する。 The non-adhesive polymer (A) constituting the screw resin composition of the present invention will be described below.
非粘着性重合体（Ａ）（中和前共重合体）の製造に用いるα、β−エチレン性不飽和カルボン酸としては、例えばアクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、無水マレイン酸等を挙げることができ、これら単量体の１種又は２種以上を用いることができる。α、β−エチレン性不飽和カルボン酸の使用量は、かかる不飽和カルボン酸及び他の共重合性単量体を共重合して得られる、塩基で中和する前の共重合体（中和前共重合体）の酸価が、中和前共重合体１ｇ当たり３０〜２６０ｍｇＫＯＨ／ｇになる量である。中和前共重合体の酸価が、中和前共重合体１ｇ当たり、３０ｍｇＫＯＨ／ｇ未満であるとこれを塩基で中和しても水に良好に溶解又は分散し得る共重合体を得ることが困難になり、一方２６０ｍｇＫＯＨ／ｇを超えると耐水性が劣ったものとなる。上記酸価を与えるα、β−エチレン性不飽和カルボン酸の使用量は、用いる不飽和カルボン酸の種類によって異なるが、中和前共重合体の製造に用いられる全単量体の合計重量に基づいて、通常３〜４０重量％程度であるのが好ましい。 Examples of the α, β-ethylenically unsaturated carboxylic acid used in the production of the non-adhesive polymer (A) (pre-neutralization copolymer) include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itacone. An acid, citraconic acid, maleic anhydride, etc. can be mentioned, One or more of these monomers can be used. The amount of α, β-ethylenically unsaturated carboxylic acid used is a copolymer obtained by copolymerizing such unsaturated carboxylic acid and other copolymerizable monomers before neutralization with a base (neutralization The acid value of the (pre-copolymer) is such an amount that it is 30 to 260 mgKOH / g per 1 g of the copolymer before neutralization. When the acid value of the pre-neutralization copolymer is less than 30 mg KOH / g per gram of the pre-neutralization copolymer, a copolymer that can be dissolved or dispersed well in water even when neutralized with a base is obtained. On the other hand, if it exceeds 260 mgKOH / g, the water resistance becomes inferior. The amount of α, β-ethylenically unsaturated carboxylic acid that gives the acid value varies depending on the type of unsaturated carboxylic acid used, but the total weight of all monomers used in the production of the copolymer before neutralization In general, it is preferably about 3 to 40% by weight.
非粘着性重合体（Ａ）（中和前共重合体）を製造するために上記したα、β−エチレン性不飽和カルボン酸と共に用いる疎水性のラジカル重合性単量体としては、水１００ｇに対する溶解度が２ｇ以下のものである必要があり、例えば、メタクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ−ノニル及び（メタ）アクリル酸イソノニル等の（メタ）アクリル酸アルキル；スチレン、α−メチルスチレン、ビニルトルエン等のビニル芳香族系単量体等が挙げられる。上記の疎水性単量体の使用量は、非粘着性重合体（Ａ）を合成するために供される全単量体の合計量を基準にして、３０〜８０重量％が好ましい。 The hydrophobic radical polymerizable monomer used together with the α, β-ethylenically unsaturated carboxylic acid described above to produce the non-adhesive polymer (A) (copolymer before neutralization) is based on 100 g of water. The solubility must be 2 g or less, for example, methyl methacrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) acrylic Alkyl (meth) acrylates such as n-nonyl acid and isononyl (meth) acrylate; styrene, α-methylstyrene, Vinyl aromatic monomers such as Nirutoruen like. The amount of the hydrophobic monomer used is preferably 30 to 80% by weight based on the total amount of all monomers provided to synthesize the non-adhesive polymer (A).
また、非粘着性重合体（Ａ）を合成するために、上記したα、β−エチレン性不飽和カルボン酸以外の親水性ラジカル重合性単量体を必要に応じて使用することもでき、かかる親水性ラジカル重合性単量体としては、例えば、アクリル酸メチル、酢酸ビニル、アクリロニトリル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、ポリエチレングリコールモノ（メタ）アクリレート 、ポリプロピレングリコールモノ（メタ）アクリレート、（メタ）アクリル酸アミド、Ｎ−メチロールアクリルアミド、メタクリル酸グリシジル、スチレンスルホン酸及びそのナトリウム塩並びに２−アクリルアミド−２−メチルプロパンスルホン酸及びそのナトリウム塩等が挙げられる。 Moreover, in order to synthesize the non-adhesive polymer (A), a hydrophilic radical polymerizable monomer other than the above-described α, β-ethylenically unsaturated carboxylic acid can be used as necessary. Examples of the hydrophilic radical polymerizable monomer include methyl acrylate, vinyl acetate, acrylonitrile, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, Examples include polypropylene glycol mono (meth) acrylate, (meth) acrylic acid amide, N-methylol acrylamide, glycidyl methacrylate, styrene sulfonic acid and its sodium salt, and 2-acrylamido-2-methylpropane sulfonic acid and its sodium salt. .
上記したα、β−エチレン性不飽和カルボン酸、疎水性のラジカル重合性単量体及び必要に応じて用いられる親水性のラジカル重合性単量体の種類並びに使用割合は、得られる重合体のＴｇが２０℃以上となるように、上記した計算式（１）に基づいて選択される。 The types and use ratios of the α, β-ethylenically unsaturated carboxylic acid, the hydrophobic radical polymerizable monomer and the hydrophilic radical polymerizable monomer used as necessary are as follows. It is selected based on the above-described calculation formula (1) so that Tg is 20 ° C. or higher.
上記した中和前共重合体を得るための重合法としては、種々の重合法が採用でき、例えば放射線照射による重合法、ラジカル重合開始剤を用いる方法などの公知の方法を使用できる。そのうちでも、ラジカル重合開始剤を用いる重合法が重合操作の容易性、得られる中和前共重合体における分子量調節の容易性などの点から好ましい。また、重合法としては、溶液重合法、バルク重合法、懸濁重合法、乳化重合法、沈殿重合法などがあげられるが、溶液重合法が好ましく、α、β−エチレン性不飽和カルボン酸及び他の共重合性単量体を有機溶媒に溶解し、適当なラジカル重合開始剤を用いて重合を行うことによって中和前共重合体を円滑に得ることができる。 As a polymerization method for obtaining the above-mentioned copolymer before neutralization, various polymerization methods can be adopted, and for example, a known method such as a polymerization method by radiation irradiation or a method using a radical polymerization initiator can be used. Among these, a polymerization method using a radical polymerization initiator is preferable from the viewpoints of ease of polymerization operation and ease of molecular weight adjustment in the resulting pre-neutralization copolymer. Examples of the polymerization method include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and a precipitation polymerization method, but a solution polymerization method is preferable, and α, β-ethylenically unsaturated carboxylic acid and A copolymer before neutralization can be obtained smoothly by dissolving other copolymerizable monomers in an organic solvent and performing polymerization using an appropriate radical polymerization initiator.
均質で安定な非粘着性重合体（Ａ）（中和前共重合体）を得るためには、可能な限り反応系中の単量体比率を一定に保つように単量体の滴下速度をコントロールすることが望ましい。具体的には、共重合性が乏しく反応性の低い単量体を重合の初期にその一部又は全量を反応器中に仕込み、そして反応速度の速い単量体を反応の途中に滴下する方法、反応速度の遅い単量体の一部と反応速度の速い単量体の一部を反応器に仕込んでおいて反応速度の速い単量体の消費速度に合わせて反応速度の遅い単量体を反応器中に滴下する方法などを採用することによって均質な非粘着性重合体（Ａ）（中和前共重合体）を得ることができる。 In order to obtain a homogeneous and stable non-adhesive polymer (A) (pre-neutralization copolymer), the monomer dropping rate should be set to keep the monomer ratio in the reaction system as constant as possible. It is desirable to control. Specifically, a method in which a monomer having poor copolymerization and low reactivity is charged in the reactor at the initial stage of polymerization, and a monomer having a high reaction rate is dropped in the middle of the reaction. A monomer having a slow reaction rate and a monomer having a fast reaction rate are charged in a reactor and the monomer having a slow reaction rate is matched to the consumption rate of the monomer having a fast reaction rate. A homogeneous non-adhesive polymer (A) (copolymer before neutralization) can be obtained by adopting a method of dropping the solution into the reactor.
上記した溶液重合を行う場合に好ましく用いられる有機溶媒としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒；酢酸エチル、酢酸ブチル等の酢酸エステル系溶媒；ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒；シクロヘキサン、ヘキサン、ヘプタン等の脂肪族炭化水素系溶媒；メタノール、エタノール、イソプロパノール、メチルセロソルブ、エチルセロソルブ、ノルマルブチルセロソルブ、エチレングリコール、プロピレングリコール、トリメチロールプロパン、グリセリン等のアルコール系溶媒；テトラヒドフラン、ジオキサン、ジメチルホルムアミド、ジメチルスルホキシド、ヘキサメチルホスホアミド等を挙げることができ、これらの有機溶媒は単独で使用しても又は２種以上併用してもよい。そのうちでも、有機溶媒として、メチルエチルケトン及び／又はイソプロピルアルコールがより好ましく用いられる。 Examples of the organic solvent that is preferably used in performing the above-described solution polymerization include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; acetate solvents such as ethyl acetate and butyl acetate; benzene, toluene, xylene, and the like. Aromatic hydrocarbon solvents; aliphatic hydrocarbon solvents such as cyclohexane, hexane, heptane; alcohols such as methanol, ethanol, isopropanol, methyl cellosolve, ethyl cellosolve, normal butyl cellosolve, ethylene glycol, propylene glycol, trimethylolpropane, glycerin Examples of the solvent include tetrahydrfuran, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoamide and the like. These organic solvents may be used alone or in combination of two kinds. It may be above combination. Among them, methyl ethyl ketone and / or isopropyl alcohol are more preferably used as the organic solvent.
また、上記した溶液重合で用いるラジカル重合開始剤としては、一般のラジカル重合に用いられているもののいずれもが使用可能であり、例えば過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩系重合開始剤；２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−メチルブチロニトリル）等のアゾ系重合開始剤；過酸化ベンゾイル、ラウロイルパーオキサイド等の有機過酸化物；クメンヒドロパーオキサイド、ｔｅｒｔ−ブチルハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド等の有機ハイドロパーオキサイド類からなる酸化剤と、ロンガリット、亜硫酸水素ナトリウム、アスコルビン酸等の還元剤との組み合わせによるレドックス系重合開始剤等を挙げることができる。重合開始剤の好ましい使用量は、単量体の合計量を基準にして、０．１〜５重量％である。 In addition, as the radical polymerization initiator used in the above solution polymerization, any of those used in general radical polymerization can be used. For example, persulfate polymerization initiators such as potassium persulfate and ammonium persulfate; Azo polymerization initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2-methylbutyronitrile); organic peroxides such as benzoyl peroxide and lauroyl peroxide; cumene hydro Redox polymerization initiators in combination with an oxidizing agent comprising organic hydroperoxides such as peroxide, tert-butyl hydroperoxide, diisopropylbenzene hydroperoxide and a reducing agent such as Rongalite, sodium bisulfite, ascorbic acid, etc. Can be mentioned. A preferable use amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the monomers.
また、上記した溶液重合では、得られる中和前共重合体の分子量調整のために、連鎖移動剤を重合系に適宜添加してもよく、その際の連鎖移動剤としては、例えば、メルカプト酢酸、メルカプトプロピオン酸、２−プロパンチオール、１−ブタンチオール、２−メチル−２−プロパンチオール、２−メルカプトエタノール、エチルメルカプトアセテート、チオフェノール、２−ナフタレンチオール、ドデシルメルカプタン及びチオグリセロール等を挙げることができる。 In the above-described solution polymerization, a chain transfer agent may be appropriately added to the polymerization system in order to adjust the molecular weight of the resulting pre-neutralization copolymer. Examples of the chain transfer agent at that time include, for example, mercaptoacetic acid. , Mercaptopropionic acid, 2-propanethiol, 1-butanethiol, 2-methyl-2-propanethiol, 2-mercaptoethanol, ethyl mercaptoacetate, thiophenol, 2-naphthalenethiol, dodecyl mercaptan, thioglycerol, etc. Can do.
中和前共重合体を得るための重合温度は、１０〜１５０℃程度であるのが好ましく、６０〜１００℃であるのがより好ましい。また、重合時間は１〜１００時間が適当であり、より好ましくは３〜１０時間である。 The polymerization temperature for obtaining the copolymer before neutralization is preferably about 10 to 150 ° C, more preferably 60 to 100 ° C. Moreover, 1-100 hours are suitable for superposition | polymerization time, More preferably, it is 3 to 10 hours.
そして、中和前共重合体はその数平均分子量が１，０００〜５００，０００であることが好ましい。中和前共重合体の数平均分子量が1，０００未満であると、ねじ用樹脂層の耐水性や耐湿性が劣ったものになり易く、一方５００，０００を超えると高粘度となって中和前共重合体自体の製造が困難になる。 And it is preferable that the number average molecular weights of the copolymer before neutralization are 1,000-500,000. If the number-average molecular weight of the copolymer before neutralization is less than 1,000, the water and moisture resistance of the screw resin layer tends to be inferior, while if it exceeds 500,000, the viscosity becomes high. It becomes difficult to produce the Wazen copolymer itself.
次に、上記重合によって得られる中和前共重合体中のカルボキシル基の一部又は全部を、沸点が１１０℃以下の塩基によって中和して、本発明で用いる非粘着性重合体（Ａ）に変換する。中和に使用する塩基の沸点が１１０℃を超えると、塗工乾燥後の粘着剤層中に塩基が残存して、粘着剤層の耐水性及び耐湿性が劣ったものとなる。中和前共重合体のカルボキシル基の中和に用いる、沸点１１０℃以下の塩基の具体例としては、アンモニア、メチルアミン、エチルアミン、プロピルアミン、イソプロピルアミン、ブチルアミン、アミルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジイソプロピルアミン、トリメチルアミン、トリエチルアミン及びアリルアミン等を挙げることができ、そのうちでもアンモニアが好ましく用いられる。 Next, the non-adhesive polymer (A) used in the present invention is obtained by neutralizing a part or all of the carboxyl groups in the pre-neutralization copolymer obtained by the polymerization with a base having a boiling point of 110 ° C. or lower. Convert to When the boiling point of the base used for neutralization exceeds 110 ° C., the base remains in the pressure-sensitive adhesive layer after coating and drying, resulting in poor water resistance and moisture resistance of the pressure-sensitive adhesive layer. Specific examples of bases having a boiling point of 110 ° C. or lower used for neutralization of the carboxyl group of the copolymer before neutralization include ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, dimethylamine, diethylamine, Examples thereof include propylamine, diisopropylamine, trimethylamine, triethylamine and allylamine, among which ammonia is preferably used.
中和前共重合体のカルボキシル基の中和量は、３０モル％以上であることが好ましく、５０モル％以上であることがより好ましい。中和前共重合体のカルボキシル基の中和量が５０モル％未満であると、非粘着性重合体（Ａ）の界面活性能及び水溶性が低下し易い。 The neutralization amount of the carboxyl group of the copolymer before neutralization is preferably 30 mol% or more, and more preferably 50 mol% or more. When the neutralization amount of the carboxyl group of the copolymer before neutralization is less than 50 mol%, the surface active ability and water solubility of the non-adhesive polymer (A) are likely to be lowered.
中和前共重合体中のカルボキシル基を塩基で中和するに当たっては、上記した溶液重合などにより得られる中和前共重合体を、反応媒体から回収せずにそのまま反応媒体中に存在させた状態（特に有機溶媒中に溶解した状態）にしておき、そこに中和用の塩基を添加して行うのが操作が容易である点から好ましい。その際に、中和用の塩基を、水溶液として添加すると、カルボキシル基の中和が円滑に行われるのでより好ましい。 In neutralizing the carboxyl group in the pre-neutralization copolymer with a base, the pre-neutralization copolymer obtained by solution polymerization or the like was allowed to exist in the reaction medium as it was without being recovered from the reaction medium. It is preferable from the viewpoint of easy operation that it is in a state (particularly in a state dissolved in an organic solvent) and a neutralizing base is added thereto. At that time, it is more preferable to add a neutralizing base as an aqueous solution because the neutralization of the carboxyl group is carried out smoothly.
上記によってカルボキシル基の一部又は全部が中和された非粘着性重合体（Ａ）を得ることができる。非粘着性重合体（Ａ）は、中和処理を行った反応系から取り出して、（メタ）アクリル酸アルキルエステルから主としてなるラジカル重合性単量体の乳化重合に用いてもよい。しかしながら、中和前共重合体を溶液重合によって製造し、それに中和用の塩基の水溶液を添加して中和前共重合体中のカルボキシル基を中和して反応媒体中に非粘着性重合体（Ａ）を形成させた後、系に存在する有機溶媒を適当な方法（例えば減圧下）で除去して非粘着性重合体（Ａ）の濃度が１０〜６０重量％程度の水溶液又は水性分散液の形態にし、その一部又は全量を取り出して次の水性エマルションの製造工程で用いることが好ましい。 As described above, a non-adhesive polymer (A) in which part or all of the carboxyl groups are neutralized can be obtained. The non-adhesive polymer (A) may be taken out from the reaction system subjected to the neutralization treatment and used for emulsion polymerization of a radical polymerizable monomer mainly composed of (meth) acrylic acid alkyl ester. However, a pre-neutralization copolymer is produced by solution polymerization, and an aqueous solution of a neutralizing base is added thereto to neutralize the carboxyl groups in the pre-neutralization copolymer, thereby eliminating the non-adhesive heavy in the reaction medium. After forming the coalescence (A), the organic solvent present in the system is removed by an appropriate method (for example, under reduced pressure) to remove the non-adhesive polymer (A) in an aqueous solution or aqueous solution having a concentration of about 10 to 60% by weight. It is preferable to make it into the form of a dispersion and to use a part or all of it in the production process of the next aqueous emulsion.
そして、本発明で用いる水性重合体エマルションは、上記した非粘着性重合体（Ａ）の存在下に、（メタ）アクリル酸アルキルエステルを主成分とするガラス転移温度が−１０℃以下の粘着性重合体（Ｂ）を与えるラジカル重合性単量体を乳化重合することによって形成される。水性重合体エマルションを形成するための（メタ）アクリル酸アルキルエステルを主成分とするラジカル重合性単量体としては、（メタ）アクリル酸アルキルエステルを主成分とし、必要に応じてこれと共重合し得る他のラジカル重合性単量体（以下これを「共重合性単量体」ということがある）を少量（好ましくは４０重量％以下）併用したものが好ましく用いられる。 And the aqueous polymer emulsion used by this invention is the adhesiveness whose glass transition temperature which has (meth) acrylic-acid alkylester as a main component is -10 degrees C or less in presence of the above-mentioned non-adhesive polymer (A). It is formed by emulsion polymerization of a radically polymerizable monomer that gives the polymer (B). As a radical polymerizable monomer mainly composed of (meth) acrylic acid alkyl ester for forming an aqueous polymer emulsion, it is composed mainly of (meth) acrylic acid alkyl ester and copolymerized therewith if necessary. A combination of a small amount (preferably 40% by weight or less) of another radical polymerizable monomer (hereinafter sometimes referred to as “copolymerizable monomer”) that can be used is preferably used.
水性重合体エマルションの製造に用いられる上記の（メタ）アクリル酸アルキルエステルとしては、そのアルキル基の炭素数が１〜１２である（メタ）アクリル酸アルキルエステルが好ましく用いられ、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ−ノニル及び（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ラウリル等を挙げることができ、これらの（メタ）アクリル酸アルキルエステルの１種又は２種以上を用いることができる。特に、本発明では、水性重合体エマルションの製造に当たって、（メタ）アクリル酸アルキルエステルとして、アルキル基の炭素数が４〜９である（メタ）アクリル酸アルキルエステルの１種又は２種以上を主成分として用いるのが好ましい。 As said (meth) acrylic-acid alkylester used for manufacture of aqueous polymer emulsion, the (meth) acrylic-acid alkylester whose carbon number of the alkyl group is 1-12 is used preferably, for example, (meth) acrylic Methyl acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, ( (Meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-octyl, (meth) acrylic acid isooctyl, (meth) acrylic acid n-nonyl and (meth) acrylic acid isononyl, (meth) Decyl acrylate, lauryl (meth) acrylate, etc. It can be used et of the (meth) one or more of acrylic acid alkyl esters. In particular, in the present invention, in the production of the aqueous polymer emulsion, as the (meth) acrylic acid alkyl ester, one or more (meth) acrylic acid alkyl esters having 4 to 9 carbon atoms in the alkyl group are mainly used. It is preferable to use it as a component.
また、上記したように、水性重合体エマルションの製造に当たっては、（メタ）アクリル酸アルキルエステルと共に他の共重合性単量体を少量成分として用い得るが、そのような共重合性単量体としては、例えば、スチレン、α−メチルスチレン、ビニルトルエン等のビニル芳香族系単量体；（メタ）アクリル酸、クロトン酸、ケイ皮酸、イタコン酸、フマル酸、マレイン酸等の不飽和カルボン酸；イタコン酸モノエチルエステル、フマル酸モノブチルエステル、マレイン酸モノブチルエステル等の不飽和ジカルボン酸のモノアルキルエステル；（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等の水酸基含有ビニル単量体；（メタ）アクリロニトリル、酢酸ビニル、（メタ）アクリルアミド、Ｎ−メチロールアクリルアミド、メタクリル酸グリシジル、酢酸ビニル、塩化ビニル、塩化ビニリデン等を挙げることができ、これらの共重合性単量体の１種又は２種以上を用いることができる。 In addition, as described above, in the production of the aqueous polymer emulsion, other copolymerizable monomers can be used as a minor component together with the (meth) acrylic acid alkyl ester. Is, for example, vinyl aromatic monomers such as styrene, α-methylstyrene, vinyltoluene; unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, itaconic acid, fumaric acid, maleic acid, etc. Monoalkyl esters of unsaturated dicarboxylic acids such as itaconic acid monoethyl ester, fumaric acid monobutyl ester, maleic acid monobutyl ester; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, polyethylene Glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate Hydroxyl group-containing vinyl monomers such as (meth) acrylonitrile, vinyl acetate, (meth) acrylamide, N-methylolacrylamide, glycidyl methacrylate, vinyl acetate, vinyl chloride, vinylidene chloride and the like, and their copolymerization 1 type (s) or 2 or more types can be used.
上記した他の共重合性単量体を用いる場合は、水性重合体エマルションの製造に用いるラジカル重合性単量体の合計重量に基づいて、該他の共重合性単量体の使用割合が、上記したように４０重量％以下であることが好ましい。他の共重合単量体の使用割合が４０重量％を超えると、水性重合体エマルションから形成される粘着剤層の粘着性が不足しやすくなって、ねじの締め付け時に粘着性が発現しにくくなる。 When using the other copolymerizable monomer described above, based on the total weight of the radical polymerizable monomer used in the production of the aqueous polymer emulsion, the use ratio of the other copolymerizable monomer is: As described above, it is preferably 40% by weight or less. When the proportion of the other copolymerizable monomer exceeds 40% by weight, the adhesive layer formed from the aqueous polymer emulsion tends to have insufficient adhesiveness, and the adhesiveness is less likely to be exhibited when tightening the screws. .
水性重合体エマルションの製造法は特に制限されず、従来公知の乳化重合と同様に行うことができる。すなわち、非粘着性重合体（Ａ）の存在下に、（メタ）アクリル酸アルキルエステルを主成分とするラジカル重合性単量体を水性媒体中に均一に分散させ、重合開始剤を用いて乳化重合することにより水性重合体エマルションを得ることができる。かかる乳化重合においては、非粘着性重合体（Ａ）が界面活性剤（乳化剤）として機能するので、乳化重合時に一般的に使用されるポリビニルアルコール等の保護コロイドや、ラウリル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム等の界面活性剤などの乳化剤の使用量を通常の乳化重合の場合よりも少量にでき、所望により他の乳化剤は一切使用しないことも可能である。 The method for producing the aqueous polymer emulsion is not particularly limited, and can be carried out in the same manner as conventionally known emulsion polymerization. That is, in the presence of the non-adhesive polymer (A), a radical polymerizable monomer mainly composed of (meth) acrylic acid alkyl ester is uniformly dispersed in an aqueous medium and emulsified using a polymerization initiator. An aqueous polymer emulsion can be obtained by polymerization. In such emulsion polymerization, the non-adhesive polymer (A) functions as a surfactant (emulsifier). Therefore, protective colloids such as polyvinyl alcohol generally used during emulsion polymerization, sodium lauryl sulfate, dodecylbenzene sulfone. The amount of an emulsifier such as a surfactant such as sodium acid can be used in a smaller amount than in the case of ordinary emulsion polymerization, and any other emulsifier can be used if desired.
また、乳化重合において使用し得る重合開始剤としては、乳化重合に一般に用いられている重合開始剤のいずれもが使用可能であり、例えば前記した非粘着性重合体（Ａ）を得るためのラジカル重合開始剤として例示したのと同様の有機過酸化物、無機過酸化物又はアゾ系化合物等を使用することができる。重合開始剤の好ましい使用量は、単量体の合計量を基準にして、０．１〜５重量％である。 Moreover, as a polymerization initiator that can be used in emulsion polymerization, any polymerization initiator generally used in emulsion polymerization can be used. For example, a radical for obtaining the non-adhesive polymer (A) described above. The same organic peroxides, inorganic peroxides or azo compounds as exemplified as the polymerization initiator can be used. A preferable use amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the monomers.
水性重合体エマルションを製造するための上記した乳化重合において、得られる重合体の分子量の調節のために連鎖移動剤を使用してもよく、かかる連鎖移動剤としては、非粘着性重合体（Ａ）の製造に関して上記で説明したのと同じようなメルカプト基を有する連鎖移動剤が好ましく用いられる。 In the above-described emulsion polymerization for producing an aqueous polymer emulsion, a chain transfer agent may be used for adjusting the molecular weight of the resulting polymer. As such a chain transfer agent, a non-adhesive polymer (A A chain transfer agent having a mercapto group similar to that described above for the production of) is preferably used.
また、水性重合体エマルションを製造する際の重合温度は、０〜１５０℃程度であるのが好ましく、２０〜９０℃であるのがより好ましい。また、その際の重合時間は１〜２４時間程度であるのが好ましく、３〜８時間程度であるのがより好ましい。 Moreover, it is preferable that the polymerization temperature at the time of manufacturing an aqueous polymer emulsion is about 0-150 degreeC, and it is more preferable that it is 20-90 degreeC. In addition, the polymerization time at that time is preferably about 1 to 24 hours, and more preferably about 3 to 8 hours.
上記の海島構造を有する塗膜において、それを形成する非粘着性重合体（Ａ）：粘着性重合体（Ｂ）の重量割合が、固形分の重量比で、２０：８０〜３５：６５であることが必要であり、２５：７５〜３０：７０であることがより好ましい。非粘着性重合体（Ａ）部分が２０重量％未満であると、得られるねじ用樹脂組成物では、その乾燥後の塗膜がねじ締めの前から粘着性を生じるために、ねじの潤滑性が悪くなり、強いトルク締め込み力を必要とする。一方、非粘着性重合体の割合が、３５重量％を超えると、乾燥後の塗膜が硬くなり過ぎて、加圧により発現する粘着性能が劣り、ねじを締めこんだ際に発生した金属粉捕獲が不十分になる。
In the coating film having the sea-island structure described above, the weight ratio of the non-adhesive polymer (A): adhesive polymer (B) forming the coating is 20:80 to 35:65 in terms of the weight ratio of the solid content. It is necessary to be, and it is more preferable that it is 25: 75-30: 70. When the non-adhesive polymer (A) portion is less than 20% by weight, the resulting resin composition for a screw produces a stickiness before screw tightening in the resulting resin composition for a screw. Worse, requiring strong torque tightening force. On the other hand, when the ratio of the non-adhesive polymer exceeds 35% by weight, the coating film after drying becomes too hard, the adhesive performance expressed by pressurization is inferior, and the metal powder generated when the screw is tightened Capture is insufficient.
本発明のねじ用樹脂組成物に用いる上記した水性重合体エマルションは、必要に応じて、一般的な粘着剤に通常使用される消泡剤、界面活性剤、防カビ剤、香料、中和剤、粘着付与剤、増粘剤、レベリング調整剤、凍結防止剤、発泡剤、酸化防止剤、紫外線吸収剤、補強剤、充てん剤、染料、顔料、蛍光増白剤、帯電防止剤、抗ブロッキング剤、難燃剤、架橋剤、可塑剤、滑剤、又は有機溶剤等の１種又は２種以上を含有していてもよい。 The above-mentioned aqueous polymer emulsion used in the resin composition for screws of the present invention is, if necessary, an antifoaming agent, a surfactant, an antifungal agent, a fragrance, and a neutralizing agent that are usually used for general adhesives. , Tackifiers, thickeners, leveling regulators, antifreezing agents, foaming agents, antioxidants, UV absorbers, reinforcing agents, fillers, dyes, pigments, fluorescent whitening agents, antistatic agents, antiblocking agents 1 type, or 2 or more types, such as a flame retardant, a crosslinking agent, a plasticizer, a lubricant, or an organic solvent, may be contained.
＜非粘着性重合体（Ａ）に相当する重合体ＡＸ１の製造＞
（ｉ）はじめに仕込む原料として「アルフォンＵＰ−１０８０」（東亞合成社製の商品名、構成単量体単位がアクリル酸ブチルであり、数平均分子量６，０００、Ｔｇ−５４℃のマクロモノマー）を１４５部、メタクリル酸メチル（Ｔｇ１０５℃）１８部、スチレン（Ｔｇ１００℃）１４部、アクリル酸エチル（Ｔｇ−２２℃）２１部、メタクリル酸（Ｔｇ１３０℃）１８部、２−メルカプトエタノール（連鎖移動剤）６．５部及びメチルエチルケトン（溶媒）４３５部の混合液を準備した。上記混合液６５７．５部を、攪拌機、コンデンサー、温度計、窒素導入管を備えたフラスコに仕込み、窒素雰囲気下８１℃に昇温した。
２，２’−アゾビス（２−メチルブチロニトリル）（重合開始剤）１４．３部を添加し３０分後に次に連続添加する原料であるメタクリル酸メチル７２部、スチレン５６部、アクリル酸エチル８４部、メタクリル酸７２部およびメチルエチルケトン１００部と２，２’−アゾビス（２−メチルブチロニトリル）９．５部の混合液３９３．５部を５時間かけて連続的に滴下した。温度を滴下終了〜滴下終了３０分後にかけて７９℃になる様にし、滴下終了後３０分後と滴下終了１時間後に各々２．４部の２，２’−アゾビス（２−メチルブチロニトリル）を投入した。
次に滴下終了１．５時間後に、ｔ−ブチルハイドロパーオキシドを１部投入し同温度でさらに５時間加熱した。３０℃まで冷却し固形分含量が５０％の重合体のメチルエチルケトン溶液を得た。重合体ＡＸ１の数平均分子量は約１２，０００であった。
（ｉｉ）上記（ｉ）で得られた重合体のメチルエチルケトン溶液１０７０．１部に、撹拌しながら２５％アンモニア水７４部とイオン交換水１１７５部を加えて重合体が有するカルボキシル基の中和度１００％とした後、減圧下に温度５０℃でメチルエチルケトンならびイオン交換水を除去し、カルボキシル基の中和された重合体ＡＸ１の水溶液（固形分含量３０％）を得た。ｐＨは８．１であった。
ＡＸ１をスチール基板にはけ塗り法で約５0ミクロンの膜厚で塗布し、次に４０℃で１０分間乾燥し、被覆材層を該スチール基板上に形成させた。ＡＸ１の加圧前の粘着性を調べるために、この形成された被覆材層に幅２５ｍｍ長さ２００ｍｍに切り出した２５μｍ厚みのポリエステルフィルムを合わせた試料を１００ｇの加圧ローラーで貼り合せを行い、１８０度剥離試験を試みたところ、２５μｍ厚みのポリエステルフィルムが自重で落下剥離したことから、実質的に非粘着と判断した。
ＡＸ１の加圧後の粘着性を調べるために、加圧ローラーの自重１２ｋｇに変えた以外は同様の評価したところ、２５μｍ厚みのポリエステルフィルムが自重で落下剥離したことから、実質的に非粘着と判断した。
<Production of polymer AX1 corresponding to non-adhesive polymer (A)>
(I) “Alfon UP-1080” (trade name, manufactured by Toagosei Co., Ltd., a structural monomer unit of butyl acrylate, a number average molecular weight of 6,000, a macromonomer having a Tg of −54 ° C.) as a raw material charged first 145 parts, 18 parts of methyl methacrylate (Tg 105 ° C.), 14 parts of styrene (Tg 100 ° C.), 21 parts of ethyl acrylate (Tg-22 ° C.), 18 parts of methacrylic acid (Tg 130 ° C.), 2-mercaptoethanol (chain transfer agent) ) A mixture of 6.5 parts and 435 parts of methyl ethyl ketone (solvent) was prepared. 657.5 parts of the mixed solution was charged into a flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, and heated to 81 ° C. in a nitrogen atmosphere.
2,2'-azobis (2-methylbutyronitrile) (polymerization initiator) 14.3 parts is added, and after 30 minutes, 72 parts of methyl methacrylate, 56 parts of styrene, ethyl acrylate, which are subsequently added continuously A mixture of 393.5 parts of 84 parts, 72 parts of methacrylic acid and 100 parts of methyl ethyl ketone and 9.5 parts of 2,2′-azobis (2-methylbutyronitrile) was continuously added dropwise over 5 hours. The temperature was adjusted to 79 ° C. from the end of dropping to 30 minutes after completion of dropping, and 2.4 parts of 2,2′-azobis (2-methylbutyronitrile) were obtained 30 minutes after completion of dropping and 1 hour after completion of dropping. Was introduced.
Next, 1.5 hours after the completion of the dropping, 1 part of t-butyl hydroperoxide was added, and the mixture was further heated at the same temperature for 5 hours. The polymer was cooled to 30 ° C. to obtain a methyl ethyl ketone solution of a polymer having a solid content of 50%. The number average molecular weight of the polymer AX1 was about 12,000.
(Ii) The neutralization degree of the carboxyl group of the polymer by adding 74 parts of 25% aqueous ammonia and 1175 parts of ion exchange water to 1070.1 parts of the methyl ethyl ketone solution of the polymer obtained in (i) above while stirring. After 100%, methyl ethyl ketone and ion-exchanged water were removed under reduced pressure at a temperature of 50 ° C. to obtain an aqueous solution (solid content 30%) of the polymer AX1 neutralized with carboxyl groups. The pH was 8.1.
AX1 was applied to a steel substrate by a brushing method to a film thickness of about 50 microns, and then dried at 40 ° C. for 10 minutes to form a coating layer on the steel substrate. In order to examine the adhesiveness of AX1 before pressurization, a sample in which a 25 μm-thick polyester film cut into a width of 25 mm and a length of 200 mm was combined with the formed covering material layer was bonded with a 100 g pressure roller, When a 180-degree peel test was attempted, the polyester film having a thickness of 25 μm was dropped and peeled by its own weight, so that it was determined to be substantially non-adhesive.
In order to investigate the adhesiveness of AX1 after pressurization, the same evaluation was performed except that the weight of the pressure roller was changed to 12 kg. The polyester film with a thickness of 25 μm was dropped and peeled by its own weight. It was judged.
＜非粘着性重合体（Ａ）に相当する重合体ＡＸ２の製造＞
ＡＸ２は、はじめに仕込む原料としてメタクリル酸メチル３５０部、スチレン４５部及びアクリル酸（Ｔｇ１０５℃）５部、３−メチルプロピオン酸（連鎖移動剤）６部、メチルエチルケトン４３５部からなる混合液と、次に連続添加する原料であるメタクリ酸メチル５０部、スチレン５部及びアクリル酸４５部、メチルエチルケトン１００部とした以外はＡＸ１と同様に製造した。中和前の重合体ＡＸ２の数平均分子量は約１０，０００であった。得られた重合体ＡＸ２の水溶液（固形分含量３０％）を得た。ｐＨは７．８であった。ＡＸ２をスチール基板にはけ塗り法で約５0ミクロンの膜厚で塗布し、次に４０℃で１０分間乾燥したところ、塗膜が細かくひび割れた状態でスチール基板上に形成された。
ＡＸ２の加圧前の粘着性を調べるために、この被覆材層に幅２５ｍｍ長さ２００ｍｍに切り出した２５μｍ厚みのポリエステルフィルムを合わせた試料を１００ｇの加圧ローラーで貼り合せを行い、１８０度剥離試験を試みたところ、２５μｍ厚みのポリエステルフィルムが自重で落下剥離したことから、実質的に非粘着と判断した。
ＡＸ２の加圧後の粘着性を調べるために、加圧ローラーの自重１２ｋｇに変えた以外は同様の評価したところ、２５μｍ厚みのポリエステルフィルムが自重で落下剥離したことから、実質的に非粘着と判断した。
<Production of polymer AX2 corresponding to non-adhesive polymer (A)>
AX2 is a mixture of 350 parts of methyl methacrylate, 45 parts of styrene, 5 parts of acrylic acid (Tg 105 ° C.), 6 parts of 3-methylpropionic acid (chain transfer agent), 435 parts of methyl ethyl ketone, It was produced in the same manner as AX1 except that 50 parts of methyl methacrylate, 5 parts of styrene and 45 parts of acrylic acid, and 100 parts of methyl ethyl ketone, which were raw materials to be continuously added, were used. The number average molecular weight of the polymer AX2 before neutralization was about 10,000. An aqueous solution (solid content 30%) of the obtained polymer AX2 was obtained. The pH was 7.8. AX2 was applied to a steel substrate by a brushing method to a film thickness of about 50 microns, and then dried at 40 ° C. for 10 minutes to form a finely cracked coating film on the steel substrate.
In order to investigate the adhesiveness of AX2 before pressurization, a sample in which a 25 μm thick polyester film cut into a width of 25 mm and a length of 200 mm was combined with this covering material layer was bonded with a 100 g pressure roller, and peeled 180 degrees. When the test was attempted, the polyester film having a thickness of 25 μm was dropped and peeled by its own weight.
In order to investigate the pressure-sensitive adhesiveness of AX2 after pressurization, the same evaluation was performed except that the weight of the pressure roller was changed to 12 kg. It was judged.
＜ねじ用樹脂組成物Ｘ１の製造＞
重合体ＡＸ１存在下において重合体ＢＸ１を製造した。
アクリル酸ブチル（Ｔｇ−５４℃）９９部、メタクリル酸２−ヒドロキシエチル（Ｔｇ−５４℃）１部を混合して単量体混合物とした。この単量体混合物１００部に、上記重合体ＡＸ１の水溶液５０部（有効成分１５部）とイオン交換水３７部を混合し、撹拌により乳化させて単量体乳化物を調製した。撹拌機、コンデンサー、温度計及び窒素導入管を備えたフラスコにイオン交換水５０部と重合体ＡＸ１の水溶液６３部（有効成分１８．９部）を仕込み、窒素雰囲気下でフラスコ内を７０℃に昇温した後、撹拌しながらｔ−ブチルハイドロパーオキサイドの５０％水溶液１部し、重亜硫酸曹達の２％水溶液３０部及び上記単量体乳化物１８７部を３時間かけて滴下した。滴下終了から更に２時間同温度を維持した後、反応液を冷却して重合を終了させ、５％アンモニア水を０．１部投入により中和してｐＨを８とし、固形分含量約４０％のエマルションＸ１を得た。該エマルションＸ１は重合体ＡＸ１および重合体ＢＸ１を含有する。式（１）より重合体ＢＸ１のガラス転移温度Ｔｇは−５３．３℃である。仕込み比率から計算すると非粘着性重合体（Ａ）：粘着性重合体（Ｂ）の重量割合が、固形分の重量比で２５：７５となった。
<Manufacture of screw resin composition X1>
Polymer BX1 was produced in the presence of polymer AX1.
99 parts of butyl acrylate (Tg-54 ° C.) and 1 part of 2-hydroxyethyl methacrylate (Tg-54 ° C.) were mixed to obtain a monomer mixture. To 100 parts of this monomer mixture, 50 parts of the aqueous solution of the polymer AX1 (15 parts of active ingredient) and 37 parts of ion-exchanged water were mixed and emulsified by stirring to prepare a monomer emulsion. A flask equipped with a stirrer, a condenser, a thermometer and a nitrogen introduction tube was charged with 50 parts of ion exchange water and 63 parts of an aqueous solution of polymer AX1 (active ingredient 18.9 parts), and the inside of the flask was brought to 70 ° C. in a nitrogen atmosphere. After raising the temperature, 1 part of a 50% aqueous solution of t-butyl hydroperoxide was added with stirring, and 30 parts of a 2% aqueous solution of sodium bisulfite and 187 parts of the monomer emulsion were added dropwise over 3 hours. After maintaining the same temperature for 2 hours from the end of the dropping, the reaction solution is cooled to complete the polymerization, neutralized by adding 0.1 part of 5% aqueous ammonia to pH 8, and the solid content is about 40%. Emulsion X1 was obtained. The emulsion X1 contains a polymer AX1 and a polymer BX1. From the formula (1), the glass transition temperature Tg of the polymer BX1 is −53.3 ° C. When calculated from the charging ratio, the weight ratio of non-adhesive polymer (A): adhesive polymer (B) was 25:75 as the weight ratio of the solid content.
＜ねじ用樹脂組成物Ｘ２の製造＞
ＢＸ２と同様に重合体ＡＸ２存在下において重合体ＢＸ２を製造した。
アクリル酸２−エチルヘキシル（Ｔｇ−８５℃）９９部、メタクリル酸２−ヒドロキシエチル１部を混合して単量体混合物とした。この単量体混合物１００部に、上記重合体ＡＸ２の水溶液８０部（有効成分２４部）とイオン交換水５０部を混合し、撹拌により乳化させて単量体乳化物を調製した。撹拌機、コンデンサー、温度計及び窒素導入管を備えたフラスコにイオン交換水３５部と重合体ＡＸ１の水溶液６０部（有効成分１８部）を仕込み、窒素雰囲気下でフラスコ内を７０℃に昇温した後、撹拌しながらｔ−ブチルハイドロパーオキサイドの５０％水溶液１部し、重亜硫酸曹達の２％水溶液３０部及び上記単量体乳化物２３０部を３時間かけて滴下した。滴下終了から更に２時間同温度を維持した後、反応液を冷却して重合を終了させ、５％アンモニア水を０．１部投入により中和してｐＨを８とし、固形分含量約４０％のエマルションＸ２を得た。該エマルションＸ２は重合体ＡＸ２および重合体ＢＸ２を含有する。式（１）より重合体ＢＸ２のガラス転移温度Ｔｇは−８４．２℃である。仕込み比率から計算すると非粘着性重合体（Ａ）：粘着性重合体（Ｂ）の重量割合が、固形分の重量比で３０：７０となった。
<Manufacture of screw resin composition X2>
Similarly to BX2, polymer BX2 was produced in the presence of polymer AX2.
A monomer mixture was prepared by mixing 99 parts of 2-ethylhexyl acrylate (Tg-85 ° C) and 1 part of 2-hydroxyethyl methacrylate. To 100 parts of this monomer mixture, 80 parts of the aqueous solution of the polymer AX2 (24 parts of active ingredient) and 50 parts of ion-exchanged water were mixed and emulsified by stirring to prepare a monomer emulsion. A flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 35 parts of ion exchange water and 60 parts of an aqueous solution of polymer AX1 (18 parts of active ingredient), and the temperature in the flask was raised to 70 ° C. in a nitrogen atmosphere. Then, 1 part of a 50% aqueous solution of t-butyl hydroperoxide was added while stirring, and 30 parts of a 2% aqueous solution of sodium bisulfite and 230 parts of the monomer emulsion were added dropwise over 3 hours. After maintaining the same temperature for 2 hours from the end of the dropping, the reaction solution is cooled to complete the polymerization, neutralized by adding 0.1 part of 5% aqueous ammonia to pH 8, and the solid content is about 40%. Emulsion X2 was obtained. The emulsion X2 contains a polymer AX2 and a polymer BX2. From the formula (1), the glass transition temperature Tg of the polymer BX2 is −84.2 ° C. When calculated from the charging ratio, the weight ratio of non-adhesive polymer (A): adhesive polymer (B) was 30:70 in terms of the solid weight ratio.
＜ねじ用樹脂組成物Ｘ３の製造＞
重合体ＡＸ１存在下において重合体ＢＸ１を製造した。
アクリル酸ブチル９９部、メタクリル酸２−ヒドロキシエチル１部を混合して単量体混合物とした。この単量体混合物１００部に、上記重合体ＡＸ１の水溶液９０部（有効成分２７部）とイオン交換水５０部を混合し、撹拌により乳化させて単量体乳化物を調製した。撹拌機、コンデンサー、温度計及び窒素導入管を備えたフラスコにイオン交換水２５部と重合体ＡＸ１の水溶液１００部（有効成分３０部）を仕込み、窒素雰囲気下でフラスコ内を７０℃に昇温した後、撹拌しながらｔ−ブチルハイドロパーオキサイドの５０％水溶液２部し、重亜硫酸曹達の３％水溶液３０部及び上記単量体乳化物２４０部を３時間かけて滴下した。滴下終了から更に２時間同温度を維持した後、反応液を冷却して重合を終了させ、５％アンモニア水を０．１部投入により中和してｐＨを８とし、固形分含量約４０％のエマルションＸ３を得た。該エマルションＸ３は重合体ＡＸ１および重合体ＢＸ１を含有する。仕込み比率から計算すると非粘着性重合体（Ａ）：粘着性重合体（Ｂ）の重量割合が、固形分の重量比で３６：６４となった。
<Manufacture of screw resin composition X3>
Polymer BX1 was produced in the presence of polymer AX1.
A monomer mixture was prepared by mixing 99 parts of butyl acrylate and 1 part of 2-hydroxyethyl methacrylate. To 100 parts of this monomer mixture, 90 parts of the aqueous solution of polymer AX1 (27 parts of active ingredient) and 50 parts of ion-exchanged water were mixed and emulsified by stirring to prepare a monomer emulsion. A flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 25 parts of ion exchange water and 100 parts of an aqueous solution of polymer AX1 (30 parts of active ingredient), and the temperature in the flask was raised to 70 ° C. in a nitrogen atmosphere. Then, 2 parts of a 50% aqueous solution of t-butyl hydroperoxide was added with stirring, and 30 parts of a 3% aqueous solution of sodium bisulfite and 240 parts of the monomer emulsion were added dropwise over 3 hours. After maintaining the same temperature for 2 hours from the end of the dropping, the reaction solution is cooled to complete the polymerization, neutralized by adding 0.1 part of 5% aqueous ammonia to pH 8, and the solid content is about 40%. Emulsion X3 was obtained. The emulsion X3 contains a polymer AX1 and a polymer BX1. When calculated from the charging ratio, the weight ratio of non-adhesive polymer (A): adhesive polymer (B) was 36:64 as the weight ratio of the solid content.
＜ねじ用樹脂組成物Ｘ４の製造＞
重合体ＡＸ２存在下において重合体ＢＸ１を製造した。
アクリル酸ブチル９９部、メタクリル酸２−ヒドロキシエチル１部を混合して単量体混合物とした。この単量体混合物１００部に、上記重合体ＡＸ１の水溶液８０部（有効成分２４部）とイオン交換水５０部を混合し、撹拌により乳化させて単量体乳化物を調製した。撹拌機、コンデンサー、温度計及び窒素導入管を備えたフラスコにイオン交換水３０部と１％ラウリル硫酸ナトリウム水溶液１５部を仕込み、窒素雰囲気下でフラスコ内を７０℃に昇温した後、撹拌しながらｔ−ブチルハイドロパーオキサイドの５０％水溶液２部し、重亜硫酸曹達の３％水溶液３０部及び上記単量体乳化物２３０部を３時間かけて滴下した。滴下終了から更に２時間同温度を維持した後、反応液を冷却して重合を終了させ、５％アンモニア水を０．１部投入により中和してｐＨを８とし、固形分含量約４０％のエマルションＸ４を得た。該エマルションＸ４は重合体ＡＸ２および重合体ＢＸ１を含有する。仕込み比率から計算すると非粘着性重合体（Ａ）：粘着性重合体（Ｂ）の重量割合が、固形分の重量比で１９：８１となった。
<Manufacture of screw resin composition X4>
Polymer BX1 was produced in the presence of polymer AX2.
A monomer mixture was prepared by mixing 99 parts of butyl acrylate and 1 part of 2-hydroxyethyl methacrylate. To 100 parts of this monomer mixture, 80 parts of the aqueous solution of the polymer AX1 (24 parts of active ingredient) and 50 parts of ion-exchanged water were mixed and emulsified by stirring to prepare a monomer emulsion. A flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 30 parts of ion exchange water and 15 parts of a 1% sodium lauryl sulfate aqueous solution, and the temperature in the flask was raised to 70 ° C. in a nitrogen atmosphere, followed by stirring. While adding 2 parts of 50% aqueous solution of t-butyl hydroperoxide, 30 parts of 3% aqueous solution of sodium bisulfite and 230 parts of the monomer emulsion were added dropwise over 3 hours. After maintaining the same temperature for 2 hours from the end of the dropping, the reaction solution is cooled to complete the polymerization, neutralized by adding 0.1 part of 5% aqueous ammonia to pH 8, and the solid content is about 40%. Emulsion X4 was obtained. The emulsion X4 contains a polymer AX2 and a polymer BX1. When calculated from the charging ratio, the weight ratio of non-adhesive polymer (A): adhesive polymer (B) was 19:81 in terms of the solid weight ratio.
＜ねじ用樹脂組成物Ｘ５の製造＞
重合体ＢＸ１を製造した。
アクリル酸ブチル９９部、メタクリル酸２−ヒドロキシエチル１部を混合して単量体混合物とした。この単量体混合物１００部に１％ラウリル硫酸ナトリウム水溶液３０部、イオン交換水４０部を混合し、撹拌により乳化させて単量体乳化物を調製した。撹拌機、コンデンサー、温度計及び窒素導入管を備えたフラスコにイオン交換水５０部を仕込み、窒素雰囲気下でフラスコ内を７０℃に昇温した後、撹拌しながらｔ−ブチルハイドロパーオキサイドの５０％水溶液２部し、重亜硫酸曹達の３％水溶液３０部及び上記単量体乳化物１７０部を３時間かけて滴下した。滴下終了から更に２時間同温度を維持した後、反応液を冷却して重合を終了させ、５％アンモニア水を０．１部投入により中和してｐＨを８とし、固形分含量約４０％のエマルションＸ５を得た。該エマルションＸ５は重合体ＢＸ１のみを含有する。仕込み比率から計算すると非粘着性重合体（Ａ）：粘着性重合体（Ｂ）の重量割合が、固形分の重量比で０：１００となった。
<Manufacture of screw resin composition X5>
Polymer BX1 was produced.
A monomer mixture was prepared by mixing 99 parts of butyl acrylate and 1 part of 2-hydroxyethyl methacrylate. To 100 parts of this monomer mixture, 30 parts of a 1% sodium lauryl sulfate aqueous solution and 40 parts of ion-exchanged water were mixed and emulsified by stirring to prepare a monomer emulsion. A flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 50 parts of ion-exchanged water, the temperature in the flask was raised to 70 ° C. in a nitrogen atmosphere, and 50 t-butyl hydroperoxide was stirred while stirring. 2 parts of a 30% aqueous solution, 30 parts of a 3% aqueous solution of sodium bisulfite and 170 parts of the monomer emulsion were added dropwise over 3 hours. After maintaining the same temperature for 2 hours from the end of the dropping, the reaction solution is cooled to complete the polymerization, neutralized by adding 0.1 part of 5% aqueous ammonia to pH 8, and the solid content is about 40%. Emulsion X5 was obtained. The emulsion X5 contains only the polymer BX1. When calculated from the charging ratio, the weight ratio of non-adhesive polymer (A): adhesive polymer (B) was 0: 100 in terms of the solid weight ratio.
（ａ）実施例１
前記製造例で得られた水性エマルションＸ１に着色剤として大日精化社製 商品名「ＡＦ Ｂｌｕｅ Ｅ−２Ｂ」を１％配合し、スチール基板にはけ塗り法で約５0ミクロンの膜厚で塗布し、次に４０℃で１０分間乾燥し、被覆材層を該スチール基板上に形成させた。
加圧前の粘着性を調べるために、この形成された被覆材層に幅２５ｍｍ長さ２００ｍｍに切り出した２５μｍ厚みのポリエステルフィルムを合わせた試料を１００ｇの加圧ローラーで貼り合せを行い、１８０度剥離試験を試みたところ、２５μｍ厚みのポリエステルフィルムが自重で落下剥離したことから、実質的に非粘着と判断した。
加圧後の粘着性を調べるために、加圧ローラーの自重１２ｋｇに変えた以外は同様の評価したところ、約４５０ｇの粘着力が発生した。
前記の着色剤を配合した水性エマルションＸ１を、同様に塗布乾燥した被覆材層をねじ溝内に有したタッピングねじａ１を用い、また溝なし開孔を予め設けて有するマグネシウム合金の板状の取付け用部品を用い且つ溝なし下穴を予め開孔して設けてあるマグネシウム合金の板状部材（ワークピース）を用い、そして前記のタッピングねじａ１を取付け用部品の開孔を通して、取付け用部品の下面上に置かれた前記の板状部材（ワークピース）の下穴の中にねじ込む作業を行った。該タッピングねじａ１のねじ込み作業中は、約４ｋｇｆ−ｃｍの軽いトルク締め込み力でも円滑に下穴にねじ込むことができてねじの潤滑性が良いことが認められた。下穴に切削成形された雌ねじ溝の下方で下穴に残る開孔部中から切削成形屑が脱落する現象は全く観察されなかった。
(A) Example 1
1% of the product name “AF Blue E-2B” manufactured by Dainichi Seika Co., Ltd. as a colorant is added to the aqueous emulsion X1 obtained in the above production example, and applied to a steel substrate with a film thickness of about 50 microns by a brush coating method. And then dried at 40 ° C. for 10 minutes to form a coating layer on the steel substrate.
In order to examine the adhesiveness before pressurization, a sample in which a 25 μm-thick polyester film cut out to a width of 25 mm and a length of 200 mm was combined with this formed covering material layer was bonded with a 100 g pressure roller, and 180 ° When a peeling test was attempted, the polyester film having a thickness of 25 μm was dropped and peeled by its own weight, so that it was determined to be substantially non-adhesive.
In order to examine the adhesiveness after pressing, the same evaluation was conducted except that the weight of the pressing roller was changed to 12 kg, and an adhesive force of about 450 g was generated.
Magnesium alloy plate-like mounting using a tapping screw a1 having a coating material layer coated in the same manner and dried in the thread groove, and having a groove-free opening in advance. And a magnesium alloy plate-like member (workpiece) provided with a grooved pilot hole in advance and using the tapping screw a1 through the opening of the mounting part. An operation of screwing into the prepared hole of the plate-like member (workpiece) placed on the lower surface was performed. During the screwing operation of the tapping screw a1, it was confirmed that even a light torque tightening force of about 4 kgf-cm can be smoothly screwed into the pilot hole and the screw has good lubricity. There was no observation of the phenomenon in which the cutting scraps dropped out of the hole remaining in the pilot hole below the female screw groove cut and molded in the pilot hole.
（ｂ）実施例２
水性エマルションＸ２を用いて実施例１同様に着色剤を配合した被覆材層を該スチール基板上に形成させた。加圧前の粘着性を調べるために、この形成された被覆材層に幅２５ｍｍ長さ２００ｍｍに切り出した２５μｍ厚みのポリエステルフィルムを合わせた試料を１００ｇの加圧ローラーで貼り合せを行い、１８０度剥離試験を試みたところ、２５μｍ厚みのポリエステルフィルムが自重で落下剥離したことから、実質的に非粘着と判断した。
加圧後の粘着性を調べるために、加圧ローラーの自重１２ｋｇに変えた以外は同様の評価したところ、約４００ｇの粘着力が発生した。
前記の着色剤を配合した水性エマルションＸ２を、同様に塗布乾燥した被覆材層をねじ溝内に有したタッピングねじａ２を用い、また溝なし開孔を予め設けて有するマグネシウム合金の板状の取付け用部品を用い且つ溝なし下穴を予め開孔して設けてあるマグネシウム合金の板状部材（ワークピース）を用い、そして前記のタッピングねじａ２を取付け用部品の開孔を通して、取付け用部品の下面上に置かれた前記の板状部材（ワークピース）の下穴の中にねじ込む作業を行った。該タッピングねじａ２のねじ込み作業中は、約４ｋｇｆ−ｃｍの軽いトルク締め込み力でも円滑に下穴にねじ込むことができてねじの潤滑性が良いことが認められた。下穴に切削成形された雌ねじ溝の下方で下穴に残る開孔部中から切削成形屑が脱落する現象は全く観察されなかった。
(B) Example 2
A coating layer containing a colorant was formed on the steel substrate using the aqueous emulsion X2 in the same manner as in Example 1. In order to examine the adhesiveness before pressurization, a sample in which a 25 μm-thick polyester film cut out to a width of 25 mm and a length of 200 mm was combined with this formed covering material layer was bonded with a 100 g pressure roller, and 180 ° When a peeling test was attempted, the polyester film having a thickness of 25 μm was dropped and peeled by its own weight, so that it was determined to be substantially non-adhesive.
In order to examine the adhesiveness after pressing, the same evaluation was conducted except that the weight of the pressing roller was changed to 12 kg, and an adhesive force of about 400 g was generated.
Magnesium alloy plate-like mounting using a tapping screw a2 having a coating material layer coated in the same manner and dried in the thread groove, and having a groove-free opening in advance. A magnesium alloy plate-shaped member (workpiece) provided with a pre-drilled pilot hole is used, and the tapping screw a2 is passed through the hole of the mounting part. An operation of screwing into the prepared hole of the plate-like member (workpiece) placed on the lower surface was performed. During the screwing operation of the tapping screw a2, it was recognized that even a light torque tightening force of about 4 kgf-cm can be smoothly screwed into the pilot hole and the screw has good lubricity. There was no observation of the phenomenon in which the cutting scraps dropped out of the hole remaining in the pilot hole below the female screw groove cut and molded in the pilot hole.
（ｃ）比較例１
水性エマルションＸ３を用いて実施例１同様に着色剤を配合した被覆材層を該スチール基板上に形成させた。加圧前の粘着性を調べるために、この形成された被覆材層に幅２５ｍｍ長さ２００ｍｍに切り出した２５μｍ厚みのポリエステルフィルムを合わせた試料を１００ｇの加圧ローラーで貼り合せを行い、１８０度剥離試験を試みたところ、２５μｍ厚みのポリエステルフィルムが自重で落下剥離したことから、実質的に非粘着と判断した。
加圧後の粘着性を調べるために、加圧ローラーの自重１２ｋｇに変えた以外は同様の評価したところ、約１０ｇの粘着力が発生した。
前記の着色剤を配合した水性エマルションＸ３を、同様に塗布乾燥した被覆材層をねじ溝内に有したタッピングねじａ３を用い、また溝なし開孔を予め設けて有するマグネシウム合金の板状の取付け用部品を用い且つ溝なし下穴を予め開孔して設けてあるマグネシウム合金の板状部材（ワークピース）を用い、そして前記のタッピングねじａ３を取付け用部品の開孔を通して、取付け用部品の下面上に置かれた前記の板状部材（ワークピース）の下穴の中にねじ込む作業を行った。該タッピングねじａ３のねじ込み作業中は、約４ｋｇｆ−ｃｍの軽いトルク締め込み力でも円滑に下穴にねじ込むことができてねじの潤滑性が良いことが認められた。下穴に切削成形された雌ねじ溝の下方で下穴に残る開孔部中から切削成形屑の脱落が観察された。
(C) Comparative Example 1
A coating layer containing a colorant was formed on the steel substrate using the aqueous emulsion X3 in the same manner as in Example 1. In order to examine the adhesiveness before pressurization, a sample in which a 25 μm-thick polyester film cut out to a width of 25 mm and a length of 200 mm was combined with this formed covering material layer was bonded with a 100 g pressure roller, and 180 ° When a peeling test was attempted, the polyester film having a thickness of 25 μm was dropped and peeled by its own weight, so that it was determined to be substantially non-adhesive.
In order to examine the adhesiveness after pressing, the same evaluation was performed except that the weight of the pressing roller was changed to 12 kg, and an adhesive force of about 10 g was generated.
Magnesium alloy plate-like attachment having a tapping screw a3 having a coating material layer coated in the same manner and dried in the thread groove and having a groove-free opening in advance. A magnesium alloy plate-like member (workpiece) provided with a pre-drilled pilot hole is used, and the tapping screw a3 is passed through the hole of the mounting part. An operation of screwing into the prepared hole of the plate-like member (workpiece) placed on the lower surface was performed. During the screwing operation of the tapping screw a3, it was confirmed that even a light torque tightening force of about 4 kgf-cm can be smoothly screwed into the pilot hole and the screw has good lubricity. It was observed that the scraps of the cutting moldings dropped out from the hole portion remaining in the pilot hole below the female screw groove cut and molded in the pilot hole.
（ｄ）比較例２
水性エマルションＸ４を用いて実施例１同様に着色剤を配合した被覆材層を該スチール基板上に形成させた。加圧前の粘着性を調べるために、この形成された被覆材層に幅２５ｍｍ長さ２００ｍｍに切り出した２５μｍ厚みのポリエステルフィルムを合わせた試料を１００ｇの加圧ローラーで貼り合せを行い、１８０度剥離試験を試みたところ、約５０ｇの粘着力が発生したために粘着性有りと判断した。
加圧後の粘着性を調べるために、加圧ローラーの自重１２ｋｇに変えた以外は同様の評価したところ、約５００ｇの粘着力が発生した。
前記の着色剤を配合した水性エマルションＸ４を、同様に塗布乾燥した被覆材層をねじ溝内に有したタッピングねじａ４を用い、また溝なし開孔を予め設けて有するマグネシウム合金の板状の取付け用部品を用い且つ溝なし下穴を予め開孔して設けてあるマグネシウム合金の板状部材（ワークピース）を用い、そして前記のタッピングねじａ４を取付け用部品の開孔を通して、取付け用部品の下面上に置かれた前記の板状部材（ワークピース）の下穴の中にねじ込む作業を行った。該タッピングねじａ４のねじ込み作業中は、約４ｋｇｆ−ｃｍの軽いトルク締め込み力では円滑に下穴にねじ込むことができず、約６ｋｇｆ−ｃｍの強いトルク締め込み力を要すことからねじの潤滑性が悪いことが認められた。下穴に切削成形された雌ねじ溝の下方で下穴に残る開孔部中から切削成形屑が脱落する現象は全く観察されなかった。
(D) Comparative example 2
A coating material layer containing a colorant was formed on the steel substrate using the aqueous emulsion X4 in the same manner as in Example 1. In order to examine the adhesiveness before pressurization, a sample in which a 25 μm-thick polyester film cut out to a width of 25 mm and a length of 200 mm was combined with this formed covering material layer was bonded with a 100 g pressure roller, and 180 ° When a peel test was attempted, an adhesive force of about 50 g was generated, so that it was determined that there was adhesiveness.
In order to investigate the adhesiveness after pressurization, when the same evaluation was performed except that the weight of the pressure roller was changed to 12 kg, an adhesive force of about 500 g was generated.
Magnesium alloy plate-like mounting using a tapping screw a4 having a coating material layer coated in the same manner and dried in the thread groove, and having a groove-free opening in advance. And a magnesium alloy plate-like member (workpiece) provided with a grooved pilot hole in advance and using the tapping screw a4 through the opening of the mounting part. An operation of screwing into the prepared hole of the plate-like member (workpiece) placed on the lower surface was performed. During the screwing operation of the tapping screw a4, it is impossible to smoothly screw into the pilot hole with a light torque tightening force of about 4 kgf-cm, and a strong torque tightening force of about 6 kgf-cm is required. Poor sex was observed. There was no observation of the phenomenon in which the cutting scraps dropped out of the hole remaining in the pilot hole below the female screw groove cut and molded in the pilot hole.
（ｅ）比較例３
水性エマルションＸ５を用いて実施例１同様に着色剤を配合した被覆材層を該スチール基板上に形成させた。加圧前の粘着性を調べるために、この形成された被覆材層に幅２５ｍｍ長さ２００ｍｍに切り出した２５μｍ厚みのポリエステルフィルムを合わせた試料を１００ｇの加圧ローラーで貼り合せを行い、１８０度剥離試験を試みたところ、約１５０ｇの粘着力が発生したために粘着性有りと判断した。
加圧後の粘着性を調べるために、加圧ローラーの自重１２ｋｇに変えた以外は同様の評価したところ、約５８０ｇの粘着力が発生した。
前記の着色剤を配合した水性エマルションＸ５を、同様に塗布乾燥した被覆材層をねじ溝内に有したタッピングねじａ５を用い、また溝なし開孔を予め設けて有するマグネシウム合金の板状の取付け用部品を用い且つ溝なし下穴を予め開孔して設けてあるマグネシウム合金の板状部材（ワークピース）を用い、そして前記のタッピングねじａ５を取付け用部品の開孔を通して、取付け用部品の下面上に置かれた前記の板状部材（ワークピース）の下穴の中にねじ込む作業を行った。該タッピングねじａ５のねじ込み作業中は、約７ｋｇｆ−ｃｍの軽いトルク締め込み力では円滑に下穴にねじ込むことができなく、約９ｋｇｆ−ｃｍの強いトルク締め込み力を要すことからねじの潤滑性が悪いことが認められた。下穴に切削成形された雌ねじ溝の下方で下穴に残る開孔部中から切削成形屑が脱落する現象は全く観察されなかった。
(E) Comparative Example 3
A coating layer containing a colorant was formed on the steel substrate using the aqueous emulsion X5 in the same manner as in Example 1. In order to examine the adhesiveness before pressurization, a sample in which a 25 μm-thick polyester film cut out to a width of 25 mm and a length of 200 mm was combined with this formed covering material layer was bonded with a 100 g pressure roller, and 180 ° When a peel test was attempted, an adhesive force of about 150 g was generated.
In order to investigate the adhesiveness after pressurization, when the same evaluation was performed except that the weight of the pressure roller was changed to 12 kg, an adhesive force of about 580 g was generated.
Magnesium alloy plate-shaped mounting using a tapping screw a5 having a coating layer similarly coated and dried in the screw groove, and having a groove-free opening in advance. And a magnesium alloy plate-like member (workpiece) provided with a grooved pilot hole in advance and using the tapping screw a5 through the opening of the mounting part. An operation of screwing into the prepared hole of the plate-like member (workpiece) placed on the lower surface was performed. During the screwing operation of the tapping screw a5, a light torque tightening force of about 7 kgf-cm cannot be smoothly screwed into the pilot hole, and a strong torque tightening force of about 9 kgf-cm is required. Poor sex was observed. There was no observation of the phenomenon in which the cutting scraps dropped out of the hole remaining in the pilot hole below the female screw groove cut and molded in the pilot hole.
＜海島構造の観察＞
水性エマルションＸ１〜５各々を用いた被材層を、ルテニウム酸水溶液の存在下において蒸気染色し、更にエポキシ樹脂包理したものを、超薄切片法により透過型電子顕微鏡（ＴＥＭ）を用いて、倍率１００，０００で観察した。水性エマルションＸ１〜４はルテニウム酸により染色されやすい部分（非粘着性重合体Ａ；染色されやすいスチレンが共重合されている）が海となり染色されにくい部分（粘着性重合体Ｂ）が島となった海島構造が形成されていることが判った。一方、水性エマルションＸ５は海島構造が形成されていないことが判った。
<Observation of sea-island structure>
The material layer using each of the aqueous emulsions X1 to X5 was vapor-stained in the presence of an aqueous ruthenic acid solution, and further embedded with an epoxy resin, using a transmission electron microscope (TEM) by an ultrathin section method, Observation was performed at a magnification of 100,000. In the aqueous emulsions X1 to X4, the portion that is easily dyed by ruthenic acid (non-adhesive polymer A; copolymerized with styrene that is easily dyed) becomes the sea, and the portion that is difficult to dye (adhesive polymer B) becomes an island. It was found that a sea-island structure was formed. On the other hand, it was found that the sea-island structure was not formed in the aqueous emulsion X5.
Claims (1)
上記非粘着性重合体（Ａ）がα、β−エチレン性不飽和カルボン酸単位及び水１００ｇに対する溶解度が２ｇ以下である疎水性のラジカル重合性単量体単位を主構成単位とし、共重合体におけるカルボキシル基の一部又は全量が沸点１１０℃以下の塩基で中和されている水溶性又は水分散性の共重合体であり、上記粘着性重合体（Ｂ）として、（メタ）アクリル酸アルキルエステルを主成分とするガラス転移温度が−３０℃以下の重合体を与えるラジカル重合性単量体を乳化重合することによって得られる水性重合体エマルションからなり、かつ、非粘着性重合体（Ａ）：粘着性重合体（Ｂ）の重量割合が、固形分の重量比で、２０：８０〜３５：６５であることを特徴とするねじ用樹脂組成物。 It is a resin composition applied to a thread groove, and has a sea-island structure in which the non-adhesive polymer (A) is a continuous phase before the screw is tightened, and the adhesive polymer (B) is island-shaped, the continuous phase is tightened at the same time as adhesive polymer of the screw (B), a non-tacky polymer (a) is Rene Ji resin composition to change the island structure comprising an island-shaped,
The non-adhesive polymer (A) is composed mainly of an α, β-ethylenically unsaturated carboxylic acid unit and a hydrophobic radical polymerizable monomer unit having a solubility in 100 g of water of 2 g or less as a main constituent unit. Is a water-soluble or water-dispersible copolymer in which a part or all of the carboxyl groups in the base is neutralized with a base having a boiling point of 110 ° C. or lower. As the adhesive polymer (B), an alkyl (meth) acrylate A non-adhesive polymer (A) comprising an aqueous polymer emulsion obtained by emulsion polymerization of a radical polymerizable monomer that gives a polymer having an ester as a main component and a glass transition temperature of -30 ° C or lower. : The resin composition for screws, wherein the weight ratio of the adhesive polymer (B) is 20:80 to 35:65 by weight ratio of the solid content.
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