JP5822531B2 - Copolymer latex for water-based antirust coating - Google Patents
Copolymer latex for water-based antirust coating Download PDFInfo
- Publication number
- JP5822531B2 JP5822531B2 JP2011105200A JP2011105200A JP5822531B2 JP 5822531 B2 JP5822531 B2 JP 5822531B2 JP 2011105200 A JP2011105200 A JP 2011105200A JP 2011105200 A JP2011105200 A JP 2011105200A JP 5822531 B2 JP5822531 B2 JP 5822531B2
- Authority
- JP
- Japan
- Prior art keywords
- mass
- copolymer latex
- parts
- monomer
- water
- 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.)
- Expired - Fee Related
Links
- 239000004816 latex Substances 0.000 title claims description 98
- 229920000126 latex Polymers 0.000 title claims description 98
- 229920001577 copolymer Polymers 0.000 title claims description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 43
- 239000011248 coating agent Substances 0.000 title description 48
- 238000000576 coating method Methods 0.000 title description 48
- 239000000178 monomer Substances 0.000 claims description 98
- 239000003973 paint Substances 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 54
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 48
- 230000003449 preventive effect Effects 0.000 claims description 31
- 150000001993 dienes Chemical class 0.000 claims description 15
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 9
- 239000008199 coating composition Substances 0.000 description 44
- -1 carboxylic acid hydroxyalkyl ester Chemical class 0.000 description 36
- 238000006116 polymerization reaction Methods 0.000 description 32
- 238000000034 method Methods 0.000 description 26
- 239000003995 emulsifying agent Substances 0.000 description 25
- 238000001035 drying Methods 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 14
- 230000002265 prevention Effects 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
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- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012986 chain transfer agent Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
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- 239000002562 thickening agent Substances 0.000 description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 239000002585 base Substances 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
Description
本発明は、水性防錆塗料組成物として好ましく使用される共重合体ラテックスに関する。更に詳しくは、防錆性や基材への密着性等に優れた水性防錆塗料組成物を実現することが可能な、共重合体ラテックスに関する。 The present invention relates to a copolymer latex preferably used as a water-based anticorrosive coating composition. More specifically, the present invention relates to a copolymer latex capable of realizing an aqueous rust preventive coating composition excellent in rust prevention and adhesion to a substrate.
近年、地球環境保護の観点から、各種塗料においては、溶剤系の塗料から水系の塗料への移行が進んでいる。防錆塗料でも溶剤系から水系に移行しつつあるが、従来の水系防錆塗料は、溶剤系防錆塗料に比べて防錆性が劣るという大きな問題点がある。
こうした水系防錆塗料の課題を解決する為、数多くの先行技術が開示されている。例えば、特定の原料単量体を含む共重合体ラテックス（特許文献１）が提案されている。更に、特定のガラス転移温度を有する共重合体ラテックスを含むエマルジョン組成物が提案されている（特許文献２）
In recent years, from the viewpoint of protecting the global environment, the transition from solvent-based paints to water-based paints is progressing in various paints. Even rust-proof paints are shifting from solvent-based to water-based, but conventional water-based rust-proof paints have a major problem in that they are inferior in rust-proofing properties compared to solvent-based rust-proof paints.
In order to solve such problems of water-based anticorrosive paints, many prior arts have been disclosed. For example, a copolymer latex containing a specific raw material monomer (Patent Document 1) has been proposed. Furthermore, an emulsion composition containing a copolymer latex having a specific glass transition temperature has been proposed (Patent Document 2).
しかしながら、溶剤系に比べて、防錆性を向上させつつ、同時に塗料としての各種課題、例えば基材への密着性等をバランスよく両立する低温乾燥型（乾燥温度：４０〜８０℃）の水性防錆塗料組成物を実現する観点からは、まだ十分満足できるものが得られていないのが実情である。 However, it is a low-temperature dry type (drying temperature: 40 to 80 ° C.) aqueous solution that improves the anticorrosion properties and at the same time balances various problems as a paint, for example, adhesion to a substrate, etc. From the viewpoint of realizing a rust-proof coating composition, the actual situation is that a satisfactory product has not yet been obtained.
そこで本発明は、防錆性に優れ、同時に、基材への密着性、塗料組成物の乾燥性等に優れた低温乾燥型の水性防錆塗料組成物を実現可能な水性防錆塗料用共重合体ラテックスを提供する事を課題とする。 Accordingly, the present invention provides an aqueous rust-preventive coating material that can realize a low-temperature drying-type aqueous rust-preventive coating composition that has excellent rust-preventing properties, and at the same time has excellent adhesion to a substrate and drying properties of the coating composition. It is an object to provide a polymer latex.
本発明者らは、上述の課題を解決するために鋭意検討した結果、水性防錆塗料組成物の構成材料として用いられる共重合体ラテックスに関し、共役ジエン系単量体及びヒドロキシアルキル基を有する単量体を必須成分とした共重合体ラテックスを用いることに着目し、本発明をなすに至った。
即ち、本発明は、以下の水性防錆塗料用共重合体ラテックス及び水性防錆塗料を提供する。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a copolymer latex used as a constituent material of a water-based anticorrosive coating composition is a monomer having a conjugated diene monomer and a hydroxyalkyl group. Focusing on the use of a copolymer latex having a monomer as an essential component, the present invention has been made.
That is, the present invention provides the following copolymer latex for water-based anticorrosive paint and water-based antirust paint.
［１］（ａ）共役ジエン系単量体１．０質量部〜６０．０質量部、（ｂ）ヒドロキシアルキル基を有する単量体（（ａ）共役ジエン系単量体に該当するものを除く）０．５質量部〜１０．０質量部、及び（ｃ）１種又は複数種の他の共重合可能な単量体３０．０質量部〜９８．５質量部（ただし、（ａ）＋（ｂ）＋（ｃ）＝１００．０質量部）からなる単量体混合物を乳化重合して得られる水性防錆塗料用共重合体ラテックス。
［２］前記単量体混合物１００質量部中の（ｃ１）エチレン系不飽和カルボン酸単量体含有量が０〜１．４質量部である、［１］記載の水性防錆塗料用共重合体ラテックス。
［３］前記単量体混合物１００質量部中の（ｃ１）エチレン系不飽和カルボン酸単量体含有量が０〜１．０質量部である、［１］又は［２］記載の水性防錆塗料用共重合体ラテックス。
［４］前記単量体混合物１００質量部中に前記（ｂ）ヒドロキシアルキル基を有する単量体を１．０質量部〜９．０質量部含む、［１］〜［３］のいずれか１つに記載の水性防錆塗料用共重合体ラテックス。
［５］［１］〜［４］のいずれか１つに記載の水性防錆塗料用共重合体ラテックスを含む水性防錆塗料。
[1] (a) 1.0 to 60.0 parts by mass of a conjugated diene monomer, (b) a monomer having a hydroxyalkyl group (one corresponding to (a) a conjugated diene monomer Excluding) 0.5 parts by mass to 10.0 parts by mass, and (c) one or more other copolymerizable monomers 30.0 parts by mass to 98.5 parts by mass (provided that (a) Copolymer latex for water-based anticorrosive paint obtained by emulsion polymerization of a monomer mixture comprising: (b) + (c) = 100.0 parts by mass).
[2] Copolymer for aqueous rust preventive paint according to [1], wherein the content of (c1) ethylenically unsaturated carboxylic acid monomer in 100 parts by mass of the monomer mixture is 0 to 1.4 parts by mass. Combined latex.
[3] The aqueous rust preventive according to [1] or [2], wherein the content of (c1) ethylenically unsaturated carboxylic acid monomer in 100 parts by mass of the monomer mixture is 0 to 1.0 part by mass. Copolymer latex for paint.
[4] Any one of [1] to [3], wherein 1.0 part by mass to 9.0 parts by mass of the monomer (b) having a hydroxyalkyl group are contained in 100 parts by mass of the monomer mixture. Copolymer latex for water-based anticorrosive paint as described in 1.
[5] An aqueous rust preventive paint comprising the copolymer latex for an aqueous rust preventive paint according to any one of [1] to [4].
本発明の水性防錆塗料用共重合体ラテックスを水性防錆塗料組成物の構成材料として用いることにより、水性防錆塗料組成物における課題である、防錆性を向上させることが可能である。同時に、基材との密着性等が優れた水性防錆塗料組成物を実現し得る。また、本発明の水性防錆塗料用共重合体ラテックスを用いることにより、水性防錆塗料組成物の安定性が優れ、加温と冷却を繰り返した後（温冷繰返し後）の基材との密着性が優れ、低温乾燥工程において水性防錆塗料組成物の使用が可能になり、工場のライン物塗料として水性防錆塗料組成物の使用が可能になり、有機溶剤に起因して発生するＶＯＣ問題等や、塗料の乾燥性が優れることによる乾燥時間の短縮による生産性の改善や乾燥エネルギーコストの削減が可能である。 By using the copolymer latex for aqueous rust preventive coating composition of the present invention as a constituent material of the aqueous rust preventive paint composition, it is possible to improve the rust preventive property which is a problem in the aqueous rust preventive paint composition. At the same time, an aqueous rust preventive coating composition having excellent adhesion to the substrate and the like can be realized. Moreover, by using the copolymer latex for aqueous rust preventive paint of the present invention, the stability of the aqueous rust preventive paint composition is excellent, and after repeated heating and cooling (after repeated heating and cooling) with the base material Excellent adhesion, enables use of water-based anti-corrosion paint composition in low-temperature drying process, enables use of water-based anti-corrosion paint composition as factory line paint, VOC generated due to organic solvent It is possible to improve productivity and reduce the drying energy cost by shortening the drying time due to problems such as problems and excellent drying characteristics of the paint.
以下、本発明を実施するための形態（以下、発明の実施の形態）について詳細に説明する。尚、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, modes for carrying out the present invention (hereinafter, embodiments of the present invention) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
本発明の水性防錆塗料用共重合体ラテックスは、共役ジエン系単量体（ａ）、ヒドロキシアルキル基を有する単量体（ｂ）、及び当該単量体（ａ）及び（ｂ）と共重合可能な他の単量体（ｃ）を乳化重合して形成することができる。 The copolymer latex for aqueous rust preventive paint of the present invention comprises a conjugated diene monomer (a), a monomer (b) having a hydroxyalkyl group, and the monomers (a) and (b). Other polymerizable monomers (c) can be formed by emulsion polymerization.
（ａ）共役ジエン系単量体
本発明で用いられる共役ジエン系単量体（ａ）は、共重合体ラテックスに防錆性や柔軟性を付与するために重要な成分である。共役ジエン系単量体（ａ）の好ましい例としては、例えば、１，３−ブタジエン、イソプレン、２−クロロ−１，３−ブタジエン等を挙げることができる。これらは１種を単独で、又は２種以上を組み合わせて用いることができる。
(A) Conjugated diene monomer The conjugated diene monomer (a) used in the present invention is an important component for imparting rust prevention and flexibility to the copolymer latex. Preferable examples of the conjugated diene monomer (a) include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and the like. These can be used alone or in combination of two or more.
共役ジエン系単量体（ａ）が、全単量体混合物１００質量部中に占める割合としては、通常１．０質量部〜６０．０質量部、好ましくは３．０質量部〜５０．０質量部である。共役ジエン系単量体（ａ）の使用量の下限を上記範囲に設定する事により、共重合体ラテックスを用いた水性防錆塗料組成物の温冷繰返し後の密着性を向上させることができる。また、共役ジエン系単量体（ａ）の使用量の上限を上記範囲に設定する事により、共重合体ラテックスを用いた水性防錆塗料組成物の防錆性を向上させることができる。 The proportion of the conjugated diene monomer (a) in 100 parts by mass of the total monomer mixture is usually 1.0 part by mass to 60.0 parts by mass, preferably 3.0 parts by mass to 50.0. Part by mass. By setting the lower limit of the amount of the conjugated diene monomer (a) to be within the above range, it is possible to improve the adhesiveness after repeated heating and cooling of the aqueous rust preventive coating composition using the copolymer latex. . Moreover, the antirust property of the water-based antirust coating composition using copolymer latex can be improved by setting the upper limit of the usage-amount of a conjugated diene monomer (a) to the said range.
（ｂ）ヒドロキシアルキル基を有する単量体
前記、ヒドロキシアルキル基を有する単量体（ｂ）は、共重合体ラテックスを用いた水性防錆塗料組成物に、例えば基材への優れた密着性と塗料の安定性を発現させる目的で用いられる。
(B) Monomer having a hydroxyalkyl group The monomer (b) having a hydroxyalkyl group is excellent in adhesion to a water-based anticorrosive coating composition using a copolymer latex, for example, a substrate. It is used for the purpose of expressing the stability of the paint.
ここで、前記ヒドロキシアルキル基を有する単量体としては、少なくとも１つのヒドロキシアルキル基を有する単量体であって、上記共役ジエン系単量体（ａ）に該当しないものであればよく、それ以外に特に制限はない。例えば、エチレン性不飽和カルボン酸ヒドロキシアルキルエステル系単量体、アリルアルコール、及びＮ−メチロールアクリルアミド等が挙げられ、１種を単独で、又は２種以上を組み合わせて用いることができる。エチレン性不飽和カルボン酸ヒドロキシアルキルエステル系単量体としてより具体的には、例えば（メタ）アクリル酸２−ヒドロキシエチルが挙げられる。 Here, the monomer having a hydroxyalkyl group may be any monomer having at least one hydroxyalkyl group and not corresponding to the conjugated diene monomer (a). There is no particular limitation other than. Examples thereof include ethylenically unsaturated carboxylic acid hydroxyalkyl ester monomers, allyl alcohol, and N-methylol acrylamide. These can be used alone or in combination of two or more. More specifically, examples of the ethylenically unsaturated carboxylic acid hydroxyalkyl ester monomer include 2-hydroxyethyl (meth) acrylate.
また、前記ヒドロキシアルキル基を有する単量体（ｂ）が前記全単量体混合物１００質量部中に占める割合としては、好ましくは０．５質量部〜１０．０質量部、より好ましくは１．０質量部〜９．０質量部、さらに好ましくは２．０質量部〜８．０質量部である。ヒドロキシアルキル基を有する単量体の使用量の下限を上記範囲に設定する事により、共重合体ラテックスを用いた水性防錆塗料組成物は、温冷繰返し後の基材への密着性、塗料の安定性を向上させることができる。ヒドロキシアルキル基を有する単量体（ｂ）の使用量の上限を上記範囲に設定する事により、共重合体ラテックスを用いた水性防錆塗料組成物は、防錆性、塗料の乾燥性を向上させることができる。 The proportion of the hydroxyalkyl group-containing monomer (b) in 100 parts by mass of the total monomer mixture is preferably 0.5 parts by mass to 10.0 parts by mass, more preferably 1. It is 0 mass part-9.0 mass parts, More preferably, it is 2.0 mass parts-8.0 mass parts. By setting the lower limit of the amount of the monomer having a hydroxyalkyl group within the above range, the aqueous rust preventive coating composition using the copolymer latex can be used for adhesion to a substrate after repeated heating and cooling, coating Stability can be improved. By setting the upper limit of the amount of the monomer (b) having a hydroxyalkyl group within the above range, the aqueous rust preventive coating composition using the copolymer latex improves the rust prevention and the drying property of the paint. Can be made.
（ｃ）他の共重合可能な単量体
本発明で用いられる他の共重合可能な単量体（ｃ）は、その種類を適宜選択することにより、共重合体ラテックスにさまざまな特性を付与できる。他の共重合可能な単量体（ｃ）は、共役ジエン系単量体（ａ）及びヒドロキシアルキル基を有する単量体（ｂ）と共重合可能な単量体（前記単量体（ａ）又は（ｂ）に該当するものを除く）であればよく、それ以外に特に制限はない。他の共重合可能な単量体（ｃ）の好ましい例としては、例えば、エチレン系不飽和カルボン酸単量体（ｃ１）、シアン化ビニル系単量体（ｃ２）、芳香族ビニル系単量体（ｃ３）、（メタ）アクリル酸アルキルエステル系単量体（ｃ４）、等が挙げられ、単独で用いても、２種以上を組み合わせて用いてもよい。他の共重合可能な単量体（ｃ）が、前記全単量体混合物１００質量部中に占める割合としては３０．０質量部〜９８．５質量部である。
(C) Other copolymerizable monomers The other copolymerizable monomers (c) used in the present invention impart various characteristics to the copolymer latex by appropriately selecting the type thereof. it can. The other copolymerizable monomer (c) is a monomer copolymerizable with the conjugated diene monomer (a) and the monomer (b) having a hydroxyalkyl group (the monomer (a ) Or (b) except those that fall under this, and there are no other restrictions. Preferred examples of the other copolymerizable monomer (c) include, for example, an ethylenically unsaturated carboxylic acid monomer (c1), a vinyl cyanide monomer (c2), and an aromatic vinyl monomer. Body (c3), (meth) acrylic acid alkyl ester monomer (c4), and the like. These may be used alone or in combination of two or more. The proportion of the other copolymerizable monomer (c) in 100 parts by mass of the total monomer mixture is 30.0 parts by mass to 98.5 parts by mass.
前記エチレン系不飽和カルボン酸単量体（ｃ１）としては、例えば、アクリル酸、メタクリル酸等の一塩基性エチレン系不飽和カルボン酸単量体、イタコン酸、マレイン酸、フマル酸等の二塩基性エチレン系不飽和カルボン酸単量体等が挙げられる。これらは１種を単独で、又は２種以上を組み合わせて用いることができる。 Examples of the ethylenically unsaturated carboxylic acid monomer (c1) include monobasic ethylenically unsaturated carboxylic acid monomers such as acrylic acid and methacrylic acid, and dibasic substances such as itaconic acid, maleic acid, and fumaric acid. And an ethylenically unsaturated carboxylic acid monomer. These can be used alone or in combination of two or more.
前記エチレン系不飽和カルボン酸単量体（ｃ１）が、前記全単量体混合物１００質量部中に占める割合としては、好ましくは０〜１．４質量部、より好ましくは０〜１．０質量部、さらに好ましくは０〜０．７質量部、なお好ましくは０〜０．４質量部、最も好ましくは０〜０．３質量部である。エチレン系不飽和カルボン酸単量体（ｃ１）の使用量を上記範囲に設定する事により、共重合体ラテックスを用いた水性防錆塗料組成物の防錆性と乾燥性を高める効果を得ることができる。 The proportion of the ethylenically unsaturated carboxylic acid monomer (c1) in 100 parts by mass of the total monomer mixture is preferably 0 to 1.4 parts by mass, more preferably 0 to 1.0 parts by mass. Parts, more preferably 0 to 0.7 parts by mass, still more preferably 0 to 0.4 parts by mass, and most preferably 0 to 0.3 parts by mass. By setting the amount of the ethylenically unsaturated carboxylic acid monomer (c1) used in the above range, the effect of improving the rust prevention and drying properties of the aqueous rust prevention coating composition using the copolymer latex is obtained. Can do.
前記シアン化ビニル系単量体（ｃ２）としては、例えば、アクリロニトリル、メタクリロニトリル、α−クロルアクリロニトリル等が挙げられる。これらは１種を単独で、又は２種以上を組み合わせて用いることができる。 Examples of the vinyl cyanide monomer (c2) include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like. These can be used alone or in combination of two or more.
また、前記シアン化ビニル系単量体（ｃ２）が、前記全単量体混合物１００質量部中に占める割合としては、好ましくは２５．０質量部以下、より好ましくは２０．０質量部以下である。シアン化ビニル系単量体（ｃ２）の使用量を当該範囲に設定する事により、共重合体ラテックスの重合安定性を低下させることなく、共重合体ラテックスを用いた水性防錆塗料組成物の基材との密着性や温冷繰返し後の基材への密着性を高める効果を得ることができる。 The proportion of the vinyl cyanide monomer (c2) in 100 parts by mass of the total monomer mixture is preferably 25.0 parts by mass or less, more preferably 20.0 parts by mass or less. is there. By setting the use amount of the vinyl cyanide monomer (c2) within the above range, the water-based anticorrosive coating composition using the copolymer latex can be obtained without reducing the polymerization stability of the copolymer latex. The effect which improves the adhesiveness with a base material and the base material after a heating / cooling repetition can be acquired.
前記芳香族ビニル系単量体（ｃ３）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、ｐ−メチルスチレン等が挙げられる。これらは１種を単独で、又は２種以上を組み合わせて用いることができる。 Examples of the aromatic vinyl monomer (c3) include styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene. These can be used alone or in combination of two or more.
前記（メタ）アクリル酸アルキルエステル系単量体（ｃ４）としては、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）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ドデシル等が挙げられる。これらは１種を単独で、又は２種以上を組み合わせて用いることができる。 Examples of the (meth) acrylic acid alkyl ester monomer (c4) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples thereof include cyclohexyl (meth) acrylate and dodecyl (meth) acrylate. These can be used alone or in combination of two or more.
前記単量体混合物には、上述した各種単量体（ｃ１）〜（ｃ４）以外にも、種々の他の共重合可能な単量体（ｃ）を配合することができる。そのような単量体としては、例えば、アクリル酸アミノエチル、アクリル酸ジメチルアミノエチル、アクリル酸ジエチルアミノエチルなどのアミノアルキルエステル類；２−ビニルピリジン、４−ビニルピリジンなどのピリジン類；アクリル酸グリシジル、メタクリル酸グリシジルなどのグリシジルエステル類；アクリルアミド、メタクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−メチルメタクリルアミド、グリシジルメタクリルアミド、Ｎ，Ｎ−ブトキシメチルアクリルアミドなどのアミド類；酢酸ビニルなどのカルボン酸ビニルエステル類；塩化ビニルなどのハロゲン化ビニル類；ジビニルベンゼン、（ポリ）エチレングリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、アリル（メタ）アクリレート等の多官能ビニル系単量体；等が挙げられる。これらは１種を単独で、又は２種以上を組み合わせて用いる事ができる。 In addition to the various monomers (c1) to (c4) described above, various other copolymerizable monomers (c) can be blended in the monomer mixture. Examples of such monomers include aminoalkyl esters such as aminoethyl acrylate, dimethylaminoethyl acrylate, and diethylaminoethyl acrylate; pyridines such as 2-vinylpyridine and 4-vinylpyridine; glycidyl acrylate Glycidyl esters such as glycidyl methacrylate; amides such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylacrylamide, N-methylmethacrylamide, glycidylmethacrylamide, N, N-butoxymethylacrylamide; vinyl acetate, etc. Carboxylic acid vinyl esters; vinyl halides such as vinyl chloride; divinylbenzene, (poly) ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, , 4-butanediol di (meth) acrylate, polyfunctional vinyl monomers such as allyl (meth) acrylate; and the like. These can be used individually by 1 type or in combination of 2 or more types.
得られる共重合体ラテックスの安定性の観点からは、他の共重合可能な単量体（ｃ）として、スチレン、（メタ）アクリル酸メチル、（メタ）アクリル酸２−エチルヘキシル、アクリロニトリルを配合することが好ましい。 From the viewpoint of the stability of the obtained copolymer latex, styrene, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and acrylonitrile are blended as other copolymerizable monomer (c). It is preferable.
本実施の形態において、本願発明の共重合体中のトルエン不溶分としては、好ましくは８０質量％以下、より好ましくは７５質量％以下、さらに好ましくは７０質量％以下である。トルエン不溶分の上限を上記範囲に調整することにより、本実施の形態の共重合体ラテックスを用いた水性防錆塗料組成物は、防錆性を向上させることができる。トルエン不溶分は公知の方法で制御できるが、連鎖移動剤の量により調整することが実用上重要な手段である。 In the present embodiment, the toluene insoluble content in the copolymer of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less. By adjusting the upper limit of the toluene insoluble content to the above range, the aqueous rust preventive coating composition using the copolymer latex of the present embodiment can improve the rust preventive property. The toluene insoluble matter can be controlled by a known method, but it is a practically important means to adjust by the amount of the chain transfer agent.
上記共重合体ラテックスの重合には連鎖移動剤を用いる。連鎖移動剤は特に限定されないが、例えば、核置換α−メチルスチレンの二量体のひとつであるα−メチルスチレンダイマー；ｎ−ブチルメルカプタン、ｔ−ブチルメルカプタン、ｔ−ドデシルメルカプタン、ｎ−オクチルメルカプタン、ｎ−ラウリルメルカプタンなどのメルカプタン類；テトラメチルチウラジウムジスルフィド、テトラエチルチウラジウムジスルフィドなどのジスルフィド類；四塩化炭素、四臭化炭素などのハロゲン化誘導体、２−エチルヘキシルチオグリコレートなどが挙げられる。これらの中でもメルカプタン類が好適に使用できる。これらは１種を単独で、又は２種以上を組み合わせて用いることができる。 A chain transfer agent is used for the polymerization of the copolymer latex. The chain transfer agent is not particularly limited. For example, α-methylstyrene dimer which is one of dimers of nucleus-substituted α-methylstyrene; n-butyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan And mercaptans such as n-lauryl mercaptan; disulfides such as tetramethylthuradium disulfide and tetraethylthuradium disulfide; halogenated derivatives such as carbon tetrachloride and carbon tetrabromide, and 2-ethylhexylthioglycolate. Among these, mercaptans can be preferably used. These can be used alone or in combination of two or more.
連鎖移動剤の使用量は、前記単量体混合物１００質量部に対し、割合としては通常０．１質量部〜４．０質量部、好ましくは０．１質量部〜３．０質量部、さらに好ましくは０．２〜２．５質量部である。連鎖移動剤の使用量を上記範囲に設定することにより、本実施の形態の共重合体ラテックスのトルエン不溶分を上記範囲に設定することができる。 The amount of the chain transfer agent used is usually 0.1 to 4.0 parts by weight, preferably 0.1 to 3.0 parts by weight, and more preferably 100 parts by weight of the monomer mixture. Preferably it is 0.2-2.5 mass parts. By setting the amount of chain transfer agent used within the above range, the toluene insoluble content of the copolymer latex of the present embodiment can be set within the above range.
連鎖移動剤の添加方法としては、例えば、一括添加、回分添加、連続添加、あるいはこれらの組み合わせなど公知の添加方法が用いられる。 As the addition method of the chain transfer agent, for example, a known addition method such as batch addition, batch addition, continuous addition, or a combination thereof is used.
本実施の形態における共重合体ラテックスは、示差走査熱量測定において、ガラス転移温度が好ましくは−４０℃〜７０℃、より好ましくは−３０〜６０℃、さらに好ましくは−２０〜５０℃の範囲にあることが好ましい。共重合体ラテックスのガラス転移温度を上記範囲に調整することにより、本実施の形態の共重合体ラテックスを用いた水性塗料組成物は、防錆性、基材への密着性、温冷繰返し後の基材への密着性を向上させることができる。示差走査熱量曲線の微分曲線（温度−電力／時間曲線）におけるピークを検出することができるが、ピークが１点のもの、２点以上あるもの、又は明確なピークを示さず台形状の曲線を示すもの、いずれでも構わない。本実施の形態における共重合体ラテックスのガラス転移温度は、ＡＳＴＭ法より算出したガラス転移温度である。 The copolymer latex in the present embodiment has a glass transition temperature of preferably −40 ° C. to 70 ° C., more preferably −30 to 60 ° C., and still more preferably −20 to 50 ° C. in differential scanning calorimetry. Preferably there is. By adjusting the glass transition temperature of the copolymer latex to the above range, the water-based coating composition using the copolymer latex of the present embodiment is rust-proof, adherence to a substrate, after repeated heating and cooling. The adhesion to the substrate can be improved. The peak in the differential curve (temperature-power / time curve) of the differential scanning calorimetry curve can be detected, but the peak has one point, two or more points, or a trapezoidal curve without showing a clear peak. Any of those shown may be used. The glass transition temperature of the copolymer latex in the present embodiment is a glass transition temperature calculated by the ASTM method.
本実施の形態の共重合体ラテックスを製造するに際し、乳化重合の系内に単量体混合物を添加する方法についても種々の方法を採用し得る。例えば、単量体混合物の一部を一括して予め乳化重合系内に仕込み重合した後、残りの単量体混合物を連続的もしくは間欠的に仕込む方法が挙げられる。また、単量体混合物を最初から連続的又は間欠的に仕込む方法が挙げられる。これらの重合方法は組み合わせることも可能である。 In producing the copolymer latex of the present embodiment, various methods can be employed for the method of adding the monomer mixture into the emulsion polymerization system. For example, a method may be mentioned in which a part of the monomer mixture is collectively charged in an emulsion polymerization system in advance and then the remaining monomer mixture is charged continuously or intermittently. Moreover, the method of charging a monomer mixture continuously or intermittently from the beginning is mentioned. These polymerization methods can also be combined.
また単量体混合物を添加する工程において、単量体混合物の組成が連続的に変化するような、いわゆるパワーフィード法を用いることも可能である。 In the step of adding the monomer mixture, it is also possible to use a so-called power feed method in which the composition of the monomer mixture continuously changes.
本実施の形態において、共重合体ラテックスの数平均粒子径としては、好ましくは５０ｎｍ〜５００ｎｍであり、より好ましくは６０ｎｍ〜４００ｎｍ、さらに好ましくは７０ｎｍ〜３５０ｎｍ、最も好ましくは８０ｎｍ〜３３０ｎｍである。数平均粒子径を上記範囲に調製することにより、本実施の形態の共重合体ラテックスを用いた水性防錆塗料組成物は、防錆性、基材への密着性、温冷繰返し後の基材への密着性、塗料の乾燥性、塗料の安定性を向上させることができる。 In the present embodiment, the number average particle size of the copolymer latex is preferably 50 nm to 500 nm, more preferably 60 nm to 400 nm, still more preferably 70 nm to 350 nm, and most preferably 80 nm to 330 nm. By adjusting the number average particle diameter within the above range, the aqueous rust preventive coating composition using the copolymer latex of the present embodiment has a rust preventive property, adhesion to a substrate, and a base after repeated heating and cooling. The adhesion to the material, the drying property of the paint, and the stability of the paint can be improved.
数平均粒子径は、乳化重合により製造する際の、乳化剤の使用量を調節する方法や公知のシード重合法を用いることで調整することが可能である。シード重合法としては、シードを作製後同一反応系内で共重合体ラテックスの重合を行うインターナルシード法、別途作製したシードを用いるエクスターナルシード法などの方法を、適宜選択して用いることができる。 The number average particle diameter can be adjusted by using a method for adjusting the amount of emulsifier used in the production by emulsion polymerization or a known seed polymerization method. As the seed polymerization method, a method such as an internal seed method in which a copolymer latex is polymerized in the same reaction system after producing the seed, or an external seed method using a separately produced seed can be selected and used as appropriate.
本実施の形態において、共重合体ラテックスの製造法については、例えば、水性媒体中で乳化剤の存在下、ラジカル開始剤により重合を行う等の方法を採用することができる。 In the present embodiment, as a method for producing the copolymer latex, for example, a method of performing polymerization with a radical initiator in the presence of an emulsifier in an aqueous medium can be employed.
ここで、使用する乳化剤としては、従来公知のアニオン性乳化剤、カチオン性乳化剤、両性乳化剤、ノニオン性乳化剤に挙げられる非反応性乳化剤、親水基と親油基を有する乳化剤の化学構造式の中にエチレン性２重結合を導入した、いわゆる反応性乳化剤を用いることができる。 Here, as the emulsifier to be used, the chemical structural formulas of the conventionally known anionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, non-reactive emulsifiers exemplified by nonionic emulsifiers, emulsifiers having hydrophilic groups and lipophilic groups A so-called reactive emulsifier into which an ethylenic double bond is introduced can be used.
非反応性乳化剤としては、例えば非反応性のアルキル硫酸エステル、ポリオキシエチレンアルキルエーテル硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルキルスルホコハク酸塩、アルキルジフェニルエーテルジスルホン酸塩、ナフタレンスルホン酸ホルマリン縮合物、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩、ポリオキシエチレンジスチレン化フェニルエーテル硫酸エステル塩、脂肪酸塩、アルキルリン酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩などのアニオン性乳化剤が挙げられ、また非反応性のポリオキシエチレンアルキルエーテル、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレン多環フェニルエーテル、ポリオキシエチレンジスチレン化フェニルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンアルキルアミン、アルキルアルカノールアミド、ポリオキシエチレンアルキルフェニルエーテルなどのノニオン性乳化剤が挙げられる。 Examples of non-reactive emulsifiers include non-reactive alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, naphthalene sulfonic acids. Anionic emulsifiers such as formalin condensate, polyoxyethylene polycyclic phenyl ether sulfate, polyoxyethylene distyrenated phenyl ether sulfate, fatty acid salt, alkyl phosphate, polyoxyethylene alkylphenyl ether sulfate Non-reactive polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene polycyclic phenyl ether, polyoxyethylene disti Phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide, polyoxyethylene alkylphenyl ether, etc. Nonionic emulsifiers.
反応性乳化剤としては、例えばアニオン性反応性乳化剤としては、スルホン酸基、スルホネート基又は硫酸エステル基及びこれらの塩を有するエチレン性不飽和単量体であり、スルホン酸基、又はそのアンモニウム塩かアルカリ金属塩である基（アンモニウムスルホネート基、又はアルカリ金属スルホネート基）を有する化合物であることが好ましい。例えばアルキルアリルスルホコハク酸塩（例えば三洋化成（株）エレミノール（商標）ＪＳ−２、ＪＳ−５、例えば花王（株）製ラテムル（商標）Ｓ−１２０、Ｓ−１８０Ａ、Ｓ−１８０等が挙げられる）、例えばポリオキシエチレンアルキルプロペニルフェニルエーテル硫酸エステル塩（例えば第一工業製薬（株）製アクアロン（商標）ＨＳ−１０、ＨＳ−１０２５等が挙げられる）、例えばα−〔１−〔（アリルオキシ）メチル〕−２−（ノニルフェノキシ）エチル〕−ω−ポリオキシエチレン硫酸エステル塩（例えば旭電化工業（株）製アデカリアソープ（商標）ＳＥ−１０２５Ｎ等が挙げられる）、例えばアンモニウム＝α−スルホナト−ω−１−（アリルオキシメチル）アルキルオキシポリオキシエチレン（例えば第一工業製薬（株）製アクアロンＫＨ−１０などが挙げられる）など、スチレンスルホン酸塩が挙げられる。 As the reactive emulsifier, for example, as an anionic reactive emulsifier, an ethylenically unsaturated monomer having a sulfonic acid group, a sulfonate group or a sulfate ester group and a salt thereof, a sulfonic acid group, or an ammonium salt thereof. A compound having a group (ammonium sulfonate group or alkali metal sulfonate group) which is an alkali metal salt is preferable. For example, alkylallylsulfosuccinate (for example, Sanyo Kasei Co., Ltd., Eleminol (trademark) JS-2, JS-5, for example, Laomul (trademark) S-120, S-180A, S-180 manufactured by Kao Corporation), etc. ), For example, polyoxyethylene alkyl propenyl phenyl ether sulfate ester salt (for example, Aqualon (trademark) HS-10, HS-1025 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), for example, α- [1-[(allyloxy) Methyl] -2- (nonylphenoxy) ethyl] -ω-polyoxyethylene sulfate ester salt (for example, Adeka Soap (trademark) SE-1025N manufactured by Asahi Denka Kogyo Co., Ltd.), for example, ammonium = α-sulfonate -Ω-1- (allyloxymethyl) alkyloxypolyoxyethylene (for example, Daiichi Kogyo Seiyaku Co., Ltd. Ltd., etc. Aqualon KH-10 and the like) and the like, and a styrene sulfonic acid salt.
また、反応性乳化剤でノニオン性反応性乳化剤としては、例えばα−〔１−〔（アリルオキシ）メチル〕−２−（ノニルフェノキシ）エチル〕−ω−ヒドロキシポリオキシエチレン（例えば旭電化工業（株）製アデカリアソープＮＥ−２０、ＮＥ−３０、ＮＥ−４０等が挙げられる）、例えばポリオキシエチレンアルキルプロペニルフェニルエーテル（例えば第一工業製薬（株）製アクアロンＲＮ−１０、ＲＮ−２０、ＲＮ−３０、ＲＮ−５０等が挙げられる）などが挙げられる。 Examples of reactive emulsifiers and nonionic reactive emulsifiers include α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (for example, Asahi Denka Kogyo Co., Ltd.). Adekaria soap NE-20, NE-30, NE-40, etc., such as polyoxyethylene alkylpropenyl phenyl ether (for example, Aqualon RN-10, RN-20, RN- manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 30, RN-50, etc.).
使用される乳化剤の量としては、前記単量体混合物１００質量部に対して、好ましくは０．１質量部〜５．０質量部、より好ましくは０．１質量部〜４．５質量部、さらに好ましくは０．１質量部〜４．０質量部である。乳化剤は、非反応性乳化剤及び反応性乳化剤の中から選ばれる１種を単独で、又は２種類以上を組み合わせて用いることができる。 The amount of the emulsifier used is preferably 0.1 parts by mass to 5.0 parts by mass, more preferably 0.1 parts by mass to 4.5 parts by mass, with respect to 100 parts by mass of the monomer mixture. More preferably, it is 0.1 mass part-4.0 mass parts. An emulsifier can be used individually by 1 type chosen from a non-reactive emulsifier and a reactive emulsifier, or in combination of 2 or more types.
非反応性乳化剤は、単量体混合物１００質量部に対して好ましくは１．０質量部以下、より好ましくは０．７質量部以下、さらに好ましくは０．５質量部以下、最も好ましくは０．４質量部以下を用いることができる。反応性乳化剤は、全単量体混合物１００質量部に対して好ましくは５．０質量部以下、より好ましくは４．５質量部以下、さらに好ましくは４．０質量部以下を用いることができる。乳化剤を上記範囲に設定する事により、本実施の形態の共重合体ラテックスは重合の安定性を向上させることができ、また、本実施の形態の共重合体ラテックスを用いた水性防錆塗料組成物は、防錆性を向上させることができる。 The non-reactive emulsifier is preferably 1.0 part by mass or less, more preferably 0.7 part by mass or less, further preferably 0.5 part by mass or less, and most preferably 0.00 part by mass or less with respect to 100 parts by mass of the monomer mixture. 4 parts by mass or less can be used. The reactive emulsifier can be used in an amount of preferably 5.0 parts by mass or less, more preferably 4.5 parts by mass or less, and still more preferably 4.0 parts by mass or less with respect to 100 parts by mass of the total monomer mixture. By setting the emulsifier within the above range, the copolymer latex of the present embodiment can improve the stability of the polymerization, and the aqueous antirust coating composition using the copolymer latex of the present embodiment Things can improve rust prevention.
ラジカル開始剤としては、熱又は還元剤の存在下でラジカル分解して単量体の付加重合を開始させるものであり、無機系開始剤、有機系開始剤のいずれも使用することが可能である。好ましい開始剤の例としては、例えば、ペルオキソ二硫酸塩、過酸化物、アゾビス化合物などを挙げることができる。 The radical initiator is one that initiates addition polymerization of a monomer by radical decomposition in the presence of heat or a reducing agent, and both inorganic and organic initiators can be used. . Examples of preferred initiators include peroxodisulfate, peroxide, azobis compound and the like.
このような開始剤としてより具体的には、例えば、ペルオキソ二硫酸カリウム、ペルオキソ二硫酸ナトリウム、ペルオキソ二硫酸アンモニウム、過酸化水素、ｔ−ブチルヒドロペルオキシド、過酸化ベンゾイル、２，２−アゾビスブチロニトリル、クメンハイドロパーオキサイド等が挙げられる。これらは１種を単独で、又は２種以上を組み合わせて用いることができる。 More specific examples of such initiators include, for example, potassium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, 2,2-azobisbutyro Nitrile, cumene hydroperoxide and the like can be mentioned. These can be used alone or in combination of two or more.
また、酸性亜硫酸ナトリウム、アスコルビン酸やその塩、エリソルビン酸やその塩、ロンガリットなどの還元剤を上述の重合開始剤と組み合わせて用いる、いわゆるレドックス重合法を用いることもできる。 In addition, a so-called redox polymerization method in which a reducing agent such as acidic sodium sulfite, ascorbic acid or a salt thereof, erythorbic acid or a salt thereof or Rongalite is used in combination with the above-described polymerization initiator can also be used.
共重合体ラテックスを製造する場合の重合温度としては、例えば、４０℃〜１００℃である。ここで、生産効率と、得られる共重合体ラテックスの柔軟性等の品質の観点から、重合開始時から単量体混合物の添加終了時までの期間における重合温度として、好ましくは４５℃〜９５℃、より好ましくは５５℃〜９０℃である。 The polymerization temperature when producing the copolymer latex is, for example, 40 ° C to 100 ° C. Here, from the viewpoint of the production efficiency and the quality of the obtained copolymer latex such as flexibility, the polymerization temperature in the period from the start of polymerization to the end of addition of the monomer mixture is preferably 45 ° C to 95 ° C. More preferably, it is 55 degreeC-90 degreeC.
また、全単量体混合物を重合系内に添加終了後に、各単量体の重合転化率を引き上げる為に重合温度を上げる方法（いわゆるクッキング工程）を採用する事も可能である。このような工程における重合温度としては、好ましくは８０℃〜１００℃である。 It is also possible to employ a method of raising the polymerization temperature (so-called cooking step) in order to increase the polymerization conversion rate of each monomer after the addition of the entire monomer mixture into the polymerization system. The polymerization temperature in such a process is preferably 80 ° C to 100 ° C.
共重合体ラテックスを製造する場合の重合固形分濃度（重合が完結した際の固形分濃度。乾燥により得られた固形分質量の、元の共重合体ラテックス（水等を含む）質量に対する割合をいう。）としては、生産効率と乳化重合時の粒子径制御の観点から、好ましくは４０質量％〜６０質量％、より好ましくは４３質量％〜５７質量％である。 Polymerization solid content concentration in the case of producing a copolymer latex (solid content concentration when polymerization is completed. The ratio of the solid content mass obtained by drying to the mass of the original copolymer latex (including water) ) Is preferably 40% by mass to 60% by mass, more preferably 43% by mass to 57% by mass, from the viewpoint of production efficiency and particle size control during emulsion polymerization.
前記共重合体ラテックスの製造に際しては、必要に応じて公知の各種重合調整剤を乳化重合時又は乳化重合終了時に用いることができる。例えばｐＨ調整剤、キレート化剤、などを使用することができる。 In the production of the copolymer latex, various known polymerization regulators can be used at the time of emulsion polymerization or at the end of emulsion polymerization, if necessary. For example, a pH adjuster, a chelating agent, etc. can be used.
ｐＨ調整剤の例としては、水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム、炭酸水素ナトリウム、リン酸水素二ナトリウム、モノエタノールアミンやジメチルエタノールアミンやトリエタノールアミンやトリエチルアミンなどのアミン類等が挙げられる。これらの中でも水酸化アンモニウムや、モノエタノールアミンやジメチルエタノールアミンやトリエタノールアミンやトリエチルアミンなどのアミン類を用いるのが好ましい。これらは１種を単独で、又は２種以上を組み合わせて用いることができる。 Examples of pH adjusters include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, disodium hydrogen phosphate, amines such as monoethanolamine, dimethylethanolamine, triethanolamine, and triethylamine. It is done. Among these, ammonium hydroxide, and amines such as monoethanolamine, dimethylethanolamine, triethanolamine, and triethylamine are preferably used. These can be used alone or in combination of two or more.
キレート化剤としては、例えば、エチレンジアミン四酢酸ナトリウム等が挙げられる。 Examples of the chelating agent include sodium ethylenediaminetetraacetate.
本実施の形態の共重合体ラテックスは、通常、溶媒中に分散された状態で最終製品として提供される。この場合の固形分濃度としては、好ましくは４０質量％〜６０質量％である。 The copolymer latex of the present embodiment is usually provided as a final product in a state of being dispersed in a solvent. In this case, the solid content concentration is preferably 40% by mass to 60% by mass.
ここで、本実施の形態の共重合体ラテックスには、その効果を損ねない限り、必要に応じて各種添加剤を添加したり、あるいは他のラテックスを混合して用いたりすることができる。例えば乳化剤、分散剤、消泡剤、老化防止剤、耐水化剤、殺菌剤、増粘剤、保水剤、印刷適性剤、滑剤、架橋剤などを添加することができる。また、アルカリ感応型ラテックス、有機顔料、ウレタン樹脂ラテックス、アクリル樹脂系ラテックスなどを混合して用いることもできる。なお、本発明の効果を損なわない範囲で、他の（ジエン系）共重合体ラテックスを併用してもよい。 Here, various additives may be added to the copolymer latex of the present embodiment as needed, or other latexes may be mixed and used as long as the effect is not impaired. For example, an emulsifier, a dispersant, an antifoaming agent, an anti-aging agent, a water-resistant agent, a bactericide, a thickener, a water retention agent, a printability agent, a lubricant, a crosslinking agent, and the like can be added. Further, alkali-sensitive latex, organic pigment, urethane resin latex, acrylic resin latex and the like can be mixed and used. In addition, other (diene) copolymer latex may be used in combination as long as the effects of the present invention are not impaired.
本実施の形態の水性防錆塗料用共重合体ラテックスは、そのままコーティング剤としてクリヤー皮膜を形成させるために使用することもできるし、各種充填剤、添加剤、他種エマルジョン、有機材料等が添加されて、水性防錆塗料（組成物）として使用してもよい。 The copolymer latex for water-based anticorrosive paint of this embodiment can be used as it is to form a clear film as a coating agent, and various fillers, additives, other types of emulsions, organic materials, etc. are added. And may be used as a water-based anticorrosive paint (composition).
塗料組成物中に用いられる充填剤の例としては、例えば、炭酸カルシウム、カオリンクレー、タルク、珪藻土、シリカ、マイカ、水酸化アルミニウム、水酸化マグネシウム、炭酸マグネシウム、セピオライト、アルミナ、酸化チタン、硫酸バリウム、タルク、ベンガラ等の無機顔料；ガラスビーズ、発泡ガラスビーズ、火山ガラス中空体、ガラス繊維等のガラス材料；カーボンブラック等の有機顔料、トリポリリン酸二水素アルミニウム等の防錆顔料が挙げられる。これらは１種を単独で、又は２種以上を併用して使用することができる。 Examples of fillers used in the coating composition include, for example, calcium carbonate, kaolin clay, talc, diatomaceous earth, silica, mica, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, sepiolite, alumina, titanium oxide, barium sulfate. Inorganic pigments such as talc and bengara; glass materials such as glass beads, foamed glass beads, volcanic glass hollow bodies and glass fibers; organic pigments such as carbon black; and rust preventive pigments such as aluminum dihydrogen phosphate. These can be used alone or in combination of two or more.
また、塗料組成物中に用いられる充填剤の添加量としては、共重合体ラテックスの固形分１００質量部に対し、好ましくは４００質量部以下である。このような範囲とする事で、得られた塗料組成物は、防錆性、基材への密着性、温冷繰返し後の基材への密着性、塗料の乾燥性、塗料の安定性を向上させることができる。 The amount of the filler used in the coating composition is preferably 400 parts by mass or less with respect to 100 parts by mass of the solid content of the copolymer latex. By making such a range, the obtained coating composition has rust prevention, adhesion to the substrate, adhesion to the substrate after repeated heating and cooling, drying of the coating, and stability of the coating. Can be improved.
塗料組成物中に用いられる添加剤としては、例えば、可塑剤、タレ防止剤、増粘剤、消泡剤、分散剤、発泡剤、コロイド安定剤、防腐剤、ＰＨ調整剤、老化防止剤、着色剤、架橋剤、硬化剤、保水剤等が挙げられる。これらは１種を単独で、又は２種以上を併用して使用する事が可能である。 Examples of additives used in the coating composition include plasticizers, anti-sagging agents, thickeners, antifoaming agents, dispersants, foaming agents, colloidal stabilizers, preservatives, pH adjusting agents, anti-aging agents, A coloring agent, a crosslinking agent, a hardening | curing agent, a water retention agent, etc. are mentioned. These can be used alone or in combination of two or more.
塗料組成物中に用いられる増粘剤としては、例えば、ポリカルボン酸塩類、ウレタン会合型、ポリエーテルタイプ、セルロースエーテル、ポリアクリル型、ポリアクリルアミド等を挙げることができる。 Examples of the thickener used in the coating composition include polycarboxylic acid salts, urethane association type, polyether type, cellulose ether, polyacrylic type, polyacrylamide and the like.
塗料組成物中に用いられる架橋剤・硬化剤としては、例えば、多官能エポキシ化合物、ブロックイソシアネート、メラミン樹脂、オキソザリン化合物等を挙げることができる。 Examples of the crosslinking agent / curing agent used in the coating composition include polyfunctional epoxy compounds, blocked isocyanates, melamine resins, oxozaline compounds, and the like.
塗料組成物中に用いられる発泡剤としては、例えば、重曹、炭酸アンモニウム、ニトロソ化合物、アゾ化合物、スルホニルヒドラジド等の化合物を挙げる事ができる。 Examples of the foaming agent used in the coating composition include compounds such as sodium bicarbonate, ammonium carbonate, nitroso compounds, azo compounds, and sulfonyl hydrazides.
塗料組成物中に用いられる他種エマルジョンとしては、例えば、天然ゴムラテックス、アクリル樹脂系ラテックス、酢酸ビニル系ラテックス、ウレタン樹脂ラテックス、エポキシ樹脂ラテックス等が挙げられる。 Examples of other emulsions used in the coating composition include natural rubber latex, acrylic resin latex, vinyl acetate latex, urethane resin latex, and epoxy resin latex.
また、塗料組成物中に用いられる有機材料としては、例えば、各種樹脂粉末、ゴム粉末、ポリエチレングリコール、カーボンブラック、ホワイトカーボン、セルロースパウダー、澱粉等を挙げる事ができる。 Examples of the organic material used in the coating composition include various resin powders, rubber powders, polyethylene glycol, carbon black, white carbon, cellulose powder, and starch.
本実施の形態の共重合体ラテックスを用いて塗料組成物を調製する場合、従来公知の各種分散装置を用いることができる。分散装置としては、例えばバタフライミキサー、プラネタリーミキサー、スパイラルミキサー、ロータリーミキサー、ニーダー、ディゾルバー、ペイントコンディショナー等を使用する事ができる。 When preparing a coating composition using the copolymer latex of this Embodiment, conventionally well-known various dispersion apparatuses can be used. As the dispersing device, for example, a butterfly mixer, a planetary mixer, a spiral mixer, a rotary mixer, a kneader, a dissolver, a paint conditioner, or the like can be used.
また、本実施の形態の共重合体ラテックスを使用した塗料組成物は、従来公知の方法、例えば、ヘラ、刷毛、エアスプレー、エアレススプレー、モルタルガン、リシンガン、ロール塗工機等を用いて基材に塗布する事が可能である。 In addition, the coating composition using the copolymer latex of the present embodiment is based on a conventionally known method such as a spatula, a brush, an air spray, an airless spray, a mortar gun, a lysine gun, a roll coating machine, or the like. It can be applied to the material.
本実施の形態の共重合体ラテックスは、水性塗料用として好ましく用いる事ができるが、さらに好ましくは水性防錆塗料用として用いる事ができる。また、工場のライン物塗料用として用いることができ、さらに他の用途として船底防汚塗料、カーペットバッキング剤、オレフィン等を基材とする各種接着剤、各種塗料、塗工紙用バインダー、各種コーティング剤などにも用いる事ができる。 The copolymer latex of the present embodiment can be preferably used for water-based paints, but more preferably can be used for water-based anticorrosive paints. It can also be used for line paints in factories, and for other uses such as ship bottom antifouling paints, carpet backing agents, various adhesives based on olefins, various paints, binders for coated paper, various coatings, etc. It can also be used for agents.
次に、実施例及び比較例を挙げて本実施の形態をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。尚、各物性の評価は、以下の通りの方法で行った。
（１）トルエン不溶分：
ｐＨ９に調製した共重合体ラテックスを１３０℃で３０分間乾燥し、乾燥物（ラテックスフィルム）を得た。このラテックスフィルム０．５ｇをトルエン３０ｍｌと混合して３時間振とうした後、目開き３２μｍの金属網にてろ過し、残留物の乾燥質量を秤量した。もとのラテックスフィルム質量に対する残留物の乾燥質量の割合をトルエン不溶分（質量％）とした。
（２）ガラス転移温度：
ｐＨ９に調製した共重合体ラテックスを１３０℃で３０分間乾燥し、乾燥物を得た。示差走査熱量計（エスアイアイ・ナノテクノロジー株式会社製；ＤＳＣ６２２０）を使用し、ＡＳＴＭ法（Ｄ３４１８−９７）に従い、温度−１２０℃から＋１６０℃まで、２０℃／ｍｉｎ．の速度で昇温し、本発明共重合体ラテックスの示差走査熱量曲線を得て、ガラス転移温度を求めた。
（３）共重合体ラテックスの数平均粒子径：
共重合体ラテックスの数平均粒子径を動的光散乱法により、光散乱光度計（シーエヌウッド社製、モデル６０００）を用いて、初期角度４５度−測定角度１３５度で測定した。
（４）防錆性評価：
アセトンで洗浄した鉄板（ＳＰＣＣ−ＳＤ、０．８ｍｍ×７０ｍｍ×１５０ｍｍ）に、乾燥膜厚が３０μｍとなるよう各共重合体ラテックスを含む塗料組成物を塗布し、熱風乾燥機を用いて、６０℃で２０分間乾燥し、乾燥塗膜を得た。乾燥塗膜にカッターナイフを用いてクロスカットを入れた。この場合、鉄板と乾燥塗膜との界面までナイフが入るようにした。５％の塩化ナトリウム水溶液中にクロスカットを入れた乾燥塗膜を入れ、２３℃で１週間浸漬した。防錆性を以下に示す方法で判定した。防錆性は△以上であることが好ましい。より好ましくは○である。
○：カット部の錆の発生幅が片側２ｍｍ以内
△：カット部の錆の発生幅が片側３〜５ｍｍ
×：カット部の錆の発生幅が片側５ｍｍ以上
（５）密着性
アセトンで洗浄した鉄板（ＳＰＣＣ−ＳＤ、０．８ｍｍ×７０ｍｍ×１５０ｍｍ）に、乾燥膜厚が３０μｍとなるよう各共重合体ラテックスを含む塗料組成物を塗布し、熱風乾燥機を用いて、６０℃で２０分間乾燥し、乾燥塗膜を得た。乾燥塗膜の表面に、カッターナイフを用いて等間隔で１ｍｍクロスカットを入れた。この場合、鉄板と乾燥塗膜との界面までナイフが入るようにした。次にクロスカット部の中心にセロハンテープを貼り付け、セロハンテープを一定の力で引き剥がした。引き剥がした後の乾燥塗膜の状態を目視にて観察し、以下に示す基準で評価した。密着性は△以上であることが好ましい。より好ましくは○である。
○：１ｍｍクロスカット部が鉄板上に全て残っていた。
△：１ｍｍクロスカット部が一部剥がれていた。
×：１ｍｍクロスカット部が半分以上剥がれていた。
（６）温冷繰返し後の密着性：
アセトンで洗浄した鉄板（ＳＰＣＣ−ＳＤ、０．８ｍｍ×７０ｍｍ×１５０ｍｍ）に、乾燥膜厚が３０μｍとなるよう各共重合体ラテックスを含む塗料組成物を塗布し、熱風乾燥機を用いて、６０℃で２０分間乾燥し、乾燥塗膜を得た。乾燥塗膜にカッターナイフを用いてクロスカットを入れた。この場合、鉄板と乾燥塗膜との界面までナイフが入るようにした。次に乾燥塗膜について、２３℃３時間→６０℃３時間を１サイクルとする温冷繰返し試験を１０サイクル行った後、乾燥塗膜の鉄板からのハガレやヒビ割れを観察した。ハガレやヒビ割れがあるものを×と判定した。乾燥塗膜の鉄板からのハガレやヒビ割れがないものは、さらにクロスカット部の中心にセロハンテープを貼り付け、セロハンテープを一定の力で引き剥がした。引き剥がした後の乾燥塗膜の状態を目視にて観察し、ハガレやヒビ割れがないものを○、ハガレやヒビ割れがあるものを△で判定した。温冷繰返し後の密着性は△以上であることが好ましい。より好ましくは○である。
（７）乾燥性：
アセトンで洗浄した鉄板（ＳＰＣＣ−ＳＤ、０．８ｍｍ×７０ｍｍ×１５０ｍｍ）に、乾燥膜厚が３０μｍとなるよう各共重合体ラテックスを含む塗料組成物を塗布し、熱風乾燥機を用いて、温度６０℃、湿度２０％で５分間乾燥した。乾燥後、塗膜の中央を指先で軽く触れて、指先の汚れ状態を観察し、以下の基準で判定した。乾燥性は△以上であることが好ましい。より好ましくは○である。
○：指先が汚れない
△：指先の一部が汚れる
×：指先の全面が汚れる
（８）塗料安定性：
アセトンで洗浄した鉄板（ＳＰＣＣ−ＳＤ、０．８ｍｍ×７０ｍｍ×１５０ｍｍ）に、乾燥膜厚が３０μｍとなるよう各共重合体ラテックスを含む塗料組成物を塗布した。塗布した塗料組成物中に、凝集物があるかを目視で観察し、以下の基準で判定した。塗料安定性は△以上であることが好ましい。より好ましくは○である。
○：塗料組成物中に凝集物がない
△：塗料組成物中に凝集物が１０箇所以下ある
×：塗料組成物中に凝集物が１０箇所以上ある
Next, although an Example and a comparative example are given and this Embodiment is demonstrated more concretely, unless this summary is exceeded, this invention is not limited to a following example. Each physical property was evaluated by the following method.
(1) Toluene insoluble matter:
The copolymer latex adjusted to pH 9 was dried at 130 ° C. for 30 minutes to obtain a dried product (latex film). After 0.5 g of this latex film was mixed with 30 ml of toluene and shaken for 3 hours, it was filtered through a metal net having an opening of 32 μm, and the dry mass of the residue was weighed. The ratio of the dry mass of the residue to the original latex film mass was defined as the toluene insoluble content (% by mass).
(2) Glass transition temperature:
The copolymer latex adjusted to pH 9 was dried at 130 ° C. for 30 minutes to obtain a dried product. Using a differential scanning calorimeter (SII NanoTechnology Co., Ltd .; DSC6220), according to ASTM method (D3418-97), the temperature was from -120 ° C to + 160 ° C, 20 ° C / min. The glass transition temperature was determined by obtaining a differential scanning calorimetric curve of the copolymer latex of the present invention.
(3) Number average particle diameter of copolymer latex:
The number average particle diameter of the copolymer latex was measured by a dynamic light scattering method using a light scattering photometer (model 6000, manufactured by CNN Wood) at an initial angle of 45 degrees and a measurement angle of 135 degrees.
(4) Rust prevention evaluation:
A coating composition containing each copolymer latex was applied to an iron plate (SPCC-SD, 0.8 mm × 70 mm × 150 mm) washed with acetone so that the dry film thickness was 30 μm. Drying at 20 ° C. for 20 minutes gave a dry coating film. A crosscut was put into the dried coating film using a cutter knife. In this case, the knife entered the interface between the iron plate and the dried coating film. A dried coating film in which a cross cut was put in a 5% aqueous sodium chloride solution was placed and immersed at 23 ° C. for 1 week. The antirust property was determined by the following method. The antirust property is preferably Δ or more. More preferably, it is (circle).
○: Rust generation width of cut part is within 2 mm on one side Δ: Rust generation width of cut part is 3-5 mm on one side
×: Rust generation width of cut part is 5 mm or more on one side (5) Adhesiveness Each copolymer so that the dry film thickness becomes 30 μm on an iron plate (SPCC-SD, 0.8 mm × 70 mm × 150 mm) washed with acetone. A coating composition containing latex was applied and dried at 60 ° C. for 20 minutes using a hot air dryer to obtain a dried coating film. A 1 mm cross cut was made at equal intervals on the surface of the dried coating film using a cutter knife. In this case, the knife entered the interface between the iron plate and the dried coating film. Next, a cellophane tape was attached to the center of the cross cut portion, and the cellophane tape was peeled off with a certain force. The state of the dried coating film after peeling off was visually observed and evaluated according to the following criteria. The adhesion is preferably Δ or more. More preferably, it is (circle).
○: All 1 mm crosscut portions remained on the iron plate.
Δ: A part of the 1 mm cross cut part was peeled off.
×: More than half of the 1 mm cross cut part was peeled off.
(6) Adhesiveness after repeated heating and cooling:
A coating composition containing each copolymer latex was applied to an iron plate (SPCC-SD, 0.8 mm × 70 mm × 150 mm) washed with acetone so that the dry film thickness was 30 μm. Drying at 20 ° C. for 20 minutes gave a dry coating film. A crosscut was put into the dried coating film using a cutter knife. In this case, the knife entered the interface between the iron plate and the dried coating film. Next, the dry coating film was subjected to 10 cycles of a hot and cold repeated test with one cycle of 23 ° C. for 3 hours → 60 ° C. for 3 hours, and then the peeling and cracking of the dry coating film from the iron plate were observed. Those with peeling or cracks were judged as x. In the case where the dry paint film was not peeled off or cracked, a cellophane tape was attached to the center of the cross-cut portion, and the cellophane tape was peeled off with a certain force. The state of the dried coating film after peeling off was visually observed, and those having no peeling or cracking were judged as ◯, and those having peeling or cracking were judged as Δ. The adhesion after repeated heating and cooling is preferably Δ or more. More preferably, it is (circle).
(7) Dryability:
A coating composition containing each copolymer latex was applied to an iron plate (SPCC-SD, 0.8 mm × 70 mm × 150 mm) washed with acetone so that the dry film thickness was 30 μm, and the temperature was measured using a hot air dryer. The film was dried at 60 ° C. and 20% humidity for 5 minutes. After drying, the center of the coating film was lightly touched with a fingertip, and the dirt state of the fingertip was observed and judged according to the following criteria. The drying property is preferably not less than Δ. More preferably, it is (circle).
○: The fingertip is not dirty Δ: Part of the fingertip is dirty ×: The entire surface of the fingertip is dirty (8) Paint stability:
The coating composition containing each copolymer latex was apply | coated to the iron plate (SPCC-SD, 0.8 mm x 70 mm x 150 mm) wash | cleaned with acetone so that a dry film thickness might be set to 30 micrometers. The applied coating composition was visually observed for the presence of aggregates, and judged according to the following criteria. The paint stability is preferably Δ or more. More preferably, it is (circle).
○: There is no aggregate in the coating composition Δ: There are 10 or less aggregates in the coating composition ×: There are 10 or more aggregates in the coating composition
［製造例Ａ１］
耐圧反応容器に重合初期原料として水７５質量部、ドデシルベンゼンスルホン酸ナトリウム０．１質量部、イタコン酸０．１質量部を含む重合初期原料を一括して仕込み、８０℃にて十分に攪拌した。次いで、表１記載の単量体混合物と連鎖移動剤との混合物（以下、「単量体等混合物」と略記する）を、６時間かけてこの耐圧容器内に連続的に添加した。一方、単量体等混合物の添加開始から１０分後より、水２０質量部、ペルオキソ二硫酸ナトリウム１．１質量部からなる水系混合物の添加を開始し、重合反応を開始させた。この水系混合物については、６時間５０分かけて連続的に添加した。
[Production Example A1]
A pressure-resistant reaction vessel was charged with a polymerization initial raw material containing 75 parts by weight of water, 0.1 part by weight of sodium dodecylbenzenesulfonate, and 0.1 part by weight of itaconic acid as a polymerization initial raw material, and stirred sufficiently at 80 ° C. . Next, a mixture of the monomer mixture and the chain transfer agent shown in Table 1 (hereinafter abbreviated as “monomer mixture”) was continuously added into the pressure vessel over 6 hours. On the other hand, 10 minutes after the start of the addition of the monomer mixture, the addition of an aqueous mixture composed of 20 parts by mass of water and 1.1 parts by mass of sodium peroxodisulfate was started to initiate the polymerization reaction. The aqueous mixture was continuously added over 6 hours and 50 minutes.
水系混合物の添加終了後、耐圧容器内の温度を９０℃に昇温させ、重合反応を継続させて重合転化率を高めた。重合反応を終了した時の重合転化率は９５％以上であった。 After the addition of the aqueous mixture, the temperature in the pressure vessel was raised to 90 ° C., and the polymerization reaction was continued to increase the polymerization conversion rate. The polymerization conversion rate when the polymerization reaction was completed was 95% or more.
この共重合体ラテックスに、水酸化アンモニウムを添加してｐＨを９．０に調整し、最後に固形分濃度を５０質量％に調整した。この共重合体ラテックスを３２５メッシュのフィルターを通過させて濾過し、水性防錆塗料用共重合体ラテックスＡ１を得た。水性防錆塗料用共重合体ラテックスＡ１の各物性の評価結果を表１に記載する。 To this copolymer latex, ammonium hydroxide was added to adjust the pH to 9.0, and finally the solid content concentration was adjusted to 50% by mass. This copolymer latex was filtered through a 325 mesh filter to obtain a copolymer latex A1 for aqueous rust preventive paint. Table 1 shows the evaluation results of physical properties of the copolymer latex A1 for water-based anticorrosive paint.
［製造例Ａ２、Ａ４−Ａ１３、Ｂ２−Ｂ４］
重合初期原料、単量体等混合物、水系混合物の組成を、表１に記載した通りに変更した事以外は、全て製造例Ａ１と同じ手順で水性防錆塗料用共重合体ラテックスＡ２、Ａ４−Ａ１３、Ｂ２−Ｂ４を製造した。これらの各物性の評価結果を表１に記載する。
[Production Examples A2, A4-A13, B2-B4]
Except that the composition of the initial polymerization raw material, the monomer mixture, and the aqueous mixture were changed as described in Table 1, all of the latex latex copolymer A2, A4- A13 and B2-B4 were produced. The evaluation results of these physical properties are shown in Table 1.
［製造例Ａ３］
耐圧反応容器に重合初期原料として水７５質量部、ドデシルベンゼンスルホン酸ナトリウム０．１質量部、数平均粒子径４０ｎｍのポリスチレン製シードラテックス０．２質量部を含む重合初期原料を一括して仕込み、８０℃にて十分に攪拌した。次いで、表１記載の単量体等混合物を、６時間かけてこの耐圧容器内に連続的に添加した。一方、単量体等混合物の添加開始から１０分後より、水２０質量部、ペルオキソ二硫酸ナトリウム１．１質量部からなる水系混合物の添加を開始し、重合反応を開始させた。この水系混合物については、６時間５０分かけて連続的に添加した。
[Production Example A3]
A pressure-resistant reaction vessel is charged with 75 parts by weight of water as a polymerization initial material, 0.1 parts by weight of sodium dodecylbenzenesulfonate, 0.2 parts by weight of polystyrene seed latex having a number average particle diameter of 40 nm, The mixture was sufficiently stirred at 80 ° C. Subsequently, the monomer mixture shown in Table 1 was continuously added into the pressure vessel over 6 hours. On the other hand, 10 minutes after the start of the addition of the monomer mixture, the addition of an aqueous mixture composed of 20 parts by mass of water and 1.1 parts by mass of sodium peroxodisulfate was started to initiate the polymerization reaction. The aqueous mixture was continuously added over 6 hours and 50 minutes.
水系混合物の添加終了後、耐圧容器内の温度を９０℃に昇温させ、重合反応を継続させて重合転化率を高めた。重合反応を終了した時の重合転化率は９５％以上であった。 After the addition of the aqueous mixture, the temperature in the pressure vessel was raised to 90 ° C., and the polymerization reaction was continued to increase the polymerization conversion rate. The polymerization conversion rate when the polymerization reaction was completed was 95% or more.
この共重合体ラテックスに、水酸化アンモニウムを添加してｐＨを９．０に調整し、最後に固形分濃度を５０質量％に調整した。この共重合体ラテックスを３２５メッシュのフィルターを通過させて濾過し、水性防錆塗料用共重合体ラテックスＡ３を得た。水性防錆塗料用共重合体ラテックスＡ３の各物性の評価結果を表１に記載する。 To this copolymer latex, ammonium hydroxide was added to adjust the pH to 9.0, and finally the solid content concentration was adjusted to 50% by mass. This copolymer latex was filtered through a 325 mesh filter to obtain a copolymer latex A3 for aqueous rust preventive paint. Table 1 shows the evaluation results of physical properties of the copolymer latex A3 for water-based anticorrosive paint.
［製造例Ａ１４、Ｂ１］
重合初期原料、単量体等混合物、水系混合物の組成を、表１に記載した通りに変更した事以外は、全て製造例Ａ３と同じ手順で水性防錆塗料用共重合体ラテックスＡ１４、Ｂ１を製造した。これらの各物性の評価結果を表１に記載する。
[Production Examples A14 and B1]
Except that the composition of the initial polymerization raw material, the monomer mixture, and the aqueous mixture were changed as described in Table 1, all the copolymer latexes A14 and B1 for aqueous anticorrosive paint were prepared in the same procedure as in Production Example A3. Manufactured. The evaluation results of these physical properties are shown in Table 1.
［実施例１］
水性防錆塗料用共重合体ラテックスＡ１と以下の構成材料とを使用し、均一に混合して水性防錆塗料組成物を調製した。尚、以下の配合（質量部）は、水を除いて、全て固形分に換算した値である。
共重合体ラテックス（Ａ１） １００質量部
増粘剤 ０．３質量部
なお、増粘剤としては商品名ＳＮシックナー６３４（サンノプコ社製）を使用した。この水性防錆材の固形分濃度は約５０％であった。
[Example 1]
A copolymer latex A1 for aqueous rust preventive paint and the following constituent materials were used and mixed uniformly to prepare an aqueous rust preventive paint composition. In addition, the following mixing | blendings (mass part) are the values converted into solid content altogether except water.
Copolymer latex (A1) 100 parts by mass Thickener 0.3 parts by mass In addition, a trade name SN thickener 634 (manufactured by San Nopco) was used as the thickener. The solid content concentration of this water-based rust preventive was about 50%.
次いで、このようにして得られた水性防錆塗料組成物を、上記（４）から（８）に記載の条件で、塗布、乾燥し、防錆性、密着性、温冷繰返し後の密着性、乾燥性、及び塗料安定性の評価を行った。結果を表２に記載する。 Subsequently, the aqueous rust preventive coating composition thus obtained is applied and dried under the conditions described in (4) to (8) above, and the rust prevention, adhesion, and adhesion after repeated heating and cooling are performed. Evaluation of drying property and coating stability was performed. The results are listed in Table 2.
実施例１で得られた塗膜は、防錆性、密着性、温冷繰返し後の密着性、乾燥性、塗料安定性をバランスよく両立する塗膜であった。 The coating film obtained in Example 1 was a coating film that balances rust prevention, adhesion, adhesion after repeated heating and cooling, drying properties, and coating stability.
［実施例２〜７、１０、１２〜１４］
水性防錆塗料用共重合体ラテックスをＡ１に代えてＡ２〜Ａ７、Ａ１０、Ａ１２〜Ａ１４に変更した事以外は、全て実施例１と同じ条件で水性防錆塗料組成物を調製し、乾燥させて塗膜を形成させた。結果を表２に記載する。実施例２〜７、１０、１２〜１４で得られた塗膜は、防錆性、密着性、温冷繰返し後の密着性、乾燥性、塗料安定性をバランスよく両立する塗膜であった。
［参考例１〜３］
水性防錆塗料用共重合体ラテックスをＡ１に代えてＡ８、Ａ９、Ａ１１に変更した事以外は、全て実施例１と同じ条件で水性防錆塗料組成物を調製し、乾燥させて塗膜を形成させた。結果を表２に記載する。
[Examples 2 to 7, 10, 12 to 14]
A water-based anticorrosive paint composition was prepared under the same conditions as in Example 1 except that the copolymer latex for water-based anticorrosive paint was changed to A2- A7, A10, A12- A14 instead of A1, and dried. A coating film was formed. The results are listed in Table 2. The coating films obtained in Examples 2 to 7, 10, and 12 to 14 were coating films that balance rust prevention, adhesion, adhesion after repeated heating and cooling, drying properties, and coating stability in a well-balanced manner. .
[Reference Examples 1-3]
A water-based anticorrosive paint composition was prepared under the same conditions as in Example 1 except that the copolymer latex for water-based anticorrosive paint was changed to A8, A9, A11 instead of A1, and the coating film was dried. Formed. The results are listed in Table 2.
［比較例１］
水性防錆塗料用共重合体ラテックスをＡ１に代えてＢ１に変更した事以外は、全て実施例１と同じ条件で水性防錆塗料組成物を調製し、乾燥させて塗膜を形成させた。結果を表２に記載する。比較例１で得られた塗膜は、温冷繰返し後の密着性が劣る塗膜であった。
[Comparative Example 1]
A water-based anticorrosive coating composition was prepared under the same conditions as in Example 1 except that the copolymer latex for the water-based anticorrosive coating was changed to B1 instead of A1, and a coating film was formed by drying. The results are listed in Table 2. The coating film obtained in Comparative Example 1 was a coating film having poor adhesion after repeated heating and cooling.
［比較例２］
水性防錆塗料用共重合体ラテックスをＡ１に代えてＢ２に変更した事以外は、全て実施例１と同じ条件で水性防錆塗料組成物を調製し、乾燥させて塗膜を形成させた。結果を表２に記載する。比較例２で得られた塗膜は、防錆性が劣る塗膜であった。
[Comparative Example 2]
A water-based anticorrosive coating composition was prepared under the same conditions as in Example 1 except that the copolymer latex for water-based anticorrosive coating was changed to B2 instead of A1, and a coating film was formed by drying. The results are listed in Table 2. The coating film obtained in Comparative Example 2 was a coating film with poor rust prevention.
［比較例３］
水性防錆塗料用共重合体ラテックスをＡ１に代えてＢ３に変更した事以外は、全て実施例１と同じ条件で水性防錆塗料組成物を調製し、乾燥させて塗膜を形成させた。結果を表２に記載する。比較例３で得られた塗膜は、温冷繰返し後の密着性、塗料安定性が劣る塗膜であった。
[Comparative Example 3]
A water-based anticorrosive coating composition was prepared under the same conditions as in Example 1 except that the copolymer latex for water-based anticorrosive coating was changed to B3 instead of A1, and a coating film was formed by drying. The results are listed in Table 2. The coating film obtained in Comparative Example 3 was a coating film having poor adhesion and coating stability after repeated heating and cooling.
［比較例４］
水性防錆塗料用共重合体ラテックスをＡ１に代えてＢ４に変更した事以外は、全て実施例１と同じ条件で水性防錆塗料組成物を調製し、乾燥させて塗膜を形成させた。結果を表２に記載する。比較例４で得られた塗膜は、防錆性、乾燥性が劣る塗膜であった。
[Comparative Example 4]
A water-based anticorrosive coating composition was prepared under the same conditions as in Example 1 except that the copolymer latex for water-based anticorrosive coating was changed to B4 instead of A1, and a coating film was formed by drying. The results are listed in Table 2. The coating film obtained in Comparative Example 4 was a coating film with poor rust prevention and drying properties.
本発明の水性防錆塗料用共重合体ラテックスは、防錆性、基材との密着性等に優れた水性防錆塗料を実現し得るので、産業の各分野において、高い利用可能性を有する。 The copolymer latex for aqueous rust preventive paint of the present invention can realize an aqueous rust preventive paint excellent in rust prevention, adhesion to a substrate, etc., and thus has high applicability in various industrial fields. .
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