CN108727930A - 一种铝合金表面涂装前处理液 - Google Patents
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 64
- 239000007788 liquid Substances 0.000 title claims abstract description 37
- 238000000576 coating method Methods 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 24
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 21
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 21
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 12
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 238000002604 ultrasonography Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
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- 150000002825 nitriles Chemical class 0.000 claims 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
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- 229960003493 octyltriethoxysilane Drugs 0.000 description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
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- 230000037431 insertion Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 238000002444 silanisation Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/002—Pretreatement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/102—Pretreatment of metallic substrates
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- C09D5/08—Anti-corrosive paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
本发明公开了一种铝合金表面涂装前处理液,属于金属表面加工技术领域。该处理液每100重量份中由下列组分组成:粘结剂50~60份;增强剂3~5份;三乙醇胺4~5份;pH调节剂2~5份;余量为去离子水。所述粘结剂是由甲基丙烯酸甲脂、丙烯酸、丙烯酸丁酯、环氧树脂、引发剂、无水乙醇、正丁醇制得;所述引发剂为过氧化二异丙苯、过氧化二叔丁基、过氧化苯甲酰、偶氮二异丁腈、偶氮二异庚腈中的任一种;所述增强剂是由硅烷偶联剂、无水乙醇、去离子水、pH调节剂制得。本发明铝合金表面涂装前处理液与铝合金的结合更好,不易脱落,防腐性能更好,效果更佳。同时本发明不会带来沉渣、含磷及磷化后废水等环境污染问题,环保性能更优。
Description
技术领域
本发明属于金属表面加工技术领域,具体涉及一种铝合金表面涂装前处理液及其制备方法和应用。
背景技术
随着铝材的广泛应用,人们也在不断的对铝材提出更高的要求,不但要求铝材有较高的机械性能,还要求其有良好的外观和耐腐蚀性能,随着镁、锌、铜、铬等元素的加入,使得铝合金抗拉强度有所提升,但其耐蚀性降低。为了弥补铝合金耐蚀的下降,通常通过对铝合金表面进行处理,表面处理的首要问题是要保持铝合金表面光滑,尤其是铝合金表面极其容易形成氧化膜,导致涂膜附着力差,易气泡、开裂等问题。为了更好地与涂料配套,增强涂膜附着力和耐蚀性,其中磷化工艺可以使铝合金与涂料之间的附着力得到提升。
专利CN101892479A和CN105463432A中都是提出了一种铝合金表面磷化液的制备,但是铝合金表面磷化会带来沉渣、含磷及磷化后废水等环保问题。专利CN103087572A采用松香作为反应原料,与顺丁烯二酸酐以及硅烷反应制得铝合金表面硅烷化处理液,可以在铝合金表面形成较好的保护膜,有效的提高了铝合金的耐腐蚀性能。但是采取松香作为原料,其制备过程中的反应温度较高,达到了160℃,且其制备时间较长,制得的处理液不易保存,容易硬化。专利CN104278260A是将部分水解的硅烷、有机成膜剂、金属螯合物、长链醇和无机金属化合物粉末在一定条件下进行反应制得铝合金表面硅烷处理液。制备处理的条件相对简便,处理方法对相对简单。但是其处理液的主要混合方法就是简单的机械搅拌,并且其采用了金属化合物粉末增加其性能,在机械搅拌的过程中很难达到混合得非常均匀,不利于成膜的平展性。
发明内容
为克服现有技术的不足,本发明的目的是提供一种铝合金表面涂装前处理液,以期该铝合金表面涂装前处理液与铝合金结合紧密,不易脱落,防腐性能更好,环保性能更优。
本发明是通过以下技术方案予以实现的。
一种铝合金表面涂装前处理液,每100重量份处液中由下列组分组成:粘结剂50~60份;增强剂3~5份;三乙醇胺4~5份;pH调节剂2~5份;余量为去离子水。
所述粘结剂是由甲基丙烯酸甲脂、丙烯酸、丙烯酸丁酯、环氧树脂、引发剂、无水乙醇、正丁醇制得;所述引发剂为过氧化二异丙苯、过氧化二叔丁基、过氧化苯甲酰、偶氮二异丁腈、偶氮二异庚腈中的任意一种。
所述增强剂是由硅烷偶联剂、无水乙醇、去离子水、pH调节剂制得。
所述粘结剂的制备方法如下:
(a)称取15~25重量份甲基丙烯酸甲酯、20~35重量份丙烯酸丁酯、2~6重量份丙烯酸、0.5~2重量份引发剂、20~30重量份正丁醇与无水乙醇的混合物、2~4重量份环氧树酯;
(b)将上述甲基丙烯酸甲酯、丙烯酸丁酯、引发剂混合,搅拌均匀;
(c)在装有冷凝管、恒压滴液漏斗、温度计的三口烧瓶中加入正丁醇与无水乙醇的混合物、环氧树酯,用磁力搅拌器加热搅拌至溶解,升温至110℃,溶剂开始回流;保持温度110℃,将步骤b中的混合液加入到恒压滴液漏斗中,缓慢滴加混合液,滴加完成后继续保温110℃,反应3h,出料制得粘结剂。
所述增强剂的制备方法如下:
(a)将硅烷偶联剂、无水乙醇和去离子水按1∶7∶12比例混合;
(b)再用pH调节剂调节pH至4.5-5.0,放入80℃恒温水浴锅中水解24h,出料,得到增强剂。
所述硅烷偶联剂为氨丙基三乙氧基硅烷、2-氨乙基-氨丙基三甲基氧基硅烷、乙烯基三甲氧基硅烷、乙烯基-三(2-甲氧基乙氧基)硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、甲基三甲氧基硅烷、辛基三乙氧基硅烷中的一种或几种。
本发明同时提供了上述铝合金表面涂装前处理液的制备方法,包括如下步骤:将粘结剂和增强剂混合后,加入三乙醇胺,用磁力搅拌器进行搅拌10min,并用去离子水稀释,pH调节剂调节pH值至7~8,制得铝合金表面涂装前处理液。
本发明同时提供了上述铝合金表面涂装前处理液的应用,包括如下步骤:
(a)先采用800目金相砂纸对铝合金表面进行打磨,再将铝合金片放入丙酮中超声清洗,15min后取出,并用去离子水冲洗表面,置于7%氢氧化钠中浸蚀除去铝合金表面的氧化膜和油渍,立即用去离子水清洗;
(b)在表面处理完成的铝合金表面涂覆铝合金表面涂装前处理液,自然风干。
本发明科学原理:
本发明铝合金表面涂装前处理液中添加了丙烯酸环氧树脂,使硅烷偶联剂水解后生成的硅醇与丙烯酸环氧树脂部分交联,使处理液在铝合金表面成膜效果更佳,并可以使铝合金表面和涂层之间生成化学键合。同时本发明中加入了三乙醇胺,使铝合金表面发生钝化,起到微蚀作用,在铝合金表面形成小凹槽,增大了涂料与铝合金之间的接触面积,使涂层“嵌入”铝合金中,有效的防止了涂层的脱落。
与现有技术相比,本发明具有以下技术效果:
1、本发明铝合金表面涂装前处理液与铝合金的结合更好,不易脱落,防腐性能更好,效果更佳。
2、本发明不会带来沉渣、含磷及磷化后废水等环境污染问题,环保性能更优。
具体实施方式
以下结合具体实施例详述本发明,但本发明不局限于下述实施例。
实施例1
一种铝合金表面涂装前处理液,每100重量份处液中由下列组分组成:粘结剂50份;增强剂3份;三乙醇胺4份;pH调节剂2份;余量为去离子水;其制备方法将粘结剂和增强剂混合后,加入三乙醇胺,用磁力搅拌器进行搅拌10min,并用去离子水稀释,pH调节剂调节pH值至7~8,制得铝合金表面涂装前处理液。并将其应用于铝合金表面:先采用800目金相砂纸对铝合金表面进行打磨,再将铝合金片放入丙酮中超声清洗,15min后取出,并用去离子水冲洗表面,置于7%氢氧化钠中浸蚀除去铝合金表面的氧化膜和油渍立即用去离子水清洗;在表面处理完成的铝合金表面涂覆铝合金表面涂装处理液,自然风干。
其中所述粘结剂是由:15重量份甲基丙烯酸甲酯、20重量份丙烯酸丁酯、2重量份丙烯酸、0.5重量份过氧化二异丙苯、20重量份正丁醇与无水乙醇的混合物、2重量份环氧树酯制备而成;制备方法如下:
(a)称取甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、0.5份引发剂、20份正丁醇与无水乙醇的混合物、2份环氧树酯;
(b)将上述甲基丙烯酸甲酯、丙烯酸丁酯、引发剂混合,搅拌均匀;
(c)在装有冷凝管、恒压滴液漏斗、温度计的三口烧瓶中加入正丁醇与无水乙醇的混合物、环氧树酯,用磁力搅拌器加热搅拌至溶解,升温至110℃,溶剂开始回流;保持温度110℃,将步骤b中的混合液加入到恒压滴液漏斗中,缓慢滴加混合液,滴加完成后继续保温110℃,反应3h,出料制得粘结剂。
所述增强剂是通过将氨丙基三乙氧基硅烷、无水乙醇和去离子水按1∶7∶12比例混合;再用pH调节剂调节pH至4.5-5.0,放入80℃恒温水浴锅中水解24h,出料制得。
实施例2
一种铝合金表面涂装前处理液,每100重量份处液中由下列组分组成成:粘结剂60份;增强剂5份;三乙醇胺5份;pH调节剂5份;余量为去离子水。
所述粘结剂是由:25重量份甲基丙烯酸甲酯、35重量份丙烯酸丁酯、6重量份丙烯酸、2重量份过氧化二叔丁基、30重量份正丁醇与无水乙醇的混合物、4重量份环氧树酯制备而成;所述增强剂是通过将2-氨乙基-氨丙基三甲基氧基硅烷、无水乙醇和去离子水按1∶7∶12比例混合;再用pH调节剂调节pH至4.5-5.0,放入80℃恒温水浴锅中水解24h,出料制得。
其余方法步骤同实施例1。
实施例3
一种铝合金表面涂装前处理液,每100重量份处液中由下列组分组成成:粘结剂55份;增强剂4份;三乙醇胺4.5份;pH调节剂3份;余量为去离子水。
所述粘结剂是由:20重量份甲基丙烯酸甲酯、28重量份丙烯酸丁酯、4重量份丙烯酸、1.5重量份过氧化苯甲酰、25重量份正丁醇与无水乙醇的混合物、3重量份环氧树酯制备而成;所述增强剂是通过将乙烯基三甲氧基硅烷和乙烯基-三(2-甲氧基乙氧基)硅烷、无水乙醇和去离子水按1∶7∶12比例混合;再用pH调节剂调节pH至4.5-5.0,放入80℃恒温水浴锅中水解24h,出料制得。
其余方法步骤同实施例1。
实施例4
一种铝合金表面涂装前处理液,每100重量份处液中由下列组分组成成:粘结剂55份;增强剂4份;三乙醇胺4.5份;pH调节剂3份;余量为去离子水。
所述粘结剂是由:20重量份甲基丙烯酸甲酯、28重量份丙烯酸丁酯、4重量份丙烯酸、1.5重量份偶氮二异丁腈、25重量份正丁醇与无水乙醇的混合物、3重量份环氧树酯制备而成;所述增强剂是通过将甲基丙烯酰氧基丙基三甲氧基硅烷、无水乙醇和去离子水按1∶7∶12比例混合;再用pH调节剂调节pH至4.5-5.0,放入80℃恒温水浴锅中水解24h,出料制得。
其余方法步骤同实施例1。
实施例5
一种铝合金表面涂装前处理液,每100重量份处液中由下列组分组成成:粘结剂55份;增强剂4份;三乙醇胺4.5份;pH调节剂3份;余量为去离子水。
所述粘结剂是由:20重量份甲基丙烯酸甲酯、28重量份丙烯酸丁酯、4重量份丙烯酸、1.5重量份偶氮二异庚腈、25重量份正丁醇与无水乙醇的混合物、3重量份环氧树酯制备而成;所述增强剂是通过将甲基三甲氧基硅烷和辛基三乙氧基硅烷、无水乙醇和去离子水按1∶7∶12比例混合;再用pH调节剂调节pH至4.5-5.0,放入80℃恒温水浴锅中水解24h,出料制得。
其余方法步骤同实施例1。
将上述5个实施例处理过的铝合金样品按照GB/T10125-1997标准在盐雾试验机中进行实验:
盐雾实验条件:连续300小时,氢氧化钠质量浓度5%,盐水pH值6.9,喷雾量为2ml/H,测试时间300小时,气压120Kpa,压力桶温度37℃,室内温度25℃,工作放置角度15°,盐水桶温度35℃。实验结果显示:5个实施例样品,涂层附着力均为1级,且300小时后样品表面无明显变化。
Claims (6)
1.一种铝合金表面涂装前处理液,其特征在于,每100重量份处液中由下列组分组成:粘结剂50~60份;增强剂3~5份;三乙醇胺4~5份;pH调节剂2~5份;余量为去离子水;
所述粘结剂是由甲基丙烯酸甲脂、丙烯酸、丙烯酸丁酯、环氧树脂、引发剂、无水乙醇、正丁醇制得;所述引发剂为过氧化二异丙苯、过氧化二叔丁基、过氧化苯甲酰、偶氮二异丁腈、偶氮二异庚腈中的任意一种;
所述增强剂是由硅烷偶联剂、无水乙醇、去离子水、pH调节剂制得。
2.根据权利要求1所述的铝合金表面涂装前处理液,其特征在于,所述粘结剂是通过以下步骤予以制备的:
(a)称取15~25重量份甲基丙烯酸甲酯、20~35重量份丙烯酸丁酯、2~6重量份丙烯酸、0.5~2重量份引发剂、20~30重量份正丁醇与无水乙醇的混合物、2~4重量份环氧树酯;
(b)将上述甲基丙烯酸甲酯、丙烯酸丁酯、引发剂混合,搅拌均匀;
(c)在装有冷凝管、恒压滴液漏斗、温度计的三口烧瓶中加入正丁醇与无水乙醇的混合物、环氧树酯,用磁力搅拌器加热搅拌至溶解,升温至110℃,溶剂开始回流;保持温度110℃,将步骤b中的混合液加入到恒压滴液漏斗中,缓慢滴加混合液,滴加完成后继续保温110℃,反应3h,出料制得粘结剂。
3.根据权利要求1所述的铝合金表面涂装前处理液,其特征在于,所述增强剂是通过以下步骤予以制备的:
(a)将硅烷偶联剂、无水乙醇和去离子水按1∶7∶12比例混合;
(b)再用pH调节剂调节pH至4.5-5.0,放入80℃恒温水浴锅中水解24h,出料,得到增强剂。
4.根据权利要求3所述的铝合金表面涂装前处理液,其特征在于,所述硅烷偶联剂为氨丙基三乙氧基硅烷、2-氨乙基-氨丙基三甲基氧基硅烷、乙烯基三甲氧基硅烷、乙烯基-三(2-甲氧基乙氧基)硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、甲基三甲氧基硅烷、辛基三乙氧基硅烷中的一种或几种。
5.如权利要求1所述的铝合金表面涂装前处理液的制备方法,其特征在于包括如下步骤:将粘结剂和增强剂混合后,加入三乙醇胺,用磁力搅拌器进行搅拌10min,并用去离子水稀释,pH调节剂调节pH值至7~8,制得铝合金表面涂装前处理液。
6.根据权利要求1所述的铝合金表面涂装前处理液的应用,其特征在于包括如下步骤:
(a)先采用800目金相砂纸对铝合金表面进行打磨,再将铝合金片放入丙酮中超声清洗,15min后取出,并用去离子水冲洗表面,置于7%氢氧化钠中浸蚀除去铝合金表面的氧化膜和油渍,立即用去离子水清洗;
(b)在表面处理完成的铝合金表面涂覆铝合金表面涂装前处理液,自然风干。
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Effective date of registration: 20210202 Address after: 243000 Ma'anshan industrial transfer demonstration park, Ma'anshan City, Anhui Province Patentee after: Anhui Jingtian New Energy Technology Co.,Ltd. Address before: 243002 No. 59 East Lake Road, Anhui, Ma'anshan Patentee before: ANHUI University OF TECHNOLOGY |
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CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200728 |