CN113136048A - 一种可激光打标的无机阻燃剂及其制备方法 - Google Patents
一种可激光打标的无机阻燃剂及其制备方法 Download PDFInfo
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- 239000012796 inorganic flame retardant Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000010330 laser marking Methods 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 13
- 239000000347 magnesium hydroxide Substances 0.000 claims description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
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- 150000003839 salts Chemical class 0.000 claims description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- HRQDCDQDOPSGBR-UHFFFAOYSA-M sodium;octane-1-sulfonate Chemical compound [Na+].CCCCCCCCS([O-])(=O)=O HRQDCDQDOPSGBR-UHFFFAOYSA-M 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
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- 229940114930 potassium stearate Drugs 0.000 claims description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 2
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
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- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
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- 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 14
- 239000003063 flame retardant Substances 0.000 description 14
- 239000003550 marker Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
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- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000001119 stannous chloride Substances 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 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 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
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- 238000005562 fading Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
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- 239000011342 resin composition Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910001607 magnesium mineral Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
本发明提供了一种可激光打标的无机阻燃剂及其制备方法,其各组分及其无机阻燃剂粉体为90~97%,激光打标助剂为2~10%,分散剂0.5~3%。其制备步骤分为:(1)先将水、无机阻燃剂、表面活性剂混合均匀,形成无机阻燃剂的水相分散液。其中无机阻燃剂的中位径为1~100μm,所述表面活性剂的添加量与无机阻燃剂的质量比为0.5:100~5:100;(2)在上述无机阻燃剂水相分散液中加入含有锡盐的溶液,边搅拌边滴加浓氨水进行反应,在无机阻燃剂表面形成胶状沉淀,将所述的分散液干燥、研磨、即得可用于激光打标的无机阻燃剂。上述制备方法具有反应平稳、操作简单、条件易控等优点,所制备的可激光打标无机阻燃剂经试验验证在浅色塑料表面能够形成清晰的对比强烈的标识,且不会导致塑料受热降解、印迹平整清晰、不掉色、不褪色,综合物理性能优异。
Description
技术领域
本发明涉及一种塑料制造的无机阻燃剂,特别是涉及一种用于激光打标的助剂及其制备方法。
背景技术
激光打标具有灵活、快速、高效、非接触等优点,广泛应用于产品生产日期、使用日期、条形码、产品批号等标记打码,尤其是在非平面也可以高速、清晰的成型。对于激光打码最基本的要求激光打码后在材料表面产生足够清晰的印迹,且经久耐磨。许多塑料如聚烯烃和聚苯乙烯由于其本身透明,大部分的激光能量直接通过穿过塑料本身而不会引起任何反应,在塑料表面不能形成肉眼可见的标记,即便采用非常高功率的激光输出也很难形成比较明显、肉眼可辨识的印迹。ABS、HIPS等不透明的材料在激光入射时能够吸收足够的能量,即便是非常小的激光输出功率也会造成塑料降解,激光打标后印迹边缘毛糙、模糊,也很难得到清晰的标识。要使塑料具有较好的激光吸收能力,且在受激光照射时能够形成边缘平滑、标识清晰、能够长久保持的标识,通常是在塑料树脂基体中添加激光打标助剂。
目前,对于白色或者浅色塑料主要是利用激光器产生的能量使塑料表面产生炭化变色形成颜色较深的打标印迹。对于深色塑料则需在黑色或者深色表面产生白色或者接近白色的效果,且要印迹清晰。一种由丙烯酸系树脂和苯乙烯系树脂与黑色染颜料组成的树脂组合物(特开平11-1596公报号)和一种含有橡胶接枝共聚物和不饱和羧酸烷基酯共聚物和乙烯系共聚物以及炭黑组成的树脂组合物(特开平2000-198903号公报)是采用不同树脂作为载体添加黑色颜染料作为打标助剂,此种类型的激光打标剂有效成分含量低,载体树脂需根据树脂基体进行调整,否则会因载体树脂与基体树脂相容性问题,对材料最终物理性能造成影响,此种类型的激光打标剂普适性不佳。
对于激光打标助剂,为了配方简单化,希望打标助剂在具备可激光打标特性的同时也具有相应的阻燃性能。公开号CN 1010851350(申请号:200910057004)报道了一种塑料用打标助剂及其制备方法则是采用氢氧化物、碳酸钙、溴系阻燃剂、氧化锡、金属锑、分散剂等进行简单的物理混合,添加到ABS中起到可激光打标的作用。此种类型的激光打标剂主要是靠金属氧化物催化溴系阻燃剂在ABS中略微成炭,从而具有一定的显色效果,但随着环保要求越来越高,含卤素阻燃剂的材料应用领域越来越受到限制,且此种采用简单物理混合,起显色作用的有效成分较少,若需达到较为清晰的打标效果添加量较大,对从材料物理综合性能影响大。添加含磷阻燃剂、氮磷系阻燃剂、无机填充阻燃剂等,再辅助添加激光打标剂的方式制备的可激光打标阻燃复合材料存在痕迹不明显,甚至肉眼难以明显辨别,痕迹边缘毛糙、使用过程容易褪色等问题。公开号CN 107033586(申请号:201610931215.4)报道了一种可激光标记的无卤阻燃导热复合材料及其制备方法和应用,其是采用基础树脂、导热阻燃剂、激光打标剂、玻璃纤维、润滑剂抗氧剂和偶联剂等组成,其中导热阻燃剂为氢氧化镁、激光打标剂为硫酸钡、钛白粉、硅酸钙、三氧化二锑、滑石粉等至少三种组成。此种复合材料中的导热阻燃剂和激光打标剂采用简单的物理混合,容易计量不准且分散不均的问题,影响最终的材料助剂的有效均匀分布,难以实现塑料中较好的激光打标时的显色效果,且激光打标剂全部为色泽较白粉体如钛白粉、硫酸钡,难以实现浅色复合材料上显现黑色标记或出现标识不清等问题。
因此,针对上述目前业内在激光打标领域所遇到的问题,本发明采用环保的无机阻燃剂为载体将激光打标剂沉积在其表面,一方面不同于采用简单的物理混合的激光打标助剂,不会存在使用时出现计量偏差,影响后续打标效果的缺点;另一方面避免了常规激光打标复合材料中外加氮磷系阻燃剂、氮系阻燃剂等再复合激光打标助剂,存在的打标痕迹不明显、标识难辨识、标识边缘粗糙使用过程中易褪色等问题。本发明制备的激光打标剂可实现在浅色塑料表面形成清晰对比强烈的标识,且具备不会导致塑料受热降解、印迹平整清晰、不掉色、不褪色等特性。
发明内容
本发明的目的在于克服现有技术中所存在的以某些树脂作为激光打标剂载体或者采用简单物理混合制备激光打标剂对树脂性能影响明显等问题。本发明提供一种可激光打标无机阻燃剂,将其添加在塑料中,可以通过激光打标在塑料制品表面形成对比明显的印迹,且边缘光滑,长久使用不褪色。
一种可激光打标的无机阻燃剂及其制备方法,其各组分及其无机阻燃剂粉体为90~97%,激光打标助剂为2~10%,分散剂0.5~3%。,其方法包括以下步骤:
(1)将水、无机阻燃剂、表面活性剂混合均匀,形成含有无机阻燃剂的水相分散液;
(2)将含有锡盐的溶液加入上述水相分散液中,然后一边搅拌一边滴加浓氨水,充分反应后在无机阻燃剂表面形成胶状沉淀,将上述得到的分散液进行抽滤、洗涤、干燥和研磨处理,即得可用于激光打标的无机阻燃剂;
其中,所述的浓氨水溶液在0℃~40℃边搅拌边在0.5h~3h内匀速滴加到锡盐溶液中,含有锡盐的溶液和浓氨水在80℃~100℃加热搅拌2h~6h。
所述的无机阻燃剂的中位径为1~100μm,表面活性剂与无机阻燃剂的质量比为0.5:100~5:100,无机阻燃剂与水的质量比为1:1~1:10,优选1:2~1:5。
所述的无机阻燃剂为氢氧化镁或氢氧化铝中的一种或两种,其中氢氧化镁可以为合成法的氢氧化镁和矿物法的氢氧化镁。
所述的表面活性剂为为硬脂酸、硬质酸钠、硬脂酸钾、十二烷基磺酸钠、辛烷基磺酸钠、对十二烷基苯磺酸钠中的一种或几种,优选十二烷基磺酸钠、辛烷基磺酸钠。
所述的的锡盐为可溶性四价锡盐和二价亚锡盐,优选五水合四氯化锡、氯化亚锡。
所述的锡盐的溶液的溶剂为甲醇、乙醇、异丙醇、乙二醇中的一种或几种,优选乙醇、异丙醇。
所述的浓氨水质量百分数为18%~28%的氨水,锡盐与浓氨水的质量比为1:2~1:10,浓氨水过量有利于溶液中的锡盐完全反应生成氢氧化锡沉淀。
本发明的优点在于:
(1)选用水相作为反应介质,反应平稳;
(2)相比于选用树脂作为载体或者与其他组分,有效成分更高,对复合材料的物理性能影响小;
(3)材料不含有卤素和重金属,符合环保要求;
(4)材料颜色为白色,适用于白色、蓝色、黑色等不同颜色要求的树脂基体中,在激光打标时能够形成非常鲜明的对比标识,辨识度高,印迹边缘平整、长期使用不变色、不褪色,具有广泛的应用领域。
具体实施方式
结合具体实施方式对本发明做进一步说明,但本发明的实施方式不局限于此。
实施例1
在1000ml三口烧瓶中添加500g去离子水,添加矿物法氢氧化镁(中位径为5~7μm)200g,十二烷基磺酸钠1.0g,五水合四氯化锡20g,在30℃条件下搅拌0.5h使其搅拌和分散均匀,滴加浓度为18%的浓氨水60ml,待滴加完毕后升温至80℃搅拌4h,用布氏漏斗将混合物过滤,并用去离子水洗涤至滤液用硝酸银溶液测试无白色沉淀为止,将粉体置于鼓风干燥箱100℃烘干5h,收集备用。
实施例2
在1000ml三口烧瓶中添加500g去离子水,添加矿物法氢氧化镁(中位径为5~7μm)200g,硬脂酸钠2.0g,五水合四氯化锡15g,在30℃条件下搅拌0.5h使其搅拌和分散均匀,滴加浓度为22%的浓氨水60ml,待滴加完毕后升温至80℃搅拌4h,用布氏漏斗将混合物过滤,并用去离子水洗涤至滤液用硝酸银溶液测试无白色沉淀为止,将粉体置于鼓风干燥箱100℃烘干5h,收集备用。
实施例3
在10000ml三口烧瓶中添加800g去离子水,添加矿物法氢氧化镁(中位径为15~22μm)500g,新烷基磺酸钠15.0g,氯化亚锡30g,在25℃条件下搅拌1.5h使其搅拌和分散均匀,滴加浓度为28%的浓氨水240ml,待滴加完毕后升温至80℃搅拌5h,用布氏漏斗将混合物过滤,并用去离子水洗涤至滤液用硝酸银溶液测试无白色沉淀为止,将粉体置于鼓风干燥箱120℃烘干5h,收集备用。
实施例4
在20000ml三口烧瓶中添加1200g去离子水,添加矿物法氢氧化镁(中位径为50~60μm)800g,十二烷基苯磺酸钠15.0g,五水合四氯化锡20g,在25℃条件下搅拌2.0h使其搅拌和分散均匀,滴加浓度为25%的浓氨水300ml,待滴加完毕后升温至80℃搅拌4h,用布氏漏斗将混合物过滤,并用去离子水洗涤至滤液用硝酸银溶液测试无白色沉淀为止,将粉体置于鼓风干燥箱120℃烘干5h,收集备用。
实施例5
在20000ml三口烧瓶中添加1200g去离子水,添加合成法氢氧化镁(中位径为15~22μm)800g,十二烷基苯磺酸钠15.0g,五水合四氯化锡20g,在25℃条件下搅拌2.0h使其搅拌和分散均匀,滴加浓度为20%的浓氨水300ml,待滴加完毕后升温至80℃搅拌4h,用布氏漏斗将混合物过滤,并用去离子水洗涤至滤液用硝酸银溶液测试无白色沉淀为止,将粉体置于鼓风干燥箱120℃烘干5h,收集备用。
实施例6
在10000ml三口烧瓶中添加800g去离子水,添加合成法氢氧化镁(中位径为50~60μm)500g,十二烷基苯磺酸钠10.0g,氯化亚锡30g,在25℃条件下搅拌1.5h使其搅拌和分散均匀,滴加浓度为22%的浓氨水240ml,待滴加完毕后升温至80℃搅拌5h,用布氏漏斗将混合物过滤,并用去离子水洗涤至滤液用硝酸银溶液测试无白色沉淀为止,将粉体置于鼓风干燥箱120℃烘干5h,收集备用。
对比例
选用矿物发氢氧化镁(中位径为15~22μm)500g,新烷基磺酸钠10.0g,氯化亚锡30g,在25℃条件下用高速分散机1500r/min搅拌1.5h使粉体得到充分搅拌并分散均匀,将粉体置于鼓风干燥箱120℃烘干5h,收集备用。
实施例和对比例的激光标记性能对比表
上述实施例激光标记是采用光纤激光打标机实现的,从表中可知:通过上述实施例方法制备的可激光打标无机阻燃剂添加在塑料基体中通过激光打标方式可实现塑料制件清晰标识,同时上述实施例的制备方法,明显有别于对比例的简单混合所制备材料在复合材料中激光打标后标识模糊、难以区分。
上述实施例仅表达了本发明的几个实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明的专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可做出若干的变形和改进,这些都属于本发明的保护范围。
Claims (7)
1.一种可激光打标的无机阻燃剂及其制备方法,其各组分及其无机阻燃剂粉体为90~97%,激光打标助剂为2~10%,分散剂0.5~3%。,其方法包括以下步骤:
(1)将水、无机阻燃剂、表面活性剂混合均匀,形成含有无机阻燃剂的水相分散液;
(2)将含有锡盐的溶液加入上述水相分散液中,然后一边搅拌一边滴加浓氨水,充分反应后在无机阻燃剂表面形成胶状沉淀,将上述得到的分散液进行抽滤、洗涤、干燥和研磨处理,即得可用于激光打标的无机阻燃剂。
2.根据权利要求1所述的方法,其特征在于,所述的无机阻燃剂的中位径为1~100μm,表面活性剂与无机阻燃剂的质量比为0.5:100~5:100,无机阻燃剂与水的质量比为1:1~1:10。
3.根据权利要求1所述的方法,其特征在于,所述的无机阻燃剂为氢氧化镁或氢氧化铝中的一种或两种。
4.根据权利要求1所述的方法,其特征在于,所述的表面活性剂为硬脂酸、硬质酸钠、硬脂酸钾、十二烷基磺酸钠、辛烷基磺酸钠、对十二烷基苯磺酸钠中的一种或几种。
5.根据权利要求1所述的方法,其特征在于,所述的锡盐为可溶性四价锡盐和二价亚锡盐。
6.根据权利要求1所述的方法,其特征在于,所述的浓氨水的浓度为18%~28%。
7.根据权利要求1所述的方法,其特征在于,所述的锡盐溶液的溶剂为甲醇、乙醇、异丙醇、乙二醇中的一种或几种。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101108743A (zh) * | 2006-07-19 | 2008-01-23 | 中南大学 | 一种制备纳米二氧化锡的方法 |
CN101851350A (zh) * | 2009-03-31 | 2010-10-06 | 上海金发科技发展有限公司 | 一种塑料用激光标记助剂及其制备方法 |
CN105330898A (zh) * | 2015-12-08 | 2016-02-17 | 四川大学 | 一种激光标记添加剂及其制备方法与应用 |
CN106750547A (zh) * | 2016-12-29 | 2017-05-31 | 广东宇星阻燃新材股份有限公司 | 一种高效氢氧化铝阻燃剂及其在聚烯烃中的应用 |
CN109517220A (zh) * | 2018-11-13 | 2019-03-26 | 云南锡业集团(控股)有限责任公司研发中心 | 一种纳米锡基膨胀阻燃剂的制备方法 |
CN110862574A (zh) * | 2019-12-03 | 2020-03-06 | 苏州诺博恩新材料科技有限公司 | 高效抑烟的氢氧化镁/锡类化合物微胶囊阻燃剂及其制备方法 |
CN112210123A (zh) * | 2020-10-22 | 2021-01-12 | 云南锡业集团(控股)有限责任公司研发中心 | 一种低成本包覆式阻燃抑烟剂的制备方法 |
CN112280102A (zh) * | 2020-11-11 | 2021-01-29 | 云南锡业集团(控股)有限责任公司研发中心 | 一种仿生合成技术制备锡基复合阻燃剂的方法 |
-
2021
- 2021-04-08 CN CN202110378780.3A patent/CN113136048A/zh active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101108743A (zh) * | 2006-07-19 | 2008-01-23 | 中南大学 | 一种制备纳米二氧化锡的方法 |
CN101851350A (zh) * | 2009-03-31 | 2010-10-06 | 上海金发科技发展有限公司 | 一种塑料用激光标记助剂及其制备方法 |
CN105330898A (zh) * | 2015-12-08 | 2016-02-17 | 四川大学 | 一种激光标记添加剂及其制备方法与应用 |
CN106750547A (zh) * | 2016-12-29 | 2017-05-31 | 广东宇星阻燃新材股份有限公司 | 一种高效氢氧化铝阻燃剂及其在聚烯烃中的应用 |
CN109517220A (zh) * | 2018-11-13 | 2019-03-26 | 云南锡业集团(控股)有限责任公司研发中心 | 一种纳米锡基膨胀阻燃剂的制备方法 |
CN110862574A (zh) * | 2019-12-03 | 2020-03-06 | 苏州诺博恩新材料科技有限公司 | 高效抑烟的氢氧化镁/锡类化合物微胶囊阻燃剂及其制备方法 |
CN112210123A (zh) * | 2020-10-22 | 2021-01-12 | 云南锡业集团(控股)有限责任公司研发中心 | 一种低成本包覆式阻燃抑烟剂的制备方法 |
CN112280102A (zh) * | 2020-11-11 | 2021-01-29 | 云南锡业集团(控股)有限责任公司研发中心 | 一种仿生合成技术制备锡基复合阻燃剂的方法 |
Non-Patent Citations (1)
Title |
---|
杨玲: "羟基锡酸锌包覆氢氧化镁对软质PVC燃烧性能的影响", 《消防科学与技术》 * |
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