CN102585579B - Metal powder directional resin composition - Google Patents

Metal powder directional resin composition Download PDF

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CN102585579B
CN102585579B CN 201210028720 CN201210028720A CN102585579B CN 102585579 B CN102585579 B CN 102585579B CN 201210028720 CN201210028720 CN 201210028720 CN 201210028720 A CN201210028720 A CN 201210028720A CN 102585579 B CN102585579 B CN 102585579B
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acrylate
meth
monomer
metal powder
glass transition
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CN 201210028720
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CN102585579A (en )
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萧伯卓
萧裕霖
吴兼昇
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长兴化学工业股份有限公司
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Abstract

本发明提供一种金属粉定向树脂组合物,其包含聚合物和溶剂,该聚合物包含以下单体作为聚合单元:(a)甲基丙烯酸甲酯单体;(b)高玻璃化转变温度的单体;及(c)低玻璃化转变温度的单体,其中该聚合物的重均分子量为至少约50,000。 The present invention provides a metal powder is oriented resin composition comprising a polymer and a solvent, the polymer comprises as polymerized units: (a) methyl methacrylate monomer; (b) high glass transition temperature monomer; and (c) a low glass transition temperature of the monomers, wherein said polymer has a weight average molecular weight of at least about 50,000. 本发明的金属粉定向树脂组合物,对于金属粉的定向排列有显著的效果,可用于金属涂料中,具有良好的耐水性和耐醇性,同时与其它树脂兼容性佳,可以体现更高的亮度和金属镜面效果。 Metal powder is oriented resin composition of the present invention, for the alignment of the metal powder has a significant effect, be used for metal coatings, having good water resistance and alcohol resistance, and good compatibility with other resins, may be embodied higher brightness and metallic mirror effect.

Description

金属粉定向树脂组合物 Metal powder is oriented resin composition

技术领域 FIELD

[0001] 本发明涉及一种金属粉定向树脂组合物,尤指一种可用于金属涂料组合物中的金属粉定向树脂组合物。 [0001] The present invention relates to a metal powder is oriented resin composition, particularly to a metal powder for metal coating composition directional resin composition.

背景技术 Background technique

[0002] 汽车的金属抛光通常经由磷酸锌等预处理钢片,然后用金属涂料涂布,接着以湿压湿(wet-on-wet)方式在上面涂布透明涂料,然后一起烘烤此二涂层来形成。 Metal polishing [0002] The vehicle typically via zinc phosphate pretreated steel, and then coated with a metal coating, followed by wet-on-wet (wet-on-wet) manner on top clear coating, and then baked together these two coating layer is formed.

[0003] 已知的金属涂料,例如金属漆或亦称银粉漆,是指掺杂铝粉末后的涂料,用以使涂装后的车体或3C电子产品表面具有明亮度,且在不同的角度下,可因光线的反射,使车体或3C电子产品颜色外观看起来层次更丰富,色泽更饱满。 [0003] Known metallic paint, for example, also known as silver paint or metallic paint, the coating means the doped aluminum powder to the vehicle body after coating or surface 3C electronic products having brightness, and at different at an angle, it may be due to the reflection of light, or the vehicle body 3C electronic products color appearance looks level richer, more full color. 然而,一般金属漆或银粉漆所使用的铝粉,结构为片状,在漆中呈不规则排列,因此光线在金属漆中的反射路径不同,造成光线散射,故视觉效果不佳。 However, aluminum or silver metallic paint typically used in paint, a sheet-like structure, irregularly arranged in the paint, and therefore reflects the light path in the metallic paints, resulting in scattering of light, so that the visual effect is poor. 为得到较佳的反射效果一般会添加金属粉定向剂,促进铝粉漂浮到涂层表面,且让银粉规则排列,提高表面光滑性,从而增加表面亮度和光泽度。 In order to obtain the reflection effect is generally preferred metal powder is added directing agent, leafing to facilitate the coating surface, and are regularly arranged so that silver, to improve surface smoothness, thereby increasing the surface brightness and gloss. 目前业界,多以添加硝化纤维素、氯醋或醋酸丁酸纤维素于金属漆涂料中以促进金属漆中铝粉的定向。 The industry, to add multiple nitrocellulose, cellulose acetate butyrate or acetate-chloro-metallic paint coating in order to promote oriented metallic aluminum powder paint. 但是,硝化纤维素耐候不佳,易使所产生的金属涂层黄化;氯醋含氯有环保问题;而醋酸丁酸纤维素有使涂料粘度上升、层间粘着不佳、耐溶剂性不佳及价格昂贵等问题。 However, poor weather nitrocellulose, easy to make the metal coating layer resulting yellow; vinegar chloride with a chlorine-containing environmental problems; cellulose acetate butyrate and the paint has increased viscosity, poor interlayer adhesion, solvent resistance is not good and expensive issues.

发明内容 SUMMARY

[0004] 有鉴于此,本发明提供一种金属粉定向树脂组合物,有优异的金属粉定向排列效果,其耐溶剂性与耐候性佳且具有良好的层间粘着,故可解决醋酸丁酸纤维素耐溶剂性与层间粘着不佳等问题,又无硝化纤维素有耐候性不佳及氯醋树脂含卤素的问题。 [0004] Accordingly, the present invention provides a resin composition for oriented metal powder, metal powder has excellent alignment effect, solvent resistance and weather resistance and having good interlayer adhesion, it is solved acetate butyrate cellulose solvent resistance and inter layer adhesion in such problems, nor nitrocellulose and have poor weatherability vinegar chloride resin containing a halogen problems.

[0005]本发明主要目的在于提供一种金属粉定向树脂组合物,其包含聚合物和溶剂,该聚合物包含以下单体作为聚合单元:(a)甲基丙烯酸甲酯单体;(b)高玻璃化转变温度的单体;及(c)低玻璃化转变温度的单体,其中该聚合物的重均分子量为至少约50, 000。 [0005] The main object of the present invention to provide a metal powder is oriented resin composition comprising a polymer and a solvent, the polymer comprises as polymerized units: (a) methyl methacrylate monomer; (b) a high glass transition temperature monomer; and (c) a low glass transition temperature of the monomer, wherein the weight average molecular weight of at least about 50, 000.

[0006]本发明另一目的在于提供一种金属涂料组合物,其包含金属粉;粘合剂;稀释剂及如上述的金属粉定向树脂组合物。 [0006] Another object of the present invention is to provide a metal coating composition comprising a metal powder; binder; diluents, and metal powder as described above is oriented resin composition.

[0007]本发明的有益效果是:本发明的金属粉定向树脂组合物可有效促进金属涂料中的金属粉排列,使用本发明金属粉定向树脂组合物的金属涂料,其涂膜具有优异的光泽度,且涂膜硬度高,此外,又具有良好的黏着度、耐水性、耐醇性与层间黏着。 [0007] Advantageous effects of the invention are: metal powder of the present invention is directed to a resin composition effective to promote metal powder are arranged in the metal coating, metal powder of the present invention is directed to a metal coating resin composition, which coating film having excellent gloss degree, and a high coating film hardness, in addition, also has a good degree of adhesion, water resistance, alcohol resistance and inter-layer adhesion.

具体实施方式 detailed description

[0008]本发明的金属粉定向树脂组合物,包含聚合物和溶剂,该聚合物包含以下单体作为聚合单元:(a)甲基丙烯酸甲酯(methylmethacrylatea,MMA)单体;(b)高玻璃化转变温度(Tg)的单体;及(c)低玻璃化转变温度的单体。 [0008] The metal powder of the present invention is directed to a resin composition comprising a polymer and a solvent, the polymer comprises as polymerized units: (a) methyl methacrylate (methylmethacrylatea, MMA) monomer; (b) High single glass transition temperature (Tg); and (c) a low glass transition temperature of the monomers. 一般而言,聚合物的分子量大,于金属涂料中的溶剂挥发时,具有促使金属粉朝同一方向排列的效果,其中该聚合物的重均分子量为至少约50, 000。 Generally the molecular weight of the polymer is large, the solvent in the coating when the metal evaporation, metal powder having a cause an effect in the same direction are arranged, wherein the weight average molecular weight of at least about 50, 000. 若该聚合物分子量小于50, 000,则干燥速度慢,膜收缩力小,定向效果不佳;若其分子量大于150, 000,则流平性不佳,不易施工。 If the molecular weight of the polymer is less than 50, 000, the slow drying, film shrinkage force is small, the effect of poor orientation; if its molecular weight greater than 150, 000, the poor leveling, easy construction. 因此,本发明的金属粉定向树脂组合物的聚合物分子量优选为约50, 000至约150, 000,更佳为约70, 000至约120, 000。 Thus, the metal powder of the present invention is directed to a resin composition polymer molecular weight is preferably about 50,000 to about 150,000, more preferably from about 70, 000 to about 120, 000.

[0009] 本发明所使用的甲基丙烯酸甲酯单体,主要作用为促进溶剂由涂膜中移除,表面干燥能力强,且使涂膜容易收缩又能兼顾流平达到良好的外观与银粉定向效果,当涂膜固化后可增加涂层的硬度与耐溶剂性。 [0009] The methyl methacrylate monomer used in the present invention, the main role is to facilitate removal of the solvent from the coating film strong surface drying capability, and the coating film tends to shrink and take care to achieve good leveling and appearance silver orientation effect, increase when the cured coating film hardness and solvent resistance. 根据本发明,甲基丙烯酸甲酯单体的用量以单体总重量计,为约30重量%至约80重量%,优选为约40重量%至约70重量%。 According to the present invention, the amount of methyl methacrylate monomer to the total weight of the monomers, about 30 wt% to about 80 wt%, preferably from about 40 wt% to about 70 wt%.

[0010] 可用于本发明的"高玻璃化转变温度(Tg)的单体",一般而言是指具有玻璃化转变温度大于约70°C的单体,适用于本发明的高玻璃化转变温度的单体可为玻璃化转变温度大于约70°C的(甲基)丙烯酸酯单体、苯乙烯单体或其混合物,上述(甲基)丙烯酸酯单体例如但不限于:(甲基)丙烯酸异冰片酯单体或(甲基)丙烯酸环己酯单体。 [0010] can be used in "high glass transition temperature (Tg) monomer" of the present invention, generally refers to having a glass transition temperature greater than about 70 ° C monomers useful in the present invention has high glass transition the monomers may be temperature glass transition temperature greater than about 70 ° C of (meth) acrylate monomer, a styrene monomer or a mixture thereof, the (meth) acrylate monomers such as, but not limited to, meth ) acrylate monomer or (meth) acrylate monomers. 根据本发明的一个优选实施方式,高玻璃化转变温度(Tg)的单体可选自,但不限于:(甲基)丙烯酸异冰片酯单体、(甲基)丙烯酸环己酯单体、苯乙烯单体或其组合。 According to a preferred embodiment of the present invention, a high glass transition temperature (Tg) of a monomer selected from, but not limited meth) acrylate monomers, (meth) acrylate monomers, styrene monomer, or a combination thereof. 根据本发明,高玻璃化转变温度的单体的用量,以单体总重量计,为约2重量%至约60重量%,优选为约5重量%至约50重量%。 The amount of the monomers of the high glass transition temperature of the present invention, the total monomer weight, from about 2 wt% to about 60 wt%, preferably from about 5 wt% to about 50 wt%.

[0011] 可用于本发明的"低玻璃化转变温度(Tg)的单体",一般而言是指具有玻璃化转变温度小于约70°C的单体,适用于本发明的低玻璃化转变温度的单体可为玻璃化转变温度小于约70°C的(甲基)丙烯酸酯单体,其例如,但不限于:丙烯酸甲酯(methylacrylate)、 (甲基)丙烯酸乙酯(ethyl(meth)acrylate)、(甲基)丙烯酸丙酯(propyl(meth) acrylate)、(甲基)丙烯酸正丁酯(n-butyl(meth)acrylate)、(甲基)丙烯酸2-乙基己酯(2-ethylhexyl(meth)acrylate)、(甲基)丙烯酸正辛酯(n-octyl(meth)acrylate)、(甲基)丙烯酸己酯(hexyl(meth)acrylate)、(甲基)丙烯酸戊酯(pentyl(meth)acrylate)、 (甲基)丙烯酸庚酯(heptyl(meth)acrylate)、(甲基)丙烯酸异辛酯(isooctyl(meth) acrylate)、(甲基)丙烯酸壬酯(nonyl(meth)acrylate)、(甲基)丙烯酸异丁酯(isobutyl(meth)acrylate)、(甲基)丙烯酸_2_ 丁酯、(甲基 [0011] can be used to "monomer a low glass transition temperature (Tg)" of the present invention, generally refers to having a glass transition temperature of less than about 70 ° C a monomer, a low glass transition useful in the present invention the temperature may be monomers glass transition temperature of less than about 70 ° C of (meth) acrylate monomers, for example, but not limited to: methyl acrylate (methylacrylate), (meth) acrylate, ethyl (ethyl (meth ) acrylate), (meth) acrylate, propyl (propyl (meth) acrylate), (meth) acrylate, n-butyl (n-butyl (meth) acrylate), (meth) acrylate, 2-ethylhexyl acrylate (2 -ethylhexyl (meth) acrylate), (meth) acrylate, n-octyl (n-octyl (meth) acrylate), (meth) acrylate, hexyl (hexyl (meth) acrylate), (meth) acrylate, amyl (pentyl (meth) acrylate), (meth) acrylate, heptyl (heptyl (meth) acrylate), (meth) acrylate, isooctyl (isooctyl (meth) acrylate), (meth) acrylate, nonyl (nonyl (meth) acrylate ), (meth) acrylate, isobutyl (isobutyl (meth) acrylate), (meth) acrylate _2_ butyl (meth 丙烯酸癸酯(decyl(meth) acrylate)、(甲基)丙烯酸异癸酯(isodecyl(meth)acrylate)、(甲基)丙烯酸异三癸酯(isotridecyl(meth)acrylate)、(甲基)丙烯酸节酯(benzyl(meth)acrylate)、(甲基) 丙烯酸月桂酯(dodecyl(meth)acrylate)或其组合。 Acrylate, decyl (decyl (meth) acrylate), (meth) acrylate, isodecyl (isodecyl (meth) acrylate), (meth) acrylate, iso-tridecyl (isotridecyl (meth) acrylate), (meth) acrylic section ester (benzyl (meth) acrylate), (meth) acrylate, lauryl (dodecyl (meth) acrylate), or a combination thereof. 根据本发明的一个优选实施方式,低玻璃化转变温度(Tg)的单体可选自,但不限于:丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基) 丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸异辛酯或其组合。 According to a preferred embodiment of the present invention, a low glass transition temperature (Tg) of a monomer selected from, but not limited to: acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth yl) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl acrylate, or combinations thereof. 根据本发明,低玻璃化转变温度的单体的用量以单体总重量计,为约2重量%至约60 重量%,优选为约5重量%至约50重量%。 According to the present invention, the amount of the monomer of a low glass transition temperature of the total monomer weight, from about 2 wt% to about 60 wt%, preferably from about 5 wt% to about 50 wt%.

[0012] 前述高玻璃化转变温度的单体及低玻璃化转变温度的单体用于调整所产生的金属粉定向树脂组合物的玻璃化转变温度。 [0012] a high glass transition temperature of the monomers and the low glass transition temperature of the metal powder produced by the monomers used to adjust the orientation of the glass transition temperature of the resin composition. 高玻璃化转变温度的单体及低玻璃化转变温度的单体的用量比通常取决于所欲得金属漆涂料的性质需求,可介于约1 : 10至10 : 1之间, 优选介于约1 : 5至5 : 1之间。 Monomers and low glass transition temperature of the monomers higher glass transition temperature than is generally dependent on the nature of the demand with the metallic paint coatings enriching can be between about 1: 10 to 10: 1, preferably between between 1: about 1: 5-5. 本发明的金属粉定向树脂组合物具有约55°C至约135°C 的玻璃化转变温度,优选为具有约70°C至约120°C的玻璃化转变温度。 Metal powder of the present invention is a resin composition having an orientation of about 55 ° C to the glass transition temperature of about to 135 ° C, preferably about 70 ° C and about the glass transition temperature to 120 ° C. 若所产生的金属粉定向树脂组合物的玻璃化转变温度过高,易造成金属粉定向树脂组合物流平性与操作性不佳,且使涂膜过脆并使涂膜对基材粘着下降;而若金属粉定向树脂组合物的玻璃化转变温度过低,易使金属粉定向树脂组合物硬度不足,造成定向效果及耐醇(溶剂)性不佳。 If metal powder produced by orienting the resin composition of the glass transition temperature is too high, the metal powder easy to cause orientation of the resin composition and level of operability poor, and the coating film and the coating film too brittle decreased adhesion to the substrate; If the metal powder and glass oriented resin composition of the transition temperature is too low, easy to make the metal powder is oriented resin composition insufficient hardness, resulting in (solvent) resistance and alcohol resistance orientation effect is poor.

[0013]本发明所使用的溶剂并无特殊限制,为本领域技术人员所熟知的溶剂皆可用于本发明,优选为具沸点约70°c至约200°C的溶剂,其例如但不限于烷烃类、酮类、酯类、芳烃类、醇类、醚醇类或其混合物。 [0013] The solvent used is not particularly limited in the present invention, those skilled in the art used in the present invention Jieke solvent, preferably having a boiling point of about 70 ° c to about the solvent to 200 ° C, such as, but not limited to, alkanes, ketones, esters, aromatic hydrocarbons, alcohols, ethers, alcohols or mixtures thereof.

[0014]适用于本发明的烷烃类溶剂可选自但不限于正己烷、正庚烷、异庚烷或其混合物。 [0014] applicable to the present invention alkane solvent selected from, but not limited to, n-hexane, n-heptane, iso-heptane, or a mixture thereof. 适用于本发明的芳族烃类溶剂可选自但不限于苯、甲苯、二甲苯或其混合物。 Aromatic hydrocarbon solvents useful in the present invention are selected from, but not limited to, benzene, toluene, xylene, or mixtures thereof. 适用于本发明的酮类溶剂可选自但不限于甲基乙基酮(MEK)、丙酮、甲基异丁基酮、环己酮、4-羟基-4-甲基-2-戊酮或其混合物。 Ketone solvents useful in the present invention are selected from, but not limited to, methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone or mixtures thereof. 适用于本发明的酯类溶剂可选自但不限于乙酸异丁酯(IBAC)、乙酸乙酯(EAC)、乙酸丁酯(BAC)、甲酸乙酯、乙酸甲酯、乙酸乙氧基乙酯、乙酸乙氧基丙酯、异丁酸乙酯、单甲基醚丙二醇乙酸酯、乙酸戊酯或其混合物。 Ester solvents useful in the present invention are selected from, but not limited to, isobutyl acetate (IBAC), ethyl acetate (EAC), butyl acetate (BAC), ethyl formate, methyl acetate, ethoxyethyl acetate , ethoxypropyl acetate, ethyl isobutyrate, propylene glycol monomethyl ether acetate, amyl acetate or mixtures thereof. 适用于本发明的醇类溶剂可选自但不限于乙醇、异丙醇、正丁醇、异戊醇及其混合物;适用于本发明的醚醇类溶剂例如但不限于乙二醇丁醚(BCS)、乙二醇乙醚乙酸酯(CAC)、乙二醇乙醚(ECS)、丙二醇甲醚、丙二醇甲醚乙酸酯(PMA)、丙二醇单甲醚丙酸酯(PMP)、丁二醇甲醚(DBE)或其混合物。 Alcohol solvents useful in the present invention are selected from, but not limited to, ethanol, isopropanol, n-butanol, iso-pentanol and mixtures thereof; ether alcohol solvents suitable for the present invention, such as but not limited to ethylene glycol butyl ether ( the BCS), ethylene glycol ethyl ether acetate (the CAC), ethylene glycol diethyl ether (the ECS), propylene glycol methyl ether, propylene glycol methyl ether acetate (PMA), propylene glycol monomethyl ether propionate (PMP), butanediol ether (DBE) or a mixture thereof. 根据本发明的一个优选实施方式,溶剂可选自甲苯、二甲苯、乙酸乙酯、乙二醇丁醚、丁二醇甲醚、甲基乙基酮、乙酸丁酯及其组合。 According to a preferred embodiment of the present invention, a solvent selected from toluene, xylene, ethyl acetate, ethylene glycol butyl ether, butylene glycol methyl ether, methyl ethyl ketone, butyl acetate, and combinations thereof. 溶剂的用量以金属粉定向树脂组合物的总重量计为约20重量%至约80重量%,优选为约30重量%至约70重量%。 The amount of solvent to metal powder is oriented on the total resin composition weight from about 20 wt% to about 80 wt%, preferably from about 30 wt% to about 70 wt%.

[0015]为产生分子与分子间的化学接合,提高涂膜强度,本发明的金属粉定向树脂组合物可视需要进一步包含一交联单体,以形成交联(crosslinking)。 [0015] The chemically bonded molecules and between molecules, improved coating strength, the metal powder of the present invention is directed to a resin composition optionally further comprises a cross-linking monomer to form a crosslinked (crosslinking). 可用于本发明的交联单体具有至少一能产生交联反应的官能基,该官能基选自羟基(-0H)、羧基(-C00H)、氨基(_NH2)、环氧基及其组合,优选为羟基。 Crosslinkable monomer may be used in the present invention has at least one functional group capable of crosslinking reaction, the functional group is selected from hydroxy (-0H), carboxy (-C00H), amino (_NH2), an epoxy group, and combinations thereof, preferably a hydroxy group. 上述交联单体选自(甲基)丙烯酸、环氧(甲基)丙烯酸酯、丙烯酸-2-羟基乙酯(HEA)、丙烯酸-2-羟基丙酯(HPA)、丙烯酸-2-羟基丁酯、甲基丙烯酸-2-羟基乙酯(HEMA)、甲基丙烯酸-2-羟基丙酯(HPMA)、甲基丙烯酸-4-羟基丁酯、 甲基丙烯酸缩水甘油酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、甲基丙烯酸乙酰乙酯、双丙酮丙烯酰胺、己二酸二酰肼、N-羟甲基丙烯酰胺、2-(二甲氨基)丙烯酸乙酯、2-(二甲氨基) 甲基丙烯酸乙酯、三羟甲基丙烷三甲基丙烯酸酯、二乙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、1,4_ 丁二醇二丙烯酸酯、1,6_己二醇二丙烯酸酯、(甲基)丙烯酰胺、N-丁氧基甲基丙烯酰胺、N-甲氧基(甲基)丙烯酰胺及其组合。 The above-described crosslinking monomers selected from (meth) acrylate, epoxy (meth) acrylate, 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (the HPA), acrylic acid-2-hydroxybutyric methacrylate, 2-hydroxyethyl methacrylate (HEMA), 2-hydroxy propyl methacrylate (HPMA), 4-hydroxy butyl methacrylate, glycidyl methacrylate, allyl acrylate, allyl methacrylate, methyl methacrylate acetoacetate, diacetone acrylamide, adipic acid dihydrazide, N- methylol acrylamide, 2- (dimethylamino) ethyl acrylate, 2- (dimethylamino amino) ethyl methacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1,4_-butanediol diacrylate, 1,6 _ hexanediol diacrylate, (meth) acrylamide, N- butoxymethyl acrylamide, N- methoxy (meth) acrylamide and combinations thereof. 根据本发明的一个优选实施方式,交联单体可选自丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯、 丙烯酸-2-羟基丙酯及其组合。 According to a preferred embodiment of the present invention, a crosslinking monomer selected from 2-hydroxyethyl acrylate, methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy propyl acrylate, esters and combinations thereof. 若需添加时,该交联单体的用量以单体总重量计,最高达约30重量%,优选为约5重量%至约15重量%。 When To add, the amount of crosslinking monomer to the total weight of the monomers, up to about 30 wt%, preferably from about 5 wt% to about 15 wt%.

[0016] 本发明的树脂组合物可进一步包含粘着促进剂,用以增加金属粉定向树脂组合物与基材的粘着性。 Resin composition [0016] of the present invention may further comprise an adhesion promoter to increase the adhesion of the metal powder is oriented resin composition to a substrate. 上述粘着促进剂的种类可为本领域技术人员所熟知,其例如但不限于:硅烷偶合剂、磷酸酯类化合物、多价金属盐或酯类、有机高分子树脂、或氯化聚烯烃等。 The type of the adhesion promoter may be known to those skilled in the art, such as, but not limited to: a silane coupling agent, phosphate-based compounds, polyvalent metal salt or an ester, an organic polymer resin, or chlorinated polyolefin. 本领域技术人员可视基材的种类而定,选择与该基材的附着力佳的粘着促进剂,举例而言,当基材为金属或塑料时,可选用有机高分子树脂,如环氧树脂或聚酯树脂。 Those skilled in the art depending on the type of the substrate visible, good adhesion with the selected adhesion promoter of the substrate, for example, when the substrate is a metal or plastic, the choice of the organic polymer resin, such as epoxy resins or polyester resins. 本发明的一具体实施例是使用聚酯树脂为粘着促进剂,其通常可利用任何本领域技术人员所熟知的技术获得,例如由酸组分(诸如多羟基的羧酸及/或其酸酐)与多羟基醇的缩聚作用来制备。 A particular embodiment of the present invention is a polyester resin as an adhesion promoter, which typically can be by any well known to those skilled in the art to obtain, for example an acid component (such as carboxylic acids and / or anhydrides of polyhydric) prepared and polycondensation of polyhydric alcohols. 市售聚酯树脂例子包括:ETERKYD3330-X-70-2、ETERKYD5052-R-60(长兴化学工业制)。 Examples of commercially available polyester resin comprising: ETERKYD3330-X-70-2, ETERKYD5052-R-60 (Eternal Chemical Industries, Ltd.). 根据本发明,若需添加时,该粘着促进剂的用量以单体总重量计,最高达约30重量%,优选为约5重量%至约20重量%。 According to the present invention, when To add, the amount of the adhesion promoter to the total weight of the monomers, up to about 30 wt%, preferably from about 5 wt% to about 20 wt%.

[0017] 本发明的金属粉定向树脂组合物可由本领域技术人员所熟知的任何一种方式制备,例如可由包含以下步骤的方法制得: [0017] The metal powder of the present invention is directed to prepare a resin composition in any way to those skilled in the art may be, for example, by a method comprising the following steps have prepared:

[0018] (1)将溶剂加热。 [0018] (1) heating the solvent.

[0019] (2)用于聚合作用以制备聚合物的各种单体,与适合的溶剂及视需要适当的引发剂加以混合,于适当的温度及反应时间条件下进行聚合作用。 [0019] (2) In the polymerization for the preparation of polymers of various monomers, and optionally a suitable solvent and a suitable initiator to be mixed, at a suitable polymerization temperature and reaction time conditions.

[0020] (3)于适当时间内将聚合物滴入溶剂中。 [0020] (3) at the appropriate time the polymer is added dropwise a solvent.

[0021] (4)接着保温固化。 [0021] (4) followed by incubation for curing.

[0022] 上述步骤(1),溶剂约加热至60°C至150°C,上述步骤⑵所使用的引发剂为热引发剂,可为任何本领域技术人员所熟知者,其例如可为过氧化物或偶氮化物。 [0022] In the above step (1), a solvent from about heated to 60 ° C to 150 ° C, an initiator above step ⑵ used as thermal initiators, can be known by any skilled in the art, for example, may be too oxide or azo compounds. 适用于本发明的过氧化物可为:过氧化2-乙基己酸特丁酯(tert-butylperoxy-2-ethylhexanoate)、 过氧化2-乙基己酸特戊酯(tert-amylperoxy-2-ethylhexanoate)、特丁基过氧化氢(tert-butylhydroperoxide)、异丙苯过氧化氢(cumenehydroperoxide)、过氧化二特丁基(di-tert-butylperoxide)、过氧化二异丙苯(dicumylperoxide)、过氧化苯甲酸特丁酯(tert-butylperoxybenzoate)或过氧化二苯甲醜(dibenzoylperoxide);适用于本发明的偶氮化物可为:2,2'-偶氮二异丁腈(2,2' -azodi(isobutronitrile)或2,2'-偶氮二(2-甲基丁腈)(2,2^ -azodi(2_methylbutronitrile)。引发剂的用量以单体总重量计,为约〇. 1重量%至约10重量%,优选为约〇. 5重量%至约5重量%。上述步骤(3)是于约30分钟至约4小时的时间内将聚合物滴入溶剂中,而于上述步骤(4)中,保温固化时间约1〜5小时。 Useful in the present invention may be a peroxide: peroxy-2-ethylhexanoate, tert ester (tert-butylperoxy-2-ethylhexanoate), peroxy-2-ethylhexanoate Laid-amyl (tert-amylperoxy-2- ethylhexanoate), tert-butyl hydrogen peroxide (tert-butylhydroperoxide), cumene hydroperoxide (cumenehydroperoxide), t-butyl peroxide (di-tert-butylperoxide), dicumyl peroxide (dicumylperoxide), over acid tert oxide esters (tert-butylperoxybenzoate) or benzoyl peroxide ugly (dibenzoylperoxide); useful in the present invention may be the azo compounds: 2,2'-azobisisobutyronitrile (2,2 '- azodi (isobutronitrile) or 2,2'-azobis (2-methylbutyronitrile) (2,2 ^ -azodi (2_methylbutronitrile). the amount of initiator to total monomer weight, is about square. 1 wt% to about 10% by weight, preferably about square. 5 wt.% to about 5 wt%. step (3) is in the range of about 30 minutes to about 4 hours the polymer was added dropwise to a solvent, and in the step ( 4) and incubated for a curing time of about 1 ~ 5 hours.

[0023] 本发明的金属粉定向树脂组合物不含卤素,对于金属粉的定向排列有显著的效果,又耐溶剂性与耐候性佳,且具有良好的层间粘着。 [0023] The metal powder of the present invention is directed to halogen-free resin composition, the orientation arrangement of the metal powder has a significant effect, but also solvent resistance and weather resistance, and good interlayer adhesion. 所以本发明的金属粉定向树脂组合物可直接添加金属粉以制成涂料,而施用于任何合适的基材表面。 Therefore, the metal powder of the present invention is directed to a resin composition can be directly added to prepare a coating metal powder, and applied to the surface of any suitable substrate. 或者,本发明的金属粉定向树脂组合物用于金属涂料组合物,当作金属粉定向剂,帮助金属粉定向排列。 Alternatively, the metal powder of the present invention is directed to a resin composition for coating a metal composition, as agent directed metal powder, metal powder assist alignment.

[0024] 适用的基材,例如可为瓷砖、木材、皮革、石材、玻璃、金属、合金、纸张、塑料、纤维、 棉织品等,优选为金属、合金或塑料。 [0024] Suitable substrates, for example, a metal, an alloy or a plastics tile, wood, leather, stone, glass, metals, alloys, paper, plastics, fibers, cotton and the like, preferably. 所述塑料基材,尤指3C电子产品、家电及化妆品用的塑料基材,例如为丙烯睛-丁二烯-苯乙烯(ABS)、聚碳酸酯(PC)、聚丙烯(PP)、聚甲基丙烯酸甲酯(PMMA)或其混合物。 The plastic substrate, especially a plastic substrate 3C electronic products, home appliances and used in cosmetics, for example acrylonitrile - butadiene - styrene (ABS), polycarbonate (PC), polypropylene (PP), poly methyl methacrylate (PMMA) or mixtures thereof. 上述的金属粉例如为金属或合金着色或未着色的金属材料。 For example, the above-described metal powder or a metal alloy, a metal material colored or pigmented. 上述金属材料并无任何限制,例如为铝、氧化铝、铜、锌、铁、镍或其类似物,优选的金属粉为错粉。 The metal material does not have any restrictions, for example, aluminum, alumina, copper, zinc, iron, nickel, or the like, preferably metal powder is wrong powder.

[0025] 如上述,本发明另提供一种金属涂料组合物,其包含:金属粉;粘合剂(binder); 稀释剂及如上述的金属粉定向树脂组合物。 [0025] As described above, the present invention further provides a metallic paint composition, comprising: a metal powder; binder (Binder); diluents, and metal powder as described above is oriented resin composition. 本发明的金属涂料组合物可以和其它面漆形成良好层间附着,体现更高的亮度和银粉镜面效果。 Metal coating compositions of the invention may be formed between the paint and the other layer is attached well reflect higher brightness and silver mirror effect.

[0026] 上述的金属粉种类如本文先前所定义。 [0026] The type of metal powder as previously defined herein. 根据本发明,金属粉的用量以金属涂料组合物总重量计,为约0. 1重量%至约15重量%,优选为约1重量%至约10重量%。 According to the present invention, the amount of metal powder to metal coating weight of the total composition, from about 0.1 wt% to about 15 wt%, preferably from about 1% to about 10 wt%.

[0027] 上述的粘合剂一般可使用,但不限于环氧树脂、氨基树脂、聚氨酯树脂、聚酯树脂、 硅基树脂、丙烯酸树脂或其混合物,优选为丙烯酸树脂、聚酯树脂或其混合物,更佳为丙烯酸树脂。 [0027] The pressure-sensitive adhesives may be used, but is not limited to an epoxy resin, an amino resin, a polyurethane resin, a polyester resin, a silicon resin, an acrylic resin or a mixture thereof, preferably an acrylic resin, a polyester resin or a mixture thereof , more preferably an acrylic resin. 根据本发明,粘合剂的用量以金属涂料组合物总重量计,为约10重量%至约50重量%,优选为约15重量%至约40重量%。 According to the present invention, the amount of binder metal in the total weight of the coating composition, of from about 10 wt% to about 50 wt%, preferably from about 40 wt% to about 15 wt%.

[0028] 添加稀释剂于金属涂料组合物中以调整粘度在适合操作的范围。 [0028] The diluent is added to the metal in the coating composition to adjust the viscosity in a suitable range of operation. 稀释剂可在调配各成分时添加,亦可在最终进行涂布时添加。 Diluent may be added in the allocation of the respective components, may be added in the final coating. 根据本发明的一实施方式,稀释剂宜在调配各成分时适当添加,以控制固含量(solidcontent)在约10〜90%的范围,并在最终调整粘度时,进一步调整到喷涂的粘度,使固含量在约5〜70%的范围。 According to an embodiment of the present invention, a suitable diluent should be added during formulation of the components, to control the solid content (solidcontent) is in the range of about 10 ~ 90%, and final adjustment of the viscosity is further adjusted to a spraying viscosity, so that solids content in the range of about 5~70% by weight. 稀释剂的含量并无任何限制,可依实际的条件及需求而进行调整,获得所需的涂料粘度即可。 The content of the diluent is not any restriction, as per the conditions and needs to be adjusted to obtain the desired coating viscosity. 上述的稀释剂,并无特殊限制,可为任何本领域普通技术人员所已知的有机溶剂,其例如但不限于烷烃类、芳烃类、酮类、酯类、醇类、醚醇类或其混合物。 The above-described diluent is not particularly limited, and may be any of those of ordinary skill in the art of organic solvents, such as, but not limited to, alkanes, aromatic hydrocarbons, ketones, esters, alcohols, ether alcohols or mixture. 适用于本发明的烷烃类溶剂可选自但不限于正己烷、正庚烷、异庚烷或其混合物。 Alkane solvent useful in the present invention are selected from, but not limited to, n-hexane, n-heptane, iso-heptane, or a mixture thereof. 适用于本发明的芳族烃类溶剂可选自但不限于苯、甲苯、二甲苯或其混合物。 Aromatic hydrocarbon solvents useful in the present invention are selected from, but not limited to, benzene, toluene, xylene, or mixtures thereof. 适用于本发明的酮类溶剂可选自但不限于甲基乙基酮(MEK)、丙酮、甲基异丁基酮、环己酮、4-羟基-4-甲基-2-戊酮或其混合物。 Ketone solvents useful in the present invention are selected from, but not limited to, methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone or mixtures thereof. 适用于本发明的酯类溶剂可选自但不限于乙酸异丁酯(IBAC)、乙酸乙酯(EAC)、乙酸丁酯(BAC)、甲酸乙酯、乙酸甲酯、乙酸乙氧基乙酯、乙酸乙氧基丙酯、异丁酸乙酯、单甲基醚丙二醇乙酸酯、乙酸戊酯或其混合物。 Ester solvents useful in the present invention are selected from, but not limited to, isobutyl acetate (IBAC), ethyl acetate (EAC), butyl acetate (BAC), ethyl formate, methyl acetate, ethoxyethyl acetate , ethoxypropyl acetate, ethyl isobutyrate, propylene glycol monomethyl ether acetate, amyl acetate or mixtures thereof. 适用于本发明的醇类溶剂可选自但不限于乙醇、异丙醇、正丁醇、异戊醇或其混合物;适用于本发明的醚醇类溶剂例如但不限于乙二醇丁醚(BCS)、乙二醇乙醚乙酸酯(CAC)、乙二醇乙醚(ECS)、丙二醇甲醚、丙二醇甲醚乙酸酯(PMA)、丙二醇单甲醚丙酸酯(PMP)、丁二醇甲醚(DBE)或其混合物。 Alcohol solvents suitable for the present invention are selected from, but not limited to, ethanol, isopropanol, n-butanol, isoamyl alcohol or mixtures thereof; ether alcohol solvents suitable for the present invention, such as but not limited to ethylene glycol butyl ether ( the BCS), ethylene glycol ethyl ether acetate (the CAC), ethylene glycol diethyl ether (the ECS), propylene glycol methyl ether, propylene glycol methyl ether acetate (PMA), propylene glycol monomethyl ether propionate (PMP), butanediol ether (DBE) or a mixture thereof. 优选的稀释剂为二甲苯、甲基乙基酮、乙酸丁酯、乙二醇丁醚、丙二醇甲醚乙酸酯或丁二醇甲醚。 Preferred diluents are xylene, methyl ethyl ketone, butyl acetate, ethylene glycol butyl ether, propylene glycol methyl ether acetate or glycol ether.

[0029] 已知金属涂料组合物中大多使用醋酸丁酸纤维素(celluloseacetate butyrate,CAB)、硝化纤维素(nitrocellulose,NC)或氯醋(vinylchloride-vinyl acetate)作为金属粉定向剂,其都有一些缺点。 [0029] Known metallic coating compositions frequently used cellulose acetate butyrate (celluloseacetate butyrate, CAB), nitrocellulose (nitrocellulose, NC), or chlorine vinegar (vinylchloride-vinyl acetate) directing agent as metal powder, which has some drawbacks. 本发明的金属粉定向树脂组合物用于金属涂料组合物中,展现优异的溶剂释放性(快干),尺寸稳定性(促进银粉排列),且具有耐水性,耐化学性(耐醇性)和耐刮性(硬度高)。 Metal powder of the present invention is directed to a resin composition for a metal coating composition, exhibits excellent solvent release (fast drying), dimensional stability (alignment promoting silver), and has water resistance, chemical resistance (alcohol resistance) and scratch resistance (high hardness). 同时与其它的金属粉定向剂,例如硝化纤维素(nitrocellulose,NC)、氯醋(vinylchloride-vinylacetate)或醋酸丁酸纤维素(celluloseacetatebutyrate,CAB)等具有优异的兼容性。 Metal powder simultaneously with other directing agents, e.g. nitrocellulose (nitrocellulose, NC), chlorine vinegar (vinylchloride-vinylacetate) or cellulose acetate butyrate (celluloseacetatebutyrate, CAB) and the like having an excellent compatibility. 所以本发明的金属粉定向树脂组合物,可以单独使用,也可视需要与其它的金属粉定向剂混合使用。 Therefore, the metal powder of the present invention is directed to a resin composition, may be used alone, or optionally in admixture with other metal powder directing agent used. 根据本发明,金属粉定向树脂的用量以金属涂料组合物总重量计,为约1重量%至约40重量%,优选为约2重量%至约30重量%。 According to the present invention, the metal powder is oriented in the metal coating amount of the resin composition total weight, from about 1% to about 40 wt%, preferably from about 2 wt% to about 30 wt%.

[0030] 视需要,本发明金属涂料组合物可添加色料,该色料可为透明、半透明或不透明的材料,为可给予本发明的组合物及由该等组合物形成的涂层实质颜色或修饰材料表面缺陷的颜料、染料或填料,所述颜料、染料和填料可以单独使用或者两种以上组合使用。 [0030] If desired, a metal coating composition of the invention may be added a colorant, the colorant may be transparent, translucent or opaque material, for the compositions of the invention may be administered and substance of the coating formed from such a composition modifying the surface or material defects color pigments, dyes or fillers, the pigments, dyes and fillers may be used singly or two or more thereof. 优选的色料为颜料,该颜料的实例有有机颜料,诸如偶氮鳌合物型颜料、不溶的偶氮型颜料、经稠和的偶氮型颜料、二酮吡咯并吡咯型颜料、苯并咪唑酮型颜料、酞花菁型颜料、靛蓝型颜料、茈酮(perynone)型颜料、二苯并蒽型颜料、二型颜料、酮型颜料、异吲哚啉酮(isoindorinone)型颜料及金属鳌合物型颜料;无机颜料,诸如铬黄、黄色氧化铁、铁丹、碳黑及氧化钛;及其类似物。 Preferred organic pigments are colorant, examples of pigments of the pigment, such as azo chelate pigments, insoluble azo type pigments, and condensed azo-type by pigments, diketopyrrolopyrrole type pigment, benzo imidazolone type pigments, phthalocyanine type pigment, an indigo type pigment, perylene-one (perynone) type pigment, an anthracene type pigment dibenz, two type pigment, a ketone-based pigment, isoindolinone-one (isoindorinone) type pigments and metal chelate type pigment; inorganic pigments such as chrome yellow, yellow iron oxide, red iron oxide, carbon black and titanium oxide; and the like. 本发明所使用的色料除了颜料以外还可以搭配充填颜料,诸如碳酸钙、硫酸钡、粘土、滑石及其类似物,具有增加涂层膜厚、提高涂层硬度、填充基材孔洞、降低成本等功效。 The toner used in the present invention, in addition to the pigment may also be filled with pigments, such as calcium carbonate, barium sulfate, clay, talc and the like, having a coating film thickness increases, to improve the coating hardness, substrate filled holes, cost reduction and other effects.

[0031]依照所需成品涂膜的用途,本发明涂料组合物可进一步包含一或多种本发明所属 [0031] In accordance with the desired use of the finished coating film, the coating compositions of the invention may further comprise one or more relevant to the present invention

技术领域中惯用的助剂。 Adjuvants customary in the art. 可视需要采用的助剂例如包括粘着促进剂、防沉剂、分散剂、消光齐IJ、消泡剂、抗氧化剂,流变助剂、安定剂、流平剂、润湿剂、防浮色剂及其组合,这些助剂的种类为本领域技术人员所知,而其用量亦为本领域技术人员依不同需求而可轻易决定。 Where necessary, additives include, for example, adhesion promoters, anti-settling agents, dispersing agents, matting together IJ, defoamers, antioxidants, rheology aids, stabilizers, leveling agents, wetting agents, anti-floating agents and combinations of these types of additives known to those skilled in the art, and it is also known to those skilled in amounts according to different needs can be easily determined.

[0032] 上述金属涂料组合物可由任何本领域技术人员所知的方式涂覆至基材的表面上, 形成一涂膜,之后烘干,形成厚度约为5至20微米的涂层,上述涂布方式,可采用喷雾式涂布(spraycoating)、刷涂(brushcoating)、棍涂(rollercoating)、线杆涂布(bar coating)、狭缝式模压涂布(slotdiecoating)、凸版印刷涂布(gravurecoating)、斜板式涂布(slidecoating)或淋幕式涂布(curtaincoating);所述的基材的种类如本文先前所定义。 [0032] The metal coating composition of the present art by any manner known in the art applied to the upper surface of the substrate to form a coating film, after drying, the coating is formed from about 5 to 20 microns thickness of the coating cloth manner, using spray coating (spraycoating), brushing (brushcoating), stick coating (RollerCoating), the coating rod (bar coating), slot die coating (slotdiecoating), letterpress printing coating (gravurecoating ), slide coating (slidecoating) or curtain coating (curtaincoating); the type of the substrate as previously defined herein.

[0033] 以下实施例是用于对本发明作进一步说明,并非用以限制本发明的范围。 Example [0033] The following is a further description of the present invention is not intended to limit the scope of the present invention. 任何本领域技术人员可轻易达成的修饰及改变均包括于本申请说明书揭示内容及所附权利要求书的范围内。 Anyone skilled in the art can easily achieve modifications and variations are included within the scope disclosed in the present specification and appended claims.

[0034]实施例1金属粉定向树脂组合物的制备 [0034] Example 1 Preparation of resin composition embodiment metal powder is oriented

[0035] 取580克的甲苯放入四口反应瓶中加热至85°C,将50克的甲基丙烯酸异冰片酯单体、250克的甲基丙烯酸甲酯单体、150克的甲基丙烯酸丁酯单体、50克的丙烯酸丁酯单体、 70克的聚酯树脂(ETERKYD3330-X-70-2 (长兴))与10克过氧化苯甲酰预混合后滴入反应瓶中,约2小时滴完,并保温固化3小时后包装,以格式粘度计(BYK-Gardner粘度管)测量得到粘度Z1〜Z2,固含量50%的树脂。 [0035] Take 580 g of toluene were placed in four reaction flask was heated to 85 ° C, the isobornyl acrylate monomer 50 g methacrylic acid, 250 g of methyl methacrylate monomer, 150 g of methyl butyl acrylate monomer, 50 g of butyl acrylate monomer, 70 g of a polyester resin (ETERKYD3330-X-70-2 (Eternal)) after 10 g of benzoyl peroxide and the reaction flask was added dropwise a premixed, dropwise for about 2 hours, and cured after 3 hours incubation packaging format viscometer (BYK-Gardner viscometer) viscosity measured Z1~Z2, a resin solids content of 50%.

[0036] 实施例2金属粉定向树脂组合物的制备 [0036] Preparation of resin composition of Example 2 oriented metal powder

[0037] 取295克的甲苯与260克的乙酸丁酯放入四口反应瓶中加热至115°C,并将75克的甲基丙烯酸异冰片酯单体、300克的甲基丙烯酸甲酯单体、75克的丙烯酸丁酯单体、50克的甲基丙烯酸丁酯单体、50克的聚酯树脂(ETERKYD5052-R-60(长兴))与5克过氧化苯甲酸特丁酯预混合后,滴入反应瓶中,约2小时滴完,并保温固化3小时后包装,以格式粘度计(BYK-Gardner粘度管)测量可得到粘度Y〜Z,固含量50%的树脂。 [0037] Take 295 g of toluene and 260 g of butyl acetate were put in four reaction flask was heated to 115 ° C, and 75 g of isobornyl acrylate monomers methacrylic acid, methyl methacrylate, 300 grams monomer, 75 g of butyl acrylate monomer, 50 g of butyl methacrylate monomer, 50 g of a polyester resin (ETERKYD5052-R-60 (Eternal)) and 5 g peroxybenzoate tert pre ester after mixing, the reaction flask dropwise, dropwise for about 2 hours, and cured after 3 hours incubation packaging format viscometer (BYK-Gardner viscometer) viscosity measurements gave Y~Z, 50% of the solids content of the resin.

[0038] 实施例3金属粉定向树脂组合物的制备 Preparation of resin composition [0038] Example 3 oriented metal powder

[0039] 取250克的二甲苯与250克的乙酸丁酯放入四口反应瓶中加热至125°C,并将25 克的甲基丙烯酸异冰片酯单体、225克的甲基丙烯酸甲酯单体、150克的苯乙烯、50克的丙烯酸异丁酯单体、50克的羟乙基丙烯酸酯单体与5克过氧化苯甲酸特丁酯预混合后,滴入反应瓶中,约3小时滴完,并保温固化3小时后包装,以格式粘度计(BYK-Gardner粘度管) 测量可得到粘度X〜Y,固含量50%的树脂。 250 grams of xylene and butyl acetate [0039] 250 grams taken into four reaction flask was heated to 125 ° C, and 25 g monomer is isobornyl methacrylate, 225 g of methyl methacrylate ester monomer, 150 grams of styrene, 50 g of isobutyl methacrylate monomer, 50g hydroxyethyl acrylate monomer pre peroxybenzoate tert ester was mixed with 5 grams of added dropwise to the reaction flask, dropwise for about 3 hours, and cured after 3 hours incubation packaging format viscometer (BYK-Gardner viscometer) viscosity measurements gave X~Y, 50% of the solids content of the resin.

[0040] 前述实施例1至3的树脂组合物的成分整理如下表1。 [0040] the component of the resin composition in Example 1 to 3 are summarized as follows in Table 1 of the embodiment.

[0041]表1 [0041] TABLE 1

[0042] [0042]

Figure CN102585579BD00091

[0043] 实施例4依下表2的金属漆配方,配制金属漆涂料。 [0043] 4 metallic paint formulation according to the table 2, the metallic paint coatings formulated embodiment.

[0044] 表2:金属漆涂料测试配方 [0044] Table 2: Metallic Coatings Test formulation

[0045] [0045]

Figure CN102585579BD00101

[0046] 单位:重量份 [0046] Unit: parts by weight

[0047] 实施例5 [0047] Example 5

[0048] 依实施例4中表2的金属漆配方,配制金属漆涂料,其中金属粉定向树脂依以下重量份调配: [0048] The metallic paint formulation according to Example 4 of Table 2 embodiment, a metal lacquer coating formulation, wherein the metal powder is oriented by resin parts by weight of the following formulation:

Figure CN102585579BD00102

[0050] 并且乙酸丁酯用量改为10. 5重量份。 [0050] and the amount of butyl acetate was changed to 10.5 parts by weight.

[0051] 比较例1 [0051] Comparative Example 1

[0052] 依实施例4中表2的金属漆配方,配制金属漆涂料,其中金属粉定向树脂改为市售金属粉定向树脂CAB381-2.0(20% ),EASTMAN公司制,用量20重量份;乙酸丁酯用量改为1. 5重量份。 [0052] The metallic paint formulation according to Table 2 of Example 4, a metal lacquer coating formulation, wherein the metal powder is oriented to a commercially available metal powders oriented resin resin CAB381-2.0 (20%), EASTMAN Corporation, 20 parts by weight of an amount; The amount of butyl acetate was changed to 1.5 parts by weight.

[0053] 比较例2 [0053] Comparative Example 2

[0054] 依实施例4中表2的金属漆配方,配制金属漆涂料,但不加金属粉定向树脂;热固性丙烯酸树脂,用量改为48重量份;乙酸丁酯用量改为17. 5重量份。 [0054] The metallic paint formulation according to Example 4 of Table 2, formulated metallic lacquer coating, but without the metal powder is oriented resin; thermosetting acrylic resin, used was changed to 48 parts by weight; amount of butyl acetate was changed to 17.5 parts by weight .

[0055] 将实施例4及5与比较例1及2配制完成的金属漆喷涂于基材上,烘干后进行涂膜测试,其作业条件如下:以稀释剂将上述所得的金属涂料组合物稀释至固成分约20%后, 涂布上述的金属涂料组合物于基板上,之后于150〜160°C烘干20分钟,以形成干燥厚度为8至12微米的金属基底涂层,之后进行以下相关测试;进行层间粘着测试时,需重复上述步骤5次(5涂5烤)后,再进行测试。 [0055] Examples 4 and 5 and Comparative Examples 1 and 2 to complete the preparation of metallic paint sprayed on a substrate, a coating film after drying the test, its operational conditions were as follows: diluent mixture obtained above to a metal coating composition after dilution to a solids content of about 20%, applying the coating composition to a metal substrate, followed by drying at 150~160 ° C 20 minutes to form a dried coating thickness of the metal substrate 8 to 12 microns, followed by the following correlation test; when the interlayer adhesion test, repeat the sequence five times (5 bake coating 5), and then tested.

[0056] 测试方法 [0056] Test Method

[0057] 光泽度:利用光泽计[VG2000,NipponDenshoku公司],以ASTMD523方法将光源以60°入射角投射至待测样品表面,再于60°反射角位置量测其表面光泽度。 [0057] Gloss: Using a glossmeter [VG2000, NipponDenshoku Company], a method to ASTMD523 light projected onto the surface of the sample to be tested to 60 ° angle of incidence, and then measured for surface gloss at 60 ° angle of reflection position quantity.

[0058] 粘着度:以百格刮刀刮于涂膜表面,后以胶带粘紧后,90°撕起,判定剥落格数。 [0058] The degree of adhesion: cross hatch blade to scrape the surface of the coating film, after the tape on to, 90 ° since the tear, spalling is determined the number of cells.

[0059] 硬度:利用铅笔硬度试验机[Elcometer3086,SCRATCHB0Y],以三菱Uni铅笔(1H,2H)用JISK-5400方法测试涂膜微结构层表面的铅笔硬度。 [0059] hardness: a pencil hardness tester [Elcometer3086, SCRATCHB0Y], Mitsubishi Uni Pencil Hardness Pencil (1H, 2H) method with JISK-5400 micro-surface structure of the coating layer of the test.

[0060] 耐水性:将待测样品以45°C浸泡120小时,观察表面状态。 [0060] Water resistance: The sample to be tested immersed in 120 hours 45 ° C, the surface state was observed.

[0061] 耐醇性:以95%酒精擦拭涂膜表面100次,观察表面状态。 [0061] Alcohol resistance: 95% alcohol wipe coating surface 100 times, the surface state was observed.

[0062] 层间粘着:以百格刮刀刮于涂膜表面,后以胶带粘紧后,90°撕起,判定剥落格数。 Between [0062] the adhesive layer: A hundred cells scraper blade on the coating film surface after the tape on to, 90 ° since the tear, spalling is determined the number of cells.

[0063] 上述粘着度与层间粘着判定标准如下: [0063] The degree of adhesion between said adhesive layer and the following criteria:

Figure CN102585579BD00111

[0065] 测试结果: [0065] Test results:

[0066] 上述所得的测试结果记录于表3。 [0066] The obtained test results are reported in Table 3.

[0067]表3 [0067] TABLE 3

Figure CN102585579BD00112

[0069]由表3可知,使用本发明的金属粉定向树脂组合物的金属涂料,相较于不添加金属粉定向树脂(比较例2),其涂膜具有良好的光泽度,显示本发明的金属粉定向树脂具有良好的金属定向能力;使用本发明的金属粉定向树脂组合物的金属涂料,其涂膜硬度高且具有良好的粘着度、耐水性、耐醇性与层间粘着,相较于市售的金属粉定向树脂组合物(比较例1),添加本发明的金属粉定向树脂组合物的涂膜具有优选的硬度、耐醇性与层间粘着, 当以本发明的金属粉定向树脂组合物部分取代市售的金属粉定向树脂组合物(实施例5), 可以提高涂膜的硬度、耐醇性与层间粘着,改善市售的金属粉定向树脂组合物硬度不高及耐醇性不佳的缺点。 [0069] As apparent from Table 3, the metal coating of the present invention is the use of metal powder orientation of the resin composition, as compared to without addition of metal powder is oriented resin (Comparative Example 2), which film has good gloss, the present invention show metal powder resin has a good directional orientation capabilities metal; metal powder of the present invention is directed to a resin composition of the metal coating, and a high hardness coating film which has a good degree of adhesion, water resistance, alcohol resistance and inter-layer adhesion, compared commercially available metal powder is oriented in the resin composition (Comparative Example 1), adding metal powder of the present invention is a coating resin composition having a preferred orientation of hardness, resistance and interlayer adhesion between the alcohol resistance, when the metal powder of the present invention is directed the resin composition of the metal powder partially substituted commercially oriented resin composition (Example 5), the film hardness can be improved, and the resistance of the interlayer adhesion between the alcohol, a commercially available metal powder to improve the orientation of the resin composition of high hardness and resistance to alcoholic poor drawbacks.

[0070] 本发明的金属粉定向树脂,可有效促进金属涂料中的金属粉排列(包含甲基丙烯酸甲酯单体,分子量大,于金属涂料中的溶剂挥发时,其向上或向下压时的力量具有促使金属粉朝同一方向排列的效果),并可单独或与其它树脂一并使用(与氯醋树脂、硝基纤维素、醋酸丁酸纤维素及热塑性丙烯酸树脂具有良好的兼容性)。 When [0070] the present invention, the metal powder is oriented resin, the metal powder can effectively promote the alignment of metallic paint (containing methyl methacrylate monomer, molecular weight, the solvent is volatilized in the metal coating, which is pressed downward or upward the force causes the metal powder having the same direction are arranged effect), and may be used alone or in conjunction with other resins (resin vinegar and chlorine, nitrocellulose, cellulose acetate butyrate and the thermoplastic acrylic resin has good compatibility) . 此外,其抗磨耗、耐水及耐醇性佳,又具有良好的层间粘着,故所配制的金属漆得以与透明面漆(UV面漆)形成良好层间附着,显现更高的亮度及金属粉镜面效果。 In addition, its anti-wear, water resistance and alcohol resistance, but also has good interlayer adhesion, it is formulated to be formed between the metallic paint layer good adhesion to the clear top coat (UV top coat), show higher brightness and metal powder mirror effect.

[0071] 使用本发明的金属粉定向树脂组合物的金属涂料,不需纤维素衍生物;且即便其含有纤维素衍生物,亦仅需要少量(可大幅降低纤维素衍生物的用量达至少60%)。 [0071] using a metal powder of the present invention is directed to a metal coating resin composition without cellulose derivatives; and even if it contains a cellulose derivative, also requires only a small (can significantly reduce the capacity of the cellulose derivative with at least 60 %). 本发明的金属漆涂料组合物亦不用氯醋及硝化纤维素。 Metallic coating compositions of the invention also without chlorine acetate and nitrocellulose. 故本发明的金属漆涂料组合物耐候性佳(不易黄化)、环保(不含卤素)及价格便宜(醋酸丁酸纤维素价格高)。 Therefore, metallic paint coating composition of the present invention, weather resistance (yellowing is not easy), green (halogen-free) and inexpensive (cellulose acetate butyrate high prices). 此外,其具有优异的物理性能,尤指其耐磨耗性、层间粘着及色泽丰满度佳,以及耐溶剂。 In addition, it has excellent physical properties, especially among the wear resistance, interlayer adhesion and good color fullness, and solvent.

Claims (9)

  1. 1. 一种金属粉定向树脂组合物,其特征在于,包含聚合物和溶剂,该聚合物包含以下单体作为聚合单元:(a)甲基丙烯酸甲酯单体;(b)高玻璃化转变温度的单体,该高玻璃化转变温度的单体为具有玻璃化转变温度大于70°C的单体;及(c)低玻璃化转变温度的单体,该低玻璃化转变温度的单体为具有玻璃化转变温度小于70°C的单体,其中该金属粉定向树脂组合物具有55°C至135°C的玻璃化转变温度,该聚合物的重均分子量为50, 000至150, 000 ;该甲基丙烯酸甲酯单体的用量,以单体总重量计,为40重量%至70重量%,该高玻璃化转变温度的单体为(甲基)丙烯酸异冰片酯单体、(甲基)丙烯酸异冰片酯单体和(甲基)丙烯酸环己酯单体的混合物、(甲基)丙烯酸异冰片酯单体和苯乙烯单体的混合物或(甲基)丙烯酸异冰片酯单体和(甲基)丙烯酸环己酯单体和苯乙 A metal powder is oriented resin composition comprising a polymer and a solvent, the polymer comprises as polymerized units: (a) methyl methacrylate monomer; (b) high glass transition monomers temperature, high glass transition temperature of the monomers into a monomer having a glass transition temperature greater than 70 ° C; and (c) a low glass transition temperature of the monomers, the low glass transition temperature of the monomers monomer having a glass transition temperature of less than 70 ° C, wherein the metal powder is oriented resin having a glass composition to 55 ° C to 135 ° C transition temperature, a weight average molecular weight of the polymer is 50, 000 to 150, 000; amount of the methyl methacrylate monomer, the total weight of monomer, 40% by weight to 70% by weight, the monomers of a high glass transition temperature of the (meth) acrylate monomers, (meth) acrylate ester monomer and a mixture of isobornyl (meth) acrylate monomers, (meth) acrylate monomer and styrene monomer or a mixture of (meth) acrylate, isobornyl monomers and (meth) acrylate monomer and styrene 单体的混合物;该低玻璃化转变温度的单体选自:丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸己酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸-2- 丁酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸异三癸酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸月桂酯及其组合。 Mixture of monomers; monomers of the low glass transition temperature is selected from: methyl acrylate, (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, hexyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, isooctyl acrylate, (meth) acrylate, nonyl (meth) acrylate, isobutyl (meth) acrylate, 2-butyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, iso-tridecyl (meth) acrylate, benzyl (meth) acrylate, lauryl acrylate, and combinations thereof.
  2. 2. 如权利要求1所述的树脂组合物,其特征在于,该高玻璃化转变温度的单体的用量, 以单体总重量计,为2重量%至60重量%。 The resin composition according to claim 1, wherein the amount of the monomer of the high glass transition temperature, total monomer weight, of 2 wt% to 60 wt%.
  3. 3. 如权利要求1所述的树脂组合物,其特征在于,该低玻璃化转变温度的单体的用量, 以单体总重量计,为2重量%至60重量%。 The resin composition according to claim 1, wherein the amount of the monomer of the low glass transition temperature, total monomer weight, of 2 wt% to 60 wt%.
  4. 4. 如权利要求1所述的树脂组合物,其特征在于,所述溶剂选自:沸点70-200°C的烷烃类、酮类、酯类、芳烃类、醇类、醚醇类及其混合物。 The resin composition according to claim 1, wherein said solvent is selected from: alkanes having a boiling point of 70-200 ° C, ketones, esters, aromatic hydrocarbons, alcohols, ether alcohols and mixture.
  5. 5. 如权利要求1所述的树脂组合物,其特征在于,该溶剂的用量,以树脂组合物的总重量计,为20重量%至80重量%。 The resin composition according to claim 1, wherein the solvent is used in an amount, based on the total weight of the resin composition, of 20 wt% to 80 wt%.
  6. 6. -种金属涂料组合物,其特征在于,它包含金属粉;粘合剂;稀释剂及权利要求1的树脂组合物。 6. - metal coating composition, characterized in that it comprises a metal powder; binder; and diluent resin composition as claimed in claim 1.
  7. 7. 如权利要求6所述的金属涂料组合物,其特征在于,该金属粉为金属或合金着色或未着色的金属材料。 7. The metallic coating composition according to claim 6, wherein the metallic material is a metal powder or a metal alloy, colored or pigmented.
  8. 8. 如权利要求6所述的金属涂料组合物,其特征在于,该粘合剂为环氧树脂、氨基树月旨、聚氨酯树脂、聚酯树脂、硅基树脂、丙烯酸树脂或其混合物。 8. The metallic coating composition according to claim 6, wherein the adhesive is an epoxy resin, an amino tree month purpose, a polyurethane resin, a polyester resin, a silicon resin, an acrylic resin or a mixture thereof.
  9. 9. 如权利要求6所述的涂料组合物,其特征在于,该稀释剂为选自烷烃类、芳烃类、酮类、酯类、醇类、醚醇类及其混合物的有机溶剂。 9. The coating composition according to claim 6, wherein the diluent is an organic solvent selected from alkanes, aromatic hydrocarbons, ketones, esters, alcohols, ether alcohols, and mixtures thereof.
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CN101486864A (en) * 2009-02-18 2009-07-22 中山创美涂料有限公司 Waterborne metallic paint and preparation thereof
WO2011037732A2 (en) * 2009-09-17 2011-03-31 Avery Dennison Corporation Activatable adhesive, labels, and related methods

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