CN114685910A - 着色剂、着色材料及制备方法 - Google Patents
着色剂、着色材料及制备方法 Download PDFInfo
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- CN114685910A CN114685910A CN202210269637.5A CN202210269637A CN114685910A CN 114685910 A CN114685910 A CN 114685910A CN 202210269637 A CN202210269637 A CN 202210269637A CN 114685910 A CN114685910 A CN 114685910A
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- pigment
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Classifications
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- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C08J2423/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
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- 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
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- 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
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
本发明公开了一种着色剂、着色材料及制备方法,该着色剂为按照特定的配方比例制作的单色颜料微粒或几种单色颜料微粒的混合物,所述单色颜料微粒按重量份计,包括如下组分:载体43‑97.6份,颜料1‑40份,加工助剂1‑15份,抗氧剂0.4‑2份。所述着色材料,包括被着色物料和上述着色剂,本发明通过单色颜料微粒用于制成着色剂,根据颜色性能可以调整着色剂添加比例及各单色颜料微粒的比例含量等,实现颜色管控手段,能够实现稳定的在线连续式的着色生产,颜色前后均匀,同时力学冲击性能进一步提升。
Description
技术领域
本发明涉及塑料着色配色技术领域,尤其涉及针对苯乙烯基材料的挤出造粒着色应用的着色剂、着色材料及制备方法。
背景技术
苯乙烯基材料作为传统应用最为成熟的热塑性材料之一,通过不同的单体比例进行聚合及共混改性衍生出了一系列的产品,其中包含PS,HIPS,ABS,SAN,ASA及共混改性的PC/ABS,PVC/ABS,此类产品已经广泛应用于家电外壳,仪表面板,电子设备外壳及包装等。作为外观制件不但需要高表面光泽,对颜色外观瑕疵也精益求精,常规应用母粒注塑着色很难满足外观要求,因此大部分外观制件都通过挤出造粒着色。
目前挤出着色造粒方法主要还是应用色粉与被着色物料进行混配着色,混料均匀性并不理想,还需要进行后续的产品均化处理,另外粉尘污染严重影响车间生产环境及产品交叉污染;另外也有应用母粒着色形式,但对母粒的配色设计及母粒形态,颜料含量,混配模式等没有形成有效设计,导致着色产品颜色稳定性不理想,甚至比色粉着色效果还差,所以没有正式推广应用。
因此,开发环保、着色稳定且可应用于规模化连续生产的着色材料,具有非常大的市场效益。
发明内容
为了克服上述现有技术的缺陷,本发明通过对着色剂的组成及配方进行设计,并设计通过按指定比例范围的混配模式,可结合精准计量设备实现连续生产。
具体通过以下技术方案实现:
一种着色剂,包括至少一种单色颜料微粒,所述单色颜料微粒按重量份计,包括如下组分:
所述载体由丙烯晴-苯乙烯共聚物、苯乙烯-马来酸酐共聚物和甲基丙烯酸甲酯-苯乙烯-丁二烯共聚物组成,按重量比计,丙烯晴-苯乙烯共聚物:苯乙烯-马来酸酐共聚物:甲基丙烯酸甲酯-苯乙烯-丁二烯共聚物为(23-91):(2-15):(4-25)。
进一步的,丙烯晴-苯乙烯共聚物:(苯乙烯-马来酸酐共聚物+甲基丙烯酸甲酯-苯乙烯-丁二烯共聚物)重量份比值为(1-15):1,优选地,丙烯晴-苯乙烯共聚物:(苯乙烯-马来酸酐共聚物+甲基丙烯酸甲酯-苯乙烯-丁二烯共聚物)重量份比值为(3-7):1。
其中,丙烯晴-苯乙烯共聚物又记为SAN,苯乙烯-马来酸酐共聚物又记为SMA,甲基丙烯酸甲酯-苯乙烯-丁二烯共聚物又记为MBS。
应用SAN与MBS和SMA复配作为载体,一方面能够保证与苯乙烯基类被着色材料有良好的相容性能,保证着色后产品的冲击强度,另一方面组合载体能有效保证单色颜料微粒生产时颗粒尺寸控制,具有良好的加工性能。
在制备每一所述单色颜料微粒时,仅使用单一种颜料,以解决现有技术中采用色粉所带来的粉尘污染、配色不精准问题,实现环保添加、精准配色的效果。目前行业中普遍应用的色粉或色沙着色,由于色粉或色沙的颗粒太过微细,容易产生粉体污染,与粗粒径的树脂颗粒混合时难达到均匀分散,而且粉末状的形态难以实现自动化输送计量生产模式。
进一步的,所述颜料包括无机颜料、有机颜料、染料、金属效果颜料或荧光增白剂中的任一种。
具体的,所述无机颜料为钛白粉、硫化锌、炭黑、群青、钛黄、铁黄或铁红、钴蓝、铁黑等;
有机颜料为偶氮类颜料、酞青类颜料、二噁嗪类颜料、喹吖啶酮类颜料、异吲哚啉类颜料、异吲哚啉酮类颜料、苝系颜料、喹酞酮类颜料、蒽醌类颜料或金属络合物颜料;
所述染料为蒽醌类染料、偶氮类染料、亚甲基类染料、氨基酮类染料、甲亚胺类染料、喹酞酮类染料、稠环类染料、苝系染料或香豆素类染料。
进一步的,加工助剂包括氧化乙烯蜡、硬脂酸盐、乙撑双硬脂酰胺(EBS)、季戊四醇酯、酯类蒙旦蜡、金属酯类、乙烯-丙烯酸共聚物,白矿油或硅油中的任一种或多种。为了实现良好的混合分散效果,所述加工助剂的形态为粉末状或液体状,所述加工助剂与苯乙烯基材料有良好的相容增容性能,提高颜料分散效果。
进一步的,所述抗氧剂包括酚类主抗氧剂、亚磷酸酯辅抗氧剂或抗静电剂中的任一种或多种复配。
进一步的,所述单色颜料微粒为圆柱体颗粒、球形颗粒、类球形颗粒或不规则立体颗粒,并且在室温环境下测量,所述单色颜料微粒的100粒重为0.31-0.67克,所述单色颜料微粒的平均粒径为1-2mm。其中,优选的,所述单色颜料微粒为圆柱体颗粒,平均颗粒直径为1-2mm,平均颗粒长度为1-2mm。
为了实现调色配色,进一步的,所述着色剂包括至少2种不同颜色的所述单色颜料微粒。且在本方案中,每一所述单色颜料微粒在所述着色剂中的重量百分比不低于5%,可实现良好的混合均匀性和计量精准度。
进一步的,为了保证混合物各组分的均匀分布及形成稳定的混合物,着色剂中任意两种单色颜料微粒的密度比在0.7-1.43范围内。
上述着色剂的制备方法,包括如下步骤:将所述单色颜料微粒的配方各组分称量后进行混合,并通过熔融密炼押出造粒形成单色颜料微粒;将所述单色颜料微粒称量并混合,得到所述着色剂。
进一步地,上述单色颜料微粒的制备方法包括:按照配方比例称量各组分物料,按照设计次序先后投入高速混合机,将混合好的物料投入螺杆杆挤出计量设备,螺杆温度设定为180-210℃,螺杆转速300-500转/分钟,喂料速度100-300kg/h,挤出拉条切粒,用可调切粒长度切粒机切粒;控制切粒尺寸规格为颗粒直径为1-2mm,长度为1-2mm,100粒重为0.31-0.67克。切粒长度在1-2mm有利于单色颜料微粒达到预期效果。
进一步地,着色剂可以是包含按照一定配方比例制作的单色颜料微粒或几种单色颜料微粒的共混物,将物料通过计量或称量模式投入混合机进行中速混合即可;着色剂中各种单色颜料微粒之间的密度比为0.7-1.43之间,着色剂中各个单色颜料微粒在组合物中占重量百分比>5%。
本发明还提供一种着色材料,包括被着色物料,以及上述的着色剂,其中,按重量百分比计,所述被着色物料为90-98%,所述着色剂为2-10%。
进一步优选地,被着色材料和着色剂的重量比为100:(3-6)。
进一步的,所述被着色物料为苯乙烯基材料,具体包括苯乙烯、高抗冲聚苯乙烯(HIPS)、丙烯晴-丁二烯-苯乙烯共聚物(ABS)、丙烯晴-苯乙烯共聚物、ABS/PC共混改性材料或PVC/ABS共混改性材料中的一种或多种。
上述着色材料的制备方法,包括步骤:将所述被着色物料与所述着色剂分别称重,挤出造粒形成所述着色材料。
具体地,所述被着色物料与所述着色剂分别通过失重式计量秤进行精准计量,被着色物料可以是单一组分计量或几种组分混合计量,着色剂采用独立计量形式;用双螺杆挤出着色造粒。
本发明所提供的着色剂,可应用于苯乙烯基材料着色。本发明所提供的着色材料,采用苯乙烯基材料作为被着色物料,可应用于产品外观制件。
与现有技术相比,本发明的有益效果是:本发明制作的着色剂应用于苯乙烯基系材料,不但着色效果良好,外观光泽好,同时由于具有跟基体树脂有良好的兼容增韧作用,有效提升着色材料的抗冲击性能。
本发明制作的着色剂还可以应用于挤出型材、注塑成型等材料着色,能实现自动化计量生产。通过本发明提供的方法生产的着色产品,不仅在下游使用颜色性能稳定,颜料分散良好,而且机械性能能够完全吻合实验开发设计的匹配性。
通过单色颜料微粒用于制成着色剂,根据颜色性能可以调整着色剂添加比例及各组分比例含量等,实现颜色管控手段,能够实现稳定的在线连续式的着色生产,颜色前后均匀,同时力学冲击性能进一步提升。
采用本发明的着色剂在计量过程中不存在飘逸污染环境现象,可以实现在线连续生产调整颜色配方,提高生产效率。
通过本发明方法生产的着色材料,不仅在下游使用颜色性能稳定,颜料分散良好,而且机械性能能够完全吻合实验开发设计的匹配性。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明还提供了着色材料的挤出着色计量工艺路线和着色剂、单色颜料微粒的制作工艺路线,应用现代高精度计量技术及物料中央供应系统,形成连续试的挤出造粒着色生产技术。
为了更好的解释本发明,通过以下具体的实施案例进一步说明,但本发明不局限于下面的实施案例。
本实施所用的设备仪器如下:
1)双螺杆挤出机,科倍隆(南京)机械有限公司,长径比44:1;
2)计台式螺旋秤,梅特勒——托利多有限公司,
3)注塑机,ME-90,广州正茂精机
4)分光光谱仪,爱色丽CI-7000A
5)标准光源灯箱,X-Rit额Macbeth
6)切粒机,常规市售产品,切粒机可以提供不同规格的切粒长度。
本实施方式的具体配方组分原材料说明如下表1:
表1.具体配方组分原材料
实施例1至6:
(1)单色颜料微粒:如下表2,按照配方比例称量各组分物料,按照载体-颜料-加工助剂-抗氧剂顺序先后投入高速混合机,混合机转速为600转/分,混料时间300秒,将混合好的物料投入螺杆挤出计量设备,螺杆温度设定为180-210度,螺杆转速400转/分钟,喂料200kg/h,挤出拉条切粒,用可调切粒长度切粒机切粒,控制切粒尺寸规格为颗粒直径为1-2mm,长度为1-2mm,100粒重为0.31-0.67克;
(2)着色剂:按照表3,将制备所得的单色颜料微粒按照实施例配方比例进行配比混合均匀得到着色剂;
(3)着色材料:按照表3,被着色物料和着色剂按照设定的配色计量比例分别独立计量,实施例1、2、5挤出温度为200-220度,实施例3、6挤出温度为240-260度,实施例4挤出温度为190-200度;螺杆转速为400转,总产出量设定为200kg/h,挤出拉条造粒,得到着色材料;
总投料量为200kg,分别在第15、30、45、60分钟在线取样2kg样品总共4组样品,120度烘干干燥4小时后每组样品单独进行注塑成型色板10块,在标准光源灯箱下观察色板的色板,颜色均匀性能,用分光光度计测试颜色色差,以第15分钟取样做为参考标准,第30、45、60分钟3组样品作为对比样,每组样品测量5块色板取平均值,如果颜色总色差ΔE<0.5表明着色颜色均匀稳定,前后没有明显色差,满足在线连续生产要求。
表2.单色颜料微粒配方方案
表3.实施例1-6的着色材料实施方案
表4所列对比例1至5的具体方案,与实施例的差异如下:
(1)对比例1的着色材料按照与实施例3的相同配方和挤出工艺,但投料模式改为将着色剂用完全等同对应的色粉替换,并且采用一锅混模式与所有被着色物料混合均匀投料挤出着色。
(2)对比例2与实施例4配方模式和生产工艺相同,但着色剂中单色颜料微粒组份比例小于5%(炭黑微粒3%,小于5%)。
(3)对比例3与实施例5配方模式和生产工艺相同,但是对比例3中将钛白粉微粒的钛白粉重量百分比从35%提高为54%,即对比例3中使用的是钛白粉微粒2(其中,钛白粉重量百分比为54%),而实施例5中使用的是钛白粉微粒1(其中,钛白粉重量百分比为35%),35%钛白粉重量百分比的钛白粉微粒1的密度为1.44g/cm3,54%钛白粉重量百分比的钛白粉微粒2的密度为1.80g/cm3。着色剂配方组合中奎啉酮黄微粒密度为1.10g/cm3,按照着色剂中任意单色颜料微粒密度比参数,对比例3中,钛白粉微粒2密度(1.80g/cm3)与奎啉酮黄微粒密度(1.1g/cm3)的比值为1.636,大于1.43,或者奎啉酮黄微粒密度(1.1g/cm3)/钛白粉微粒2密度(1.80g/cm3)小于0.7,不在0.7-1.43范围内。
(4)对比例4与实施例6比,对比例4的着色剂中,将单色颜料微粒炭黑微粒制作为为直径为2-3mm,长度为2.5-3mm的颗粒尺寸。着色剂组分中其他单色颜料微粒的颗粒尺寸维持直径1-2mm,长度为1-2mm,这样由于炭黑微粒与其他单色颜料微粒颗粒大小形态差异大,混合后物料容易产生沉降。
(5)对比例5与实施例6对比,将被着色物料和着色剂直接用一锅混模式混合计量。将着色剂与被着色物料按照实施例6的重量百分比进行一锅混混合;
表4.对比例1-5着色材料实施方案
实施例1-6的测量测试结果如下:
实施例 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 |
颜色 | 白色 | 灰色 | 蓝色 | 绿色 | 红色 | 蓝灰 |
密度比 | 0.833 | 0.7-1.43 | 0.7-1.43 | 0.7-1.43 | 0.7-1.43 | 0.7-1.43 |
单色颜料微粒占比 | >5% | >5% | >5% | >5% | >5% | >5% |
100粒重(g) | 0.31-0.67 | 0.31-0.67 | 0.31-0.67 | 0.31-0.67 | 0.31-0.67 | 0.31-0.67 |
色斑/色纹 | 无 | 无 | 无 | 无 | 无 | 无 |
颜色波动性 | 无 | 无 | 无 | 无 | 无 | 无 |
冲击保留% | 102% | 103% | 104% | 104% | 103% | 107% |
颜色波动幅度ΔE | <0.5 | <0.5 | <0.5 | <0.5 | <0.5 | <0.5 |
对比例的测试结果如下:
测量方法:冲击强度保留测试标准为ISO 180-2000@23℃。条纹/色斑,颜色波动性在标准光源灯箱下观察10块色板外观(条纹指塑料制品表面或内部存在的线条转条纹缺陷,色斑指塑料制品表面出现的通常为肉眼可见的斑点痕迹,如白点,黑点或带颜色的斑点),颜色波动幅度ΔE按照ISO 9001-2015执行。密度的测试标准为GB/T 1033。
从实施例实验结果来看,实施例1-6着色剂包含2-5个不同颜色的单色颜料微粒,着色剂组分中任意两种不同颜色的单色颜料微粒密度比在0.7-1.43之间,每种颜色的单色颜料微粒占比都>5%,粒径控制单色颜料微粒直径为1-2mm,长度为1-2mm,100粒重为0.31-0.67克;连续生产取样对比颜色ΔE<0.5,而且颜色均匀一致,力学冲击强度对比被着色聚合物有提高,满足连续生产管控要求。
而从对比例1-5实验结果来看,一锅混模式或者着色剂匹配性能不合理,都会引起生产过程中颜色波动,没有添加单色颜料微粒的配方(对比例1)力学性能存在挤出后衰减现象。对比例2中,单色颜料微粒组份比例小于5%,则颜色波动性大,颜色波动幅度ΔE不合格;对比例3中,密度比大于1.4或小于0.7,则导致颜色波动幅度ΔE也不合格;对比例4中,颗粒大小形态差异大,混合后物料容易产生沉降,导致体系中混合物不均匀引起颜色波动幅度ΔE也不满足要求。对比例5由于直接用一锅混模式生产,也导致颜色波动大。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (12)
2.根据权利要求1所述的着色剂,其特征在于,所述载体由丙烯晴-苯乙烯共聚物、苯乙烯-马来酸酐共聚物和甲基丙烯酸甲酯-苯乙烯-丁二烯共聚物组成,按重量比计,丙烯晴-苯乙烯共聚物:苯乙烯-马来酸酐共聚物:甲基丙烯酸甲酯-苯乙烯-丁二烯共聚物为(23-91):(2-15):(4-25)。
3.根据权利要求1所述的着色剂,其特征在于,所述颜料包括无机颜料、有机颜料、染料、金属效果颜料或荧光增白剂中的任一种;
所述无机颜料为钛白粉、硫化锌、炭黑、群青、钛黄、铁黄或铁红;有机颜料为偶氮类颜料、酞青类颜料、二噁嗪类颜料、喹吖啶酮类颜料、异吲哚啉类颜料、异吲哚啉酮类颜料、苝系颜料、喹酞酮类颜料、蒽醌类颜料或金属络合物颜料;所述染料为蒽醌类染料、偶氮类染料、亚甲基类染料、氨基酮类染料、甲亚胺类染料、喹酞酮类染料、稠环类染料、苝系染料或香豆素类染料。
4.根据权利要求1所述的着色剂,其特征在于,所述加工助剂包括氧化乙烯蜡、硬脂酸盐、乙撑双硬脂酰胺、季戊四醇酯、酯类蒙旦蜡、金属酯类或白矿油或硅油中的任一种或多种。
5.根据权利要求1所述的着色剂,其特征在于,所述抗氧剂包括酚类主抗氧剂、亚磷酸酯辅抗氧剂或抗静电剂中的任一种或多种复配。
6.根据权利要求1所述的着色剂,其特征在于,所述单色颜料微粒为圆柱体颗粒、球形颗粒、类球形颗粒或不规则立体颗粒,每100粒所述单色颜料微粒的重量为0.31-0.67克,所述单色颜料微粒的平均粒径为1-2mm。
7.根据权利要求1所述的着色剂,其特征在于,所述着色剂包括至少2种不同颜色的所述单色颜料微粒,每一所述单色颜料微粒在所述着色剂中的重量百分比不低于5%。
8.根据权利要求7所述的着色剂,其特征在于,着色剂中任意两种单色颜料微粒的密度比在0.7-1.43范围内。
9.一种制备如权利要求1-8任一项所述着色剂的方法,其特征在于,包括如下步骤:将所述单色颜料微粒的各组分称量后进行混合,并通过押出成型装置成型为单色颜料微粒;将所述单色颜料微粒称量并混合,得到所述着色剂。
10.一种着色材料,其特征在于,包括被着色物料,以及根据权利要求1-8任一项所述的着色剂,其中,按重量百分比计,所述被着色物料为90-96%,所述着色剂为4-10%。
11.根据权利要求9所述的着色材料,其特征在于,所述被着色物料包括苯乙烯、高抗冲聚苯乙烯、丙烯晴-丁二烯-苯乙烯共聚物、丙烯晴-苯乙烯共聚物、ABS/PC共混改性材料或PVC/ABS共混改性材料中的一种或多种。
12.一种制备如权利要求10或11所述着色材料的方法,其特征在于,将所述被着色材料与所述着色剂分别称重,挤出造粒形成所述着色材料。
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