CN111040334A - 一种添加活性竹炭的环保pvc发泡板材及其制造方法 - Google Patents

一种添加活性竹炭的环保pvc发泡板材及其制造方法 Download PDF

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CN111040334A
CN111040334A CN201911232498.3A CN201911232498A CN111040334A CN 111040334 A CN111040334 A CN 111040334A CN 201911232498 A CN201911232498 A CN 201911232498A CN 111040334 A CN111040334 A CN 111040334A
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activated bamboo
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陈永禄
陈丁桂
范有发
洪丽华
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Fujian University of Technology
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Abstract

本发明公开了一种添加活性竹炭的环保PVC发泡板材及其制造方法,该类板材不添加含苯、邻苯、重金属的化合物,利用活性竹炭的多孔性和光触媒的光催化作用,实现对有害物质(尤其是甲醛)的有效吸附与降解,并消除异味,结合成型工艺控制,使其含水率、静曲强度、弹性模量、握钉力、吸水厚度膨胀等性能均优于现行国标,并具有防水、防潮、防霉性能,隔音效果好,耐酸碱腐蚀,导热保暖性良好,安装施工方便快捷,生产过程实现有害气体零排放及产品边料的可再生性。本发明生产的活性竹炭板可进一步应用于墙体、门窗、柜体、柜门、雕花面板、茶具等领域,经表面装饰(贴面)处理后,还可用于生产高级贴面板和复合地板,具有广泛的应用领域。

Description

一种添加活性竹炭的环保PVC发泡板材及其制造方法
技术领域
本发明属于材料领域,特别是一种添加活性竹炭的环保PVC发泡板材及其制造方法。
背景技术
随着房地产行业的飞速发展,装修用材的环保问题一直是人们追求健康居家环境的讨论热点。板材是房屋装修装饰过程中的主要用材,基材种类繁多,款式多样,其中,人造板材更是占据重要市场份额。为规范人造板材市场,2018年5月1日,新修订出台的国家标准《室内装饰装修材料人造板及其制品中甲醛释放限量》(GB18580-2017)正式实施。新国标直击行业环保痛点,最引人关注的就是提升了甲醛释放量限量要求,对当前板材市场格局产生巨大的冲击。
竹炭板是目前装修装饰市场中最为引人注目的一类人造板材,其本质是一种添加了竹炭粉及其它功能性组分的硬质PVC结皮发泡实心板。通过组分与成型工艺优化,实现硬度高、强度大、握钉力强、不变形、不开裂、吸湿放湿、防腐防潮防蛀、去异味添芳香等特点,并将逐步取代目前市面上密度板、木工板、胶合板、贴面板、指接板等污染严重的复合装饰板材,以及目前市面上流行的木塑装饰板材,在装修装饰行业中被誉为“未来的木材”。然而,目前市售的竹炭板质量参差不齐。比如,使用常规炭化竹炭替代经活化处理的竹炭粉,在大幅度降低成本的同时,也大幅度降低竹炭对甲醛等有毒挥发物质的吸附作用;此外,还有厂家将常规炭化竹炭以规则炭块(板)或炭包的形式嵌附、封闭的在多层PVC板中,难以满足板材的施工工艺要求。在环保要求方面,有些竹炭板在生产过程中为了降低成本、提高成型性能或满足某些性能要求,添加了含有苯、邻苯、重金属的化合物,成为装修装饰中的直接污染源。
CN 108610574 A公开了一种含有竹炭的复合板材配方,其质量份组成为:聚氯乙烯(PVC)、树脂100份、竹炭25份、氯化聚乙烯(CPE)10份、纳米活性碳酸钙7份、钙锌复合稳定剂6份、聚醋增塑剂11份、硼酸醋偶联剂1.5份、AC发泡剂1.2份、碳酸氢钠0.6份、发泡调节剂3份、硬脂酸甘油脂0.6份、聚乙烯蜡0.5份。该发明基于环保目的,说明添加了竹炭,但未说明竹炭的性状。
CN 106836731 A公开了一种环保竹炭板及其制作方法,该竹炭板包括竹炭板基板和设置在所述竹炭板基板表面的装饰层,所述竹炭板基板按照质量份为40~60份的竹炭粉、30~50份的树脂粉、1.5~5份的稳定剂、2~8份的CPE、0.2~1份的PE蜡、0.3~1.5份的润滑脂、4~6份的发泡调节剂和0.5~2份发泡剂组成。本发明简要说明了竹炭板的生产过程,并指出该竹炭板可有效吸附和降解甲醛等有害物质,具有高环保、无污染、无公害、可循环利用性能。
CN 105647219 A公开了一种竹炭板及其制作方法。该竹炭板的原料按照质量份主要包含30~100份由炭粉和竹细纤维粉混合组成的吸附基质(竹细纤维粉占吸附基质质量的5~95%)以及10~130份树脂基料,还包含1~10份固定剂、1~5份润滑剂、0.1~0.5份膨胀剂,并描述其生产工艺流程。本发明未说明在权利要求中未明确所述炭粉为竹炭粉或活性竹炭粉,根据发明内容,可以理解为所谓竹炭板中的“竹”主要指竹细纤维粉。此外,发明在描述炭粉的吸附作用时混淆了石墨和活性炭的结构,石墨为碳的单质,无孔,而活性炭不仅含有碳单质,还含有有机或者无机的官能团,是密集的孔隙结构。
CN 105111752 A公开了一种能有效吸附和自动降解甲醛的环保竹炭板材,按质量百分比,由以下原料组成:200目的高温竹炭微粒10~50%,120目低温竹炭微粒15%~50%,天然树脂18~19%,复合稳定剂2~3%,密度降低剂1~2%,竹纤维或芦苇纤维或炭化竹粉2~7%,纳米级二氧化钛粉1~1.5%,相溶剂1~1.5%,轻质碳酸钙0.5~1%,氧化钙0.5~1%,外滑剂PE蜡1~2%,内滑剂硬脂酸1. 5%,CPE0.5~1%,分散剂0.5%,偶联剂0.5~1%,发泡剂0.5~1%。该发明有效解决了竹炭在吸收甲醛后无法自动降解的问题,避免二次污染,且具有高环保、无污染、无公害、可循环利用性能。
上述专利技术中存在的主要问题为:1.制作原料的选取和配比不够合理,造成竹炭板的吸附能力不够强;2.原料组分和加工方式不合理,造成了竹炭板静曲强度不足、干热尺寸变化率偏大、受热易翘曲、握钉力差等缺陷;3.一些竹炭板仅有吸附能力,而缺乏降解甲醛等有害物质的能力,净化空气的能力有限。
发明内容
针对上述不足,本发明提出一种添加了活性竹炭粉的环保板材及其生产工艺,该类板材不添加含苯、邻苯、重金属的化合物,利用活性竹炭的多孔性和光触媒的光催化作用,实现对有害物质(尤其是甲醛)的有效吸附与降解,并消除异味,结合成型工艺控制,使其含水率、静曲强度、弹性模量、握钉力、吸水厚度膨胀等性能均优于现行国标,并具有防水、防潮、防霉性能,隔音效果好,耐酸碱腐蚀,导热保暖性良好,安装施工方便快捷,生产过程实现有害气体零排放及产品边料的可再生性。本发明生产的活性竹炭板可进一步应用于墙体、门窗、柜体、柜门、雕花面板、茶具等领域,经表面装饰(贴面)处理后,还可用于生产高级贴面板和复合地板,具有广泛的应用领域。
一种添加活性竹炭的环保PVC发泡板材,其特征在于,包括如下重量份的组分:
聚氯乙烯:40~46份
碳酸钙粉:24~30份
活性竹炭粉:15~21份
钙锌稳定剂:1.6~3.0份
PVC发泡调节剂ACR:4.2~5.5份
增强剂:0.5~2份
增韧剂:0.1~1.5份
外润滑剂:0.5~1份
内润滑剂:0.3~0.7份
AC黄发泡剂:0.1~0.4份
NC白发泡剂:0.4~0.8份。
进一步的,聚氯乙烯为SG-7型或SG-8型树脂与SG-5型树脂混合使用,SG-7型或SG-8型树脂与SG-5型树脂的质量比为(70~80):(30~20)。
进一步的,所述为碳酸钙粉为粒度不高于200目重质碳酸钙粉或超细活性碳酸钙。
进一步的,PVC发泡调节剂ACR为DFL-300和T-218按2:1的质量比混合得到。
进一步的,外润滑剂为PE蜡(LC-108)和OPE蜡(GMT-1816)按质量比3:2混合得到。
进一步的,活性竹炭粉的粒度不高于200目。
进一步的,还包括如下重量份的组分:
光触媒剂:0.8~2.0份
硅烷偶联剂:0.5~2.5份。
进一步的,所述光触媒剂由20~30%质量分数的1~3微米的玻璃微珠和80~70%质量分数的纳米尺寸级别的二氧化钛、氧化锌、氧化锡或二氧化锆中的一种或几种的混合物组成;
硅烷偶联剂为氨基硅烷或环氧基硅烷。
一种添加活性竹炭的环保PVC发泡板材的制造方法,其特征在于,包括如下步骤:
步骤一)配料与混合:将PVC树脂加入到高速热混机中,约500r/min搅拌升温至55~65℃;投入钙锌稳定剂,约600r/min搅拌升温至85~95℃,再依次加入增强剂、增韧剂、内润滑剂、钙粉、活性竹炭粉、发泡剂、PVC发泡调节剂,持续搅拌;再加入外润滑剂、光触媒剂、硅烷偶联剂,硅烷偶联剂以喷洒方式加入,所有物料总投入量应控制在热混锅有效容积的50~70%,约700r/min高速搅拌升温至110~125℃,继续搅拌5~10 min;在约60r/min低转速下将物料排入通有冷却水的冷混机中,搅拌5~10min,35~45℃出料;
步骤二)结皮发泡、挤出:挤出温度采用多级、多点独立加热的方式控制:加热系统沿进料端至出料端采用多级、多点独立加热的方式,控温精度为0.5℃。正常生产时各区域温度控制范围为:给料区175~180℃、压缩区168~172℃、熔融区164~166℃、计量区163~165℃、合流芯160~162℃、模具一区170~172℃、模具二区174~176℃、模具三区180~184℃、模具四区181~185℃、模具五区181~185℃、模具六区172~176℃、口模区170~174℃、螺杆油温75~90℃;
螺杆转速控制在15~24r/min,挤出速度控制在2.2~4m/min,挤出压力控制在13.5~16MPa;
步骤三)冷却定型:挤出的物料进入到模具中,采用四级冷却定型工艺,第1级模板真空度 0.01~0.05MPa,各级定型模板温度控制在10~15℃,模板内表面粗糙度为达Ra0.8μm以上;
步骤四)牵引切割:根据板材配方、厚度、泡孔尺寸及质量要求,牵引力控制在30~45kN,牵引速率在0.5~5m/min。
如权利要求9所述的一种添加活性竹炭的环保PVC发泡板材的制造方法,其特征在于,还包括如下步骤:
步骤五)养生、检测、后续处理、包装、出货:将活性竹炭板在室温下水平堆叠存放24~48h,待充分养生后,板材尺寸稳定,即进行产品检测,合格产品包装后出货。
本发明取得的有益效果有:
1、优化设计活性竹炭环保PVC板材的组分,详细说明其加料顺序及其工艺参数,确定采用PVC为树脂基料,取材方便且性状可调整,并可与工艺参数明确对应。
2、添加了活性竹炭,简化炭粉组分的选择与添加工艺,并提高综合吸附能力。
3、光触媒剂的有效组分有了更多选择,并明确加入有利于提高纳米粒子分散性的硅烷偶联剂及其加入方式,玻璃微珠还可同时提高板材强度与热稳定性。
4、明确了活性竹炭板厚度方向截面结构、形貌与板材性能之间的关系,有利于更好地利用组分与工艺调整来有效改善板材的性能。
5、活性竹炭板的综合性能好,应用范围更广。
附图说明
图1为18mm竹炭板的板厚截面形貌(从左到右为板厚方向)
具体实施方式:
本专利以活性竹炭环保板材组分优化为基础,结合成型工艺流程及工艺参数优化,提升板材的成型质量及综合性能。
、组分设计
按各组分的质量百分比(%)计算,本发明优化设计的活性竹炭板组分为:
聚氯乙烯(PVC):40~46%
钙粉:24~30%
钙锌稳定剂(LG612M):1.6~3.0%
PVC发泡调节剂ACR:4.2~5.5%
增强剂(LC-20):0.5~2%
增韧剂(L-900):0.1~1.5%
外润滑剂(PE蜡+OPE蜡):0.5~1%
内润滑剂(硬脂酸,LC-60):0.3~0.7%
AC黄发泡剂:0.1~0.4%
NC白发泡剂:0.4~0.8%
活性竹炭粉:15~21%
光触媒剂:0.8~2.0%
硅烷偶联剂:0.5~2.5%
2、主要组分的作用与设计特点
(1)PVC可选择SG-7型或SG-8型树与SG-5型混合使用,二者的比例可控制在:(70~80):(30~20)。
(2)钙粉在竹炭板材中主要起骨架作用,可用于提高板材的硬度、刚性、耐热性和阻燃性,改善加工性能,并降低成本,一般选择重质碳酸钙粉,粒度不高于200目。如果产品质量要求高,也可选用超细活性碳酸钙ACC进行部分替换或全部替换。
(3)PVC发泡调节剂ACR主要由DFL-300和T-218按2:1配合使用。
(4)外润滑剂选用PE蜡(LC-108)和OPE蜡(GMT-1816)按质量比3:2混用。
(5)活性竹炭粉的粒度不高于200目。利用活性炭自身的炭质气孔有效地吸附空气中一部分浮游物质,对硫化物、氢化物、甲醛、苯、酚等有害化学物质起到吸附、分解异味和除臭净化空气的作用。
(6)光触媒剂主要由质量分数为20~30%的1~3微米的玻璃微珠(主要为SiO2)和质量分数为80~70%的纳米尺寸级别的二氧化钛(TiO2)、氧化锌(ZnO)、氧化锡(SnO2)、二氧化锆(ZrO2)中的1~2种氧化物粉体组成。结合活性竹炭粉的吸附作用与光触媒剂的光催化功能,将甲醛等有害有机物氧化分解为CO2和H2O,实现对甲醛的不断地吸附与降解,并由此形成良性循环效应。
(7)硅烷偶联剂可选用KH550(氨基硅烷)或KH560(环氧基硅烷),主要用于提高活性竹炭粉与光触媒剂粉体在板材中的分散性,进一步提高活性竹炭板材中上述组分的有益作用,其添加量可根据填料数量与粒径尺寸决定,采用喷洒方式加入,以促进混合均匀。
、工艺设计
(1)配料与混合工艺
Figure DEST_PATH_IMAGE001
将物料按配方比例进行称重,对于固态物料需事先干燥;
Figure 275197DEST_PATH_IMAGE002
将PVC树脂加入到高速热混机中,约500r/min搅拌升温至55~65℃。
Figure DEST_PATH_IMAGE003
投入钙锌稳定剂,约600r/min搅拌升温至85~95℃,再依次加入增强剂、增韧剂、内润滑剂、钙粉、活性竹炭粉、发泡剂、PVC发泡调节剂,持续搅拌。
Figure 732723DEST_PATH_IMAGE004
加入外润滑剂、光触媒剂、硅烷偶联剂,硅烷偶联剂以喷洒方式加入,所有物料总投入量应控制在热混锅有效容积的50~70%,约700r/min高速搅拌升温至110~125℃,在此温度下搅拌5~10 min后进入冷混。
Figure DEST_PATH_IMAGE005
在约60r/min低转速下将物料排入通有冷却水的冷混机中,搅拌5~10min,于35~45℃出料。
(2)结皮发泡、挤出工艺
Figure 609413DEST_PATH_IMAGE001
温度控制:加热系统沿进料端至出料端采用多级、多点独立加热的方式,控温精度为0.5℃。正常生产时各区域温度控制范围为(热电偶测试温度):给料区175~180℃、压缩区168~172℃、熔融区164~166℃、计量区163~165℃、合流芯160~162℃、模具一区170~172℃、模具二区174~176℃、模具三区180~184℃、模具四区181~185℃、模具五区181~185℃、模具六区172~176℃、口模区170~174℃、螺杆油温75~90℃
Figure 900717DEST_PATH_IMAGE002
螺杆转速、挤出速度与挤出压力
螺杆转速与熔体挤出速度、挤出压力、板材的挤出产量成正比,与板材的密度成反比。根据板材厚度和泡孔要求,螺杆转速控制在15~24r/min,挤出速度控制在2.2~4m/min,挤出压力控制在13.5~16MPa。
(3)冷却定型工艺
采用四级冷却定型工艺,第1级模板真空度 0.01~0.05MPa,各级定型模板温度控制在10~15℃,冷却应尽量均匀、缓慢,模板内表面粗糙度为达Ra0.8μm以上,根据不同配方条件下发泡体的收缩特性,模板内腔预留出一定收缩量。
(4)牵引切割工艺
牵引工艺直接影响板材的密度、泡孔结构和出料的均匀性。根据板材配方、厚度及质量要求,牵引力控制在30~45kN,牵引速率在0.5~5m/min范围内连续可调。冷却定型后的板材经定长与定宽双边平行切割,可根据客户需要获得合适的长度与宽幅。
(5)养生、检测、后续处理、包装、出货
将活性竹炭板在室温下水平堆叠存放24~48h,待充分养生后,板材尺寸稳定,即进行产品检测,合格产品可进行后续工艺处理(贴皮、上漆、雕刻等)或直接包装后出货。
、活性竹炭板的性能
对厚度为18mm,设计密度为1.0g/cm3的活性竹炭板进行检测,其主要测试结果为:
(1)理化性能
含水率0.5%、静曲强度33.4MPa、弹性模量2880MPa、24h吸水厚度膨胀率0.01%、板面握螺钉力2630N、干热尺寸变化率(纵向:+0.28%;横向:+0.3%)。
(2)甲醛释放量(72h,mg/m3
未检出。
(3)空气声隔声量
32dB。
(4)重金属含量
Ba:<5ppm;Pb:<5ppm;Cd:<5ppm;Sb:<5ppm;Se:<5ppm;Cr:<5ppm;Hg:<5ppm;As:<2.5ppm。
5、竹炭板结皮层厚度、泡孔尺寸与力学性能的对应关系
对于18mm竹炭板,以板材半厚度为界(见图1),当单边结皮层厚度大于20%,发泡孔尺寸小于0.5mm且较为均匀,静曲强度和弹性模量可满足要求。

Claims (10)

1.一种添加活性竹炭的环保PVC发泡板材,其特征在于,包括如下重量份的组分:
聚氯乙烯:40~46份
碳酸钙粉:24~30份
活性竹炭粉:15~21份
钙锌稳定剂:1.6~3.0份
PVC发泡调节剂ACR:4.2~5.5份
增强剂:0.5~2份
增韧剂:0.1~1.5份
外润滑剂:0.5~1份
内润滑剂:0.3~0.7份
AC黄发泡剂:0.1~0.4份
NC白发泡剂:0.4~0.8份。
2.如权利要求1所述的一种添加活性竹炭的环保PVC发泡板材,其特征在于,聚氯乙烯为SG-7型或SG-8型树脂与SG-5型树脂混合使用,SG-7型或SG-8型树脂与SG-5型树脂的质量比为(70~80):(30~20)。
3.如权利要求1所述的一种添加活性竹炭的环保PVC发泡板材,其特征在于,所述为碳酸钙粉为粒度不高于200目重质碳酸钙粉或超细活性碳酸钙。
4.如权利要求1所述的一种添加活性竹炭的环保PVC发泡板材,其特征在于,PVC发泡调节剂ACR为DFL-300和T-218按2:1的质量比混合得到。
5.如权利要求1所述的一种添加活性竹炭的环保PVC发泡板材,其特征在于,外润滑剂为PE蜡(LC-108)和OPE蜡(GMT-1816)按质量比3:2混合得到。
6.如权利要求1所述的一种添加活性竹炭的环保PVC发泡板材,其特征在于,活性竹炭粉的粒度不高于200目。
7.如权利要求1所述的一种添加活性竹炭的环保PVC发泡板材,其特征在于,还包括如下重量份的组分:
光触媒剂:0.8~2.0份
硅烷偶联剂:0.5~2.5份。
8.如权利要求7所述的一种添加活性竹炭的环保PVC发泡板材,其特征在于,所述光触媒剂由20~30%质量分数的1~3微米的玻璃微珠和80~70%质量分数的纳米尺寸级别的二氧化钛、氧化锌、氧化锡或二氧化锆中的一种或几种的混合物组成;
硅烷偶联剂为氨基硅烷或环氧基硅烷。
9.一种添加活性竹炭的环保PVC发泡板材的制造方法,其特征在于,包括如下步骤:
步骤一)配料与混合:将PVC树脂加入到高速热混机中,约500r/min搅拌升温至55~65℃;投入钙锌稳定剂,约600r/min搅拌升温至85~95℃,再依次加入增强剂、增韧剂、内润滑剂、钙粉、活性竹炭粉、发泡剂、PVC发泡调节剂,持续搅拌;再加入外润滑剂、光触媒剂、硅烷偶联剂,硅烷偶联剂以喷洒方式加入,所有物料总投入量应控制在热混锅有效容积的50~70%,约700r/min高速搅拌升温至110~125℃,继续搅拌5~10 min;在约60r/min低转速下将物料排入通有冷却水的冷混机中,搅拌5~10min,35~45℃出料;
步骤二)结皮发泡、挤出:挤出温度采用多级、多点独立加热的方式控制,加热系统沿进料端至出料端采用多级、多点独立加热的方式,控温精度为0.5℃;正常生产时各区域温度控制范围为:给料区175~180℃、压缩区168~172℃、熔融区164~166℃、计量区163~165℃、合流芯160~162℃、模具一区170~172℃、模具二区174~176℃、模具三区180~184℃、模具四区181~185℃、模具五区181~185℃、模具六区172~176℃、口模区170~174℃、螺杆油温75~90℃;
螺杆转速控制在15~24r/min,挤出速度控制在2.2~4m/min,挤出压力控制在13.5~16MPa;
步骤三)冷却定型:挤出的物料进入到模具中,采用四级冷却定型工艺,第1级模板真空度 0.01~0.05MPa,各级定型模板温度控制在10~15℃,模板内表面粗糙度为达Ra0.8μm以上;
步骤四)牵引切割:根据板材配方、厚度、泡孔尺寸及质量要求,牵引力控制在30~45kN,牵引速率在0.5~5m/min。
10.如权利要求9所述的一种添加活性竹炭的环保PVC发泡板材的制造方法,其特征在于,还包括如下步骤:
步骤五)养生、检测、后续处理、包装、出货:将活性竹炭板在室温下水平堆叠存放24~48h,待充分养生后,板材尺寸稳定,即进行产品检测,合格产品包装后出货。
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