CN1250344C - 在多孔或吸收材料上产生涂层的方法 - Google Patents
在多孔或吸收材料上产生涂层的方法 Download PDFInfo
- Publication number
- CN1250344C CN1250344C CN01816245.2A CN01816245A CN1250344C CN 1250344 C CN1250344 C CN 1250344C CN 01816245 A CN01816245 A CN 01816245A CN 1250344 C CN1250344 C CN 1250344C
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- China
- Prior art keywords
- porous
- absorbing material
- coating
- smears
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
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- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/3179—Next to cellulosic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31899—Addition polymer of hydrocarbon[s] only
- Y10T428/31902—Monoethylenically unsaturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
Abstract
本发明涉及在多孔或吸收材料上通过液态涂布剂的辐射诱导聚合产生涂层的方法。
Description
技术领域
本发明涉及在多孔或吸收材料上通过液体涂布剂的辐射诱导聚合产生涂层的方法。
背景技术
基于低粘度(甲基)丙烯酸酯的可通过辐射硬化的涂布剂，例如可从DE-A 37 06 355得知。此种典型动态粘度低于1000mPa.s的涂布剂不使用溶剂但加入光引发剂并任选地加入添加剂，采用诸如辊涂之类的各种各样方法施涂到待涂布基材上，然后依靠紫外射线的作用硬化。
该涂布剂的低粘度对施涂薄层至关重要，但若待涂布基材是具有孔隙和/或吸收性质的材料则又是不利的。譬如，液态、低粘度涂布剂会渗透到基材中，结果，当随后接受辐照时，已经渗入的那部分涂布剂将受不到射线的辐照或辐照得不充分，因此不硬化或硬化不完全。该未硬化、依然是液态的组分于是将对涂层的质量产生负面影响。特别是，将出现本领域技术人员所谓的“发汗”现象，此时液态组分透过硬化膜渗出并在涂层表面上可看到。此种效应可出现在哪怕非常短的时间以后，例如数小时，或者只有经过较长时间，例如，数月之后才出现。
发明内容
本发明的目的是提供一种通过施涂涂布剂，然后利用紫外射线使其硬化，从而在多孔或吸收材料上产生涂层的方法，该方法可防止未硬化组分发汗。
现已发现，该目的可利用通常被用作触变剂的属于聚酰胺或者低聚或聚合脂肪酸酰胺类的某种添加剂实现。
本发明涉及一种通过施涂包含至少一种动态粘度低于2000mPa.s、具有(甲基)丙烯酰基团的组分的液态涂布剂并随后以辐射诱导聚合，在多孔和/或吸收材料上产生涂层的方法，其特征在于，该涂布剂包含0.1～10wt％，相对于其非挥发组分而言，选自聚酰胺和/或低聚或聚合脂肪酸酰胺的添加剂。
可通过辐射硬化的液态涂布剂是已知的，例如描述在P.K.T.Oldring(主编)，《涂料、油墨和油漆的紫外和电子束制剂的化学与技术》，卷2，1991，SITA技术，伦敦，p.31～235。作为例子提到环氧丙烯酸酯、聚氨酯丙烯酸酯、聚酯丙烯酸酯以及胺改性的和未改性的聚醚丙烯酸酯。这些产品有市售供应并且，视组成而定，粘度在约100mPa.s～约100,000mPa.s之间变化。它们可单独也可作为共混物使用。
高粘度涂布剂通常与稀释剂混合，后者在紫外-硬化期间也将参与(共)聚合。此类稀释剂描述在P.K.T.Oldring(主编)，《涂料、油墨和油漆的紫外和电子束制剂的化学与技术》，卷2，1991，SITA技术，伦敦，p.237～285。作为例子给出丙烯酸和甲基丙烯酸的酯，优选为下列醇的丙烯酸酯。一元醇是各种异构的丁醇、戊醇、己醇、庚醇、辛醇、壬醇和癸醇，还有环脂族醇，例如，异冰片醇、环己醇和烷基化环己醇、二环戊醇，芳基脂族醇，例如，苯氧基乙醇和壬基苯基乙醇，乃至四氢糠醇。这些醇的烷氧基化衍生物也可使用。二元醇是例如诸如乙二醇、丙二醇-1，2、丙二醇-1，3、二甘醇、二丙二醇、异构的丁二醇、新戊二醇、己二醇-1，6、2-乙基己二醇和三丙二醇之类的醇，或这些醇的烷氧基化衍生物。优选的二元醇是己二醇-1，6、二丙二醇和三丙二醇。三元醇是甘油或三羟甲基丙烷或其烷氧基化衍生物。优选丙氧基化甘油。诸如季戊四醇或二(三羟甲基丙烷)之类的醇或其烷氧基化衍生物可作为多元醇使用。
用于本发明方法的涂布剂包含至少一种此种具有(甲基)丙烯酰基团的组分，其动态粘度低于2000mPa.s，优选低于1000mPa.s，尤其优选低于500mPa.s。
本发明方法使用的涂布剂包含已知引发剂，它能够在用诸如紫外光之类的高能射线辐照后引发自由基聚合反应。此种光引发剂例如描述在P.K.T.Oldring(主编)，《涂料、油墨和油漆的紫外和电子束制剂的化学与技术》，卷3，1991，SITA技术，伦敦，p.61～325。它们的用量介于0.1～10重量份，优选2～7重量份，尤其优选3～4重量份，相对于液态涂布剂而言。
该涂布剂还包含，相对于其非挥发组分含量，0.1～10wt％，优选0.3～5wt％，尤其优选0.5～2wt％选自聚酰胺或低聚或聚合脂肪酸酰胺的添加剂。本发明的聚酰胺例如是蜡状聚酰胺聚合物和/或脂肪酸-改性的聚酰胺，有市售供应，例如，按商品名CrayvallacSuper(Lubrizol Coating Additives公司，Ritterhude，德国)或Disparlon6200、6500或6600(C.H.Erbslh，Krefeld，德国)；脂肪酸酰胺例如描述在DE-A 31 35 183中。低聚或聚合脂肪酸酰胺也有市售供应，例如，CrayvallacMT和CrayvallacSF(酰胺-改性的、氢化的蓖麻油产品，Lubrizol Coating Additives公司，Ritterhude，德国)。这些产品按本发明观察到的效果是惊人的，因为许多其他触变剂在本发明方法中没有任何效果，因此不合适。
按本发明制备的涂布剂还可与种类繁多的助剂和添加剂混合使用。这些包括填料、颜料、染料、光滑剂、消光剂或流平剂，它们可按传统用量使用。对自由基聚合呈惰性的溶剂也可使用。本发明方法因此包括，在涂布与硬化加工之间，通风或溶剂从液态涂层中的蒸发。
本发明方法适合在吸收性和/或多孔基材，例如，纸、纸板、皮革、织物、木材、木质材料如中密度纤维板，陶磁或矿物材料以及在多孔塑料上，产生高品质涂层。
该涂布剂在待涂布材料上的施涂可采用传统和已知用于挥发性漆技术的方法，例如，喷涂，刮刀涂布、辊涂、流涂、浸涂、旋涂和喷雾(vaccumate)。液态涂布剂通过以紫外光进行辐照达到硬化。为此，令涂布的材料从汞中压辐射器下面通过。采用紫外-射线的硬化按已知方法实施并描述在P.K.T.Oldring(主编)，《涂料、油墨和油漆的紫外和电子束制剂的化学与技术》，卷1，1991，SITA技术，伦敦，p.167～269。
具体实施方式
实施例
按照下表(数字以重量份为单位)配制涂布剂并通过分散达到均化。涂布剂以手工刮刀施涂到橡木胶合板上，层厚约30μm。随后，片材从一种输出为每厘米灯长度80瓦的汞高压辐射器下面通过。每种情况都形成硬、耐溶剂膜(试验采用浸泡在乙酸丁酯中的棉球做50次往返擦洗)。为试验发汗表现，打磨漆膜并让磨毛的粉末呆在漆膜或板上过夜。次日清晨，评估磨毛粉末的潮湿程度并作为发汗的尺度。完全干爽的磨毛粉末评定为0，非常潮的磨毛粉末定为5。
| 配方[重量份] | 参照 | 本发明 | ||||||||
| 实施例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| RoskydalUA VP LS2299 | 84 | 84 | 84 | 84 | 84 | 84 | 84 | 84 | ||
| LaromerPO 84F | 100 | 100 | ||||||||
| TPGDA | 16 | 16 | 16 | 16 | 16 | 16 | 16 | |||
| DPGDA | 16 | |||||||||
| EsacureTZT | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| Byk410 | 2 | |||||||||
| Aerosil300 | 2 | |||||||||
| CrayvallacMT | 2 | |||||||||
| CrayvallacSF | 2 | |||||||||
| CrayvallacSuper | 2 | 2 | ||||||||
| Disparlon6500 | 2 | 2 | ||||||||
| 试验[评分] | ||||||||||
| 配方[重量份] | 参照 | 本发明 | ||||||||
| 发汗10.0m/min | 3 | 5 | 4 | 3 | 0 | 0 | 0 | 1 | 0 | 0 |
| 发汗20.0m/min | 5 | 5 | 5 | 3 | 0 | 0 | 0 | 1 | 0 | 0 |
| 发汗30.0m/min | 5 | 5 | 5 | 3 | 1 | 1 | 0 | 1 | 0 | 0 |
| 发汗40.0m/min | 5 | 5 | 5 | 4 | 1 | 2 | 0 | 2 | 0 | 0 |
配方：数字以重量份为单位
RoskydalUA VP LS 2299(拜尔公司，Leverkusen，德国)-胺改性的聚醚丙烯酸酯，粘度约800mPa.s。
LaromerPO84F(BASF，Ludwigshafen，德国)-胺改性的低聚醚丙烯酸酯，粘度约1000mPa.s
TPGDA-三丙二醇的二丙烯酸酯
DPGDA-二丙二醇的二丙烯酸酯
EsacureTZT(Lamberti，Aldizzate，意大利)，光引发剂(改性的二苯酮)
Byk410(Byk-Chemie，Wesel，德国)-改性脲的溶液
Aerosil300(Degussa-Hüls，法兰克福，德国)-火成硅酸
CrayvallacMT和CrayvallacSF(Lubrizol CoatingAdditives公司，Ritterhude，德国)-酰胺改性的氢化蓖麻油
CrayvallacSuper(Lubrizol Coating Additives公司，Ritterhude，德国)-聚酰胺蜡
Disparlon6500(C.H.Erbslh，Krefeld，德国)-脂肪酸改性的聚酰胺
各种不同的板在不同皮带速度(10、20、30、40m/min)的条件下进行硬化，然后试验其发汗表现：0＝最佳得分，5＝最差得分。
这些实施例清楚地表明，本发明方法(实施例5～10)与参照方法(实施例1～4)相比显著地减少了、常常完全防止了发汗。
Claims (10)
1.一种通过施涂包含至少一种动态粘度低于2000mPa.s、具有(甲基)丙烯酰基团的组分的液态涂布剂并随后进行辐射诱导聚合，从而在多孔和/或吸收材料上产生涂层的方法，其特征在于，该涂布剂包含0.1～10wt％，相对于其非挥发组分而言，选自聚酰胺和/或低聚或聚合脂肪酸酰胺的添加剂。
2.权利要求1的方法，其特征在于，纸被用作多孔和/或吸收材料。
3.权利要求1的方法，其特征在于，纸板被用作多孔和/或吸收材料。
4.权利要求1的方法，其特征在于，织物被用作多孔和/或吸收材料。
5.权利要求1的方法，其特征在于，木材被用作多孔和/或吸收材料。
6.权利要求1的方法，其特征在于，木质材料被用作多孔和/或吸收材料。
7.权利要求1的方法，其特征在于，纤维板被用作多孔和/或吸收材料。
8.权利要求1的方法，其特征在于，陶磁材料被用作多孔和/或吸收材料。
9.权利要求1的方法，其特征在于，矿物材料被用作多孔和/或吸收材料。
10.权利要求1的方法，其特征在于，多孔塑料被用作多孔和/或吸收材料。
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| PL361018A1 (en) | 2004-09-20 |
| CA2422935A1 (en) | 2003-03-21 |
| US6902769B2 (en) | 2005-06-07 |
| US6635699B2 (en) | 2003-10-21 |
| ES2336767T3 (es) | 2010-04-16 |
| EP1328354A2 (de) | 2003-07-23 |
| DE10047290A1 (de) | 2002-04-11 |
| US20020106524A1 (en) | 2002-08-08 |
| EE200300118A (et) | 2005-04-15 |
| HUP0302626A3 (en) | 2008-01-28 |
| EP1328354B1 (de) | 2010-01-06 |
| CN1466494A (zh) | 2004-01-07 |
| WO2002024343A3 (de) | 2002-11-07 |
| AU2002213905A1 (en) | 2002-04-02 |
| ATE454222T1 (de) | 2010-01-15 |
| CZ2003861A3 (cs) | 2003-08-13 |
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