CN105556034B - 用于离型纸的浸渍材料 - Google Patents
用于离型纸的浸渍材料 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 37
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 34
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 239000011111 cardboard Substances 0.000 claims abstract description 3
- 239000011087 paperboard Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 150000003283 rhodium Chemical class 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 28
- 239000000123 paper Substances 0.000 description 24
- 229910000077 silane Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000037452 priming Effects 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
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- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 polysiloxanes Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 229920006268 silicone film Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
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Abstract
本发明涉及可通过含烯属C‑C双键的聚乙烯醇与含硅烷基团的交联剂和含烯属C‑C双键的硅酮化合物的反应得到的浸渍剂。优选使用纸或纸板作为纤维素基材料。
Description
本发明涉及使用含烯属双键的聚乙烯醇浸渍表面，特别是纸张的方法。
技术领域
为制造所谓的离型纸,长期以来已知的是，提供具有硅酮层的纸载体，由此获得脱粘（dehäsive）性质。
直接在纸载体上，即直接在纤维素纤维上施加硅酮层是困难的，并产生不令人满意的离型性质。因为大多数纸张包含聚乙烯醇作为底漆，并且硅酮层更易于粘合到这种聚合物上，所以已制定了一系列的用聚乙烯醇硅酮化纸表面的方法。
如，EP 1625254 A1为此建议使含硅烷的聚乙烯醇与乙烯基封端的聚硅氧烷和含H的硅氧烷反应。所使用的含硅烷的聚乙烯醇在聚合物的主链中包含Si 基团，并且可由一种或多种乙烯基酯与含硅烷的烯属不饱和单体的共聚得到。这种方法的缺点是，该含硅烷的聚乙烯醇制备复杂，并且硅油与该底漆的粘合并非通过化学相互作用，而是通过物理相互作用（氢键）进行。因此，所得到的浸渍层机械性能不足。
由WO 2009/147283 A1已知使用在侧链中具有Si基团的缩醛化聚乙烯醇作为浸渍剂。这样的含硅烷的聚乙烯醇缩醛可通过用合适的硅烷取代的酮或醛使聚乙烯醇缩醛化来得到。硅烷改性的醛或酮的制备非常复杂，并且其与聚乙烯醇，尤其是已引入纸张中的聚乙烯醇的反应困难。这种硅烷改性的聚乙烯醇与交联剂和硅油的反应通过氢键进行，因此，这里也产生机械性能同样不令人满意的层。
因此，目的在于提供浸渍表面，尤其用于制造离型纸的方法，所述方法提供机械和化学稳定的涂层并避免提供硅烷改性的聚乙烯醇。
令人惊讶地已发现，可为聚乙烯醇提供烯属不饱和C-C双键，并且这些双键可用于硅氧烷交联剂的化学键合。用这种方法可以用硅氧烷化合物浸渍施加有这种改性聚乙烯醇的表面，这对于纸表面而言尤其产生所谓的离型纸。
因此，本发明的主题是可通过包含烯属C-C双键的聚乙烯醇与含硅烷基团的交联剂和含烯属C-C双键的硅酮化合物的反应得到的浸渍剂。
该反应尤其用铂-、钯-或铑盐或-配合物来催化。优选使用铂和烯烃的配合物，因为，由此可在室温下催化该反应。包含氮化合物的铂配合物如吡啶、苄腈或苯并三唑在高温下催化该反应。
所述聚乙烯醇优选在主链中包含烯属C-C双键。这种化合物例如可通过热处理聚乙烯醇得到。在主链中具有烯属C-C双键的聚乙烯醇由Kuraray Europe GmbH在类型名称Poval L8、L9或L10下提供。
优选使用通式I的化合物:
其中n=100-3000
或者,该聚乙烯醇可在侧链中包含烯属C-C双键。这种化合物可通过例如根据下述反应方程式的乙酸乙烯酯与二乙烯基醚的共聚获得：
在这两种方案中，聚乙烯醇的水解度为90-99 mol %，烯属C-C双键的比例为0.01-5mol %。
在本发明的浸渍剂中，优选使用通式II的化合物作为含硅烷基团的交联剂
。
在本发明的浸渍剂中，优选使用通式III的化合物作为含烯属C-C双键的硅酮化合物:
。
含烯属C-C双键的硅酮化合物与含硅烷基团的交联剂反应，生成例如以通式IV表示的中间产物
。
随后，该中间产物与含烯属C-C双键的聚乙烯醇反应，生成例如以通式V表示的浸渍剂。
用于根据本发明的方法的优选基底是由纸或纸板构成的纤维素基材料。
本发明还涉及通过施加浸渍剂浸渍纤维素基材料的方法，所述浸渍剂可通过包含烯属C-C双键的聚乙烯醇与含硅烷基团的交联剂和含烯属C-C双键的硅酮化合物的反应得到。
优选如此进行根据本发明的方法，即，将包含烯属C-C双键的聚乙烯醇施加在纤维素基材料上，然后与含硅烷基团的交联剂和含烯属C-C双键的硅酮化合物反应。
所有描述用于浸渍剂的实施方案均可用于本发明的方法中。
实施例
在蒸汽溶解站中，在98℃下，将所用聚乙烯醇溶解约40分钟，然后过滤，以除去可能的未溶解的颗粒。
给商购可得的80g/m2 纸配备由Erikson的K – Control-Coater K202构成的底漆。随后，借助刮刀施加PVA溶液，并将涂覆过的纸用Dow的干燥带在130℃下干燥2次。然后在120℃下在干燥箱中继续干燥2 分钟，以确定单位面积重量。将涂覆过的纸用熨斗在100℃下预先熨平1分钟。然后使该纸在50℃和85 %的相对湿度下回潮24小时，以使其随后在1.8 kN/cm 80℃下用2个压延辊（nips）压延。
将如此得到的纸用实验室方法硅酮化。在制备该混合物时要注意配料顺序。所述纸的硅酮化借助线刮刀用Erikson的K-Control Coater K202进行。
为设定希望的单位面积重量，用合适的溶剂(ICP溶剂CAS 64742-47-8)稀释硅酮混合物。输送该纸2次通过168℃下的干燥段。然后，在干燥(在干燥箱中在120℃下2 分钟)后测定单位面积重量。
制备具有下述涂层的纸：
| 实验 | 组成 |
| A | 100 GT Mowiol 15-99, 得自Kuraray Europe GmbH 的聚乙烯醇，不含烯属双键，非根据本发明的 |
| B | 100 GT KRE-509, 得自Kuraray Europe GmbH的聚乙烯醇，具有0.35 mol % 的烯属双键和1000的聚合度, 根据本发明的 |
| 实验 | 组成 |
| C | 100 GT Mowiol 15-99 |
| 100 GT Silicoleas 树脂 11362 | |
| 5 GT Silicoleas 交联剂12031 | |
| 5 GT Silicoleas 催化剂12070 |
| 实验 | 组成 |
| D | 100 GT KRE-509 |
| 100 GT Silicoleas 树脂 11362 | |
| 5 GT Silicoleas 交联剂12031 | |
| 5 GT Silicoleas 催化剂12070 |
硅酮的施加量为2或3 g/m2。
将现配备有面漆的纸用熨斗在100℃下熨平1分钟。
在熨烫后立即进行首次“擦除实验”。随后，将该纸储存在23℃和50 %的相对空气湿度下，在1天、1周后和随后8周每周一次进行该实验。
如下进行该检测：
在硅酮膜上用手指摩擦10次，应如此选择压力，以使手指明显变热。如果在倾斜的光源下观察被检测的纸，硅酮层的损坏表现为被擦掉的凸起（擦除）的形式，并显现为亚光处（涂迹）。
表1示出，用含烯属双键的聚乙烯醇得到机械方面明显的硅酮锚固（Silikonverankerung）。这导致擦除的明显改善和因此硅酮在纸上的粘附的明显改善。
作为纸表面的机械应力的额外评价，用PVA检测试剂（碘-碘-钾碱-溶液）处理检测面，以通过纸的着色强度表明硅酮锚固的稳定性。硅酮涂层越机械稳定，聚乙烯醇底漆覆盖越多且着色越少。
表2示出，根据本发明使用的聚乙烯醇能够实现明显更机械耐受的硅酮锚固。
。
Claims (7)
1.浸渍剂，其可通过含烯属C-C双键的聚乙烯醇与含硅烷基团的交联剂和含烯属C-C双键的硅酮化合物的反应得到，其特征在于，使用通式I的烯属C-C双键化合物作为聚乙烯醇，
其中n=100-3000。
2.根据权利要求1的浸渍剂，其特征在于，使用通式II的化合物作为含硅烷基团的交联剂
。
3.根据权利要求1或2的浸渍剂，其特征在于，使用通式III的化合物作为含烯属C-C双键的硅酮化合物:
。
4.通过施加浸渍剂来浸渍纤维素基材料的方法，所述浸渍剂可通过含烯属C-C双键的聚乙烯醇与含硅烷基团的交联剂和含烯属C-C双键的硅酮化合物的反应得到，其中使用通式I的烯属C-C双键化合物作为聚乙烯醇，
其中n=100-3000。
5.根据权利要求4的方法，其特征在于，将所述含烯属C-C双键的聚乙烯醇施加在纤维素基材料上，随后与含硅烷基团的交联剂和含烯属C-C双键的硅酮化合物反应。
6.根据权利要求4或5的方法，其特征在于，所述反应用铂-、钯-或铑盐或-配合物来催化。
7.根据权利要求4或5的方法，其特征在于，使用纸或纸板作为纤维素基材料。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102013107329.8A DE102013107329A1 (de) | 2013-07-10 | 2013-07-10 | Imprägnierungsmaterialien für Release-Papiere |
| DE102013107329.8 | 2013-07-10 | ||
| PCT/EP2014/064314 WO2015004017A1 (de) | 2013-07-10 | 2014-07-04 | Imprägnierungsmaterialien für release-papiere |
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| CN105556034A CN105556034A (zh) | 2016-05-04 |
| CN105556034B true CN105556034B (zh) | 2018-11-09 |
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| US (1) | US20160160446A1 (zh) |
| EP (1) | EP3019661B1 (zh) |
| JP (1) | JP2016535805A (zh) |
| KR (1) | KR20160034308A (zh) |
| CN (1) | CN105556034B (zh) |
| DE (1) | DE102013107329A1 (zh) |
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| WO2018124241A1 (ja) * | 2016-12-28 | 2018-07-05 | 株式会社クラレ | ポリビニルアルコール組成物及びその用途 |
| WO2018181735A1 (ja) * | 2017-03-30 | 2018-10-04 | 株式会社クラレ | 剥離紙原紙及びその製造方法、並びに剥離紙 |
| FI20205625A1 (en) * | 2020-06-15 | 2021-12-16 | Upm Kymmene Corp | SUPPORT LAYER FOR REMOVABLE PAPER |
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| CN102056994A (zh) * | 2008-06-03 | 2011-05-11 | 芬欧汇川集团公司 | 防粘衬层组合物,基础材料和生产基础材料的方法,和基础材料的表面处理剂和表面处理剂的用途 |
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| JP4530255B2 (ja) * | 2003-10-16 | 2010-08-25 | 信越化学工業株式会社 | 水分散型撥水撥油剤及びそれを用いた撥水撥油紙及びシート |
| DE10323203A1 (de) | 2003-05-22 | 2004-12-23 | Wacker Polymer Systems Gmbh & Co. Kg | Verwendung von silanfunktionellen Polyvinylalkoholen in Grundierungsmitteln für Trennpapiere und -folien |
| JP4451710B2 (ja) * | 2004-05-07 | 2010-04-14 | 王子タック株式会社 | 剥離基材およびその製造方法、粘着シートおよび粘着テープ |
| WO2007015432A1 (ja) * | 2005-08-02 | 2007-02-08 | Oji Tac Co., Ltd. | 工程剥離シートおよび合成皮革の製造方法 |
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2014
- 2014-07-04 KR KR1020167001892A patent/KR20160034308A/ko not_active Application Discontinuation
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- 2014-07-04 JP JP2016524759A patent/JP2016535805A/ja active Pending
- 2014-07-04 US US14/900,847 patent/US20160160446A1/en not_active Abandoned
- 2014-07-04 EP EP14734838.7A patent/EP3019661B1/de not_active Not-in-force
- 2014-07-04 WO PCT/EP2014/064314 patent/WO2015004017A1/de active Application Filing
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| JP3620031B2 (ja) * | 1993-12-21 | 2005-02-16 | 荒川化学工業株式会社 | 剥離紙用アンダーコート剤 |
| US5616672A (en) * | 1995-11-17 | 1997-04-01 | General Electric Company | Paper release compositions having improved release characteristics |
| CN102056994A (zh) * | 2008-06-03 | 2011-05-11 | 芬欧汇川集团公司 | 防粘衬层组合物,基础材料和生产基础材料的方法,和基础材料的表面处理剂和表面处理剂的用途 |
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| EP3019661A1 (de) | 2016-05-18 |
| KR20160034308A (ko) | 2016-03-29 |
| WO2015004017A1 (de) | 2015-01-15 |
| EP3019661B1 (de) | 2017-06-21 |
| CN105556034A (zh) | 2016-05-04 |
| DE102013107329A1 (de) | 2015-01-15 |
| US20160160446A1 (en) | 2016-06-09 |
| ES2635636T3 (es) | 2017-10-04 |
| JP2016535805A (ja) | 2016-11-17 |
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