CN1232554C - 由特殊多元醇和草酸构成的涂层 - Google Patents
由特殊多元醇和草酸构成的涂层 Download PDFInfo
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- CN1232554C CN1232554C CNB018189164A CN01818916A CN1232554C CN 1232554 C CN1232554 C CN 1232554C CN B018189164 A CNB018189164 A CN B018189164A CN 01818916 A CN01818916 A CN 01818916A CN 1232554 C CN1232554 C CN 1232554C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/06—Homopolymers or copolymers of esters of polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
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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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
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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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/8305—Miscellaneous [e.g., treated surfaces, etc.]
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- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
- Materials For Medical Uses (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及通过烘烤不含酯基团多元醇与草酸的混合物生产的涂层、所述涂层的生产方法以及以此种方式涂布的基材。
Description
本发明涉及通过烘烤不含酯基团的多元醇与草酸的混合物生产的涂层、其生产方法以及以此种方式涂布的基材。
已知，多元醇可在较高温度下与氨基树脂或封闭的异氰酸酯进行交联(参见《Ullmann’s Encyclopedia of IndustrialChemistry》第五版，第A18卷，第404～405和414～418页)。在此操作期间，消去不希望的物质如甲醛或封闭剂。
因此，本发明的目的是提供主要消去诸如水之类无害产物的烤漆。
现已发现，不含酯的多元醇与草酸的混合物在高温交联生成耐溶剂、坚硬的涂层。
因此，本发明提供一种涂层，该涂层可通过在基材上将以下组分的混合物于120℃～250℃的温度烘烤1～100min获得：
A)1重量份羟基含量1～10％的不含酯的多元醇，
B)0.05～1重量份草酸，
C)0.2～5重量份有机溶剂以及
D)任选地，颜料和涂料助剂。
涂漆(混合物在基材上的施涂)可由刮刀涂布、喷涂、流涂或浸涂完成。随后在120℃～250℃的温度在空气或惰性气体存在下烘烤1～100min。
按本发明使用的不含酯多元醇A)是由不含酯的乙烯基单体如苯乙烯、3-或4-甲基苯乙烯、丙烯腈、α-甲基苯乙烯、环己基乙烯基醚、丁基乙烯基醚或甲基乙烯基醚，与不含酯的羟基官能乙烯基共聚单体如烯丙醇、被环氧乙烷或环氧丙烷羟烷基化的烯丙醇、羟甲基降冰片烯、三羟甲基丙烷单烯丙基醚、甘油单烯丙基醚、羟乙基乙烯基醚、羟丁基乙烯基醚或环己烷二甲醇单乙烯基醚所制备的共聚物，它们优选用二异氰酸酯如双(4-异氰酸根合环己基)甲烷、4，4’-二异氰酸根合二苯甲烷、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯进行预增链。
按照本发明，还可将不含酯的单体与烯丙基缩水甘油醚进行共聚，随后借助水、一元醇或仲胺将环氧环打开，继而任选地采用二异氰酸酯进行预增链。
多元醇如三羟甲基丙烷、三羟甲基乙烷或季戊四醇，或者它们与环氧乙烷或环氧丙烷的反应产物被二异氰酸酯预增链的产物(预聚物)，也可在本发明中用作组分A)。
由缩酮基团保护的多元醇，如季戊四醇与丙酮、环己酮或苯甲醛的单缩酮，或糖醇的二缩酮，例如山梨醇或甘露醇与丙酮、环己酮或苯甲醛的二缩酮，也可与二异氰酸酯起反应生成缩聚产物，其中缩酮保护基团随后被消去。
优选包含氨基甲酸酯基团的组分A)。
组分B)是草酸，它优选在与其他组分混合之前预溶解在偶极-非质子溶剂中，优选在N-甲基吡咯烷酮、二甲基乙酰胺和/或二甲基甲酰胺中，该溶液的浓度优选为10～40重量％。
组分C)是，例如，芳烃，如，甲苯、二甲苯或烷基化芳烃混合物，含酯溶剂，如乙酸丁酯、乙酸甲氧基丙酯、乙酸甲氧基乙酯或乙酸乙酯，含醚溶剂，如乙二醇二甲醚、乙二醇二乙醚、二甘醇二甲醚、二噁烷或四氢呋喃，或者偶极-非质子溶剂，如N-甲基吡咯烷酮、二甲基乙酰胺、二甲基甲酰胺、二甲基亚砜、N-甲基己内酰胺、二甲基砜或环丁砜，其中优选用偶极-非质子溶剂来预溶解草酸。
组分A)～D)原则上可以任意顺序在低于50℃的温度、在剪切(例如，搅拌)下进行混合。草酸优选预溶解在偶极-非质子溶剂中，对此，该溶液可在任意时间加入到其他组分中。
组分A)～D)的混合物在室温可保持稳定至少2周，这就是说，可配制一种贮藏稳定的单罐装漆。然而，草酸在偶极-非质子溶剂中的溶液也可在临施涂前按比例配入。
除了草酸以外，还可加入其它固化剂，例如，氨基树脂、封闭的异氰酸酯或优选环氧化物，其用量介于1～20重量份，基于每100重量份A)～D)的混合物。
本发明涂层可用于任何在160℃以上保持稳定的基材上，例如，金属、玻璃、高温塑料或矿物基材。因此，本发明还提供一种用本发明涂料涂布的基材。
它们的特征在于硬度和耐溶剂能力高。烘烤期间，仅释放出溶剂和水(源于羟基基团与草酸之间的酯化反应)，而没有诸如甲醛或异氰酸酯封闭剂之类的产物。
实施例
实施例1
将270g SAA(苯乙烯/烯丙醇共聚物；分子量Mn＝1600，羟基含量6％)与200g MPA(乙酸甲氧基丙酯)合并，向其中加入6.5gMD I(4，4’-二异氰酸根合二苯基甲烷)在34g NMP(N-甲基吡咯烷酮)中的溶液，并在120℃加热4h。
将100重量份原封供货形式的该配制物与30重量份33％草酸在NMP中的溶液进行混合。
实施例2
将300g SAA在286g MPA中与15.1g HDI(六亚甲基二异氰酸酯)混合，并在120℃加热4h。
将100重量份原封供货形式的该配制物与30重量份33％草酸在NMP中的溶液进行混合。
实施例3
将300g SAA在286g MPS中与20g IPDI(异佛尔酮二异氰酸酯)混合，并在120℃加热4h。
将100重量份原封供货形式的该配制物与30重量份33％草酸在NMP中的溶液进行混合。
实施例4
将300g SAA在286g MPA中与17.7g双(4-异氰酸根合环己基)甲烷混合，并在120℃加热4h。
将100重量份原封供货形式的该配制物与30重量份33％草酸在NMP中的溶液进行混合。
将实施例1～4的混合物在玻璃板上以刮刀涂布至180μm湿膜厚并在160℃烘烤10、20和30min。获得如下摆测硬度(Knig方法[s])：
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | |
| 10min | 166 | 172 | 136 | 174 |
| 20min | 177 | 180 | 166 | 174 |
| 30min | 180 | 182 | 144 | 177 |
所有涂层都耐受100次MEK往复擦拭试验。
对比例
将40g甲基丙烯酸羟乙酯、40g苯乙烯、20g丙烯酸丁酯、80g MPA和0.5g偶氮二异丁腈的混合物在65℃加热24h，并在120℃加热1h。
将该混合物与54g 33％草酸在NMP中的溶液混合。
在160℃下烘烤30min。漆膜发粘并可溶于MEK中。
羟基基团通过酯基团附着到漆树脂上。这将明显地阻止混合物的交联。
Claims (8)
1.一种涂层，该涂层可通过在基材上将以下组分的混合物于120℃～250℃的温度下烘烤1～100min获得：
A)1重量份羟基含量1～10％的不含酯的多元醇，选自由不含酯的乙烯基单体与不含酯的羟基官能的乙烯基共聚单体所制备的共聚物、多元醇或者它们与环氧乙烷或环氧丙烷的反应产物被二异氰酸酯预增链的产物，
B)0.05～1重量份草酸，
C)0.2～5重量份有机溶剂以及
D)任选地，颜料和涂料助剂。
2.权利要求1的涂层，其中不含酯的乙烯基单体选自苯乙烯、3-或4-甲基苯乙烯、丙烯腈、α-甲基苯乙烯、环己基乙烯基醚、丁基乙烯基醚和甲基乙烯基醚。
3.权利要求1的涂层，其中不含酯的羟基官能的乙烯基共聚单体选自烯丙醇、被环氧乙烷或环氧丙烷羟烷基化的烯丙醇、羟甲基降冰片烯、三羟甲基丙烷单烯丙基醚、甘油单烯丙基醚、羟乙基乙烯基醚、羟丁基乙烯基醚和环己烷二甲醇单乙烯基醚。
4.权利要求1的涂层，其中的多元醇选自三羟甲基丙烷、三羟甲基乙烷或季戊四醇。
5.权利要求1的涂层，其中由不含酯的乙烯基单体与不含酯的羟基官能乙烯基共聚单体所制备的共聚物被二异氰酸酯预增链。
6.权利要求1或5的涂层，其中的二异氰酸酯选自双(4-异氰酸根合环己基)甲烷、4，4’-二异氰酸根合二苯甲烷、甲苯二异氰酸酯、异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯。
7.权利要求1的涂层的生产方法，其特征在于，将组分A)～D)的混合物施涂到基材上，并在120℃～250℃的温度下烘烤1～100min。
8.按照权利要求1涂布的基材。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10056759.2 | 2000-11-16 | ||
| DE10056759A DE10056759A1 (de) | 2000-11-16 | 2000-11-16 | Beschichtungen aus speziellen Polyolen und Oxalsäure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1481401A CN1481401A (zh) | 2004-03-10 |
| CN1232554C true CN1232554C (zh) | 2005-12-21 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018189164A Expired - Fee Related CN1232554C (zh) | 2000-11-16 | 2001-11-05 | 由特殊多元醇和草酸构成的涂层 |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US6479106B2 (zh) |
| EP (1) | EP1339768B1 (zh) |
| JP (1) | JP2004514036A (zh) |
| KR (1) | KR20040030458A (zh) |
| CN (1) | CN1232554C (zh) |
| AT (1) | ATE337348T1 (zh) |
| AU (1) | AU2002221809A1 (zh) |
| CA (1) | CA2428523A1 (zh) |
| DE (2) | DE10056759A1 (zh) |
| DK (1) | DK1339768T3 (zh) |
| ES (1) | ES2271121T3 (zh) |
| HK (1) | HK1063808A1 (zh) |
| MX (1) | MXPA03004247A (zh) |
| PL (1) | PL366424A1 (zh) |
| PT (1) | PT1339768E (zh) |
| RU (1) | RU2293752C2 (zh) |
| WO (1) | WO2002040565A2 (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104604988A (zh) * | 2015-01-29 | 2015-05-13 | 施家乐 | 一种新型玛格丽特饼干的生产方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1111001A (en) * | 1964-03-31 | 1968-04-24 | Vinyl Products Ltd | Improvements in or relating to surface-coating compositions |
| RU467614C (ru) * | 1972-06-12 | 1993-01-23 | Предприятие П/Я Р-6476 | Состав дл дезактивации |
| JPH01229085A (ja) * | 1988-03-09 | 1989-09-12 | Sekisui Chem Co Ltd | 木質板用接着剤 |
| DE19627903A1 (de) * | 1996-07-11 | 1998-01-15 | Bayer Ag | Acylbernsteinsäurepolyester, Verfahren zu ihrer Herstellung und ihre Verwendung für Duromere und Überzüge |
-
2000
- 2000-11-16 DE DE10056759A patent/DE10056759A1/de not_active Withdrawn
-
2001
- 2001-11-05 DE DE50110830T patent/DE50110830D1/de not_active Expired - Lifetime
- 2001-11-05 AT AT01996570T patent/ATE337348T1/de not_active IP Right Cessation
- 2001-11-05 CA CA002428523A patent/CA2428523A1/en not_active Abandoned
- 2001-11-05 EP EP01996570A patent/EP1339768B1/de not_active Expired - Lifetime
- 2001-11-05 WO PCT/EP2001/012777 patent/WO2002040565A2/de active IP Right Grant
- 2001-11-05 CN CNB018189164A patent/CN1232554C/zh not_active Expired - Fee Related
- 2001-11-05 AU AU2002221809A patent/AU2002221809A1/en not_active Abandoned
- 2001-11-05 RU RU2003117795/04A patent/RU2293752C2/ru not_active IP Right Cessation
- 2001-11-05 KR KR10-2003-7006617A patent/KR20040030458A/ko active IP Right Grant
- 2001-11-05 DK DK01996570T patent/DK1339768T3/da active
- 2001-11-05 MX MXPA03004247A patent/MXPA03004247A/es active IP Right Grant
- 2001-11-05 JP JP2002543570A patent/JP2004514036A/ja active Pending
- 2001-11-05 PT PT01996570T patent/PT1339768E/pt unknown
- 2001-11-05 PL PL01366424A patent/PL366424A1/xx unknown
- 2001-11-05 ES ES01996570T patent/ES2271121T3/es not_active Expired - Lifetime
- 2001-11-13 US US10/008,427 patent/US6479106B2/en not_active Expired - Fee Related
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2004
- 2004-09-01 HK HK04106577A patent/HK1063808A1/xx not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ES2271121T3 (es) | 2007-04-16 |
| ATE337348T1 (de) | 2006-09-15 |
| US20020119322A1 (en) | 2002-08-29 |
| WO2002040565A3 (de) | 2002-09-06 |
| CA2428523A1 (en) | 2002-05-23 |
| WO2002040565A2 (de) | 2002-05-23 |
| PT1339768E (pt) | 2006-12-29 |
| MXPA03004247A (es) | 2005-08-16 |
| HK1063808A1 (en) | 2005-01-14 |
| CN1481401A (zh) | 2004-03-10 |
| EP1339768A2 (de) | 2003-09-03 |
| DE50110830D1 (de) | 2006-10-05 |
| AU2002221809A1 (en) | 2002-05-27 |
| DE10056759A1 (de) | 2002-05-23 |
| KR20040030458A (ko) | 2004-04-09 |
| US6479106B2 (en) | 2002-11-12 |
| JP2004514036A (ja) | 2004-05-13 |
| EP1339768B1 (de) | 2006-08-23 |
| DK1339768T3 (da) | 2006-11-13 |
| RU2293752C2 (ru) | 2007-02-20 |
| PL366424A1 (en) | 2005-01-24 |
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