TW200424022A

TW200424022A - Method for forming functional layers

Info

Publication number: TW200424022A
Application number: TW092136210A
Authority: TW
Inventors: Martin Kunz; Michael Bauer; Andreas Baranyai
Original assignee: Ciba Sc Holding Ag
Priority date: 2002-12-20
Filing date: 2003-12-19
Publication date: 2004-11-16
Also published as: TWI325794B; DE50311739D1

Abstract

The invention relates to a method for forming functional layers on an inorganic or organic substrate, characterized in that a) the inorganic or organic substrate is exposed to a low-temperature plasma, a corona discharge, an intense irradiation and/or a flame-treatment, b) 1) at least one activatable initiator or 2) at least one activatable initiator and at least one ethylenically unsaturated compound in the form of melts, solutions, suspensions or emulsions is/are applied to the inorganic or organic substrate, whereby at least one function regulating group, which regulates the desired surface characteristics of the treated substrate, is incorporated into the activatable initiator and/or the ethylenically unsaturated compound and c) the coated substrate is heated and/or irradiated with electromagnetic waves to regulate the desired surface characteristics. The invention also relates to substrates coated according to the method and to the use of the substrates.

Description

200424022 玖、發明說明： t發明戶斤屬之技術領域3 發明領域本發明係有關一種在一無機或有機基質上形成功能層 5 之方法，及以該方法處理之基質與其應用。 L先前技術】發明背景電漿法長久以來已被應用於在表面上形成功能層的製作上。尤其電漿聚合在這方面經常被應用。其中，可聚合 10 之前驅物通過氣相而形成一低壓電漿，並且在表面上以聚合狀態沈積。有關所應用之技術及由此所產生之表面及其等之應用記載於例如”Plasma Surface Modification and Plasma Poly-merization von N. Inagaki， Technomic Publishing Company Inc·，Lancaster 1996，，、”Plasma 15 Polymerization von H. Yasuda，Academic Press Inc.，New York 1985”，以及”Plasma Polymerization Processes von H. Biederman，U. Osada, Elsevier Science Publishers， Amsterdam 1992”。可聚合化合物之電漿輔助沈積經常在分子的平面上造 20 成不可預見的結構變化。尤其當分子中具有功能性基團時，會導致分解反應及其他變化。功能性基團在電漿中可以容易地被氧化或解離。此外，所添加的分子也可以透過電漿中所存在的短波輻射及高能量物種，如離子和自由基，而被完全地破壞。所沈積的或聚合的薄膜可因而表現出大 5 '咸>、或者和原來所添加的化合物完全不同之特性。為以最大私度保持結構，需要添加增多脈衝的電漿，其係在用以啟動聚合翻的短電漿脈衝之後接著—個較長相仅的脈衝’電漿在該相位時是關閉的，然而可聚合化合物的 /、應〃卩、准持不變。惟此乃一效率較低且會導致製程之較高複雜性。相關的方法由G· Kiihn et al.發表於Surfaces and200424022 (ii) Description of the invention: Technical Field of the Invention 3 Field of the Invention The present invention relates to a method for forming a functional layer 5 on an inorganic or organic substrate, and a substrate treated by the method and its application. [Prior art] Background of the invention The plasma method has long been applied to the production of functional layers on the surface. In particular, plasma polymerization is often used in this regard. Among them, the polymerizable 10 precursor passes through the gas phase to form a low-pressure plasma, and is deposited on the surface in a polymerized state. The applied technology and the resulting surface and its application are described in, for example, "Plasma Surface Modification and Plasma Poly-merization von N. Inagaki, Technomic Publishing Company Inc., Lancaster 1996,", "Plasma 15 Polymerization von H. Yasuda, Academic Press Inc., New York 1985 ", and" Plasma Polymerization Processes von H. Biederman, U. Osada, Elsevier Science Publishers, Amsterdam 1992 ". Plasma-assisted deposition of polymerizable compounds is often on the molecular plane Makes 20 unpredictable structural changes. Especially when there are functional groups in the molecule, it will lead to decomposition reactions and other changes. Functional groups can be easily oxidized or dissociated in the plasma. In addition, the added molecules It can also be completely destroyed by the short-wave radiation and high-energy species such as ions and free radicals present in the plasma. The deposited or polymerized film can thus show a large 5 'salt>, or the original The added compounds have completely different characteristics. In order to maintain the structure with maximum privacy, it is necessary to add A pulse-increasing plasma is followed by a short plasma pulse used to initiate polymerization, followed by a longer-phase pulse. The plasma is closed at this phase, but the polymerizable compounds /, The standard remains unchanged. However, this is a less efficient and will lead to higher complexity of the process. The related method was published by G. Kiihn et al. In Surfaces and

Coatings Technology i 42, 2001 第 494 頁。此外’上述電漿技術必需在真空中實施，因此設備費用高且製程耗時。再者，必需先使所要塗布或者要聚合的 10化合物（前驅物）蒸發，再令其於基質上冷凝，而這有可能造成高度的熱負荷，在許多情形中更可能導致分解。另外，蒸發-及沈積率低，因此要製作厚度足夠的形成層不但困難且費時。 DE 19732901 Cl ’ G. Bolte，S. Kluth在Coating 2/98第 38 15 頁，及G· Bolte，R. Onemann在Coating 10/2001 第 364頁記載一在大氣壓力下之表面電暈處理的應用，其中，前驅物的狀態為蒸氣、氣溶膠(Aerosole)或粉塵，放電空間被引入其中且會沈積在待處理的表面上。在此情形中，前驅物也要承受高熱能、UV-光和活性氣體(例如臭氧），這些都可能 20 導致可聚合化合物的崩解。此外，因氣溶膠之生產速率故塗覆率低，且其可能覆蓋在電極上，而有必需經常清理，機為、因而需停止運轉的結果。再者，可以液相添加的僅有水’使得可添加的化合物和前驅物在選擇上受到相當的限制0 6 200424022 【發明内容】發明概要本發明意外地發現-可在沒有上述缺點的情況下製造功能層之方法。本發明乃有關在一無機或有機基質上形成 5 功能層之方法，其係 a) 在該無機或有機基質上使一低溫電漿、一電暈放電、一能量輻射及/或一火焰處理產生作用， b) 將1)至少一可活化起始劑或2)至少一可活化起始劑及至少一種乙烯系不飽和化合物之融熔物、溶液、懸浮液 10或乳劑塗布於該無機或有機基質上，其中該可活化起始劑及/或乙稀系不飽和化合物至少合併有一個功能調整基團，藉以賦與受處理基質一所需之表面特性，及 c) 加熱及/或以電磁波在賦與所需之表面特性的條件下照射該經過被覆之基質。 15 做為可活化起始劑者主要係添加形成自由基的起始劑。本發明之方法之優點在於··以所記載之方法可以在一大尺寸多樣化之基質上形成清澈透明的層，且黏著性良好。與單或多乙烯系不飽和化合物（單體、低聚物或聚合物）組合，則可以使所製得之形成層的特性能更廣範圍地做變 2〇化。厚度的控制同樣獲得簡化且可以含蓋相當廣的範圍。本發明之優點在於其可於常壓下進行，而不需要有任何昂貴的真空設備。基質和所添加物質之過度熱負荷都得以避免，因此可以在欲獲得之特性條件下目標明確地導入化學官能度。因為可以運用傳統的塗布方法，故沈積率报高而 7 200424022 且實際上不受限制。由於不需蒸發任何物質，因而亦可添加黏性或高分子量化合物。因此，化合物的選擇空間大且可谷易地量身打造特殊的特性。在-較佳實施態樣中功能調整基團係形成如后： 5 1) _親水性或疏水性基目，用以難親水性/疏水性； ii) -酸性、中性或驗性官能基團，用以調整酸勝性質； iii) 顯現-高或低增量折射之一官能基團，用以調整折射率。 1〇對細胞及7或生物的生長具有影響之一官能基團，用以控制生物特性； V) 對易燃性具有影響之一官能基團，用以調整防火特性，及/或 VI) 對於導電性具有影響之一官能基團，用以調整抗靜 15 電特性。親水性基團以使用一極性基團為宜，例如醇_、喊-、酸 …酯…醛-、酮-、醣-、酚-、脲_、丙烯酸酯_、乙烯醚… 環氧化物-、醯胺-、縮駿-、縮酿I _、酸酐_、季胺_、醯亞胺_ 、碳酸根-或硝基-基團，一酸之鹽類，或一（聚）乙二醇單元 20 。結果特佳者係使用丙烯酸、丙浠醯胺、乙醯氧基苯乙烯 (Acetoxystyrol)、丙烯酸酐、丙烯琥珀醯亞胺 (Acryl-succinimid)、烯丙基縮水甘油醚(Allylglycidylether) 、細丙基甲氧基苯酉分(Allylmethoxyphenol)、聚乙二醇二丙婦酸醋(400)(P〇lyethylenglycol (400)Diacrylat)、二甘醇二丙 8 200424022 稀酸酯（Diethyleneglycoldiacrylat)、二氨基曱酸二曱基丙稀酸 S旨(Diurethandimethacrylat)、二乙烯乙二醇酉旨 (Divinylglycol)、乙二醇二縮水甘油醚 (Ethylenglycoldiglycidylether)、縮水甘油丙烯酸酉旨 5 (Glycidylacrylat)、乙二醇甲基丙烯酸酯（Glycomethacrylat) 、4-經丁基曱基丙烯酸酯（4-Hydroxy-butylmethnacrylat)、2-經乙基丙稀酸酯（2-Hydroxyethyl-acrylat)、2-經乙基甲基丙浠酸酉旨（2-Hydroxyethylmeth-acrylat)、N-(2-經丙基）曱基丙醯胺(N-(2-Hydroxypropyl)methacrylamid)、曱基丙烯酸經乙 10 基糖苷（Methacryloxy-ethylglucosid)、頌化苯乙烯(Nitostyrol) 、石黃基乙基甲基丙烯酸醋（Sulfoethylmethacrylat)、3-石黃基丙基丙烯酸（3-Sulfo-propylacrylat)、4-乙烯基苯甲酸 (4-Vinylbenzoesaure)、乙烯基二甲减(Vinylniethylsulfon)、乙酸苯乙稀酯（Vinylphenyl-acetat)之納鹽，或乙烯尿素 15 (Vinylharnstoff)做為親水性基團。以下所示物質同樣適用： h2ch2c ο όCoatings Technology i 42, 2001 p. 494. In addition, the above-mentioned plasma technology must be implemented in a vacuum, so the equipment cost is high and the manufacturing process is time-consuming. Furthermore, the 10 compounds (precursors) to be coated or polymerized must be evaporated first and then allowed to condense on the substrate, which may cause a high thermal load and in many cases may lead to decomposition. In addition, the evaporation-and-sedimentation rate is low, and it is difficult and time-consuming to form a sufficient thickness. DE 19732901 Cl 'G. Bolte, S. Kluth in Coating 2/98, page 38 15 and G. Bolte, R. Onemann in Coating 10/2001, page 364-Application of surface corona treatment under atmospheric pressure Among them, the state of the precursor is vapor, aerosol or dust, and the discharge space is introduced therein and will be deposited on the surface to be treated. In this case, the precursors are also subject to high thermal energy, UV-light, and reactive gases (such as ozone), all of which may cause the disintegration of polymerizable compounds. In addition, due to the production rate of the aerosol, the coating rate is low, and it may cover the electrodes, and it must be cleaned frequently, resulting in the machine stopping operation. Furthermore, the only water that can be added in the liquid phase makes the selection of the compounds and precursors that can be added quite limited. [Summary of the Invention] Summary of the Invention The present invention has unexpectedly discovered that-without the above disadvantages Method for manufacturing functional layer. The invention relates to a method for forming a 5-functional layer on an inorganic or organic substrate, which is a) generating a low-temperature plasma, a corona discharge, an energy radiation and / or a flame treatment on the inorganic or organic substrate; Function, b) applying 1) at least one activatable starter or 2) at least one activatable starter and a melt, solution, suspension 10 or emulsion of an ethylenically unsaturated compound to the inorganic or organic On the substrate, wherein the activatable initiator and / or ethylenically unsaturated compound has at least one functional adjustment group to impart a desired surface characteristic to the treated substrate, and c) heating and / or electromagnetic waves The coated substrate is irradiated under conditions that impart desired surface characteristics. 15 As an activatable initiator, it is mainly the addition of a radical-forming initiator. The advantages of the method of the present invention are that the method described can form a clear and transparent layer on a substrate of large size and diversity, and has good adhesion. In combination with mono- or polyethylenically unsaturated compounds (monomers, oligomers or polymers), the properties of the formed layers can be changed in a wider range. Control of thickness is also simplified and can cover a fairly wide range. The advantage of the present invention is that it can be performed at atmospheric pressure without the need for any expensive vacuum equipment. Excessive thermal load on both the matrix and the added substance can be avoided, so the chemical functionality can be explicitly introduced under the desired characteristics. Because the traditional coating method can be used, the deposition rate is reported to be high and it is virtually unlimited. Since no substance needs to be evaporated, viscous or high molecular weight compounds can also be added. Therefore, the choice of compounds is large and special properties can be easily tailored. In the preferred embodiment, the function-adjusting group is formed as follows: 5 1) _ Hydrophilic or hydrophobic moieties for difficult hydrophilicity / hydrophobicity; ii)-Acidic, neutral or experimental functional groups Group to adjust the acid properties; iii) Appearance-a functional group with high or low incremental refraction for adjusting the refractive index. 10 a functional group that has an effect on the growth of cells and 7 or organisms to control biological characteristics; V) a functional group that has an effect on flammability to adjust fire resistance characteristics, and / or VI) for Conductivity has a functional group that affects static electricity. It is suitable to use a polar group for the hydrophilic group, such as alcohol, alkoxide, acid, ester, aldehyde, ketone, sugar, phenol, urea, acrylate, vinyl ether, epoxide, etc. , Sulfonamide-, sulfonate-, condensation I _, anhydride _, quaternary amine _, fluorenimine _, carbonate- or nitro- group, a salt of an acid, or a (poly) ethylene glycol Unit 20. The best results were obtained using acrylic acid, propylamine, Acetoxystyrol, acrylic anhydride, Acryl-succinimid, Allylglycidylether, fine propyl Allylmethoxyphenol, Polyethylene Glycol (400) (Diacrylat), Diethylene Glycol 8 200424022 Diethyleneglycoldiacrylat, Diaminoglycine Diurethandimethacrylat, Divinylglycol, Ethylenglycoldiglycidylether, Glycidylacrylat, Glycidyl methacrylic acid Glycomethacrylat, 4-Hydroxy-butylmethnacrylat, 2-Hydroxyethyl-acrylat, 2-Hydroxyethyl-acrylat Purpose (2-Hydroxyethylmeth-acrylat), N- (2-Hydroxypropyl) methacrylamid, Methacrylic acid via Methacryloxy-ethylglucosid, Songhua Styrene (Nitost yrol), Sulfoethylmethacrylat, 3-Sulfo-propylacrylat, 4-Vinylbenzoesaure, Vinylniethylsulfon , Sodium salt of Vinylphenyl-acetat, or Vinylharnstoff as the hydrophilic group. The following substances also apply: h2ch2c ο ό

9 2004240229 200424022

π ?' C—C--OH CH,π? 'C--C--OH CH,

疏水性基團以添加一非極性基團為宜，可舉例如一分枝或未分枝烷基·、稀基-、炔基-，部分或完全_化之烧基 5或烯基或炔基，烴化胺基…線狀或分枝狀矽烷基-或矽氧烷基-基團，或一部分或完全鹵化之芳族或非芳族環基團。其中尤其合適者為丙浠酸叔丁 i旨（tert-Butylacrylat)-、苯乙稀、丁基三甲氧基石夕烧(61^)^1411^]1〇义3^如11)、丙稀酸環己酯 (Cyclohexylacrylat)、癸二醇-二曱基丙烯酸酯 10 (Decandiol-dimethacrylat)、二乙烯基苯（Divinylbenzol)、 2-(2-乙氧基乙氧基）乙基丙稀酸g旨（2-(2-Ethoxyethoxy)ethyl-acrylat)、1H，1H-七氟-丁基丙烯酸酯（1H， lH-Heptafluor-butylacrylat)、丙稀酸节黯（Benzylacrylat)、 1H，1H，7H-十二氟庚基甲基丙烯酸酯（1H，1H， 15 7H-Dodecafluoroheptyl-methacrylat)、萘基丙稀酸酉旨 (Naphthylacrylat)、五溴苯基丙稀酸酯（Pentabromo -phenylacrylat)、三氟乙基丙稀酸酉旨（Trifluoroethylacrylat) 或乙稀基三苯基石夕烧(Vinyltriphenyl-silan)。以下所示物質同樣可以適用： 10 200424022It is suitable to add a non-polar group to the hydrophobic group. For example, a branched or unbranched alkyl group, a dilute group, an alkynyl group, a partially or completely alkynyl group 5 or an alkenyl group or an alkynyl group may be used. , Alkylated amine groups ... linear or branched silyl- or siloxy-groups, or partially or fully halogenated aromatic or non-aromatic ring groups. Among them, particularly suitable are tert-Butylacrylat-, styrene, butyltrimethoxylithium (61 ^) ^ 1411 ^] 10 meaning 3 ^ such as 11), acrylic acid Cyclohexylacrylat, Decandiol-dimethacrylat 10, Divinylbenzol, 2- (2-ethoxyethoxy) ethylpropionic acid (2- (2-Ethoxyethoxy) ethyl-acrylat), 1H, 1H-Heptafluor-butylacrylat, Benzylacrylat, 1H, 1H, 7H-Ten Difluoroheptyl methacrylate (1H, 1H, 15 7H-Dodecafluoroheptyl-methacrylat), Naphthylacrylat, Pentabromo-phenylacrylat, trifluoroethyl Trifluoroethylacrylat or Vinyltriphenyl-silan. The following substances are also applicable: 10 200424022

4_乙烯氧基Μ氧基^二苯甲㈣愚加声加邮 -oxy-45 -chlorbenzophenon) 乙稀乳基I厌氧基-4 -氟一本甲_ (Vinyloxycarbonyloxy 5 ·4 ’ -fluorbenzophenon) 2-乙烯氧基羰氧基-5-氟-4、氯二苯甲酮（2-Vinyloxy- carbonyloxy-5-fluor-4?-chlorbenzophenon) 200424022 做為酸/鹼性質調整官能基團者以添加一碳酸-、磺酸_ 、石粦酸-、硫酸-、苯紛-、氨基酸-，或氨基-、Π比ϋ定-、Π密Π定-、哌啶、吡咯-，或咪唑-基團為宜。特別合適者係添加烯丙胺、2-氨乙基曱基丙稀酸酉旨（2-Aminoethylmethyacrylat)、4-5 乙烯基吡啶（4-Vinylpyridin)、乙烯基吡咯烷酮 (Vinyl-pyrrolidon)、乙稀基味 σ坐(Vinylimidazol)、嗎琳代乙基丙稀酸酯（Morpholinoethylacrylat)、丙稀酸、2-丙烯-1-石黃酸（2-Propene-l-Sulfonsaure)、山梨酸（Sorbinsaure)、肉桂酸 (Zimtsaure)，或馬來酸(Maleinsaure)。 10 為調整折射率以使用苄基-、部分或全部鹵化之苄基- 、部分或全部鹵化之烷基-、烯基-或炔基基團，其中尤以丙烯酸苄酯(Benzylacrylat)、1H，1H，7H-十二氟庚基曱基丙烯酸酉旨（1H，1H，7H-Dodecafluoroheptyl-methacrylat)、1H, 1H-七氟-丁基丙烯酸 S旨（1H，1 H-Heptafluor-butylacrylat)及丙烯 15 酸三氟乙酉旨（Trifluorethylacrylat)最合適。做為生物特性控制基團者可以採用一具有抗污 (anti-fouling)性質之基團，例如甲基丙烯酸銅 (II)(Kupfer(II)methacrylat)、二丁基馬來酸錫 (Dibutylzinnmaleat)、曱基丙烯酸錫（II)(Zinn(II)methacrylat) 20 或二曱基丙稀酸鋅(Zink-dimethacrylat)。另一種控制生物特性的方式係採用生物系生長所需的基團。合適者有琥ί白酸亞胺(Succinimid)-、糖苷（Glucosid)-及糖基團’其中尤以N-醯氧基琥珀醯亞胺或2-甲基丙烯醯氧基乙基糖 4 (2-Methacryloxyethylglucosid)之結果特佳。 12 200424022 做為防火性質調整基團者係採用一含完全或部分氣化溴化之烷基-或含氮-或含磷的基團。其中尤以苯基三漠二甲石風(Phenyltribromomethylsulphon)、2，2，2-三氣小[4-(ι ι_ 二曱基乙基）苯基]-乙酮（2，2，2-Trichl〇ro小[4-(1， 5 l-di-methylethyl)phenyl]-ethanon、三溴新戊基甲基丙烯酸酉旨（Tribromoneopentylmethacrylat)、雙(2-甲基丙烯基氧乙基 )填酸酯（Bis(2-methacryloxyethyl)phosphat)或單丙烯基氧乙基鱗酸醋（Monoacryloxyethylphosphat)。抗靜電性亦可透過選擇合適的官能基團加以調整。特 10 別適合於達成此目的之功能基團為三元胺基-、經乙基化胺基-(ethoxylierte Animo-)、烧醇醯胺-(Alkanolamid-)、甘油硬脂酸酯（Glycerinstearat)、山梨糖醇酐-(Sorbitan-)或績酸 -(Sulfonat-)基團，尤其2-二異丙胺基乙基甲基丙稀酸酉旨 (2-Diisopropylaminoethylmethacrylat)、3-二甲胺基新戊基丙 15 稀酸醋（3-Dimethylaminoneopentylacrylat)或油稀基雙（2-經乙基）胺（〇leybis(2-hydroxyethyl)amin)、硬脂醯丙稀酸酯 (Stearylacrylat)及/或硬脂酸乙烯酿（Vinylstearat)。以下所示物質同樣可以適用。4_vinyloxyMoxy ^ dibenzophenone-oxy-45 -chlorbenzophenon) Vinyloxycarbonyl 4 -Fluorobenzyl (Vinyloxycarbonyloxy 5 · 4 '-fluorbenzophenon) 2-Vinyloxy-carbonyloxy-5-fluoro-4, chlorobenzophenone (2-Vinyloxy-carbonyloxy-5-fluor-4? -Chlorbenzophenon) 200424022 As an acid / basic adjustment functional group to add Monocarbonic acid-, sulfonic acid-, carbamic acid-, sulfuric acid-, benzophenone-, amino acid-, or amino-, pibitidine-, pimididine-, piperidine, pyrrole-, or imidazole-group Better. Particularly suitable are allylamine, 2-Aminoethylmethyacrylat, 4-Vinylpyridin, Vinyl-pyrrolidon, Ethyl Flavor sigma (Vinylimidazol), Morphholinoethylacrylat, Acrylic acid, 2-Propene-l-Sulfonsaure, Sorbinsaure, Cinnamon Acid (Zimtsaure), or maleinsaure. 10 To adjust the refractive index to use benzyl-, partially or fully halogenated benzyl-, partially or fully halogenated alkyl-, alkenyl- or alkynyl groups, among which benzyl acrylate (Benzylacrylat), 1H, 1H, 7H-dodecafluoroheptylfluorenyl acrylic acid (1H, 1H, 7H-Dodecafluoroheptyl-methacrylat), 1H, 1H-Heptafluoro-butylacrylic acid (1H, 1H-Heptafluor-butylacrylat) and propylene 15 Trifluorethylacrylat is most suitable. As the biological property control group, an anti-fouling group can be used, such as copper (II) methacrylat, Dibutylzinnmaleat , Zinn (II) methacrylat 20 or Zink-dimethacrylat. Another way to control biological properties is to use groups that are needed for the growth of biological systems. Suitable are Succinimid-, Glucosid- and sugar groups, of which N-methoxyoxysuccinimide or 2-methacrylic acidoxyethyl sugar 4 ( 2-Methacryloxyethylglucosid) with particularly good results. 12 200424022 As the fire-resistance-adjusting group, a radically or partially gasified brominated alkyl- or nitrogen- or phosphorus-containing group is used. Among them, Phenyltribromomethylsulphon, 2,2,2-triazine [4- (ιιι_Dimethylethyl) phenyl] -ethyl ketone (2,2,2-Trichl 〇ro small [4- (1, 5 l-di-methylethyl) phenyl] -ethanon, tribromoneopentylmethacrylat, bis (2-methacryloxyethyl) filler (Bis (2-methacryloxyethyl) phosphat) or Monoacryloxyethylphosphat. Antistatic properties can also be adjusted by selecting appropriate functional groups. Especially 10 functional groups that are particularly suitable for this purpose It is tri-amino-, ethoxylierte Animo-, Alkanolamid-, Glycerinstearat, Sorbitan- or Acid- (Sulfonat-) groups, especially 2-Diisopropylaminoethylmethacrylat, 3-Dimethylaminoneopentylacrylat Or oil-based bis (2-transethyl) amine (〇leybis (2-hydroxyethyl) amin), Stearylacryla t) and / or Vinylstearat. The substances shown below are also applicable.

13 200424022 基質在形態上可以粉末、纖維、織物、賊毛、薄膜或三度空間的工件存在。較佳的基質為合成或天然聚合物、金屬氧化物、玻璃、半導體、石英或金屬，或含有其等之材料。半導體基質尤其可舉例如矽，其可以例如”晶圓 5 (Wavern)，，的形態存在。合適之金屬有用以製造高價值鏡頭，例如望遠鏡或自動聚光燈之鋁、鉻、鋼、釩等。特別合適者為鋁。天然與合成聚合物或合成材料可舉例如后： i) 單-或雙烯煙之聚合物，例如聚丙烯、聚異丁浠、 10聚卜丁烯（P〇lybuten-l)、聚冰曱基小戊烯 (Poly-4-methyl-penten-l)、聚異戊烯(Polyisopren)或聚丁二烯（Polybutadien)，以及環烯烴，例如環戊烯或二環庚烯 (Norbornen)之聚合物；此外，聚乙烯（必要時可以形成交聯網狀(vernetzt))，例如高密度聚乙烯(HDPE)、高密度高分子量聚乙烯（HDPE-HMW)、高密度超高分子量聚乙烯 (HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE) 、線型低密度聚乙烯(LLDPE)、（VLDPE)及(ULDPE); ii) i)所述聚合物之混合物，例如聚丙烯與聚異丁烯之混合物，聚丙烯與聚乙烯(例如PP/HDPE，PP/LDPE)，以及 2〇不同的聚乙烯類型（例如LDPE/HPDE)之混合物； iii) 單-和雙烯烴彼此間或與其他乙浠單體之共聚物，例如乙烯-丙烯-共聚物，線型低密度聚乙烯(LLDPE)和其與低密度聚乙烯(LDPE)之混合物；此外，此等共聚物彼此間及與i)所述之聚合物，例如聚丙烯/乙烯-丙烯•共聚物、 14 200424022 LDPE/乙烯-醋酸乙烯-共聚物、LDPE/乙烯-丙烯酸-共聚物 (LDPE/Etylen-Arylsaure-Copolymere)、LLDPE/乙稀-醋酸乙烯-共聚物、LLDPE/乙烯-丙烯酸-共聚物，以及交錯或統計平均地合成之聚烯烴/一氧化碳·聚合物及其等與其他聚合 5 物，例如聚醯胺之混合物； iv) 烴系樹脂（例如C5-C9)包含其之水合改性產物 (hydriete Modifikationen)(例如賦黏性樹脂）’及聚烯煙混合物和澱粉； v) 聚苯乙烯、聚-(p-曱基苯乙烯）、聚-(α-甲基苯乙烯）； 1〇 vi)苯乙烯或α -甲基苯乙烯與二烯烯或丙烯酸衍生物之共聚物，例如苯乙烯-丁二烯、苯乙烯-丙烯腈 (Styrol-Acrylnitril)、苯乙烯-烷基甲基丙烯酸酯 (Styrol-Alkylmeth-acrylat)、苯乙浠-丁二烯-烧基丙稀酸酿 (StyroKButadien-Alkylacrylat)和-甲基丙烯酸酯、苯乙烯-馬 15 來酸酐（Styrol-Maleinsaureanhydrid)、苯乙浠-丙稀腈-甲基丙烯酸酯； vii) 苯乙烯或曱基苯乙烯之接枝共聚物，例如聚丁二烯上接枝苯乙烯、聚丁二烯-苯乙烯·或聚丁二烯-丙烯腈-共聚物上接枝苯乙烯、聚丁二烯上接枝苯乙烯及丙烯腈（或 20 曱基丙烯腈）；以及其等與世無vi)所述之共聚物的混合物，例如已知者有ABS-、MBS-、ASA-或AES-聚合物； viii) 含鹵素聚合物，例如聚氯丁稀、氯化橡膠 (Chlor-kautschuk)、由異丁稀-異戊二烯經氣化或溴化而成之聚合物（鹵化丁稀橡膠(Halobutylkautschuk))、氯化或氣石黃 15 200424022 醢化聚乙稀、乙稀和氯化乙稀之共聚物、環氧氯丙燒翠、矛口 -共聚物(Epichlorhydrinhomo- und -copolymere)，特別是γ 經鹵化的乙烯化合物所獲得之聚合物，例如聚氯乙埽、聚偏氯乙烯(Polyvinyldienchlorid)、聚氟乙烯、聚偏氟乙稀； 5 以及其等之共聚物，例如氯乙烯-偏氯乙烯、氯乙烯-醋酸乙烯或偏氯乙烯-醋酸乙烯共聚物；13 200424022 The matrix can be morphologically present as powder, fiber, fabric, scarlet, film, or a three-dimensional workpiece. Preferred substrates are synthetic or natural polymers, metal oxides, glass, semiconductors, quartz or metals, or materials containing them. The semiconductor substrate may be, for example, silicon, which may exist in the form of “Wavern”. Suitable metals are useful for making high-value lenses, such as aluminum, chromium, steel, vanadium, etc. for telescopes or automatic spotlights. In particular Suitable materials are aluminum. Examples of natural and synthetic polymers or synthetic materials include the following: i) Mono- or diene-based polymers, such as polypropylene, polyisobutylene, and 10 polybutene-l ), Poly-4-methyl-penten-l, polyisopren or polybutadiene, and cycloolefins such as cyclopentene or dicycloheptene (Norbornen) polymers; In addition, polyethylene (vernetzt can be formed if necessary), such as high density polyethylene (HDPE), high density high molecular weight polyethylene (HDPE-HMW), high density ultra high molecular weight Polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE), and (ULDPE); ii) i) of the polymers described Mixtures, such as polypropylene and polyisobutylene, polypropylene and polyethylene (such as PP / HDPE, PP / LDPE), and mixtures of 20 different polyethylene types (such as LDPE / HPDE); iii) copolymers of mono- and diolefins with each other or with other ethyl acetate monomers, such as ethylene-propylene-copolymers Materials, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE); moreover, these copolymers are with each other and with the polymers described in i), such as polypropylene / ethylene-propylene copolymers Material, 14 200424022 LDPE / ethylene-vinyl acetate-copolymer, LDPE / ethylene-acrylic acid-copolymer (LDPE / Etylen-Arylsaure-Copolymere), LLDPE / ethylene-vinyl acetate-copolymer, LLDPE / ethylene-acrylic acid-copolymer Materials, and staggered or statistically averaged polyolefin / carbon monoxide · polymers and their mixtures with other polymers, such as polyamines; iv) Hydrocarbon resins (such as C5-C9) containing hydration modifications Products (hydriete Modifikationen) (such as tackifying resins) and polyolefin smoke mixtures and starch; v) polystyrene, poly- (p-fluorenylstyrene), poly- (α-methylstyrene); 1 〇vi) Styrene or α-methylstyrene with diene or acrylic acid Biological copolymers, such as styrene-butadiene, styrene-acrylonitrile (Styrol-Acrylnitril), styrene-alkyl methacrylate (Styrol-Alkylmeth-acrylat), styrene-butadiene-butadiene-carbon StyroKButadien-Alkylacrylat and -methacrylate, styrene-maleinsaureanhydrid, phenethylfluorene-acrylonitrile-methacrylate; vii) styrene or fluorenyl Graft copolymers of styrene, such as styrene grafted on polybutadiene, polybutadiene-styrene or polybutadiene-acrylonitrile-copolymer, and styrene grafted on polybutadiene Branched styrene and acrylonitrile (or 20 fluorenyl acrylonitrile); and mixtures thereof with the copolymers described in vi), for example, ABS-, MBS-, ASA- or AES-polymers are known; viii) Halogen-containing polymers, such as polychloroprene, chlorinated rubber (Chlor-kautschuk), polymers made from the vaporization or bromination of isobutylene-isoprene (halobutylkautschuk) ), Chlorinated or gas yellow 15 200424022 tritiated polyethylene, copolymers of ethylene and vinyl chloride, epichlorohydrin Epichlorhydrinhomo-und-copolymere, especially polymers obtained from halogenated ethylene compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene fluoride Ethylene; 5 and copolymers thereof, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate, or vinylidene chloride-vinyl acetate copolymers;

ix)從α，/3 -不飽和酸和其等之衍生物所衍生之聚合物，例如聚丙烯酸S旨和聚曱基丙烯酸g旨，以丙稀酸丁 g旨進行衝擊韌性改質之聚甲基丙烯酸甲酉旨 10 (Polymethylmeth-acrylate)、聚丙烯酸醯胺和聚丙烯腈； X) ix)所述之單體彼此間或與其他不飽和單體所形成之共聚物，例如丙稀腈-丁二烯-共聚物、丙烯腈-丙烯酸烧基酯-共聚物、丙烯腈-丙烯酸烷氧烷基酯-共聚物、丙烯腈-鹵化乙烯-共聚物，或丙烯腈-曱基丙烯酸烧基酯-丁二浠-三 15 元共聚物；ix) Polymers derived from α, / 3-unsaturated acids and their derivatives, such as polyacrylic acid (S) and polyacrylic acid (Gly), and acrylic polymers for impact toughness modification. Polymethylmeth-acrylate 10, polymethylamine acrylate and polyacrylonitrile; X) ix) Copolymers of monomers described with each other or with other unsaturated monomers, such as acrylic -Butadiene-copolymer, acrylonitrile-alkylene acrylate-copolymer, acrylonitrile-alkoxyalkyl acrylate-copolymer, acrylonitrile-halogenated ethylene-copolymer, or acrylonitrile-fluorenyl acrylate Ester-butadiene-tri 15-member copolymer;

xi) 由不飽和醇和胺，或其等之醯衍生物 (Acetyl-derivaten)或縮醛（Acetalen)所衍生之聚合物，例如聚乙烯醇，聚乙烯醋酸酯、-硬脂酸酯、-苯甲酸酯、-馬來酸酯，聚乙稀醇縮丁醛(Polyvinylbutyral)、聚浠丙基鄰苯二 20 曱酸酯（Polyallylphtlialat)、聚烯丙基三聚氰胺 (Polyallylmelamin);以及第1點所述之烯烴； xii) 環醚之單-及共聚物，例如聚烯烴乙二醇 (Poly-alkylenglykole)、聚環氧乙烯(Polyethylenoxyd)、聚環氧丙烯（Polypropylenoxyd)或其等與雙縮水甘油醚 16 200424022 (Bisglyddyl-ethern)之共聚物； xiii)聚縮醛(Polyacetale)，含有如聚甲醛，以及此等聚曱醛類，共聚用單體，例如環氧乙烷；以熱塑性聚氨醋、丙烯酸酯或MBS改質之聚縮醛； 5 xiv)聚苯醚(Polyphenylenoxide)及·硫醚和其等與苯乙烯聚合物或聚醯胺之混合物； xv) 由一末端具有羥基且另一方面具有脂肪族或芳香族聚異氰酸酯所衍生之聚氨酯，及其等之預產物； xvi) 由二胺和二碳酸及/或由氨基酸或對應的内醯胺 10 (Lactonen)所衍生之聚醯胺與共聚醯胺，例如聚醯胺4、聚醯胺6、聚醯胺6/6, 6/10, 6/9, 6/12, 4/6, 12/12、聚醯胺u、聚醯胺12，得自m-二曱苯、二胺和環戊烷酸(Adipin-saure) 之芳香族聚醯胺；前述聚醯胺與聚烯烴、烯烴-共聚物、離子鍵型共聚物或化學鍵結或接枝之彈性體，或與聚醚 15 (Polyethern)，例如聚乙二醇、聚丙撐二醇 (Polypropylen-glykol)或聚四亞甲基二醇xi) Polymers derived from unsaturated alcohols and amines, or Acetyl-derivaten or Acetalen, such as polyvinyl alcohol, polyvinyl acetate, -stearate, -benzene Formates, -maleates, Polyvinylbutyral, Polyisopropyl phthalate (Polyallylphtlialat), Polyallylmelamine (Polylylmelamine); and Point 1 Xii) mono- and copolymers of cyclic ethers, such as poly-alkylenglykole, polyethylenoxyd, polypropylenoxyd, or the like with diglycidyl ether 16 200424022 (Bisglyddyl-ethern) copolymer; xiii) Polyacetale, which contains, for example, polyacetal, and polyacetals, and comonomers, such as ethylene oxide; thermoplastic polyurethane, Acrylate or MBS modified polyacetal; 5 xiv) Polyphenylenoxide and thioethers and their mixtures with styrene polymers or polyamides; xv) from one end with a hydroxyl group and on the other Derived from aliphatic or aromatic polyisocyanate Polyurethanes and their pre-products; xvi) Polyamines and copolyamides derived from diamines and dicarbonates and / or amino acids or the corresponding Lactonen 10, such as polyamine 4, polyamine Pyramid 6, Pyramid 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, Pyramid u, Pyramid 12 from m-dioxobenzene, diamine Aromatic polyamidoamines of amines and cyclopentanoic acid (Adipin-saure); the aforementioned polyamidoamines and polyolefins, olefin-copolymers, ionomers or chemically bonded or grafted elastomers, or polyethers 15 (Polyethern), such as polyethylene glycol, polypropylen-glykol, or polytetramethylene glycol

(Polytetramethylenglykol)的嵌段共聚物。此外，有以 EPDM 或ABS改質之聚醯胺或共聚醯胺，以及在加工過程中凝縮成之聚醯胺(”RIM-聚醯胺系”）； 2〇 xvii)聚脲、聚醯亞胺、聚醯胺-醯亞胺、聚醚醯亞胺 (Polyetherimide)、聚酯亞胺（Polyesterimide)、聚乙内醯脲 (Polyhydantoine)和聚苯并咪 t»坐； xviii)由一石反酸和二醇及/或由醇酸(Hydroxycarbon -sSure)或其對應之内醯胺衍生出之聚酯，例如聚對苯二甲 17 200424022 酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚對苯二曱酸-1，4-二經甲基乙二醇酯(Poly-1，4-dimethylolcyclohexanterephthalat)、聚經基苯曱酸酯（Polyhydroxybenzoate)，以及由具有經末端基團之聚醚衍生成的嵌段-聚醚-醋；此外還有以聚碳酸酯或 5 MBS改質之聚酯； xix)聚碳酸_和聚S旨碳酸醋（Polyestercarbonate); XX) 聚礙類、聚S旨礙類（Polyestersulfone)和聚醚酮 (Polyetherketone)； xxi) 由一方面為醛類另一方面為酚類、尿素或三聚氰 10 胺所交聯成之聚合物，例如酚-甲醛…尿素-甲醛-和三聚氰胺-曱醛樹脂； xxii) 濕式或非濕式醇酸樹脂； xxiii) 由飽和及不飽和二碳酸與多價醇，和以乙烯化合物做為交聯劑而獲得之不飽和聚g旨樹脂，及其等之含鹵素 15 的難燃改質產物； xxiv) 由經取代之丙烯酸酯衍生而得，例如由環氧丙烯酸酉旨（Epoxyacrylatet!)、氨基曱酸-丙烯酸酯 (Urethan-acrylaten)或聚酯 _ 丙烯酸 _ (p〇lyester acrylat_en) 之交聯丙烯酸樹脂； 20 xxv)與三聚氰胺樹脂、尿素樹脂、異氰酸酯、三聚異氰酸酯（Isocyamimten)、聚異氰酸酯或環氧樹脂交聯之醇酸樹脂、聚酯樹脂和丙稀酸樹脂； xxvi)由脂肪族、環脂族、雜環或芳香族之縮水甘油化合物（GlyCidylVerbmdungen)所衍生之交聯環氧樹脂，例如 18 200424022 雙酉分-A-雙縮水甘油基-醚(Bisphenol-A-diglycidyl-ethern)、雙酉分，F-雙縮水甘油基-®E(Bisphenol-F-diglycidyl-etheni)，藉一般的硬化劑，例如酐類或胺類，在催化或不催化下交而成的產物； 5 xxvii)含矽聚合物，例如聚矽氧烷和聚矽烷，及其等之交聯及/或共聚合衍生物； xxviii) 天然聚合物，例如纖維素、天然橡膠、明膠，以及其等之同系聚合物化學變位衍生物，例如乙酸纖維素、丙酸纖維素及丁酸纖維素，或纖維素醚，如甲基纖維素 10 ，以及松香樹脂(Kolophomiumharze)與衍生物；(Polytetramethylenglykol) block copolymer. In addition, there are polyamides or copolymers modified with EPDM or ABS, and polyamides ("RIM-polyamines") that are condensed during processing; 20xvii) polyurea, polyamide Amines, polyamidoamines, polyimides, polyetherimide, polyesterimide, polyhydantoine, and polybenzimidides; xviii) a single acid inversion And diols and / or polyesters derived from alkyd (Hydroxycarbon-sSure) or its corresponding lactam, such as polyethylene terephthalate 17 200424022 ethylene glycol ester, polybutylene terephthalate , Poly-1,4-dimethylolcyclohexanterephthalat, Polyhydroxybenzoate, and a polymer with a terminal group Ether-derived block-polyether-vinegar; there are also polyesters modified with polycarbonate or 5 MBS; xix) polycarbonates and polyScarbonates (Polyestercarbonate); XX) S is Polyestersulfone and Polyetherketone; xxi) is an aldehyde on the one hand, and a phenol, urea or melamine on the other 10 Amine cross-linked polymers, such as phenol-formaldehyde ... urea-formaldehyde- and melamine-formaldehyde resins; xxii) wet or non-wet alkyd resins; xxiii) from saturated and unsaturated dicarbonic acid and polyvalent Alcohols, unsaturated polyg resins obtained using ethylene compounds as cross-linking agents, and flame retardant modified products containing halogen 15; xxiv) derived from substituted acrylates, such as from cyclic Epoxyacrylatet !, amino acid-acrylate (Urethan-acrylaten) or polyester_acryl_ (p〇lyester acrylat_en) cross-linked acrylic resin; 20 xxv) and melamine resin, urea resin, isocyanate, Trisodium isocyanate (Isocyamimten), polyisocyanate or epoxy resin crosslinked alkyd resin, polyester resin and acrylic resin; xxvi) aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compound (GlyCidylVerbmdungen ) -Derived cross-linked epoxy resins, such as 18 200424022 Bisphenol-A-diglycidyl-ethern, Bisphenol, F-bisglycidyl-®E (Bisphenol -F-digl ycidyl-etheni), the product obtained by the general hardener, such as anhydrides or amines, catalyzed or uncatalyzed; 5 xxvii) silicon-containing polymers, such as polysiloxanes and polysilanes, and so on Cross-linked and / or copolymerized derivatives; xxviii) natural polymers, such as cellulose, natural rubber, gelatin, and their homologous polymer chemically-derived derivatives, such as cellulose acetate, cellulose propionate, and butyl Acid cellulose, or cellulose ethers, such as methyl cellulose 10, and rosin resin (Kolophomiumharze) and derivatives;

xxix) 上述聚合物之混合物（Polyblends)，例如 PP/EPDM、聚醯胺/-EPDM或ABS、PVC/EVA、PVC/ABS 、PVC/MBS、PC/ABS、PBTP/ABS、PC/ASA、PC/PBT、 PVC/CPE、PVC/丙烯酸酯、POM/熱性PUR、PC/熱性PUR 15 、POM/-丙烯酸酯、p〇m/MBS、PPO/HIPS、PPO/PA 6.6及共聚物，PA/HDPE、PA/PP、PA/PPO、PBT/PC/ABS或PBT /PET/PC 〇就天然的聚合物而言，特另值得一提的有碳纖維、纖維素、澱粉、棉花、橡膠、松香、木材、亞麻、西沙爾麻 20 (Sisal)、多肽、聚氨基酸和其等之衍生物。就合成的聚合物而言，以聚碳酸酯、聚酯、含鹵素聚合物、聚丙烯酸酯、聚烯烴、聚醯胺、聚氨酯、聚苯乙烯及/或聚醚為佳。合成材料可為薄膜、喷射鑄造部件(Spritzgussteilen)、 19 200424022 擠壓工件（Extrusionswekstiicken)、纖維、絨毛或織物的形態。除了供汽車工業用之構件外，也可以將一功能層配備在如眼鏡或隱型眼鏡的物件。真空條件下獲得電漿的途徑在文獻中已有許多說明。 5 電能可以利用電感或電容的方式耦合。其可為直流電或交流電，其中交流電之頻率可在數kHz至MHz的區域變動。在微波區域(GHz)的饋電也是可行的。電衆生成與維持的原則記載於例如 J· R· Holahan與A. T. Bell，Wiley，New York (1974)出版之”Technology and Application of piasma 10 Che-mistry” 中，A. T. Bell 之”Fundamentals of Plasma Chemistry”，或H. Suhr之Plasma Chem. Plasma Process 3(1)， 1，（1983)。做為一次電漿氣體者可利用，例如氦、氬、氙、N2、〇2、H2、水蒸氣或空氣。依據本發明之方法本身對電能的 15 耦合並不敏感。該方法可以在批次作業，例如在一轉鼓或在薄膜、纖維或織物的連續操作中進行。此等方法為習知且在現有技術中已有記載。本發明之方法亦可在電暈-放電條件下進行。電暈放電係在常壓條件下生成，其最常使用空氣做為離子化氣體。 20 但是原則上也可以使用其他氣體及混合物，例如COATING V〇l. 2001，No. 12, 426,（2001)中所敘述者。在電暈放電中用空氣做為離子化氣體的優點在於，可在一朝外開啟的設備中進行處理，而且可以讓例如一薄膜在放電電極間連續通過。此種製程配置屬習知’且在例如J. Adhesion Sci. Technol. 20 200424022xxix) Polyblends of the above polymers, such as PP / EPDM, polyamide / -EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermal PUR, PC / thermal PUR 15, POM / -acrylate, pom / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE , PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC 〇In terms of natural polymers, carbon fiber, cellulose, starch, cotton, rubber, rosin, wood , Flax, Sisal 20 (Sisal), peptides, polyamino acids and derivatives thereof. As the synthetic polymer, polycarbonate, polyester, halogen-containing polymer, polyacrylate, polyolefin, polyamide, polyurethane, polystyrene, and / or polyether are preferred. Synthetic materials can be in the form of films, spray-cast parts (Spritzgussteilen), 19 200424022 Extrusionswekstiicken, fibers, fluff or fabric. In addition to components for the automotive industry, it is also possible to equip a functional layer with objects such as glasses or contact lenses. Many ways to obtain plasma under vacuum have been described in the literature. 5 Electrical energy can be coupled by means of inductance or capacitance. It can be either direct current or alternating current, where the frequency of the alternating current can range from several kHz to MHz. Feeding in the microwave region (GHz) is also possible. The principles of generation and maintenance of electric crowds are described in, for example, "Technology and Application of piasma 10 Che-mistry" published by J.R. Holahan and AT Bell, Wiley, New York (1974), and "Fundamentals of Plasma Chemistry" by AT Bell. , Or H. Suhr's Plasma Chem. Plasma Process 3 (1), 1, (1983). Available as primary plasma gas, such as helium, argon, xenon, N2, 02, H2, water vapor or air. The method according to the invention is itself not sensitive to the coupling of electrical energy. The method can be performed in a batch operation, such as in a rotating drum or in a continuous operation of film, fiber or fabric. These methods are well known and documented in the prior art. The method of the present invention can also be performed under corona-discharge conditions. Corona discharges are generated at atmospheric pressure, and air is most commonly used as the ionizing gas. 20 However, other gases and mixtures can also be used in principle, such as those described in COATING Vol. 2001, No. 12, 426, (2001). The advantages of using air as the ionizing gas in a corona discharge are that it can be processed in a device that is turned on outwards and, for example, a thin film can be passed continuously between the discharge electrodes. Such a process configuration is conventional ’and is described in, for example, J. Adhesion Sci. Technol. 20 200424022

Vol 7, No. 1〇, ii〇5 (1993)中有载。三維工件可以採用一無電漿照射加以處理，其中輪廓可藉助機器人來檢查。本發明之方法可以在一廣壓力範圍内進行，其中該放電特性隨著純低溫電漿漸增的壓力而朝電暈放電的方向移 5動，最終在約100(M10G mbar的大氣壓力轉移成一純電暈放電。 - 本發明之方法以在一 10-6 mbar至大氣壓力（1013 mbar) 的製程壓力下進行為佳，特別是在大氣壓力下以電暈法進行者為佳。 · 10 本發明之方法以使用一惰性氣體，或一惰性氣體與一活性氣體之混合物做為電漿氣體而進行者為佳。若使用一電暈放電操作則氣體係採用空氣、（：02及/或氮。特別合適者係單獨或混合使用H2、c〇2、He、Ar、Kr 15 、Xe、N2、〇2或H20做為電漿氣體。同樣地亦可採用高能量照射，例如以光、UV-光、電子 -及離子照射的型式，進行表面之活化。 · 只要是可藉加熱及/或以電磁波照射而產生一或多種自由基（或中間物）之所有化合物或化合物之混合物都可以 2〇做為玎活化起始劑。除了大部分係利用熱活化之化合物或 ^ 租成，例如過氧化物和過氧化氫(與催化劑，例如胺及/或鈷 . 藥組合者亦可）以外，胺醚(NOR-化合物）以及可光化學活化之化合物（例如笨偶因（Benzoine))或發色團（Chro-mophoren) 與C〇_起始劑（例如二苯曱蒙1 (Benzophenon)連同叔胺）之組 21 200424022 合或其等之混合物亦屬之。同樣地，可添加感光劑與c〇_ 起始劑（例如硫雜蒽酮（Thioxanthone)連同叔胺）或發色團（例如硫雜蔥酮連同胺酮）。同樣可以使用氧化還原系，例如出〇2連同鐵(II)鹽。亦可添加電子傳遞對，例如染料和硼酸 5鹽及/或胺。做為起始劑者可以使用選自過氧化物、過二碳酸鹽（Peroxodicarbonate)、過硫酸鹽、苯頻那醇(Benzpinak〇le) 、聯苯、二硫化物、偶氮化合物、氧化還原系、苯偶因、苄縮酮(Benzilketale)、苯乙酮(Acetophenone)、經基烧基苯酮 (Hydroxyalkylphemme)、胺基烷基苯酮（Amin〇alkylphen〇ne) 10 、醢基鱗化氧（Acylphosphinoxide)、醯基鱗化硫 (Acylphosphinsulfide)、醯氧基亞氨酮(Acyl_〇xyimin〇ket〇ne) 、鹵化本乙酮、苯醢曱酸g旨（Phenylglyoxa-late)、二苯甲酮 (Benzophenone)、將和將酯（〇ximester)、硫雜蔥酮、樟腦· (Camphorquinone)、二茂鐵（Ferrocene)、二茂鈦（Titanocene) 15 、鎏鹽(Sulfoniumsalze)、蛾鑽鹽(Iodonium salze)、重氮鑽鹽 (Diazoniumsalze)、鍇鹽（Oniumsalze)、硼烷(Boralkyle)、石朋酸酉旨、三嗔(Triazine)、雙味。坐(Bisimida-zole)、聚石夕燒和染料’以及對應之聯合起始劑（Coinitiator)及/或感光劑。較佳者為：過氧化二苯曱醯(Dibenzoylperoxid)、過氧 2〇化苯甲醯、過氧化二異丙苯(Dicumylperoxid)、說過氧化異丙苯（Cumylhydroperoxid)、過氧化二碳酸二異丙酉旨 (Diiso-propylperoxidicarbonat) 、丁酮過氧化物 (Methylethylketon-peroxid)、過氧化二碳酸二(4_t-丁基環己基）酉旨（Bis(4-t-butyl -cyclohexyl)peroxidicarbonat)、過氧化 22 200424022 單硫酸銨（Ammo-niumperoxomonosulfat)、過氧化二硫酸錄 (Ammonium-peroxodisulfat)、過二硫酸鉀（Dikaliumpersulfat) 、過二硫酸鈉（Dinatriumpersulfat)、N，N-偶氮二異丁腈 (N，N-Azobisiso-butyronitril)、2,2’-偶氮二（2,4-二甲基戊腈 5 )(2,2’-azobis (2,4-dimethylpentannitril))、2,2’-偶氮二(2-曱基丙腈）(2,2’-azobis(2-methylpropannitril))、2,2’-偶氮二(2-曱基丁腈）(2,2、7〇1^(2-11^1^11)1^1111汾丨1))、1，1’-偶氮二（氰環己烷）（1，1’42〇1^〇}^1100}^1〇116乂&11)、苯甲酸過氧化叔戊酯 (tert-Amylperoxobenzoat)、2，2’-二（過氧化叔丁基）丁烷 10 (2,2’-Bis(tert，butylperoxy)butan)、1，1 ’-二（過氧化叔丁基)環己烧（l，l’-Bis(tert-butylperoxy)cyclohexan)、2,5-二（過氧化叔丁基）-2,5-二曱基己烧（2,5-Bis (tert-butylperoxy) -2,5-dimethyl-hexan)、2,5-二(過氧化叔丁基)-2,5-二甲基-3-己快(2,5-Bis (tert-butylperoxy) -2,5-dimethyl-3-hexyn)、1，Γ_-二（過氧化叔丁基）-3,3,5-三曱基環己烷（i，i，_Bis (tert-butyl-peroxy)-3,3,5-trimetliylcyclohexan)、叔丁基過氧化氫(tert-Butyl-hydro-peroxid)、過乙酸叔丁酉旨（tert-Butylacetat) 、叔丁基過氧化物(tert-Butylperoxid)、苯曱酸過氧化丁酯 (tert-Butyl-peroxobenzoat)、過氧化異丙基碳酸叔丁醋 20 (tert-Butyl-peroxyisopropylcarbonat)、過氧化環己酮 (Cyclohexanon-peroxid)、過氧月桂醯(Lauroylperoxid)、過氧化2,4-戊二酮（2,4-Pentandicmperoxid)、2,5-二甲基-2,5-二(過氧叔丁基)-己烧(2,5-dimethyl-2,5-di(tert-butylperoxy)-hexan) 、一(2-過氧叔丁基異丙基)苯醯(Di-(2-tert-butylperoxyisopropyl) 23 200424022 benzol、辛酸姑（Cobaltoctanoat)、二環戊二浠基鉻 (Dicyclo-pentadienylchrome)、過乙酸，苯頻那醇(Benzpinakol) 與聯苯衍生物，例如二甲基-2,3-聯苯丁烷 (Dimethyl-2,3-Di-phenylbutan)、3,4-二甲基 _3,4_聯苯己烷 5 (354-Dimethyl-3,4-diphenylhexan)、聚-1，4-二異丙基苯 (Poly-l，4-diisopropyl-benzol)、N，N-二曱基環己銨二丁基二硫代氨基甲酸醋（N，N-Dimethyl-Cyclohexyl-Ammonium-Dibutyl -Dithiocarbamat)、N-叔丁基-2_苯并嘆唑績酸醯胺 (N-tert-2-benzothiazole-sulfenamid)、二石荒化苯并 σ塞口坐 10 (Benzothiazyldisulfid)和二硫化四苄基秋蘭姆 (Tetrabenzyl-thiuramdisulfid)。可光活化系統之典型例係如下所示，既可單獨亦可混合使用。例如二苯曱酮、二苯曱酮衍生物、苯乙酮、苯乙酮衍生物，例如α-羥基環烷基苯基酮 15 (α-Hydroxycyclo-alkylphenylketone)或 2-羥基-2-甲基-1 -苯基-丙酮、二烷氧基-苯乙酮、a-羥基-或a-胺基苯乙酮，以及例如（4-曱硫基苯曱醯基）-1_甲基-1-嗎啉代乙烷 ((4_Methylthiobenzoyl)-l-metyl-l-morpholino，ethan))、（4-嗎琳代-苯曱醯基）小苄基-1-二曱基氨基丙烷 20 ((4-Morpholino-benzoyl)-1 -benzyl-1 -di-methylaminopropan) 、4-芳醯基-1，3-二氧雜戊環(4-Aroyl-l，3-Dioxolane)、安息香烷基醚(Benzoinalkylether)和苯偶醯縮酮（Benzilketale)，例如苯彳禹醯二曱基縮酮(Benzildimethyl-ketal)、苯醯曱酸酯及其衍生物，苯醯曱酸酯二聚物，單醯基磷化氧 24 200424022Vol 7, No. 10, ii〇5 (1993). Three-dimensional workpieces can be processed with a plasma-free irradiation, where the contour can be inspected by a robot. The method of the present invention can be performed in a wide pressure range, in which the discharge characteristics are shifted in the direction of corona discharge with the increasing pressure of pure low-temperature plasma, and finally transferred into an atmospheric pressure of about 100 (M10G mbar). Pure corona discharge.-The method of the present invention is preferably performed at a process pressure of 10-6 mbar to atmospheric pressure (1013 mbar), especially the corona method is performed at atmospheric pressure. The method of the invention is preferably performed using an inert gas, or a mixture of an inert gas and an active gas as the plasma gas. If a corona discharge operation is used, the gas system uses air, (: 02 and / or nitrogen). Particularly suitable is to use H2, co2, He, Ar, Kr15, Xe, N2, 02, or H20 as the plasma gas alone or in combination. High-energy irradiation can also be used, such as light, UV -Light, electron-, and ion irradiation to activate the surface. As long as it is all compounds or mixtures of compounds that can generate one or more free radicals (or intermediates) by heating and / or irradiation with electromagnetic waves 2 〇Do玎 Activation initiators. In addition to most of the compounds that are activated by heat or leased, such as peroxides and hydrogen peroxide (with catalysts, such as amines and / or cobalt. Combination drugs can also be), amine ethers ( NOR-compounds) and photochemically-activatable compounds (eg Benzoine) or chromophores (Chro-mophoren) and Co-starters (eg Benzophenon with tertiary amines) Group 21 200424022 or a mixture thereof is also included. Similarly, a sensitizer and a co-starter (such as Thioxanthone together with a tertiary amine) or a chromophore (such as thia onion) can be added. Ketones together with amine ketones). Redox systems can also be used, such as 〇2 together with iron (II) salts. Electron transfer pairs can also be added, such as dyes and boric acid salts and / or amines. As initiators can be used Selected from peroxides, peroxodicarbonates, persulfates, Benzpinakole, biphenyls, disulfides, azo compounds, redox systems, benzoin, benzalketals (Benzilketale), acetophenone, acetophenone (Hydroxyalkylphemme), AminOalkylphenone 10, Acylphosphinoxide, Acylphosphinsulfide, Acylphosphinsulfide, Acylphosphinsulfide 〇ne), halogenated acetophenone, phenylglyoxa-late, benzophenone, oximester, thia allanone, camphor (Camphorquinone), two Ferrocene, Titanocene 15, Sulfoniumsalze, Iodonium salze, Diazoniumsalze, Oniumsalze, Boralkyle, Shipeng Sour taste, Triazine, double taste. Bisimida-zole, poly-stone yaki and dyes', and corresponding joint initiators and / or sensitizers. Preferred are: dibenzoylperoxid, benzoylperoxide 20, dicumylperoxid, cumylhydroperoxid, diisoperoxydicarbonate Diiso-propylperoxidicarbonat, Methylethylketon-peroxid, Bis (4-t-butyl-cyclohexyl) peroxidicarbonat, Oxidation 22 200424022 Ammo-niumperoxomonosulfat, Ammonium-peroxodisulfat, Dikaliumpersulfat, Dinatriumpersulfat, N, N-Azobisisobutyronitrile N, N-Azobisiso-butyronitril), 2,2'-azobis (2,4-dimethylvaleronitrile 5) (2,2'-azobis (2,4-dimethylpentannitril)), 2,2'- Azobis (2-fluorenylpropionitrile) (2,2'-azobis (2-methylpropannitril)), 2,2'-azobis (2-fluorenylbutyronitrile) (2,2,7〇1 ^ (2-11 ^ 1 ^ 11) 1 ^ 1111fen1)), 1,1'-azobis (cyanocyclohexane) (1,1'42〇1 ^ 〇} ^ 1100} ^ 1〇116乂 & 11), tert-amyl benzoate (ter t-Amylperoxobenzoat), 2,2'-bis (tert-butylperoxy) butane 10 (2,2'-Bis (tert, butylperoxy) butan), 1,1'-bis (tert-butylperoxy) ring L, l'-Bis (tert-butylperoxy) cyclohexan), 2,5-bis (tert-butylperoxy) -2,5-difluorenyl hexane (2,5-Bis (tert-butylperoxy) -2,5-dimethyl-hexan), 2,5-bis (tert-butylperoxy) -2,5-dimethyl-3-hexane (2,5-Bis (tert-butylperoxy) -2,5 -dimethyl-3-hexyn), 1, Γ_-bis (tert-butyl peroxide) -3,3,5-tris-methylcyclohexane (i, i, _Bis (tert-butyl-peroxy) -3,3 5-trimetliylcyclohexan), tert-Butyl-hydro-peroxid, tert-Butylacetat, tert-Butylperoxid, benzoate peroxidation Tert-Butyl-peroxobenzoat, tert-Butyl-peroxyisopropylcarbonat, Cyclohexanon-peroxid, Lauroylperoxid, peroxo 2 2,4-Pentandicmperoxid, 2,5-dimethyl-2,5-di (peroxyt-butyl) -hexane (2,5-dimethyl-2,5 -di (tert-butylperoxy) -hexan), Di- (2-tert-butylperoxyisopropyl) 23 200424022 benzol, Cobaltoctanoat, dicyclopentane Dicyclo-pentadienylchrome, peracetic acid, Benzpinakol and biphenyl derivatives, such as Dimethyl-2,3-Di-phenylbutan, 3,4-dimethyl_3,4_biphenylhexane 5 (354-Dimethyl-3,4-diphenylhexan), Poly-1,4-diisopropyl-benzol ), N, N-Dimethylcyclohexyl ammonium dibutyl dithiocarbamate (N, N-Dimethyl-Cyclohexyl-Ammonium-Dibutyl-Dithiocarbamat), N-tert-butyl-2_benzobenzoxazole N-tert-2-benzothiazole-sulfenamid, Benzothiazyldisulfid and Tetrabenzyl-thiuramdisulfid. A typical example of a photoactivatable system is shown below, which can be used alone or in combination. For example benzophenone, benzophenone derivative, acetophenone, acetophenone derivative, such as α-Hydroxycyclo-alkylphenylketone 15 or 2-hydroxy-2-methyl -1 -phenyl-acetone, dialkoxy-acetophenone, a-hydroxy- or a-aminoacetophenone, and for example (4-fluorenylthiophenylfluorenyl) -1_methyl-1 -(4_Methylthiobenzoyl) -l-metyl-l-morpholino (ethan)), (4-morpholino-phenylfluorenyl) benzyl-1-difluorenylaminopropane 20 ((4 -Morpholino-benzoyl) -1 -benzyl-1 -di-methylaminopropan), 4-Aroyl-1,3-Dioxolane, Benzoinalkylether ) And Benzilketale, such as Benzildimethyl-ketal, benzoate and its derivatives, benzoate dimers, monofluorenyl phosphate Oxygen 24 200424022

(Monoacylphosphinoxide)，例如（2,4,6-三曱基苯甲醯基)-苯基-磷化氧（(2,4,6-Trimethylbenzoyl)-phenylphos-phinoxid) ，二醢基填化氧(Bisacylphophinoxide)，例如二(2, 6-二曱氧基苯甲醯基）-(2,4,4-三曱基-戊-1-基）磷化氧（Bis(25 5 6-dimethoxybenzoyl)-(254?4-trimethyl-pent-1 -yl)phosphin-ox id)、二（2,4,6_三曱基苯甲醯基）苯基-磷化氧（Bis (254?6-trimethylbenzoyl)phenyl-phosphinoxid) ^ — (25456-甲基苯甲醯基）-(2,4-二戊氧基苯基）-磷化氧 (Bis(2,4,6-trimethyl-benzoyl)-(2,4-dipentoxyphenyl)-phophin 10 oxid)，三醯基填化氧，二茂鐵化合物或二茂鈦，例如（η5-2,4-環戊二烯-1-基）[1，2,3,4,5,6-11]-(1-甲基乙基）苯]鐵(+)-六氟石粦酸鹽〇1) (η5-2,4- cyclopentadien-1-yl) [1，2,3,4,5,6-η] -(1-methylethyl) benzene] iron (+)-hexafluorophosphat (-1)或二環戊二烯-二(2，6-二氣比洛并苯)-鈦(Dicyclopentadienyl-bis 15 (2,6-difluoro -3- pyrrolo-phenyl)- titan。鎏鹽和蛾鏘鹽係例如二[4 -(二苯礙并）-苯]硫化二六氟磷酸（Bis [4 -(diphenyl-sulphonio) -phenyl] sulphid bishexafluorophosphat) 、（4-異丁基苯基)-p-曱苯基-碘鑽六氟磷酸(4-isobutylphenyl) -p.tolyl-iodoniumhexa-fluorophosphat) 〇 20 聯合起始劑可以考慮使用例如感光劑，其推移或擴展光譜靈敏度，並藉而促成光聚合反應之加速。此情形尤其可以添加芳香族羰基化合物，例如二苯甲酮-、硫雜蔥酮-、尤其亦可添加異丙基硫雜蔥酮、蔥醌(Anthrachinon)-和3-醯基氧染萘鄰酮衍生物（3-Acylcumarinderivate)、三口秦 25 200424022 (Triazine)、氧染萘鄰酮（Coumarine)、聯三苯、苯乙稀嗣 (Styrylketone)，以及3-(芳醯基亞曱基）-噻唑嘛 (3-(Aroyl-methylen)-thiazoline)、樟腦醌(Campherchinon)，而伊紅-(Eosin-)、若丹明-(Rhodamin-)和赤蘚紅納鹽 5 -(Erythrosin-)等染料亦可被應用。此外如季胺、硫醇(Thi〇le) 、硼酸鹽（Borate)、苯基甘油、膦(phosphine)及其它給電子化合物亦可添加。所添加之起始劑以含有乙烯系不飽和基團者為佳，因其以此種方式於聚合反應程序中形成聚合物鏈並藉以形成 10 所需之層。乙烯系不飽和基團除了乙烯基-和亞乙烯基 (Vinyliden)基團外，尤其可以考慮丙烯酸酯-、曱基丙烯酸酯-、稀丙基-和乙稀醚-基團。乙稀系不飽和化合物可以含有一或多個稀烴雙鍵其等可為低分子量（單體）或高分子量（低聚物、聚合物）。透過合 15 適的選擇，可以將功能層之特性控制在一廣範圍内。因此，在使用水溶性化合物的情形下可以製成親水性層。在使用疏水性化合物（例如氟化化合物或丙烯酸化蠟）的情形下可以製成耐水層。具有雙鍵之單體可舉例如烷基-或羥烷基-丙烯酸酯，或 20 -甲基丙烯酸酯，例如曱基-、乙基-、丁基-或2-羥乙基丙烯酸酉旨、異冰片基丙稀酸酉旨（Isobornylacrylat)、曱基-或乙基甲基丙烯酸酯。可以使用者尚有矽（甲基）丙烯酸鹽和氟化丙烯酸I旨或曱基丙烯酸酯。此外，亦可添加不飽和化合物之鹽類或氯化氫加成物（例如3-磺基丙基丙烯酸之鈉鹽、2-氨基 26 200424022 乙基甲基丙烯酸酯氫氣化物）。其它包括丙烯腈；丙烯醯胺 ;甲基丙烯醯胺；N-取代之甲基丙烯醯胺；乙烯酯，如乙酸乙烯；乙烯醚，如異丁基乙烯醚；苯乙烯，烷基_和鹵化苯乙烯；馬來酸或馬來酸酐；N-乙稀基啦略烧酮、氣乙浠 5 或偏氯乙烯。帶有酸性、中性或鹼性反應性(例如烯丙胺、 2-氨基乙基甲基丙烯酸酯、4-乙稀基π比ϋ定、丙稀酸、2-丙烯 -1-磺酸)之附加基團的不飽和化合物同樣可以添加。具有不飽和基團之金屬有機化合物亦可添加。具有數個雙鍵之單體可舉例如乙二醇-、丙二醇_、新戊 10 二醇-、1，6-己二醇(Hexzmethylenglykol)·或雙酚-Α-二丙烯酸酯（Bisphenol-A-diacylat)、4,4-二(2_丙烯醯氧基乙氧基)-一苯基丙烧（4,4-Bis(2-acryloyloxyethoxy)-diphenylpropan) 、二·曱基丙烧-三丙稀酸 g旨（Trimethylolpropan-triacrylat) 、季戊四醇三丙稀酸g旨（pentaerythrittriacrylat)或-四丙烯酸 15 醋、乙烯丙稀酸S旨、二乙稀基苯(Divinylbenzol)、琥轴酸二乙烯基酯（Divinylsuccinat)、鄰苯二甲酸二烯丙基酯、磷酸三稀丙基酯（Triallylphosphat)、三聚異氰酸三烯丙基酯 (Tri-allylisocyanurat)、三（羥乙基）三聚異氰酸-三丙烯酸酯 (Tris(hydroxyethyl)isocyanurat-triacrylat)或三-(2-丙稀醯基 20 乙基二聚異氰酸酯（Tris-(2-acryloylethyl)-isocyanurat) 〇高分子量（低聚物、聚合物）多重不飽和化合物之例有丙烯酸化環氧樹脂，丙烯酸化或含乙烯醚_或環氧_基團之聚酯、聚氨酯和聚醚。不飽和低聚物之其它例有不飽和聚酯樹脂’其大多係由馬來酸、苯二酸與一或數種二元醇所製得 27 200424022 ，且具有約500至3000之分子量。其他亦可考慮添加乙烯醚 -單體和-低聚物，及以馬來酸酯做為末端基之低聚物連同聚酯-、聚氨酯-、聚醚-，以及環氧主鏈。尤其帶有乙烯醚基團之低聚物與聚合物，如WO 90/01512中所記載者特別合適 5 。此外，亦可考慮使用得自乙烯醚之共聚物及馬來酸功能化之單體。此等不飽和低聚物亦可表示為預聚物。特別適用者可舉例如，得自乙烯系不飽和碳酸與多元醇或聚環氧化物(Polyepoxiden)之酯，以及鏈中或側枝基團中有乙烯系不飽和基團的聚合物，例如不飽和聚酯、聚醯 10胺和聚氨酯，及得自其等之共聚物，醇酸樹脂(Alkydharze) 、聚丁一稀與丁二稀-共聚物、聚異戊二稀與異戊二浠_共聚物、側鏈中具有曱基丙烯酸基團之共聚物，以及該等聚合物之一或多種的混合物。不飽和碳酸之例包括丙烯酸、甲基丙烯酸、丁稀酸 15 (Crotonsaure)、衣康酸(Itac〇nsSure)、肉桂酸；不飽和脂肪酉义如亞麻feL(LinolensSure)或油酸(〇eisaxire)。較佳者為丙稀 -和甲基丙稀酸。合適的多兀醇有芳香族和尤其是脂肪族與環脂族多元醇。芳香族多元醇有對苯二盼(jjydrochinon)、4，‘二 20苯、2,2-二(4-經基苯基丙燒，以及祕(N〇v〇iake)^甲醛(Resole)。聚氧化物之例係以所謂的多元醇，尤其是芳香族多元醇與環氧氯丙烧為基底者。此外，在聚合物鍵或側鏈基團中含有經基基團合物和共聚物，例如聚乙稀醇及由之所製得的共聚物，或聚甲基丙烯酸經烧基醋或由之所製 28 2〇〇424〇22 得的共聚物亦適合做為多元醇使用。其它合適的多元醇係具有羥末端基團的低聚酯。脂肪族與環脂族多元醇為具有較佳為2至1〇個^原子之稀烛一轉，例如乙一 if·、1，2-或1，3 -丙二醇、12-、13_ 5或丨，4·丁二醇、戊二醇、己二醇、辛二醇、十二烧二醇、二甘醇（Diethylenglykol)、三甘醇（Tdethylenglykol)、分子量較佳為200至1500之聚乙二醇、ι，3·環戊二醇、i，2-、1，3-或 1，4-環己二醇、1，4-二羥甲基環己烷、甘油、三_(万_羥乙基 )胺、三經曱基乙烧、三經曱基丙烧、季戊四醇(Pentaerythrit) 10 、二季戊四醇和山梨糖醇（Sorbit)。該等多元醇可部分或完全以一個或不同的不飽和碳酸加以取代，藉而使自由羥基基團在部分酯基中被改質，例如可以被醚化或以其它的碳酸取代。酯類可舉例如： 15 三輕甲基丙烧三丙稀酸酷、三經甲基乙烧三丙烯酸酉旨、三羥甲基丙烷三曱基丙烯酸酯、三羥甲基乙烷三甲基丙烯酸醋、四甲二醇二甲基丙烯酸酉旨 (Tetramethylenglykol-dimethacrylat)、三乙二醇二曱基丙稀酸酉旨（Triethylenglykol-dimethyacrylat)、四乙二醇二丙稀酸 20 酿（tetraethylenglykol-diacrylat)、季戊四醇二丙稀酸酉旨 (Pentaerythritdiacrylat)、季戊四醇三丙稀酸酉旨 (Pentaerythritriacrylat)、季戊四醇四丙稀酸S旨、二季戊四醇二丙稀酸S旨（Dipentaerythritdiacrylat)、二季戊四醇三丙稀酸酉旨（Dipentaerythritriacrylat)、二季戊四醇四丙烯酸_、二季 29 200424022 戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、三季戊四醇八丙稀酸酿（Tripentaerythritocta-acrylat)、季戍四醇二曱基丙烯酸醋（Pentaerythritdimeth-acrylat)、季戊四醇三甲基丙烯酸醋（Pentaerythrittrimeth-acrylat)、二季戊四醇二甲基丙 5 稀酸酉旨（Dipentaerythritdi-methacrylat)、二季戊四醇四甲基丙烯酸 _ (Dipentaerythrit-tetramethacrylat)、三季戊四醇八甲基丙稀酸酯（Tripenta-erythritoctamethacrylat)、季戊四醇二衣康酸酯（Pentaery-thritdiitaconat)、季戊四醇三衣康酸酯 (Pentaerythrittris-itaconat)、二季戊四醇五衣康酸酯 10 (Dipentaerythritpenta-itaconat)、二季戊四醇六衣康酸酉I (Dipentaerythrithexa-itaconat)、乙二醇二丙浠酸S旨、1，3-丁二醇二丙烯酸酯、1，3- 丁二醇二曱基丙烯酸酯 (l，3-Butandioldimethaxrylat)、1，4- 丁二醇二衣康酸酯 (l，4-Butandioldiitaconat)、山梨糖醇三丙稀酸酯 15 (Sorbittriacrylat)、山梨糖醇四丙烯酸酯（Sorbit-tetraacrylat) 、季戊四醇-改質-三丙稀酸酉旨（Pentaerythrit -modifiziert-triacrylat)、山梨糖醇四曱基丙稀酸酯（Sorbit-tetramethacrylat)、山梨糠醇五丙浠酸酯（Sorbitpentaacrylat) 、山梨糖醇六丙稀酸酯（Sorbithexaacrylat)，低聚酯丙烯酸 2〇酯（Oligoesteracrylate)和-甲基丙稀酸酯，甘油二-及-三丙稀酸酯，1，4-環己烷二丙烯酸酯，分子量200至1500之聚乙二醇的雙丙稀酸酯（Bisacrylate)和雙甲基丙稀酸酯 (Bismeth-acrylate)，或其等之混合物。合適的成分尚包括具有較佳為2至6,更佳為2至4個氨 30 200424022 基基團之芳香族、環脂族和脂肪族多胺的相同或相異不飽和碳酸之醯胺。此等多胺之例有乙二胺、1，2-或1，3_丙二胺、：U2-，1,3-或 1,4-丁二胺、1，5-戊二胺、1，6-己二胺、辛二胺、十二烧二胺(Dodecylendiamin)、1,4-二氨基環己炫、異佛 5 爾酮二胺（Isohorondiamin)、苯二胺、雙苯二胺 (Bis-phenylendiamin)、：|L*6®|(Di-p-axninoethylether)、二乙#三胺（Diethylentriamin)、三乙推四胺 (Triethylentetramin)、二(β-氨基乙氧基)-或（β-氨基丙氧基) 乙烷。其它適用的多胺類為具有必要時在側鏈有額外的氨 10 基基團之聚合物和共聚物，和具有氨基末端基之低聚醯胺。此等不飽和醯胺類為：曱撐’雙丙烯醯胺 (Methylen-bis-acrylamid)、1，6-六曱撐雙丙烯醯胺 (1，6-Hexamethylen-bis-acrylamid)、二乙撑三胺-三-甲基丙稀醯胺（Diethylentriamin-tris-methacrylamid)、雙（曱基丙稀 15 醢胺丙氧基）-乙烧（Bis(methacrylamidopropoxy)-ethan、β-甲基丙烯醯胺基乙基曱基丙烯酸酯（β-Meth-acrylamidoethylmethacryla)、Ν[(β-經乙氧基）乙基])-丙烯酿胺0 適用的不飽和聚酯頭多胺係從例如馬來酸和二元醇或 20 二胺衍生而來。馬來酸可部分為其它二碳酸所取代。其等可以和乙稀系不飽和共聚用單體一同被添加。聚g旨和多胺亦可由二碳酸和乙稀系不飽和二元醇或二胺，特別是具有例如6至20個C-原子之長鏈衍生而得。聚氨酯之例係從飽和或不飽和二異氰酸S旨，和不飽和或飽和二元醇所合成。 31 200424022 聚丁二烯與聚異戊二烯和得自其等之共聚物屬已知。適用之共聚用單體有例如烯烴類之乙烯、丙烯、丁烯、己烯、曱基丙烯酸酯、丙烯腈、苯乙烯或氯乙烯。侧鏈上有曱基丙烯酸酯基團之聚合物同屬已知。其可為例如以酚醛 5 基底（Novolak-basis)之環氧樹脂和曱基丙烯酸的反應產物，以曱基丙烯酸酯化之乙烯醇類或其等之羥烷基衍生物的單-或共聚物，或以羥烷基曱基丙稀酸酯酯化之甲基丙烯酸酯的單-或共聚物。特別合適者係使用一丙烯酸酯-、甲基丙烯酸酯-或乙烯 10 醚化合物做為單或多不飽和烯烴基化合物。最佳者係如前述之多不飽和丙烯酸醋化合物。原則上，最好儘可能迅速地塗布該等溶液、懸浮液或乳劑。但是就各種不同的目的而言亦可以一時程上的遲延實施步驟b)。然而最好還是在製程步驟a)之後，直接或在24 15 小時以内進行製程步驟b)。該等溶液、懸浮液或乳劑之塗布可以用不同的技術或方式來完成。該塗布可以採用電泳離析、浸潰、濺鍍、塗抹、刷塗、刮塗、捲塗、輥塗、印染、旋塗及澆注等。供塗布用之液體所含起始劑的濃度為0.01至20%，較佳 20 為0.1至5%。該溶液中所含乙烯系不飽和化合物之濃度可為 0.1至30%，較佳為0.1至10%。該液體可另含其它物質，例如消泡劑、乳化劑、界面活性劑（Tenside)、防污劑、濕潤劑及其它漆-或染料工業中所使用的添加物。 200424022 所塗布之層在乾燥狀態下的厚度同樣要符合後續應用之需求’且達到-個單分子層至2麵，較佳為2nm至誦 μιη ’ 特佳者為 2 nn^1〇〇〇 _。、基本上最好將贿物、溶液、液或乳難可能迅速地加熱、乾燥或照光，因為所形成的層將經由這個步驟而固著且安定。就各種不同的目的而言，亦可在一時程上的遲1下貫知步驟c)。然而最好還是在製程步驟的之後，直接或在24小時以内進行製程步驟c)。 ίο 在形成塗層時的加熱/乾燥作業已知有多種可行方式，，其等全數可依所需製㈣被應用。因此可以使用例如熱亂、IR-照射、以爐子加熱之滾筒，及以微波處理。所採用之概度係依所添加之原料的溫度安定性而調整，通常在〔至3〇〇°C之間變動，較佳者係介於0至200°c間。 15 、§存在對溫度特別敏感的原料時。以電磁波照射就極為有利。其間需注意所使用之起始劑也是吸收該波長範圍 j光而UV-吸收劑在該範圍則沒有或僅顯示微量吸收。所开^成之層的照射可以用各種放射具有可以被所使用的光起 20 所吸收之波長的電磁波之光源來進行。通常光源係放 $具有介於200 nms 2〇〇〇 11111範圍的波長之電磁照射。除了白用的放射線和燈以外，亦可使用雷射及LEDs(發光二極體 )〜曝光可以採平面或局部地進行。局部曝光在僅需黏著特，區域時是有利的。也可以用電子射線來進行照射。照射可以疋平面的及/或局部的，例如藉助於以光罩曝光或藉助雷射照射來完成。藉此即可僅在狀㊣賴颜形成之層 33 200424022 的固著於安定化。該形成層可以進一步將未曝光區域洗去從而完成其結構化。步驟C)可以在空氣或惰性氣體中進行。惰性氣體除了氮氣之外，亦可考慮使用其它惰性氣體如C〇2或氬、氦等， 5或其等之混合物。適用的設備和儀器乃此項技藝者所周知且可由市售取得。通吊本發明在製程結束後並不需要塗布另一層。但是在某些個別情況下預加另一層，例如一配色層是有其優點的。然而’例如以光起始劑形成塗層的基質，不能以至少 10含有一乙烯系不飽和單體或低聚物的組成來形成塗層，並藉UV/VIS照射來使該塗覆層硬化。此外，請求依據上述製程所製得之各塗覆層。同樣地，附有以一依據上述請求之一者的塗覆層之產物亦屬請求範圍。 15 藉上述方法可以迅速、簡單且有弹性地製作功能層並調整其等之性質。因此玎以調整形成有塗覆層之基質的例如親水性或疏水性或表面張力等。藉使用水溶性或疏水性起始劑，及水溶性或親水性乙烯系不飽和化合物，即可以製造親水層並得以控制濕潤工程。此種形成層可以當做例 20 如防霧層或用以改善在表面上的細胞固著與生長。藉應用經氟化之不飽和化合物或對應的疏水性單體，例如矽壓克力（Siliconacrylate)可以製成防塗鴨層（Antigraffitischichte) 及/或調整滑動與摩擦特性。藉使用帶有在中性、酸性或驗性中反應（例如烯丙胺、2-氨基乙基曱基丙烯酸酯、4-乙烯 34 200424022 基啦啶、丙烯酸、2-丙烯-1-磺酸)額外基團之乙烯系不飽和化合物，則亦可調整酸/鹼-特性。藉使用合適的化合物即可以調整折射率。因此可以藉添加例如苄基丙稀酸酯而獲得高折射率，而透過 5 十三氟庚基曱基丙稀酸酉旨（1H，1H，7H-(Monoacylphosphinoxide), such as (2,4,6-Trimethylbenzoyl) -phenyl-phosphine ((2,4,6-Trimethylbenzoyl) -phenylphos-phinoxid) Bisacylphophinoxide), such as bis (2,6-dimethoxybenzoyl)-(2,4,4-trifluorenyl-pent-1-yl) phosphine (Bis (25 5 6-dimethoxybenzoyl)- (254? 4-trimethyl-pent-1 -yl) phosphin-ox id), bis (2,4,6-trimethylphenylbenzyl) phenyl-phosphine (Bis (254? 6-trimethylbenzoyl) phenyl-phosphinoxid) ^ — (25456-methylbenzylidene)-(2,4-dipentoxyphenyl) -phosphine (Bis (2,4,6-trimethyl-benzoyl)-(2, 4-dipentoxyphenyl) -phophin 10 oxid), trifluorenyl-filled oxygen, ferrocene compounds or titanocene, for example (η5-2,4-cyclopentadien-1-yl) [1,2,3, 4,5,6-11]-(1-methylethyl) benzene] iron (+)-hexafluorocarboxylate 〇1) (η5-2,4-cyclopentadien-1-yl) [1,2 , 3,4,5,6-η]-(1-methylethyl) benzene] iron (+)-hexafluorophosphat (-1) or dicyclopentadiene-bis (2,6-digas bilocene)- Titanium (Dicyclopentadienyl-bis 15 (2,6-difluoro-3-pyrolo-phenyl)-titan. Salt and moth salt For example, Bis [4-(diphenyl-acene) -benzene] dihexafluorophosphoric acid (Bis [4-(diphenyl-sulphonio) -phenyl] sulphid bishexafluorophosphat), (4-isobutylphenyl) -p-fluorene 4-isobutylphenyl-p.tolyl-iodoniumhexa-fluorophosphat) 〇20 Joint initiators can be considered using, for example, photosensitizers, which shift or extend the spectral sensitivity, and thereby accelerate the photopolymerization reaction . In this case, especially aromatic carbonyl compounds, such as benzophenone-, thia allanone-, especially isopropyl thia allanone, anthrachinon-, and 3-fluorenyloxynaphthalene Ketone derivatives (3-Acylcumarinderivate), Sanzou 25 200424022 (Triazine), oxanthranone (Coumarine), bitriphenylene, styrene (Styrylketone), and 3- (arylfluorenylidene) -thiazole (3- (Aroyl-methylen) -thiazoline), camphor quinone (Campherchinon), and dyes such as Eosin-, Rhodamin- and Erythrosin- Can also be applied. In addition, quaternary amines, thiols, borate, phenyl glycerol, phosphine, and other electron-donating compounds can be added. The added starter is preferably one containing an ethylenically unsaturated group, because it forms a polymer chain in the polymerization process in this way, thereby forming a layer required by 10. In addition to vinyl- and vinylidenyl groups, ethylenically unsaturated groups include acrylate-, fluorenyl acrylate-, di-propyl-, and ethylene-ether groups. Ethylene unsaturated compounds may contain one or more dilute hydrocarbon double bonds, etc. They may be low molecular weight (monomer) or high molecular weight (oligomer, polymer). Through proper selection, the characteristics of the functional layer can be controlled in a wide range. Therefore, when a water-soluble compound is used, a hydrophilic layer can be formed. Where a hydrophobic compound such as a fluorinated compound or an acrylated wax is used, a water resistant layer can be made. The monomer having a double bond may be, for example, an alkyl- or hydroxyalkyl-acrylate, or a 20-methacrylate, such as a fluorenyl-, ethyl-, butyl-, or 2-hydroxyethyl acrylate, Isobornylacrylat, fluorenyl- or ethyl methacrylate. Users may also have silicon (meth) acrylate and fluorinated acrylic acid or fluorenyl acrylate. In addition, salts of unsaturated compounds or hydrogen chloride adducts (such as the sodium salt of 3-sulfopropyl acrylic acid, 2-amino 26 200424022 ethyl methacrylate hydrogenate) can also be added. Others include acrylonitrile; acrylamide; methacrylamide; N-substituted methacrylamide; vinyl esters, such as vinyl acetate; vinyl ethers, such as isobutyl vinyl ether; styrene, alkyl, and halogenated Styrene; maleic acid or maleic anhydride; N-ethylenolone, acetamidine 5 or vinylidene chloride. With acidic, neutral or basic reactivity (e.g. allylamine, 2-aminoethyl methacrylate, 4-ethenyl pipyridine, acrylic acid, 2-propylene-1-sulfonic acid) Unsaturated compounds with additional groups can also be added. Metal organic compounds having unsaturated groups may also be added. Monomers having several double bonds include, for example, ethylene glycol-, propylene glycol, neopentyl 10 glycol-, 1,6-hexanediol (Hexzmethylenglykol), or bisphenol-A-diacrylate (Bisphenol-A -diacylat), 4,4-Bis (2-acryloyloxyethoxy) -diphenylpropan, 4,4-Bis (2-acryloyloxyethoxy) -diphenylpropan) Trimethylolpropan-triacrylat, pentaerythrittriacrylat or pentaerythrittriacrylat or acetic acid 15 vinegar, ethylene acrylic acid S purpose, divinylbenzol, divinyl succinate (Divinylsuccinat), diallyl phthalate, triallylphosphat, tri-allylisocyanurat, tris (hydroxyethyl) tris isocyanate Tris (hydroxyethyl) isocyanurat-triacrylat or Tris- (2-acryloylethyl-isocyanurat) 〇High molecular weight (oligomer, polymer Examples of polyunsaturated compounds are acrylated epoxy resins, acrylated or vinyl ether- or epoxy-containing groups Polyesters, polyurethanes, and polyethers. Other examples of unsaturated oligomers include unsaturated polyester resins, which are mostly made from maleic acid, phthalic acid, and one or more glycols. 27 200424022 Molecular weight of about 500 to 3000. Others can also consider the addition of vinyl ether-monomers and-oligomers, and oligomers with maleate as a terminal group together with polyester-, polyurethane-, polyether-, and Epoxy backbone. Especially oligomers and polymers with vinyl ether groups, such as those described in WO 90/01512 are particularly suitable.5 In addition, the use of copolymers derived from vinyl ether and maleic acid can also be considered. Functionalized monomers. These unsaturated oligomers can also be represented as prepolymers. Particularly suitable are, for example, esters derived from ethylenically unsaturated carbonic acid with a polyol or polyepoxide, and Polymers with ethylenically unsaturated groups in the chain or pendant groups, such as unsaturated polyesters, polyfluorene 10 amines and polyurethanes, and copolymers derived therefrom, alkydharze, polybutadiene Diluted with butadiene-copolymer, polyisoprene and isoprene-copolymer, side chain A copolymer having a fluorenyl acrylic group in the polymer, and a mixture of one or more of these polymers. Examples of unsaturated carbonic acid include acrylic acid, methacrylic acid, crotonsaure 15, itaconic acid ), Cinnamic acid; unsaturated fatty acids such as flax feL (LinolensSure) or oleic acid (〇eisaxire). Preferred are acrylic acid and methyl acrylic acid. Suitable polyols are aromatic and especially aliphatic and cycloaliphatic polyols. Aromatic polyols include jjydrochinon, 4, 'di20benzene, 2,2-bis (4-triphenylphenylpropane, and Novoiake) formaldehyde (Resole). Examples of polyoxides are those based on so-called polyhydric alcohols, especially aromatic polyols and epichlorohydrin. In addition, polymer bonds or copolymers are contained in polymer bonds or side chain groups. For example, polyvinyl alcohol and the copolymer made therefrom, or polymethacrylic acid based on calcined vinegar or the copolymer made from 28 2 0424 0222 is also suitable for use as a polyol. Others Suitable polyols are oligoesters with hydroxyl end groups. Aliphatic and cycloaliphatic polyols are dilute candles with a rotation of preferably 2 to 10 ^ atoms, such as ethylene-if ·, 1,2- Or 1,3-propanediol, 12-, 13_5 or 丨, butanediol, pentanediol, hexanediol, octanediol, dodecadiol, diethylenglykol, triethylene glycol ( Tdethylenglykol), polyethylene glycol having a molecular weight of preferably 200 to 1500, ι, 3 · cyclopentanediol, i, 2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxyl Methylcyclohexane, glycerol, tris _ (10,000_hydroxyethyl) amine, tris (3,4-tetramethyl) ethyl, 3- (3,4-tetramethyl) propane, pentaerythrit 10, dipentaerythritol, and sorbitol (Sorbit). These polyols can be partially or completely Or different unsaturated carbonic acid is substituted, so that the free hydroxyl group is modified in some ester groups, for example, it can be etherified or substituted with other carbonic acid. Examples of esters include: 15 trimethylolpropane Tri-acrylic acid, methyl triethylene glycol triacrylate, trimethylolpropane trimethyl acrylate, trimethylolethane trimethacrylate, tetramethyl glycol dimethacrylate (Tetramethylenglykol-dimethacrylat), Triethyleneenglykol-dimethyacrylat, Tetramethylenglykol-diacrylat, Pentaerythritdiacrylat , Pentaerythritol tripropionate (Pentaerythritriacrylat), pentaerythritol tetrapropionate S, dipentaerythritol dipropionate S (dipentaerythritdiacrylat), dipentaerythritol tripropionate (Dipentaerythr itriacrylat), dipentaerythritol tetraacrylic acid, second quarter 29 200424022 pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritocta-acrylat, pentaerythritol diacetate (Pentaerythritdimeth- acrylat), pentaerythritol trimethacrylate (Pentaerythrittrimeth-acrylat), dipentaerythritol dimethylpropion 5 dipentaerythritdi-methacrylat, dipentaerythritol tetramethacrylic acid (Dipentaerythrit-tetramethacrylat), tripentaerythritol octamethyl Tripenta-erythritoctamethacrylat, Pentaery-thritdiitaconat, Pentaerythrittris-itaconat, Dipentaerythritpenta-itaconat, Dipentaerythritol Dipentaerythrithexa-itaconat, ethylene glycol dipropionate S, 1,3-butanediol diacrylate, 1,3-butanediol difluorenyl acrylate (l, 3- Butandioldimethaxrylat), 1,4-butanediol diitaconat , Sorbittriacrylat 15 (Sorbittriacrylat), Sorbit-tetraacrylat (Pentaerythrit-modifiziert-triacrylat), Sorbitol-tetraacrylat Sorbit-tetramethacrylat, Sorbitpentaacrylat, Sorbithexaacrylat, Oligoesteracrylate, and -methyl propylene Acid esters, glycerol di- and -tripropionates, 1,4-cyclohexane diacrylate, polyethylene glycol bis-acrylates and molecular weights of 200 to 1500 Bismeth-acrylate, or a mixture thereof. Suitable ingredients also include the same or different unsaturated carbonic acid amidines of aromatic, cycloaliphatic, and aliphatic polyamines having groups of preferably 2 to 6, more preferably 2 to 4 ammonia 30 200424022. Examples of these polyamines are ethylenediamine, 1,2- or 1,3-propanediamine, U2-, 1,3- or 1,4-butanediamine, 1,5-pentanediamine, 1 , 6-hexanediamine, octanediamine, dodecylendiamin, 1,4-diaminocyclohexane, Isohorondiamin, phenylenediamine, bisphenylenediamine ( Bis-phenylendiamin) ,: | L * 6® | (Di-p-axninoethylether), Diethylentriamin, Triethylentetramin, bis (β-aminoethoxy)-or ( β-aminopropoxy) ethane. Other suitable polyamines are polymers and copolymers having additional amino 10 groups in the side chain when necessary, and oligomeric amines having amino terminal groups. These unsaturated amines are: Methylen-bis-acrylamid, 1,6-Hexamethylen-bis-acrylamid, Diethylene Diethylentriamin-tris-methacrylamid, Bis (methacrylamidopropoxy) -ethan, β-methacrylamido Ethyl ethyl fluorenyl acrylate (β-Meth-acrylamidoethylmethacryla), N [(β-Ethoxy) ethyl])-acrylamine 0 Suitable unsaturated polyester head polyamines are derived from, for example, maleic acid and Derived from glycol or 20 diamine. Maleic acid may be partially substituted by other dicarbonic acids. These can be added together with ethylenically unsaturated comonomers. Polyglycerides and polyamines can also be derived from dicarbonic acid and ethylenically unsaturated diols or diamines, particularly long chains having, for example, 6 to 20 C-atoms. Examples of polyurethanes are synthesized from saturated or unsaturated diisocyanate S and unsaturated or saturated diols. 31 200424022 Polybutadiene and polyisoprene and copolymers derived therefrom are known. Suitable comonomers are, for example, olefins such as ethylene, propylene, butene, hexene, fluorenyl acrylate, acrylonitrile, styrene or vinyl chloride. Polymers having a fluorenyl acrylate group on the side chain are also known. It may be, for example, a reaction product of a Novolak-basis epoxy resin and a fluorenyl acrylic acid, a mono- or copolymer of a vinyl alcohol or a hydroxyalkyl derivative thereof esterified with a fluorenyl acrylate. , Or mono- or copolymers of methacrylate esterified with hydroxyalkyl fluorenyl acrylate. Particularly suitable are mono- or polyunsaturated olefin-based compounds using monoacrylate-, methacrylate- or ethylene 10 ether compounds. The best is a polyunsaturated acrylic acid ester compound as described above. In principle, it is best to apply such solutions, suspensions or emulsions as quickly as possible. However, for various purposes, step b) can also be carried out with a time delay. However, it is best to perform process step b) directly after process step a), or within 24 to 15 hours. The application of such solutions, suspensions or emulsions can be accomplished using different techniques or methods. The coating can be performed by electrophoretic separation, dipping, sputtering, smearing, brush coating, blade coating, roll coating, roll coating, printing and dyeing, spin coating, pouring and the like. The concentration of the initiator contained in the coating liquid is 0.01 to 20%, preferably 20 to 0.1 to 5%. The concentration of the ethylene-based unsaturated compound in the solution may be 0.1 to 30%, preferably 0.1 to 10%. The liquid may additionally contain other substances, such as defoamers, emulsifiers, surfactants (tensides), antifouling agents, wetting agents and other additives used in the paint or dye industry. 200424022 The thickness of the coated layer in the dry state must also meet the needs of subsequent applications 'and reach-a single molecular layer to 2 sides, preferably 2nm to μμιη' Particularly preferred is 2 nn ^ 1〇〇〇_ . It is basically best to quickly heat, dry, or illuminate bribes, solutions, liquids, or milk, because the formed layer will be fixed and stable through this step. For various purposes, step c) can also be performed at a later time. However, it is best to carry out process step c) directly or within 24 hours after the process step. There are many feasible ways of heating / drying during the formation of the coating, all of which can be applied as required. It is therefore possible to use, for example, thermal disturbance, IR-irradiation, rollers heated by a furnace, and microwave treatment. The degree of use is adjusted according to the temperature stability of the added raw materials, and usually varies between [to 300 ° C, preferably between 0 to 200 ° c. 15. § When there are raw materials that are particularly sensitive to temperature. It is extremely advantageous to irradiate with electromagnetic waves. In the meantime, it should be noted that the initiator used also absorbs light in this wavelength range, and the UV-absorber in this range has no or only minimal absorption. Irradiation of the formed layer can be performed with various light sources that emit electromagnetic waves having a wavelength that can be absorbed by the light used. Usually, the light source emits electromagnetic radiation with a wavelength in the range of 200 nms 200011111. In addition to white radiation and lamps, lasers and LEDs (light emitting diodes) can also be used. Exposure can be performed flat or locally. Partial exposure is advantageous when only adhesive features are needed. Irradiation may also be performed with an electron beam. The irradiation may be flat and / or local, for example by means of a photomask exposure or by means of laser irradiation. In this way, only the layer formed in the state of Lai Yan 33 200424022 can be fixed and stabilized. The formation layer can further wash away the unexposed areas to complete its structuring. Step C) can be carried out in air or inert gas. In addition to nitrogen, other inert gases such as CO2 or argon, helium, etc., or a mixture of 5 or the like can also be considered. Appropriate equipment and instruments are well known to those skilled in the art and are commercially available. Through hanging the invention, it is not necessary to coat another layer after the process is finished. However, in some individual cases, pre-adding another layer, such as a color matching layer, has its advantages. However, 'for example, a substrate formed with a photoinitiator cannot form a coating with a composition containing at least 10 ethylenically unsaturated monomers or oligomers, and harden the coating by UV / VIS irradiation. . In addition, each of the coating layers prepared according to the above-mentioned process is requested. Similarly, a product with a coating layer based on one of the above claims is also within the scope of the request. 15 The above method can be used to quickly, easily and flexibly make functional layers and adjust their properties. Therefore, it is necessary to adjust, for example, hydrophilicity or hydrophobicity or surface tension of the substrate on which the coating layer is formed. By using a water-soluble or hydrophobic initiator and a water-soluble or hydrophilic ethylenically unsaturated compound, a hydrophilic layer can be manufactured and the wet process can be controlled. Such a formation layer can be used as an example 20 such as an anti-fog layer or to improve cell adhesion and growth on the surface. By applying fluorinated unsaturated compounds or corresponding hydrophobic monomers, such as Silicon Acrylate, it is possible to make Antigraffitischichte and / or adjust sliding and friction characteristics. By using a reaction that is neutral, acidic, or qualitative (eg, allylamine, 2-aminoethylfluorenyl acrylate, 4-ethylene 34 200424022 yliridine, acrylic acid, 2-propylene-1-sulfonic acid) The group of ethylene-based unsaturated compounds can also adjust the acid / base-characteristics. The refractive index can be adjusted by using a suitable compound. Therefore, it is possible to obtain a high refractive index by adding, for example, benzyl propionate, and pass through the tridecylfluoroheptylfluorenyl propionate (1H, 1H, 7H-

Docecafluroheptyl-methacrylat)之添加則可以得到較低的折 * 射率。添加生物活性物質之作法可以被應用在形成層的製作上’使得生物無法生長或侵#。例如以馬來酸二丁錫鲁 10 (Di-butylzinnmaleat)可以製作防污層。另一方面亦可藉適當選擇化合物而製作需要有生物系之固著與生長的表面。其例可考慮N-醢氧基琥拍酸亞胺(N-Acyloxysuccinimid)、2-曱基丙稀氧乙基葡糖菩（2-methacryloxyethylglucosid)。此外，防火特性亦可藉使用鹵化化合物而獲得，例如 15 添加三溴新戊基曱基丙烯酸酉旨（Tribromoneopentylmeth -acrylat) 〇 . _ 【實施方式】較佳實施例之詳細說明以下實施例將使本發明更臻明瞭。實施例1 : 一染成白色之聚丙稀薄膜(300 μπι)藉助於一間隔約1-2 nun的陶竟電極(Handcoronastation Typ CEE 42-0-1 MD，寬度330 mm，廠商SOFTAL)，並以600 W的功率及10 cm/s的操作速度，在空氣上做四次電暈處理。在該薄膜之受處理 35 200424022 側塗布一含有〇·5%具下列結構式之起始劑 ΗΟThe addition of Docecafluroheptyl-methacrylat) can get a lower discount * emissivity. The method of adding a biologically active substance can be applied to the formation of the formation layer 'so that the organism cannot grow or invade. For example, Di-butylzinnmaleat 10 can be used as an antifouling layer. On the other hand, it is also possible to produce surfaces that require biological system fixation and growth by proper selection of compounds. Examples include N-Acyloxysuccinimid and 2-methacryloxyethylglucosid. In addition, fire-resistant properties can also be obtained by using halogenated compounds, such as 15 added Tribromoneopentylmethacrylic acid (Tribromoneopentylmeth-acrylat) 〇. _ [Embodiment] Detailed description of preferred embodiments The following examples will make The invention becomes clearer. Example 1 A white dyed polypropylene film (300 μm) was aided by a ceramic electrode (Handcoronastation Typ CEE 42-0-1 MD, width 330 mm, manufacturer SOFTAL) spaced about 1-2 nun apart, and Corona treatment on air with 600 W power and 10 cm / s operating speed. The treated side of the film 35 200424022 was coated with an initiator containing 0.5% of the following structural formula: ΗΟ

與0.5% 1乙一醇(400)一丙缚酸醋（sart〇mei)的乙醇溶液，以藉助於一4μπι刮刀（Erichsen)之方式展開。樣品經過 5短暫的置放’直到乙醇被蒸發完且樣品乾燥為止。然後以一具有微波激發之Hg-燈且功率為12〇 w/cm之UV-處理機( 熔融系統），在15 m/min的送帶速度下進行照射處理。表面張力係藉Testtinten測定且得到之數值為56 mN/m，此數值即使經過6週的置放亦無變化。未處理之薄膜所測得數值< 10 34 mN/m 〇實施例2 : 一透明的聚乙烯薄膜(LDPE 150 μηι)藉助於一間隔約 1-2 mm的陶兗電極(Handcoronastation Typ CEE 42-0-1 MD ，寬度330 mm，廠商SOFTAL)，並以400 W的功率及i〇 cm/s 15的操作速度，在空氣上做四次電暈處理。在該薄膜之受處理側塗布一含有1 %具下列結構式之起始劑An ethanol solution with 0.5% 1 ethylene glycol (400) -sartome was developed by means of a 4 μm spatula (Erichsen). The sample was left for 5 short periods' until the ethanol was evaporated and the sample dried. Then, the irradiation treatment was performed with a UV-processor (melting system) having a microwave-excited Hg-lamp and a power of 120 w / cm at a feed speed of 15 m / min. Surface tension is measured by Testtinten and the value obtained is 56 mN / m. This value remains unchanged even after 6 weeks of storage. Measured value of untreated film < 10 34 mN / m 〇 Example 2: A transparent polyethylene film (LDPE 150 μηι) with the aid of a ceramic electrode (Handcoronastation Typ CEE 42- 0-1 MD, width 330 mm, manufacturer SOFTAL), and corona treatment on air four times with 400 W power and operation speed of 10 cm / s 15. Apply a starter containing 1% of the following structural formula to the treated side of the film

的乙醇溶液，以藉助於一 4 μηι刮刀（Erichsen)的方式展開。樣品經過短暫的置放，直到乙醇被蒸發完且樣品乾燥 °為止。然後以一具有微波激發之Hg-燈且功率為120 W/cm 36 200424022 之UV-處理機(溶融系統）’在15 m/min的送帶速度下進行照射處理。表面張力係藉Testtinten測定且得到之數值為48 mN/m，此數值即使經過6週的置放亦無變化。未處理之薄膜所測得數值<34 mN/m。實施例3 : 如實施例1，惟曝光作業中以鋁片覆薄膜的一部分。接著將該薄膜在乙醇中以超音波處理1分鐘。在未曝光區域因薄膜具有較南的疏水性故水滴顯示一大棱角，而在曝光區域則稜角小且水滴流散。實施例4 : 一透明的聚丙烯薄膜(BOPP 50 μπι)藉助於一間隔約The ethanol solution was spread by means of a 4 μm spatula (Erichsen). The sample was placed briefly until the ethanol was evaporated and the sample dried. The irradiation treatment was then carried out with a UV-processor (melting system) 'with a microwave-excited Hg-lamp and a power of 120 W / cm 36 200424022' at a speed of 15 m / min. Surface tension is measured by Testtinten and the value obtained is 48 mN / m. This value does not change even after 6 weeks of placement. The measured value of the untreated film < 34 mN / m. Example 3: As in Example 1, except that a part of the film was covered with an aluminum sheet during the exposure operation. Then, the film was subjected to ultrasonic treatment in ethanol for 1 minute. In the unexposed area, the water droplets show a large edge because the film is relatively southerly hydrophobic, while in the exposed area, the edges are small and the water droplets are scattered. Example 4: A transparent polypropylene film (BOPP 50 μm)

1-2 mm的陶瓷電極(Handcoronastation Typ CEE 42-0-1 MD ，寬度330 mm，廠商SOFTAL)，並以600 W的功率及1〇 cm/s 的操作速度，在空氣上做四次電暈處理。在該薄膜之受處 15 理側塗布一含有1 %具下列結構式之起始劑1-2 mm ceramic electrode (Handcoronastation Typ CEE 42-0-1 MD, width 330 mm, manufacturer SOFTAL), and corona on air four times with 600 W power and 10 cm / s operating speed deal with. Apply a starting agent containing 1% of the following structural formula to the treated side of the film

與1% 2-羥乙基甲基丙烯酸酯（Fluka)的乙醇溶液，以藉助於一4 μπι刮刀（Erichsen)的方式展開。樣品經過短暫的置放，直到乙醇被蒸發完且樣品乾燥為止。然後以一具有微 20 波激發之Hg-燈且功率為120 W/cm之UV-處理機(熔融系統) ，在15 m/min的送帶速度下進行照射處理。所形成的膜清澈且非常薄。覆蓋層側朝下地將該膜放置於内有以水浸濕 37 之紙張的玻璃皿上。薄膜與紙相距約0.5 cm。然後在薄膜之未經處理的一側上滴一滴水，以便冷卻薄膜並使蒸發的水分凝結。未處理薄膜經過短時間後即在面對紙張側上形成水滴。經處理的薄膜則未觀察到水滴的形成（霧化）。實施例5 : 一透明的聚乙烯薄膜(LDPE 200 μιη)藉助於一間隔約 1-2 mm的陶竟電極(Handcoronastation Typ CEE 42-0-1 MD ’寬度330 mm，廠商SOFTAL)，並以250 W的功率及l〇 cm/s 的操作速度，在空氣上做四次電暈處理。在該薄膜之受處理側塗布一含有1 %具下列結構式之起始劑A 1% solution of 2-hydroxyethyl methacrylate (Fluka) in ethanol was developed by means of a 4 μm spatula (Erichsen). The sample was placed for a short time until the ethanol was evaporated and the sample dried. Then, a UV-treatment machine (melting system) with a Hg-lamp with a microwave excitation of 120 W / cm and a power of 120 W / cm was used for the irradiation treatment at a speed of 15 m / min. The resulting film is clear and very thin. The film was placed with the cover side down on a glass dish containing 37 sheets of paper moistened with water. The distance between film and paper is about 0.5 cm. A drop of water is then placed on the untreated side of the film to cool the film and condense the evaporated water. After a short time, the untreated film forms water droplets on the side facing the paper. No water droplet formation (atomization) was observed in the treated film. Example 5: A transparent polyethylene film (LDPE 200 μιη) with the aid of a ceramic electrode (Handcoronastation Typ CEE 42-0-1 MD 'width 330 mm, manufacturer SOFTAL) spaced about 1-2 mm apart, and 250 The power of W and the operating speed of 10 cm / s were corona treated in air four times. Apply a starter containing 1% of the following structural formula to the treated side of the film

與1% 2-羥乙基甲基丙烯酸酯（Fluka)的乙醇溶液，以藉助於一4 μιη刮刀（Erichsen)的方式展開。樣品經過短暫的置放’直到乙醇被蒸發完且樣品乾燥為止。然後以一具有微波激發之Hg-燈且功率為120 W/cm之UV-處理機（炫融系統），在15 m/min的送帶速度下進行照射處理。所形成的膜清澈且非常薄。覆蓋層側朝下地將該膜放置於内有以水浸濕之紙張的玻璃孤上。薄膜與紙相距約〇·5 cm。然後在薄膜之未經處理的一側上滴一滴水，以便冷卻薄膜並使蒸發的水分凝結。未處理薄膜經過短時間後即在面對紙張側上形成水滴。經處理的溥膜則未觀察到水滴的形成（霧化）。 200424022 I：圖式簡單說明】無【圖式之主要元件代表符號表】無A 1% solution of 2-hydroxyethyl methacrylate (Fluka) in ethanol was developed by means of a 4 μm spatula (Erichsen). The sample is placed briefly 'until the ethanol is evaporated and the sample is dry. Then, an Hg-lamp with microwave excitation and a UV-processor (power of 120 W / cm) with a power of 120 W / cm was used for the irradiation treatment at a speed of 15 m / min. The resulting film was clear and very thin. The film was placed with the cover side down on a glass lid with paper wet with water. The distance between film and paper was about 0.5 cm. A drop of water is then dropped on the untreated side of the film to cool the film and condense the evaporated water. After a short time, the untreated film forms water droplets on the side facing the paper. No water droplet formation (atomization) was observed in the treated diaphragm. 200424022 I: Schematic description] None [The main components of the diagram represent the symbol table] None

3939

Claims

200424022 拾、申請專利範圍： 1. 一種在一無機或有機基質上形成功能層的方法，特徵在於 a) 在該無機或有機基質上使一低溫電聚、一電暈放 5 電、一能量輻射及/或一火焰處理產生作用， b) 將1)至少一可活化起始劑或2)至少一可活化起始劑及至少一種乙烯系不飽和化合物之融溶物、溶液、懸浮液或乳劑塗布於該無機或有機基質上，其中該可活化起始劑及/或乙烯系不飽和化合物至少合併有一個功 10 能調整基團，藉以賦與受處理基質一所需之表面特性，及 c) 加熱及/或以電磁波在賦與所需之表面特性的條件下照射該經過被覆之基質。 2. 如申請專利範圍第1項之方法，特徵在於該功能調整基 15 團被形成如下： i) 一親水性或疏水性基團，用以調整親水性/疏水性； ii) 一酸性、中性或鹼性官能基團，用以調整酸/鹼-性質； iii) 顯現一高或低增量折射之一官能基團，用以調整 20 折射率。 iv) 對細胞及/或生物的生長具有影響之一官能基團，用以控制生物特性； v) 對易燃性具有影響之一官能基團，用以調整防火特性，及/或 40 200424022 vi)對於導電性具有影響之一官能基團，用以調整抗靜電特性。 3. 如申請專利範圍第1或第2項之方法，特徵在於使用一種極性基團做為親水性基團，例如醇-、醚-、酸-、 5 醛-、酮-、醣-、酚-、脲-、丙烯酸酯-、乙烯醚-、環氧化物-、醯胺-、縮醛-、縮酮-、酸酐-、季胺-、醯亞胺-、碳酸根-或硝基-基團，一酸之鹽類，或一（聚）乙二醇單兀。 4. 如前述申請專利範圍中之至少一項的方法，特徵在於使 10 用丙烯酸、丙烯醯胺、乙醯氧基苯乙烯、丙烯酸酐、丙烯琥珀醯亞胺、烯丙基縮水甘油醚、烯丙基曱氧基苯酚、聚乙二醇二丙烯酸酯（400)、二甘醇二丙烯酸酯、二氨基曱酸二曱基丙烯酸酯、二乙烯乙二醇酯、乙二醇二縮水甘油醚、縮水甘油丙稀酸S旨、乙二醇曱基丙稀酸醋、 15 4-羥丁基曱基丙烯酸酯、2-羥乙基丙烯酸酯、2-羥乙基甲基丙烯酸酯、N-(2-羥丙基）曱基丙醯胺、曱基丙烯酸羥乙基糖苷、硝化苯乙烯、磺基乙基曱基丙烯酸酯，3-磺基丙基丙烯酸、4-乙烯基苯曱酸、乙烯基二甲颯、乙酸苯乙烯酯之鈉鹽，或乙烯尿素做為親水性基團。 20 5.如前述申請專利範圍中之至少一項的方法，特徵在於使用一非極性基團做為疏水性基團，例如一分枝或未分枝烷基-、烯基-、炔基-，部分或完全il化之烷基或烯基或炔基，烴化胺基-、線狀或分枝狀矽烷基-或矽氧烷基-基團，或一部分或完全鹵化之芳族或非芳族環基團。 41 200424022 6. 如前述申請專利範圍中之至少一項的方法，特徵在於使用丙烯酸叔丁酯-、苯乙烯、丁基三曱氧基矽烷、丙烯酸環己酯、癸二醇-二曱基丙烯酸酯、二乙烯基苯、2-(2-乙氧基乙氧基）乙基丙烯酸酯、1H，1H-七氟-丁基丙烯酸 5 S旨、丙烯酸苄酯、1H，1H，7H-十二氟庚基甲基丙烯酸酯、萘基丙烯酸酯、五溴苯基丙烯酸酯、三氟乙基丙烯酸酯或乙烯基三苯基矽烷。 7. 如前述申請專利範圍中之至少一項的方法，特徵在於使用一碳酸-、項酸-、填酸-、硫酸-、苯紛-、氨基酸-，或 10 氨基-、咐咬-、嘴咬-、喊。定、17比洛-，或味σ坐-基團做為酸/鹼性質調整官能基團。 8. 如前述申請專利範圍中之至少一項的方法，特徵在於使用烯丙胺、2-氨乙基曱基丙烯酸酯、4-乙烯基吡啶、乙烯基吡咯烷酮、乙烯基咪唑、嗎啉代乙基丙烯酸酯、丙 15 烯酸、2-丙烯-1-磺酸、山梨酸、肉桂酸，或馬來酸做為酸/鹼性質調整官能基團。 9. 如前述申請專利範圍中之至少一項的方法，特徵在於使用苄基-、部分或全部鹵化之苄基-、部分或全部鹵化之烷基-、烯基-或炔基基團做為調整折射率的基團。 20 10.如前述申請專利範圍中之至少一項的方法，特徵在於使用丙烯酸苄酯、1Η，1Η，7Η-十二氟庚基曱基丙烯酸酯、 1Η，1Η-七氟-丁基丙烯酸酯或丙烯酸三氟乙酯做為調整折射率的基團。 11.如前述申請專利範圍中之至少一項的方法，特徵在於採 42 200424022 5 15 用一具有抗污性質之基團，如甲基丙稀酸銅（Π)、二丁基馬來酸錫、甲基丙烯酸錫(II)或二曱基丙烯酸鋅做為生物特性控制基團。 12·如前述申請專利範圍中之至少一項的方法，特徵在於採用生物系生長所需的基團，如琥珀酸亞胺-、糖苷-或糖基團做為生物特性控制基團。 13·如前述申請專利範圍中之至少一項的方法，特徵在於採用’ N-醯氧基琥珀醯亞胺或2_曱基丙烯醯氧基乙基糖苷做為生物系生長所需的基團。 •如前述申請專利範圍中之至少一項的方法，特徵在於採用一含完全或部分氯化溴化之烷基-或含氮-或含磷的基 1團做為防火性質調整基團。月1J述申％專利範圍中之至少一項的方法，特徵在於採来一溴新戊基甲基丙烯酸酯、雙(2_曱基丙烯基氧乙基) 、··曰或單内烯基氧乙基鱗酸酯做為防火性質調整基 #200424022 Scope of patent application: 1. A method for forming a functional layer on an inorganic or organic substrate, characterized in a) on the inorganic or organic substrate, a low-temperature electropolymerization, a corona discharge, an electric radiation, and an energy radiation And / or a flame treatment effect, b) a melt, solution, suspension or emulsion of 1) at least one activatable initiator or 2) at least one activatable initiator and at least one ethylenically unsaturated compound Coated on the inorganic or organic substrate, wherein the activatable initiator and / or the ethylenically unsaturated compound has at least one function 10 functional adjustment group to impart a desired surface characteristic to the treated substrate, and c ) The coated substrate is heated and / or irradiated with electromagnetic waves under conditions that impart the required surface characteristics. 2. The method according to item 1 of the scope of patent application, characterized in that the 15 groups of the function adjusting group are formed as follows: i) a hydrophilic or hydrophobic group for adjusting hydrophilicity / hydrophobicity; ii) an acidic, medium Basic or basic functional groups, used to adjust the acid / base-property; iii) A functional group that exhibits a high or low incremental refraction, used to adjust the 20 refractive index. iv) a functional group that has an effect on the growth of cells and / or organisms to control biological characteristics; v) a functional group that has an effect on flammability to adjust fire resistance characteristics, and / or 40 200424022 vi ) A functional group that has an effect on conductivity and is used to adjust antistatic properties. 3. The method according to item 1 or 2 of the patent application scope is characterized by using a polar group as a hydrophilic group, such as alcohol-, ether-, acid-, 5 aldehyde-, ketone-, sugar-, phenol -, Urea-, acrylate-, vinyl ether-, epoxide-, fluorenamine-, acetal-, ketal-, anhydride-, quaternary amine-, fluorenimine-, carbonate- or nitro-group Group, a salt of an acid, or a (poly) ethylene glycol unit. 4. The method according to at least one of the aforementioned patent applications, characterized in that acrylic acid, acrylamide, ethoxylated styrene, acrylic anhydride, acryl succinimide, allyl glycidyl ether, alkenyl Propyl alkoxyphenol, polyethylene glycol diacrylate (400), diethylene glycol diacrylate, diamino acetic acid difluorenyl acrylate, diethylene glycol ester, ethylene glycol diglycidyl ether, Glycidyl succinate, ethylene glycol methyl acrylate, 15 4-hydroxybutyl methyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- ( 2-Hydroxypropyl) fluorenylpropanamine, hydroxyethylglycoside of fluorenyl acrylate, nitrostyrene, sulfoethylfluorenyl acrylate, 3-sulfopropylacrylic acid, 4-vinylphenylarsinic acid, ethylene Sodium salt of dimethylformamidine, styrene acetate, or ethylene urea is used as the hydrophilic group. 20 5. The method according to at least one of the aforementioned patent applications, characterized in that a non-polar group is used as the hydrophobic group, such as a branched or unbranched alkyl-, alkenyl-, alkynyl- , Partially or fully illuminated alkyl or alkenyl or alkynyl, alkylated amino-, linear or branched silyl- or siloxy-groups, or partially or fully halogenated aromatic or non-halogenated Aromatic ring group. 41 200424022 6. The method according to at least one of the aforementioned patent applications, characterized by using tert-butyl acrylate-, styrene, butyltrimethoxysilane, cyclohexyl acrylate, decanediol-difluorenyl acrylic acid Ester, divinylbenzene, 2- (2-ethoxyethoxy) ethyl acrylate, 1H, 1H-heptafluoro-butyl acrylic acid 5 S, benzyl acrylate, 1H, 1H, 7H-twelve Fluorheptyl methacrylate, naphthyl acrylate, pentabromophenyl acrylate, trifluoroethyl acrylate or vinyltriphenylsilane. 7. The method according to at least one of the aforementioned patent applications, characterized in using monocarbonic acid-, naphthoic acid-, filling-acid-, sulfuric acid-, benzophenone-, amino acid-, or 10 amino-, biting-, mouth Bite-and shout. As the acid / basic property adjustment functional group, a 17-bilo-, or sigma-sat- group is used. 8. A method as claimed in at least one of the foregoing patent claims, characterized by using allylamine, 2-aminoethylfluorenyl acrylate, 4-vinylpyridine, vinylpyrrolidone, vinylimidazole, morpholinoethyl Acrylate, propionic acid, 2-propene-1-sulfonic acid, sorbic acid, cinnamic acid, or maleic acid are used as the acid / basic property adjustment functional group. 9. A method as claimed in at least one of the foregoing patent claims, characterized by using benzyl-, partially or fully halogenated benzyl-, partially or fully halogenated alkyl-, alkenyl- or alkynyl groups A group that adjusts the refractive index. 20 10. The method according to at least one of the foregoing patent claims, characterized by using benzyl acrylate, 1Η, 1Η, 7Η-dodecylfluoroheptylfluorenyl acrylate, 1Η, 1Η-heptafluoro-butyl acrylate Or trifluoroethyl acrylate is used as a group for adjusting the refractive index. 11. The method according to at least one of the aforementioned patent applications, characterized in that 42 200424022 5 15 is used with a group having antifouling properties, such as copper (II) methyl acrylate, dibutyl tin maleate , Tin (II) methacrylate or zinc diacrylic acid acrylate as the biological property control group. 12. A method according to at least one of the aforementioned patent applications, characterized in that a group required for the growth of a biological system, such as an imine succinate-, a glycoside- or a sugar group, is used as a biological property control group. 13. The method according to at least one of the aforementioned patent applications, characterized in that the use of 'N-methoxyoxysuccinimide or 2-fluorenylpropenyloxyethyl glycoside as a group required for the growth of the biological system . The method according to at least one of the aforementioned patent applications, characterized in that an alkyl- or nitrogen- or phosphorus-containing group 1 containing completely or partially chlorinated bromide is used as the fireproofing property adjusting group. The method described in at least one of the patent scopes of January 1J is characterized by using monobromo neopentyl methacrylate, bis (2-fluorenylpropenyloxyethyl), ... or mono-alkenyl Oxyethylphosphonic acid ester is used as the base for adjusting fire resistance #

20 ^迚申明專利範圍中之至少一項的方法，特徵在於採用三元胺基·、^ _ ^ 搜乙基化胺基…燒醇醯胺-、甘油硬脂酸 17 · 4山^糖醇軒-或續酸-基團做為抗靜電性調整基團。用2 乂申明專利範圍中之至少一項的方法，特徵在於採 …丙胺基乙基曱基丙烯酸酯、3-二甲胺基新戊基稀夂S日或'由稀基雙(玲乙基)胺、硬脂醯丙稀酸g旨及/ 三、更月曰I乙烯g旨做為抗靜電性調整基團。 •如前述中請專利範圍中之至少—項的方法，特徵在於該 43 有機或無機基質為合成或天铁 ί自、^ “、、t合物、金屬氧化物、玻璃、+導體、石英或金屬1 19. 如前述申請專利範圍中之至+ ，、專之材料右嬙I所& 4人夕一項的方法，特徵在於該有機基貝為，或含有均聚、、^ r ^ ^ 欺段_、接枝-及/或共聚物及/或其等之一混合物。 20. 如前述申請專利範圍中之至小 ^ ^ ^ —項的方法，特徵在於該有機基貝為，或含有聚碳釀 p 曰、聚酯、鹵化聚合物、聚丙烯酸酯、聚烯烴、聚醯胺、疏…⑺1 1氨酯、聚苯乙烯、聚芳 10 醯fe(P〇lyaramid)、聚醚或聚矽氧烷/矽。 21·如前述申請專利範圍中之至小 ^ 一項的方法，特徵在於該起始難由氧化物、過二錢鹽、過硫酸鹽、苯頻那醇、二、二硫化物、偶氮化合物、氧化還原系、苯偶因午縮_ ¥乙酮、經基烧基苯酉同、胺基烧基苯酮、醯 15 基填化氧、祕化硫、醯氧基亞氨酮、_化苯乙酮、笨曱馱酉曰、二笨甲酮、肟和肟酯、硫雜蔥酮二茂鐵、一茂鈦、鎏鹽、碘鏘鹽、重氮鍇鹽、鏘鹽、硼酸酯、三嗪、雙咪唑、聚矽烷和染料，以及對應之聯合起始劑及/ 或感光劑的族群中選出之一種化合物或化合物之組合。 20 22.如則述申4專利範圍中之至少一項的方法，特徵在於該起始劑至少具有一乙烯系不飽和基團，特別是乙烯基一、亞乙烯基、、丙烯酸酯_、甲基丙烯酸酯_、烯丙基-和乙烯醚•基團。 23·如刖述申清專利範圍中之至少-項的方法，特徵在於該乙烯系不飽和化合物可以一單體、低聚物及/或聚合物 44 200424022 之形式添加。 24.如前述申請專利範圍中之至少一項的方法，特徵在於該乙烯系止飽和化合物為一單-、二-、三-、四-或多-官能基之丙烯酸酯、曱基丙烯酸酯或乙烯醚。 5 25.如前述申請專利範圍中之至少一項的方法，特徵在於其係用空氣、水、惰性氣體、反應性氣體或上述氣體之混合物做為電漿氣體。 26. 如前述申請專利範圍中之至少一項的方法，特徵在於步驟b)所添加之液體含有濃度0.01至20%，較佳為0.1至5% 10 的起始劑。 27. 如前述申請專利範圍中之至少一項的方法，特徵在於步驟b)所添加之液體含有濃度0.1至30%，較佳為0.1至10% 的不飽和化合物。 28. 如前述申請專利範圍中之至少一項的方法，特徵在於特 15 徵在於步驟b)所添加之液體另含有其它物質，如消泡劑、乳化劑、界面活性劑、防污劑、濕潤劑及其它漆-或染料工業中所使用的添加物。 29. 如前述申請專利範圍中之至少一項的方法，特徵在於該塗布層在乾燥狀態下的厚度係自一個單分子層至2 mm 20 ，較佳為2 nm至1000 μπι，更佳者為2 nm至1000 nm。 30. 如前述申請專利範圍中之至少一項的方法，特徵在於步驟c)中之一照射係以放射具有介於200 nm至20000 nm 範圍的波長之電磁波做光源，或藉電子照射來完成，必要時可以預先以乾燥步驟加以處理。 45 200424022 31 ·如前述申請專利範圍中之至少一項的方法，特徵在於步驟c)中之照射係採平面或局部地進行。 32. 如前述申請專利範圍中之至少一項的方法，特徵在於步驟c)中之照射係採局部地進行且接著將未曝光材料移 5 除。 33. —種具有功能層之基質，係依據上述申請專利範圍中之 ^ 任一項的方法所製得。 34. —種產品，其配置有依據上述申請專利範圍中之任一項的形成層。 · 10 35. —種功能層之應用，係做為防霧-、抗塗鴨-、防黏著-、防污-或防火層，或用以調節表面張力、濕潤性、折射率、抗靜電性、平滑性、酸性或鹼性，或用以改善生物系之固著與生長性。 46 200424022 柒、指定代表圖： (一）本案指定代表圖為：第（）圖。 (二) 本代表圖之元件代表符號簡單說明：無捌、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 200424022 發明專利說明書匕 (本說明書格式、順序及粗體字，請勿任意更動，※記號部分請勿填寫） ※申請案號： ※申請日期：Θ ※IPC分類：壹、發明名稱：（中文/英文）形成功能層的方法貳、申請人：（共1人）姓名或名稱：（中文/英文）席巴特製品化學股份有限公司 CIBA SPECIALTY CHEMICALS HOLDING INC. 代表人：（中文/英文） 1. 威特林漢斯-彼得/ WITTLIN，HANS-PETER 2. 克里溫瓦特/ KLEEWEIN，WALTER 住居所或營業所地址：（中文/英文）瑞士貝斯爾·克里貝克街141號 Klybeckstrasse 141， 4057 Basel, Switzerland 國籍：（中文/英文）瑞士/ Switzerland 參、發明人：（共3人）姓名：（中文/英文） 1. 庫茲馬汀/KUNZ，MARTIN 2. 包爾麥克/BAUER，MICHAEL 3. 巴蘭耶安德列/BARANYAI，ANDREAS 住居所地址：（中文/英文） 1. 德國艾佛琳根一基辛•巴斯勒街13/5號 Baslerstrasse 13/5, 79588 Efringen-Kirchen, Germany 2. 德國梅茲奥森•雷哈德-波茲街28號 Reinhard-Booz-Strasse 28, 79249 Merzhausen, Germany 3. 德國海特赛姆•艾恩茲格里12號 In der Ziegelei 12, 79423 Heitersheim, Germany 國籍：（中文/英文） 1.-3.德國/Germany20 ^ 迚 Declaration of at least one method in the patent scope, characterized by the use of a trivalent amino group, ^ _ ^ search for ethylated amine groups ... alcohol alcohol amine-, glyceryl stearate 17. 4 ^ sugar alcohol Hexane- or dicarboxylic acid-groups are used as antistatic adjusting groups. The method of claiming at least one of the patent claims is characterized by the use of ... propylaminoethylfluorenyl acrylate, 3-dimethylamino neopentyl disulfide or ) Amine, stearic acid, acrylic acid and / or three or more months, ethylene vinyl is intended as an antistatic adjustment group. • A method as claimed in at least one of the above patents, characterized in that the 43 organic or inorganic matrix is a synthetic or iron-based compound, metal oxide, glass, + conductor, quartz or Metal 1 19. As described in the scope of the aforementioned patent application, the method of the material is right and I & 4 people, characterized in that the organic base is or contains a homopolymer, ^ r ^ ^ Smell, graft-and / or copolymer and / or a mixture thereof. 20. The method as described in the scope of the aforementioned patent application to the smallest ^ ^ ^ —, characterized in that the organic base is or contains Polycarbonates, polyesters, halogenated polymers, polyacrylates, polyolefins, polyamides, sulphur ... 1 1 urethanes, polystyrenes, polyaromatics 10 (feature), polyethers or polyethers Siloxane / silicon. 21. The method as described in one of the aforementioned patent applications, characterized in that the starting is difficult to be composed of an oxide, a peroxo salt, a persulfate, a benzyl alcohol, a dioxin, a dioxin Sulfide, azo compound, redox system, benzoin due to afternoon shrinkage Phenylphenone, Aminobenzophenone, Phenyl-15 Group Filler Oxygen, Sedimentary Sulfur, Phenoxyiminones, Acetophenone, Benzophenone, Dibenzone, Oxime and Oxime Esters, thiaallionone ferrocene, titanocene, sulfonium salt, iodonium salt, diazonium salt, sulfonium salt, borate, triazine, bisimidazole, polysilane, and dyes, and corresponding joint initiators And / or a compound or combination of compounds selected from the group of sensitizers. 20 22. The method of at least one of the patent scope of claim 4 is characterized in that the initiator has at least one ethylenically unsaturated group. In particular, vinyl-, vinylidene-, acrylate-, methacrylate-, allyl-, and vinyl ether • groups. 23. As described in the method of claiming at least one of the scope of patents, It is characterized in that the ethylenically unsaturated compound may be added in the form of a monomer, oligomer and / or polymer 44 200424022. 24. The method according to at least one of the scope of the aforementioned patent application, characterized in that the ethylenically unsaturated compound Mono-, di-, tri-, tetra- or poly-functional propylene Esters, fluorenyl acrylates or vinyl ethers. 5 25. The method according to at least one of the scope of the aforementioned patent applications, characterized in that it uses air, water, an inert gas, a reactive gas or a mixture of these gases as the plasma Gas. 26. The method according to at least one of the aforementioned patent applications, characterized in that the liquid added in step b) contains a starter at a concentration of 0.01 to 20%, preferably 0.1 to 5% 10. 27. As previously described The method according to at least one of the patent claims is characterized in that the liquid added in step b) contains unsaturated compounds at a concentration of 0.1 to 30%, preferably 0.1 to 10%. 28. The method according to at least one of the aforementioned patent applications, characterized in that the liquid added in step b) additionally contains other substances, such as defoamers, emulsifiers, surfactants, antifouling agents, wetting Additives and other additives used in the paint or dye industry. 29. The method according to at least one of the aforementioned patent applications, characterized in that the thickness of the coating layer in a dry state is from a monomolecular layer to 2 mm 20, preferably 2 nm to 1000 μπ, and more preferably 2 nm to 1000 nm. 30. The method according to at least one of the aforementioned patent applications, characterized in that one of the irradiations in step c) is performed by emitting an electromagnetic wave having a wavelength in a range of 200 nm to 20000 nm as a light source, or by electron irradiation, If necessary, it can be processed in advance in a drying step. 45 200424022 31-The method according to at least one of the scope of the aforementioned patent application, characterized in that the irradiation in step c) is carried out flat or locally. 32. A method as claimed in at least one of the foregoing patent applications, characterized in that the irradiation in step c) is performed locally and then the unexposed material is removed. 33. A substrate with a functional layer, which is prepared according to any one of the methods in the scope of the aforementioned patent application. 34. A product configured with a formation layer according to any one of the above patent application scopes. · 10 35. —The application of a functional layer is used as an anti-fog-, anti-duck-resistant, anti-adhesive-, anti-fouling- or fire-resistant layer, or to adjust surface tension, wettability, refractive index, and antistatic properties , Smoothness, acidity or alkalinity, or to improve the fixation and growth of biological systems. 46 200424022 (1) Designated representative map: (1) The designated representative map in this case is: (). (II) Brief description of the component representative symbols in this representative diagram: No, if there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: 200424022 Specification for invention patents Please make changes at will, ※ Please do not fill in the marked part) ※ Application number: ※ Application date: Θ ※ IPC classification: 1. Name of the invention: (Chinese / English) Method of forming the functional layer 贰 Applicant: (1 person in total) Name Or Name: (Chinese / English) CIBA SPECIALTY CHEMICALS HOLDING INC. Representative: (Chinese / English) 1. Wittling Hans-Peter / WITTLIN, HANS-PETER 2. Kreven Watt / KLEEWEIN, WALTER Address of residence or business office: (Chinese / English) Klybeckstrasse 141, 4057 Basel, Switzerland Nationality: (Chinese / English) Switzerland / Swiss Participants, Inventors: (total 3 persons) Name: (Chinese / English) 1. Kuzmatin / KUNZ, MARTIN 2. Bauer / Bauer, Michael 3. Bar Yeandeli / BARANYAI, ANDREAS Address: (Chinese / English) 1. Baslerstrasse 13/5, 79588 Efringen-Kirchen, Germany 2. Germany Reinhard-Booz-Strasse 28, 79249 Merzhausen, Germany 3. Inder der Ziegelei 12, 79423 Heitersheim, Germany Nationality : (Chinese / English) 1.-3. Germany / Germany