TWI291596B

TWI291596B - Photosensitive thermosetting composition

Info

Publication number: TWI291596B
Application number: TW90102995A
Authority: TW
Inventors: Chau-Huei Tzeng; Fu-Lung Chen
Original assignee: Advance Materials Corp
Priority date: 2001-02-12
Filing date: 2001-02-12
Publication date: 2007-12-21

Abstract

The present invention provides a photosensitive thermosetting composition comprising (A) a resin composition; (B) a photopolymerizable photosensitive monomer or photosensitive oligomer; (C) a photoinitiator; (D) an epoxy compound containing at least two epoxide groups; and (E) an organic solvent, in which the resin composition (A) is formed of (in proportion): (a) an epoxy compound containing at least two epoxide groups; (b) a mono-unsaturated acid at least containing two double bonds; (c) a saturated or unsaturated diacid; and (d) a saturated or unsaturated acid anhydride. The photosensitive thermosetting composition is coated on the substrate and cured into the green paint after baking, drying, exposing, developing, and ultraviolet irradiation or heating.

Description

1291596 九、發明說明：【發明所屬之技術領域】本發明係提供一種感光熱固型組成物，係由樹脂，光可聚合之感光單體及或感光寡聚物、光起始劑、環氧化合物形成，與有機溶劑所組成，於基材上固化後形成防焊綠漆。【先前技術】印刷電路板（printed circuit board，PCB)大量應用在各式電子產品中，於印刷電路板完成線路後，需將防焊綠漆（solder mask)(油墨，ink)，又名抗焊綠漆（green paint )或防（抗）焊阻劑（s〇ider resist )，塗佈於然需焊錫之處，可防止電子元件封裝於電路板上時焊錫之附著，並密封防潮及作為電子元件與導線之間的絕緣層，以防止灰塵、手指印與潮濕空氣等對線路的傷害。一般常用的防焊綠漆依種類列可分為： (1 )紫外光硬化型（ultraviolet curable):採網版印刷（screen printing)，主要用於單面板。 (2 )熱硬化型（thermosetting):採網版印刷，主要用於雙面板（double-sided board); (3 )液態感光成像型（liquid photoimageable solder mask ’ LPISM) ·•採網版印刷，是目前最流行的防焊方式；及 1291596 (4 )乾膜感光成像型（dry film photoimageable solder mask )。依照防焊綠漆之塗佈方式則可分為：網版印刷、簾塗法（curtain coating)、喷塗法（spray coating)、滾塗法（roller coating)、浸塗法（dip coating)及乾膜壓合（lamination)等六種，其中網版印刷及簾塗法較普遍。因南岔度印刷電路板（high density interconnect ，HDI)及咼階封裝技術的發展，對液態感光綠漆的要求亦隨之提高’如：預烤（prebake)後需不黏手；冷卻/曝光後膜面不留下底片之壓痕；後烤（後膜面夠硬之耐加工性；良好之密著性；夠高的絕緣電阻；允許軟烤溫度之變異；軟烤置放二、三天後仍能顯影出圖案之顯影寬容性；愈小愈好的側蝕（undercut);高解析及容易重工（rework)之去墨性；至少26〇。〇的耐熱性；較高的玻璃軟化，皿度（glass transition temperature，Tg) ; 2〜3 mil ( 1/1000 inch)解析度的防焊堤寬（s〇lder dam);耐酸驗溶劑之财化性等。、，彔漆硬烤後之製程以噴锡（h〇tairS〇ider leveling， HASL)為主’其夂為化鎳浸金nickel and immersion gold，EN/IG)，而有機預焊處理（organic 1291596 solderatnlity preservatlves，0SP)及金手指（g〇lden finger)則較少。歐盟立法推動環境保護，故於1999年3月完成WEEE (Waste Electrical and Electrical Equipment) 第二版之草案，•提出電子產品於2004年一月起不得使用錯金屬，故綠漆材料必須提南其耐化性及对熱性，以因應新衣私，例如以化學锡取代嘴錫的無錯化製程中，必須使用 pH值小於1的強酸葯水，所以，綠漆如果沒有良好的耐酸性及密著性，極易發生滲鍍（attack)或防焊層浮離 (peeling)等問題而影響良率，目前習知之綠漆均未能符合不含鉛之化學錫製程所要求的耐酸性及密著性。一般而言，液態感光成像型綠漆包含”主體試劑”，簡稱主劑（main part)與能夠和主劑產生熱交聯之”硬化試劑”，簡稱硬化劑（curingagent)，這兩種成份無論是一起直接使用的一液型，或分開為二使用前再加以混合的二液型’其組成不外乎： (1) 帶有酸基及光可聚合之含雙鍵樹脂組成物（A); (2) 光可聚合、含雙鍵之單體或寡聚物，或稱感光單體 (photomonomer)、感光寡聚物（photooligomer) ( B ); (3 )光起始劑（photoinitiator)，或稱感光劑 (photoactive compound) ( C );與 (4)硬化劑。 !291596 如美國專利案第4, 722, 947號、第4, 745, 138號、第 5, 087, 552號、第5, 114, 830號、第5, 296, 334號與第 6, 007, 966號，可使用經修飾之苯乙烯/馬林酸酐樹脂 (styrene-maleic anhydride，SMA)做為樹脂組成物，此類樹脂製造過程中之酯化反應會產生副產物水，殘存於樹脂組成物甲’該水份不僅不利於綠漆之物性，還會使酸酐進一步開環而產生酸價（acid value，mgKOH/g)偏高（> 200mgKOH/g)且不易控制等問題，如要將酸價控制在可用之範圍’則必須有高比例未反應的酸酐殘存於樹脂中，如此更不利於綠漆之物性，故美國專利案第4, 722, 947號及第 5, 087, 552號提到，在合成SMA樹脂時需收集產生的水或加入除水劑’以減少水份殘存於樹脂中，雖是如此，但樹脂仍難以在防焊製程中兼顧製程寬容度與耐化金、耐化學錫與耐噴錫等特性。另外，如美國專利案第4, 943, 516號、第5, 009, 982號、第5, 100, 767號、第5, 538, 821號及第5, 753, 722號，以酸修飾之環氧樹脂做為樹脂組成物，其係以丙烯酸（或其衍生物）將環氧盼搭樹脂之環氧基開環後導入雙鍵，最後再與酸酐反應使高分子繼帶有魏基，或如美國專利案第 5, 821，G31號，酸（或其衍生物）先將含有環氧基之丙烯酸醋共聚合物開環以導入雙鍵，最後與酸酐反紐高 1291596 分子之側鍵帶有羧酸基。此種感光組成物因環氧化合物之開環反應慢且不易反應完全，故需使用過量且含有毒性的不飽和單酸（如丙烯酸或其衍生物），加速反應進行並使反應元全，但恶法避免未反應的不飽和單酸殘存於組成物，不僅危害人體健康，更會使喷錫與化鎳浸金等製程良率變差，甚至在化學錫製程中產生滲鍍及浮離等問題。再者，如美國專利案第5, 821，031號研究發現，若硬化劑含有不溶於（sparingly solubility)配方稀釋劑，即所謂「非溶劑溶解型」之環氧化合物，其顆粒粉末需經研磨工具攪碎，雖在防焊製程中，有利於預烤與顯影的寬容度，但粒徑減少有限，增加製造成本，且對耐熱性、耐化性均無明顯效用。【發明内容】爰是，本發明之主要目的，在於解決上述之缺失，避免上述缺失之存在，本發明係提供一種感光熱固型組成物’硬化後其性質能符合不含鉛之化學錫製程要求。本發明之又一目的，係提供一種感光熱固型組成物，將有危吾人體健康之虞的不飽和單酸（如丙稀酸及其衍生物）使用量降至最低。本發明之又一目的，係提供一種感光熱固型組成物，所使用之環氧化合物可先溶解於綠漆之配方溶劑中備用，省去機械研磨帶來的粉塵，而將之放在硬化劑組成份中亦可省去研磨之電量消耗，降低防污成本及製造成本。 1291596 本發明之又一目的，係提供一種感光熱固型組成物，邊樹脂之主體，由於殘存酸量較低，故較不具嗆鼻之酸氣，對人體皮膚較不具腐蝕性。為達上述之目的，本發明係以一由至少含二個環氧基之環氧化合物（a)，至少含二個雙鍵之不飽和單酸 (b )，飽和或不飽和雙酸（c)，與飽和或不飽和酸酐（d)，依比例組成之樹脂組成物（A)，一光可聚合之感光單體及或感光寡聚物（B)，一光起始劑（c)，含至> 一個環氧基之環氧化合物（D)，與一有機溶劑所組成（E)，經硬化後形成之防焊綠漆。有關本發明之詳細說明及技術内容，茲配合圖式說明如下：【實施方式】如『第1圖』所示，係為本發明之實施流程圖，本發明中樹脂組成物之製備1，係由下列組成物：至少含二個環氧基之環氧化合物（a)，至少含二個雙鍵之不飽和單酸（b)，飽和或不飽和雙酸（c)與飽和或不飽和酸酐 (d)，至少含二個環氧基之環氧化合物（a)，至少含二個雙鍵之不飽和單酸（b)及飽和或不飽和雙酸（c) 之莫耳（mole)比例為1 : 〇· 〇9〜〇· 95 : 〇· 〇25〜〇· 〇5，在適當反應條件下可反應生成酸價介於4〇〜49mgK〇H/g之樹 10 1291596 脂組成物（A)。至少含一個環氧基之環氧化合物（a)在常溫下可為固體、半固體及液體，或固體、半固體及液體混合使用之 έ盼類及其衍生物之環氧樹脂或丙烯酸酯類及其衍生物，以曱紛環氧樹脂或酚環氧樹脂等含酚類之環氧樹脂較為適用’其中曱紛環氧樹脂，如：LG Chem公司之Ν665、Ν670、腿73、N673-80M、N680、N690、N690-80M、N695 等；Nanya 公司之NPCN7(U、NPCN702、NPCN703、NPCN704 ; CibaGeigy 之ECN1273、ECN1280、ECN1285、ECN1299、ECN9511 ;長春公司之CNE-200、CNE-202、CNE-220。酚環氧樹脂如：LG Chem 公司之N730、N740、N740-80M、N770、N865、N870 ; Nanya 公司之NPPN638、NPPN683A80、NPPN638K80 ;長春公司之 PNE-173、PNE-177、PNE-177H、PNE-177B90等，只要能溶解於合成時樹脂所用的溶劑，使合成反應在均勻相中進行’均為本發明專利所選用。至少含二個雙鍵之不飽和單酸（b)可為丙烯酸或甲基丙烯酸，其中丙稀酸較適用；飽和或不飽和雙酸（c ) 係具有HOOC — R — COOH之結構，其_尺基團可為具有一至十二個碳原子之脂肪族或芳香族，若R基團屬於脂肪族，則飽和或不飽和雙酸（c)可為選自下列化合物之至少其中一種：反一丁烯二酸（fumaric acid)、順一 1291596 丁烤二酸（maleicacid)、酸草醯乙酸（oxaiaceticacid)、 .己一S文（adipic acid)及其衍生物、戊二酸（giutaric acid) 及其衍生物、號珀酸（succinic acid)、丙二酸（mai〇nic acid)及其衍生物、庚二酸（pimelic acid)、1，8 一辛一k (suberic acid)、壬二酸（azelaic acid)、癸二酸（sebacic acid);若R基團屬於芳香族，則飽和或不飽和雙酸（c)可為選自下列化合物之至少其中一種：對苯二甲酸（terephthalicacid)及其衍生物、間苯二甲酉夂（isophthalic acid)及其衍生物等，以上之飽和或不飽和雙I (c)均可早獨或混合使用。飽和或不飽和酸肝 (d)可為選自下列化合物之至少其中一種：飽和之無水六駄酸酐（hexahydro-phthalic acid anhydride)及其衍生物、不飽和之無水四氫醜酸酐（tetrahydrophtal ic acid anhydride)及其衍生物或無水酞酸酐（phthalic acid anhydride)及其衍生物。本發明中感光熱固型組成物之製備2，感光熱固型組成物係由下列組成物··一含量介於30〜50 wt%之樹脂組成物（A)，一含量介於5〜20wt%之光可聚合之感光單體及或感光寡聚物（B )，一含量介於2. 0〜6· Owt%之光起始劑（C ) ’ 一含量介於1〇〜2〇wt%之含至少二個環氧基之環氧化合物（D)，與一含量介於25〜40wt%之有機溶劑 1291596 (E) ’以上（A)〜（E)之總和為lOOwt%。本發明感光組成物中之光可聚合之感光單體及或感光寡聚物（B )，選自Sartomer等商品，較常用之感光單體可為雙官能基脂肪族或含笨環之不飽和雙鍵感光單體，如·· SR205、SR306、CD4(H、SR508、SR603、SR9036，可為1291596 IX. Description of the Invention: [Technical Field] The present invention provides a photosensitive thermosetting composition comprising a resin, a photopolymerizable photosensitive monomer and or a photo-oligomer, a photoinitiator, an epoxy The compound is formed, and is composed of an organic solvent, and is cured on the substrate to form a solder resist green paint. [Prior Art] A printed circuit board (PCB) is widely used in various electronic products. After the printed circuit board is completed, a solder mask (ink, ink) is also known. Green paint or anti-resist resist is applied to the place where solder is needed to prevent the solder from sticking when the electronic component is packaged on the circuit board, and to seal against moisture and An insulating layer between the electronic components and the wires to prevent damage to the circuit caused by dust, fingerprints and humid air. Commonly used anti-weld green paint can be divided into categories according to the category: (1) Ultraviolet curable: screen printing, mainly used for single panel. (2) thermosetting: screen printing, mainly used for double-sided board; (3) liquid photoimageable solder mask (LPISM) · • screen printing, Currently the most popular solder mask method; and 1291596 (4) dry film photoimageable solder mask. According to the coating method of the solder resist green paint, it can be divided into: screen printing, curtain coating, spray coating, roller coating, dip coating and Six kinds of dry film lamination, etc., in which screen printing and curtain coating are more common. Due to the development of high-density interconnect (HDI) and packaging technology, the requirements for liquid-sensitive green paint have also increased. For example: pre-baked (prebake), no need to stick; cooling/exposure The film surface does not leave the indentation of the film; after baking (the film surface is hard enough to resist the processing; good adhesion; high insulation resistance; allow the soft baking temperature variation; soft baking placed two or three The developmental tolerance of the pattern can still be developed after the day; the smaller the better the undercut; the higher resolution and the rework of the deinking; at least 26 〇. The heat resistance of the ;; the higher glass softening , glass transition temperature (Tg); 2 to 3 mil (1/1000 inch) resolution of the welding dyke width (s〇lder dam); acid-proof solvent for the chemical properties, etc. The latter process is mainly sprayed with tin (h〇tairS〇ider leveling, HASL), which is the nickel and immersion gold (EN/IG), and organic pre-weld treatment (organic 1291596 solderatnlity preservatlves, 0SP) and There are fewer gold fingers (g〇lden fingers). EU legislation promotes environmental protection, so the draft of the second edition of WEEE (Waste Electrical and Electrical Equipment) was completed in March 1999. • It is proposed that electronic products should not be used in January 2004. Therefore, green paint materials must be Chemical resistance and heat resistance, in order to respond to new clothes, such as chemical tin to replace the mouth tin in the process of error-free, must use a pH of less than 1 strong acid syrup, so if the green lacquer does not have good acid resistance and adhesion Sexually, it is prone to problems such as attack or peeling of the solder resist layer, which affects the yield. Currently, the green paints fail to meet the acid resistance and adhesion required for the lead-free chemical tin process. Sex. In general, a liquid photosensitive image type green paint contains a "main body agent", which is simply referred to as a "main part" and a "hardening agent" capable of thermally crosslinking with a main agent, referred to as a curing agent, both of which are It is a one-liquid type that is used directly together, or a two-component type that is separately mixed before use. The composition is nothing more than: (1) a double-bonded resin composition having an acid group and a photopolymerizable group (A) (2) photopolymerizable, double bond-containing monomers or oligomers, or photomonomers, photooligomers (B); (3) photoinitiators, Or photoactive compound (C); and (4) hardener. !291596, as in U.S. Patent Nos. 4, 722, 947, 4, 745, 138, 5, 087, 552, 5, 114, 830, 5, 296, 334 and 6, 007 No. 966, a modified styrene-maleic anhydride (SMA) can be used as a resin composition. The esterification reaction in the manufacture of such a resin produces by-product water and remains in the resin composition. The water's moisture is not only detrimental to the physical properties of the green paint, but also causes the acid anhydride to further open the ring to produce an acid value (mgKOH/g) which is too high (> 200 mgKOH/g) and is difficult to control. The acid price is controlled within the usable range', and a high proportion of unreacted acid anhydride must remain in the resin, which is more detrimental to the physical properties of the green paint. Therefore, U.S. Patent Nos. 4,722,947 and 5,087,552 No. It is mentioned that in the synthesis of SMA resin, it is necessary to collect the produced water or add a water-removing agent to reduce the residual moisture in the resin. However, it is still difficult for the resin to balance the process tolerance and chemical resistance in the soldering process. It is resistant to chemical tin and spray-resistant tin. In addition, as in U.S. Patent Nos. 4,943,516, 5, 009, 982, 5, 100, 767, 5, 538, 821 and 5, 753, 722, acid-modified The epoxy resin is used as a resin composition, which is obtained by deactivating the epoxy group of the epoxy resin with acrylic acid (or a derivative thereof) and then introducing the double bond, and finally reacting with the acid anhydride to cause the polymer to carry the Wei group. Or, as in U.S. Patent No. 5,821, G31, the acid (or a derivative thereof) first opens an epoxy group-containing acrylic vinegar copolymer to introduce a double bond, and finally, with an acid anhydride, a high side of 1,291,596 molecules. With a carboxylic acid group. Since the photosensitive composition is slow in ring-opening reaction of the epoxy compound and is not easily reacted completely, it is necessary to use an excessive amount of unsaturated monoacid (such as acrylic acid or a derivative thereof) to accelerate the reaction and make the reaction element complete, but The evil method avoids the unreacted unsaturated monoacid remaining in the composition, which not only endangers human health, but also deteriorates the process yield of spray tin and nickel immersion gold, and even causes plating and floating in the chemical tin process. problem. Furthermore, as disclosed in U.S. Patent No. 5,821,031, it is found that if the hardener contains a sparingly soluble formulation diluent, a so-called "non-solvent-dissolved" epoxy compound, the granule powder needs to be ground. The tool is pulverized. Although it is advantageous in pre-baking and developing latitude in the solder resist process, the particle size reduction is limited, the manufacturing cost is increased, and the heat resistance and the chemical resistance are not significantly effective. SUMMARY OF THE INVENTION The main purpose of the present invention is to solve the above-mentioned defects and avoid the existence of the above-mentioned defects. The present invention provides a photosensitive thermosetting composition which is capable of conforming to a lead-free chemical tin process after being hardened. Claim. It is still another object of the present invention to provide a photographic thermosetting composition which minimizes the use of unsaturated monoacids such as acrylic acid and its derivatives which are dangerous to human health. Another object of the present invention is to provide a photosensitive thermosetting composition, which can be dissolved in a formulation solvent of a green paint before use, eliminating the dust caused by mechanical grinding and placing it on hardening. In the composition of the agent, the power consumption of the grinding can be omitted, and the antifouling cost and the manufacturing cost can be reduced. 1291596 Another object of the present invention is to provide a photosensitive thermosetting composition. The main body of the side resin is less corrosive to human skin because of the lower amount of residual acid. For the above purposes, the present invention comprises an epoxy compound (a) having at least two epoxy groups, an unsaturated monoacid (b) containing at least two double bonds, a saturated or unsaturated diacid (c). a resin composition (A), a photopolymerizable photosensitive monomer and or a photo-oligomer (B), a photoinitiator (c), in a ratio of saturated or unsaturated anhydride (d), An epoxy compound (D) containing an epoxy group, and an organic solvent (E), which is cured to form a solder resist green paint. The detailed description and the technical contents of the present invention are as follows: [Embodiment] As shown in the "Fig. 1", it is a flowchart of the implementation of the present invention, and the preparation of the resin composition of the present invention is The following composition: an epoxy compound having at least two epoxy groups (a), an unsaturated monoacid having at least two double bonds (b), a saturated or unsaturated diacid (c) and a saturated or unsaturated anhydride (d) an epoxy compound (a) having at least two epoxy groups, an unsaturated monoacid (b) having at least two double bonds, and a mole ratio of a saturated or unsaturated diacid (c) 1 : 〇· 〇9~〇· 95 : 〇· 〇25~〇· 〇5, can react under appropriate reaction conditions to form a tree with an acid value of 4〇~49mgK〇H/g 10 1291596 Fat composition ( A). An epoxy compound having at least one epoxy group (a) may be a solid, a semi-solid or a liquid at a normal temperature, or an epoxy resin or an acrylate of a mixture of a solid, a semi-solid and a liquid, and a derivative thereof. And its derivatives, such as phenolic epoxy resin or phenolic epoxy resin, etc. are more suitable for 'there are 环氧树脂环氧树脂 epoxy resin, such as: LG Chem's Ν665, Ν670, leg 73, N673-80M , N680, N690, N690-80M, N695, etc.; Nanya company's NPCN7 (U, NPCN702, NPCN703, NPCN704; CibaGeigy's ECN1273, ECN1280, ECN1285, ECN1299, ECN9511; Changchun's CNE-200, CNE-202, CNE- 220. Phenol epoxy resin such as: N730, N740, N740-80M, N770, N865, N870 of LG Chem Company; NPPN638, NPPN683A80, NPPN638K80 of Nanya Company; PNE-173, PNE-177, PNE-177H of Changchun Company, PNE-177B90, etc., as long as it can be dissolved in the solvent used in the synthesis of the resin, the synthesis reaction is carried out in a homogeneous phase, which is selected for use in the present invention. The unsaturated monoacid (b) containing at least two double bonds may be acrylic acid. Or methacrylic acid, of which propylene More suitable; the saturated or unsaturated diacid (c) has a structure of HOOC-R-COOH, and the _ group can be an aliphatic or aromatic having one to twelve carbon atoms, if the R group is aliphatic And the saturated or unsaturated diacid (c) may be at least one selected from the group consisting of fumaric acid, singer 1291596, maleic acid, oxaiacetic acid. , adipic acid and its derivatives, giutaric acid and its derivatives, succinic acid, malic acid and its derivatives, Geng Pimelic acid, 1,8 suberic acid, azelaic acid, sebacic acid; if the R group is aromatic, saturated or unsaturated diacid (c) may be at least one selected from the group consisting of terephthalic acid and its derivatives, isophthalic acid and its derivatives, and the like saturated or unsaturated double I (c) can be used alone or in combination. Saturated or unsaturated acid liver (d) can be At least one selected from the group consisting of saturated hexahydro-phthalic acid anhydride and derivatives thereof, unsaturated anhydrous tetrahydrophtal ic acid anhydride and derivatives thereof or anhydrous phthalic anhydride ( Phthalic acid anhydride) and its derivatives. In the preparation of the photosensitive thermosetting composition of the present invention 2, the photosensitive thermosetting composition is composed of the following composition: a resin composition (A) having a content of 30 to 50% by weight, and a content of 5 to 20 wt. % of light-polymerizable photosensitive monomer and or photosensitive oligomer (B), a content of between 2. 0~6·Owt% of light initiator (C) 'One content is between 1〇~2〇wt The epoxy compound (D) containing at least two epoxy groups, and the organic solvent 1291596 (E) of a content of 25 to 40% by weight, the sum of (A) to (E) above is 100% by weight. The photopolymerizable photosensitive monomer and or the photosensitive oligomer (B) in the photosensitive composition of the present invention are selected from the group consisting of Sartomer and the like, and the commonly used photosensitive monomer may be a bifunctional aliphatic or a stupid ring-containing unsaturated. Double-button photosensitive monomer, such as SR205, SR306, CD4 (H, SR508, SR603, SR9036, can be

三官能基脂肪族或含苯環之不飽和雙鍵感光單體，如： SR350、SR444、CD501、SR9021 ;可為四官能基以上脂肪族或含苯環之不飽和雙感光單體，如：31^295、81^355、31^399、 SR494、SR9041 ;或五官能基脂肪族或含苯環之不飽和雙鍵感光单體與六官能基脂肪族或含苯環之不飽和雙鍵感光單體，也可為多官能基之丙烯酸g旨寡聚物（epoxy acrylate)，或其他多官能基之尿g旨丙烯酸酯寡聚物（urethane acrylate)等，如：CN929、CN970、CN104、CN120等；或自Photomer等商品取得如3000系列，4000系列及5000系列A trifunctional aliphatic or benzene ring-containing unsaturated double bond photosensitive monomer, such as: SR350, SR444, CD501, SR9021; may be a tetrafunctional or higher aliphatic or benzene ring-containing unsaturated double photosensitive monomer, such as: 31^295, 81^355, 31^399, SR494, SR9041; or a pentafunctional aliphatic or benzene ring-containing unsaturated double bond photosensitive monomer and a hexafunctional aliphatic or benzene ring-containing unsaturated double bond photosensitive The monomer may also be a polyfunctional acrylate acrylate, or other polyfunctional urethane acrylate, such as CN929, CN970, CN104, CN120. Etc.; or from products such as Photomer, such as 3000 series, 4000 series and 5000 series

等。光起始劑（C)，可用者為安息香類化合物，二苯甲酮類化合物（benzophenone)，蔥i昆（an仕iraquinones) 等，如·· Ciba-Geigy公司 Irgacure系列之907、369、184、 1173、1700、4265、500 ; Lambson公司之Speedcure系列或 Sartomer之Esacure系列等，它們可單獨使用或二種以上混合使用。 13 1291596 含至少一個環氧基之環氧化合物（D)在常溫下可為固體、半固體及液體，或固體、半固體及液體混合使用，包括有：含酚類及其衍生物之環氧樹脂、雙酚類之環氧樹脂、含鹵素之環氧樹脂或丙烯酸酯類及其衍生物，較適用者為含紛類之環氧樹脂，較常用者為甲朌環氧樹脂或盼環氧樹脂，甲酴氧樹脂，如：LG Chem公司之N665、N670、N673、 N673-80M、N680、N690、N690-80M、N695等；Nanya公司之 NPCN7(U 、 NPCN702 、 NPCN703 、 NPCN704 ; Ciba Geigy之 ECN1273、ECN1280、ECN1285、ECN1299、ECN9511 ;長春公司之CNE-200、CNE-202、CNE-220。盼環氧樹脂如：LG Chem 公司之N730、N740、N740-80M、N770、N865、N870 ; Nanya 公司之NPPN638、NPPN638K80、NPPN683A80 ;長春公司之 PNE-173、PNE-177、PNE-177H、PNE-177B90等。只要能溶解於綠漆配方溶劑中，不管是單獨使用或二種以上混合使用，均為本發明專利所選用。有機溶劑（E )可為選自下列化合物之至少其中一種：酮類、醚類、醇類、酯類或石油溶劑類（petr〇leum naphtha)，其中以醚類、酯類、石油溶劑類最為適用，例如·乙氧基乙酸曱酉旨（ethyleneglycol monomethyl ether acetate)、乙氧基乙醚（ethylene glycol monobutyl ether)、乙氧基丁酸甲酯（ethylene glycol monobutyl 1291596 ether acetate)、二乙二醇甲醚（diethylene glycol monoethyl ether)、二乙二醇曱醚酯（diethyleneglycol monoethyl ether acetate)、丙氧基乙醚（pr〇pyiene giyc〇i monomethylether)、丙氧基乙酸曱酯（pr〇pyienegiyc〇i monomethyi ether acetate)、二丙氧基乙醚（dipr〇pyiene glycol monomethyl ether)，Exxon 公司之Aromatic 100、Wait. The photoinitiator (C) can be used as a benzoin compound, a benzophenone, an iraquinones, etc., such as 907, 369, 184 of the Ciba-Geigy Irgacure series. , 1173, 1700, 4265, 500; Lambson's Speedcure series or Sartomer's Esacure series, etc., which may be used alone or in combination of two or more. 13 1291596 Epoxy compound (D) containing at least one epoxy group may be solid, semi-solid and liquid at normal temperature, or a mixture of solid, semi-solid and liquid, including: epoxy containing phenols and derivatives thereof Resin, bisphenol epoxy resin, halogen-containing epoxy resin or acrylate and its derivatives, suitable for epoxy resin containing more than one type, more commonly used as formazan epoxy resin or epoxy Resin, formazan resin, such as: LG Chem's N665, N670, N673, N673-80M, N680, N690, N690-80M, N695, etc.; Nanya's NPCN7 (U, NPCN702, NPCN703, NPCN704; Ciba Geigy ECN1273, ECN1280, ECN1285, ECN1299, ECN9511; Changchun Company's CNE-200, CNE-202, CNE-220. Hope epoxy resin such as: LG Chem's N730, N740, N740-80M, N770, N865, N870; Nanya The company's NPPN638, NPPN638K80, NPPN683A80; Changchun company's PNE-173, PNE-177, PNE-177H, PNE-177B90, etc.. As long as it can be dissolved in the green paint formulation solvent, either alone or in combination of two or more Selected for the invention patent. The organic solvent (E) may be at least one selected from the group consisting of ketones, ethers, alcohols, esters or petroleum solvents (petr〇leum naphtha), among which ethers, esters, petroleum solvents are the most Suitable, for example, ethyleneglycol monomethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl 1291596 ether acetate, diethylene glycol methyl Diethylene glycol monoethyl ether, diethyleneglycol monoethyl ether acetate, propoxyphene diethyl ether (pr〇pyiene giyc〇i monomethylether), pr〇pyienegiyc〇i monomethyi ether Acetate), dipr〇pyiene glycol monomethyl ether, Exxon Aromatic 100,

Aromatic 150、Aromatic 200等，它們可單獨使用或二種以上混合使用。除了（A)〜（D)四項組成物外，可視需要加入其他化合物或填充劑（fillers)來強化油墨之特性，如：為了促進環氧樹脂之熱硬化性，可在感光組成物中加入氰胍類（dicyandiamide)、咪唑類（imidazoles)、或胺類 (amines)等催化劑（catalyst)，來加速環氧樹脂之熱聚合反應，為了促進綠漆之表面硬度、耐化性等，可加入Aromatic 150, Aromatic 200, etc., which may be used singly or in combination of two or more. In addition to the four components (A) to (D), other compounds or fillers may be added as needed to enhance the characteristics of the ink, such as: in order to promote the thermosetting property of the epoxy resin, it may be added to the photosensitive composition. Catalysts such as dicyandiamide, imidazoles, or amines to accelerate the thermal polymerization of epoxy resins, in order to promote the surface hardness and chemical resistance of green paints, etc.

填充劑，如：硫酸鋇（barium sulfate )、滑石（talc )、一氧化石夕（silica)、碳酸i弓（calcium carbonate )、氧化銘等無機物，或如犧之類的有機物；消泡劑 (anti-foaming agent)，如：含矽利光、氟碳化合物；平坦劑（leveling agent)，如：氟碳化合物、高分子寡聚物、矽利光等，顏料或染料；熱聚合抑制劑（thermal inhibitor)如：對苯二酚（hydroquinone)類、甲氧基苯 15 1291596 (methoxyphenol)類化合物等，及其他添加劑如分散, (dispersant)、耐燃劑（flameretardant)等化合物或填充劑可選擇加人主劑之中、錢处化 …心T、或均勻分配於主劑和硬化劑之中。上述之感光性组成物為求儲存安全性，通常將主劑與硬化劑分開配料、研磨及儲存，在塗佈使用前才加以^ 均勻，並最好是在二十四小時内使用完畢。一般而言，含有填充劑、顏料之主劑配完料後，先加以攪拌分散均勻，及用三滾筒（triple roll mill)研磨機予以細磨至細小粉末狀，以使得綠漆膜面有好的平坦性及光澤性，至於硬化劑組成物，可加入也可不加入填充劑，加入填充劑可以提高固含量及黏度，但必需加以研磨，而增加一道製程步驟，故需視組成配方而定。本發明中感光熱固型組成物之硬化製程3，包括下列加工過程·將感光熱固型組成物塗佈於基材上，再經過烘烤乾燥、曝光、顯影’最後用紫外光照射或加熱方式，來得到硬化的物質。〔實施例1，本發明〕在一四口反應器中加入220. 0 g的Carbitol acetate及 220· 〇 g的Solvent Naphtha 150，加熱至90°C 時加入460 g 甲酚環氧樹脂（軟化點：92. 5。(：，環氧當量·· 230)，攪拌 16 1291596 溶解，再加入對笨二盼〇· 4〇g，丙稀酸134. Og( 1· 8莫耳），反一丁烯二酸11· 6g (〇·1莫耳）及三苯基磷 (Triphenylphosphine) 2.5g，於110它反應至少20小時，再加入四鄰笨二曱酐（Tetrahydrophthalic anhydride) 130.7g (〇·86莫耳），1HTC繼續反應8小時，測其酸價為 45mgK0H/g。〔實施例2，本發明〕在一四口反應器中加入220.0g的Carbitol acetate及 220· Og的溶劑Naphtha 150，加熱至90°C時加入396g甲酚環氧樹脂（軟化點：82t，環氧當量：198)，攪拌溶解，再加入對苯二酚〇· 40 g，丙烯酸131 g (1.82莫耳），己二酸13· 14g (0· 09莫耳）及三苯基磷2. 5g，於11(TC反應至少20小時，再加入四鄰苯二甲酐以&鉍（〇· 90莫耳），110 °匚繼續反應8小時，測其酸價為48mgK0H/g。〔實施例3，本發明〕在一四口反應器中加入220. 0g的Carbitol acetate及Fillers, such as: barium sulfate, talc, silica, calcium carbonate, oxidized minerals, or organic substances such as sacrificial; defoamer ( Anti-foaming agent, such as: fluorene-containing light, fluorocarbon; leveling agent, such as: fluorocarbon, high molecular oligomer, blush, etc., pigment or dye; thermal polymerization inhibitor Such as: hydroquinone, methoxybenzene 15 1291596 (methoxyphenol) compounds, and other additives such as dispersion, (dispersant), flame retardant (flameretardant) compounds or fillers can choose to add people Among the agents, the money is ... the heart T, or evenly distributed among the main agent and the hardener. In order to achieve storage safety, the above-mentioned photosensitive composition is usually prepared by separately mixing, grinding and storing the main agent and the hardener, and is uniformly applied before being used for coating, and is preferably used within twenty-four hours. Generally, after the main agent containing the filler and the pigment is finished, it is uniformly stirred and dispersed, and finely ground to a fine powder by a triple roll mill to make the green paint film surface good. The flatness and glossiness. As for the hardener composition, the filler may or may not be added. The addition of the filler may increase the solid content and the viscosity, but it is necessary to grind and add a process step, so it depends on the formulation. The hardening process 3 of the photosensitive thermosetting composition of the present invention comprises the following processing steps: coating the photosensitive thermosetting composition on a substrate, and then baking, exposing, developing, and finally irradiating or heating with ultraviolet light. Ways to get a hardened substance. [Example 1, the present invention] In a four-port reactor, 220. 0 g of Carbitol acetate and 220·〇g of Solvent Naphtha 150 were added, and when heated to 90 ° C, 460 g of cresol epoxy resin was added (softening point) :92. 5. (:, epoxy equivalent · · 230), stir 16 1291596 dissolved, then add to the stupid two 〇 · 4 〇 g, acrylic acid 134. Og (1 · 8 m), anti-d Oleic acid 11.6g (〇·1 mole) and Triphenylphosphine 2.5g, it reacts for at least 20 hours at 110, and then adds Tetrahydrophthalic anhydride 130.7g (〇·86 Mo) Ear), 1HTC continued to react for 8 hours, and its acid value was 45 mgK0H/g. [Example 2, the present invention] 220.0 g of Carbitol acetate and 220·Og of solvent Naphtha 150 were added to a four-port reactor, and heated to Add 396 g of cresol epoxy resin (softening point: 82 t, epoxy equivalent: 198) at 90 ° C, stir to dissolve, add hydroquinone 〇 40 g, acrylic acid 131 g (1.82 mol), adipic acid 13· 14g (0·09 mol) and triphenylphosphine 2. 5g, at 11 (TC reaction for at least 20 hours, then add tetraphthalic anhydride to &am 0克的卡比特ol acetate 。。 bit 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 Car Car Car Car and

220· 〇g的Solvent Naphtha 150，加熱至90°C 時加入430 g 甲酚環氧樹脂（軟化點8(TC，環氧當量：215)，攪拌溶解，再加入對笨二酚〇.4〇g，丙烯酸I34.0g (1.86莫耳），庚二酸11.2g (0.07莫耳）及三苯基磷2.5g，於110°C反應至少 20小時，再加入四鄰笨二曱酐i39.8g (0.92莫耳），ll〇°C 17 1291596 繼續反應8小時，測其酸價為44 mgKOH/g。〔實施例4，本發明〕在一四口反應器中加入220. Og的Carbitol acetate及 220.0 g的Solvent Naphtha 150，加熱至90°C 時加入420g 甲酚環氧樹脂（軟化點：81°C，環氧當量：210)，攪拌溶解，再加入對苯二酚0.40g，丙烯酸135.4g(1.88莫耳），癸二酸12· 12g (0· 06莫耳）及三笨基磷2. 5g，於110°C反應至少20小時，再加入四鄰苯二甲酐142. 9g( 0.94莫耳）， 110°C繼續反應8小時，測其酸價為46mgK0H /g。〔實施例5，本發明〕在一四口反應器中加入220. 〇g的Carbitol acetate及 220· 〇g的Solvent Naphtha 150，加熱至90°C 時加入404 g 甲酚環氧樹脂（軟化點：76°C，環氧當量：202)，攪拌溶解’再加入對苯二酚〇.4〇g，丙烯酸137.0g (1.9莫耳），十六烧二酸（Thapsic acid，又名Hexadecanedioic acid) 14· 3g (0· 05莫耳）及三苯基磷2. 5g，於1HTC反應至少20 小時’再加入四鄰笨二甲酐152.〇g (ι·〇莫耳），11〇。〇繼續反應8小時，測其酸價為43mgK0H/g。〔實施例6，本發明〕在一四口反應器中加入220· 0 g的Carbitol acetate 及220· 0 g的s〇ivent Naphtha 150，加熱至90°C 時加入404 18 1291596 S曱紛環氧樹脂（軟化點：76°C，環氧當量：202)，攪拌溶解，再加入對苯二酚0.40g,丙烯酸137.0g(1.9莫耳），對笨二甲酸16· 6 g (〇· 1莫耳）及三苯基磷2. 5g，於110°C 反應至少20小時，再加入四鄰笨二曱酐152. 〇g(l· 0莫耳）， ll〇°C繼續反應8小時，測其酸價為49mgK〇H /g。〔實施例7，習知技術〕在一四口反應器中加入220.0 g的Carbitol acetate220· Solg Solvent Naphtha 150, when heated to 90 ° C, add 430 g of cresol epoxy resin (softening point 8 (TC, epoxy equivalent: 215), stir to dissolve, then add to the stupid phenolphthalein. g, acrylic acid I34.0g (1.86 moles), pimelic acid 11.2g (0.07 moles) and triphenylphosphine 2.5g, reacted at 110 ° C for at least 20 hours, then add tetrazoic phthalic anhydride i39.8g ( The reaction was continued for 8 hours, and the acid value was determined to be 44 mgKOH/g. [Example 4, the present invention] 220. Og of Carbitol acetate and 220.0 were added to a four-port reactor. g Solvent Naphtha 150, heated to 90 ° C, add 420g cresol epoxy resin (softening point: 81 ° C, epoxy equivalent: 210), stir to dissolve, then add hydroquinone 0.40g, acrylic acid 135.4g ( 1.88g (0.94mol), adipic acid 12·12g (0.66 mol) and three stupid phosphorus 2. 5g, reacted at 110 ° C for at least 20 hours, then added tetraphthalic anhydride 142. 9g (0.94 mol The reaction was continued at 110 ° C for 8 hours, and the acid value was measured to be 46 mg K0H / g. [Example 5, the present invention] 220. 〇g of Carbitol acetate and 220· was added to a four-port reactor. Solg Solvent Naphtha 150, heated to 90 ° C, add 404 g cresol epoxy resin (softening point: 76 ° C, epoxy equivalent: 202), stir to dissolve 'and then add hydroquinone 〇. 4 〇 g , 137.0g (1.9m) of acrylic acid, Thapsic acid (also known as Hexadecanedioic acid) 14·3g (0.55 mol) and triphenylphosphine 2. 5g, reacted at 1HTC for at least 20 hours' Further, tetra-dophosic anhydride 152. 〇g (ι·〇莫耳), 11 〇 was added. The reaction was continued for 8 hours, and the acid value was measured to be 43 mg K0H/g. [Example 6, the present invention] Add 220. 0 g of Carbitol acetate and 220·0 g of s〇ivent Naphtha 150, and add 404 18 1291596 S 曱 epoxy resin when heated to 90 ° C (softening point: 76 ° C, epoxy equivalent: </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> °C reaction for at least 20 hours, then add tetra-n-phenyl phthalic anhydride 152. 〇g (l·0 mol), continue reaction for 8 hours at ll ° ° C, and measure its acid value of 49 mg K 〇 H / g. [Example 7, conventional technique] 220.0 g of Carbitol acetate was added to a four-port reactor.

及220· 〇g的s〇ivent Naphtha 150，加熱至90°C 時加入460 g 甲紛環氧樹脂（軟化點：92· 5°C，環氧當量：230 )，攪拌溶解，再加入對苯二酚〇· 40 g，丙烯酸134· 〇 g (丨· 80莫耳）’及三苯基磷2.5g，於ll〇°C反應至少20小時，再加入四鄰笨二甲酐l〇6.4g (0.70莫耳），1HTC繼續反應8小時，測其酸價為33 mgKOH/g。〔實施例8，習知技術〕And 220· 〇g s〇ivent Naphtha 150, heated to 90 ° C, add 460 g of A resin (softening point: 92 · 5 ° C, epoxy equivalent: 230), stir to dissolve, then add benzene Diphenol hydrazide · 40 g, acrylic acid 134 · 〇g (丨 · 80 moles) ' and triphenylphosphine 2.5g, reacted at ll ° ° C for at least 20 hours, then add tetrazoic phthalic anhydride l 6.4g ( 0.70 mol), 1HTC continued to react for 8 hours, and its acid value was measured to be 33 mgKOH/g. [Embodiment 8, Conventional Technology]

在一四口反應器中加入220·0 g的Cafbitol acetate 及220.0 g的Solvent Naphtha 150，加熱至9〇°C 時加入460 g甲酚環氧樹脂（軟化點·· 92·51，環氧當量：230)，攪拌溶解，再加入對苯二酚0· 40g，丙烯酸172· 8g ( 2· 40莫耳）’及三笨基填2· 5g，於11(TC反應至少20小時，再加入四鄰笨二甲酐139·^ (〇·92莫耳），i1(rC繼續反應8小時，測其酸價為112mgK0H/g。 19 •1291596 〔實施例9，f知技術〕在一四口反應器中加入220.0 g的Carbitol acetate 及220· 0 g的Solvent Naphtha 150，加熱至90°C 時加入430 g曱酚環氧樹脂（軟化點：80°C，環氧當量：215)，授拌溶解，再加入對苯二紛0· 40g，丙稀酸134· 0g (1· 86莫耳）及三苯基麟2· 5 g，於110°C反應至少20小時，再加入四鄰苯二甲酐183.0g (1.40莫耳），ll〇°c繼續反應8小時，測其酸價為7 6mgK0H/g。 φ 實施例1〜6係以本發明合成樹脂組成物（a)，實知例7〜9係以習知技術合成樹脂組成物（a)，如表1 —1及1 — 2所示，係為本發明進行樹脂合成與習知技術進行樹脂合成時，合成樹脂中環氧化樹脂（a)之莫耳當量’不飽和單酸（b )之丙烯酸的莫耳當量，飽和雙酸（c ) 之種類及其莫耳數’酸肝⑷之莫耳數，環氧樹脂⑷ /丙婦酸（b)/飽和或不飽和雙酸（c)之莫耳數比，φ 與合成後樹脂之酸價。〔實施例1〇，本發明〕實施例10係由實施例1製備得到之樹脂組成物，依表2-1中所列組成主劑’高速授掉二至三小時後，用三 2研磨機研磨分散；依表2、2所顺成硬化劑，以高個半小時到二個小時製得硬化劑溶液，若硬化劑 20 1291596 組成含有填充劑，則須用三滾輪研磨機加以研磨分散。上述研磨過之主劑，與溶解完全或經研磨分散完全之硬化劑，均勻混合攪拌約十五分鐘後即成為本發明之液態感光型防焊綠漆。〔實施例11，本發明〕實把例1 1係由實施例2製備得到之樹脂組成物，依表2 — 1所列組成主劑，高速攪拌二至三小時後，用三滚輪研磨機研磨分散；依表2 — 2所列組成硬化劑，以高速春授拌個半小時到一個小時製得硬化劑溶液，若硬化劑組成含有填充劑，則須用三滾輪研磨機加以研磨分散。上述研磨過之主劑，與溶解完全或經研磨分散完全之 · 硬化劑，均勻混合攪拌約十五分鐘後即成為本發明之液態感光型防焊綠漆。〔實施例12，本發明〕實施例12係由實施例3製備得到之樹脂組成物，依 _ 表2 — 1所列組成主劑，高速攪拌二至三小時後，用三滾輪研磨機研磨分散；依表2 — 2所列組成硬化劑，以高速攪拌一個半小時到二個小時製得硬化劑溶液，若硬化劑組成含有填充劑，則須用三滾輪研磨機加以研磨分散。上述研磨過之主劑，與溶解完全或經研磨分散完全之硬化劑，均勻混合攪拌約十五分鐘後即成為本發明之液態 21 1291596 感光型防焊綠漆。〔實施例13，本發明〕實施例1 3係由實施例4觀得到之樹脂組成物，依表2 — 1所列組成主劑，高速_二至三小時後，用三滾輪研磨機研磨分散；絲2 — 2所列組成硬化劑，以高速攪拌-個半小時到二個小時製得硬化劑溶液，若硬化劑組成含有填充劑’則_三滾輪研磨機加以研磨分散。上述研磨過之主劑，與溶解完全或經研磨分散完全之硬化劑，均自混合讎約十五分鐘後即成為本發明之液態感光型防焊綠漆。〔實施例14，本發明〕實施例14係由實施例5製備得到之樹脂組成物，依表2 — 1所列組成主劑，高速攪拌二至三小時後，用三滚輪研磨機研磨分散；依表2 ~ 2所列組成硬化劑，以高速稅拌一個半小時到二個小時製得硬化劑溶液，若硬化劑組成含有填充劑，則須用三滾輪研磨機加以研磨分散。上述研磨過之主劑，與溶解完全或經研磨分散完全之硬化劑，均勻混合攪拌約十五分鐘後即成為本發明之液態感光型防焊綠漆。〔實施例15，本發明〕實施例15係由實施例6製備得到之#f脂組成物，依 22 1291596 表2〜1所列組成主劑，高速攪拌二至三小時後，用三滾輪研磨機研磨分散；依表2 — 2所列組成硬化劑，以高速授拌個半小時到一個小時製得硬化劑溶液，若硬化劑組成含有填細’則_三滾輪研賴加㈣磨分散。上述研磨過之主劑，與溶解完全或經研磨分散完全之更化劑’均勻混合獅1約十五分鐘後即成為本發明之液態感光型防焊綠漆。〔實施例16，習知技術〕 _ 實施例16係由實施例7製備得到之樹脂組成物，依表2 — 3所列組成主劑，高速攪拌二至三小時後，用三滾 · 輪研磨機研磨分散，依表2 一 4所列組成硬化劑，以高速 . 攪拌-個半小時到二個小時製得硬化劑溶液，若硬化劑組成含有填絲丨’貞彳綱三滚輪研磨機加以研磨分散。上述研磨過之主劑，與溶解完全或經研磨分散完全之硬化劑，均勻混合攪拌約十五分鐘後即成為習知技術之液 _ 態感光型防焊綠漆。〔實施例17，習知技術〕實施例17係由實施例8製備得到之樹脂組成物，依表2 — 3所列組成主劑，高速攪拌二至三小時後，用三滾輪研磨機研磨分散；絲2 一 4所列組成硬化劑，以高速 · 餅-個半小時到二個小時製得硬化劑溶液，若硬化劑、组 23 1291596 成含有填細，則_三錄研賴加靖磨分散。上述研磨過之主劑，與溶解完全或經研磨分散完全之硬化劑，均勻混合攪拌約十五分鐘後即成為習知技術之液態感光型防焊綠漆。〔實施例18，習知技術〕實施例18由實施例9製備得到之樹脂組成物，依表 2 — 3所列組成主劑，高速攪拌二至三小時後，用三滾輪研磨機研磨分散，絲2 — 4所列、喊硬化劑，以高速授摔個半小時到二個小時製得硬化劑溶液，若硬化劑組成 3有填充劑’賴肖三滾輪研磨機純研磨分散。上述研磨過之主劑，與溶解完全或經研磨分散完全之硬化劑’均㈣合勝約十五分鐘後即成為習知技術之液態感光型防焊綠漆。〔實施例19，習知技術〕實施例1 9由實施例7製備得到之樹齡成物，依表 2- 3所列組成主劑，高速半二至三小時後，用三滾輪研磨機研磨分散；絲2 —摘顺成硬化劑，以高速攪摔個半小日谓二個小時製得硬化劑溶液，若硬化劑組成含有填充9彳’彫貞用二滚輪研磨機力σ以研磨分散。上述研磨過之主劑，與溶解完全或經研磨分散完全之硬化劑’肖勻混合湖1約十五分鐘後即成為習知技術之液 24 1291596 態感光型防焊綠漆。以本發明施行之實施例10〜15合成感光熱固型組成物，與彻習知技術施行之實施例i 6〜〗9合成感光熱固型組成物，其中所含之各成份種類與含量分別整理如表2 — 1、2 — 2、2 —3及2 —4所示。依實施例1 〇〜1 9配製之防焊綠漆，以1〇〇網目 (mesh)的網版印刷方式，分別均勻塗佈於經過表面處理之銅落基板及已製作線路之基板上，放入別。c之烤箱中進# 行預烤’取出冷卻後覆蓋工作底片（art财k)，以⑽獅紫外線曝光機設定450mJ/cm2曝光量，然後進入輸送帶式的顯影機進行_顯像1作，其娜齡為旧影液濃度：· 1· 〇wt%K20)3水雜，顯影祕度·· 3Q±rc，倾 · 1.5kg/cm2 ’顯影時間·· 9〇秒，得出線路圖案後，置於 160C之烤箱巾輯5〇分鐘，即絲熱交聯反應。為測試本發明之特性，覆進行以下評估實驗： 1·預烤寬容度測試：將烘箱溫度設至8〇°C，分別烘烤30分鐘、5〇分鐘及7〇分鐘，經曝絲織，用光學臟織細_線寬/線距線路是否顯影乾淨。 π ·顯影寬容度測試·· 將供箱溫度設至8〇t，烘烤30分鐘後，將板子於常溫、 25 1291596 頁光狀態下’分別放置48小時及72小時，再施予曝光顯影，用光學顯微鏡觀查70 // m線寬/線距是否顯影乾淨〇 Π·焊錫測試：將已作好圖案、硬化完全之綠漆線路板，施以焊錫工程，260 CxlO秒x3次，再用3 μ膠帶進行密著性測試。 IV ·化鎳浸金測試：將已作好圖案、硬化完全之綠漆線路板，施以化鎳浸金工程’鎳厚150//in，金厚3//in，再用3Μ膠帶進行密著性測試。 V·化學錫測試：將已作好圖案、硬化完全之綠漆線路板，施以化學錫工程’錫厚40//in，再用3Μ膠帶進行密著性測試。如表3所示，係為綠漆性質測試結果，本發明之感光熱固型組祕帽驗祕（Α)最傾介於40 〜49mgK0ii/g，若酸價過低，則會有顯影不潔或露足，或預烤寬容度、顯影寬容度變窄的問題，若酸價過高，則會有耐化性不佳’意即在喷錫、化錄浸金及化學錫製程中，綠漆在銅縣板上的㈣性將會變差；樹馳成物在感光熱固型級成物中最適合之重量比例為3〇〜5〇峨，太低或太π同樣會有前述之問題。有關感光熱固型組成物之光可 26 1291596 聚合㈣及感光寡聚物（B)，其功能為加強綠漆之交聯雄、度，最佳者為5〜20wt%，若太低則會因為交聯密度不足影響耐化性，若過高則預烤後膜面呈現粘手性，容易刮傷及污染工作底片；感光熱固型組成物之起始劑（C)，其最佳使用範®係為2· G〜6· Gwt%，若太侧會感光不足， ’IV曰臈面硬度，若過咼則有解析不佳，無法忠實反映出底片圖案等缺點；感光熱固型組成物之環氧化合物（D)，其功能為提供樹脂組成物之熱硬化，最佳使用範圍為1〇〜鲁 20wt/^右太低貝1丨硬烤後膜面硬度不足，耐化性變差，而若太高，則會有顯影寬容度不足的問題；至於感光熱固型 · 組成物之有機溶劑（E)，其目的在調整綠漆之固含量，Add 220.0 g of Cafbitol acetate and 220.0 g of Solvent Naphtha 150 to a four-port reactor, and add 460 g of cresol epoxy resin when heated to 9 ° C (softening point · · 92 · 51, epoxy equivalent : 230), stir and dissolve, then add hydroquinone 0. 40g, acrylic acid 172. 8g (240 meters) and three stupid base 2·5g, at 11 (TC reaction for at least 20 hours, then add four neighbors Stupid dimethyl anhydride 139·^ (〇·92 mol), i1 (rC continued to react for 8 hours, and its acid value was 112 mg K0H/g. 19 • 1291596 [Example 9, f-technical] in a four-port reactor 220.0 g of Carbitol acetate and 220·0 g of Solvent Naphtha 150 were added, and when heated to 90 ° C, 430 g of phenolic epoxy resin (softening point: 80 ° C, epoxy equivalent: 215) was added, and the mixture was dissolved. Then add p-benzoic acid 0. 40g, acrylic acid 134. 0g (1·86 mol) and triphenyl lining 2.5 g, react at 110 ° C for at least 20 hours, then add tetraphthalic anhydride 183.0 g (1.40 mol), ll 〇 °c continued the reaction for 8 hours, and the acid value was determined to be 7 6 mg K0H / g. φ Examples 1 to 6 were based on the synthetic resin composition (a) of the present invention, and examples 7 to 9 were known. The synthetic resin composition (a) according to the prior art, as shown in Tables 1-1 and 1-2, is an epoxidized resin (a) in a synthetic resin when the resin is synthesized by the resin synthesis according to the present invention. Mohr equivalent 'unsaturated monoacid (b) molar equivalent of acrylic acid, type of saturated diacid (c) and its molar number 'molar number of sour liver (4), epoxy resin (4) / propyl fumarate (b / molar ratio of saturated or unsaturated diacid (c), φ and acid value of the resin after synthesis. [Example 1 〇, the present invention] Example 10 is a resin composition prepared in Example 1, According to the composition listed in Table 2-1, the main agent is transferred at high speed for two to three hours, and then ground and dispersed with a three-two grinder; according to Tables 2 and 2, the hardener is used, and the height is from half an hour to two hours. A hardener solution is obtained. If the hardener 20 1291596 is composed of a filler, it must be ground and dispersed by a three-roll mill. The above-mentioned ground main agent is uniformly mixed with a hardener dissolved completely or by grinding. After five minutes, it became the liquid photosensitive type solder resist green paint of the present invention. 11, the present invention] Example 1 1 is the resin composition prepared in Example 2, according to the composition listed in Table 2-1, the high-speed stirring for two to three hours, after grinding and dispersion with a three-roller mill; The hardeners listed in Table 2-2 are prepared by mixing them at high speed for half an hour to one hour to obtain a hardener solution. If the hardener composition contains a filler, it must be ground and dispersed by a three-roll mill. The above-mentioned ground main agent is uniformly mixed with the hardener which is completely dissolved or dispersed by grinding and is stirred for about fifteen minutes to become the liquid photosensitive anti-welding green paint of the present invention. [Example 12, the present invention] Example 12 is a resin composition prepared in Example 3, which is composed of the main components listed in Table 2-1, stirred at high speed for two to three hours, and then ground and dispersed by a three-roll mill. According to the composition of the hardener listed in Table 2-2, the hardener solution is obtained by stirring at high speed for one and a half hours to two hours. If the hardener composition contains a filler, it must be ground and dispersed by a three-roll mill. The above-mentioned ground main agent is uniformly mixed with the hardener which is completely dissolved or ground and dispersed for about fifteen minutes to become the liquid 21 1291596 photosensitive anti-welding green paint of the present invention. [Example 13 of the present invention] Example 1 3 is a resin composition obtained in Example 4, and the main component is listed in Table 2-1, and after two to three hours at high speed, it is ground and dispersed by a three-roll mill. The composition of the hardener listed in the wire 2-2 is obtained by stirring at a high speed for one and a half hours to two hours to obtain a hardener solution, and if the hardener composition contains a filler, the three-roller grinder is ground and dispersed. The above-mentioned ground main agent is a liquid photosensitive anti-welding green paint of the present invention after being mixed with the hardener which is completely dissolved or completely dispersed by grinding for about fifteen minutes. [Example 14, the present invention] Example 14 is a resin composition prepared in Example 5, according to the composition of the main components listed in Table 2-1, stirred at high speed for two to three hours, and then ground and dispersed by a three-roll mill; According to the composition of the hardener listed in Table 2 ~ 2, the hardener solution is prepared by mixing the high-speed tax for one and a half hours to two hours. If the hardener composition contains the filler, it must be ground and dispersed by a three-roll mill. The above-mentioned ground main agent is uniformly mixed with a hardener which is completely dissolved or ground and dispersed for about fifteen minutes to become the liquid photosensitive anti-welding green paint of the present invention. [Example 15, the present invention] Example 15 is a #f lipid composition prepared in Example 6, according to the composition of the composition listed in Table 2 to 1 of 22 1291596, stirred at high speed for two to three hours, and then ground with three rollers. The machine is ground and dispersed; according to the composition of the hardener listed in Table 2-2, the hardener solution is prepared by mixing at a high speed for half an hour to one hour. If the hardener composition contains a packed thinner, then the three-wheel mill is used to grind. The above-mentioned ground main agent is uniformly mixed with the terrarium 1 which is completely or completely dispersed by grinding, and becomes the liquid photosensitive anti-welding green paint of the present invention after about fifteen minutes. [Example 16, Conventional Technology] _ Example 16 is a resin composition prepared in Example 7, which is composed of the main components listed in Table 2-3, stirred at high speed for two to three hours, and then ground by a three-roller wheel. Machine grinding and dispersing, according to the composition of the hardener listed in Table 2 to 4, at high speed. Stir - one and a half hours to two hours to obtain a hardener solution, if the hardener composition contains a wire 丨 '贞彳纲三轮磨磨机Grinding dispersion. The above-mentioned ground main agent is uniformly mixed with a hardener which is completely dissolved or ground and dispersed, and is uniformly mixed for about fifteen minutes to become a liquid-state anti-welding green paint of the prior art. [Example 17, conventional technique] Example 17 is a resin composition prepared in Example 8, which is composed of the main components listed in Table 2-3, stirred at high speed for two to three hours, and then ground and dispersed by a three-roll mill. The composition of the hardener listed in the wire 2 to 4, the high-speed cake - one and a half hours to two hours to obtain a hardener solution, if the hardener, group 23 1291596 into a thinner, then _ Sanluyan Lai Jiajing mill dispersion. The above-mentioned ground main agent is uniformly mixed with a hardener which is completely dissolved or dispersed by grinding, and is uniformly mixed for about fifteen minutes to become a liquid photosensitive anti-welding green paint of the prior art. [Example 18, conventional technique] Example 18 The resin composition prepared in Example 9 was stirred at a high speed for two to three hours according to the composition of the composition listed in Table 2-3, and then dispersed by a three-roll mill. Wire 2 - 4 listed, shouting hardener, high-speed drop for half an hour to two hours to obtain a hardener solution, if the hardener composition 3 has a filler 'Lai Sha three roller grinder pure grinding dispersion. The above-mentioned ground main agent is a liquid photosensitive anti-welding green paint of the prior art after a total of about fifteen minutes of complete dissolution or hardening of the hardener. [Example 19, conventional technique] Example 1 9 The age-reduced product prepared in Example 7, according to the composition of the main components listed in Table 2 - 3, after two to three hours at high speed, grinding and dispersing with a three-roll mill Silk 2 - picking up into a hardener, stir it at a high speed for half an hour and say that the hardener solution is obtained for two hours. If the hardener composition contains 9 彳' 贞贞, use the two roller grinder force σ to grind and disperse. The above-mentioned ground main agent is a known type of liquid 24 1291596 state-sensitive anti-welding green paint after about 15 minutes from the dissolution of the hardened or fully dispersed hardener. The photosensitive thermosetting composition was synthesized by the examples 10 to 15 which were carried out according to the present invention, and the photosensitive thermosetting composition was synthesized according to the examples i 6 to 9 which were carried out by a conventional technique, and the types and contents of the components contained therein were respectively The finishing is shown in Table 2 - 1, 2 - 2, 2 - 3 and 2 - 4. According to the first embodiment, the anti-welding green paint prepared by the 〇~1 9 is uniformly coated on the surface-treated copper-drop substrate and the substrate on which the line has been produced by a screen printing method of 1 mesh. Enter the farewell. In the oven of c, pre-bake in the oven. After taking out the cooling, cover the working negative film (art money k), set the exposure amount of 450mJ/cm2 with (10) lion ultraviolet exposure machine, and then enter the conveyor type developing machine for _ imaging 1 Its age is the concentration of old shadow liquid: · 1· 〇wt%K20) 3 water miscellaneous, development secretity · · 3Q ± rc, tilt · 1.5kg / cm2 'development time · · 9 〇 seconds, after the line pattern is obtained , placed in a 160C oven towel for 5 minutes, that is, silk heat crosslinking reaction. In order to test the characteristics of the present invention, the following evaluation experiments were carried out: 1. Pre-baking tolerance test: The oven temperature was set to 8 ° C, and baked for 30 minutes, 5 minutes, and 7 minutes, respectively, after being exposed to silk, Use optical dirty woven fine _ line width / line distance line to develop clean. π ·Development latitude test ·· Set the temperature of the supply box to 8〇t, and after baking for 30 minutes, place the board at room temperature and 25 1291596 light state for 48 hours and 72 hours respectively, and then apply exposure and development. Use an optical microscope to check whether the 70 / m line width / line spacing is developed 〇Π · Solder test: The green paint circuit board that has been patterned and hardened is applied to the soldering project, 260 CxlO seconds x 3 times, and then used 3 μ tape was tested for adhesion. IV · Nickel immersion gold test: The green lacquer circuit board that has been patterned and hardened is applied with nickel immersion gold project 'nickel thickness 150//in, gold thickness 3//in, and then dense with 3 Μ tape. Sex test. V·Chemical Tin Test: The green paint circuit board that has been patterned and hardened is applied to the chemical tin project 'tin thickness 40//in, and the adhesion test is performed with 3 inch tape. As shown in Table 3, it is the green paint property test result. The photosensitive thermosetting group cap of the present invention has the most inclination of 40~49mgK0ii/g. If the acid value is too low, it will be unclean. Or exposure, or pre-baking tolerance, development latitude narrowing problem, if the acid price is too high, there will be poor chemical resistance 'meaning that in the tin, chemical immersion gold and chemical tin process, green The (four) properties of the paint on the copper plate will be worse; the most suitable weight ratio of the tree-like product in the photosensitive thermosetting grade is 3〇~5〇峨, too low or too π will also have the aforementioned problem. The photo-thermosetting composition of the light can be polymerized (4) and the photosensitive oligomer (B), the function of which is to strengthen the cross-linking degree of the green paint, the best is 5 to 20 wt%, if too low Because the insufficient crosslink density affects the chemical resistance, if it is too high, the film surface exhibits stickiness after pre-baking, which is easy to scratch and contaminate the working film; the initiator (C) of the photosensitive thermosetting composition is optimally used. Fan® system is 2·G~6·Gwt%. If the side is too light, 'IV face hardness, if it is too, there is poor resolution, can not faithfully reflect the negative film pattern and other defects; photosensitive thermosetting composition The epoxy compound (D) has the function of providing thermal hardening of the resin composition. The best use range is 1〇~Lu 20wt/^right too low. 1丨 Hard-baked, the film surface hardness is insufficient, and the chemical resistance is changed. Poor, and if it is too high, there will be a problem of insufficient development tolerance; as for the organic solvent (E) of the photosensitive thermosetting type composition, the purpose is to adjust the solid content of the green paint.

使塗膜預烤後之厚度能控制在需要之範圍。【圖式簡單說明】第1圖本發明之實施流程圖。【主要元件符號說明】樹脂組成物之製備......... 感光熱固型組成物之製備...... 感光熱固型組成物之硬化製程···· 【圖表簡單說明】表1一1，本發明進行樹脂合成。表1~ 2，習知技術進行樹脂合成。表2—1，本發明主劑之組成。 27 1291596 表2 — 2，本發明硬化劑之組成。表2 — 3，習知技術主劑之組成。表2 — 4，習知技術硬化劑之組成。表3 ’綠漆性質測試結果。The thickness of the pre-baked film can be controlled to the extent required. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the implementation of the present invention. [Description of main component symbols] Preparation of resin composition......... Preparation of photosensitive thermosetting composition... Hardening process of photosensitive thermosetting composition···· Description] In Table 1-1, the present invention performs resin synthesis. Tables 1 to 2, conventional techniques for resin synthesis. Table 2-1, the composition of the main agent of the present invention. 27 1291596 Table 2-2, the composition of the hardener of the present invention. Table 2 - 3, the composition of the prior art main agent. Table 2 - 4, the composition of the prior art hardener. Table 3 'Green paint properties test results.

28 1291596 表1 -1 本發明進行樹脂合成實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 擐氬樹脂 (莫耳當量） 2.0 2.0 2.0 2.0 2.0 2.0 丙烯酸 (莫耳） 1.80 1.82 1.86 1.88 1.90 1.90 飽和或不飽和雙酸 (莫耳）反一丁烯二酸 (0.10) 己二酸 (0.09) 庚二酸 (0.07) 癸二酸 (0.06) Thapsic acid (0.05) 對苯二甲酸 (0.10) 酸酐 (莫耳） 0.86 0.90 0.92 0.94 1.00 1.00 環氧樹脂/ 丙烯酸/ 飽和或不飽和雙酸之莫耳比 1:0.9:0.05 1:0.91:0.045 1:0.93:0.035 1:0.94:0.03 1:0.95:0.025 1:0.95:0.05 酸價 (mgKOH/g) 45.0 48.0 44.0 46.0 43.0 48.0 29 1291596 表1 — 2 習知技術進行樹脂合成28 1291596 Table 1-1 The present invention was subjected to resin synthesis Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Helium argon resin (mole equivalent) 2.0 2.0 2.0 2.0 2.0 2.0 Acrylic (mole) 1.80 1.82 1.86 1.88 1.90 1.90 saturated or unsaturated diacid (mole) anti-monomethic acid (0.10) adipic acid (0.09) pimelic acid (0.07) sebacic acid (0.06) Thapsic acid (0.05) terephthalic acid (0.10) Anhydride (mole) 0.86 0.90 0.92 0.94 1.00 1.00 Epoxy resin / acrylic acid / molar ratio of saturated or unsaturated diacid 1:0.9:0.05 1:0.91:0.045 1:0.93:0.035 1:0.94:0.03 1:0.95:0.025 1:0.95:0.05 Acid value (mgKOH/g) 45.0 48.0 44.0 46.0 43.0 48.0 29 1291596 Table 1-2 Conventional techniques for resin synthesis

實施例7 實施例8 實施例9 環氧樹脂 (莫耳當量） 2.0 2.0 2.0 丙烯酸 (莫耳） 1.80 2.40 1.90 飽和或不飽和雙酸 — — — (莫耳） — 一 — 酸酐 (莫耳） 0.70 0.92 1.50 環氧樹脂/ 丙烯酸/ 飽和或不飽和雙酸 1:0.9:0 1:1.2:0 1:0.95:0 莫耳比酸價 (mgKOH/g) 31.0 112.0 76.0Example 7 Example 8 Example 9 Epoxy Resin (Mole Equivalent) 2.0 2.0 2.0 Acrylic (Molar) 1.80 2.40 1.90 Saturated or Unsaturated Diacid - (Mole) - I - Anhydride (Moule) 0.70 0.92 1.50 Epoxy Resin / Acrylic Acid / Saturated or Unsaturated Diacid 1:0.9:0 1:1.2:0 1:0.95:0 Mohric Acid Price (mgKOH/g) 31.0 112.0 76.0

30 1291596 表2 — 1 本發明進行主劑之製備主劑組成 mwn 〇 mwn i mwn 2 mwn 3 實酬14實酬15 ◎樹脂主體實施例1 mm^2 mmi3 mmu *S_6 34.0 34.0 38.0 35.0 32.0 30.0 ◎感光單體/感光寡聚物 -Dipentaerythritol hexaacrylate 3.0 6.0 5.0 -Pentaerythritol tetraacrylate 11.0 — 8.0 — 7.0 7.0 -Dipentaerythritol pentaacrylate — 5.0 — — — — -Trimethylolpropane triacrylate — — 4.0 2.0 — 3.0 -Epoxy acrylate — — — 4.0 3.0 4.0 ◎其他 -DC350 (Deuchem Trading Co )(平坦劑） 1.0 1.0 1.0 1.0 1.0 1.0 -KS-66 (消泡劑） 1.5 1.5 1.5 1.5 1.5 1.5 -Phthalocyanine green (顏料） 1.7 1.7 1.7 1.7 1.7 1.7 •硫酸鋇 20.0 20.0 21.0 23.0 25.0 20.0 -Aerosil 200 (二氧化砂） 1.0 1.0 1.0 1.0 1.0 1.0 -Aerosil972(二氧化砂） 1.2 1.2 1.2 1.2 1.2 1.2 -Dicyandiamide (衡携J) 1.5 1.5 1.5 1.5 1.5 1.5 滑石 4.0 4.0 4.0 4.0 4.0 4.0 -對苯二酚 0.1 0.1 0.1 0.1 0.1 0.1 ◎溶劑 31 1291596 -Carbitol acetate 10.0 9.5 10.0 11.0 11.5 10.0 -Solvent Naphtha 150 10.0 9.5 10.0 11.0 11.5 10.0 合計 100.0 100.0 100.0 100.0 100.0 100.030 1291596 Table 2 - 1 Preparation of the main agent of the present invention The composition of the main agent is mwn 〇mwn i mwn 2 mwn 3 Remuneration 14 Remuneration 15 ◎ Resin main body Example 1 mm^2 mmi3 mmu *S_6 34.0 34.0 38.0 35.0 32.0 30.0 ◎ Photosensitive monomer/photosensitive oligomer-Dipentaerythritol hexaacrylate 3.0 6.0 5.0 -Pentaerythritol tetraacrylate 11.0 — 8.0 — 7.0 7.0 -Dipentaerythritol pentaacrylate — 5.0 — — — —Trimethylolpropane triacrylate — — 4.0 2.0 — 3.0 —Epoxy acrylate — — — 4.0 3.0 4.0 ◎Others-DC350 (Deuchem Trading Co) (flattening agent) 1.0 1.0 1.0 1.0 1.0 1.0 -KS-66 (antifoaming agent) 1.5 1.5 1.5 1.5 1.5 1.5 -Phthalocyanine green (pigment) 1.7 1.7 1.7 1.7 1.7 1.7 • Barium sulfate 20.0 20.0 21.0 23.0 25.0 20.0 - Aerosil 200 (sand dioxide) 1.0 1.0 1.0 1.0 1.0 1.0 - Aerosil972 (sand dioxide) 1.2 1.2 1.2 1.2 1.2 1.2 -Dicyandiamide 1.5 1.5 1.5 1.5 1.5 1.5 Talc 4.0 4.0 4.0 4.0 4.0 4.0 - hydroquinone 0.1 0.1 0.1 0.1 0.1 0.1 ◎ Solvent 31 1291596 - Carbitol acetate 10.0 9.5 10.0 11. 0 11.5 10.0 -Solvent Naphtha 150 10.0 9.5 10.0 11.0 11.5 10.0 Total 100.0 100.0 100.0 100.0 100.0 100.0

32 1291596 本發明進行硬化劑之製備硬化劑組成 mwn 〇 mwn 1 mwn 2 mwn 3 實 mn 4實酬15 ◎光起始劑 -2-Methy 1 -1 -(4-(methylt hio)phenyl)-2"morpholin opropane-l-one 4.0 3.0 3.5 4.2 3.8 4.0 -Isopropylthioxanthone 1.0 0.8 0.8 0.9 0.7 1.0 ◎環氧化合物甲_氧樹脂 16.0a 20.0b 17.7C 10.0d 8.0e 10.0a 麵氧樹脂 — — — 8.0f 11.0f 6.0f ◎其他 -硫酸鋇 — — 3.0 — 3.0 — ◎溶劑 -Carbitol acetate 3.8 2.4 4.0 3.8 4.2 3.8 -Solvent Naphtha 150 3.8 2.4 4.0 3.8 4.2 3.8 合計 28.6 28.6 32.9 30.7 34.9 28.6 a軟化點：92.5〇C，環氧當量 :230 ; b 軟化點：82°C ’環氧當量: 198 ; c軟化點 :80°C，環氧當量：215 d軟化點：81°C，環氧當量：210 ; < ϊ軟化點：76°C，環氧當量：202 ; f半固體，環氧當量: 180。 a〜f :可溶於配方溶劑之環氧樹脂。32 1291596 The present invention is a hardener preparation for the preparation of a hardener composition mwn 〇mwn 1 mwn 2 mwn 3 real mn 4 remuneration 15 ◎ light initiator -2-Methy 1 -1 -(4-(methylt hio)phenyl)-2&quot ;morpholin opropane-l-one 4.0 3.0 3.5 4.2 3.8 4.0 -Isopropylthioxanthone 1.0 0.8 0.8 0.9 0.7 1.0 ◎Epoxy compound A_oxy resin 16.0a 20.0b 17.7C 10.0d 8.0e 10.0a Oxygen resin — — — 8.0f 11.0 f 6.0f ◎ Other - barium sulfate - 3.0 - 3.0 - ◎ Solvent - Carbitol acetate 3.8 2.4 4.0 3.8 4.2 3.8 - Solvent Naphtha 150 3.8 2.4 4.0 3.8 4.2 3.8 Total 28.6 28.6 32.9 30.7 34.9 28.6 a Softening point: 92.5 〇C, Epoxy equivalent: 230; b Softening point: 82 ° C 'epoxy equivalent: 198 ; c softening point: 80 ° C, epoxy equivalent: 215 d softening point: 81 ° C, epoxy equivalent: 210; < Softening point: 76 ° C, epoxy equivalent: 202; f semi-solid, epoxy equivalent: 180. a~f : Epoxy resin soluble in the formulation solvent.

33 1291596 表2 習知技術進行主劑之製備主劑組成實麵1 6實腑U1 7實删1 8實删1 9 列7 38.0 35.0 32.0 ◎樹脂主體 ◎感光單體/感光寡聚物 -Dipentaerythritol hexaacrylate -Pentaerythritol tetraacrylate -Dipentaerythritol pentaacrylate -Trimethylolpropane triacrylate -Epoxy acrylate ◎其他 -DC350 (DeuchemTradingCo)(平坦劑） -KS-66 (消泡劑） -Phthalocyanine green (顏料） -硫酸鋇 -Aerosil200 (二氧化砂） -Aerosil 972 (二氧化石夕） -Dicyandiamide (催化劑） -滑石 -對苯二酚 ◎溶劑 -Carbitol acetate -Solvent Naphtha 150 合計列7 30.0 6.0 — 5.0 — — 8.0 — 7.0 5.0 — — 一 — 4.0 2.0 — — — 4.0 3.0 1.0 1.0 1.0 1.0 1.5 1.5 1.5 1.5 1.7 1.7 1.7 1.7 20.0 21.0 23.0 25.0 1.0 1.0 1.0 1.0 1.2 1.2 1.2 1.2 1.5 1.5 1.5 1.5 4.0 4.0 4.0 4.0 0.1 0.1 0.1 0.1 9.5 10.0 11.0 11.5 9.5 10.0 11.0 11.5 100.0 100.0 100.0 100.0 34 J291596 表2 - 4 習知技術進行硬化劑之製備硬化劑組成實施例1 6實删1 7實施例1 8實删1 9 ◎光起始劑 2-Methy 1 -1 -((methylthio)pheny l)-2-morpholinopr opane-l-one 3.0 3.5 4.2 3.8 -Isopropylthioxanthone 0.8 0.8 0.9 0.7 ◎環氧化合物 • triglycidyl terephthalate 樹脂g 20.0 17.7 10.0 8.0 -bixylenol epoxy 樹脂 h 一 — 8.0 11.0 ◎其他 -硫酸鋇 — 3.0 — 3.0 ◎溶劑 -Carbitol acetate 2.4 4.0 3.8 4.2 -Solvent Naphtha 150 2.4 4.0 3.8 4.2 合計 28.6 32.9 30.7 34.9 g及h :不溶於配方溶劑之環氧樹脂 35 1291596 表3 綠漆性質測試結果33 1291596 Table 2 Preparation of the main agent by the prior art The composition of the main agent is solid 1 6 腑 U1 7 real deletion 1 8 real deletion 1 9 column 7 38.0 35.0 32.0 ◎ resin body ◎ photoreceptor / photo oligo - Dipentaerythritol Hexaacrylate -Pentaerythritol tetraacrylate -Dipentaerythritol pentaacrylate -Trimethylolpropane triacrylate -Epoxy acrylate ◎Other -DC350 (DeuchemTradingCo) (flat agent) -KS-66 (antifoaming agent) -Phthalocyanine green (pigment) -Barium sulfate-Aerosil200 (sand dioxide) Aerosil 972 (Diachrome eve) - Dicyandiamide (catalyst) - talc - hydroquinone ◎ Solvent - Carbitol acetate - Solvent Naphtha 150 Total column 7 30.0 6.0 — 5.0 — — 8.0 — 7.0 5.0 — — A — 4.0 2.0 — — — 4.0 3.0 1.0 1.0 1.0 1.0 1.5 1.5 1.5 1.5 1.7 1.7 1.7 1.7 20.0 21.0 23.0 25.0 1.0 1.0 1.0 1.0 1.2 1.2 1.2 1.2 1.5 1.5 1.5 1.5 4.0 4.0 4.0 4.0 0.1 0.1 0.1 0.1 9.5 10.0 11.0 11.5 9.5 10.0 11.0 11.5 100.0 100.0 100.0 100.0 34 J291596 Table 2 - 4 Conventional techniques for preparing hardeners Composition of hardeners Example 1 6 Delete 1 7 Example 1 8 Delete 1 9 ◎ Photoinitiator 2-Methy 1 -1 -((methylthio)pheny l)-2-morpholinopr opane-l-one 3.0 3.5 4.2 3.8 -Isopropylthioxanthone 0.8 0.8 0.9 0.7 ◎ Epoxy compound • triglycidyl terephthalate resin g 20.0 17.7 10.0 8.0 -bixylenol epoxy resin h - 8.0 11.0 ◎ other - barium sulfate - 3.0 - 3.0 ◎ solvent - Carbitol acetate 2.4 4.0 3.8 4.2 - Solvent Naphtha 150 2.4 4.0 3.8 4.2 Total 28.6 32.9 30.7 34.9 g and h: Epoxy resin insoluble in formula solvent 35 1291596 Table 3 Green paint properties test results

10 11 12 13 14 15 16 17 18 1910 11 12 13 14 15 16 17 18 19

80〇C*30min 〇〇〇〇〇〇〇〇〇〇 80〇C*50min 〇〇〇〇〇〇 Δ 〇〇 Δ 80〇C*70min 〇〇 Δ 〇 Δ 〇 X 〇〇 X 驟須容度 48hr 〇〇〇〇〇〇 Δ 〇〇 Δ 72hr 〇〇 Δ 〇 Δ 〇 X 〇〇 X 〇〇〇〇〇〇 ο 〇〇〇讎臓〇〇〇〇〇〇〇 Δ Δ 〇〇〇〇〇〇〇〇 X X 〇〇：表顯影完全，線路之間無殘渣（Scum)或露足（Foot)。 △:表顯影有部份缺陷，線路之間有輕微殘渣或露足。 X:表完全無線路圖案出現。 3680〇C*30min 〇〇〇〇〇〇〇〇〇〇80〇C*50min 〇〇〇〇〇〇Δ 〇〇Δ 80〇C*70min 〇〇Δ 〇Δ 〇X 〇〇X Step capacity 48hr 〇〇〇〇〇〇Δ 〇〇Δ 72hr 〇〇Δ 〇Δ 〇X 〇〇X 〇〇〇〇〇〇ο 〇〇〇雠臓〇〇〇〇〇〇〇Δ Δ 〇〇〇〇〇〇〇〇 XX 〇〇: The table is fully developed, and there is no residue (Scum) or Foot (Foot) between the lines. △: The surface development has partial defects, and there is slight residue or exposure between the lines. X: The table shows the complete wireless road pattern. 36

Claims

Please patent garden: 1. A photosensitive thermosetting composition comprising: (A) a resin composition obtained by reacting the following composition: (a) an epoxy containing at least one soil oxygen a compound; (b) an unsaturated monoacid having at least two double bonds; (c) a saturated or unsaturated diacid having the following structure: HOOC-R-COOH ^ R : c1 to C12, which may be a fatty acid or an aromatic; (d) a saturated or unsaturated acid anhydride; an epoxy compound (a) having at least one epoxy group, an unsaturated monoacid (b) having at least 3 double bonds, and a saturated or unsaturated diacid (c) The ratio of the ears is 1: 〇·09~〇· 95 : 0· 025~0· 05, and the obtained resin composition has an acid value of 40 to 49 mgKOH/g; (B) at least one photopolymerizable photosensitive monomer and/or Photosensitive oligomer; (C) at least one photoinitiator; (D) at least one epoxy compound containing at least two epoxy groups, which may be solid, semi-solid or liquid at ordinary temperature, which is soluble in organic solvents (E) at least one organic solvent; wherein the resin composition (A) content is between 30 and 50 wt%, photopolymerizable photosensitive The content of the body and or the photosensitive oligomer (B) is between 5 and 20% by weight. The content of the photoinitiator (c) is between 2·〇6·〇wt%, and the epoxy containing at least two epoxy groups. The compound (D) content is from 1 〇 to 20 wt%, and the 37 1291596 organic solvent (E) content is from 25 to 40% by weight, and the sum of (A) to (E) is 100% by weight. 2. The photosensitive thermosetting composition according to claim 1, wherein the epoxy compound (a) having at least two epoxy groups is an epoxy resin of a phenol or a cresol, and is at a normal temperature. Used as a solid, semi-solid, liquid, or solid/semi-solid/liquid mixture. 3. The photosensitive thermosetting composition according to claim 1, wherein the unsaturated monobasic acid (b) having at least two double bonds is acrylic acid or methyl acetoacetate. 4. The photosensitive thermosetting composition according to claim 1, wherein the saturated or unsaturated diacid (c) may be at least one selected from the group consisting of fumaric acid. , Maleic acid, 〇xaiacetic acid, Adipic acid and its derivatives, Glutaric acid and its derivatives, Succinic acid ), Malonic acid and its derivatives, pimeic acid, 1,8-suberic acid, Azelaic acid, Sebacic acid, Terephthalic acid and its derivatives, isophthalic acid (IS0phthalic deduction) and its derivatives. 5. The photosensitive thermosetting composition according to claim 1, wherein the saturated or unsaturated acid anhydride (d) in 38 J291596 may be at least one selected from the group consisting of: hexahydrophthalic acid An anhydride) and its derivatives, anhydrous tetrahydrophtalic acid anhydride and its derivatives or anhydrous phthalic acid anhydride and its derivatives. 6. The photosensitive thermosetting composition according to claim 1, wherein the photopolymerizable photosensitive monomer and or the photosensitive oligomer (B) may be at least one selected from the group consisting of difunctional groups. Aliphatic or benzene ring-containing unsaturated double bond photosensitive monomer, trifunctional aliphatic or benzene ring-containing unsaturated double bond photosensitive monomer, tetrafunctional aliphatic or benzene ring-containing unsaturated double bond photosensitive monomer , pentafunctional aliphatic or benzene ring-containing unsaturated double bond photosensitive monomer, hexafunctional aliphatic or benzene ring-containing unsaturated double bond photosensitive monomer, other polyfunctional acrylate oligomer (epoxy acrylate) ) or other polyfunctional urethane acrylate. 7. The photosensitive thermosetting composition according to claim 1, wherein the photoinitiator (C) may be at least one selected from the group consisting of isopropylthiodibenzopyrene (ISOpr) 〇pylthioxanthone), 2-mercapto~1~[4-(indolylthio)benzene]-2-(1,4-oxazine)-propyl-1-one (2-Methyl-1-() (methylthio) pheny 1)-2i〇rphol inopropane-1-one). 8) The photosensitive thermosetting composition according to item i of the patent application, wherein the epoxy compound (D) of 39 1291596 == mercapto group may be selected from the group consisting of phenolic epoxy resin, Phenolic resin, double epoxy resin, bismuth-containing epoxy resin at room temperature: they can be _, semi- or liquid, so that (4) can be solid, semi-solid, liquid 'or _ / half _ / (d) mixed use. 9. The photosensitive thermosetting composition according to claim 2, wherein the organic solvent (E) is at least one selected from the group consisting of a ketone, an ether, an alcohol, an ester or an oil. Solvents. 10 · The photosensitive thermosetting composition as described in the patent application, the object formed by the hardening, including the τ column urging process, the photosensitive thermosetting composition is coated on the substrate, and then baked. Bake dry, expose, develop, and finally use ultraviolet light or heat to obtain a hardened substance. 11 species of tree sorghum are obtained by reacting the following components: (a) an epoxy compound containing at least one epoxy group; (b) an unsaturated monoacid containing at least one double bond; a saturated or unsaturated diacid having the following structure: HOOC-R-COOH R : C1 to C12, which may be a fatty acid or an aromatic; (d) a saturated or unsaturated acid anhydride; an epoxy having at least two epoxy groups The molar ratio of the compound (a), the unsaturated monoacid (b) containing at least two double bonds, and the saturated or unsaturated diacid (c) 1291596 is 1: 〇· 〇9~〇· 95 · · 0· 025~〇· 〇5 The fat composition has an acid value of 40 to 49 mgKOH/g. 1 2 . The composition of the tree according to the scope of claim 2, wherein at least two Wei-based compounds (a) are _ or methyl epoxide, which may be solid or semi-solid at normal temperature. , liquid, or a mixture of solid / semi-solid / liquid. 1 3 · If you apply for a patent scope! The composition of the tree of the present invention, wherein the unsaturated monobasic acid having at least two double bonds (b) is acrylic acid or mercapto acrylic acid 0 1 4 · as described in claim 1 of the patent scope a fat composition, wherein the saturated or unsaturated diacid (c) may be at least one selected from the group consisting of: fumaric acid, maleic acid, and acid acid acetic acid. (Oxalacetic acid), Adipic acid and its bamboo organisms, Glutaric acid and its derivatives, Succinic acid, Malic acid and its derivatives, Geng Pimelic acid, 1,8-suberic acid, Azelaic acid, Sebacic acid, Terephthalic acid and its derivatives, isophthalic acid Isophthalic acid and its derivatives. The resin composition according to claim 11, wherein the saturated or unsaturated acid anhydride (d) may be at least 41 1291596 selected from the following compounds: hexahydroplrthalic acid anhydride And derivatives thereof, anhydrous tetrahydrophtalic acid anhydride and derivatives thereof or phthalic acid anhydride and derivatives thereof.

42 1291596 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: