TW538092B - Photo/thermo-curable resin composition - Google Patents

Abstract

The present invention discloses a photo-curable and thermo-curable resin composition which can be used as paints, inks, photoresists or photo-sensitive insulating films for printed circuit boards. The composition comprises: (a) 5 to 60 wt% of a photosensitive resin; (b) 5 to 50 wt% of a reactive diluent; (c) 0.01 to 20 wt% of a modified curcumin having at least two ethy1enica11y unsaturated bonds and at least two carboxyl groups in its molecule; (d) 0.1 to 15 wt% of a photo-initiator; and (e) 0.5 to 40 wt% of a thermo-curable resin. The resin composition according to the invention excels in resistance to heat, humidity, electroplating, and electroless plating. The resin composition is also advantageous in its high developing speed and is particularly suitable for use as solder resist inks in printed circuit boards.

Description

Field of the Invention: The present invention is applied to coatings, and is particularly suitable for printing inks, and is a thermosetting photosensitive resin composition for printing on printed circuits. Photoresist for circuit boards, photosensitive insulation layers, etc. paint. BACKGROUND OF THE INVENTION In recent years, printed support can be highly dense, and the surface protection coating of small surface materials (ink). Due to solder heat resistance, developing temperature and high humidity, the current demand is for 'the present circuit board to be all-inclusive.' The green color that requires physical properties is the workability, high speed, and other properties. It is clear. The needle is an indispensable main part to provide the main electronic products for the installation and interconnection of electronic components. . As electronic products are moving towards thin, light, short, portable, and high-power development 'and electronic components have a high number of 丨 / 0, the technology for fine-grained printed circuit boards must be continuously improved, and the demand is relatively increased. Among them, it is applied to the surface paint of printed circuit boards (also known as solder resist photoresist, s ο 1 derresist and application conditions are more stringent, in addition to the original insulation, hardness, chemical resistance and other physical properties, it must also have high resolution, resistance The green paint with electrolytic plating, non-electrolytic plating resistance, and high resistance to 0 has been unable to achieve these high functional physical properties, and the above problems must be improved. Known skills: ^ This patent publication gazette No. 1 1-21 327 discloses Zhiguang Shiyue Yueyue said, it is served by mounting epoxy resin / (meth) acrylic acid and improving its secrets first. Among them, the monocarboxylic acid compound% Xin Chengcheng has eight or more, which can be light-hardened and unsaturated.

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The improvement of the light time is based on the fact that the photocuring property of the composition is not greatly saved by the exposure method. The amount of exposure is small, but it is highly effective and has no effect on the adhesion and development speed. It has the function of the composition of η I two-resistance ink disclosed in Japanese Patent Application Laid-open No. 10-274849. However, the development speed is slow and the high-performance physical properties such as high temperature and humidity resistance are poor. Light tree r (eight / meat ^ and kai kai kaihei 5-20202332) The composition contains a photosensitive resin with a molecular weight of less than 100. It refers to the dryness of electricity:. The nature is "worry" but the invention is summarized: Provide a heat hardening Photosensitive resin constitutes a photoresist for printed circuit boards, and is one of the objects of the present invention to be applied to paints, oil-edge layers, etc. Another object of the present invention is to provide a photoresist composition for printing. Circuit board The third object of the present invention is to provide a fast solder resist photoresist ink (green paint). A green paint with a highly functional heat-curable surface protective coating film. A high-resolution and developed object of the present invention The fourth is to provide lacquer), which has excellent resistance to high temperature and high humidity electrolytic plating. ^ A variety of solder resist photoresist inks (green, electrolytic plating resistance and non-resistance). · R, c Support a thermosetting photosensitive resin composition, Wang Yaobao 3 · (a) 5 to 60 weight percent white resin; (b) 5 to 5 0

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^ ^ Percentage of reactive diluent; (c). 0-20 weight percent of ginger = CUrCUmin. Modified product, which has at least two unsaturated double bonds and two wei acid groups, (d) 〇1 ～ η 番 夏 石 八 卜 'r " η "a photoinitiator of a weight ratio of nondan; and (e) a thermosetting resin of 0.5 to 40% by weight. In addition, other additives such as fillers and colorants can be added. The main feature of the present invention is the addition of the component (c) curcumin to shellfish, which can be formed by the reaction of the amount of kappa and acid anhydride, and its structural characteristics are of great help to the physical properties required for green paint. The resin composition obtained according to the present invention has high temperature and high humidity resistance (121,100% RH, 100hr), electrolytic plating resistance (60 ° C, pH = 3,3min), and electroless plating resistance. (80 ° C, ρΗ = 4.55, 30min), fast development (10sec) and other characteristics, very suitable as a green paint for the protective coating film on the printed circuit board surface. Detailed description of the invention: The thermosetting photosensitive resin composition according to the present invention, wherein the component (a) is a photosensitive resin. The photosensitive resin used in the present invention is preferably an epoxy resin modified product having an ethylenically unsaturated bond and a carboxyl group. Such photosensitive resins as those skilled in the art can be made by reacting epoxy resin, unsaturated monocarboxy 1 ic acid and acid anhydride to form suitable epoxy resins for synthesizing such photosensitive resins. $ Bi sphenol type epoxy resin, novolac epoxy resin; phenol novo 1 ac type epoxy resin, cresol novolac type resin, naphthalene epoxy resin

538092 5. Description of the invention (4) (naphthalene type epoxy resin), polycyclic epoxy resin, glycidy 1 ester resin, glycidyl 1 am ne resin, containing N, S 0 atom heterocyclic epoxy resin and halogenated epoxy resin. Unsaturated monocarboxylic acids suitable for the synthesis of photosensitive resins include: acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, 2-methacrylic acid 2-methacryloyloxyethyl succinate, 2-acryloyyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate Hydrogen Skate (2-methacryloyloxyethyl hexahydrophthalate), 2-acryloyloxyethyl hexahydrophthalate (2-acry1oyloxyethy1 hexahydrophtha1 ate), 2-methylpropanoyloxyethyl hexahydrophthalate methacryloyloxyethyl phthalate), and 2-acryloyloxyethyl phthalate (2-acry1oy1oxyethy 1 phtha1 ate). Of these, (meth) acrylic acid is preferred. The anhydrides that can be used to synthesize photosensitive resins include: maleic anhydride (ma 1 eic anhydride), phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride (methyl tetrahydrophthalic anhydride), ethyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride

0424-6434TWF; 02900011; Esmond.ptd page 9 538092 5. Description of the invention (5) (ethylhexahydrophthalic anhydride), succinic anhydride, and itaconic anhydr i de. The acid value of the photosensitive resin (a) is preferably in the range of 30 to 300 mgKOH / g. Within this range, the solder resist photoresist is capable of being removed by lye and has good chemical resistance. The weight average molecular weight of the photosensitive resin is generally between 4,000 to 50,000, g / mQi, and preferably between 8,000 to 50,000. According to the thermosetting photosensitive resin composition of the present invention, the component (b) is a reactive diluent. The reactive diluent used in the present invention is preferably a reactive diluent containing unsaturated double bonds, such as an acrylic monomer having two or more unsaturated double bonds. Suitable reactive diluents are, for example: 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Propionate (1, 6-hexanediol di (meth) acrylate), neopentylglycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (Polyethyleneglycol di (meth) acrylate), neopentylglycol di (meth) acrylate adipate di (meth) acrylate, neopentylethylene glycol di (meth) acrylate carboxyl Neopentylglycol di (meth) acry1 ate hydroxypivalate, dicyclopentadienyl di (meth) acrylate, caprolacton modified bis (a) Group) dicyclopentadienyl acrylate, allyl cyclohexyl di (meth) acrylate

0424-6434TWF; 02900011; Esmond.ptd Page 10 538092 V. Description of the Invention (6) di (meth) acrylate, isocyanurate di (meth) acrylate, trimethodine Trimethylol propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentyl modified by propionic acid Erythritol tri (meth) acrylate, penterythritol tri (meth) acrylate, propylene oxide modified trimethyl propyl tri (meth) acrylate, tri (propylene oxide) Tris (acryloxyethyl) isocyanurate, propionic acid modified dipenterythritol penta (fluorenyl) acrylate, dipenterythritol hexa (meth) acrylate SI ° according to the invention The thermosetting photosensitive resin composition, the component (c) is a curcumin modified product, which has at least two unsaturated double bonds and at least two acidogenic groups. In the present invention, curcumin (cur cum i η; 1,7-bis (4-hydroxymethoxyphenyl) -1,6-heptadiene-3, 5-di one) is used as the main chemical structure, and acid anhydride is introduced for modification. For example, curcumin can be reacted with tetrahydrophthalic anhydride to form a curcumin modified product, as shown in the following reaction formula:

0424-6434TWF; 02900011; Esmond.ptd Page 11 538092 V. Description of Invention (7) 〇

〇 cummin tetrahydrophthalic anhydride

Curcumin and other suitable anhydrides for modification include: maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, Ethyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, succinic anhydride, it aeon ic anhydride ), Alicyclic anhydride, 3,3 ', 4,4'-benzophenone tetraacid dianhydride (3,3', 4,4 '-benzophenone

〇424_6434TWF; 02900011; Esmond.ptd Page 12 538092 V. Description of the invention (8) tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'_diphenyltetracarboxylic acid di Anhydride (3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride), 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2,2' -bis- (3 , 4-dicarboxyphenyl) hexafluoropropane dianhydride), 4,4'-oxydiphthalic anhydride, 3,3 ', 4,4'-diphenylsyringate dianhydride (3 , 3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydr ide), 5- (2,5-dioxotetrahydro) -3-methyl-3 -cyclohexene-1,2-diacid anhydride (5 — ( 2,5 — dioxotetrahydrol) — 3 —meihy1 — 3 —cyclohexene — 1, 2-dicarboxylic anhydride, ethylene glycol bis (anhydro-trimellitate). In the present invention, one or more acid anhydrides can be used for modification. The acid value of the curcumin modifier (c) is preferably between 30 and 400 mgKOH / g. The curcumin modified product used in the present invention has the following characteristics: (a) Since it has a benzene ring structure, the heat resistance and adhesiveness of the resin composition can be greatly improved. … (B) It has two or more unsaturated double bonds, which can be bonded to other unsaturated double bond-containing compounds in the product by light hardening to increase the composition. (C) It has two or more The development speed of the substrate can be increased by thermal curing and increase the crosslinking density. (d) Comprehensive (a), (b), (c) can increase high resistance, can promote resin composition, high temperature and humidity resistance, and electrolytic resistance

538092 5. Description of the invention (9) High functional physical properties such as electroplating property and resistance to electroless plating. It is known that the component (d) of the thermosetting photosensitive resin composition of the present invention is a photo-initiator, and can generate radicals upon irradiation with light. Photoinitiators suitable for use in the present invention include, for example, benzoin, benzoin alkyl ether, benzil, ketals, and phenethyl S with compounds (acetophenones), benzophenone, 4, 4'-dimethyl-amino-dibenzophenone (4,4'-dimethyl-amin〇-benzophenone), Ishidai Xanthenes are < thioxanthones and morphine ino-propanone. In the thermosetting photosensitive resin composition according to the present invention, the component (e) is a thermosetting resin. A preferred thermosetting resin is a bad oxygen resin ', especially an oxygen generating resin having two or more epoxy groups in one molecule. The epoxy resins suitable for the present invention include: bisphenol type epoxy resin, phenol novo 1ac type epoxy resin, and cresol novo lac type epoxy resin) Formaldehyde epoxy resin, polycyclic epoxy resin, glycid idyl ester resin, glycid idyl amine resin, heterocyclic epoxy resin and toothed ring & amp Shi Yuezhi (halogenatedepoxyresin) and so on. ^ In the resin composition of the present invention, the 'component (a) photosensitive resin accounts for about 5 to 60% by weight' of the component (b) the reactive diluent accounts for about $ ~ 0, and the content of the component (c) is flavin. The modified product accounts for about 0.011% by weight. (D) The photoinitiator accounts for 0.15% by weight; the component (e) ^ hardened ^ resin accounts for about 0.5% to 40% by weight. Preferably, (a) the photosensitive resin accounts for about &

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I " weight. Li & hundred · ^ ratio, the component (b) reactive diluent accounts for about 10 ~ 40 weight Shiji irn 4 · /) curcumin modified matter accounts for about 0.15% by weight; f agent about Divination is 10% by weight; the composition ⑷ thermosetting tree is about 10 ~ 30% by weight. In addition to the above main components, the conventional thermosetting photosensitive resin composition of the present invention can be added with other conventional additives such as heat stabilizers, antioxidants, light stabilizers, lubricants, defoamers, flat materials, and pigments. In order to make the above and other objects, features, and advantages of the present invention more obvious and easy, it is specifically described below as a preferred embodiment, and described in detail as follows: Example Synthesis Example 1 · 74 g (0.2 mole) of curcumin, 270 g of diethylene glycol monomethyl ether acetate, λ tetrahydrophthalic anhydride (6.0 g, 0.4 mole), and azaquinone (Hydroqu inone) 0.2 g was placed in a reactor, the temperature was raised to 110 ° C., and the reaction was performed for 3 hours to obtain a curcumin modified product (c-1). Curcumin modified product synthesis example 2: 39.2g (0.4mole) of maleic anhydride was substituted for the tetrahydrogalanic anhydride of curcumin modified product synthesis example 1 to obtain a curcumin modified product (c-2). Curcumin modified product synthesis example 3: pyromellitic dianhydride

0424-6434TWF; 02900011; Esmond.ptd p.15 538092 V. Description of the invention (11) 21 · 8g (〇 · lm〇ie) and tetrahydrophthalic anhydride (30 · 4g (〇 · 2mole) instead of curcumin 5L of acetic anhydride 'of modified product synthesis example 1 to obtain curcumin modified product (c-3). Curcumin Modified Synthesis of U: Utilizing 3,3,4,4'-diphenyltetracarboxylic dianhydride (3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride) 29g (0.2mole) and Tetrahydrogen Anhydride 30.4 g (0.2 mole) was substituted for the tetrahydrophthalic anhydride of Synthesis Example 1 of the curcumin modified product to obtain a curcumin modified product (c-4). Photosensitive resin synthesis example 1: 60 g of cresol novolac type epoxy resin CNE-200 (manufactured by Changchun, epoxy equivalent = 200) and diethylene glycol monoethyl ether acetate ) 75g was placed in a reactor, dissolved at 60 ° C, 21.7g acrylic acid ((K3 equivalent), hydroqui none 0.09g 'triphenylphosphine 0.3g, 90 ° Reaction at C until the acid value approaches 0. Finally, 45.6 g (0.3 equivalent) of tetrahydrophthalic anhydride is added, and the reaction is 3111 'at 110 °° 120 °° to obtain a photosensitive resin (^ -1). Reactive dilution Synthesis Example 1: Dipentaerythritol pentaacrylate 52.4 g (0.1 equivalent), tetrahydrophthalic anhydride I5.2 g (0.1 equivalent), hydroquinone 0.06 g, and three 26 g of phenylphosphine was placed in a reactor, dissolved at 80 ° C for 1 hr, and reacted at 105 ° C for 32 hr to obtain a reactive diluent (b-3). Examples 1-4: Thermal hardening Resin composition assistant

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V. Description of the invention (12) Mix and mix the chemicals and preparation amounts shown in Table 1. It was ground with a three-roll mill at normal temperature to disperse the composition. Comparative Example 3 ·· Heat-curing Photosensitive Fat Composition Composition_Production According to the chemicals and formulation amounts shown in Table 1, and according to the example ... A comparative example of a thermosetting photosensitive resin composition was prepared. Among them, the comparative list 丨 ύ composition does not add curcumin modified matter. 2 € Table 1: Formulation chart of photoresist ink composition

0424-6434TWF; 02900011; Esmond.ptd Page 17 538092 »\ V. Description of the invention (13) Note: bl: dipentaerythritol pentaacrylate b-2: dipentaerythritol pentaacrylate Acid g purpose (pentaerythritol triacrylate) d- 1: Irgacure90 7 (Ciba) d-2: isopropyl thioxanthone e- 1: CNE-20 0 (Changchun company, cresol novolac epoxy resin) e-2: EXA- 4700 (Dainippon Ink and Chemicals Co. Ltd., naphthalene-based epoxy resin) Test piece production: A thermosetting photosensitive resin composition was coated on a copper foil substrate at 80 °. 〇 Pre-bake 30 m i η, and wait for the substrate to cool after drying. The test piece was covered with a negative film containing a gray scale and a resolution pattern, and exposed with a UV exposure machine, and developed with a 1% NCO3 aqueous solution 'to observe the development time. Then wash the test piece with water and observe its grayscale and resolution. Finally, it was baked at 50 ° C for 60 minutes to harden it and test its insulation properties, resistance to electrolytic electricity and minerals', non-electrolytic recording performance, and financial bureau's temperature and humidity. The results are shown in Table 2. Judgment criteria for each test in the basin are described as follows: 干燥 Dryness with finger touch: Touch the test piece with your hand, the sticky hand is recorded as χ, and the sticky hand is recorded as 0. _ Development speed: Development is performed with 1% N & 2003 aqueous solution, and the time required for the complete removal of the recording light pattern is recorded. *

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Number 0 Observe the resolution graph, and record the minimum line width resolution / line spacing with clear pattern. By default, the surface resistance tester is placed on the test piece 'to test the coating film insulation, the initial value. The test piece was placed at 60 ° C, 90% RH, constant temperature and humidity for 2 hours, and the sample was taken out and wiped to dry, tested for insulation and recorded. Tick μ = / wetness (PreSSUre Coker test, PCT for short): 屮 In a pressure cooker (121 ° C, 2atm, 100% RH), take C after 100hrs ϋ / 1 ΐ nt I Grid adhesiveness test. Record the number of good cells in the hundred grids. C (there is no adhesion, 100/100 is excellent adhesion). 2. Electrical resistance and electroplating: After the test piece is processed by electrolytic electroplating and gold plating process, add 2 liters of adhesion test to record the number of cells that still have good adhesion in the 100 grid (0 / 1⑽ is 4 without adhesion, 1 0 0/1 0 0 is followed by excellent). Resistance to electroless plating: The test piece is treated with the electroless plating gold plating process =, and the adhesion test is performed to record the number of good cells in the hundred cells (0/100 is no adhesion, 1 0 0/1 0 0 is followed by excellent).

0424-6434TWF; 02900011; Esmond.ptd Page 19 538092 V. Description of the invention (15) Table 2: Physical property test results Examples of light beer ink composition Comparative example 1 2 3 4 1 2 Touch dryness 〇〇〇 〇 〇 〇 Color rendering speed (sec) 11 10 8 8 50 30 Gray Pl (21 steps) 8 9 9 8 10 9 Resolution (mils) 2 2 2 2 2 3 Insulation start value ΙχΙΟ13 ΙχΙΟ13 ΙχΙΟ13 ΙχΙΟ13 ΙχΙΟ13 ΙχΙΟ13 (Ω / Mouth) 601 90% EH, 960hr 2χ1012 2χ1012 ΙχΙΟ12 2χ1012 9χ10η 2χ1012 High temperature at full temperature PCT 100/100 100/100 100/100 100/100 90/100 92/100 Electrolytic plating resistance 100/100 100 / 100 100/100 100/100 98/100 100/100 Electroless plating resistance 100/100 100/100 100/100 100/100 95/100 95/100 According to the physical property test results in Table 2, it can be known that the heat curing of the present invention The photosensitive resin composition has good touch-drying properties, developing speed, resolution, insulation, electrolytic plating resistance, electroless plating resistance, and high temperature and humidity resistance. In contrast, the composition of Comparative Example 1 does not conform to The curcumin modified product of the present invention not only has a slow development speed, but also The physical properties such as high temperature and humidity resistance and resistance to electroless plating is also poor. Comparative Example 2 did not add the amount of flavin modified product of the present invention to the formulation, its development speed was still slow, and Cainan Wennan wettability and Caiwu electroless plating performance were not good. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications and retouching without departing from the spirit and scope of the present invention. Therefore, the present invention Protection

0424-6434TWF; 02900011; Esmond.ptd Page 20 538092 V. Description of Invention (16) The scope shall be determined by the scope of the attached patent application. Page 21 0424-6434TWF; 02900011; Esmond.p t d

Claims (1)

53Έ092 ---- / \ I '' j ....... ·-. ^ ___ VI- 、 Shen Lili side 1 ·-'" ~ " ~ · ^ 1 · A thermosetting photosensitive resin composition, Including: (a) 5 to 60 weight percent photosensitive resin; (b) 5 to 50 weight percent reactive diluent; (c) 0.01 to 20 weight percent curcumin modifier, which has at least Two unsaturated double bonds and at least two carboxylic acid groups; (d) a light initiator of 0. 1 to 15 weight percent; and (e) a thermosetting resin of 0.5 to 40 weight percent. 2. The heat-curable photosensitive resin composition according to item 1 of the scope of the patent application, in which the photosensitive resin forming the wound (a) is a modified epoxy resin having an unsaturated bond and an acid-acid group. 3. The heat-curable photosensitive resin composition as described in item 2 of the patent claim 4, wherein the modified epoxy resin of the component (a) is obtained by reacting an epoxy resin, an unsaturated monocarboxylic acid, and an acid anhydride. 4. The thermosetting photosensitive resin composition according to item 3 of the application, wherein the epoxy resin is a bisphen〇1 ype epoxy resin, a phenol varnish epoxy resin. novolac type epoxy resin), formic acid epoxy resin (cres〇in〇volac type resin), naphthalene type epoxy resin (naphthalene type epoxy r = sin), epoxy resin, glycidyl ester (glycidy 1 ester) Series of resins, "amine (She idyl amine) resins, hetero-epoxy resins containing N, S, and 0 atoms, and halogenated epoxy resins 5 ”If the thermosetting photosensitive resin composition of item 3 of the patent application scope, the x-unsaturated monoweilic acid is selected from acrylic acid, methyl 0424.6434TWF; 029000H; Esmond.ptd Page 22 538092 6. Scope of patent application: metharylic acid, crotonic acid, cinnamic acid, 2-methylpropanoyloxyethyl 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate (2 -methacryloyloxyethyl hexahydrophthalate), 2-acryloyloxyethyl hexahydrophthalate, 2-methacryloyloxyethyl phthalate, and 2-methacryloyloxyethyl phthalate In the group consisting of 2-acryloyloxyethyl phthalate. 6. The thermosetting photosensitive resin composition according to item 3 of the application, wherein the anhydride is selected from maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic acid. Hexahydrophthalic anhydride, methyltetrahydrophtha 1 ic anhydride, ethyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride ethylhexahydrophthalic anhydride), succinic anhydride, and itaconic anhy dr i de. 7. The heat-curing photosensitive resin composition according to item i of the patent application, wherein the weight average molecular weight of the component (a) of the photosensitive resin is 4,000 to 500,000 g / mol. Hardened photosensitive resin composition, 0424-6434TWF; 02900011; Esmond.ptd page 23 538092 6. Scope of patent application Among them, the acid value of the component (a) photosensitive resin is 30 ~ 300mgKOH / g. 9. The heat-curable photosensitive resin composition according to item 1 of the scope of the patent application, wherein the reactive diluent of component (b) is an unsaturated double bond. I 0 The heat-curable photosensitive resin composition according to item 9 of the scope of the patent application, wherein the reactive diluent having an unsaturated double bond is an acrylic monomer. II. The thermosetting photosensitive resin composition according to item 10 of the scope of the patent application, wherein the acrylic monomer is an acrylic monomer having two or more unsaturated double bonds. 1 2 · The thermosetting photosensitive resin composition according to item 11 of the scope of the patent application, wherein the acrylic monomer having two or more unsaturated double bonds is optional free 1,4-butanediol di (fluorenyl) Acrylate (1,4-but an ediol di (meth) acrylate), 1,6-hexanediol di (meth) acrylate, neopentyl glycol Diopentylglycol di (meth) acrylate, polyethyleneglycol di (meth) acrylate, neopentylglycol di (meth) acrylate Neopentylglycol adipate di (raeth) acrylate, neopentylglycol adipate di (raeth) acrylate, neopenty1g1yco1 di (meth) acry1 ate hydroxypivalate, di (methyl) ) Dicyclopentadienyl di (meth) acrylate, caprolacton modified di (meth) acrylic acid dicyclopentadienyl di (meth) acrylate, fluorenated bis (methyl) Cyclohexyl di (meth) acrylate, bis (methyl) propionate isocyanurate ( 0424-6434TWF; 02900011; Esmond.ptd Page 24 538092 6. Application scope of patent isocyanurate di (meth) acrylate, trimethylol propane tri (meth) acrylate, Dipentaerythritol tri (meth) acrylate, propionic acid modified dipenterythritol tri (meth) acrylate, penterythritol tri (meth) acrylate Propylene oxide (trimethylol tri (meth) acrylate modified by propylene oxide, tris (acryloxyethyl) i socyanurate), propionic acid modified Dipenterythritol penta (fluorenyl) acrylate, dipenterythritol hexa (meth) acrylate and a mixture thereof. 1 3 · The thermosetting photosensitive resin composition according to item 1 of the scope of patent application, wherein the curcumin modified component of component (c) is obtained by reacting curcumin with acid anhydride. 14. The heat-curable photosensitive resin composition as described in item 13 of the scope of the patent application, wherein the anhydride is selected from maleic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. , Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride), succinic anhydride, it aeon ic anhydride, alicyclic anhydride, 3,3,4, 0424-6434TWF; 02900011; Esmond.p t d page 25 538092 6.Scope of patent application 4'-benzophenone tetracarboxylic dianhydride (3,3 ', 4,4'-benzophenone te t racarboxy 1 ic dianhydride), pyromellitic dianhydride (pyrome 1 1 itic dianhydride), 3, 3', 4, 4'-diphenyltetracarboxylic acid di- (3,3 ', 4,4'-biphenyltetracarboxylic (^ 811117 (11 ^ (16), 2,2'-bis- (3,4-dicarboxyphenyl) ) Hexafluoropropane dianhydride (2,2'-bis- (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride), 4,4'-oxydiphthalic anhydride, 3,3 ', 4,4'-diphenylsulfonate dianhydride (3,3 ', 4,4'-diphenylsulfone tet racarboxy 1 ic dianhydride), 5-(2,5 -dioxotetrahydro)-3-methyl -3 -5- (2,5-dioxotetrahydrol) -3-methyl-3 -cyclohexene-1,2-dicarboxyl ic anhydride, ethylene glycol bistrimellitic anhydride ( ethylene glycol bis (anhydro-trimellitate)) and the above-mentioned mixture. 1 5 · The thermosetting photosensitive resin composition according to item 1 of the scope of patent application, wherein the component (c) curcumin is modified The acid value of the substance is 30 ~ 400mgKOH / g. 16 · The heat-curable photosensitive resin composition according to item 1 of the scope of the patent application, wherein the photoinitiator of the component (d) is one that can generate a free radical upon irradiation with light. 1 7 The thermosetting photosensitive resin composition according to item 1 of the scope of the patent application, wherein the photoinitiator is selected from benzoin, benzoin alkyl ether, and benzoin alkyl ether. B ^ —Jun 0424-6434TWF; 02900011; Esmond.ptd page 26 i 538092 6. Application scope (benzil), ketals, acetophenones, benzophenone, 4, 4 ' -Dimethyl-amino-benzophenone (4, 4'-dimethyl-amino-benzophenone), thioxanthones and morpholino-propanone Ethnic group. 1 8 The thermosetting photosensitive resin composition according to item 1 of the scope of patent application, wherein the thermosetting resin of the component (e) is an epoxy resin. 19. The heat-curable photosensitive resin composition according to item 18 of the scope of patent application, wherein the epoxy resin is an epoxy resin having more than two epoxy groups in one molecule. 2 0. The heat-curable photosensitive resin composition as described in item 19 of the scope of patent application, wherein the epoxy resin is a bisphenol type epoxy resin, phenol novolac epoxy resin type epoxy resin), cresol novolac type epoxy resin, polycyclic epoxy resin, glycid idyl ester resin, glycid idyl amine resin, heterocyclic ring Epoxy and halogenated epoxy resin. 21 The heat-curable photosensitive resin composition according to item 丨 of the patent application scope, further comprising an additive. 22 · Thermosetting as described in item 21 of the patent application i 538092 A group of reinforcing materials. 2 3 · The thermosetting photosensitive resin composition as described in item 丨 of the patent application scope, which is applied as a green paint. 24. The heat-curable photosensitive resin composition according to item 丨 of the scope of application for a patent, which is applied as an ink. 2 5 · The thermosetting photosensitive tree composition described in item 1 of the scope of patent application, which is applied as a painter. 2 6 The heat-curable photosensitive resin composition 'as described in item 1 of the scope of patent application, which is used as a photoresist. 2 7 The heat-curable photosensitive resin composition according to item 1 of the scope of patent application, which is applied as a photosensitive insulating layer. 2 8 · A printed circuit board having a solder resist pattern thereon, which is formed of the heat-curable photosensitive resin composition described in item 1 of the scope of patent application. 0424-6434TWF; 02900011; Esmond.p t d p.28