TW575631B - Photosensitive resin composition containing hetero atoms - Google Patents

Abstract

A photosensitive resin composition containing hetero atoms comprises 5 to 60 wt% of a photosensitive resin, 5 to 50 wt% of a reactive diluent containing unsaturated bonds, 0.1 to 15 wt% of a photo initiator, and 0.5 to 30 wt% of a thermal hardening resin. The present invention can be used in coatings, inks, photoresist and green lacquers for printed circuit boards, and has excellent thermal resistance, electrolytic and electroplating resistance, and touch drying properties.

Description

575631 V. Description of the invention (1) The present invention is related to the system; the sealing composition is a photosensitive resin composition containing unsaturated 3 heteroatoms, its lipid, reactive diluent, photoacid group, sulfur and phosphorus Atomic photosensitive button, printed circuit board = 2 resistance and photosensitive insulating stomach. The main support is all; when the sub-components are installed and interconnected, because the electronic products are lighter, the I is selected, and the high I / O number for electronic components, such as ^ Ingenious and small areas require inflammation, KMA is refined 4-4- J--L AA ^ The technology of brushing road boards must be continuously improved. 4 The physical properties of materials require the water phase to cut one juice. Water is also relatively good. Among them, the green paint (also known as solder resist photoresist, Solder Resist 'surface) used in printed circuit books (also called solder resist photoresist) is more stringent in application conditions, except that In addition to the original physical properties such as insulation, tin heat resistance, hardness, and chemical resistance, it must also have high-resolution properties, electrolytic plating resistance, electroless plating resistance, and high Tg. &Amp; Japanese Unexamined Patent Publication No. 1 1 — 2 4 2 3 2 9 wherein, because it is an aqueous photosensitive resin composition, the composition is composed of a photosensitive prepolymer with Epoxy Resin /

Acrylic Acid / Synthesis of 0 nium salinated compounds containing P, S, N, which is a salt, and the salt will cause poor insulation of the coating film formed by the composition. The salt must be removed to overcome this. problem. U.S. Patent No. 4 4 8 1 190 and Japanese Patent Application Laid-Open No. 6-190 6 are added to the composition of small molecule phosphate compounds containing unsaturated bonds, which can promote adhesion, but in light and heat hardening The hardening reaction is often not completed in the preparation, and the physical properties are easily reduced (such as resistance to electroless plating). It is best to add larger molecular compounds to avoid this problem.

575631 V. Description of the invention (2) Bentokaikai 1-3 8 4 1 3, the composition of the photosensitive resin contains th i ob i spheno 1 epoxy res in / unsated monobasic acid / anhydride Good in degree, hardness, insulation and heat resistance, but the thiobisphenol dpoxy resin in the ingredients is not ordinary tree vines, and its selection-source is not easy to obtain. :; ° 丨 Therefore, how to propose a novel heteroatom photosensitive resin composition for the above problems, which can not only improve the heat resistance of the photosensitive resin, but also promote its adhesion to the substrate and increase its photosensitive resin. The molecular weight has long been the eager hope of users and the inventor of the present invention, and the inventor is based on many years of research, development, and sales practice experience in photosensitive resin element-related products, thinking and improving ideas Based on his personal expertise, through various research and design and special discussions, he finally developed a heteroatomic photosensitive resin composition with improved structure that can solve the above problems. The main purpose of the present invention is to provide a heteroatom photosensitive resin composition, which incorporates a structure of naphthalene to improve the heat resistance of the photosensitive resin. The main purpose of this volume is to provide a heteroatom photosensitive resin composition which introduces elements containing 3 or p to increase the molecular polarity of the photosensitive resin and promote the adhesion of the photoresist ink composition to the substrate. Another object of the present invention is to provide a heteroatom photosensitive resin composition which increases electrolytic plating resistance and electroless plating. 2. Another object of the present invention is to provide a photosensitive resin composition containing ^ heteroatoms, which can increase the content of the photosensitive resin with a polycarboxylic acid or a phosphoric acid compound containing S or p.

Page 6 575631 V. Description of the invention (3) Sub-quantity. Another object of the present invention is to provide a heteroatom photosensitive resin composition, which can improve the finger-drying property of the photoresist ink, and does not reduce the insulation due to covalent bonding. : The composition of the present invention is a photosensitive resin containing heteroatoms, which contains 5 to 60% by weight of a photosensitive resin, 5 to 50% by weight of a reactive diluent having an unsaturated bond, and 0 · 1 to 1 5 The weight percentage of the light initiator and the heat curing agent resin of 0.5 to 30 weight percent are composed of naphtha 1 ene type epoxy resin and unsaturated carboxylic acid, which will contain polyweilic acid or scales containing s or P element. An acid compound is obtained by an acid anhydride reaction. In addition, the photosensitive resin may be selected from one of unsaturated bond, diacid group, sulfur or filled heteroatom naphthalene type epoxy resin modification, wherein the naphthalene type epoxy resin is selected from naphthalene structure epoxy Resin, wherein the epoxy resin of the naphtha 1 ene structure may be selected from 2-({[6- (2-oxiranylmethoxy) -l-nap hthyl] oxy} methyl) oxirane, 2-{[((7- (2- oxiranylmethyl) -l-{[2- (2-oxiranylmethoxy) -1-naphthyl] methyl} -2-n aphthyl) oxy] methyl} oxirane, 2-({[l-{[2,7-di (2- 〇xir anylmethoxy) -1-naphthyl] -7- (2-〇xiranylmethoxy) -2-n aphthyl] oxy} methyl) oxirane, 2-({[2- (5-methyl-2- (2-oxiranylmethoxy)- 3-{[1- (2-oxiranylmethoxy) -2-napht hyl] methyl} benzyl) -l-naphthyl] oxy} methyl) oxirane, 2-({[7-(3-{_ [1,6-di (2-oxiranylmethoxy) 2-naphthyl] me thyl} benzyl) -1-naphthyl] oxy} methyl) oxirane, 2-({[7

575631 V. Description of the invention (4)-(3-{[1,6-di (2-〇xiranylmethoxy) -2-naphthyl] methyl} benzyl) -6- (2-〇xiranylmethoxy) -l-naphthyl] oxy} methy 1) one of oxirane, etc., wherein the unsaturated monoweilic acid can be selected from ac ry1i cacid, ra ethac ry I ic acid, croton ic acid ei nnam ic ac id " 2-me thacry 1 One of oy 1 oxy e thy 1 succinate, 2-acryloyloxyethyl succinate, 2-methacryloylethy 1 hexahydrophalate, 2-acryloyloxyethyl hexahydroph thalate, 2-methacryloyloxyethyl phthalater, and 2-acry loyloxyethyl phthalate, which contain sulfur and phosphorous atoms Polycarboxylic acids and phosphoric acid compounds can be selected from 5, 5 '-thiodisal ic ylic acid, 2, V -thiodiglucolic acid, 3, 3, -thiodipr op i on ic acid, 4, 4' -dicarboxydiphenyl sulfone, mono methacryloyloxypropyl phosphate One of monoacryloyloxypr opy1 phosphate, monomethacryloyloxyethyl phosohate, and monoacryloyloxyethyl phosphate, wherein the anhydride is selected from maleic anhrdride, phthalic anhyd One of ride, tetrahydrophthal ic anhydride, hexahydrophthalic an hydride, raethy 1 tetrahydrophthalic anhydride, ethyl tetrahydrophthal ic anhydride, methylhexahydrophtha lie anhydride, ethy lhexahydrophthalic anhydride, succinic anhydride, and itacinic anhydride, wherein the molecular weight of the photosensitive resin is 4 0 0 0 0 to 5 0 0 0 0 0 0, the acid value is 30 to 300 mgKOH / g and the glass transition temperature is greater than 150 ° C. Reactive diluent is an acrylic monomer, which is

575631 V. Description of the invention (5) The acrylic single system of unsaturated double bonds above can be selected from 1,4-butanediol di (fluorenyl) acrylate, 1,6-hexanediol di (methyl) ) Acrylate, neopentyl ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl ethylene glycol di (meth) propionate adipate, Neopentylethyl: diol di (methyl) "two. Fine: acid_group: _valeric acid purpose, di (methyl) acrylic acid dicyclopentadiene ester, caprolactone modified di d fluorenyl) dicyclopentadienyl acrylate, allyl cyclohexyl di (meth) acrylate, di (meth) acrylic isocyanurate, tricarbonate methyl tri (meth) acrylate Ester, dipenterythritol tri (meth) acrylate, propionic acid modified dipenterythritol tri (fluorenyl) acrylate, penterythritol tri (fluorenyl) acrylate, propylene oxide modified Trihydrocarbon methyltri (meth) acrylate, tris (propyleneoxyethyl) isocyanurate, propionic acid modified dipenterythritol penta (fluorenyl) acrylate and dipenterythritol hexa (Meth) c One of the acid esters. A photoinitiator is one that can generate free radicals upon irradiation with light, and can be selected from the group consisting of benzoin group, benzoin alkyl ether acetophenone group, thiodiphenyl piperazine, anthraquinone One of a group, a ketal group, a benzophenone group, and a two benzophenone group. The thermosetting resin is an epoxy resin, wherein the epoxy resin is an epoxy resin having more than two epoxy groups in one molecule, The epoxy resin can be selected from bisphenol epoxy resin, novolac epoxy resin, phenol novolac epoxy resin, polycyclic epoxy resin, g 1 cidy 1 ester resin, g 1 ycidy 1 amine resin. One of heterocyclic epoxy resin and halogenated epoxy resin. The present invention is applicable to one of green paint, ink :, paint, photoresist and photosensitive insulation layer.

575631 V. Description of the invention (6) In order to make your reviewing members have a better understanding and understanding of the structural features and achieved effects of the present invention, I would like to accompany the detailed embodiment diagrams and detailed descriptions, such as After:: First: See: Figure 1, which is a flowchart of one of the preferred embodiments of the present invention; as shown in the figure, the reactant A 1 is napthalene type epoxy resin 4 8 · 3 g The epoxy equivalent was ιβ1, and 75g of diethyllene glycol monoethyl ether acetate of reactant B 20 was placed in a reactor and dissolved by heating to 60 ° C for 3 °, and then aery of reactant C 40 was added. 1 ic acid 10. 8 g (0.15 equivalents) and monoacryloyloxyethyl phosphate 29. 4 g of reactant D 50, heated to 90 ° C. and reacted 6 0 until the acid value approaches 0, and finally add tetrahydrophthalic reactant e 7 0 Anhydride 34.2 g was reacted at 80 at 1 0 to 120 ° CT, and the reaction time was 3 hours to obtain a photosensitive resin a 1. Photosensitive resin A2 · Reactant A was replaced by naphthalene type epoxy resin 66g'Reactant D was replaced by monomethacryloyloxy propyl 31.5 g 〇Photosensitive resin A3: Reactant D was replaced by 3, 3, —Thiodipropio nic acid 13.4go A4 · Reactant A is replaced by naphthalene type epoxy resin ESN = 365 49.8g'Reactant D is replaced by 2,2'-thiodiglycolic acid 22.5g ° Photoreceptor A5 · Reactant D is replaced by acrylic acid 10 · 8g 〇Resin A6 · cresol norolac type epoxy resin

Page 10 575631 V. Description of the invention (7) CNE-200 60g and diethylene glycol monoethyl ether acetate 7 5g are placed in a reactor, dissolved at 60 ° C, and acrylic acid 21. 7g, hydroquinone 0.9g and triphenylph osphine are added. 0 · 3g, the reaction at 90 ° C until the acid value tends to over 0, and finally add te trashydrophthal ic anhydr i de 4 0g9 1 1 0 ~ 1 2 OC and react for 3 hours to obtain it. ： Photosensitive resin A-7: Put ere sol norolac type epoxy resin CNE-200 lOO〇g and meth〇xypropano 160 g in a reactor, and dissolve at 60 C. 'Add acrylic acid 36 g and hydroquinone 〇. 〇2 g' 在7 〇. It can be obtained by reacting at 0 ° C for 10 hours. Take the above photosensitive resin and dry it to make a test piece. The glass transition temperature Tg 18 8 ° C was measured with the thermal kinetic mechanical analyzer DM Α. The experimental results are shown in Appendix I. And the general glass transition temperature of the photosensitive resin is It is 134 ° C, so the glass transition temperature of the present invention is higher than that of general photosensitive resin, that is, the photoresist ink composition of the present invention has better heat resistance. 4 Examples 1 to 4 are used, as shown in Annex II, the chemicals and the configuration amount, mixed and stirred = ’Grinded at room temperature with a three-roller grinder to make the photoresist ink group j evenly spread; comparative example! ~ 3, the photoresist ink composition of the comparative example is configured according to the chemical and configuration amounts shown in the table below, and the steps of the example, where I = the photosensitive resin a of the comparative example 1 without the synthesis method of the present invention Increase the second child =, so the molecular weight is only 2 3 0 0. In Comparative Example 2, phosphorus-containing I = acrylic monomer is added to the formula. Photosensitive resin A 6 is a commonly used photosensitive resin, while the carousel 3 is used. 〇nium salt of photosensitive resin. The photoresist ink composition was coated on a steel foil substrate at an operating temperature of 8 °.

Page 11 575631 V. Description of the invention (8) Pre-bake for 30 minutes. After the substrate is cooled, observe the dryness of the finger touch. Cover the negative with gray scale and resolution graphics on the test piece, and light with an ultraviolet exposure machine. Then, develop with 1% Na aqueous solution, and then wash with water. 3 The test piece was observed for its gray scale and resolution, and finally, at the operating temperature; 15: 0 ° 〇, dried for 60 minutes, so that The hardened ice tests its insulation, electrolytic and mineral resistance, and non-electrolytic and mineral resistance. Please refer to the experimental results in Appendix III. The experimental results refer to the dryness of the touch. The objective gray scale pattern is to record the minimum number of steps when the coating film is completely washed off. The value is 9, and the resolution is checked and the minimum line width / space distance complex value 2mi Is is recorded. The surface resistance is The tester is placed on the test piece, and the test piece is placed in a 90% RH constant temperature and humidity machine in the factory. The operating time is 96 hours. After the beans are processed by the electrolytic plating process, the test value is 1 0. 0/1 0 0, which means that it is then excellent, and the test piece is processed by the electrolytic electrolytic forging process. 'Adding a 100 grid adhesion test, the test value is 100 0/1 0 0, which is expressed as the next good _, Λα "a / the test J drink has 1 Yan Gen, from the physical property test results, the light of the present invention The ink-resisting composition has conscience developability, resolution, insulation, and heat-resistant plating property. Electrolytic plating resistance and non-electrolytic resistance. In summary, the present invention is related to a product, the composition is a photosensitive resin containing unsaturated [atomic photosensitive resin group, reactive diluent, pompano ^ Carboxylic acid, sulphur and phospholipids, which are used in green paints, inks, cold & initiators and heat hardeners. Therefore, the present invention is a novel, novel, photoresist and photosensitive insulator. The patent application requirements that should meet the requirements of the "secondary and secondary industry" and "industrial use" stipulated by the Chinese Patent Law are undoubtedly

575631 V. Description of the invention (9) An invention patent application is filed. I pray that the Bureau will grant the patent as soon as possible. However, the above is only a preferred embodiment of the present invention, and is not intended to limit the scope of implementation of the present invention. For example, the shapes, structures, features, and spirits described in the scope of the patent application for the present invention are 4 equal changes and Modifications should be included in the scope of patent application of the present invention. i Brief description of drawing number: 5 10 Reactant A 20 Reactant B 30 is dissolved

4 0 reactant C

5 0 reactant D 6 0 reaction

7 0 reactant E 8 0 reaction

Page 13 575631

Page 14 575631 [Annex 1] 丨 1 Presense resin: A 1 A2 ί A3 A4 A5 A6 Tg (° C) 188 176 160 172 200 134 575631 [Annex 2] Photoresist ink, composition, composition, ^ Example b Comparative Example 1; 2, 3 4 1 2 3 i Photosensitive resin Αί 6 0; Α2 6 0 A3 60 Α4 60 Α5 60 Α6 60 Α7 60 reactive diluent B1 20 10 5 20 15 20 Β2 10 15 20 Β3 5 light Starter Cl 1 0.8 1 0.8 1 C2 2 1.5 Epoxy resin D1 22 21 22 22 D2 20 22 20 Other B a S 〇 4 7 8 7 SiO, 4 4 4 Talc 8 cyan green 0.4 0.6 0.5 0.4 0.4 0.4 0.5 B1 : dipentaerythritol pentaacrylate B2: pentaerythritol triacrylate B3: monoacryloyloxyethyl phosphate Clilrgacure 907 C2: isopropyl thioxanthone D1: CNE-200 D2: EXA-4700 575631 [Annex 3] Photoresist ink composition Γ fi ί Example Comparative Example 1; 2 3 4 1 2 3 丨 Finger touch dryness 〇〇〇〇〇〇〇〇 Gray scale (2 1 grade) 9 10 10 9 9 10 10 Resolution 2 2 2 2 2 3 3 Insulating starting material (1013) 1 1 1 1 11 0.2 6 0 ° C, 960hr (ίο11) 20 40 50 30 9 2 3 Electrolytic plating resistance 100/100 100/100 100/100 100/100 98/100 100/100 100/100 Electroless plating resistance 100 / 100 100/100 100/100 100/100 95/100 90/100 90/100

Claims (1)

Case No. 90112360 VI. Compositions covered by patent application, including package 1. A heteroatom photosensitive resin composition, which mainly contains: (a) 5 to 60 weight ratio of photosensitive resin, which is a heteroatom naphthalene type ring Oxygen resin modified product ', wherein the photosensitive resin is selected from one of unsaturated atom, carboxylic acid bond, sulfur and phosphorus heteroatom naphthalene type epoxy resin modified product, or a naphthalene type epoxy resin and One of the saturated monocarboxylic acid, sulfur-containing, phosphorus-containing polycarboxylic acid and phosphoric acid compound is reacted with acid anhydride; (b) a reactive diluent having an unsaturated double bond in a weight ratio of 5 to 50; (c) a light initiator in a weight ratio of 0 to 1 to 15; and (d) a weight ratio of 0 to 5 to 30 Thermosetting resin. 2 The composition as described in item 1 of the scope of patent application, wherein The epoxy resin of naphthalene structure can be selected from 2-({[6- (2-oxiranylmethoxy) -l-naphthyl] 〇xy} methyr) oxirane ^ 2-{[(7- (2-〇xiranylmethyl) -l- {[2- (2-oxiranylmethoxy) -l-naphthyl] methyl} -2-naphthyl) oxy] methyl} oxirane, 2-({[1-{[2, 7-di (2-oxiranylmethoxy) -1-naphthyl ] -7- (2-oxiranylmethoxy) -2-naphthyl] oxy} methyl) oxirane -2-({[2- (5-methyl-2- (2-〇xiranylmethoxy) -3-{[l-(2- 〇xiranylmethoxy) -2-naphthyl] methyl} benzyl) -1-naphthyl] oxy} methyl) oxirane, 2-({[7- (3-{[l, 6-di (2-〇xiranylmethoxy) 2-naphthyl] methyl} benzy P.15 575631 Case No. 90112360 Amendment VI. Application scope 1) -1-naphthyl] oxy} methyl) oxirane, 2-({[7- (3-{[1, 6-di (2-〇xiranylmethoxy) -2-naphthyl] methyl} benzyl) -6- (2-oxiranylmethoxy) -l-naphthyl] oxy} methyl) oxirane. The composition according to item 1 of the scope of the patent application, wherein the unsaturated mono-acrylic acid can be selected from acrylic acid, methacryl acid " croton ic acid, cinnamic acid, 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl succinate, One of 2-methacryloylethyl hexahydrophalate, 2-acryloyloxyethyl hexahydrophthalate, 2-methacryloyloxyethyl phthalater, and 2-acryloyloxyethyl phthalate. 4 The composition as described in item 1 of the scope of the patent application, wherein the polycarboxylic acid and phosphorous compound containing sulfur and phosphorus atoms can be selected from 5,5'-thiodisalicylic acid, 2,2'-thiodiglucolic # acid, One of 3,3'-thiodipropionic acid, 4,4'-dicarboxydiphenyl su1fone 'monomethacryloyloxypropyl phosphate, monoacry1oy10xypropy1 phosphate, monomethacryloyloxyethyl phosohate, and monoacryloyloxyethyl phosphate. The composition according to item 1 of the scope of patent application, wherein the anhydride is selected from maleic anhrdride, phthalic anhydride, P.16 575631 _Case No. 90112360 Amendment 6 、 Application scope of patents tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, succinic anhydride, and itacinic anhydride. The composition according to item 1 of the scope of patent application, wherein the molecular weight of the photosensitive resin of the component (a) is 40,000 to 5,000,000. 7. The composition as described in item 1 of the scope of patent application, wherein the acid value of the photosensitive resin of the component (a) is 30 to 300 mgKOH / g. 8. The composition according to item 1 of the scope of patent application, wherein the photosensitive resin of the component (a) has a glass transition temperature of more than 150 ° C. 9 The composition as described in item 1 of the scope of patent application, wherein the reactive diluent of the component (b) is an acrylic monomer. 1 0. The composition according to item 9 of the scope of the patent application, wherein the acrylic monomer is an acrylic monomer having two or more unsaturated double bonds. 1 1 · The composition as described in item 10 of the scope of patent application, wherein the acrylic single system having more than two unsaturated double bonds can be selected from 1, butanediol '-(fluorenyl) propane Dilute acid 6 purpose, 1,6-hexanedione · mono (fluorenyl) acrylic acid ester, neopentyl glycol di (fluorenyl) acrylate, polyethylene glycol mono (meth) propionic acid S Purpose, neofluorinyl glycol · mono (methyl) diamidate adipate, neopentylethylene glycol di (fluorenyl) acrylate pentyl __ Case No. 9011236 (1 ___ ± VI. Patent application scope Ester, Dicyclopentadiene di (fluorenyl) acrylate_, Dicyclopentadiene di (fluorenyl) acrylate modified by caprolactone, Allyl Cyclohexyl di (meth) acrylate, isocyanuric acid di (fluorenyl) acrylic acid, dimethyl tri (meth) acrylate, dipentyl erythritol tri (meth) acrylic acid g Purpose, propionic acid modified dipenterythritol tri (meth) acrylate, penterythritol tri (meth) acrylate, propylene oxide modified trihydrocarbon methyltri (meth) acrylate acetic acid, Tris (propyloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (fluorenyl) acrylate and dipenterythritol hexa (fluorenyl) acrylate g · The composition as described in item 1 of the scope of patent application, wherein the light initiator of component (c) is one that can generate free radicals after light irradiation. 1 3 · As described in item 2 of the scope of patent application The composition, wherein the photoinitiator is selected from the group consisting of benzoin group, benzoin alkyl ether benzyl ketone group, thiodiphenyl piperazine, anthraquinone group, One of ketone, benzophenone group and two benzophenone group. 1 4 · The composition according to item 1 of the patent application scope, wherein the thermosetting resin of the component (d) is epoxy resin. 1 5 · The composition described in item 4 of the scope of patent application, wherein the epoxy resin is an epoxy resin having more than two epoxy groups in one molecule. 1 6 · As described in item 5 of scope of patent application The composition of the epoxy resin can be selected from bisphenol epoxy resin, novolac epoxy resin, aldehyde epoxy resin, polycyclic epoxy resin, glcidyl estei ^, resin, glycid idyl amine resin, miscellaneous Cyclic epoxy resin and toothing Case No. 575631 Case No. 90112360 Amendment 6. One of the epoxy resins in the scope of patent application. 17 • The composition as described in item 1 of the scope of patent application, wherein the photosensitive resin is applicable to one of green paint, ink, paint, photoresist and photosensitive insulation layer. Φ Page 19