TW484035B - Polymeric resin based on carboxylic acid and containing unsaturated double bond, its preparation and its application - Google Patents

Abstract

The present invention relates to a polymeric resin based on carboxylic acid and containing unsaturated double bond, which is characterized in having at least two ester groups (-C(O)-O-) in the main chain of the resin or having at least two ester groups (-C(O)-O-) and an urethane group (-O-C(O)-NH-) in the main chain. The present invention also relates to a preparation method for the polymeric resin based on carboxylic acid and containing unsaturated double bond, which is characterized in being a reaction product of polyols or phenol formaldehyde resin, acid anhydrides or poly-acids, and (meth)acrylate compounds containing epoxy group, or being a reaction product of polyols or phenol formaldehyde resin, acid anhydrides or poly-acids, isocynates and (meth)acrylate compounds containing epoxy group. The present invention further relates to a photo active resin composition containing the polymeric resin based on carboxylic acid and containing unsaturated double bond. The composition has excellent heat, acid and chemical resistance and is applicable as photoresist developable in alkaline solutions during a photoreaction or as soldering-resist photoresist for printed circuit board.

Description

484035 5. Description of the invention (l) [Field of the invention] The present invention relates to a polycarboxylic acid resin containing unsaturated double bonds, which is characterized in that the main chain of the polycarboxylic acid resin contains at least two ester groups (_ (; ( 0) -0-) or the primary bond contains at least two s-groups (-c (o) -〇-) and aminoformic acid S-groups (-0-C (0) -NH-).

The present invention also relates to a method for preparing the polycarboxylic acid resin containing unsaturated double bonds, which is characterized in that a polyhydric alcohol or a methyl resin, an acid or a polyacid, and a (meth) acrylate compound containing an epoxy group are used. It is formed by a reaction or by reacting a polyol or a phenol resin, an acid anhydride or a polyacid, an isocyanate compound, and an epoxy group-containing (fluorenyl) acrylate compound. The present invention also relates to a photosensitive resin composition containing the above-mentioned polycarboxylic acid tree containing unsaturated double bonds. The composition has superior heat resistance, acid resistance, and chemical resistance, and can be used as an alkali-soluble imaging light for photoreaction. Resists, solder resists for printed circuit boards. [Background of the Invention] In the past, the main purpose of photosensitive resin compositions in the field of printed circuit boards as solder masks was to connect them during soldering time and to prevent electrical insulation of bare steel and metal conductors. Cyclic resins are often used as the mainstays of printed soldering hoods. However, in recent years, with the strict requirements for electrical insulation between printed conductors and dimensional accuracy, it has been known that screens with excellent characteristics can be used in screens. Photoresist for electroless plating. Soldering area, avoiding mutual corrosion of solders, and keeping hot components such as oxygen resins and amine-based plastic resins for a long time between conductors. The density of the brush circuit and board wiring is getting higher and higher, and the solder mask needs to have an excellent film. The printing method can no longer meet this demand.

484035 V. Description of the invention (2) Therefore, the field of printed circuit boards is looking forward to the emergence of a method that can use the Zhaoxiang method (a method of continuously exposing and developing a pattern to form a pattern) with a thick film (usually at a thickness of 25 microns) to form a precise size. It is known that it can be used as a photosensitive resin composition for welding masks. It is known that acrylic resins and photopolymerizable monomers can be used as the helmet. For example, Japanese Unexamined Patent Publication No. 53_5601 8 and Japanese Unexamined Patent Publication No. 54-1018. However, in order to impart film-forming properties to these photosensitive resin compositions, a large amount of acrylic polymer must be used, and the heat resistance of the cured film is insufficient. On the other hand, Japanese Unexamined Patent Publication No. 54_820 73 and Japanese Unexamined Patent Publication No. 58_82073 disclose the use of photosensitive epoxy resins and epoxy resin hardeners containing styrene, acrylic, and benzene as main components in the main chain. The composition is a photosensitive resin composition having good heat resistance. However, the sensitivity of the photosensitive resin composition is low, and it is difficult to form a thick film photoresist. Furthermore, flammable organic solvents such as two cyclohexanone are used as a developing solution, and there are concerns about safety. Japanese Patent Application Laid-Open No. 6 1-272 proposes a composition that can form a thick-film hardened welding mask using epoxy-containing novolac resin-type glycidyl ester and a photopolymerization initiator as main components. Although this composition has excellent: = thermal properties, it is necessary to use a mixture of trifluoroethane / lower alkanol and liquid, so there are also safety concerns. At first glance, the present inventors have conducted active research in this field based on the current long and wide range of photosensitive resin compositions, and have found a novel content; ‘saturation’

Sigh carboxylic acid resin has different heat resistance and resistance as photoresistance, so it develops light. Purpose of the invention] I invention. The bond can be light [acid resistance and chemical resistance, and solder resistance of the printed circuit board. The first object of the present invention is a polyacrylic acid resin, and its special product provides a novel ester group containing unsaturated double bonds (~ C ( 〇) -〇), and 5 are that the polyacetic acid resin main chain contains at least two urethane groups: ―. Or two of two have at least two acetic groups (-c (0) M and

The first objective of Pingming is to provide a method for preparing the above-mentioned unsaturated double bond-containing acid & ten Γ resin, which is characterized in that a polyhydric alcohol or a formic acid resin, a low-grade acid, and an epoxy-containing (methyl ) The acrylate compound is formed by reacting or reacting a polyhydric alcohol or a phenol resin, an acid anhydride or a polybasic acid, an isocyanato compound, and a (meth) acrylate compound containing an epoxy group. A third object of the present invention is to provide a photosensitive resin composition containing the above-mentioned polyacrylic acid resin containing an unsaturated double bond. The composition has superior heat resistance, acid resistance, and chemical resistance, and can be used as a photosensitivity test. Photoresist for development, solder resist for printed circuit boards. [Detailed description of the invention]

The unsaturated double bond-containing polycarboxylic acid resin of the present invention contains at least two ester groups (-C (〇) -〇-) in the main chain or at least two ester groups (-c (0)- 〇-) and urethane group (--0-C (0)-NH-) of polycarboxylic acid. The ester group is formed by the ring opening of a polyhydric alcohol or a test resin with an acid anhydride or an esterification reaction with a carboxyl group of a polyacid, and after the ring opening by an acid anhydride.

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V. Description of the invention (4) The unreacted carboxylic acid of another carboxylic acid or polyacid is formed by acetic acid reaction with epoxy group-containing (meth) acrylate epoxy group. Alcohol or melamine resin formed by the reaction of several groups with isogasic acid == cyanate groups. The method for preparing a polyacrylic acid resin containing unsaturated double bonds according to the present invention includes the following methods: Method (a):

(1) Polyol (or acetic acid resin) is esterified with an anhydride or polyacid to form a compound containing a terminal carboxylic acid. (2) The terminal weilyl group is used with a (meth) acrylic acid containing% oxy group. Acid ester reaction, (3) the compound having a radical obtained after the epoxy group is ring-opened, and then reacted with an acid anhydride or a polybasic acid " acetation reaction 'to form at least two ester groups in the main chain of the present invention and unsaturated Polycarboxylic resin with double bonds. Method (b):

(1) A polyhydric alcohol (or a melamine resin) is subjected to a condensation reaction with a diisocyanate to form a compound containing a urethane group, and (2) the unreacted warp group of the polyol (or a panic acid resin) is reused And then react with an acid anhydride or a polybasic acid to form a compound containing a urethane group and an ester group containing a carboxyl group at the end, (3) reacting the terminal carboxyl group with an epoxy group-containing (meth) acrylate, (4) The compound having a hydroxyl group obtained after the epoxy group is ring-opened is then subjected to an esterification reaction with an acid anhydride or a polybasic acid to form an unsaturated chain in the main chain of the present invention, which contains at least two ester groups and amino amido ester groups Polycarboxylic resin with double bonds. Method (c): (1) esterifying a phenol formaldehyde resin with an epoxy group-containing (fluorenyl) acrylate

C: \ Program Files \ Patent \ l 5791 .ptd Page 8 484035 V. Description of the invention (5) Chemical reaction, C2) The hydroxyl-containing compound obtained after the epoxy ring-opening is then esterified with an acid anhydride or a polybasic acid A phenol formaldehyde type polycarboxylic acid resin containing at least two ester groups and unsaturated double bonds in the main chain of the present invention is formed. The reaction sequence of method (c) is only applicable to the warp groups of phenolic aldehyde resins. This is because the hydroxyl groups of fluorenes are more reactive than the hydroxyl groups of polyols and have sufficient reactivity to open the epoxy groups. ', ^ The polyol used in the method of the present invention means that the molecule contains at least two minus compounds, including, for example, pentaerythritol, glycerol, trimethylolpropane, ethylene glycol, propylene glycol, butanediol, pentanediol , Hexanediol, etc. The carboxylic acid resin used in the method of the present invention includes, for example, DEH81 and DEH85 available from Dow Chemical Company. The acid anhydride used in the method of the present invention may be a mono-anhydride and a di-anhydride. Examples of the anhydride include, for example, phthalic anhydride, tetrahydrophthalic anhydride, hexaaza-monocarboxylic acid anhydride, succinic anhydride, and maleic anhydride, stearic acid anhydride, and dianhydride. Examples include pyromellitic anhydride, and the like. I. The polybasic acid used in the method of the present invention means a compound containing at least two carboxylic acids in the molecule, and includes, for example, aliphatic and aromatic dicarboxylic acids, trimellitic acid and the like. For example, malonic acid, succinic acid, succinic acid, adipic acid, adipic acid, succinic acid, phthalic acid, trimellitic acid, and stearic acid. The diisocyanates used in the method of the present invention include phenylmethane-4,4'-diisocyanate, acid esters, mono-Ata pine-A 4,-Yadashin ", an isomerized methylene diisocyanate, bis (4-isocyanate group) cyclohexane, and [4], a breast milk ring, and the like. And u-bis (isohelic acid methyl ester) The cyclomethyl-containing (meth) acrylic acid ester used in the method of the present invention contains

V. Description of the invention (6) For example, glycidyl acrylate 3, [epoxy cyclohexyl hexanoate, methyl formaldehyde; == glycidyl vinegar, propyl ester, propionate 3,41 oxysuccinic acid 3,4 —S-oxycyclohexylhexyloxymman-1 base tenanyl ester, 3,4 methacrylic acid ring; hydrazine 3,4-epoxy hydrazine + group! Ί = epoxy Mengman-1-yloxyethyl and so on. And step ⑴ and step ⑶, method ⑻ step ⑺ = inverse: lambda method (c) step (2), the reaction between the radical and the acid anhydride or polybasic acid is performed in a solvent, preferably 70 to 15〇. (:, The degree of UC is consumed within the range. The vertebra # is used in the temperature range of 90 to 130 ° C, more preferably in the reverse direction. When the esterification reaction is performed, Dehydration must be performed at the same time to facilitate the reaction. If necessary, a catalyst can also be added. Yak method U) step (2), method (b) step (3) and method (c) step (1), Wei acid Ionization reaction of the β methyl (meth) acrylate epoxy groups should be in a solvent. (: In the temperature range, compared with == below, in the range of 70 to 170 t: The temperature range is preferably 8G to 15GC, better _ to 110 The method (b) step (1) Zhongzhiyigan of the method of the invention > The reaction should be in a solvent. The condensation of ㈣ & & unradical and isoramic acid group is ㈣〇t, more preferably the reaction is in the temperature range of 0 =, preferably c ^ ^ Wendeng Feng 4U to 70 c The temperature is within the range of the temperature. The solvent used in the reaction is not particularly limited, as long as it is inert to the reverse shore. However, generally, for example, carbitol acetate (carnr decyl alcohol monoethyl ether acetate, paint solvent Chuan 0 (petroleum Fine 'is approved by China National Petroleum Corporation, π fork 仏), paint solvent # 1 0 0, etc. The catalyst used in the reaction can be, for example, tetrabutyl bromide, gasification tetrabutyl picture page 10C: \ Progmm Files \ Patent \ 15791.ptd 484035 5. Description of the invention (7) Basic ammonium, tetramethylammonium bromide, gasified tetramethylammonium, trimethylamine, triethylamine, triphenylphosphine, etc. The amount depends on the reaction degree of the reactant functional group to be reacted. For example, 1 equivalent of hydroxyl functional group is used relative to 1 equivalent of acid anhydride or carboxylic acid. Functional groups, but if you do not want to react all the hydroxyl groups in the polyol, you can use a relatively small amount of acid anhydride or carboxylic acid functional groups. Based on this, the proportion of each reactant is familiar to those skilled in the art based on each reaction The number of functional group equivalents is easy to determine. Tian similarly, the amount of diisohydrogenate is also determined relative to the number of functional groups of the polyol. Usually, the two official compounds of 1 mole of diisohydrogenate are used. The two groups react with the hydroxyl groups of the two-mole polyol, and the two-mole polyols can each use two kinds of one-mole polyols. The amount of epoxy-containing (meth) acrylate used is relative. Use it at the appropriate acid amount. For example, if you want to make a molar equivalent of a carboxylic acid, 'relatively use 1 molar equivalent of an epoxy group-containing (meth) acrylate. You should n’t use it for 3 It is limited to the above, and those who are familiar with the art will determine the products on the eve-the verdure rainbow, the number of functional groups of each reactant, and the number of g radicals to be reacted. 令 右 # 于 produced by the method of the present invention It has superior resistance to polyacrylic acid resin The line-type developing = path: poly unsaturated double bond acid buffer tree = Er process of this invention was prepared containing the circuit board also as a permanent solder resist for circuit board photoresist

Fifth invention description (8) agent :: package = :: also related-a kind of lye imaging type circuit imaging photoresin, photoinitiator, diluent: 2 unsaturated double bond polycarboxylic acid esters Monomers 1 and; ί, (meth) acrylic acid containing ethylenic unsaturated bonds in the plate M and filler, can also be Yan Xue φ J. The present invention is also related to one pound only to add: material. ΦEpisode ^ a kind of anti-knowledge photoresist ', which includes the private car of the present invention: a polymer containing unsaturated double bonds _ Fayuefang to the unsaturated bond (meth) acrylic acid vinegar two = agent , Hardening accelerators and fillers. The aforementioned light initiators for flat baskets are known to those skilled in the art, such as Irgacure 907 (purchased from steam = 〆 but not limited to) and diethylthio Μ ㈣ isopropyl thio onion 嗣 法 1 5: The release agent is known to those skilled in the art, 'including (but not limited to) examples of paint life # 100, paint solvent # 15〇 (Petroleum, mentioned by China Petroleum = Division 4,), propylene glycol methoxyethyl And carbitol acetate. The (fluorenyl) acrylate monomers containing ethylenic unsaturated bonds are known to those skilled in the art, and include (but are not limited to), for example, di-pentaerythritol pentaacrylate (under the trade name Sartomer SR-399 by Sartomer (Seller of the company), tripropyl methyl acrylate diacrylate and triethoxy tripropionate (sartomer SR454 under the trade name, sold by Sartomer). Other fillers are known to those skilled in the art, and include (but are not limited to), for example, barium sulfate, talc, and silicon dioxide. The aforementioned cross-linking agents are known to those skilled in the art, and include (but are not limited to), for example, epoxy resins, such as PT81 0 (provided by Ciba Jiaji),

C: \ Program Files \ Patent \ 15791.ptd Page 12 484035 V. Description of the invention (9) NPCN703, NPCN704 (provided by Nanya Corporation) and γχ400 (provided by Japan Yuka Shell Corporation). The aforementioned hardening accelerators are known to those skilled in the art, and include (but are not limited to), for example, imidazole, melamine, and dicyandiamide. The aforementioned dyes can be determined from the properties of the final product, including (but not limited to) pigments or color coarse, ον〇Λ1, materials such as 2Υ301 (provided by Japan's Toyo Corporation), and white crystal violet. , Victoria ’s AJ Yearning Blue B (Perceptual Blue), Victoria Blue B0 (Green Alkaline Blue), Victoria Dolly μ > ^ 4 Sub-Blue R (Red Alkaline Blue), Malachite Green, etc. The present invention will be described in more detail with the following examples and preparation examples, but the examples and manufacturing examples such as § 19 are for illustration only, and the present invention is not limited to these examples and manufacturing examples. Examples 1 to 6 The polycarboxylic acid resins containing unsaturated double bonds of Examples 1 to 6 were reacted in accordance with the ingredients and amounts of 3 kg according to the following Table 1 to Table 1. ^ Table 1 below is the first reaction stage of the method of the present invention.

484035 V. Description of the invention (10) Table 1 -1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Trimethylolpropane (g) 13.4 13,4 13.4 Isopentyl alcohol (g) 13.6 13.6 13.6 Carbitol E Ester (g) 74.4 74.4 73.7 97.3 97.3 96.0 Tetrahydrophthalic anhydride (g) 45.6 61.6 Hexahydroanhydride (g) 46.2 61.6 Phthalic anhydride (g) 44.4 59.2 Reaction temperature (° C) 90 90 90 90 90 90 Reaction time (hours) 5 5 5 5 5 5 丨 The reaction mixture obtained by reacting the ingredients listed in Table 1 is then reacted with the following table; the ingredients listed in columns 1-2 are reacted according to the listed reaction conditions. Table 1-2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 丨 Glycidyl methacrylate (g) 42.6 42.6 42.6 56.8 56.8 56.8 Tetrabutylammonium bromide (g) 0.41 0.41 0.54 0.53 Triphenylphosphine (g) 0.42 0.54 Hydroquinone (g) 0.14 0.14 0.14 0.18 0.18 0.18 Reaction temperature (° C) 100 100 100 100 100 100 Reaction time (hours) 7 7 7 7 7 7 The listed ingredients are reacted according to the described reaction conditions to obtain the content of the present invention. Polycarboxylic resins with saturated double bonds. Its solid content and acid value are also listed in Table 1-3. 1 1 1 C: \ ProgramFiles \ Patent \ 15791.ptd Page 14 484035 V. Description of the invention (11) Table 3 Example 1 Example 2 Example 3 Example f Example 5 Example 6 Tetrahydroanhydride (g) 36.5 36.5 36.5 48.6 48.6 48.6 Reaction temperature (C) 90 90 90 90 90 90 Reaction time (hours) 4 4 4 4 4 4 Solid content (%) 65 65 65 65 65 65 Solid component acid value (mg / g KOH) 96.6 96.2 97.4 98.4 98.4 99.8 Comparative Example 1 An epoxy resin (210 g) and acrylic acid (72 g) manufactured by NPCN703 C Nanya Corporation were prepared in carbitol acetate (208.4 g) in 0.3 g of triphenylphosphine (0 · 3 g) and hydroquinone (0.1 g), reacted at 90 ° C for 18 hours, and then reacted with tetrahydrophthalic anhydride (105. 0 g) at 90 for 4 hours to obtain a carboxyl-containing resin , Its solid content is 65%, and the solid component acid value is 99 · 2 K0H. Examples 7 to 30 The unsaturated double bond-containing polycarboxylic acid resins of Examples 7 to 30 were prepared according to the components and amounts listed in Tables 2 to 4 below and reaction conditions. The solid content and acid value of the solid content are also listed in the following table 2-4 °

C: \ Program Files \ Patent \ l 5791 .ptd Page 15 484035 V. Description of the invention (12) Table 2 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 DEHSSX grams 25.0 25.0 25.0 25.0 DEH812 ( G) 25.0 25.0 25.0 25.0 Carbitol acetate (g) 37.5 38.2 37.4 37.8 28.0 26.4 27.7 26.2 Glycidyl methylpropionate (g) 13.8 13.8 13.5 13.5 Tetrabutylammonium bromide (g) 0.16 0.16 Triphenyl Phosphine (g) 0.15 0.15 Hydroquinone (g) 0.05 0.05 0.05 0.05 Reaction temperature (C) 100.0 100.0 100.0 100.0 Reaction time (hours) 7.0 7.0 7.0 7.0 Trimellitic anhydride (g) 13.3 10.3 13.0 10.1 Tetrahydrophthalic anhydride (g 14.7 14.7 14.4 14.4 Reaction temperature (° C) 90.0 90.0 90.0 90.0 110.0 110.0 110.0 110.0 Reaction time (hours) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Glycidyl methylpropionate (g) 13.8 13.8 13.8 13.8 Tetrabromide Butylammonium (g) 0.19 0.18 Triphenylphosphine (g) 0.19 0.18 Hydrogen awakening (g) 0.06 0.06 0.06 0.06 Reaction temperature (° c) 100.0 100.0 100.0 100.0 Reaction time (hours) 7.0 7.0 7.0 7.0 Tetraphthalic anhydride (g) 8.8 5.9 8.7 5.8 Trimellitic anhydride (g) 7.7 11.5 7.5 11.3 Response temperature (° c) 110.0 110.0 110.0 110.0 Reaction time (/ j, hour ) 5.0 5.0 5.0 5.0 Solid content (%) 65.0 65.0 65,0 65.0 65.0 65.0 65.0 65.0 Solid component acid value (mg / g KOH) 107.8 121.6 106.6 120.3 147.6 121.7 146.2 120.5 Note 1 Purchased from Dow Chemical Company, USA Phenol formaldehyde resin. Note 2 Phenol-formaldehyde resin purchased from Dow Chemical Company.

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Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Trimethylolpropane (g) 13.4 13.4 13.4 13.4 Pentaerythritol (g) 13.6 13.6 13.6 13.6 Carbitol acetate (g) 61.7 56.8 50.6 51.6 77.6 78.8 71.2 73.7 pyromellitic anhydride (g) 10.9 14.5 14.5 16.4 10.9 14.5 14.5 16.4 Reaction temperature (° c) 90 90 90 90 90 90 90 90 Reaction time (hours) 5 5 5 5 5 5 5 5 Tetrahydroanhydride ( G) 30.4 25.3 25.3 22.8 45.6 40.6 40.5 38.0 reaction temperature (° c) 90 90 90 90 90 90 90 90 90 reaction time (hours) 4 4 4 4 4 4 4 4 glycidyl methylpropionate (g) 35.5 33.13 33.13 31.95 49.7 47.33 47.33 46.15 Tetrabutylammonium bromide (g) 0.34 0.28 0.43 0.40 Triphenylphosphine (g) 0.32 0.29 0.44 0.41 Hydroquinone (g) 0.11 0.11 0.09 0.10 0.14 0.15 0.13 0.14 Reaction temperature (° c) 100 100 100 100 100 100 100 100 Reaction time (hours) 7 7 7 7 7 7 7 7 Tetrahydroanhydride (g) 24.3 19,0 7.6 11.4 24.3 30.4 16.2 22.8 Reaction temperature (° c) 90 90 90 90 90 90 90 90 Reaction Time (hours) 4 4 4 4 4 4 4 4 Solid content (%) 65 65 65 65 65 65 65 65 65 Solid content acid value (mg / g KOH) 102 101.1 69.01 86.97 81.02 101.3 72.89 91.38 iimi C: \ Program Files \ Patent \ l 5791 .ptd Page 17 484035 V. Description of the invention (14) Table 4 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Trimethylolpropane (g) 13.4 13.4 13.4 13.4 Pentaerythritol (g) 13.6 13.6 13.6 13.6 Carbitol Acetic Acid Ester (g) 62.0 56.2 56.2 53.3 86.1 80.3 80.3 77.5 Diphenylmethane diisocyanate (g) 12.5 16.7 16.7 18.8 12.5 16.7 16.7 18.8 Reaction temperature (° c) 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 Reaction time (hours) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Tetrahydroanhydride (g) 30.4 25.3 25.3 22.8 45.6 40.5 40.5 38.0 Reaction temperature (° c) 90 90 90 90 90 90 90 90 Reaction time (hours) 5 5 5 5 5. .5 5 5 Glycidyl methylpropionate (g) 28.4 23.7 23.7 23.1 42.6 37.9 37.9 35.5 Tetrabutylammonium bromide (g) 0.35 0.26 0.40 0.39 Triphenylphosphine (g) 0.29 0.28 0.48 0.39 Hydroquinone (g) 0.12 0.10 0.09 0.09 0 .16 0.13 0.13 0.14 Reaction temperature (° C) 100 100 100 100 100 100 100 100 Reaction time (hours) 7 7 7 7 7 7 7 7 Tetrahydrophthalic anhydride (g) 30.4 17.7 12.7 9.1 45.6 24.3 20.3 22.8 Triphenylene Acid anhydride (g) 7.6 12.7 13.7 16.2 20.3 15.2 Reaction temperature (° c) 110 110 110 110 110 110 110 110 Reaction time (hours) 4 4 4 4 4 4 4 4 Solid content (%) 65 65 65 65 65 65 65 65 65 Solid component acid value (mg / g KOH) 96.6 104.3 114.6 113, 7 104.3 122.6 128.4 119.2

Deployment Examples In the following deployment examples, the test items used to test the properties of the formulations and their meanings are as follows: ~ Item Page 18 C: \ Program Files \ Patent \ 15791.ptd 484035

V. Description of the invention (15) Film hardness after post-baking: Measured with a pencil hardness meter, the larger the number, the harder it is. Surface tack after drying: The less the surface fingerprint is measured by finger touch, the better it is. " Photosensitivity: Stouf fer step film is used to test the light hardening ability. The higher the number of cells, the better. Resolution after development: Stouffer step film is used to test the resolution. The smaller the value, the better. Adhesion ability after development: St ouffer step film was used to test the adhesion ability. The smaller the value, the better. Film-removing ability: The door (seconds) can be peeled when soaked in 3% Na 0 Η aqueous solution at 50 ° C. The shorter the time, the better. 'Baige adhesion: After coating the composition on the decorative board and drying, the film is cut with a blade into 100 centimeters per 1 centimeter centimeter.' After sticking with the tape, pull up the tape to calculate the film still attached to the decorative board. Number of cells. Higher values indicate better results. Acid resistance: The time (minutes) before immersion in 10% Η 2 S 0 4 aqueous solution without damage. The longer the time, the better the acid resistance. Alkali resistance: The time (minutes) when immersed in 10% NaOH aqueous solution without damage. The longer the time, the better the acid resistance. Solder resistance • Immerse in 230 C solder for 30 seconds and observe the number of times that the immersion is still harmless. The greater the number of times, the better the solder resistance. Flux resistance: The time (minutes) after baking the flux at 90 ° C after coating the flux on the film obtained by the composition at room temperature. The longer the time, the better the flux capability.

C: \ Program Files \ Patent \ l 5791 .ptd Page 19 484035 V. Description of the invention (16) Isopropyl alcohol resistance: The time (minutes) of soaking in 100% isopropyl alcohol without damage. Formulation Example 6 and Comparative Formulation Example The polycarboxylic acid resin containing terminal unsaturated double bonds of the present invention synthesized by the above example and the resin obtained in Comparative Example 1 were formulated into a photoresist according to the formulation shown in Table 5 below. And test its properties as described above. The test results are also listed in Table 5-1 below. Table 5 Development Photoresist Formulation Example 1 Formulation Example 2 Formulation Example 3 Formulation Example 4 Formulation Example 5 Formulation Example 6 Comparative Formulation Example 1 Resin (Wt%) Example 1 (60.0) Example 5 (60.0) Example 8 (57.0) Example 13 (57.0) Example 19 (57.0) Example 26 (57.0) Comparative Example 1 (60.0) SR4541 (wt%) 1.00 1.00 3.00 3.00 3.00 3.00 1.00 SR3992 (wt%) 2.00 2.00 3.00 3.00 3.00 3.00 2.W Irgacure- 9073 ( wt%) 2.00 2.00 2.00 2.00 2.00 2.00 2 00 2.00 Isopropylthioanthrone (wt%) Propylene glycol monoethyl ether acetate (Wt%) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Paint solvent # 1504 (wt%) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 BaS04 (wt%) 12.00 12.00 12.00 12.00 12.00 12.00 12.00 Talc (wt%) 16.90 16.90 16.90 16.90 16.90 16.90 16.90 16.90 Malachite green (wt%) 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Total (Wt%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0

Note 1 Trifunctional acrylic monomer purchased from SARTOMER. Note 2 Pentafunctional acrylic monomer purchased from SARTOMER.

C: \ Program Files \ Patent \ 15791.ptd Page 20 V. Description of Invention (17) f3 is a light starter from Ciba Jiaji Company. ° 4 Petroleum brain solvent purchased from China National Petroleum Corporation. 3 minutes: = spread on a copper substrate and dry for 65 minutes. Photosensitive is a dry film. Post-baking is listed at 150 ° C in Table 5-1 below. The exposure energy of the crime test is 100mj ·. Test results Table 5-1 Test properties of imaging photoresist Formulation Example 1 Formulation Example 2 Formulation Example 3 Formulation Example 4 Formulation Example 5 Formulation Example 6 Comparative Formulation Example 1 The surface tackiness of the rear surface of the vehicle B is free of Μ j \ Kagawa, Μ Gamma sacrifice sensitivity 5 ~ 6 5 ~ 6 5 ~ 6 5 ~ 6 5 ~ 6 5 ~ 6 5 ~ 6 Power of post image resolution (micron) 25 25 25 25 25 25 25 Ability to attach after imaging (Micron) 25 25 25 25 25 25 25 Film hardness after post-baking HB ΗΒ ΗΒ ΗΒ ΗΒ ΗΒ ΗΒ Film removal ability (seconds) 25 25 30 25 25 25 25 100 cells 100% 100% 100% 100% 100% 100 % 100% The polycarboxylic acid resin containing terminal unsaturated double bonds of the present invention synthesized in the above example and the resin obtained in Comparative Example 1 were formulated into a solder resist photoresist according to the formula shown in Table 6 below, and according to the above method Test its nature. The test results are also listed in Table 6-1 below. ,

C: \ Progmm Files \ Patent \ 15791.ptd Page 21 484035 V. Description of the invention (18) Table 6 Solder resist photoresist (solid epoxy resin) Formulation example 1 Formulation example 2 Formulation example 3 Formulation example 4 Formulation example 5 Formulation Example 6 Comparative Formulation Example 1 Resin (wt%) Example 1 (54.0) Example 5 (54.0) Example 8 (54.0) Example 13 (54.0) Example 19 (54.0) Example 26 (54.0) Comparative Example 1 (54.0) SR4541 ( wt%) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 SR3992 (wt%) 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 Irgacure- 9073 (wt%) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Isopropylthioanthrone (wt%) 0,4 0.4 0.4 0.4 0.4 0.4 0.4 Carbitol acetate (wt%) 1.00 1.00 1'00 1.00 1.00 1.00 1.00 Paint solvent # 1504 (wt%) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 BaS04 (wt%) 14.00 14.00 14.00 14.00 14.00 14.00 14.00 Talc (wt%) 5.0 5.0 5.0 5,0 5.0 5.0 5.0 YX40005 (wt%) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 TGIC6 (wt%) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Dicyanodiamine (wt%) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Melamine (Wt%) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2Y3017 (wt%) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Aerosil- 3008 (wt%) 0.5 0.5 0 .5 0.5 0.5 0.5 0.5 Total (wt%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Note 1 Note 2 Note 3 Note 4 Note 5 Note 6 A trifunctional acrylic monomer purchased from SARTOMER. Pentafunctional acrylic monomer purchased from SARTOMER. Light starter from Ciba Geigy. Petroleum brain solvent purchased from China National Petroleum Corporation. Epoxy resin from Yuka Shell. Epoxy resin purchased from Japan's Nissan Chemical or Ciba Geigy's ring

C: \ ProgramFiles \ Patent \ 15791.ptd Page 22 484035 V. Description of the invention (19) " '一 "' --- --- oxygen resin. Note 7 Pigments purchased from Toyo Ink. Note 8 Tackifier purchased from Degussa. The solder resist obtained in Table 6 was coated on a copper substrate, and a dry film having a dry film thickness of 18 μm was obtained after being baked at 75 μm for 45 minutes. Post-baking was performed at 15 ^ for 65 minutes. The exposure energy of the sensitivity test was 475] ^. The test results are listed in Table 6-1 below. Table 6 — 1 Test Properties of Solder Resist Photoresist (Solid Epoxy Resin) # Blending Example 1 Blending Example 2 Blending Example 3 Blending Example 4 Blending Example 5 Blending Example 6 Comparative Blending Example 1 Surface tackiness after drying / frrr 111 JW \ No without button M Photosensitivity 5 ~ 6 5 ~ 6 5 ~ 6 5 ~ 6 5 ~ 6 5 ~ 6 5 ~ 6 Resolution after development (micron) 25 25 25 25 25 25 25 Adhesion ability after development (Micron) 25 25 25 25 25 25 25 Film hardness after baking 7H 7H 7H 7H 7Η 7H 7H Acid resistance (minutes) 60 60 60 60 60 60 60 Test resistance (minutes) 60 60 60 60 60 60 60 Solder resistance (Times) 5 5 5 5 5 5 5 100 grid adhesion 100% 100% 100% 100% 100% 100% 100% Flux resistance (minutes Y 30 30 30 30 30 30 30 resistance to isopropyl alcohol (minutes) 120 120 120 120 120 120 120

C: \ Progmm Files \ Patent \ l 5791 .ptd Page 23 484035 V. Description of the invention (20)

RF800 (sold by Alfa Metals (ALPHA Note 1 Flux is L0NC0 metals)) The present invention synthesized from the above example contains a terminal ^ m M ^. Polyunsaturated unsaturated double bonds and comparison of the resin obtained by the state 'as follows The formulations shown in Table 7 were formulated with J anti-phosphonium photoresist and tested for its properties according to the method described above. Tested in Table 7-1 below. Solder resist (liquid epoxy resin)

Formulation Example 1 Formulation Example 2 Formulation Example 3 Formulation Example 4 Formulation Example 5 Formulation Example 6 Comparative Formulation Example 1 Resin (wt%) Example 1 (54.0) Example 5 (54.0) Example 8 (54.0) Example 13 (54.0) Example 19 ( 54.0) Example 26 (54.0) Comparative Example 1 (54.0) SR454 (wt%) 0.5 0.5 0.5 0.5 0.5 0.5 SR399 (wt0 / 〇) 5.5 5.5 5.5 5.5 5.5 6.0 6.0 5.5 Irgacure- 9073 (wt%) 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Isopropylthioanthrone (wt%) 0.4 0.4 0.4 0.4 0, 4 0.4 0.4 ¥ Acetate (wt%) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Paint solvent # 150 (wt%) 3.00 3.00 3.00 3.00 3.00 3.00 3.00 BaS04 (wt%) 14.00 14.00 14.00 14.00 14.00 14.00 14.00 Talc (wt%) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 DEN4381 (wt%) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 NPCN7042 (wt%) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Dicyanodiamide (wt%) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Melamine (Wt%) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2Y301 (wt ° / 〇) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Aerosil-3 00 (wt %) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Total (Wt%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0

C: \ Progmm Files \ Patent \ l 5791 .ptd Page 24 484035 V. Description of the invention (21) Note 1 Epoxy resin purchased from Dow Chemical Company. Note 2 Epoxy resin purchased from Nanya. The solder resist obtained in Table 7 was coated on a copper substrate and dried at 75 ° C for 45 minutes to obtain a dry film with a thickness of 18 microns. Post-baking is performed at 150 ° C for 65 minutes. The exposure energy of the sensitivity test was 475mj. The test results are listed in Table 7-1 below. Table 7-1 Test properties of photoresist (liquid epoxy resin) Formulation Example 1 Formulation Example 2 Formulation Example 3 Formulation Example 4 Formulation Example 5 Formulation Example 6 Comparative Formulation Example 1 Surface tackiness after drying J 1 Μ Μ Μ j \\\ Parallel photosensitivity 5 to 8 5 to 8 5 to 8 5 to 8 5 to 8 5 to 8 5 to 8 Resolution after development (micron) 25 25 25 25 25 25 25 Adhesion after development Capacity (micron) 25 25 25 25 25 25 25 Film hardness after baking 7H 7Η 7H 7Η 7Η 7H 7H Acid resistance (minutes) 60 60 60 60 60 60 60 Test resistance (minutes) 60 60 60 60 60 60 60 er Solderability (times) 5 5 5 5 5 5 5 100 grid adhesion 100% 100% 100% 100% 100% 100% 100% Flux resistance (minutes 30 30 30 30 30 30 30 30% isopropyl alcohol resistance (minutes ) 120 120 120 120 120 120 120 Note 1 The flux is LONCO RF800 (sold by Alfa Metals)

C: \ Program Files \ Patent \ l 5791 .ptd Page 25 484035 5. Description of the invention (22) It is obvious from the previous examples that the polycarboxylic acid resin containing unsaturated double bonds of the present invention has excellent heat resistance and acid resistance. Resistance and chemical resistance with excellent resolution, and can be used as development photoresist and soldering resist for printed circuit boards. _

C: \ Program Files \ Patent \ l 5791 .ptd Page 26

Claims (1)

6. Patent application: A type containing unsaturated acid resin contains at least two esters in the main chain (Winter C (〇) 一 ΝΗ-) < It is formed by the (methyl) group of another ring gas group after the ring opening of the acid anhydride, and the amino group and the isocyanate group 3 · If the patent range resin is applied, it is used as the base 4 · If the patent range resin is used, it is used as Imprint 5. · A method for preparing a polyacrylic acid resin as applied (a): a double bond polycarboxylic acid resin, characterized in that the polycarboxylic acid has at least two ester groups (-C (0) -0-) or The middle group in the chain (-C (〇) -〇 一) and urethane group) The polycarboxylic acid tree containing unsaturated double bond of item 1 is composed of a polyhydric alcohol or a formic acid resin, The ester group formed by the esterification reaction of the fluorenyl group and the unreacted carboxylic acid of a monocarboxylic acid or a polybasic acid is then esterified with an epoxy group containing an acrylic acid, and the formate group is formed by a polyol or a phenol formaldehyde resin. Formed by the isocyanate reaction of a compound. Polycarboxylic acid resistive photoresist of unsaturated double bond of item 1 or 2. Item 1 or 2 Polycarboxylic acid containing unsaturated double bond Soldering photoresist for circuit boards. A method containing unsaturated double bonds in item 1 or 2 of the patent scope, the method includes one of the following: (1) a polyol (or a phenol formaldehyde resin) reacts with an acid anhydride or a polyacid to form a compound containing a terminal carboxylic acid, (2 ) Further reacting the carboxyl group with the epoxy-containing (meth) acrylate, (3) the compound having a hydroxyl group obtained after ^ radical opening% is then esterified with an acid anhydride or a polyhydric line; method (b): 484035 VI. Scope of patent application (1) Polyol (or phenol-formaldehyde resin) undergoes a condensation reaction with a diisocyanate to form a compound containing a urethane group. (2) The polyol (or phenol-formaldehyde resin) is not reused. The reacted hydroxyl group is then esterified with an acid anhydride or a polybasic acid to form a compound containing a urethane group and a terminal group containing a carboxyl group. (3) The terminal carboxyl group and an epoxy group-containing (meth) propyl group are formed. Dilute acid ester reaction, (4) the hydroxyl-containing compound obtained after the epoxy group is ring-opened and then esterified with an acid anhydride or a polybasic acid; or method (c): 〇) Phenanthrene resin and epoxy-containing (meth) acrylates undergo a dehydration reaction. (2) The hydroxyl-containing compound obtained after the epoxy group is ring-opened is then subjected to an esterification reaction with an acid field or a polybasic acid. . 6. The method according to item 5 of the patent application, wherein the polyol is a compound containing at least two hydroxyl groups in the molecule and is selected from pentaerythritol, glycerol, propylene glycol, butanediol, Group consisting of pentanediol and hexanediol. 7. The method according to claim 5 of the patent scope, wherein the anhydride is a monoanhydride or 8. The method according to claim 7 of the patent scope, wherein the monoanhydride is selected from the group consisting of benzoic anhydride and tetrahydrophthalic anhydride. , Hexahydrophthalic anhydride, succinic acid and maleic anhydride and trimellitic anhydride. 9. The method of claim 7 in the scope of patent application, wherein the dianhydride is benzene homogeneous. 10 The method of claim 5 in the scope of patent application, wherein the polyacid-based molecule contains at least two compounds of Wei acid and is Selected from aliphatic and aromatic dicarboxylic acids C: \ Program Files \ Patent \ l 5791 .ptd Page 28 484035 6. Scope of patent application Acid, tricarboxylic acid and tetracarboxylic acid. 11. The method according to item 5 of the patent application, wherein the diisocyanate is selected from the group consisting of toluene diisocyanate, diphenylmethane-4, 4'-diisocyanate, hexamethylene diisocyanate, and bis (4-isocyanate group) A group consisting of cyclohexane and 1,4-bis (isocyanatemethyl) cyclohexane. 12. The method according to item 5 of the patent application, wherein the epoxy group-containing (fluorenyl) acrylic acid S is selected from glycidyl propionate, glycidyl methacrylate, and acrylic acid 3, 4-epoxy. Cyclohexylhexyl, 3,4-epoxycyclohexylhexyl methacrylate, 3,4-epoxyindan-butyl acrylate, 3,4-epoxyindan-1 methacrylate Groups consisting of -yl ester, 3,4-epoxyhetero-1-yloxyethyl acrylate and 3,4-epoxyindane-1 -yloxyethyl methacrylate . C: \ Program Files \ Patent \ l 5791 .ptd Page 29