TW455622B - Thermosetting resin composition - Google Patents

Abstract

A thermosetting resin composition which is useful for the formation of a solder resist or an insulating interlayer in a multilayer printed circuit board is disclosed. This composition contains (A) a cyanate ester compound possessed of not less than two cyanate groups in its molecule, (B) an epoxy compound possessed of not less than two epoxy groups in its molecule, (C) a metal salt of an aliphatic carboxylic acid, and (D) an organic solvent. The metal salt of an aliphatic carboxylic acid functions as a catalyst for the reaction of the cyanate ester compound with the epoxy compound.

Description

455622 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) Background of the invention 1. Field of the invention: The present invention relates to a thermosetting resin composition, which can be used for the production of printed circuit boards, especially for the production of multilayer Insulating interlayer or solder-resistant material in printed circuit boards. 2. The previous technical description: At present, the tendency to make the size of the semiconductor components in the main parts of electronic instruments has become smaller, lighter, high-performance and multi-functional, and due to the trend of electronic equipment production, printed circuit boards have also focused on How to increase the density of printed circuits, for example, by forming thinner conductor circuits, increasing the number of constituent layers, reducing the diameter of pinholes and closed hole diameters, etc., and making small wafer components with increased surface in a pre-stable state In other ways, the increased component on the surface of the board is operated at high density, and the printed circuit board that goes hand in hand with electronic equipment has an increasing demand for multilayer printed circuit boards, and due to the increase in demand, it is necessary to develop another A new method for manufacturing multilayer printed circuit boards. The conventional method for manufacturing a multilayer printed circuit board includes an overlapping step on the surface of an internal layer sheet, wherein the layer sheet has a semi-rigid sheet-like prepreg conductor circuit formed on the sheet in advance, and the prepreg The material is first immersed a substrate such as glass cloth in an epoxy resin varnish, and then the wet substrate is dried, and further, a multilayer body formed by the overlapping layer is set by pressure and lamination, and the substrate is formed on the substrate. A copper foil or copper plate layered sheet is laminated on the material as the inner layer. The epoxy resin used in this method is mainly a double paper. The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)- 4- -------------- ΐτ ------ ^, (Please read the precautions on the back before filling out this page) The Central Government Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives Seal 5 56 2 2 A7 B7 V. Explanation of the invention 6) Solid epoxy resin in the form of phenol A, and when the epoxy resin used contains bromine, it can impart flame retardancy to the multilayer printed circuit board obtained. In the above method, the laminated body is formed into a laminated layer by the steps of heating and pressing at the same time, which will extend the time spent on heating and pressing and cause adverse effects, forcing the entire production operation to be discontinuous, and at the same time reducing the production Operational efficiency. In addition to this problem, a formation technique (organization method) of a multilayer body using a solder resist ink composition as an insulating intermediate film has been proposed. For example, an alkaline developing type liquid solder resist is first applied to form a conductive circuit pattern on the upper inner layer. A method of forming a multilayer board by paneling, then drying the solder resist layer and shielding the predetermined via hole on the element, exposing the layer to light and developing the exposure layer to remove the via hole element, and then thermally curing the exposure Layer, and apply electroless copper plate electroplating to the thermal curing exposure layer, and apply electrolytic electroplating between the constituent layers of the multilayer board to form via holes and establish electrical continuity. Alternatively, the copper film can be formed by selective etching. Conductor circuit pattern. It is also known that the above-mentioned method can be repeated until a desired multilayer board is formed. However, when the photo-cured thickness is formed by the above method, the composition layer cannot provide the required interlayer film insulation due to the problems of the required repeated steps of repeated application, exposure, development, and thermal curing of the coating layer. Another problem is that it is difficult to maintain the stability due to the limitation of the formation of via holes. In this case, a method is known which can apply a thermosetting solder resist to an inner layer panel having a conductor circuit pattern formed thereon to form a via hole, and heat-fix the resistant application layer, and excite a body lightning This method burns the resin layer on the via hole. At present, this method has played a very important role. -------- IV ----- Ί Order -------- To- (Please read first Note on the back, please fill in this page again.) This paper size applies Chinese National Standard (CNS) A4 specification (2I0X297mm) -5- 4 5 56 2 2 A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Note 6) However, the insulating interlayer film obtained by this method has the disadvantages of lacking heat resistance, insulation reproducibility, and flame retardancy compared with the conventional method of prepreg multilayer substrate. DISCLOSURE OF THE INVENTION The present invention aims at designing a method that can reduce the problems of the above-mentioned prior art, and another object of the present invention is to provide a thermosetting resin composition which can form a high-yield hardened coating film having heat resistance. Excellent properties such as resistance, insulation, water resistance, and chemical resistance ', and these properties are generally those required for solder resists, such as those used in printed circuit boards and insulating interlayer films in multilayer printed circuit boards. Still another object of the present invention is to provide a thermosetting resin composition 'which can easily form a hardenable coating film having excellent flame retardancy in addition to the above properties. In order to achieve the above object, the present invention provides a thermosetting resin composition, comprising: (A) a cyanate ester compound having two or more cyanate groups in a molecule; and (B) two or more cyanate ester compounds in a molecule. Epoxy epoxy compound, (C) metal salt of aliphatic carboxylic acid compound (D) organic solvent. In a preferred embodiment, the cyanate ester compound (A) used has a melting point of 30 to 150 ° C, and the epoxy compound (B) uses a ring in the form of phenols or phenol novolacs. Oxygen resins are preferred, and in order to impart the required flame retardancy, the bromine content per mole of epoxy resin used is not less than 10% by weight. (Please read the notes on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) Λ4 specification (2) 〇 × 297 mm -6-45 56 2 2 A7 B7 5 'Description of the invention (4) Detailed description of the invention The liquid thermosetting resin composition of the present invention is characterized by Containing: (A) a cyanate ester compound having two or more cyanate groups in a molecule, (B) an epoxy compound having two or more epoxy groups in a molecule, (C) a metal of an aliphatic carboxylic acid compound Salt. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). In detail, one of the features of the present invention is: the use of a multifunctionality in the curing reaction system of the present invention Cyanate ester compound (A) and a multifunctional epoxy compound (B); generally, when the cyanate ester compound (A) and epoxy compound (B) are not lower than 180 ° When heated under C, the cyanate group and epoxy group will react with each other and cross-link to form an oxazoline ring. The characteristics of the cyanate group can make the three cyanates themselves bond to form an S- The triazine ring, based on this fact, the content of the cyanate ester compound incorporated into the composition is calculated based on the cyanate group contained in each equivalent of the heavy epoxy group in the epoxy compound (B), from 1.0 to A range of 3.0 equivalent weight is preferable. The oxazoline ring and the S-triazine ring formed in the above reaction system may have excellent heat resistance properties. However, considering the factors of the high reaction temperature used and the performance of the printed circuit board may be deteriorated due to heat, the composition It cannot be used stably as a solder resist. Therefore, another feature of the present invention is: in order to reduce the curing reaction temperature, metal salts (C) of aliphatic carboxylic acid compounds can be incorporated into the composition, such as oleic acid, stearic acid, or cyclic acid. Zinc or manganese salts of alkanoic acid are used as a catalyst for the reaction. At the same time, the curing temperature of the reaction can be reduced to 150 ° C, and the hardened coating is formed without the thermal performance of the printed circuit board being deteriorated. The film will have excellent heat resistance and water resistance according to the Chinese paper standard (CNS) A4 specification (2] 0X297 mm) 45 56 2 2 A7 B7. The term “cyanate ester compound” herein refers to a compound having two or more 0—C CN groups per molecule, and the specific cyanate ester compound (A) can be used. Examples are: AroCy β-l0, M-10, Tl0, Fl0, L-10-Dingfu-366 and 1171787 (available from Ya 531 ^-(: Hua 31 < .1 ^, which are various Derivatives of bifunctional phenolic compounds), AroCy R E X — 3 7 1 (available from Asaln-CMba KK.K., which is a derivative of phenolic resins) and PT-30 and PT-60 ( (Available from Lonza Corp.), and such as

Asahi-Ciba KK's products AroCy B-30, B-40S, M-2030, M300S and F40S, which contain the S-triazine structure produced by the trimerization reaction of the above-mentioned difunctional cyanate esters The chemical structure and melting point of these products are as follows: (Please read the precautions on the back before filling this page)

, 1T Jun! Printed by the Employees' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) -8-4 5 56 2 2 A7 B7 V. Description of the invention

AroCy melting point CH: N = C-0

0—C = N B- 1 0 79X; N ξ C—0—C H 2—〇 -C Three N CH, ^ CH3 M- 1 0 106Ό

Ni CF3: C ~ 0 ~~ ^ 〇> —c— <〇> —0— cf3

CsN F- 1 0 87¾ (Please read the notes on the back before filling this page)

ch3 N ^ C one 0— {0 ^ ~ C H ~ (〇) —0 one C = N L-l 0

Liquid

0 1 c = N

CICIC

N 111 c o RTX-366 Semisolid 0—C = N 0—C = N 0—CsN C H2—CH2— REX-37 1

The above-mentioned cyanate ester compounds printed by the Employees Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of Semisolid may be single or a combination of two or more. These cyanate ester compounds have a melting point of 30 ° C to 50 ° C, such as AroCy B — 1 ◦ Compounds of Μ 10, F-10 and T-10 proved to be particularly effective &gt; If the melting point of the compound is lower than 30 t, the insufficient temperature will cause the composition during printing and thermal curing The viscosity of this paper applies the Chinese National Standard (CNS) A4 specification (210/297 mm) -9- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 5 5 6 2 2 A7 _W V. Description of the invention t) will be reduced , And cause negative effects such as reduction of the amount or coating. On the other hand, if the melting point is higher than 150 ° C., Too high temperature will make the compound recrystallize during the thermal curing reaction and cannot be used. At the same time, it will cause the reduction of properties and negative effects such as residues. Generally, the content of the cyanate ester compound in the composition is calculated based on the cyanate group contained in each equivalent of the epoxy group in the epoxy compound (B), and the weight is from 1.0 to 3.0 equivalents. The range is better, and if the ratio of cyanate groups is less than 1.0 equivalent weight, the lack of the amount will maintain the epoxy group and reduce the performance of heat resistance and water resistance. On the other hand, if the ratio is greater than 3. When the weight is 0 equivalent weight, the S-triazine structure formed by the trimerization reaction of cyanate groups will not be easily generated, and the unreacted cyanate groups will be easily left. Moreover, if the gel time or coating property is prolonged, A severe increase will also have a negative impact. Specific examples of the epoxy compound (B) having two or more epoxy groups per molecule in the composition include various well-known and applicable epoxy resins, including: typical glycidyl ether compounds such as bisphenol A epoxy Resin, bisphenol F epoxy resin, bisphenol S epoxy resin, brominated bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol epoxy resin, bixylenol epoxy resin, phenol novolac Lacquer epoxy resin, cresol novolac epoxy resin, brominated phenol novolac epoxy resin, bisphenol A novolac epoxy resin; glycidyl ester compounds such as diglycidyl terephthalate and Dimer diglycidyl esters; and glycidylamine compounds, such as N, N, N ', N'-tetraglycidylmethylxylene diamine, N, N'N', N'-tetraglycidyl Bis (aminomethyl) -cyclohexane, and N, N-diglycidylaniline. These epoxy resins can be single (please read the precautions on the back before filling this page), 1T paper size is applicable to China National Standards (CNS> Α4 specifications (2! 〇 × 297 mm) -10- A7 B7 455622 5 , Description of the invention) or two or more of them in combination, in which phenol or cresol phenolic lacquer epoxy resin (polyfunctional epoxy resin not containing a hydroxyl group) produces a particularly excellent effect. When a specific epoxy compound having a hydroxyl group is used, the cyanate group will react with the hydroxyl group before the cyanate group reacts with the epoxy group. Such a prior reaction will cause a decrease in heat resistance. The hardening coating of the resin composition is often required to have flame retardant properties when formed. Therefore, it is preferable to incorporate a brominated bisphenol A epoxy resin or a brominated phenol novolac epoxy resin into the composition. The content is Not less than 10% by weight per mole. Also considering the lack of heat resistance, the brominated phenol novolak epoxy resin proved to be a more beneficial choice. Therefore, the function of the epoxy compound can also be used as a varnish component of the thermosetting resin composition. The appropriate epoxy compound content in the thermosetting composition is 20 to 60% by weight (based on the total weight of the composition). ). If the content is less than 20% by weight, the insufficient content will cause negative effects such as insufficient paint components and prevent the required printability from being obtained; on the other hand, if the content is greater than 60% by weight, this excess interferes with the appropriate amount Of the cyanate ester compound into the composition, causing a negative effect. In addition, the metal salt (C) of the aliphatic carboxylic acid used in the composition of the present invention may be any known metal soap salt, such as: octanoic acid, lauric acid, myristic acid, oleic acid, stearic acid, Cobalt salts, manganese salts, lead salts, calcium salts, zinc salts, copper salts, iron salts, zirconium salts, and aluminum salts of aliphatic carboxylic acids such as naphthenic acids. Among the above metal salts, oils having high catalytic activity are used. Zinc or manganese salts of acids, stearic acids, or naphthenic acids and zinc stearate are particularly effective, and these metal salts of aliphatic carboxylic acids can be in the form of a single or a combination of two or more species, and (please (Please read the notes on the back before filling out this page) Printed by the Central Consumers' Cooperative of the Ministry of Economic Affairs. The paper is printed in accordance with Chinese National Standards (CNS) A4 (2 丨 〇 X 297 mm) -11-455622 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 ____ B7 V. DESCRIPTION OF THE INVENTION 0) The appropriate content of the metal salt incorporated into the composition is from 0.5 to 15 parts by weight (based on the aforementioned 100 parts by weight of the cyanate ester compound (A)). If the content is less than 0.5 parts by weight, the resin composition requires a long gel time and causes coating and further extension of the additional curing time; on the other hand, if the content is more than 15 parts by weight, an excessive amount of The metal salt also adversely affects the electrical properties of the formed hardenable coating film. The organic solvent (D) in the composition of the present invention may be a well-known and commonly used solvent, including: ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethyl Glycols; glycol ethers, such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl Ethers, dipropylene glycol diethyl ether, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, celloacetate acetate, butyl cellosolvate acetate, carbitol acetate Esters, butyl carbitol acetate, propylene glycol monomethyl ether ethyl ester, and propylene carbonate: aliphatic hydrocarbons, such as octane and decane; and petroleum solvents, such as petroleum ether, naphtha, and solvent-based Naphtha and so on. It is preferred that the above-mentioned organic solvent does not contain a hydroxyl group in the molecule, because the hydroxyl group of the ι: E will react with the cyanate group first, and this will adversely affect the heat resistance of the curable coating film. These organic solvents may be in the form of a single or a combination of two or more components. The content of the organic solvent incorporated in the composition of the present invention is 10 to 100 parts by weight (based on 100 parts by weight of the epoxy compound (B) forming the paint component), and if the content is less than When the content is 10 parts by weight, the viscosity of the composition will increase improperly and quickly, so that the appropriate printing is required (please read the precautions on the back before filling this page), 1T 崦 丨 · This paper size applies Chinese national standards (CNS) Α4 specification U! OX297 public money) -12- 455622 A7 B7 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and Consumer Cooperation Du printed V. Description of the invention (ίο) On the other hand, if the content is greater than 1,000 It will cause negative effects on coating and gel shrinkage. In order to improve the adhesion of the coating film to the substrate and increase the hardness of the hardening coating film, the thermosetting resin composition of the present invention can be incorporated into other well-known or customary inorganic materials, such as barium sulfate, talc, Silica, alumina, aluminum hydroxide, and calcium carbonate. When the thermosetting resin composition is used as an intermediate insulating layer, the surface of the insulating layer is easily roughened when treated with an acid, and calcium carbonate may be selected as the inorganic. It should be noted that the content of the above-mentioned inorganic filler incorporated into the composition is not more than 1,000 parts by weight (based on 100 parts by weight of the above-mentioned epoxy compound (B) which will form a paint component), and if the content is At 100 parts by weight, negative effects such as a decrease in printability and a decrease in the strength of the coating film will occur. Further, the thermosetting resin composition of the present invention can optionally incorporate well-known and conventional additives such as additives such as coloring pigments, coloring dyes, thickeners, antifoaming agents, leveling agents, and coupling agents. It can also incorporate rust inhibitors that can prevent the copper foil from oxidizing, such as dicyandiamine, 0-o-tolyldiguanide, and melamine. When the thermosetting composition of the present invention is used as a solder resist, it can be used in printing. A solder resist pattern is printed on the circuit board by aging screen to obtain a solder resist layer, wherein the printed circuit board has a formed circuit, and the printed pattern is thermally cured at 150 ° to 170 ° C as It takes about 20 to 60 minutes. When the thermosetting resin composition of the present invention is used as an insulating interlayer film, a multilayer printed circuit board can be applied by a suitable coating method-the resin composition, for example, on the entire surface of an inner substrate having a circuit formed thereon in advance. Screen printing (please read the precautions on the back before filling out this page) This paper size is applicable to China National Standards (CNS) M specifications (210x297 mm) -13 · Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5 56 2 2 A7 ____B7 V. Description of the invention (11) or roller printing, the resin composition on the application layer is thermally cured at 150 to 170 ° C for 20 to 60 minutes to excite The volume laser method burns and removes the via hole from the thermosetting layer to form a copper foil on the final insulation layer obtained from the electrolessly plated copper plate and the electrolytic copper plate, and then uses a resist to form a second circuit pattern opening layer. The second layer circuit is generated by selecting the copper foil etching method, and then the step is repeated until the step of generating the required multilayer circuit board is completed. When the thermosetting resin composition of the present invention is subjected to the manufacturing method described above, it can make the final insulating layer obtain the heat resistance and lower water absorption properties required by the conventional thermoresin composition or the photo-curable and thermosetting resin composition. It further enables the insulating layer to have the correct track of the necessary fine circuit shape that cannot be obtained by manufacturing the same level of adhesive sheet. Moreover, the resin composition can make the printed circuit board more flame-retardant, And it is easier to meet the standards required for printed circuit boards. Herein, the present invention will be specifically explained with the following related examples and comparative examples, wherein the "parts" and "%" are fixed on a weight basis unless otherwise specified. Example 1 75 parts of bisphenol A epoxy resin (made by Yuka · Shell Epoxy KK, and sold under the trade name "EPIK 0 TE" 1 0 0 1) were dissolved in 25 parts of carbitol acetate In the following, the finally obtained lacquer is designated as "A lacquer". In addition, 75 parts of cyanate PT-30 (manufactured by Lonza Corp.) is dissolved in 25 parts of carbitol acetate, and the following will be final ( Please read the precautions on the reverse side before filling out this page) '? Τ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -14- 455622 A7 ___ B7 V. Description of the invention (12) 得到The lacquer is labeled &quot; P ”lacquer". A three-roller honing machine was used to knead the blends of A lacquer and P lacquer in the following proportions to obtain a thermosetting resin composition A lacquer 1 0 0 phthalocyanine green 1 part magnesium stearate 2 parts silicone Basic ingredients resistance 1 part foaming agent P lacquer 30 parts barium sulfate 9 G parts talcum powder 10 parts fine powdered silica 2 parts carbitol acetate 5 parts total 2 4 1 parts Example 2 will be 7 5 parts Cresol novolac epoxy resin (manufactured by Dainippon's Ink and Chemical Company and sold under the trade name "EPICL ◦ n" n-6 8 0) is dissolved in 25 parts of carbitol acetate ' The resulting lacquer is hereinafter referred to as "B lacquer". A three-roll honing machine was used to knead the B varnish blend in the following proportions to obtain a thermosetting resin composition. 100 copies of B lacquer This paper size applies the Chinese National Standard (CNS) Λ4 regulations (210X297). 15---- ---; -------- 1 -----: 111. ------ ^ I.. ”(Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ 5 56 2 2 A7 B7 V. Description of the Invention (Ί3) Peptides 1 part cyanine green zinc naphthenate 2 part antifoaming agent based on silicone 1 part AroCy M ― 10 0 part barium sulfate 20 part fine powder silica 2 part carbitol acetate. 5 Parts · Total 1 9 1 parts Example 3 7 5 parts of brominated phenol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ud., And sold under the trade name "BREN — S") were dissolved in 2 5 In the parts of carbitol acetate, the resulting lacquer is hereinafter referred to as "C lacquer". A three-roll honing machine was used to knead the C varnish blend in the following proportions to obtain a thermosetting resin composition. -------— V -----_—— Order ------ Side I (Please read the notes on the back before filling out this page) Staff Consumer Cooperatives, Central Liquor Bureau, Ministry of Economic Affairs, India and Li C lacquer 100 parts phthalocyanine green 1 part zinc stearate 2 parts silicone-based anti-foaming agent 1 part dicyanodiamidine 0.2 part AroCy B — 1 0 50 parts barium sulfate 30 parts of talc powder 10 parts This paper size is in accordance with Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) 16-^ 55622 A7 _____B7_ V. Description of the invention (14) Fine silica powder 2 parts acetic acid card Bisol ester__ 5 parts total 211. 2 parts Comparative Example 1 Using a three-roll honing machine, the B varnish blend of Example 2 in the proportion of F column was kneaded to obtain a thermosetting resin composition. 100 parts of B lacquer printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, 1 part of phthalocyanine green, 1 part of mili (obtained from Shikoku Kasei Kogyo, 4 parts of KK ·, sold under the trade name "CUREZOL" 2ΜZ · ΑΑ) with silicone Anti-foaming agent as the basic ingredient 1 part of dicyanodiamidate 0.2 part of barium sulfate 30 part of talcum powder 10 part of finely divided silica 2 part of carbitol acetate 5 part --- ------.— Order -------- ^ I (Please read the notes on the back before filling out this page) Total 1 5 3. 2 Evaluation of nature: Examples 1-3 and Comparative Examples The thermosetting resin composition of 1 uses a 150 mesh screen printing board. In the printed circuit board with a circuit pattern formed in advance, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 17-4 Ministry of Economic Affairs 5 56 2 2 A7 ___ B7 printed by the Consumers' Cooperative of the Central Bureau of Standards 5. The solder resist pattern of the invention description (is) is printed several times, and then the solder resist pattern formed by the final resin composition is set. Heat-cured in a circulating hot air oven. The temperature was set to 150 ° C for 60 minutes to prepare a review. Samples of the nature of the substrate. (1) Hot solder resistance The sample substrate coated with rosin-type flux was immersed in a solder bath set at a temperature of 26 ° C for 30 seconds, and then washed with trichloroethane to remove the flux. Then, the situation of swelling, peeling, or discoloration of the anti-layer was evaluated visually at the following three levels. 〇: No observable change at all, Δ: Only a slight change was observed, X: The anti-layer showed swelling And signs of peeling. (2) Acid resistance The sample substrate is immersed in 10 v 001.% sulfuric acid aqueous solution for a certain period of time (for example, 30 minutes) at room temperature, and then washed with water and subjected to a peeling test with an adhesive tape, and then The separation and discoloration of the resistant layer were evaluated visually at the following three levels: ○: No observable change at all '△: Only a slight change was observed, X: The resistant layer showed signs of separation. (3) Water absorption (please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210x297 mm) -18- Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 455622 A7 _B7 V. Description of the invention (16) The sample substrate with a hardening coating film is prepared under the same conditions as above. It uses a glass sheet that has been weighed before chemical equilibrium to replace the printed circuit board. The weight of the curable coating film was measured. The sample substrate was immersed in boiling water for 1 hour, and then weighed to obtain the water absorption (%) of the film. (4) Insulating sample substrate with a hardenable coating film is prepared under the same conditions as above. The comb-shaped electrode B sampling tube of IPCB-2 5 is used to replace the printed circuit board, and a DC 50 0 V bias voltage is applied to the substrate. On a comb electrode, the sample substrate was tested for insulation. (5) The thermosetting resin composition of glass transition temperature examples 1 to 3 and comparative example 1 were applied to a Teflon substrate (TMIon, E.I. du Pont de Nemours &amp; Co. The registered trademark of Polytetrafluoroethylene) was thermally cured on all surfaces under the above conditions, and the final curable film was peeled off through the substrate, and then its glass transition temperature was detected by a thermomechanical analysis device. The evaluation results of the properties are shown in Table 1. ---------------- Order .------- ft (Please read the notes on the back before filling out this page) The paper size applies to China National Standard (CNS) A4 Specifications (210X297 mm) -19- 15 5 6 2 2 A7 B7 V. Description of the invention (17) Table 1 Properties Example 1 Example 2 Example 3 Comparative example 1 Hot soldering resistance 〇〇〇〇 Acid resistance 〇〇 〇Δ Water absorption (%) 0.42 0.38 0.32 1.08 Insulation (Ω) 1.2 X 10 "1.4 X 10M 1.6 X 1014 7.2 X 10 &quot; Glass transition temperature (〇C) 15 6 16 4 16 2 12 1 Some have been revealed here Specific embodiments, and the present invention can be used to describe but not limit the invention without departing from the invention, and the scope of the invention can be expressed by the scope of the claimed patent, and the invention is not limited to the foregoing description and its contents The equivalent scope or content of the application is changed. (Please read the notes on the back before filling in this page.) Printed on the paper by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) -20-

Claims (1)

-zib b6 2 2 A8 B8 C8 D8 Announcement VI. Patent Application Scope Annex A No. 87 120374 Patent Application in Chinese Application for Patent Scope Amendment The Republic of China Amendment March 1, 1990 1. Kind of Thermosetting Resin Composition} It contains (A) Cyanate esters having two or more cyanates a in the molecule &gt; The system contains A r 0 C y 13 — 1 0 B — 3 0 B — 4 0 S Μ — 1 0, Μ — 2 0 Μ 3 0, Μ — 3 0 S Τ — 1 0-F — 1 0 F — 4 0 8 L-1 0 R Τ X 3 6 6 XU 7 1 7 8 7 m (Please read the note on the back first Please fill in this page for more information) REX-3 7 1 (Asahi-Ciba KK) and PT — 3 0 and PT — 60 0 ί Lonza Corp); Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (B) The epoxy compound having two or more epoxy groups in the molecule is selected from the group consisting of bisphenol A epoxy resin> bisphenol F epoxy resin 1 bisphenol S epoxy resin, brominated bisphenol A epoxy resin, hydrogenated Bisphenol A epoxy resin &gt; Bisphenol epoxy resin, bixylenol epoxy resin, phenol novolac Enamel epoxy resin, cresol novolac epoxy resin, brominated phenol novolac epoxy resin, bisphenol A novolac epoxy resin, terephthalic acid dishrinking Diglycidyl phenylarsinate, dipolymerized diglycidyl ester, diglyceride 丨 丨 Shanky polyurethane, N, N, N ', N' tetrakisperyl perylene dixylylene diamine, N, N, N '&gt; N'-tetra-glycidyl bis (aminomethyl) -cyclohexane, and at least one of the N, N-diglycidyl aniline population; (C) aliphatic carboxylic acid Metal salts of acid compounds are selected from the group consisting of octanoic acid and monthly paper. Applicable to Chinese National Standard (CNS) A4 (2) 0 X 297 mm. A8B8C8D8 455622 6. Scope of patent application (please read the precautions on the back first) (Fill in this page again) Cobalt, manganese, lead, calcium, zinc, copper, iron, osmium, and sodium salts of lauric acid, tetradecanoic acid, oleic acid, stearic acid, and naphthenic acid, and At least __ • of the aluminum salt population; (D) organic solvents selected from the group consisting of ketones, aromatic hydrocarbons, glycol ethers, and esters Aliphatic hydrocarbons and petroleum solvents: wherein the content of the cyanate ester compound (A) incorporated in the composition is 1.0 to 3.0 equivalent weight, based on one equivalent of the epoxy compound (13) The heavy epoxy group is used as a reference; the content of the epoxy compound (B) is 20 to 60% by weight, based on the total weight of the composition; the content of the metal salt (C) of the aliphatic carboxylic acid is 0.5 To 15 parts by weight, based on 100 parts by weight of the cyanate ester compound (A); the content of the organic solvent (D) is 100 parts by weight or less, and 100 parts by weight of epoxy Compound (B) is used as a reference. 2. If the composition of the scope of the patent application item 1, the melting point of the cyanate ester compound (A) is 30 ° C to 150 °: 3. If the composition of the scope of the patent application item 1, The epoxy compound (B) is a phenol or cresol novolac epoxy resin. Printed by the Consumers' Cooperative of the Ministry of Economic Affairs, the Ministry of Economic Affairs 4. If the composition of any of the items 1 to 3 of the scope of patent application is applied, the epoxy compound (13) contains not less than 0 weight per molecule % Bromine. 5. The composition as described in any one of items 1 to 3 of the patent scope, wherein the metal salt (C) of the aliphatic carboxylic acid is at least one selected from the group consisting of oleic acid, stearic acid, and naphthenic acid. Groups of zinc salts and manganese salts of acids-6. For the composition of one of the items 1 to 3 of the scope of patent application, -2- This paper size applies to China National Standard (CNS) A4 (210 X 297) Love) 405622 A8 B8 C8 D8, the scope of patent application where the organic solvent (D) contains 10 to 100 parts by weight of the child, based on i 00 parts by weight of the epoxy compound (B). 7. If the composition of any one of items 1 to 3 of the scope of the patent application, it may additionally contain not more than 100 parts by weight of inorganic aggregates, with 100 parts by weight of the epoxy compound (B) as Benchmark. 8. The composition as claimed in any one of claims 1 to 3 | It may further contain at least one selected from the group consisting of color pigments, dyes, thickeners, anti-foaming agents, leveling agents, coupling agents and anti- Additives for rust. (Please read the note on the back before filling in this page) ^ ------- ^ — Order --------- line · Printed paper standards applicable to employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs China National Standard (CNS) A4 Specification (210 X 297 mm) -3-