TW201124451A - Polyamide compound and epoxy resin composition formed by containing the same - Google Patents

Abstract

The present invention is a polyamide compound characterized by having a partial structure represented by the following general formula (I) and/or general formula (I') in the repeating unit (wherein X in the formula represents a hydrogen atom or a hydroxyl group), and an epoxy resin composition using the said compound as a hardening agent. The polyamide compound of the present invention can impart a high peel-strength against the surface having a low surface roughness to the epoxy resin without increasing the blending amount of a filler.

Description

201124451 VI. Description of the Invention: [Technical Field] The present invention relates to a novel polyamine compound and an epoxy resin composition containing the same, and more particularly to a novel polyamine having a specific structure in a repeating unit A compound, and an epoxy resin composition containing the same suitable for a build-up type insulating material. [Prior Art] Epoxy resin is excellent in insulation, dimensional accuracy and strength. It has been widely used in printed wiring boards in the past, especially for high glass transition temperature and low linear expansion coefficient 'flexibility. From the viewpoint of the article, it has been proposed to use a polyamine compound having an illustrative radical in a hardener (Patent Document 1). On the other hand, in the case of a thin printed circuit board, there is a tendency to lower the surface roughness of the printed circuit board. Therefore, in recent years, there has been a demand for a heat-curing type capable of maintaining high peel strength on a surface having a small surface roughness. Insulating resin. In addition, in order to improve the strength, 3 there is a means for adding a filler to the resin to reduce the linear expansion property, but when the addition amount of the filler f is increased, the tensile strength of the resin is lowered. The linear expansion property was lowered without increasing the blending amount of the filler, but the material was not found. CITATION LIST Patent Literature Patent Literature 1 SUMMARY OF THE INVENTION The object of the present invention is to provide a doping which does not increase the filling of the filling agent 4/22 201124451. In the case of blending, an epoxy resin is provided to impart a high peel strength to a surface having a small surface roughness. A second object of the present invention is to provide an epoxy resin composition having high peel strength on a surface having a small surface roughness. Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-described objects. As a result, it has been found that a novel polyamine compound having a function of imparting a high peel strength to a surface having a small surface roughness is found. The present invention has been completed. That is, the present invention is a polyamine compound and an epoxy resin composition comprising the polyamine compound, characterized in that: in the repeating unit, eight have the following general formula (I) and/or general formula (Γ) indicates part of the structure;

(I,) However, x in the above general formula represents a hydrogen atom or a hydroxyl group. The polyamine compound of the present invention may have a partial structure represented by the following general formula (Π) in addition to the above partial structure having a sulfone bond in the above repeating unit.

0 II (II) 201124451 Further, the polyamine compound of the present invention may have a partial structure represented by the following general formula (ir) in addition to the above-mentioned partial structure having a sulfone bond in the above repeating unit.

The polyamine compound of the present invention especially means a polyamine compound composed of a diamine compound and a dicarboxylic acid compound, and the above-mentioned diamine compound is preferably only 3,3'-diaminodiphenyl sulfone, or It consists only of 3,3,-diaminodiphenyl sulfone and 2,4-diamine. The epoxy resin composition of the present invention must contain the polyamine compound K1 (8) parts by mass of the present invention, and more preferably the ball having an average particle diameter of 〇1〇20, with respect to 1 part by mass of the epoxy resin. A corrosive oxide and/or a scale flame retardant is used as a filler. Further, the amount of the above (4) is preferably 5 to 1 part by mass based on 1 part by mass of the total of the epoxy resin and the polyamide compound. Effect of the Invention By using the polyamine compound of the present invention as a curing agent for an epoxy resin, it is possible to obtain a thermosetting ring which has high peel strength on a surface having a small surface roughness and is suitable as a build-up type insulating material. Oxygen resin composition. [Embodiment] The polyamine compound of the present invention is a polyamine compound obtained by reacting a diamine compound mainly composed of 3,3,-diaminopyrene and a bis-acid compound. , is a compound not described in the literature. In the present invention, various diamine compounds may be used in combination with the above 3,3-aminoaminodiphenyl hydrazine. The diamine compound 6/22 201124451 which can be used together with the above 3,3'-diaminodiphenyl hard can be exemplified by m-phenylenediamine, p-diphenylamine, m-diamine, 4, 4, _ Diaminodiphenyl ether, 3,3'-dimercapto-4,4,-diaminodiphenyl ether, 3,4,-diaminodiphenyl, 3,3'-diaminodiphenyl Sulfur-, 4,4'-diaminodithiocarb, 3,3'-dimercapto-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4 ,-Diaminodiphenyl sulfide, 3,3'-dimethoxyoxy 4,4,-diaminodiphenyl sulfide; 4,4,-diaminodiphenyl ketone, 3,3' - Dimercapto-4,4,-diaminodiphenyl ketone, 3,3,-diaminodiphenyl decane, 4,4'-diaminodiphenyl decane, 2,2,-double (3-Amine-based) Propane, 2,2-bis(4-amine-phenyl)propane, benzidine, 3,3, dimercapto-phenylamine, 3,3'-dimethoxybenzidine, 3 , 3,-diaminobiphenyl; p-diphenylene diamine, m-dioxane diamine, o-diphenylene diamine; 2,2,_bis(4-aminophenoxy)propane, 1 , 3-bis(4-amine phenyloxy) stupid, 1,3, bis(3-aminophenoxyphenyl)propane; bis(4-amino-3-methylphenyl)methane, Double (4- 3-,5-didecylphenyl)decane, bis(4-amino-3-ethylphenyl)decane, bis(4-amino-3,5-diethylphenyl)anthracene Alkane, bis(4-amino-3-propylphenyl)decane, bis(4-amino-3,5-dipropylphenyl)decane; 2,2,_bis (3_amine Hexafluoropropane, 2,2,-bis(4-aminophenyl)hexafluoropropane; 2,4-diaminophenol. In the present invention, it is particularly preferable to use 3,3,-diaminodiphenyl sulfone alone or a combination of 3,3'-diaminodiphenyl sulfone and 2,4-diaminophenol. Thereby, the reactivity with various epoxy resins can be improved, so that a resin composition having a higher resin strength can be obtained. The dicarboxylic acid compound 'used by the present invention' may, for example, be o-dibenzoic acid, m-dicarboxylic acid, terephthalic acid, 4,4,-oxydisuccinic acid, 4,4,-diphenyldicarboxylic acid. , 3,3'_-althylene dibenzoic acid, 4,4,-thiodibenzoic acid, 3,3,-carbonyl dibenzoic acid, 4,4,-sulfonyl dibenzoic acid, 1,5- Naphthalene dicarboxylic acid, iota, 4-naphthalene diterpenoid, 2,6-naphthalene diterpenoid acid, iota, 2-naphthalene diteric acid, 5-perylene picolinic acid, 4-hydroxyisophthalene Acid, 2-hydroxy m-decanoic acid, 3-hydroxyisophthalic acid 7/22 201124451 丄J酉夂, 2'2-bis(3-indolylphenyl) hexafluoride, 2,2,·double Continuing benzene/, propylene-based material, the moderate thermal stability and the compounding point of the compound, _ is the key = month or para-phenylene acid. The following is specifically illustrating the present invention. The polyamine compound invention is not limited to these specific examples.

PA-I

8/22 201124451::: Small surface with high peel strength, thermosetting epoxy resin No special::: 5 Oxygen: Epoxy resin used in the fat composition: Ethylene oxime: ^ :: Fragrance: oxygen compound 'for example, ί; two: one, bisphenol A, bisphenol ρ~ 77 tetrabromobisphenol A, -hydroxybiphenyl, sulphuric acid: The valency alcohol exemplifies that the oxidizing agent having at least one alicyclic group or ring cyclizing agent will contain a ring cycline or an oxidized ring _ heart compound having a ring A diglycidyl glycerin ... W as exemplified by deuterated bisphenol 3 4别】^ 己基¥基_3,4_epoxycyclohexanoic acid 4-ylcyclohexyl_3,4·epoxy small methyl hexidine vinegar, vinegar, hexyl group ·6-methyl·3 4, epoxy cyclohexane succinic acid epoxy (3,4·epoxy Jf m, monomethylene dimethylene dichloride · again (3,4_epoxycyclohexyl) propyl, Diepoxy oxygen o-extended ethyl bis (3, core epoxy ring hexahydrate slow-acid vinegar), ring tr hex: r (four) cool, epoxy hexanitro-p-dibenzoic acid epoxide listed as aliphatic polyol or Reduced glycidyl ether, poly-long-chain polybasic acid poly, '.θ, propylene_水甘(四) or 曱(4) Acid glycidol brewing 9/22 201124451 j A homopolymer synthesized from ethylene; a dilute acid glycidol vinegar or methyl dimethyl acrylate (4) and a copolymer of other ethylene monomers synthesized by ethylene polymerization. Representative compounds include M-butanediol diglycidyl A; hexanediol glycidol shouting 'triglycerin of glycerol _, three-way tri-glycoside _, sorbitol The hexahydroglycidoxime of thorn, dipentane = diglycidyl (tetramethylene) of polyethylene glycol, and the glycidol of polyglycol, the glycidol t of the polyol is burned by 1%, from the upper part of the oxygen Into propylene glycol, tribasic propylene, glycerol (four) multi-component polyglycidol r fat expansion: - diglycidyl diglycidyl ester. In addition, can be cited as a fat "photographed single shrinking sweet _ into this Glycidyl ester, octyl ester, butyl stearate, and oil, epoxy stearic acid, hydrazine butyl acrylate, epoxidized polybutylene a diene or the like. In the acrylating composition of the r resin, 'other epoxy resin hardeners are used in addition to the polyfluorene of the present invention. By combining with other hardeners, the viscosity or hardening property, and the hardened composition of the hardened composition, together with the compound, can be used as a hardener or a polyamine. ===-The above-mentioned latent hardener can be used for the ageing of 5 substances. Miwa compounds, amine adducts, rhododendron 7 amines, hydrazine, hardships with these submarines, available ·=·, #° By using the above-mentioned latent hardening: the above-mentioned polyamine compound in the sclerosing group of the liquid type of the formula, the example of which is the preferred form of the present invention. For example, ethylenediamine may be mentioned. Diethyl three 10/22 201124451 aliphatic polyamines such as amines, triethylenetetramines, etc.; montanium di(tetra)yl...cyclohexyl heart, bis((tetra)yl)cyclohexane: polyamines $amine=) 2,4, 8 exhibits an aliphatic amine having an aromatic ring such as aliphatic A, m-xylene diamine, etc.; tetraphenyl-bimoon female, 2,2-bis (4-amine) Phenyl)propanthene, diaminodiphenylformamidine, diamine, its second stone, α,α-bis(4-amineindolyl)-p-diisopropylbenzene, tertamine base> An aromatic polyamine such as 1,1,1,3,3,3-hexafluoropropanone. , before, more complex, for example, can be listed (four) · (four), neighboring a = =: three Ding test * two ring pentylene dimethyate m two neighbors stupid two,] mountain 3 - tert-butyl, Paint & methyl butyl, butylene bis (3_t-butyl-4-yl)-based 6-methylphenyl 2,2-bis(4-hydroxyphenyl H, u, 3, 3, 3_hexafluoropropane, etc. In particular, phenol _ = 'the (four) properties and mechanical strength of the epoxy resin are suitable for use as a laminate, so it is preferred.

In the above, it is preferred to use a ruthenium compound represented by the following formula (10). R

The epoxy resin composition of the present invention may be blended with a flame retardant such as a scaly inhibitor. The amount of the blending amount of the miscellaneous amount is preferably 10 to 10 parts by mass based on the total amount of the epoxy resin blending amount of (10)f. In the present invention, R1, R2 and R3, respectively, independently represent a hydrogen atom, or a carbon atom having 1 to 8 carbon atoms, a cyclosporine atom, and Ζι and & represents a direct bond or a carbon number of 丨~4. The green or mica is extended, and the ring c represents a carbon atom 11/22 201124451 number 6 to 18 arylene, cycloalkylene or arylene-alkylene (alkylene)-arylene. The epoxy resin composition of the present invention may not use a filler, and the physical properties (high glass transition temperature, low linear expansion coefficient, tensile strength, elongation, flexibility, etc.) of the cured product are good, but preferably The filler (filling material) is used as a filler, and it is preferably a fibrous filler such as glass fiber, arsenic crystal, nitriding crystal whisker, titanium m, and oxidized crystal whisker. Alternatively, it is preferred to use a spheroidal filling of molten sulphur dioxide, such as oxidized, etc., as a filler, preferably using emulsified or spheroidal dissolved silica. Tiehan II is not limited to fibers, spheres, etc., and may also use dioxane: = =: Γ, nitrite, nitriding, oxidation I can use talc 'mica, carbon dance, glass beads, glass Ball, stone acid, hydrogen hydroxide chain, sulfuric acid # oxygen tilt, ferrite iron, various metal particles, graphite and carbon, etc. Stone Mountain II = fiber, fiber, carbon cut fiber, oxygen dimension, ': cellulose fiber, carbon fiber Organic fiber. In the case of the use of fibrous fillers in Chengyi and Zhuntian, it is better to use a filler which is more spherical and has a smaller particle size than the long axis. The season of J is particularly good for an average particle diameter of 0.01 to 2 〇 _ lion. The epoxy tree wax composition of the present invention. For example, it can be blended with natural wovens, = and plasticizers such as metal salts of acid and acid, and long-chain lunar aids; nitrile rubber, butyl type, _, sarcophagus Stress reliever of monoolefin rubber; 12/22 201124451 Antimony dioxide, antimony pentoxide, ^ ^ molybdenum, zinc borate, barium metaborate, red phosphorus, ey, tin hydroxide, calcium aluminate, etc. Resistance agent. = Alumina, magnesium hydroxide, , other than the agent - flame retardant; Wei =; = the aforementioned coupling agent,! A coupling agent such as a lysine coupling agent. The admiration of the oxidative stabilizer, silk, and anti-mystery phase: touch ^^; agent, thin _, _ 彳, other _ to give lubricants, UV absorbers, in addition, can be "曰 = ^ electric agent, Classes, ketones, vinegars, alcohols _, _ class, _; class: condensed vinegar or _ class, aromatic _ dissolve organic solvent _ class, the invention of the epoxy resin composition, is suitable The invention is described in more detail below as a composite insulating resin used as a wiring substrate, a semiconductor interposer, or a semiconductor protective film, or in a heat-resistant composite embodiment for aerospace. The present invention will be described in more detail by way of Synthesis Examples and Examples. The invention is not limited to the synthesis examples and examples. [Synthesis Example 1] Synthesis of polyamine compound having a structure of ΡΑ_1 39.7 g (〇.16 mol) of 3,3-diaminodiphenyl sulfone was dissolved. Ν 曱 曱 曱 吡 吡 吡 以下 以下 以下 以下 以下 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 的 的 的 的 的 的 的At the temperature, it was dropped into the above solution. Further, the reaction was carried out for 2 hours at a temperature of _15 to 0 ° C, and then reacted at room temperature for 2 hours. The liter of ion-exchanged water was reprecipitated, filtered, and dried under reduced pressure at 150 ° C for 3 hours to obtain 50 g (yield 83%) of white 13/22 201124451 color powder (implemented polymer PA-1). In the infrared spectrum, it was confirmed that the obtained compound had a guanamine bond, and a polymer having a mass average molecular weight of 118 Å was confirmed by gel permeation chromatography image. Further, at 25 ° C, it was based on E type. As a result of measurement by a viscometer, the viscosity was 430 mPas (30% by mass of NMP solution). [Synthesis Examples 2 to 4] The following polyamine compounds pA_2 to 4 were synthesized in the same manner as in Synthesis Example 1. The average mass of the obtained polyamine compound was obtained. The molecular weight and viscosity are as follows: PA-2: mass average molecular weight: 5970, viscosity: 200 mPas (25 ° C, 30 mass%) ^] \ solution) PA-3 : mass average molecular weight: 13540, viscosity: 525 ηιΙ ^ ( 25Τ:, 30% by mass of NMP solution) PA-4: Mass average molecular weight: 50370, Viscosity: 2500 mPas (25 ° C, 30% by mass of Lithium solution) Example 1 to 4 Using polyamido compound PA-1~PA -4 The oxygen resin composition described in Table 1 was prepared. The amount is a mass ratio. The epoxy resin composition containing polyamine is applied to the PET sheet in a thickness of 40 μm, and the film resin after drying under 丨(8) is dried. The laminate was vacuum-heated on a glass epoxy substrate at a temperature of 〇〇 ° C. Then, it was hardened at 180 ° C for 1 hour, and after the surface was cleaned, an electric clock was applied to obtain a adhesion test piece, and the following measurement was performed. 14/22 201124451 (1) According to JIS-C6481, the peel strength of the film was investigated by a 90-degree peeling test of a pattern of 1 cm width. (2) The surface roughness was measured in accordance with JIS-B0601 using VK-9710 manufactured by Keyence Corporation. (3) According to JIS-K7197, the linear expansion coefficient was measured using TMA/SS6100 manufactured by SII Technology Co., Ltd. Comparative Examples 1 to 7 The epoxy resin compositions described in Table 2 were prepared. The blending amount is the mass ratio. 15/22 201124451 Table 1 Example 1 2 3 4 5 6 EP-1 30 30 30 15 EP-2 30 15 EP-3 30 PA-1 10 PA-2 10 PA-3 10 10 10 PA-4 10 2PHZ 1 1 1 1 1 1 Ceria filler 53 53 53 53 53 53 PR-1 2.5 2.5 Leveling agent 0.2 0.2 0.2 0.2 0.2 0.2 Phosphorus-based flame retardant 10 10 10 10 20 10 Evaluation results Peel strength [kg/cm] 0.6 0.57 0.55 0.58 0.5 0.6 Surface roughness [//m] 0.44 0.34 0.33 0.32 0.3 0.32 Linear expansion coefficient [ppm] 20 . 20 20 18 19 18 EP-1 : ADEKARESIN EP-4100L bisphenol A manufactured by ADEKA Co., Ltd. Type DGE (epoxy equivalent 180) EP-2: EPICLONE HP-4032 naphthalene epoxy resin (epoxy equivalent weight 180) manufactured by DIC Co., Ltd. EP-3 : ADEKARESIN EP-3300S manufactured by ADEKA Co., Ltd. (epoxy equivalent 180 2PHZ: Siguo Chemical Industry Co., Ltd.; Hardening Catalytic Ceria Filling Material: ADMATECHS Co., Ltd.; ADMAFINE SO-E2 PR-1: MEH-7851H (phenolic biphenyl resin) made by Minghe Chemical Co., Ltd. Flat agent: F470 (Fluorine leveling agent) manufactured by Otsuka Ink Industry Co., Ltd. Phosphorus-based flame retardant: The above-mentioned acid-filled guanamine 16/22 20 1124451 Table 2 Comparative Example 1 2 3 4 5 6 7 EP-1 30 30 30 30 30 30 30 HPA-1 10 HPA-2 10 HPA-3 10 HPA-4 10 HPA-5 10 HPA-6 10 HPA-7 10 2PHZ 1 1 1 1 1 1 1 Ceria filler 53 53 53 53 53 53 53 Leveling agent 0.2 0.2 0.2 0.2 0.2 0.2 0. 2 Phosphorus-based flame retardant 10 10 10 10 10 10 10 Evaluation results Peel strength [kg /cm] 0.36 0.1 0.26 0.27 0.23 0.2 0.19 Surface roughness [ym] 0.47 0.548 0.85 0.589 0.638 0. 56 0. 64 Linear expansion coefficient [ppm] 18 18 19 21 16 18 18 The above HPA-1 to HPA-7 are The compounds shown below.

17/22 201124451

HPA-4

HPA-5111.11=1/(

From Tables 1 and 2, it is apparent that when the epoxy saponin composition of the present invention is cured, it has high peel strength even with respect to a surface having a small roughness. In particular, from the results of Comparative Example 1, it was confirmed that even if a polyamine compound having a diaminodiphenyl sulfone having an amine group at the 4-position is used as a hardener, it cannot be obtained in the third position. The polyguanamine compound of the present invention having an amine group of diaminodiphenyl sulfone has high peel strength when used as a hardener. 18/22 201124451 INDUSTRIAL APPLICABILITY By using the curing agent of the polyamine compound of the present invention, it is possible to obtain a ruthenium-free peeling thermosetting ring having a small surface roughness. An oxy-resin composition, which is a build-up type insulating resin material, and can be used in a multilayer printed circuit board, a semiconductor interposer, a semiconductor protective film, or the like, and an electronic material insulating resin and Aerospace uses heat-resistant composite materials, etc., so it is extremely useful in the industry. [Simplified description of the diagram] [Explanation of main component symbols] Μ. t\w 19/22

Claims (1)

201124451 VII. Patent application scope: 1. A polyamidamine compound characterized by having a partial structure represented by the following general formula (1) and/or general formula (Γ) in a repeating unit; However, X in the above formula represents a hydrogen atom or a hydroxyl group. 2. The polyamine compound as claimed in claim 1 which further has a partial structure represented by the following general formula (II) and/or the following general formula (II,) in the repeating unit, 3. The polyamine compound according to claim 1, wherein the polyamine compound is a t-amine compound obtained by reacting 3,3'-diaminodiphenyl sulfone with a dicarboxylic acid compound. 4. The polyamine compound according to claim 1, wherein the polyamine 20/22 201124451 5. 6. 9. The compound is such that the 3,3'-diamino group is as stupid as the 2,4_ compound. The polyamine compound is reacted.铋 铋 铋 醆 醆 醆 - - - - - - - - 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆 醆The polyamine of the item = the application for the general _ 5 counties are difficult to work with a filler. Purchase, in which the step-by-step method includes the epoxy resin agent of the sixth item of the patent application scope. The average grain scale is 〇〇1chuan^^, which is filled with 丁J桠偟马 U.01~2〇"m ball Dioxide=The total amount of the epoxy resin and the poly-compound of the epoxy resin of the fifth application of the patent scope is 5 to 100 parts by mass of the ring agent. The epoxy resin composition of the 8th item, the flame retardant is the following one ship, the main character of the octopus, and the middle side of the stone η 乐 歹! General formula (111) does not show the Wei _ compound; 0 Η-ρ-ν-Ζι--_/7Λ (III) 10. R1, R2W represent the hydrogen liver, or carbon protopor, P filament, city base or 4-cell atom, 4 and Z2 represent direct I atom number 1~4, stretching or sub-burning The group, ring c, represents a subunit of a carbon atom, a poorly extended thiol group or an arylene-extension-based (sub-alkyl)-arylene group. For example, the epoxy tree test article of the eighth item is applied for, and the step-by-step contains 21/22 201124451 with a filler. 22/22 201124451 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. : No 3/22