TW201134875A - Sulfone group-containing polyhydroxy polyether resin, resin composition containing such resin, curable resin composition containing such regin, and film obtained from these resins or resin composition - Google Patents

Abstract

This invention provides a sulfone group-containing polyhydroxy polyether that can be used for forming an insulation resin film having excellent solubility in a solvent and moisture absorbing property while the characteristics of high resistance to heat and high adhesion to metal are exhibited. It is a sulfone group-containing polyhydroxy polyether resin represented by general formula (1) having a sulfer content of 3 to 8 wt%, a methyl group content of 10 to 30 wt%, and weight average molecular weight of 10,000 to 200,000. This invention also provides a curable resin composition having the abovesaid sulfone group-containing polyhydroxy polyether resin and a thermosetting type resin as necessary components, an insulation resin film that can be obtained from the abovesaid sulfone group-containing polyhydroxy polyether resin, and an insulation resin film that can be obtained from the abovesaid curable resin composition.

Description

201134875 VI. Description of the Invention: [Technical Field] The present invention relates to an electrical and electronic field which can be used as an anisotropic conductive bonding film, an electrical laminated board, a magnetic tape adhesive, an insulating varnish, a self-melting magnetic wire varnish, and the like. And a thermoplastic polyhydroxy polyether resin which is excellent in heat resistance, water resistance, and adhesion, such as an adhesive, an insulating coating, and a film, and a resin composition containing the resin, a curable resin composition, and an insulating resin thin mold. [Prior Art] Conventionally, thermoplastic polyhydroxy polyether resins are generally used as phenoxy resins, and are excellent in flexibility, impact resistance, insulation properties, adhesion, and mechanical properties. Therefore, in the field of electrical and electronic fields, It is used in a wide range of applications such as adhesives for magnetic tapes, insulating varnishes for electrical machinery such as engines, and adhesives and films for circuit boards. However, the conventional thermoplastic polyhydroxy polyether resin is inferior in heat resistance, and in a high-temperature, high-humidity environment, the physical properties are rapidly lowered, and in particular, the adhesion is lowered. Therefore, in Patent Document 1 and Patent Document 2, it is proposed to introduce the first skeleton and the hydrogen waking skeleton in order to improve the heat resistance. Further, it is disclosed in Patent Document 3 that the guide of the double 酴S skeleton and the double wish skeleton not only has good rail resistance, low linear expansion coefficient, and no deformation or warpage, and dimensional stability is particularly relevant. The S-frame of the sulfur atom of a hetero atom is described in Patent Document 4 as being excellent in adhesion to metal. However, 1P=Document 5 describes that 'double enzyme s skeleton resin has low moisture absorption resistance. Usually, when using thermoplastic poly-based (4) to form a thin film of insulating resin 322681 8 4 201134875, the organic material (10) == In the middle of the 6th, there is a note on the adhesion of the adhesive after the use of the ethyl acetate = 2/1 (weight ratio), the blade after the pot life, and the following:飒 之 之 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Film.吏 吏 吏 吏 吏 吏 吏 吏 吏 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 环 对于 对于 对于 对于Dissolution = medium, the solubility is better 'so that it can be made into a transparent resin solution = the point of melting coal is as high as 150 ΐ or more. Therefore, in general, in such solvent conditions, the solvent remains in the film due to insufficient temperature, and the heating of = is practical and has good adhesion and heat resistance. [Prior Art Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2001-261789 (Patent Document 3) JP-A-2001-261789 (Patent Document 4) [Patent Document 5] JP-A-2009-046631 (Patent Document 6) JP-A-2005-325161 (Summary of the Invention) 322681 5 201134875 [Problems to be Solved by the Invention] Insulating Resin In the circuit-connecting structure of the film, in order to improve heat resistance and adhesion to metal, it is effective to use a sulfone group-containing polyhydroxy polyether resin as a film material user. However, there are only high-boiling ketone solvents such as cyclohexanone and cyclopentanone which are poorly volatile, guanamine-based solvents such as dimercaptoacetamide and dimethylacetamide, and diethylene glycol monobutyl There is a problem of so-called solvent solubility of a carbitol-based solvent. Therefore, in the use of an electrically insulating film, particularly in an anisotropic conductive film, formation of a good film cannot be achieved. Further, even if a film is formed, there is a problem that the moisture absorption resistance is poor and the electrical reliability is inferior. The problem to be solved by the present invention is to provide a sulfone group-containing polyhydroxy polyether resin which is excellent in solubility in a solvent and which is excellent in resistance to absorption and which is excellent in stupidity. A resin composition made of a resin, a curable resin composition, or an insulating thin film. Month 3 [Means for Solving the Problem] ^ In order to solve the above problem, the "sulfone group-containing polyhydroxy polyface resin of the present invention" is in the skeleton of a polyhydroxy polyether resin containing a sulfone group, and the turtle is a By introducing an alkyl group having a methyl group having 1 to 4 carbon atoms, it is possible to activate a so-called characteristic having high heat resistance of a double S skeleton and high adhesion to a metal, and the solvent solubility is good, and moisture absorption resistance can be formed. Excellent insulating property U] That is, the present invention provides a polyhydroxy polyether resin containing a sulfone group, having a cerium content of 3 to 8% by weight, a methyl group content of 1 Torr to 30% by weight, and a weight average molecular weight of 曰' For 1〇, 〇〇〇 to 2〇〇, 〇〇〇之式[1], 322681

6 201134875

O-C—^—c-

OH 0—A—Ο—B n 0) (wherein A is selected from the group consisting of either formula (2) or formula (3) alone or in combination of plural; B represents a hydrogen atom or formula (4) The one shown in the formula; the ruler in the formula represents a hydrogen atom, or a nicotine group having a carbon number of 1 to 4, each of which may be the same individually; n is a positive integer of 10 to 400),

(wherein R represents a hydrogen atom or a hydrocarbon group having a carbon number of i to 4, each of which may be the same or the same; X represents a direct bond, -CH2---C(CH3)2->-CHCH3-, -〇- , -C0-, -S〇2-, or -S-),

(3) (wherein R represents no hydrogen atom or a hydrocarbon group of carbon number i 4, and each of them may be the same individually) > Η -cc-ch2 (4) 0 [2] The present invention further provides a curable resin composition The polyhydroxyl polyether resin containing a mercapto group described in the above [1] and a thermosetting resin are essential components. [3] The present invention further provides an insulating resin film obtained by the above-described polyhydroxyl polyether resin containing a mill base as described in the above [1] \ 322681 7 201134875. [4] The present invention further provides an insulating resin film which is obtained from the curable resin composition described in the above [2]. The sulfur content described in the above [1] is that the sulfur content in the polyhydroxy polyether resin containing a mercapto group is expressed by weight %, and is subjected to combustion decomposition as a method of JISK 2541, and is measured as a sulfate ion in an ion chromatograph. , converted to the sulfur content of the polyhydroxy polyether resin containing a sulfone group. Here, the sulfur content is preferably from 3 to 8% by weight, and when it is less than 3 to 8% by weight, the introduction effect of the sulfone skeleton which imparts heat resistance is insufficient, and heat resistance cannot be obtained. Further, when it exceeds 8% by weight, not only sufficient solvent solubility but also poor hygroscopicity are obtained. More preferably, the sulfur content is from 3.5 to 7% by weight, more preferably from 3.8 to 6% by weight. The thiol content described in the above [1] is based on the total weight of the total sulfhydryl group contained in the sulfone group-containing polyhydroxy polyether resin expressed by the weight % of the sulfone group-containing polyhydroxy polyether resin. The proton integral value of the NMR analyzer GH-NMR was calculated. Specifically, it is a terminal methyl group in a mercapto group, an ethyl group, a propyl group, or a butyl group, for example, has three terminal mercapto groups in the third butyl group. Further, in the double-awaiting A, there are two in -C(CH3)2- as a bonding group. The methyl group content of the polyhydroxyl polyether resin containing a mercapto group is preferably from 10 to 30% by weight, more preferably from 13 to 24%. When the amount is less than 1% by weight, not only sufficient solvent solubility but also poor moisture absorption resistance are obtained. Further, those having a mercapto group content of more than 30% by weight are difficult to manufacture in terms of structure. In the polyhydroxy polyether resin containing a mill base, when the weight average molecular weight is less than 10,000, the film formation property cannot be exhibited. Moreover, when the weight average molecule 8 32268 丨 8 201134875 exceeds 200,000, even if it is, for example, a ring parent 'dimethylformamide, dimethyl acetamide, etc.: _ 等 等 点 酽 酽 酽 酽 醯 醯 醯 醯 醯 醯, diethylene glycol single T material carbitol (four) material dissolution correction high solubility in the 70 to 30% by weight of the resin concentration, because, in order to make the film can be used to dissolve the degree _ degree has to; ^, in the processing economy is not good. Further, the solvent solubility is also deteriorated, and problems occur in the formation of the film. From this situation, the amount is 15, _ to 2 〇 _, and the heart (10) to ^ is better. The thiol-containing poly-based poly-polymerization resin of the present invention is mainly used for thinning, and is used, for example, as an electrically conductive layer such as an anisotropic conductive film or a film for forming a (β_叩) laminate. Since the hard group-containing poly-based polyester has the characteristics of high heat resistance and low linear expansion coefficient of the stone-based skeleton, and also has a methyl group, not only the solvent solubility is more than that of the conventional sulfhydryl group. The hydroxypolyether resin is further improved, and the water absorption rate is also lowered, so that the electrical reliability as an insulating film is particularly improved. [Embodiment] [Formation for carrying out the invention] The production of a polyhydroxy polyether resin containing a sulfone group, a method of directly reacting a dihydric phenol with epichlorohydrin, by a dihydric phenol is known. A method of addition polymerization of a diglycidyl ether resin and a dihydric phenol, but the polyhydroxyl polyether resin containing 6 olefins used in the present invention may be obtained by any method. "In the case of direct reaction of dihydric phenols with epoxidized propane, 322681 9 201134875 is described. The dihydric phenols contain bisphenols such as bisphenol S and tetradecyl groups represented by formula [5]. Bisphenol S or the like is an essential component, and other dihydric phenols may be a dihydric phenol represented by the formula [6] or the formula [7]. The dihydric phenol of the formula [6] is, for example, bisphenol A or bisphenol. F, bisphenol AD, tetradecyl bisphenol F, 4, 4-dihydroxybiphenyl, etc., the dihydric phenol of the formula [7] is, for example, hydroquinone, 2, 5_di-t-butylhydroquinone, etc. However, the dihydric phenols may be used singly or in combination of two or more kinds.

(wherein R represents a hydrogen atom or a hydrocarbon group having a carbon number of 丨 to 4, and each may be the same or the same).

The R in the formula is not a hydrogen atom or a hydrocarbon group having a carbon number of i to 4, and each of them may be the same or the same; X represents a direct bond, or -CH2---C(CH3)2-, ~CHCH3-, 〇, , -C0-, -S〇2-, or _s_).

R R

10 322681 8 201134875 (wherein R represents a hydrogen atom or a hydrocarbon group having a carbon number of 4 to 4, each of which may be the same or the same). Will be a singular 1 mole with epoxy propylene 〇.g to 11 moles (0. 95 to 1. 08 moles are preferred, 〇 · 99 to 1. 〇 3 Moore is better) in alkali metal hydrogen In the presence of an oxide, epichlorohydrin is reacted with a dihydric phenol in a non-reactive solvent, and a sulfone group-containing polyhydroxy polyether resin having a weight average molecular weight of 10,000 or more can be obtained by a condensation reaction. Examples of the non-reactive solvent used in the reaction include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dioxane, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, and cyclohexanone. And the like is not limited to these, and the solvents may be used alone or in combination of two or more types. Further, the reaction temperature is preferably from 40 to 150 ° C, particularly preferably from 60 to 12 (TC is more preferred. The reaction pressure is usually normal pressure, and may be under pressure and reduced pressure, and 'if necessary to remove heat of reaction 'The solvent to be used may be subjected to instantaneous evaporation (or flash evaporation), condensed reflux method, indirect cooling method or the like by means of reaction heat, but is not limited thereto. In the process for the polymerization addition reaction of oxypropyl ether with binary expectation, in the diepoxypropyl group of the binary oxime, the bis-epoxide of the biguanide S type skeleton phenol described in the formula [5] When the propyl ether is used as an essential component, the 'dihydric phenol may be any one of the formulas [5], [6], and [7], and may be used singly or in combination of two or more types. In the di-epoxypropyl ether of a dihydric phenol, if the di-epoxypropyl ether of the S-type skeleton phenol described in the formula [5] is not used, in the binary expectation, the formula [5] The use of the bisphenol s-type skeleton phenol to be worn is necessary. Further, 322681 11 201134875 Other dihydric phenols are described in the formula [6] and formula [7]. It may be used alone or in combination of two or more types. In the presence of amine, σ rice, phosphine, scale salt, and metal hydroxide-based catalysts, The ratio of the bisphenol propyl ether of the above dihydric phenol to the phenolic hydroxyl group: epoxy group of the above dihydric phenol is from 0.9:1 to 1. 1:1 (from 0.95:1 to 1. 05: 1 is more preferably produced by reacting with 0.98:1 to 1.02:1. Further, as shown in the formula [1], the bisphenol S type skeleton is an essential component, and the sulfur content is set at 3. The reaction temperature is preferably from 60 to 200 ° C, particularly preferably from 90 to 180 ° C. The reaction pressure is usually normal pressure, and, if necessary, the reaction heat is removed, The solvent to be used is instantaneously evaporated, condensed and refluxed, indirectly cooled, or used in combination. The non-reactive solvent used in the reaction may, for example, be benzene, diphenyl or decyl ethyl ketone. , fluorenyl isobutyl ketone, dioxane, diethylene glycol dioxime ether, ethylene glycol ethyl ether, cyclohexanone, etc., but are not particularly limited thereto, and the solvents may be single The sulfone group-containing polyhydroxy polyether resin synthesized as described above may be used as a heat-reducing and flexible material, and may be used alone or in an epoxy resin. A thermosetting resin such as a melamine resin, an isocyanate resin, or a phenol resin, or a thermoplastic resin such as an acrylic resin. Examples of heat resistance, flame retardancy, low linear expansion ratio, and the like include, for example, sulfur dioxide and carbonic acid. | bow, talc, hydroxide, oxidized, mica, etc., but it is not limited to this. Moreover, in order to improve the adhesion, a decane coupling agent or a rubber component such as 12 322681 201134875 may be added to make the polyether-containing polyether The degree to which the physical properties of the resin are not lowered. The polysulfone group-containing polyhydroxy polyether resin of the present invention is used as the curing agent for the resin-cured composition. For example, an aromatic polyamine, dicyandiamide, an acid anhydride, various phenol resins, and the like can be given. Further, examples of the curing accelerator include benzyldimethylamine, an amine of various imidazole compounds, and a tertiary phosphine such as triphenylphosphine, but are not limited thereto. [Examples] Hereinafter, the present invention will be specifically described based on examples, and in the following examples and comparative examples, "parts" means "parts by weight". Examples 1 to 7: In the formulation shown in Table 1, 46 parts of a bifunctional epoxy resin, a divalent phenol (γ), a catalyst, and a cyclohexanone were fed into a stirring device, a thermometer, and a condenser. In a four-neck separable flask equipped with a nitrogen gas introduction device, the reaction temperature was maintained at 145 to 16 (polymerization reaction was carried out for 8 hours in TC, and then diluted with cyclohexanone to prepare a resin having a resin concentration of 40% by weight. A solution of 200 parts of this resin solution was poured into a Teflon (registered trademark) coating pan (inner diameter: 309 x 241 x 51 mm), and desolventizing was carried out in a vacuum oven under conditions of 200 ° C x 0.77 kPa x 60 to obtain a solid resin. The property value analysis of the resin thus obtained was carried out by the following method: <Weight average molecular weight>

Device: Gel permeation chromatography instrument manufactured by Tosoh Co., Ltd. HLC-8020GPC Detector · Differential refractometer Tube column: TSKgelGMHXLx2 + TSKgel manufactured by Tosoh (stock) 13 322681 201134875

G2000HXL tube temperature: 40 ° c eluent / flow: four urgent soil

(4) > Into the south (hereinafter THF) lmL / min sample injection 1 · 10 〇 to L sample adjustment: sample 〇%, 僳〇.lg dissolved in THF1〇mL molecular weight and elution use = poly benzene Ethylene was prepared as a nasal analysis device in the above apparatus to obtain an average molecular weight. The curve is converted into a resin solid fraction in the product <epoxy equivalent>. Measurement according to JIS K 7236 <Solubility Test> t 3 Polyhydroxypolyether resin solution having a sulfone group (resin / toluene / acetic acid ethyl 40 / 40 / 20 parts, resin / "mercaptoethyl ketone or Cyclohexanone" = 40/60 parts) solubility at 25t during preparation. Dissolution method: In a 200 ml Erlenmeyer flask equipped with a condenser equipped with a magnetic stirrer, the resin and the solvent are fed in the above ratio, and heated to 8 (TC-mixed and dissolved) with a magnetic stirrer attached with a temperature adjustment. When it was confirmed that it was completely dissolved, it was allowed to cool to 25 ° C. The criterion was ◎: clear (completely dissolved), 〇: slightly turbid, Δ: suspended, X: separated < methyl content> From nuclear magnetic resonance analysis (1H- NMR) Calculate the methyl group content by the ratio of the proton integral value of the peak of each measured component to the number of protons of each measured component peak. Measurement machine name: JNM-LA400 322681 201134875 manufactured by JEOL Ltd. ' Observation frequency: 399. 65MHz • Observation area: 7993. 6Hz Pulse width: 45 ° Pulse pulse waiting time: 100 seconds Accumulation times: 32 times Solvent: DMS〇-d6 Internal standard material: DMS0-d6 · 2.49ppm < Sulfur content> to JIS K 2541 The method was burned, and after being absorbed by 0.3% by weight of hydrogen peroxide, it was determined by ion chromatography. Device: IC20 manufactured by Dionex (Japan): Anion exchange column IonPac AS14 suppressor: AS RS-300 calibration curve: A calibration standard curve is prepared by measuring a mixed standard aqueous solution of S (V) having a known concentration. The measured S〇4_ content is used as the sulfur content using the calibration curve. <Non-volatiles> According to JIS K 7235, it was measured in an oven at 200 ° C for 60 minutes. The results of the analysis are shown in Table 1. 15 322681 201134875 [Table l: m Example I 83.8 | c»j c> 丨1.020 | Bu 1 N 1 60.000 1 ! 10,200 | <〇u5 L13.6 | I 98.9 I ◎ ◎ 〇<〇〇βο | 1.030 | 八(D 1 N 1 30.000 II 10,100 | u> LK” L—jM I ◎ ◎ ◎ u> Head 1 69.6 1 CM c=SI 1.020 | u> I Μ 1 49,0001 I 9.200 | CO ui ui I 96.4 | ◎ 〇 ◎ s CSJ in eo €^l 1 1.020 | 1 N 1 86,000 1 I 13.200 | eo I 23.7 j [98.9 | ◎ ◎ ◎ CO 目«ο csl ΙΑ 5 c=i | 1.020 | CO 1 N w Ο ο I 8,650 | 〇I 13.4 I «d 〇» ◎ Q ◎ CM 目^ · 1 65.2 1 1 .16-3.J 1 0.02 1 o CM 1 N 1 45,000 1 | 9,800 | co CO 〇1^· <〇ad 〇> ◎ Ο ◎ r· g 80.7 CSJ o Production 1 N 1 51,000 II & 500 | σ> I 13.4 II 9& 3 | ◎ Ο ·◎ τ- Hi CM UJ <0 U1 UJ — D- <\/ Ο. Ρ3 ο Ui U. 13 >21 43⁄4 *w 锼% % Butterfly J9) Weight average molecular weight: Mw 9 Φ Ι such as Φ1 Jwhl Φ Ι such as methyl content (weight N after solidification NV (weight 3 〇 I methyl ethyl ketone dissolved)跛¢5 〇 〇丨 〇丨 玥 玥 玥 玥 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 meaning. E1: bis-A diglycidyl ether (epoxy equivalent: 186.0 g/eq, quotient 16 322681 8 201134875 Product name: Epotohto YD-128C manufactured by Dongdu Chemical Co., Ltd.)) E2: tetradecyl bisphenol S diglycidyl Ether (epoxy equivalent: 211.4 g/eq) E3: 2, 5-di-t-butylhydroquinone diglycidyl ether (epoxy equivalent: 176. Og/eq, trade name · Epotohto YDC-1312C Dongdu Chemical (Stock) Manufactured)) E4: Tetramethyl bisphenol F diglycidyl ether (epoxy equivalent: 191. 〇g/eq, trade name: Epotohto YSLV-80XY (made by Toto Chemical Co., Ltd.)) P1: Four 曱Bisphenol S (phenolic hydroxyl equivalent: 153 g/eq) P2: bisphenol A (phenolic hydroxyl equivalent: 114 g/eq) P3: bisphenol S (phenolic hydroxyl equivalent: 125 g/eq) D: triphenyl scale Bromide (manufactured by Beixing Chemical Industry Co., Ltd.) E: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.) F: 49% aqueous sodium hydroxide solution G: triphenylphosphine (Beixing Chemical) Industrial (manufacturing)) Comparative Examples 1 to 6: The bifunctional epoxy resin (X), the divalent phenol (Y), the catalyst, and the cyclohexanone 46 parts formulated as shown in Table 2 were fed with stirring. Device, temperature In a four-piece glass separation bottle of a meter, a condenser, and a nitrogen gas introduction device, the reaction temperature was maintained at 145 to 160 ° C for 8 hours, and then cyclohexanone was added to dilute the resin having a resin concentration of 40% by weight. Solution. 200 parts of this resin solution was poured into a coating tray (described above) of Teflon (registered trademark), and a solvent was removed in a vacuum oven under the conditions of 2 〇〇〇 cxO. 7 kPa x 60 minutes to obtain a solid resin. Further, in the case of I in Table 2, Βρα type epoxy resin YP-50 (solid matter) manufactured by Soto Chemicals Co., Ltd., which is commercially available, was used as it is. 322681 201134875 The results of the analysis are shown in Table 2. [Table 2] Comparative Example 1 <D_YP-50 | I 58,000 | 丨50> 000 I 〇1 10.0 1 1 99.1 I ◎ ◎ ◎ LO s oo CSi o [1.020 1 TN 238, 000 1 23, 800 1 < n 〇Q «Ο ·»» I 97.9 IXX 〇兮0 Ο r— 〇〇I 0-01 II 1. 020 | t NI 9,500 | 1 1,900 | 〇> 1 13.8 1 I 99.0 ! ◎ ◎ @ CO SV— I 7(X6 | CM €SS 1 1.025 1 »· 1 NI 48,000 | I 8,430 1 〇〇〇ά 1 16-4 1 9& 5丨XX 〇CM Ο σ> 30.6 CM C» | 1.020Π σ> l N Γ45.000Π 8,380 csl 12.3 98.2 ο 〇◎ 〇丨老” 0.02 I 1.020 | 00 1 Nl 1 52*000 | | 9.500 | «*> ui cao uS I 98.1 XX 〇Ιϋ CM Lii α. CM (L· 00 Ql Q Ui u. Work 4 Treadmill weight average molecular weight: Mw: epoxy equivalent (g / eq) sulfur content (weight: 3⁄4) 丨 methyl content (weight NY solidified NY (% by weight) methyl Ketone solubility (toluene / ethyl acetate = 2 / 1) Solubility I cyclohexanone soluble 2 functional epoxy resin (X) 2 functional phenol (Y) Catalyst blending E1 to E2, D in Table 2 to F, Η, I, and P1 P3 is the meaning of the following contents. Ε1: bis bismuth diglycidyl ether (above) 18 322681 8 201134875 E2: tetradecyl double s diglycidyl bond (above) P1 : tetradecyl bisphenol S (above) P2: bisphenol A (described above) P3: bisphenol S (described above) D: triphenylsulfonium bromide (described above) E: 2-ethyl-4-mercaptoimidazole (described above) F : 49% aqueous sodium hydroxide solution Η : 40% aqueous solution of tetradecyl ammonium hydroxide I : Phenotohto ΥΡ-50 (manufactured by Tohto Kasei Co., Ltd.) The polyhydroxy polyether resins obtained in Examples 1 to 7 and Comparative Examples 1 to 6 are shown in Table 1 and Table 2. 40% (benzene/ethyl acetate=2/1 (weight ratio)) solution prepared by the solubility test, the resin thickness after drying the solvent was 60 /zm, and the roll coater was used to release the film. (PET) coating was carried out by solvent drying at 130 ° C for 10 minutes to obtain an insulating film. Further, an insulating film and a 35#m copper foil were laminated on a standard test plate (PM-3118M, manufactured by Nippon Test Plate Industry Co., Ltd.), and pressed at 16 (TC) by a dry laminator to obtain a copper foil peeling. Test plate for strength measurement. <Impossibility of thin film formation> 〇: It is soluble in toluene/ethyl acetate = 2/1 (weight ratio) and can be thinned. △: Insoluble in toluene/ethyl acetate = 2 In the case of /1 (weight ratio), it is not thinned, but it is soluble in cyclohexanone and can be thinned. Among them, it is thinned at 180 ° C for 30 minutes under dry conditions. X: It cannot be thinned due to insolubilization. The test method and evaluation method of the insulating film are as follows. 19 322681 201134875 <Glass transfer temperature (Tg)> According to JIS C6481 test box, the 5:17 'Using thermomechanical measuring device (Seiko Instruments (monthly, From the creation; EXSTARTMA/SS7100) is measured at a rising pulse rate of 5 C/knife clock. The transition temperature of the glass is determined by the temperature-deformation curve and the mosquitoes are placed on the straight line portion before and after the glass transition temperature ^ and the 2 The intersection temperature of the wire is the glass transfer temperature Tg. <copper foil peel strength (kN/m) > Measurement was carried out in accordance with JIS C6481 test item 5.7. Measurement equipment: Aut〇graph AGS-X manufactured by Shimadzu Corporation (share). <Water absorption rate (%)> According to JIS C 6481 test item 5. 14. Without water absorption, the water absorption rate of the insulating film was directly measured by steaming at 24 ° C for 24 hours. Water absorption rate (%) = ((m2-mi)/mi) xl〇〇 Heart: before impregnation Test piece weight (mg) m2: Test piece weight (mg) after impregnation <linear expansion coefficient> According to JIS K 7197, using a thermomechanical measuring device (Seiko Instruments (EXSTAR TMA/SS7100)) Measurement. Temperature range: 50 to 80 ° C < Whether thin filming is possible > 〇: soluble in benzene / ethyl acetate = 2 / 1 (weight ratio) and can be thinned. △: Although insoluble in toluene / Ethyl acetate was 2/1 (by weight) and it was not thinned, but it was dissolved in cyclohexanone and thinned. Among them, it was thinned under dry conditions at 18 ° C for 30 minutes. 322681 201134875 - X : It cannot be thinned because it cannot be dissolved. • Examples 8 to 14: [Table 3] <0樾5 Bu N *w^ 〇<〇LO CO <〇〇〇LA CNJ Μ m CO ·—· <Ό CO 1 M «μ· 〇CD 兮<*〇τ~ c4 u? CM ca in 1 N 〇ro ir> irS βο ·*» in C\i 罟Ln CM V·* 1 N 〇c〇卜 «〇OJ οο Ln CSJ CO (O Ο CO 1 M 〇σ> ★ 呀 C0 r·· οο » CO C^J 卜τ—· CD CM 1 NJ 〇βο 〇r> 兮m tn « 04 cO s CVi 00 1 N 〇σ» <vi r* to in csl LA u> ΟΟ i)Ht Βζ rate δ δ / /—Ν &Η JfhJ a (4) ψ»Ί 4〇®- /^\绡 4ttL condensed narrow 〇ΐ 0〇ΐ Ά u male hair. . E^f • · Dyeing dinner 21 322681 201134875 Comparative examples 7 to 12: [Table 4] JSj! 11 Csl s 1 〇ο OW c\i 〇〇<〇σ>G7> r-1 NX m aαο οό l 1 1 1 C3 1 N **-✓ 〇σ> c〇cri o ca CVI lo LA Ο cn TN < r— uS o ui 03 ο cJ CO i〇S CO 〇> 1 N w 〇csj CO cs } CO CO CO Μ γ — 卜〇 0 1 N < co in 〇o in cu w <〇KA in σ> 瓛ii»U w Q w\ 4〇Q VI Λ ¢- /^-N ΐ /- Ν 曰m magnetic m narrow 冢0. 'θ 〇4 v3 Alkali hair dyeing The polyhydroxy polyether resin obtained by the dyeing of Examples 1 to 7 and Comparative Examples 1 to 6 was prepared by the solubility test of Tables 1 and 2 (40% (toluene/acetic acid 22). 322681 8 201134875 Ethyl vinegar = 2 / 1) solution 187. 5 parts, Epotohto - YD-128 (described above) as epoxy resin 25 parts, dicyandiamide as a hardener (made by Japan Carbide Industries Co., Ltd.; DICY 0 parts of 2-ethyl-4-mercaptoimidazole (described above) as a hardening accelerator was 0.02 parts and uniformly stirred and mixed to obtain a composition varnish. The thickness of the resin after dissolving the solvent was 60/zm, and the film was applied to a release film (PET) by a roller coater, dried at 130 ° C for 5 minutes, and then peeled off from the release film. An insulating resin film was obtained. Further, an insulating resin film and a 35 // m copper foil were laminated on a standard test plate (described above), and pressed at 160 ° C by a dry laminator to obtain a test sheet for measuring the peel strength of copper foil. Examples 15 to 21: 23 322681 201134875 [Table 5] 5 卜1 N 〇<〇Lri <〇CO CO 9 ««· cO ir>〇> CO S <^S CO 1 N 〇CO ▼— m cn cvi 〇〇LA Ο CO σ> U) 1 N 〇CO ιο ▼·— in 卜 oo cvi Μ to in α〇 inch IN 〇οο 一卜co C\J tn —· in <si mm 卜^• s Γ0 1 N 〇cn 七CO ni t·· CO ca CO in ο <£> V·· CM 1 N 〇οο CO CD CO m OJ C4 CO in c»>u> ·-· r· 1 N 〇<71 60 OO v> CO ci CO m CO CO i)tn 激 KQ 一; D δ 败 m J(ht| η»η Φ(4) 9 tc|S)| ηβη w ♦ ®- Ϊ /-N 娥Magnetic whip narrow. . "s a v5 alkali hair 0〇 • Lu Li Comparative Example 13 to 18 ·· 24 322681 201134875 [Table 6]

CD m 1 〇〇to α. 〇〇Ο CNJ cO CM ▼— s Ο 卜 V·· 04 τ Ν X οο Γ〇1 1 1 I to 1 Ν 〇〇> CO CO CNJ CO r— 3 ·" » in ο 丁rsi < 卜CO ο L/i 〇> Τ-» CSI CSJ K LT) CO Ο) 1 Ν 〇^1 cO «ο CJ LT> a〇S «2 〇0 1 Ν <1 <〇ιή ιή 〇> ci CO CVJ LO u> CO Λ)〇Ι Μ m κ〇JD 2 撖Q ♦1 Q φΗ η»η φ| 4〇Β- /•"Ν /-N s V —✓ 漶JM m Narrow r-\ P "s Alkali Umbrella P • · #: [Effect of the Invention] The use of the present invention for the preparation of a low-boiling solvent with a solvent-soluble polyether-based polyether resin The curable resin composition and the insulating resin sheet 25 322681 201134875 film, because the solvent is hard to remain, it can maintain not only the heat resistance, the adhesion property, and the low linear expansion property which are characteristics of the sulfone group skeleton, but also the water absorption rate can be lowered. Trustworthiness. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the results of measurement of a polyhydroxy polyether resin (Z-1) of Example 1 by a nuclear magnetic resonance analyzer (?). [Main component symbol description] None 26 322681

Claims (1)

201134875 VII. Patent application scope: 1. A polyhydroxy polyether resin containing a sulfone group, having a sulfur content of 3 to 8 wt%, a mercapto group content of 10 to 30 wt%, and a weight average molecular weight of 10,000 to 200, As shown in the formula [1], (1) > * (wherein A is selected from the group consisting of either formula (2) or formula (3), or a complex combination of «hai, etc., and β represents a hydrogen atom or a formula (4); Wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, each of which may be the same individually; η is a positive integer of 10 to 400), A CHCH3, -〇-, -co-, standby, or _s_), . R in the formula represents a hydrogen atom, or a carbon number! The hydrocarbon groups to 4 may be the same individually; Χ represents a direct bond, -CH2---C(CH3)2-, (3) (wherein a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, each of which may be the same or the same) 322681 1 (4) 201134875 η2 η C_C*~CH2 ο 2. A curable resin composition, It is necessary to apply a sulfone group-containing polyhydroxy polyether resin and a thermosetting resin as described in claim 1 of the patent application. 3. An insulating resin film characterized by being obtained from a sulfone group-containing polyhydroxy polyether resin as described in claim i. An insulating resin film characterized by being obtained from the curable resin composition according to item 2 of the patent application. 2 322681 8