TW200842139A - Phenol resin, epoxy resin, curable resin composition, cured product the reof and production process of phenol resin - Google Patents

Abstract

The phenol resin which is prepared by reacting acethylene compounds including those of the general formula[1] and phenols; the epoxy resin which is prepared by reacting the phenol resin and epihalohydrin. The phenol resin and the epoxy resin are able to improve the toughness of the cured production thereof and to be added new function by various reaction processes.

Description

200842139 IX. Invention: [Technical Field] The present invention can be applied to insulating materials for electrical and electronic parts (high-reliability semiconductor sealing materials, etc.) and laminated boards (printed wiring boards, build-up substrates, etc.) or CFRP (Carbon fiber reinforced plastic, to Hua (10)

Plastics) is used for various composite materials, adhesives, coatings, etc., among which can be applied to laminated boards and the like; metal slabs, insulating materials for layered substrates, flexible substrate materials, etc.; The present invention relates to a phenol resin, an epoxy resin, and a cured product of the composition, and a curable resin composition which can be used as a resin composition for producing a copper laminate for use in an electronic circuit substrate. The present application claims priority on the basis of Japanese Patent Application No. 2006-336192, filed on Jan. 13, 2006, the entire entire entire entire entire entire entire entire entire entire content [Prior Art] The epoxy resin composition is widely used in electrical/electronic parts and structures due to its operability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance) of the cured product. In the field of materials, adhesives, and coatings. However, in recent years, with the development of the electric/electronic field, the industry has demanded further enhancements of the following characteristics represented by the high purity of the resin composition. · Wetness, adhesion, dielectric properties, and the purpose of making the filler sufficient The low viscosity of the filling is aimed at shortening the reactivity of the molding cycle and the like. Further, as a construction material, in aerospace materials, entertainment/sports applications, etc., 127512.doc 200842139 requires materials that are lightweight and excellent in mechanical properties. [Problem to be Solved by the Invention] The purpose of the present invention is to provide a phenol resin, an epoxy resin, a curable resin composition using the same, and a method for producing a phenol resin; wherein the phenol resin and the ring Oxygen resin can improve the toughness of the cured product, and can be applied to insulating materials for electrical and electronic parts (high-reliability semiconductor sealing materials, etc.) and laminated boards (printed wiring boards and supports) that can impart new functions by performing various processes. Layer substrate, etc.) or various composite materials, adhesives, paints, and the like represented by CFRP. [Technical means for solving the problem] A person who has worked hard to solve the above problems has finally completed the present invention. That is, the present invention relates to: (1) A phenol resin which has the formula (1) [Chemical Formula 1]

, R represents a hydrogen atom or an alkyl group having a carbon number of 1 to 1 fluorene, and X represents an alkoxy group (1 contains an oligo-epoxy group), a sulfonate group, or an atom of an atom, and each R And X may be the same or different from each other) the acetylene compound of the structure is obtained by reacting with a phenol; (2) a cerium oxide resin, which is obtained by making the phenol resin described in (1) and Table 127512 .doc 200842139 Obtained by a halo alcohol reaction; characterized by containing a phenolic resin of (3) a curable resin composition as described in (丨); a hard (two-in-one hardened product) The curable resin composition (7)-curable resin composition containing the epoxy resin and the curing agent in (7);

(6) a cured product, which is obtained by hardening the epoxy resin composition described in (5); (7) a method for producing a resin, which has the formula (1) [Chemical 2] (1)

X—C=C—C—X (wherein R represents a hydrogen atom or an alkyl group having a carbon number of 丨~(7), χ represents an alkoxy group (including an oligoalkylene oxide), a hydroxyl group, an alkylsulfonyloxy group or Any one of the halogen atoms, each of R and X may be the same or different from each other. The acetylene compound of the structure represented by the reaction reacts with the phenol. [Effects of the Invention] The phenol resin or epoxy resin of the present invention is a resin having an unsaturated bond in its molecular skeleton; not only a thermosetting reaction such as a usual phenol resin or an epoxy resin but also the use of the unsaturated bond Photohardening reactions can also exhibit new properties. Further, since the unsaturated bond remains in the hardened material, thermal polymerization can be caused at high/in (for example, several hundred degrees), and the hardening system is changed. According to I27512.doc 200842139, the phenol resin of the present invention or the ring scorpion sapphire of the present invention can be expected to have higher characteristics than the conventional simple hardening system > soiling (heat resistance, toughness, etc.) Therefore, it can be used for insulating materials for electrical and electronic parts (high-reliability semiconductor sealing materials, etc.), laminated boards (printed wiring boards, build-up boards, etc.), or various composite materials, adhesives, paints, and the like represented by cfrp. [Embodiment] The phenol resin of the present invention is obtained by having the formula (1) [Chemical 3]

(wherein R represents a hydrogen atom or a carbon number of 5, and χ represents an alkoxy group (including any of an oligomeric epoxy, a thiol group, a pyridyl ethoxy group or a _ atom, each R) And X may be the same or different from each other. The acetylene compound of the above formula (1) is characterized by having an ethynyl group in the molecular skeleton. The acetylene group has a group X which can be a leaving group on the adjacent carbon atom. The group which can be a leaving group is X (from), alkoxy (including polyalkylene oxide), alkylsulfonyloxy, _ atom The base selected; as for the alkoxylate, methoxy, ethoxy, propoxy, butoxy, oxy, ethoxy, methyl propoxy, foxymethylene The ethoxy group, the ethoxy group, the oxirane group, etc.. The alkyl sulfonyl group may, for example, beocyanate, p-toluene, etc. As for the halogen atom, a rat atom, a gas atom, a desert atom, or a helium atom. 127512.doc 200842139 Further, the carbon adjacent to the ethynyl group has a substituent R, and R represents a hydrogen atom. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. The specific compound represented by the formula (1) is exemplified by 1,4-dimethoxygen. -but-2-yne, butyne-1, 4-diol, (4-hydroxyethoxy-but-2-ynyl)

Oxygen)methanol, 2-[4-(2-hydroxy-ethoxy)-:1,:1,4-trimethyl-pent-2-ynyloxy]ethanol, 2,5-dimethyl _3-Alkyne-2,5-diol, 2,5-dimethoxyoxy 2,5-diindenyl-hexa-3-ene, 2-(2-{4_[2_(2_hydroxy) Ethoxy)ethoxy]-but-2-ynyloxy}ethoxy)ethanol, 2-(4-methylsulfonyloxy-butynyloxy)ethyl methanesulfonate, methanesulfonic acid 4 -Methanesulfonyloxy-but-2-ynyl ester, methyl sulfonium 4-methyl ketone oxime-丨山仁三methyl_pent-2-ynyl ester, p-toluenesulfonic acid 4_methane醯oxy-1,1,4-trimethyl-pentynyl ester, 4,7-dimethyl-癸_5_ alkyne_4,7·diol, 2,5-digas_2,5_ Dimethyl-hex-3-yne, 2,5-dibromo-2,5-monomethyl-hex-3-yne, 1,4-diox-but-2-enyne, etc.; these compounds can be used alone Use, you can also mix multiples. Further, in particular, when X is a hydroxyl group, a tautomer thereof is present, but if the general structure is a ketone structure, one of the isomer structures may be selected from the structure of the above formula (1). this invention. The term "phenol" as used in the present invention means a compound having a phenolic 'work group' on the aromatic ring. Specific examples thereof include: phenol, indophenol, m-cresol, p-cresol, ethylphenol, n-propylphenol, isopropylphenol, t-butylphenol, octylphenol, nonylphenol, Phenols such as phenylphenol, cyclohexylphenol, xylenol, methylpropylphenol, and methylbutylphenol are not limited to these compounds. In the present invention, it is better than 127512.doc 200842139. Further, the above-mentioned compounds may be used singly or in combination of two or more. The amount of use of the age class is preferably from 1.2 to 10 moles per mole of the acetylene compound of the formula (1). The molecular weight of the phenol resin of the present invention can be adjusted by adjusting the molar ratio of the block compound of the formula (1) to the desired one. For example, if the amount of phenols is reduced, then η "Mingzhiwang resin becomes a high molecular weight. In order to obtain a suitable raw material for obtaining an epoxy resin having good curability, the weight average of the phenolic tree in terms of ethylene in the present invention is about 200 to 5,000, preferably 300 to 3,000. Especially good is 300~1〇00. In the preparation of the phenol resin of the present invention, an acid catalyst is used as needed. As the - can use a variety of g, for example, can be used: hydrochloric acid, sulfuric acid, squaric acid and other probiotic acids; oxalic acid, a slate, ^ ^ _ ..., T, this stone only, acetic acid and other organic acids; tungstic acid and other impurities Polyacids (4): P〇lyacid), activated clay, inorganic acid, tin tetrachloride, chlorinated iron, iron dioxide, and other organic or inorganic acid salts that exhibit acidity, etc. The amount of the catalyst/catalyst used in the production of the citric acid type resin by the τ condensation reaction is usually 5 parts by weight with respect to 1 part by weight of the desired amount of G. 3 to 3 parts by weight. Among them, the optimum amount of the acid catalyst varies depending on the acidity. / should be carried out in the absence of solvent, can also use toluene, xylene, : benzene, two gas benzene and other aromatic flue-cured solvents; N-methyl 吼洛院_, 四^夫 m (di〇xane) An isotropic solvent; an organic compound such as an alcohol such as methanol, ethanol or propanol-ethyl alcohol monomethyl bond as a solvent. The reaction solvent is used in an amount of usually 5 Torr to 300% by weight, preferably 80 to 200% by weight based on the total weight of the compound to be added and 127512.doc 200842139. The reaction temperature is usually 4 Torr to 2 Torr °C, preferably 5 Torr to 150 °C. However, since the detachment energy of the leaving group X and the volume of the substituent R or the electron donating strength also function, the reaction temperature cannot be uniformly defined. Further, the reaction time is 0.5 to 1 hour, preferably 1 to 5 hours; however, depending on the structure of the substrate, the reaction temperature, the reaction time is greatly changed, and under some conditions, even if it exceeds 50 hours, the reaction is also Not finished. Therefore, the reaction system will take the gel permeation chromatography analysis of the sampled reaction mixture to obtain the end point of the disappearance of the change in the spectrum. The reaction may be carried out by adding all the raw materials together, and heating may be carried out while raising the temperature on one side; or by sequentially adding an acetylene compound while maintaining the phenols at a predetermined temperature. Further, it is also possible to add a acetylene compound by dissolution or expectation. Further, the reaction can be carried out while appropriately removing water, alcohol, and hydrogenated hydrogen which are by-produced by the reaction. (For example, if it is water, the reaction can be carried out while removing water by a tube or a similar device.) After the completion of the reaction, the reaction is neutralized and washed with water to remove the hydrogenated hydrogen contact material generated during the reaction. f. Thereafter, it can be recovered by a silk reaction age or a solvent to obtain a target phenol aralkyl resin. The recovery of the unreacted phenol or solvent is preferably carried out by distillation under normal pressure or under reduced pressure. Also available. The man is trapped in helium and is distilled off by steam distillation. Further, in the case where the subsequent treatment is carried out, for example, in the case of performing an epoxidation reaction, the catalyst or the solvent may be directly removed by steaming without removing the catalyst, and the next step may be carried out. 127512.doc -12- 200842139 The phenol resin of the present invention thus obtained has an unclear structure, but as one of its constituents, it can be confirmed that it can be analogized to the formula (2) [Chemical 4]

(In the formula, a plurality of R present, and η represents a repeating number) a compound of the structure represented by the present invention. The resin of the present invention, which is hereby passed, is mixed with, for example, hexamethylenetetramine or the like. The thermosetting resin composition is used as a curing agent for an epoxy resin or the like, and can also be used as a raw material (specifically, an epoxy resin, a benzoquinone, an antimony or the like) of various curable resins. In the present synthesis, when a compound having a bifunctional body is obtained by changing the reaction with the desired 1: method, it is also used as a raw material of the thermoplastic plastic. Synthetic method. By using the phenol resin of the present invention, the epoxy resin of the present invention is glycidylated. The table is self-contained to react with the epichlorohydrin u group in the reaction for obtaining the epoxy resin of the present invention. Epichlorohydrin, 7_甲^^ is a table _, which can make the invention know from the surface of the soil, the surface alcohol, etc.; in the * is better in industrially easy to obtain the amount relative to (four) fat (four) ^ Ear, Z-note alcohol makes 127512.doc Tongdi is 3~20 moor, better • 13·200842139 is 4 to 10 mol. The alkali metal hydroxide which can be used in the above reaction may, for example, be sodium hydroxide or potassium hydroxide; or a solid or an aqueous solution may be used. In the case of an aqueous solution, a method of τ may be employed: the aqueous solution of the metal hydroxide is continuously added to the human reaction system, and the water and the surface are continuously distilled under reduced or normal pressure to be separated by liquid separation. Water, and the table is continuously phased from the alcohol to the reaction (4). The amount of metal hydroxide used is relative to the original (four) resin (four) alpha ear 'usually (four) ~ 15 moles, preferably (four) ~ ... Moel, more Good is the ear. In order to promote the reaction, it is preferred to add tetramethylammonium chloride, tetramethylammonium bromide, trimethyl-based ammonium chloride, etc. as a catalyst. The amount is relative to the base of the raw material of the resin, usually 〇Μ ^ is preferably 0.2 to 10 g. This day's 'added methanol, B, g, B%, isopropanol and other alcohols; dimethyl hard , 曱基基亚石风, tetrahydrofuran, -σ亚, p Rongnan monoxin is not a proton The reaction is carried out by a polar solvent or the like, which facilitates the reaction. In the case of using an alcohol, the amount used is usually 2 to 5 % by weight relative to the use of the coffer alcohol, and preferably 4 to 20% by weight. Further, in the case of using an aprotic polar solvent, the amount of the alcohol used is usually 5 to 1 〇〇 by weight 0 0 / m / ° with respect to the amount of alcohol used in the table IS. Preferably, 10 to 80 The weight % 〇 reaction temperature is usually 30 to 9 (TC, the cup is from 35 to 80 ° C from ^ π sub. The reaction time is 0.5 to 10 hours, preferably 8 hours. The epoxidation is reversed. 127512.doc -14- 200842139 After the reaction of the reactants is washed with water or without washing with water, the alcohol or solvent is removed under reduced pressure. Further, in order to form an epoxy resin having less hydrolyzability, the recovered epoxy resin is dissolved in a solvent such as toluene or acetobutyl hydrazine, and a metal oxide such as sodium oxyhydroxide or potassium hydroxide is added thereto. The reaction is carried out with an aqueous solution of the substance, so that a positive closed loop can also be formed. At this time, the amount of the metal hydroxide used is relative to the hydroxyl group of the original resin used in the epoxidation! Moore, usually 〇〇1~〇3 Mo is preferably 0.05~0.2 m. The reaction temperature is usually 5 〇 to i2 〇 t, and the reaction time is passed; 0.5 to 2 hours. After completion of the reaction, the resulting salt is removed by filtration, washing with water, etc., and the solvent is evaporated under reduced pressure under reduced pressure to obtain an epoxy resin of the present invention. In order to obtain an epoxy resin having good curability, the weight average molecular weight of the epoxy resin of the present invention in terms of styrene is usually from 2 Å to 5 Å, preferably from 300 to 3,000, particularly preferably from 300 to 1,000. The obtained epoxy resin can be used as various resin raw materials. For example, propylene glycol vinegar and its derivatives, 恶xaz〇iid〇ne compound, cyclic carbonate compound, and the like can be mentioned. Hereinafter, the curable resin composition of the present invention will be disclosed. The curable resin wax composition of the present invention contains the resin of the present invention and/or the epoxy resin of the present invention. The age-receiving resin of the present invention is itself included as a '., a t-type sap, or as a curing agent for an epoxy resin, etc. The curable resin composition of the present invention comprises, in addition to the preferred curable resin composition described below, a hardening 127512.doc 15 200842139 agent comprising a known powder of the above-described resin of the present invention and six times of f-based tetraamine. Composition. Further, the present invention can be used as a photocurable resin in addition to a thermosetting resin which can be used in combination with a curing agent or a curing accelerator. 3 A curable resin combination of the present invention which is preferred from the resin of the present invention. • Morning Oxygen Tree as a further component. The phenol resin of the present invention can be used singly or in combination with other % oxyresin hardeners in such a preferred tempering composition of the present invention. In the case of the combination, the proportion of the phenol resin in all the hardeners is preferably 3 〇 or more, more preferably 40% by weight or more. In the case where the phenol resin of the present month is used as a modifier of the curable resin composition, the desired resin of the present invention is added in a ratio of 丨 to "% by weight" of all the curing agents. In the above-mentioned preferred curable resin composition, examples of the epoxy resin that can be used include a novolac type epoxy resin, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, and a triphenylmethane type ring. Oxygen resin, phenol aralkyl type % oxygen resin, etc. Specific examples thereof include bisphenol A, bisphenol s, thiodiphenol, bismuth bisphenol, terpene diphenol, and bisphenol. 2,2,-biphenol, 3,3,5,5,4-tetramethylbiphenyl]_4,4,·diol, hydroquinone, resorcinol, naphthalenediol, tris(4- Hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxyl Stupid, dihydroxynaphthalene, etc.) with benzoin, acetic acid, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, cis-basic ethyl ketone, o-acetyl acetophenone, dicyclopentadiene,糠 127 127512.doc -16 - 200842139 (furfural), 4,4,_bis(chloromethyl)], ! base)], 1丨-biphenyl, bis(chloromethyl)benzene, i 4 cone, 4 pairs (polylactide of methylmeryl group and the like and the modified substance thereof. 4: (methoxymethyl) benzene, glycidol derived from alcohol:: tetraethylene glycol amine epoxy resin, A solid or liquid epoxy resin other than the latex resin of the present invention, such as a glycidyl ester epoxy resin or a glycidyl ester epoxy resin, or an epoxy resin of the present invention, etc., is not limited thereto. These may be used alone or in combination of two or more.

In the above-mentioned preferred curable resin composition of the present invention, as for the other curing agent of the fourth embodiment of the present invention, an amine compound, an acid anhydride compound, a guanamine compound, or a phenol compound may be mentioned. a carboxylic acid compound or the like. Specific examples of the hardener which can be used include diaminodiphenylmethylamine, diethylenetriamine, triethylenetetramine, diaminodiphenylphosphonium, isophoronediamine. , dicyanodiamine, polyamine resin synthesized from dimer of linoleic acid and ethylenediamine, phthalic anhydride, phthalic anhydride, tetramethyl anhydride, horse Anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenolic resin of the present invention , bisphenol A, bisphenol F, bisphenol S, bismuth bisphenol, terpene diphenol, 4,4, _biphenol, 2,2'-biphenol, 3,3',5,5'-tetra Base-[ij,-biphenyl b, 4,4,_diol, hydroquinone, resorcinol, naphthalenediol, tris(4-hydroxyphenyl)methane, m,2,2_tetra(4- Hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxyl Benzaldehyde, o-hydroxybenzaldehyde, p-hydroxyl 127512.doc -17- 2 00842139 二笨乙, o-light acetophenone, dicyclopentadiene, furfural, hepta-4, _bis (murine methyl)-ι, ι, _ biphenyl, 4, 4, · bis (methoxy a polycondensate of methylbiphenyl, M, _ ^ soil), 1,4'-bis(methoxyindenyl)benzene, and a halogenated double test such as 53⁄4 3Λ-bei, 4> odorous double A, Savory, ammonium trifluoride sigma, hydrazine derivative, condensate of boxene and phenol, etc.; but not limited to these. These may be used alone or in combination of two or more. 3) The curable resin composition of the present invention having the epoxy resin of the present invention, and the epoxy resin of the invention may be used singly or in combination with the above solid or liquid f:% oxygen resin. In the case of use in combination, the ring of the present invention in April has a relatively good proportion of S3G by weight of the king epoxy resin, particularly preferably 4 (% by weight or more). In the case where the epoxy of the present invention is used as a modifier of the curable resin composition, the epoxy of the present invention is added at a ratio of 1 to 30% by weight/〇 in all of the Ο月曰. Resin. Eight kinds of & month of oxy-resin, the curable resin composition of the present invention,

C 3 has a hardener as the other component. Examples of the curing agent include the above-mentioned other curing agents, and the phenol resin of the present invention. The curable resin composition of the present invention (hereinafter referred to as "the epoxy resin composition") containing an epoxy resin (including the epoxy resin of the present invention) and a curing agent (including the resin of the invention) is relative to The epoxy resin of the epoxy resin = the amount of the field hardener used is preferably 〇·7 to ΐ2 equivalent. In the case of an epoxy group of 1 equivalent, the hardener is used in the case of β soil #丁化化^1, which is less than 0.7 equivalent, or more than 1.2 equivalents. Completely, it is impossible to obtain good hardening properties. This Maoyue & Latex Resin Composition allows the hardener to be used with hardening promotion J27512.doc 200842139. As the specific one of the hardening accelerators which can be used, a phosphine such as a di-based phosphine or a metal compound such as tin octylate. A hardening accelerator of 0.1 to 5.0 denier is used as needed with respect to 100 parts by weight of the epoxy resin. Further, if necessary, the t-adhesive resin may be formulated in the epoxy resin composition of the present invention. Examples of the binder resin include a butyl I resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, and a leg (acryi〇nitriIe_butadiene rubber) 酝 酝月月The 曰% oxygen_NBR-based resin, the polyamine-based resin, the polyimine-based eucalyptus, and the polyoxo-based resin are not limited to these resins. The blending amount of the binder resin is preferably in the range of flame retardancy and purity resistance of the non-destructive cured product, and is usually used in an amount of 〇·05 to 50 parts by weight, based on 1 part by weight of the resin component. It is used in an amount of 0.05 to 20 parts by weight. * Further, an inorganic filler may be added to the epoxy resin composition of the present invention as needed. As the inorganic filler, there may be mentioned: crystalline sulphur dioxide, molten sulphur oxide, oxidized sulphur, samarium, sulphuric acid, carbonic acid, carbonized, cerium nitride, boron nitride, oxidized , powders such as magnesite, talc, spinel strontium oxide, talc, or the like obtained by spheroidizing the beads, etc. 'but are not limited thereto. These can be used alone or in combination of more than one species. The amount of the inorganic filler used is from 0 to 95% in the epoxy resin composition of the present invention! %. Further, in the epoxy resin composition of the present invention, a Shixia Mixing Agent; a stearic acid such as stearic acid, palmitic acid, succinic acid, and hard 127512.doc -19-200842139 calcium citrate may be added. Various materials such as shoulder, flame retardant, and various sclerosing resins.哕笪, 丄 丄 + ^... 入 4 4, the amount of use in the epoxy resin group of the present invention accounts for 0 to 3 〇 wt%. Further, the epoxy resin composition of the present invention is dissolved in a solvent such as acetone, methyl ethyl ketone, methyl ketone, acetamide, dimethylformamide or dimethyl alpha ketone to form a varnish. Then, the glass fiber, the carbon fiber, the polyester fiber, the polyamide fiber, and the material are pressed into a heat-drying, and the obtained prepreg is formed to form the epoxy resin composition of the present invention. At this time, the amount of the solvent used is usually 10 to 70% by weight in the varnish, and 15 to 70% by weight in the rut. Soft ^ In order to improve the modification of the film-type composition (4) body is B-stage softness = 2 The epoxy resin of the present invention can be used. In the case of obtaining a sputum, the above varnish is applied to the release film to remove the granule, and the enamel phase, ^ μ , 匕 匕 is obtained as an adhesive sheet. The Taotao sheet-like adhesive can be used as an interlayer insulating layer of a multilayer base. The use of the epoxy resin composition of the invention and the invention can be applied to a coating or a coating using one of thermosetting resins such as a % milk resin, for example, an adhesive, a coating agent, and a molding material. Including flakes, films, and p-edge materials (including printed substrates, wire wraps, arbores, 夭丄 是 是 是 是 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在Other materials such as resin are added to the adhesive, and examples thereof include: civil engineering 孜m, non-use A vehicle, one boat force, medical adhesive, and electronic material #芸J 1卞 adhesive. In the 127512.doc • 20 - 200842139, as for the adhesive for electronic materials, there are many types of semiconductors such as a build-up substrate, an interlayer adhesive, a wafer bond, an underfill, and the like, and BGA. Reinforcing underfill, anisotropic conductive film (10) f), an adhesive for encapsulation such as a conductive paste (ACP), etc. As for the sealant, capacitors, transistors, diodes, and light-emitting diodes are mentioned. Filling, dipping, transfer, etc. for body, IC, LSI, etc. Mold sealant, sealant for 1C, LSI CQB, COF, TAB, etc., underfill for flip chip, etc., encapsulant for encapsulation of lc package such as QFP, BGA, csp, etc. [Examples] Hereinafter, the present invention will be more specifically described based on examples, and the following "parts" means parts by weight unless otherwise specified. Further, the present invention is not limited to such implementations. Further, in the examples, the epoxy equivalent, the softening point, and GPC (gel permeation chromatography) were measured under the following conditions: 1) Epoxy equivalent: It was measured in accordance with the method in accordance with JIS K-7236.

2) Softening point: measured according to the method of JIS K-7234 3) GPC (estimated by the measurement result of GPC by basis weight system): Model: Shodex SYSTEM-21, column: ^^-802 + 1^ 802 · 5 (X2 roots) + KP -803 linked to the solution · · THF (tetrahydro sigma): 1 ml / min, 40 ° C; detector: UV (254 nm; UV-41) Sample: about 0.4% THF solution (20 μM injection) Standard curve: Standard polystyrene using Shodex 4) GC-MS measurement conditions 127512.doc -21 - 200842139 Column ·· HP-5MS, 15 m-0.25 mm-0.25 μηι carrier gas· · Helium, L〇ml/min Oven: 50 ° C (for 2 min), l (TC / min to 300 ° C (for 20 min) Injection: 1 μl (sample concentration is about 10 mg / ml) Split 30: 1,3003⁄4 " Ionization: El, CI (using methane gas) • Example 1 In a flask equipped with a stirrer, a reflux cooling tube, a stirring device, and a Dean-Stark tube, one side was flushed with nitrogen. Adding 142 parts of 2,5-dimethyl-hex-3-cyclo-2,5-diol, 142 parts of toluene, 282 parts of phenol, wherein all of R in the above formula (1) is a methyl group and X is a trans group. 1.4 parts of p-toluenesulfonic acid at 90 The reaction was carried out at ° C. The amount of water in the Dean-Stark tube and the change in GPC were confirmed to confirm the completion of the reaction. After the completion of the reaction, the mixture was cooled to 50 ° C, and 20 parts of a 20% aqueous sodium dihydrogen phosphate solution was added thereto, and the mixture was stirred for 30 minutes, and then added. 300 parts of toluene was repeatedly washed with water until the water layer became neutral. The unreacted phenol and solvent were distilled off from the obtained organic layer by heating under reduced pressure, and the resin (PR 1 ) 2 of the present invention was obtained. 1 9 parts. The softening point of the obtained resin was 62 ° C. The GPC of the obtained phenol resin is shown in Fig. 1. The weight average of the standard polystyrene equivalent of the phenol resin of the present invention determined by GPC measurement The molecular weight was 439. Further, the molecular weight of the phenol resin was confirmed by mass spectrometry (GC_MS), and it was confirmed that all of R in the skeleton of the above formula (2) contained about 3% by weight in the detection range was sulfhydryl. The result of GC-MS measured after tms treatment was m/z: 438.5-439.5. Example 2 127512.doc -22- 200842139 Nitrogen gas was applied to one side of a flask equipped with a stirrer, a thermometer, and a cold reduction. Add the aging obtained in Example 1. 179 parts of fat, 555 parts of epichlorohydrin, and 55 parts of methanol were dissolved under stirring, and the temperature was raised to 7 (TC). and then. After scaly-like sodium chloride was added in portions at 90 knives, the post-reaction was carried out for 1 hour. After the completion of the reaction I, the water was washed with water, and the solvent such as excess surface alcohol was removed from the organic layer by heating under reduced pressure. Methyl isobutyl ketone was added to the residue to dissolve, and the temperature was raised to hydrazine. 1 part by weight of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and after 1 hour of reaction, the water was washed until the washing water became neutral, and the obtained solution was distilled at 18 Gt under reduced pressure T at a reduced pressure. Thus, methyl isobutyl ketone or the like was used, whereby 202 parts of the epoxy resin (ER1) of the present invention was obtained. The obtained epoxy resin had an epoxy equivalent of 3 〇 5 g / eq and became a resin of a = shape to a semi-solid state. The GPC chart is shown below (Figure 2). The standard polystyrene-equivalent weight average molecular weight of the epoxy resin of the present invention as determined by Gpc was 428. Example 3 and Comparative Example 1 The evaluation of the hardening of the curable resin composition (epoxy resin composition) is disclosed below. The epoxy resin (ER1) of the present invention, an o-cresol novolac type epoxy resin (EOCN-1020, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 199 g/eq·), which is an epoxy resin, is used as a hardener. Inventive phenol resin (pRl), phenol novolak type epoxy resin (manufactured by Minghe Chemical Industry Co., Ltd., H1, hydroxyl equivalent: 105 g/eq·), 2-ethylmethylimidazole (2E4MZ, as a hardening accelerator) The composition was prepared by blending with the blending ratio (parts by weight) shown in the following table 127512.doc -23 - 200842139, and the resin molded body was obtained by transfer molding at 160°. Hardening was carried out for 2 hours at C, and further hardening was carried out at 180 ° C for 8 hours. [Table 1] Example 3 Comparative Example 1 Epoxy Resin ER1 20 EOCN-1020 80 100 Hardener PR1 10 Phenol Phenolic Resin 43 52 Hardening Accelerator 2E4MZ 2.0 2.0 The physical properties of the hardened material thus obtained were measured, and the results are shown in the table. 2. Further, the measurement of the physical property value was carried out by the following method. Impact resistance test (K1C): According to JIS K-6911 IZOD impact test: according to JIS K-6911 [Table 2] Example 3 Comparative Example 1 Impact resistance test (K1C) 25 21 IZOD impact resistance test (kJm) 20 16 Example 4 The epoxy resin (ER1) of the present invention obtained in Example 2, KAYAHARD A_A (an aromatic amine type hardener, manufactured by Nippon Kayaku Co., Ltd.) as a curing agent, and the compounding ratio (parts by weight) shown in Table 3 below. The composition was prepared to prepare a composition, which was hardened by a injection molding method. As for the hardening conditions, it was allowed to harden at 160 ° C for 2 hours, and further hardened at 180 ° C for 6 hours. [Table 3] Epoxy Resin ER1 75 Hardener KAYAHARD A-A 15 127512.doc -24- 200842139 The physical properties of the cured product thus obtained were measured, and the physical property values thereof were measured by the following methods. Glass transition point: TMA thermomechanical measuring device: vacuum temperature Heating rate · 2 ° C / min. [Table 4] The results are shown in Table 4. Remanufactured (TM) Manufacture, TM-7000 Test Example 2 () minutes of treatment of the hardened material obtained in Example 4 was performed. No clear point of linear expansion change was observed. The results are shown in Fig. 3. From the above results, it is understood that the epoxy resin of the present invention is an epoxy resin excellent in toughness. X, it is understood that a cured product exhibiting a very high heat resistance can be obtained by treating the cured product at a high temperature. [Simple description of the map]

Glass transition temperature rc) TMA 98 〇 C Fig. 1 is a GPC chart of the phenol resin of the present invention obtained in Example 1.

2 is a GPC chart of the epoxy resin of the present invention obtained in Example 2. Fig. 3 is a view showing a TMA diagram of the cured product obtained in Example 4. The unit of the vertical axis is ppm. 127512.doc -25-

Claims (1)

200842139 X. Patent application scope: L A resin obtained by reacting an acetylene compound having a structure represented by the formula (1) with a hydrazine, [Chemical Formula 1] (1) (wherein R represents a hydrogen atom or a carbon number 〜~; [〇 alkyl group, a fork represents an alkoxy group (including an oligoalkylene oxide), a hydroxyl group, an alkylsulfonyloxy group or a halogen atom) Either each of R and χ may be the same or different from each other). 2. An oxygen resin obtained by reacting a phenol resin as claimed in claim 1 with epihalohydrin. A curable resin composition characterized by containing a phenol resin as required. Chemical resin composition hard 4· A cured product which is cured according to claim 3 5. A curable resin composition, 1 system χ /, containing the fat of claim 2 and a hardener Made. Long-milk epoxy resin composition 6 - a cured product obtained by the method of claim 5, wherein the acetylene compound having the formula (1) is reacted with a phenol, [Chemical 2] 127512.doc 200842139 (1) (wherein R represents a non-aero atom or an alkyl group having a carbon number of 丨~(7), and X represents an alkoxy group (including an oligoalkylene oxide), a hydroxyl group, an alkylsulfonyloxy group or a functional element atom. Each R and x can be mutually different or different. \ J 127512.doc