phenolic compounds

Abstract

To provide a phenolic compound that can give a cured product excelling in crack resistance, heat resistance, moisture resistance, moldability and the like.SOLUTION: The present invention provides a phenolic compound represented by the following formula 1. In the formula 1, R's independently represent a hydrogen atom or a C1-6 hydrocarbon group, a is an integer of 0-4, b is an integer of 0-3 and n is an integer of 0-20.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention reacts with epoxy resin and curing agent to obtain a cured product with excellent electrical properties, heat resistance, etc. This relates to phenolic compounds. [Background technology]

[0002] The cured product, which is made by reacting a phenolic compound with an epoxy resin or a curing agent, has excellent electrical properties, heat resistance, etc. Because of its excellent properties, it is used in circuit boards, semiconductor encapsulation materials, machine parts, adhesives, etc. For example, Patent Document 1 describes a phenol compound having a dicyclopentadiene skeleton. Resins with excellent heat resistance, moisture resistance, crack resistance and moldability, and compositions for semiconductor encapsulation materials It is described that it is used as [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2003 / 029323 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, higher heat resistance is required due to the increase in heat generated during use caused by the increasing density of semiconductors. However, the phenol compound having a dicyclopentadiene skeleton described in Patent Document 1 is did not have sufficient crack resistance. The present invention provides a process for producing a cured product that is excellent in crack resistance, heat resistance, moisture resistance, moldability, etc. The object of the present invention is to provide a phenol compound. [Means for solving the problem]

[0005] The gist of the present invention resides in a phenol compound having an alicyclic structure represented by the following formula 1.

[0006] [ka]

[0007] In formula 1, each R is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. is an integer of 0 to 4, and b is an integer of 0 to 3. n is an integer of 0 to 20. [Effects of the Invention]

[0008] The phenol compound of the present invention has excellent crack resistance, heat resistance, moisture resistance, moldability, etc. The cured product can be used in circuit boards, semiconductor encapsulation materials, machine parts, adhesives, paints, etc. It can be used as a civil engineering building material, an insulating material for electrical and electronic components, an optical material, etc. DETAILED DESCRIPTION OF THE INVENTION

[0009] The phenolic compound of the present invention has a structure represented by the following formula 1.

[0010] [ka]

[0011] The phenol compound of the present invention has an alicyclic structure in the novolak, which reduces the linear expansion coefficient of the cured product. The modulus and water absorption are reduced, and heat crack resistance is improved. In addition, compared to conventional phenolic resins, the hydroxyl group concentration is low and the polarity is low, The cured product has a low dielectric constant and low dielectric tangent. In the formula 1, each R is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. .

[0012] Examples of the hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. Phenyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl In terms of fluidity and curing properties, R is preferably a methyl group. Of these, an ethyl group is preferred, and a methyl group is more preferred. The bonding position (substitution position) of the R to the hydroxyl group of the benzene ring is set to be 100% because of ease of production. The ortho or para position is preferred, and the para position is more preferred.

[0013] a is an integer of 0 to 4. In terms of fluidity, a is preferably an integer of 0 to 2, more preferably an integer of 0 to 1. 0 is particularly preferred. b is an integer of 0 to 3. From the viewpoint of fluidity, b is preferably an integer of 0 to 2, more preferably an integer of 0 to 1. 0 is particularly preferred. n is an integer of 0 to 20. In terms of fluidity and curability, n is preferably an integer of 0 to 10, and 0 A value of 0 to 5 is more preferred, and 0 to 2 is particularly preferred.

[0014] Furthermore, in the present invention, the compound represented by formula 1 is preferably a phenol compound represented by formula 2 below: It's nice.

[0015] [ka]

[0016] n is an integer of 0 to 20, preferably 0 to 10 from the viewpoint of fluidity and curability, and 0 to 5 is more preferred, and 0 to 2 is particularly preferred. Standards of the phenolic compounds of the present invention measured by gel permeation chromatography (GPC) The number average molecular weight (Mn) is preferably 400 to 1,000 in terms of polystyrene. The phenolic compounds of the present invention were also measured by gel permeation chromatography (GPC). The weight average molecular weight (Mw) is preferably 450 to 1,500 in terms of standard polystyrene.

[0017] The number average molecular weight and weight average molecular weight are preferably high from the viewpoint of curability, and low from the viewpoint of fluidity. It is preferable that the temperature is lower than this. Furthermore, the hydroxyl group equivalent of the phenol compound of the present invention can be determined by, for example, The hydroxyl equivalent of the acetylated product measured by alkaline back titration is 190 or more and 300 or less. A higher hydroxyl equivalent is preferred from the viewpoint of curability, and a lower hydroxyl equivalent is preferred from the viewpoint of fluidity. It's nice.

[0018] An example of a method for producing the phenol compound represented by the formula 1 is shown below. The phenol compound of the present invention is a phenol having a phenolic hydroxyl group, which is reacted with a phenolic compound in the presence of an acid catalyst. It can be produced by reacting alcohols with tricyclopentadiene. The tricyclopentadiene used as a raw material component of the phenolic resin of the present invention is, for example, Appl. Organometal. Chem. 2014, 28, pp. 151-155 It can be synthesized from dicyclopentadiene by known methods such as the method described above.

[0019] The phenols are not particularly limited, but examples thereof include phenol, cresol, and chloroform. Silenol, ethylphenol, propylphenol, isopropylphenol, n-butylphenol butylphenol, sec-butylphenol, tert-butylphenol, pentylphenol phenol, hexylphenol, and cyclohexylphenol. Cetyl, cresol, and xylenol are preferred from the viewpoint of economy and ease of production. More than one species may be used in combination.

[0020] The molar ratio of tricyclopentadiene to phenols used in the reaction should be adjusted appropriately. This allows the molecular weight and melt viscosity of the target phenol compound to be adjusted within an appropriate range. The phenol / tricyclopentadiene molar ratio is preferably in the range of 2 to 64, and more preferably 4. The molar ratio of phenols / tricyclopentadiene is more preferably in the range of 32 to 32. The ratio is preferably high from the viewpoint of the melt viscosity of the phenol compound, and is preferably low from the viewpoint of synthesis efficiency. preferable.

[0021] Acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, as well as formic acid, acetic acid, oxalic acid, and tricarboxylic acid. Organic acids such as fluoromethanesulfonic acid and p-toluenesulfonic acid, as well as Friedel- As Kraft catalysts, boron trifluoride, boron trifluoride ether complex, boron trifluoride Boron trifluoride-phenol complex, boron trifluoride-water complex, boron trifluoride-alcohol complex, Examples of the boron chloride-amine complex include boron chloride-amine complex, and a mixture thereof can also be used. Among these, boron trifluoride-phenanthroline is particularly preferred due to its catalytic activity and ease of catalyst removal. Boron trifluoride ether complex, trifluoromethanesulfonic acid, p-toluene Preferably, sulfonic acids are used.

[0022] The amount of catalyst used is particularly limited in order to keep the molecular weight and melt viscosity of the resin within an appropriate range. For example, phenol and tricyclopentadiene are catalyzed by p-toluenesulfonic acid. When reacting with toluenediene, the reaction is p-toluenesulfonic acid / (phenol + tricyclohexyl) Pentadiene) is preferably 0.1 to 5.0% by weight, more preferably 0.5 to 3.0% by weight. stomach.

[0023] The reaction is usually carried out in a closed system with the inside of the reactor replaced with an inert gas such as nitrogen or argon. It is preferable to carry out the reaction in an open system while supplying an inert gas into the reactor. . The reaction temperature is usually 60 to 180°C, preferably 100 to 160°C, more preferably 120 In terms of reactivity, a higher temperature is preferable, and the distillation of phenols and trichloroethylene are not From the viewpoint of suppressing decomposition of cyclopentadiene, a lower value is preferred.

[0024] In the present invention, a phenol and tricyclopentadiene are reacted in the presence of an acid catalyst. In consideration of the high temperature reaction, a solvent may be used. Xylene, p-xylene, m-xylene, ethylene glycol monobutyl ether, etc. are preferred. I wish. Furthermore, the reaction is terminated by deactivating the catalyst. The deactivation method is not particularly limited. However, the amount of ionic impurities such as boron and fluorine remaining in the final phenolic resin is It is preferable to use a method that keeps the concentration of the quencher below 100 ppm. Examples include alkali metals, alkaline earth metals, and oxides, hydroxides, and carbonates thereof. Inorganic bases such as ammonium hydroxide, hydrotalcites, and ammonia gas are used. It is possible.

[0025] After the reaction is completed, the reaction mixture is filtered or separated to remove the deactivating agent and other impurities. During filtration, solvents may be added, the temperature of the filtrate may be increased, or the system may be By making the internal pressure under increased or reduced pressure, workability can be improved. After removing the deactivator, the reaction mixture is concentrated by distillation to remove unreacted phenols. The distillation can be carried out under normal pressure, elevated pressure, or reduced pressure.

[0026] The resin composition containing the phenolic compound of the present invention and an epoxy resin has crack resistance and heat resistance. The resulting cured product has excellent properties such as moisture resistance and moldability. The epoxy resin may be a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or the like. epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, Zorcin-type epoxy resin, hydroquinone-type epoxy resin, catechol-type epoxy resin, Dihydroxynaphthalene type epoxy resin, biphenol type epoxy resin, tetramethylbiphenyl Epoxy resins derived from dihydric phenols such as phenolic epoxy resins.

[0027] Phenol novolac epoxy resin, cresol novolac epoxy resin, tris Phenolmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentasiloxane Polyethylene-phenol modified epoxy resin, phenol aralkyl epoxy resin, biphenyl Phenyl aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin Ralalkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol Toluene-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde resin 3 types of epoxy resins, such as oil-modified phenolic resin type epoxy resins and biphenyl-modified novolac type epoxy resins Epoxy resins derived from phenols of higher valence.

[0028] Tetrabromobisphenol A type epoxy resin, brominated phenol novolac type epoxy However, these epoxy resins are not limited thereto. Two or more resins may be used in combination. The epoxy resin is preferably a bisphenol A epoxy resin from the viewpoints of flowability and heat resistance of the cured product. A-type epoxy resin, tetramethylbiphenol-type epoxy resin, 4,4'-biphenol type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy Resin, dicyclopentadiene-phenol modified epoxy resin, orthocresol novo Rack-type epoxy resins and trisphenolmethane-type epoxy resins are preferred.

[0029] The epoxy resin may be an epoxy resin having two or more functional glycidyl groups. More preferable. The resin composition of the present invention comprises the following: The hydroxyl equivalent of the phenol compound is usually 0.1 to 5.0, preferably 0.1 to 2.0. It is preferable that the ratio is 0.1 to 1.5. If the ratio is larger or smaller than this range, the hardness of the resin composition is low. This may result in a decrease in the curing property and a decrease in the heat resistance of the cured product.

[0030] The resin composition may contain additives such as a curing accelerator and an inorganic filler. Curing accelerators include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, and Examples of the compound include phosphorus compounds, amine complex salts, etc., and phosphorus compounds are preferred. Good too. Inorganic fillers include fused silica, crystalline silica, glass powder, alumina, silicon nitride, and talc. , aluminum hydroxide, calcium carbonate, calcium sulfate, etc., and from the viewpoint of the amount of blending, molten silica These may be used in combination of two or more kinds.

[0031] The cured product obtained by curing the resin composition of the present invention has excellent crack resistance, heat resistance, moisture resistance, moldability, etc. Excellent for semiconductor encapsulation, circuit boards and other electrical and electronic components, machine parts, adhesives, paints, civil engineering and construction It can be used for construction materials, optical materials, etc. The phenolic compound of the present invention can be cured with a curing agent such as hexamethylenetetramine. , can be used as a phenolic resin.

[0032] The phenolic resin has excellent crack resistance, heat resistance, moisture resistance, moldability, etc., and is suitable for use in circuit boards, Semiconductor encapsulants, machine parts, adhesives, paints, civil engineering and construction materials, insulating materials for electrical and electronic parts, It can be used for optical materials, etc. [Example]

[0033] The present invention will be described below with reference to examples. The present invention was evaluated by the following methods. .

[0034] <Number average molecular weight (Mn) and weight average molecular weight (Mw)> Measurement was performed using Tosoh Corporation's GPC "HLC-8220GPC" under the following measurement conditions: did. As standard polystyrene, TSK Standard Polystyrene:F- 450, F-128, F-20, F-4, F-2, A-2500, A-1000 A calibration curve was created, and the number average molecular weight and weight average molecular weight were measured as polystyrene equivalent values. Ta. Column: Tosoh Corporation "TSKGEL SuperHZM-N" x 3 Eluent: tetrahydrofuran Flow rate: 0.35ml / min Detection: RI Temperature: 40℃ Sample concentration: 0.1% by weight Injection volume: 10 μl

[0035] <Hydroxyl group equivalent> A method using an acetylating reagent in accordance with the neutralization titration method of JIS K0070-1992 The hydroxyl equivalent of the phenol compound was measured.

[0036] <Water absorption rate> The hardened test piece was stored in a constant temperature room at 23°C and 50% humidity for 24 hours or more. The previous specimen weight was measured. Nagano Science Corporation's constant temperature and humidity chamber "LH24-11P" was used to measure the temperature and humidity at 85℃ / 85 The cured test piece was left to absorb moisture under the condition of 200%RH for 168 hours, and the weight immediately after absorbing moisture was measured. The weight of the test piece after the moisture absorption test was recorded. The moisture absorption rate was calculated using the following formula (test piece size: 2 cm square, 3 mm thick). Moisture absorption rate (wt%) = ((weight of test piece after moisture absorption test - weight of test piece before moisture absorption test) / before moisture absorption test (weight of test piece) × 100 (%)

[0037] <Linear expansion coefficient> Analysis was performed using a thermomechanical analyzer "TMA / SS6100" manufactured by Seiko Instruments Inc. The cured specimen was placed in compression mode, and the first temperature increase was 5°C / min (from 30°C to 250°C). The first temperature drop was 10°C / min (from 250°C to 30°C), and the second temperature increase was 5°C / min (from 30°C The temperature was changed from 0 to 250°C, and the second linear expansion coefficient α1 was measured. is a cylindrical object with a diameter of 1 cm and a thickness of 3 mm.

[0038] <Raw materials used> The raw materials used in the following examples and comparative examples are as follows. Tricyclopentadiene (TCPD): Applied Organometallics c Chemistry), 2014, Vol. 28, p. 152. The transition metal catalyst was Pd(dba)2, and the ligand was P(p-tolyl). 3 was used. Phenol: Nacalai Tesque, Inc. p-Toluenesulfonic acid monohydrate: Fujifilm Wako Pure Chemical Industries, Ltd. Chloroform: Kanto Chemical Co., Ltd. Epoxy resin (product name "YL6677"): manufactured by Mitsubishi Chemical Corporation Dicyclopentadiene phenol compound (product name "ERM6115"): Songwon Made Curing catalyst (product name "Hokuko TPP"): manufactured by Hokko Chemical Industry Co., Ltd.

[0039] <Production Example 1 (Production of Phenol Compound)> In a four-neck flask equipped with a stirrer, a thermometer, and a dropping funnel, add 61.6 g (0.6 5 mol) and TCPD 31.0 g (0.16 mol) were added, and the mixture was purged with nitrogen gas. The internal temperature was raised to 90°C and the contents were heated to dissolve. Then, 2.4 g of p-toluenesulfonic acid monohydrate was dissolved in 3 mL of water in a dropping funnel. The aqueous solution was added and slowly dropped while maintaining the internal temperature at 90 to 100°C.

[0040] After that, the internal temperature was raised to 140°C and the reaction was carried out for 7 hours. After the internal temperature was lowered to 90°C, The catalyst was deactivated by adding 4.2 g of a 0% aqueous potassium hydroxide solution. The reaction mixture was heated to 110°C, and the unreacted phenol was distilled off under reduced pressure. The mixture was cooled to 0°C and diluted with chloroform, and then transferred to a separatory funnel. Washed with 20% aqueous potassium hydroxide solution, then washed with water until the pH of the aqueous layer reached 7. .

[0041] After removing the solvent using an evaporator, phenol compound A (TCPD / PHL novolak The Mn of phenol compound A was 668, the Mw was 934, and the hydroxyl equivalent was 25. It was 8g / eq.

[0042] Example 1 100 parts of epoxy resin (YL6677), phenol compound A15 synthesized in Production Example 1 Each raw material was weighed into an aluminum dish in the ratio of 9 parts of acetone and 1 part of curing catalyst (Hokuko TPP), and heated to 120°C. The mixture was stirred until it was homogenous. After that, it was heated at 120°C for 2 hours and then at 175°C for 6 hours to obtain a cured product. obtained. The resulting cured product was cut into test pieces of the size required for each evaluation, and the water absorption rate and linear expansion coefficient were measured. The results are shown in Table 1.

[0043] <Comparative Example 1> Epoxy resin (YL6677) 100 parts, dicyclopentadiene phenol compound (E Put 115 parts of RM6115 and 1 part of curing catalyst (Hokuko TPP) into an aluminum dish. The mixture was weighed and stirred at 120°C until it was homogenized. Then, it was stirred at 120°C for 2 hours and at 175°C for 6 hours. The mixture was heated for 1 hour to obtain a cured product. The resulting cured product was cut into test pieces of the size required for each evaluation, and the water absorption rate and linear expansion coefficient were measured. The results are shown in Table 1.

[0044] [Table 1]

[0045] From Table 1, it can be seen that dicyclopentadiene phenol compounds were used as phenol compounds. The cured product of Comparative Example 1 had a high coefficient of linear expansion and a high water absorption rate, and the cured product had poor heat crack resistance.

Claims

1. A phenol compound represented by the following formula 1: 【Chemical 1】 In Formula 1, each R is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. is an integer of 0 to 4, b is an integer of 0 to 3, and n is an integer of 0 to 20.

2. The phenol compound according to claim 1, wherein the formula 1 is represented by the following formula 2: 【Chemistry 2】 In formula 2, n is an integer of 0 to 20.

3. A resin composition comprising the phenolic compound according to claim 1 or 2 and an epoxy resin.

4. 4. The epoxy resin according to claim 3, wherein the epoxy resin has two or more functional glycidyl groups. The resin composition described above.

5. The phenol compound is used in an amount of 1 equivalent of the epoxy group of the epoxy resin in the resin composition. The resin composition according to claim 3 or 4, which contains a hydroxyl group equivalent of 0.1 or more and 1.5 or less.

6. A cured product obtained by curing the resin composition according to any one of claims 3 to 5.

7. An electric or electronic part comprising the cured product of claim 6.

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