JP6090765B2 - Phenol resin, epoxy resin, and curable resin composition - Google Patents

Description

  The present invention relates to an epoxy resin, a curable resin composition, and a cured product thereof suitable for electrical and electronic material applications that require heat resistance and flame retardancy.

  Curable resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It is used.

  However, in recent years, with the development in the electric / electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler) as well as high purity of resin composition, There is a need for further improvements in various properties such as increased reactivity to shorten the molding cycle. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment. Especially in the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), as the semiconductor transitions, it becomes increasingly complex with thinning, stacking, systematization, and three-dimensionalization. Required characteristics such as heat resistance and high fluidity are required. In particular, with the expansion of plastic packages to in-vehicle applications, the demand for improved heat resistance has become more severe, and it is necessary to respond to solder reflow with a resin with a high Tg and low linear expansion coefficient. At the same time, it is required to reduce or maintain the water absorption rate.

“2008 STRJ Report Semiconductor Roadmap Special Committee 2008 Report”, Chapter 8, p1-17, [online], March 2009, JEITA Japan Electronics and Information Technology Industries Association Semiconductor Technology Roadmap Specialist Association, [May 30, 2012 search], <http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm> Nobuyuki Takakura et al., Matsushita Electric Engineering Technical Report Car-related device technology High-temperature operation IC for vehicles, 74, Japan, May 31, 2001, pp. 35-40

  One of the characteristics particularly required for high functionality is heat resistance. Although heat resistance has been regarded as important conventionally, problems such as poor water absorption properties and poor flame retardance generally arise when heat resistance is raised.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
A phenolic resin obtained by reaction of binol with a xylylene compound,
(2)
An epoxy resin obtained by reacting the phenol resin according to the preceding item (1) with an epihalohydrin;
(3)
A curable resin composition containing at least one of the resins described in (1) and / or (2) above;
(4)
A cured product obtained by curing the curable resin composition according to item (3),
Is to provide.

  The curable resin composition using the phenol resin or epoxy resin of the present invention not only has high heat resistance, but also exhibits flame retardancy without using a flame retardant or a phosphorus compound, Epoxy resin that contributes to the reduction of flame retardants and phosphorus compounds. Insulating materials for electrical and electronic parts, laminates (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, etc. Useful for. In particular, it is extremely useful for a semiconductor sealing material for protecting a semiconductor element.

  The phenolic resin of the present invention is obtained by a reaction between binol and a xylylene compound.

The binol (BINOL) used in the present invention refers to a binaphthalene diol compound.
Binol has stereoisomers, but either chiral or racemic forms may be used. The purity is preferably 90% or more by GPC, more preferably 93% or more, and particularly preferably 98% or more. Impurities include those having a quinone structure and raw material naphthol compounds, each of which is 2% or less, preferably 1% or less. Purity can be controlled by crystallization or washing. When the said purity is low, possibility that the characteristic of the phenol resin of this reaction will fall is high and it is unpreferable. The loss on drying is 0.2% or less, preferably 0.1% or less. When the loss on drying is large, problems such as fouling the production line occur in the production process. The melting point is 200 to 220 ° C., preferably 212 to 219 ° C. These commercial products are available from Aldrich, SR-CHEM.

The xylylene compound is a compound of the following formula
(In the above formula, each X independently represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.)
Specifically, xylylene glycol, xylylene dihalide (halogen: chlorine, bromine, etc.), bisalkoxymethylbenzene (xylylene bisalkyl ether, more specifically bismethoxymethylbenzene, And C1-C6 alkoxymethyl compounds such as bisethoxymethylbenzene, bispropoxymethylbenzene, bisbutoxymethylbenzene, bisphenoxymethylbenzene, and bisallyloxymethylbenzene. In this reaction, xylylene glycol, xylylene dichloride, and bismethoxymethylbenzene are particularly preferable. In addition, although arrangement | positioning of a substituent may be any of ortho, meta, and para, para body is especially preferable from the balance of heat resistance and mechanical characteristics.

  The phenol resin of the present invention can be obtained by adding a catalyst to a mixed solution of a binol, a xylylene compound and a solvent, if necessary, and heating. Further, the xylylene compound may be gradually added to the solution in which binol is dissolved. The reaction time is 5 to 150 hours, and the reaction temperature is 40 to 150 ° C. The phenolic resin thus obtained can be used without purification depending on the use, but usually, after completion of the reaction, the reaction mixture is subjected to treatment such as neutralization as necessary before crystallization or heating under reduced pressure. It is purified by removing the solvents below and used for various purposes. The reaction molar ratio of the binol and the xylylene compound is 1.2: 1 to 20: 1, more preferably 1.5: 1 to 15: 1, and particularly preferably 1.5: 1 to 10: 1. When the reaction molar ratio is less than 1.2: 1, that is, when the binol is less than 1.2 with respect to the xylylene compound 1, the softening point of the phenol resin to be formed becomes too high, so that it is difficult to take out. Moreover, when it exceeds 20: 1, ie, when a binol exceeds 20 with respect to the xylylene compound 1, the structure of said Formula (1) will decrease and heat resistance will become scarce.

  Solvents that can be used in the synthesis of the phenolic resin of the present invention include, but are not limited to, methanol, ethanol, propanol, isopropanol, toluene, xylene, methyl isobutyl ketone, anone, cyclopentanone, methyl ethyl ketone, and the like. These may be used alone or in combination of two or more. The amount of the solvent used is usually 5 to 500 parts by weight, preferably 10 to 400 parts by weight, based on 100 parts by weight of binol.

As the catalyst, it is basically preferable to use an acidic catalyst. When the xylylene compound is a xylylene halide, the reaction can proceed smoothly without the addition of a catalyst, and a reaction without a catalyst is preferable from the viewpoint of ease of subsequent purification. When using the catalyst, specific examples of the acidic catalyst include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as oxalic acid, toluenesulfonic acid and acetic acid; heteropolyacids such as tungstic acid, activated clay, inorganic acids, Examples include stannic chloride, zinc chloride, ferric chloride, and other acidic catalysts usually used for the production of novolak resins such as organic and inorganic acid salts showing acidity. These catalysts are not limited to those mentioned above, and may be used alone or in combination of two or more. The amount of the catalyst used is usually 0.005 to 2.0 times mol, preferably 0.01 to 1.1 times mol, or 0.1 to 10 g, more preferably 0 to 100 g of binol, with respect to binol. 3-7 parts. If the amount of catalyst is small, the progress of the reaction is slow. Moreover, problems such as the need for a reaction at a high temperature and the reaction not proceeding to the end are not preferable. On the other hand, when the amount of catalyst is too large, it is not preferable because much work is required in post-treatment such as neutralization and purification.
In addition, when corrosive gas refine | purifies by reaction, it is preferable to make it exhaust from the inside of a system by sending inactive gas, such as drawing pressure or nitrogen.

  The phenol resin thus obtained has the following formula (1)

(In the formula, Ar is a binaphthalene type phenol structure. Also, n means the number of repetitions and takes a numerical value of 0 to 20).

The softening point is 45 to 190 ° C, more preferably 50 to 180 ° C, and particularly preferably 50 to 150 ° C. If the softening point is too low, the handling property is poor, and if the softening point exceeds 190 ° C., it is difficult to take out as a resin, and the viscosity becomes very high, resulting in poor handling. Moreover, the hydroxyl group equivalent is 150-300 g / eq. More preferably, 150 to 250 g / eq. It is.
The number of repetitions n is preferably 0-20, more preferably 0-15.

Although the phenol resin of this invention may be individual, it is 1-90 area% with respect to the phenol resin obtained by reaction with the binol compound which is a raw material normally by GPC area ratio, More preferably, it is 5-80 area%. Containing, particularly preferably 20 to 70 area%. If the content of the binol compound is less than 1% by area, the softening point of the resulting resin becomes very high, making it difficult to take out, handling during composition, and moldability after composition. This greatly affects the molding process. When the amount of binol is less than 1 area%, it is preferable to coexist with another phenol resin instead, and examples of the curing agent can be used later.
Further, when the binol exceeds 90%, the high heat resistance, which is a feature of the present invention, is impaired, which is not preferable.

  The phenol resin of the present invention can be used as it is as a thermoplastic (or a raw material thereof), or as a raw material for an epoxy resin and a curing agent thereof as described below.

  The epoxy resin of the present invention can be obtained by reacting the phenol resin of the present invention with epihalohydrin. Although it does not specifically limit as a method of reaction, An example of the synthesis | combining method of the epoxy resin of this invention is described below.

  As a specific structural formula of the epoxy resin of the present invention, Ar in the formula (1) is represented by the following formula (2).

It is the structure shown by these.

The epoxy resin according to the present invention has an epoxy equivalent of 200 to 450 g / eq. And more preferably 220 to 300 g / eq. It is. When the epoxy equivalent is within the above range, an epoxy resin excellent in heat resistance and electrical reliability of the cured product can be obtained. Epoxy equivalent is 450 g / eq. If the ratio exceeds 1, the epoxy ring is not completely closed, and it is expected that many compounds having no functional group are contained, and it is predicted that the epoxy equivalent is not lowered, which is not preferable. In addition, many of these compounds that could not be ring-closed often contain chlorine, and as an electronic material application, there is concern about the release of chlorine ions under high-temperature and high-humidity conditions and the resulting corrosion of wiring. Absent.
The total chlorine amount remaining in the epoxy resin is 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 2000 ppm or less. The adverse effect of the chlorine amount is the same as described above. In addition, about chlorine ion and sodium ion, 5 ppm or less is preferable respectively, More preferably, it is 3 ppm or less. Chlorine ions are described above. Needless to say, cations such as sodium ions are also very important factors particularly in power device applications, and contribute to a defective mode when a high voltage is applied.

  The epoxy resin of the present invention has a form on the resin having a softening point. Here, as a softening point, 55-130 degreeC is preferable, More preferably, it is 60-120 degreeC. If the softening point is too low, blocking during storage becomes a problem, and there are many problems such as handling at low temperatures. On the other hand, when the softening point is too high, problems such as poor handling occur during kneading with other resins. The melt viscosity is preferably 2 Pa · s or less (ICI melt viscosity 150 ° C. cone plate method) or less. When mixing and using an inorganic material (filler etc.), the fluidity | liquidity is bad, and also the glass cloth etc. have the finer mesh | network, and the subject that inferior property is inferior arises.

In the reaction for obtaining the epoxy resin of the present invention, the epihalohydrin is preferably epichlorohydrin which is easily available industrially. The amount of epihalohydrin used is usually 3.0 to 15 mol, preferably 3.0 to 10 mol, more preferably 3.5 to 8.5 mol, particularly preferably 1 mol per mol of the hydroxyl group of the epoxy resin of the present invention. 5.5 to 8.5 mol.
If the amount is less than 3.0 mol, the epoxy equivalent may be increased, and the workability of the resulting epoxy resin is likely to deteriorate. It is not preferable.

Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide and the like, and a solid substance may be used, or an aqueous solution thereof may be used. From the viewpoint of moisture, solubility, and handling, it is preferable to use a solid material molded into a flake shape.
The amount of the alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, more preferably 0.99, based on 1 mol of the hydroxyl group of the phenol resin of the present invention. ˜1.15 moles.

  In order to accelerate the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, based on 1 mol of the hydroxyl group of the phenol resin of the present invention.

In this reaction, in addition to the epihalohydrin, it is preferable to use a nonpolar proton solvent (such as dimethyl sulfoxide, sometimes oxane, dimethylimidazolidinone) or an alcohol having 1 to 5 carbon atoms. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol. The usage-amount of a nonpolar protic solvent or a C1-C5 alcohol is 2-50 weight% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 4-25 weight%. Moreover, epoxidation may be performed while controlling the moisture in the system by a technique such as azeotropic dehydration.
When the amount of moisture in the system is large, it is not preferable because the electrical reliability of the obtained epoxy resin is deteriorated, and it is preferable to synthesize by controlling the moisture to 5% or less. Moreover, when an epoxy resin is obtained using a nonpolar proton solvent, an epoxy resin excellent in electrical reliability can be obtained, and therefore a nonpolar proton solvent can be suitably used.

The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In particular, in the present invention, 60 ° C. or higher is preferable for higher-purity epoxidation, and reaction under conditions close to reflux conditions is particularly preferable. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is short, the reaction does not proceed, and if the reaction time is long, a by-product is formed, which is not preferable.
After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is a solvent containing a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). It can also be dissolved, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added to react to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the phenol resin of the present invention used for epoxidation. . The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
In the reaction with epihalohydrin, it is preferably substituted with an inert gas such as nitrogen from the beginning of the reaction, and the oxygen concentration in the cavity is preferably 10% or less. Oxygen residue affects coloration. As a method, an inert gas such as nitrogen is blown in the atmosphere (in the air or in the liquid) before the phenol resin of the present invention is charged, or after being evacuated under reduced pressure, the inert gas is replaced. If there is no substitution with an inert gas, the resulting resin may be colored. When the inert gas is blown, the amount varies depending on the volume of the kettle, but it is preferable to blow the inert gas in an amount that can replace 1 to 3 times the volume of the kettle in 0.5 to 10 hours. .

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.

Hereinafter, it describes about the curable resin composition of this invention containing the epoxy resin of this invention.
In the curable resin composition of the present invention, a phenol resin or a polymerization catalyst is used as an essential component.

In the curable resin composition of this invention, it can classify | categorize roughly into 2 types, and is expressed as the curable resin composition A and the curable resin composition B below.
The curable resin composition A necessarily contains at least one of the epoxy resin of the present invention and the phenol resin of the present invention. It is a composition containing an epoxy resin-curing agent as an essential component. Moreover, a hardening accelerator is contained as needed.
The curable resin composition B is a composition containing the epoxy resin of the present invention and a polymerization catalyst as essential components.
In the curable resin composition A of the present invention, the amount of the curing agent (which may include the phenol resin of the present invention) is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
The polymerization catalyst that can be contained in the curable resin composition B of the present invention can be used without limitation as long as it is a catalyst that initiates polymerization by heat or light, and specifically, a curing accelerator or acidic curing can be used. A catalyst can be used.

  Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diaza. -Tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc. And quaternary ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, tetrabutylphosphonium salts, and the like. (The counter ion of the quaternary salt is not particularly specified, such as halogen, organic acid ion, hydroxide ion, etc., but organic acid ion and hydroxide ion are particularly preferable), metal compounds such as tin octylate, etc. It is done. When using a hardening accelerator, 0.01-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

  As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a light or thermal cationic polymerization initiator is particularly preferable. By blending a cationic polymerization initiator that is activated by active energy rays and / or a cationic polymerization initiator that is activated by heat, it can be used as the curable resin composition B described later.

Cationic polymerization initiators that initiate cationic polymerization of the curable resin composition B of the present invention by irradiation with active energy rays include diazonium salts, iodonium salts, sulfonium salts, selenium salts, pyridinium salts, ferrocenium salts, phosphonium salts. And iodonium salts and sulfonium salts, more preferably diaryl iodonium salts and dialkylphenacyl sulfonium salts, and diaryl iodonium salts can be preferably used.

When a photocationic polymerization initiator such as iodonium salt or sulfonium salt is used in the cationic curable resin composition of the present invention, BF ₄ −, AsF ₆ −, SbF ₆ −, PF ₆ −, and B (C ₆ F ₅₎ 4 _- and the like, preferably SbF ₆ -, PF ₆ -, or _{B (C 6 F 5) 4} - , and particularly preferably SbF 6 _- or _{B (C 6 F 5) 4} - It is.

  Specific examples of the cationic photopolymerization initiator include bis (dodecylphenyl) iodonium hexafluoroantimonate (manufactured by GE Toshiba Silicone, UV-9380C main component), tricumyliodonium tetrakis (pentafluorophenyl) borate (Rhodia) PHOTOINITIATOR 2074), bis (alkyl (C = 10-14) phenyliodonium) hexafluoroantimonate (Wcation Pure Chemicals photocationic polymerization initiator WPI-016), and the like.

  A compound that is activated by heat to initiate cationic polymerization, that is, a thermal cationic polymerization initiator, can also be used in the curable resin composition B of the present invention. Examples of this include various onium salts such as quaternary ammonium salts, phosphonium salts and sulfonium salts, combinations of alkoxysilanes and aluminum complexes, and the like. Available products include Adeka Opton CP-66 and Adeka Opton CP-77 (both trade names, manufactured by Asahi Denka Kogyo Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, and Sun-Aid SI-100L (both trade names) , Sanshin Chemical Industry Co., Ltd.), and CI series (Nihon Soda Co., Ltd.).

  Hereinafter, each of the curable resin compositions A and B of the present invention will be described.

  In the curable resin composition A and the curable resin composition B, other epoxy resins than the epoxy resin of the present invention can be used in combination or alone. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more. However, when using the epoxy resin of this invention as a modifier of a curable resin composition, it adds in the ratio of 1 to 30 weight%.

  Specific examples of other epoxy resins include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of them) Has glycidyl group and / or epoxycyclohexane structure Solid or liquid epoxy resin having an epoxy resin) and the like although not limited thereto.

Hereinafter, each curable resin composition will be referred to.
Thermal curing with a curing agent (curable resin composition A)
As a hardening | curing agent which the curable resin composition A of this invention contains, another hardening | curing agent other than the phenol resin of this invention can be used together, or can be used independently. When used in combination, the proportion of the phenolic resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more. However, when using the epoxy resin of this invention as a modifier of a curable resin composition, it adds in the ratio of 1 to 30 weight%.
Specific examples of the curing agent include a phenol resin, a phenol compound, an amine compound, an acid anhydride compound, an amide compound, and a carboxylic acid compound. Specific examples of curing agents that can be used include phenolic resins, phenolic compounds; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydride Roxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1, Polycondensates with 1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene, and their modified products, and halogenated bisphenols such as tetrabromobisphenol A And polyphenols such as terpene and phenol condensates, but are not limited thereto. These may be used alone or in combination of two or more.
Preferable phenol resins include phenol aralkyl resins (resins having an aromatic alkylene structure), particularly preferably a structure having at least one selected from phenol, naphthol, and cresol, and the alkylene portion serving as the linker is benzene. A resin characterized by at least one selected from a structure, a biphenyl structure, and a naphthalene structure (specific examples include zylock, naphthol zylock, phenol biphenylene novolak resin, cresol-biphenylene novolak resin, phenol-naphthalene novolak resin, etc.) Is.)
Amine compounds, amide compounds; nitrogen-containing compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid and polyamide resins synthesized from ethylenediamine.
Acid anhydride compounds, carboxylic acid compounds; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro Phthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2, Acid anhydrides such as 3-dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride; by addition reaction of various alcohols, carbinol-modified silicone, and the above-mentioned acid anhydrides Examples thereof include carboxylic acid resins obtained.
Others: Examples thereof include, but are not limited to, imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, and the like. These may be used alone or in combination of two or more.

  In the curable resin composition A of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In the curable resin composition A of the present invention, a curing accelerator may be used in combination with the curing agent. Specific examples of the curing accelerator that can be used include those described above. When using a hardening accelerator, 0.01-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

  The curable resin composition A of the present invention may contain a phosphorus-containing compound as a flame retardant imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

  Furthermore, you may add antioxidant to the curable resin composition A of this invention as needed. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part with respect to the resin component in the curable resin composition of this invention, Preferably it is 0.01-0.5 weight part. It is.

  Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3- Til-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t) -Butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t -Butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5- Bisphenols such as (tilphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) ethyl 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 '-Hydroxy-3'-tert-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -iso Anureate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol And the like.

  Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. .

  Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. 9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxaphosphaphenanthrene oxides such as 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are exemplified.

  These antioxidants can be used alone, but two or more of them may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable.

Furthermore, you may add a light stabilizer to the curable resin composition A of this invention as needed.
As the light stabilizer, hindered amine-based light stabilizers, particularly HALS and the like are suitable. HALS is not particularly limited, but representative examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-pentamethyl-4-pi Peridyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), etc. Only one HALS is used. Two or more types may be used in combination.

  Furthermore, binder resin can also be mix | blended with the curable resin composition A of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.

  An inorganic filler can be added to the curable resin composition A of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention. Furthermore, the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers. A compounding agent and various thermosetting resins can be added.

  The curable resin composition A of the present invention is obtained by uniformly mixing each component. The curable resin composition A of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are sufficient until uniform using an extruder, kneader, roll, etc. as necessary. To obtain a curable resin composition, potting the curable resin composition, melting (without melting in the case of a liquid), molding using a casting or transfer molding machine, and further 80 to 200 ° C. The cured product of the present invention can be obtained by heating for 2 to 10 hours.

  Further, the curable resin composition A of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone as necessary, and the curable resin composition varnish. The curable resin composition of the present invention is obtained by hot press-molding a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and drying by heating. It can be set as the hardened | cured material of the thing A. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, the epoxy resin hardened | cured material containing a carbon fiber can also be obtained as it is, for example with a RTM system.

  Moreover, the curable resin composition A of this invention can be used also as a modifier of a film type composition. Specifically, it can be used to improve the flexibility of the B-stage. In such a film-type resin composition, the curable resin composition A of the present invention is applied onto a release film as the curable resin composition varnish, the solvent is removed under heating, and then B-stage is performed. Thus, it is obtained as a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

Curable resin composition B (cationic curing with acidic curing catalyst)
The curable resin composition B of the present invention that is cured using an acidic curing catalyst contains a photopolymerization initiator or a thermal polymerization initiator as an acidic curing catalyst. Furthermore, you may contain various well-known compounds, materials, such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization start adjuvant, a photosensitizer. Moreover, you may contain various well-known additives, such as an inorganic filler, a color pigment, a ultraviolet absorber, antioxidant, a stabilizer, as needed.

  As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a light or thermal cationic polymerization initiator is particularly preferable. It can be used as the curable resin composition B by blending a cationic polymerization initiator activated by active energy rays and / or a cationic polymerization initiator activated by heat.

  Examples of the cationic polymerization initiator for initiating cationic polymerization of the curable resin composition B of the present invention by irradiation with active energy rays include those described above.

  As the active energy rays for curing the curable resin composition B of the present invention, X-rays, electron beams, ultraviolet rays, visible light, and the like can be used, preferably ultraviolet rays or visible rays, particularly preferably. Is ultraviolet light. When ultraviolet rays are used, the wavelength range is not particularly limited, but is preferably 150 to 400 nm, and more preferably 200 to 380 nm. When ultraviolet rays are used, cationic polymerization can be efficiently started.

Further, in the curable resin composition B of the present invention, a sensitizer can be used in combination in order to further increase the activity of the photocationic polymerization initiator as necessary. As a sensitizer that can be used in the present invention, for example, a compound disclosed by Crivello in Advanced in Polymer Science (Adv. In Polymer Sci., 62, 1 (1984)) can be used. Specific examples include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavine. In addition, compounds widely used as photo radical polymerization initiators can also be used, and specifically, thioxanthones such as benzophenone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2,4-dichlorothioxanthone. Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-methyl-1 Α-hydroxyalkylphenones such as phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, α such as camphorquinone -Dicarbo Nil compounds and the like. In the present invention, thioxanthones and α-hydroxyalkylphenones can be particularly preferably used.

  The compounding quantity of the photocationic polymerization initiator to the curable resin composition B of this invention can be suitably adjusted according to the kind and irradiation amount of an active energy ray. For example, in the case of ultraviolet rays, the amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts, and still more preferably 1 to 3 parts relative to 100 parts by mass of the cation curable resin composition. Part. When the amount of the cationic polymerization initiator is less than 0.1 part, the curability may be inferior. On the other hand, when it exceeds 10 parts by mass, the properties necessary for the cured product are reduced to reduce the physical properties of the cured product. May decrease, or the coloring of the cured product may become intense.

  The compounding amount in the case of adding a sensitizer to the curable resin composition B of the present invention can be appropriately adjusted according to the type of active energy ray and the irradiation amount. For example, in the case of ultraviolet rays, the amount is preferably 5 parts by mass or less, more preferably 0.2 to 2 parts with respect to 100 parts by mass in total of the curable resin composition B. When the blending amount of the sensitizer is more than 5 parts by mass, the components that are truly necessary for the cured product may be reduced to deteriorate the physical properties of the cured product, or the cured product may be intensely colored.

  When the active energy ray is ultraviolet light or visible light, the cationic curable resin composition is exposed to air. At this time, the humidity of the atmosphere is preferably low, and preferably 80% humidity. H. 70% R.V. H. More preferably, it is as follows. Here, when ultraviolet rays or visible light is installed in the production line, a method of sending dry air in front of the light irradiation device or a method of reducing the humidity by attaching a heating device can be employed.

  A compound that is activated by heat to initiate cationic polymerization, that is, a thermal cationic polymerization initiator, can also be used in the curable resin composition B of the present invention. Examples of this include various onium salts such as quaternary ammonium salts, phosphonium salts and sulfonium salts, combinations of alkoxysilanes and aluminum complexes, and the like. Available products include Adeka Opton CP-66 and Adeka Opton CP-77 (both trade names, manufactured by Asahi Denka Kogyo Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, and Sun-Aid SI-100L (both trade names) , Sanshin Chemical Industry Co., Ltd.), and CI series (Nihon Soda Co., Ltd.).

  The blending ratio of the thermal cationic polymerization initiator to the curable resin composition B of the present invention is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the cation curable resin composition, more preferably. Is 0.1 to 5 parts, more preferably 0.5 to 3 parts. When the blending ratio is less than 0.01 parts by mass, the ring-opening reaction of the ring-opening polymerizable group may not be allowed to proceed sufficiently even if it is activated by the action of heat. Moreover, even if it mixes exceeding 10 mass parts, since the effect | action which advances superposition | polymerization does not increase any more and the physical property of hardened | cured material may fall, it is unpreferable.

  Furthermore, the curable resin composition B of the present invention is added with various compounding agents such as the above inorganic fillers, silane coupling materials, mold release agents, pigments, and various thermosetting resins as necessary. can do.

  The curable resin composition B of the present invention can be obtained by uniformly mixing each component. It is also possible to dissolve in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone and make it uniform, and then use it after removing the solvent by drying. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition B of the present invention and the solvent. The curable resin composition B of the present invention can be cured by irradiating with ultraviolet rays, but the amount of ultraviolet irradiation varies depending on the curable resin composition, and therefore is determined by the respective curing conditions. What is necessary is just the irradiation amount which a photocurable curable resin composition hardens | cures, and should just satisfy | fill the curing conditions with favorable adhesive strength of hardened | cured material. Since it is necessary for light to be transmitted through the details during the curing, the epoxy resin and the curable resin composition B of the present invention are highly transparent. Also. In these epoxy resin-based photocuring, it is difficult to completely cure only by light irradiation, and in applications where heat resistance is required, it is necessary to complete reaction curing by heating after light irradiation.

  The heating after the light irradiation may be performed in the normal curing temperature range of the curable resin composition B. For example, the range of 30 minutes to 7 days at room temperature to 150 ° C. is suitable. Although it changes depending on the blending of the curable resin composition B, the higher the temperature range, the more effective the curing is after light irradiation, and the short heat treatment is effective. Further, the lower the temperature, the longer the heat treatment. By performing such heat after-curing, an effect of aging treatment is obtained.

  Moreover, since the shape of the cured product obtained by curing these curable resin compositions B can be variously selected depending on the application, it is not particularly limited. For example, it may be a film shape, a sheet shape, a bulk shape, or the like. . The molding method varies depending on the applicable part and member. For example, a casting method, a casting method, a screen printing method, a spin coating method, a spray method, a transfer method, a dispenser method, or the like can be applied. Although it is mentioned, it is not limited to these. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied. In addition, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be applied in order to improve releasability from the mold.

  For example, when used for a cation curable resist, first, the photo cation curable resin composition B of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone is used as a copper-clad laminate, The composition of the present invention is applied to a film thickness of 5 to 160 μm on a substrate such as a ceramic substrate or a glass substrate by a method such as screen printing or spin coating to form a coating film. The coating film is preliminarily dried at 60 to 110 ° C., and then irradiated with ultraviolet rays (for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film having a desired pattern. Then, post-exposure baking is performed at 70 to 120 ° C. Thereafter, the unexposed part is dissolved and removed (developed) with a solvent such as polyethylene glycol monoethyl ether, and if necessary, sufficient by irradiation with ultraviolet rays and / or heating (for example, at 100 to 200 ° C. for 0.5 to 3 hours). Curing is performed to obtain a cured product. In this way, it is also possible to obtain a printed wiring board.

  The hardened | cured material formed by hardening | curing curable resin composition A and curable resin composition B of this invention can be used for various uses.

  Examples include general uses in which the curable resin composition A or the curable resin composition B is used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials ( In addition to the sealing agent, the additive to other resins, etc. are mentioned. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agent and substrate, potting sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, ICs, LSIs for COB, COF, TAB, etc. Examples include underfill for flip chip, sealing (including reinforcing underfill) and package substrate when mounting IC packages such as QFP, BGA, and CSP. Moreover, it is suitable also for the board | substrate use as which a functionality, such as a network board | substrate and a module board, is calculated | required.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
The various analysis methods used in the examples are described below.
Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001)
ICI melt viscosity: compliant with JIS K 7117-2 (ISO 3219) Softening point: compliant with JIS K 7234 Total chlorine: compliant with JIS K 7243-3 (ISO 21672-3) GPC:
Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)
The coupled eluent is tetrahydrofuran. The flow rate is 0.5 ml / min.
Column temperature is 40 ° C
Detection: RI (differential refraction detector)

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

Example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while binol (GPC purity> 99% Aldrich reagent melting point 216-218 ° C.) 71.6 parts, p-xylylene glycol (manufactured by Tokyo Chemical Industry) Reagents) 13.8 parts, methyl isobutyl ketone (Pure Chemicals reagent) 128 parts, paratoluenesulfonic acid monohydrate (Tokyo Chemicals reagent) 3.4 parts, methanol 15 parts, methanol and water produced While removing, the reaction was carried out at 70 ° C. for 1 hour, 80 ° C. for 1 hour, 100 ° C. for 2 hours, and then brought to a reflux state at 110-120 ° C. and reacted for 3 hours.
After completion of the reaction, cooling to 50 ° C and washing with water were repeated, and after confirming that the aqueous layer was neutral, the phenolic resin of the present invention was distilled off from the oil layer under reduced pressure using a rotary evaporator. 89 parts of (P-1) were obtained. The obtained phenol resin had a softening point of 129 ° C. The GPC chart is as shown in FIG. From the results of this GPC, it was confirmed that the amount of residual binol was 38.2 area% as an area ratio with respect to the phenol resin (P1).

FIG.

(Example 2)
The reaction was conducted in the same manner except that the amount of xylylene glycol in Example 1 was changed from 13.8 parts to 6.9 parts. The softening point of the obtained phenol resin (P-2) was 96 ° C., and the amount of residual binol was 68.7 area% (GPC FIG. 2) as an area ratio to the phenol resin (P2).

FIG.

(Example 3)
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, while purging with nitrogen, 38 parts of the phenol resin (P-1 hydroxyl equivalent 173 g / eq.) Of the present invention, 121 parts epichlorohydrin (6 molar equivalents) Phenol resin) and 8 parts of methanol were added, dissolved under stirring, and heated to 70-75 ° C. Next, 9 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, washing with 100 parts of water was carried out, and excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. 95 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 75 ° C. Under stirring, 0.1 part of 30% by weight aqueous sodium hydroxide solution and 1 part of methanol were added and reacted for 1 hour, and then washed with water until the washing water of the oil layer became neutral. From the resulting solution, 43 parts of the epoxy resin (EP1) of the present invention was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure using a rotary evaporator. The epoxy equivalent of the obtained epoxy resin is 251 g / eq. The softening point was 99 ° C.

(Synthesis Example 1)
To a flask equipped with a stirrer, reflux condenser, and stirrer, add 214 parts of binol, 555 parts of epichlorohydrin (4 molar equivalents to phenolic resin), and 55 parts of methanol while purging with nitrogen, and dissolve under stirring. The temperature was raised to 70-75 ° C. Next, 60 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, water was washed with 400 parts of water, and excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator. To the residue, 500 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 10 parts of a 30% by weight aqueous sodium hydroxide solution and 10 parts of methanol were added and reacted for 1 hour, followed by washing with water until the washing water of the oil layer became neutral. From the resulting solution, a rotary evaporator was used. Was used to distill off methyl isobutyl ketone and the like under reduced pressure to obtain 403 parts of the epoxy resin (EP3) of the present invention. The epoxy equivalent of the obtained epoxy resin is 230 g / eq. The softening point was 58 ° C.

Example 4 and Comparative Examples 1 and 2
<Heat resistance test and flame retardancy test>
The epoxy resin and phenol resin obtained above were blended in the proportions (parts by weight) shown in Table 1, and mixed and kneaded uniformly using a mixing roll to obtain a curable resin composition for sealing. The curable resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted curable resin composition was transfer molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation. The flame retardant test results are also shown in Table 1.
In addition, the physical property of hardened | cured material was measured in the following ways.
Flame retardance: Performed according to UL94. However, the test was conducted with a sample size of 12.5 mm wide × 150 mm long and a thickness of 0.8 mm.
・ Afterflame time: Total afterflame time after 10 times of contact with 5 samples. ・ Heat resistance (DMA)
Dynamic viscoelasticity measuring device: TA-instruments, DMA-2980
Measurement temperature range: -30 to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm)
Tg: Tan-δ peak point is defined as Tg

  From the above results, it is clear that the curable resin composition of the present invention is superior in flame retardancy and heat resistance as compared with EP3 and EP4 having similar structures, and has high heat resistance, and at the same time, halogen and It can be seen that a cured product having excellent flame retardancy can be provided without using a flame retardant such as an antimony compound.

Claims (4)

A phenol resin represented by the following formula (1).
(In the formula, Ar is a bisnaphthalene type phenol structure. Also, n means the number of repetitions and takes a value of 1 to 15. ) In lower following formula (1), an epoxy resin having the structure Ar is represented by the following formula (2).
(In the formula, n means the number of repetitions and takes a numerical value of 1 to 15.)
  A curable resin composition comprising at least one of the phenol resin according to claim 1 or the epoxy resin according to claim 2. Cured product obtained by curing the curable resin composition according to claim 3.