JP2017105898A - Epoxy resin, manufacturing method of epoxy resin, curable resin composition and cured article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin excellent in balance of thermal stability of the epoxy resin, molding shrinkage factor during heating and curing a curable composition and thermal time elastic modulus, a manufacturing method therefor, a curable resin composition and a cured article thereof.SOLUTION: There are provided an epoxy resin which is a phenol novolak type epoxy resin (A) having an allyl group as a substituent on an aromatic ring and contains a compound (B) represented by the formula (1) and a compound (C) binding a neighboring benzene ring by unfolding a pyran ring of the general formula (1) of total 0.1 to 0.6% by area percentage in a GPC measurement, a manufacturing method therefor, a curable composition containing the same and a cured article thereof.SELECTED DRAWING: None

Description

  The present invention has an excellent balance between the thermal stability of a resin, the molding shrinkage ratio at the time of heat curing, and the elastic modulus at heat, and can be suitably used for a semiconductor sealing material and the like, a method for producing the same, and the epoxy resin The present invention relates to a curable resin composition containing bismuth and its cured product.

  Curable resin compositions using epoxy resins and various curing agents are used in adhesives, molding materials, paints, photoresist materials, color developing materials, etc., and the resulting cured products have excellent heat resistance and moisture resistance. It is widely used in the electrical and electronic fields such as semiconductor sealing materials and printed wiring board insulating materials.

  Among these various applications, along with the trend toward smaller and lighter electronic devices, the trend toward higher density due to the narrower wiring pitch of semiconductor devices is remarkable. A flip chip connection method in which the device and the substrate are joined is widely used. In this flip-chip connection method, a solder ball is placed between a wiring board and a semiconductor, and the whole is heated and melt bonded to form a so-called reflow semiconductor mounting method. Therefore, the wiring plate itself is exposed to a high heat environment during solder reflow. In some cases, warping occurs due to thermal contraction of the wiring board, and a large stress is generated in the solder balls connecting the wiring board and the semiconductor, resulting in poor connection of the wiring. In order to suppress the warpage of the wiring board, it has been studied to greatly shrink while improving the thermal elastic modulus of the sealing material, and high thermal modulus and high shrinkage are also required for the sealing resin. Has been.

  Further, in the field of semiconductor sealing materials, the reflow treatment temperature has been increased due to the shift to lead-free solder, and improvement in solder crack resistance (reflow property) has been demanded. Therefore, a semiconductor sealing material is required to have a material having high heat resistance in a cured product, and a resin excellent in thermal stability is required.

  In order to meet such a demand, for example, a phenol compound having an alkyl group having 1 to 4 carbon atoms or a ru group at the ortho position is a methylene group and / or an o-hydroxyphenylmethylene group or a p-hydroxyphenylmethylene group. It has been proposed to use a liquid phenol novolac resin as a base as a curing agent for an epoxy resin (see, for example, Patent Document 1).

  By using the phenol novolak resin as a curing agent, although certain effects are obtained in the fluidity of the composition and the low water absorption property of the cured product, compared to the case of using a general phenol novolak resin, it has recently been required. The balance level between the thermal stability of the resin, the molding shrinkage ratio during heat curing and the elastic modulus during heat curing cannot be sufficiently satisfied, and further improvements are required.

  The epoxidized bisphenol having an allyl is a known compound (see, for example, Patent Document 2). This compound is polyfunctionalized by epoxidizing an allyl group. It is not a phenol compound having a group simultaneously. Although polyfunctionalization has the effect of increasing the crosslink density of the cured product to impart heat resistance, the elastic modulus at the time of curing tends to be low, and it is generally difficult to apply to the above uses. .

JP 2000-169537 A Japanese Patent Laid-Open No. 63-142019

  Therefore, the problem to be solved by the present invention is an epoxy resin excellent in the balance between the thermal stability of the epoxy resin, the molding shrinkage ratio at the time of heat curing of the curable composition, and the elastic modulus at the time of heating, its production method, and curability. It is providing the resin composition and its hardened | cured material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that the specific ratio of a specific compound in the phenol novolac epoxy resin (A) having an allyl group as a substituent on the aromatic ring in the GPC measurement By adding 0.1 to 0.6%, it is found that the balance between the thermal stability of the epoxy resin, the molding shrinkage ratio at the time of heat curing of the curable composition, and the elastic modulus at the time of heating is excellent. The invention has been completed.

That is, the present invention is a phenol novolac type epoxy resin (A) having an allyl group as a substituent on an aromatic ring, which is represented by the following general formula (1):
Wherein (1), R ¹ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group having 1 to 4 carbon atoms from 1 to 4 carbon atoms, p is 1 to 3 independently Represents an integer. ]
Compound (B) represented, and the following general formula (2)
[In Formula (2), R ² each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Represents an integer. ]
An epoxy resin, a method for producing the same, and a curable resin composition containing the epoxy resin, containing a total of 0.1% to 0.6% by area ratio in GPC measurement Product and its cured product.

  According to the present invention, an epoxy resin that is excellent in the balance between the thermal stability of the resin, the molding shrinkage ratio at the time of heat-curing, and the elastic modulus at the time of heat, and can be suitably used for a semiconductor encapsulating material, etc. A resin composition, a cured product having the above performance, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, a buildup film, a buildup board, a fiber reinforced composite material, and a fiber reinforced molded product can be provided.

FIG. 1 is a GPC chart of the epoxy resin (A-1) synthesized in Synthesis Example 2. FIG. 2 is an FD-MS spectrum of the epoxy resin (A-1) synthesized in Synthesis Example 2. FIG. 3 is a ¹³ C-NMR spectrum of the epoxy resin (A-1) synthesized in Synthesis Example 2. FIG. 4 is a GPC chart of the epoxy resin (A-2) synthesized in Synthesis Example 4. FIG. 5 is a GPC chart of the epoxy resin (A-3) synthesized in Synthesis Example 6.

<Epoxy resin>
Hereinafter, the present invention will be described in detail.
The epoxy resin of the present invention is a phenol novolac type epoxy resin (A) having an allyl group as a substituent on an aromatic ring, and has the following general formula (1)
Wherein (1), R ¹ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group having 1 to 4 carbon atoms from 1 to 4 carbon atoms, p is 1 to 3 independently Represents an integer. ]
Compound (B) represented, and the following general formula (2)
[In Formula (2), R ² each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Represents an integer. ]
The compound (C) represented by the formula is characterized by containing a total of 0.1% to 0.6% by area ratio in GPC measurement.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, t-propyloxy group, butoxy group, isobutyloxy group, t-butyloxy group and the like.

Among these, R ¹ is preferably a hydrogen atom from the viewpoint of the balance between the thermal stability of the resin, the molding shrinkage ratio during heat curing and the elastic modulus during heat curing, and from the viewpoint of industrial availability of raw materials.

  When the total content of the compounds (B) and (C) in the epoxy resin is less than 0.1%, the residual rate of double bonds in the resin is increased, and the thermal stability is increased. It becomes worse and unsuitable for manufacturing. If it exceeds 0.6%, the crosslink density tends to be low, the thermal elastic modulus becomes small, and the molding shrinkage tends to decrease.

  In addition, the total content of the compound (B) and the compound (C) in the epoxy resin of the present invention is superior to the balance between the thermal stability of the resin, the molding shrinkage rate at the time of heat curing, and the elastic modulus at the time of heating. The area ratio in the measurement is more preferably in the range of 0.2% to 0.5%.

  In addition, the epoxy equivalent of the epoxy resin of the present invention is in the range of 220 g / eq to 280 g / eq from the viewpoint that the balance between the thermal stability of the resin, the molding shrinkage ratio at the time of heat curing, and the elastic modulus at the time of heat increase. Is preferred.

In addition, the content rate of the compounds (B) and (C) in this invention is the ratio of the peak area of the said compound with respect to the total peak area of an epoxy resin calculated by GPC measurement by the following conditions.
<GPC measurement conditions>
Measuring device: “HLC-8320 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refractometer)
Data processing: “GPC workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC workstation EcoSEC-WorkStation”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

As described above, the epoxy resin of the present invention is a phenol novolac type epoxy resin (A) having an allyl group as a substituent on an aromatic ring containing a specific amount of the aforementioned compounds (B) and (C). Examples of the epoxy resin (A) include the following general formula (3)
[In Formula (3), each R ³ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and each r independently represents 1 to 3 carbon atoms. An integer is represented, and n is an average of the number of repetitions and is 1 to 10. ]
It is represented by

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ³ in the general formula (3) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. Can be mentioned. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, t-propyloxy group, butoxy group, isobutyloxy group, t-butyloxy group and the like.

Among these, R ³ is preferably a hydrogen atom from the viewpoint of the balance between the thermal stability of the resin, the molding shrinkage ratio during heat curing and the elastic modulus during heat curing, and from the viewpoint of industrial availability of raw materials.

  Moreover, n in the said General formula (3) is an average of the number of repetitions, and it is more preferable that it is the range of 1.5-8 from a viewpoint of coexistence of a thermal elasticity and thermal stability.

<Method for producing epoxy resin>
The epoxy resin of the present invention described in detail above is obtained by adding the aforementioned compounds (B) and (C) to the phenol novolac type epoxy resin (A) having an allyl group as a substituent on the aromatic ring in an area ratio of GPC of 0. It can manufacture by mix | blending so that it may be contained in the ratio of 1%-0.6%. Furthermore, when the method for producing an epoxy resin of the present invention is used, it is easy to make the epoxy resin even more excellent in industrial productivity and in the uniformity of the resulting epoxy resin.

  The method for producing an epoxy resin of the present invention is a phenol novolac type epoxy resin obtained by obtaining a phenol novolak having an allyl group as a substituent on an aromatic ring using 2-allylphenol and formaldehyde, and then reacting with an epihalohydrin for epoxidation. In which the molar ratio of 2-allylphenol to formaldehyde is in the range of 0.50 to 0.95 and is maintained in the range of 170 to 200 ° C. for 5 to 10 hours.

<Step 1>
As described above, in step 1, 2-allylphenol and formaldehyde are used in a molar ratio of 0.50 to 0.95 and held in a range of 170 to 200 ° C. for 5 to 10 hours. Have. By having such a step, it is possible to contain a specific amount of a precursor phenol compound of so-called compounds (B) and (C) in which the epoxy group portion of the compounds (B) and (C) is a hydroxyl group. It becomes. In Step 1, it is preferable to give a heat history of 5 to 10 hours in the range of 170 to 200 ° C. after carrying out the dehydration condensation reaction using an acid catalyst under normal pressure and inert gas atmosphere. The normal pressure is a pressure when neither depressurizing nor pressurizing specially, and usually refers to a pressure equal to the atmospheric pressure.

  2-allylphenol can be produced by a general production method, that is, phenol allyletherification, followed by a Claisen rearrangement reaction, or a commercially available product can be used as it is. The formaldehyde may be a formalin solution in the form of an aqueous solution or paraformaldehyde in a solid state.

  Examples of the acid catalyst used here include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, and anhydrous aluminum chloride. And Lewis acids such as zinc chloride. The amount used is preferably in a range of 0.001 to 2.0 times the molar amount of the total number of phenolic hydroxyl groups of the raw material components cresol and naphthol compound.

  The inert gas is not limited as long as it is an inert gas with respect to the chemical reaction or the compound, but it is preferable to use nitrogen or argon from the viewpoint of production cost.

  The reaction may be performed in an organic solvent, and examples of the organic solvent that can be used include methyl cellosolve, isopropyl alcohol, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is not particularly limited, and is, for example, in the range of 10 to 300 parts by mass per 100 parts by mass of o-allylphenol as a raw material component from the viewpoint of work efficiency. Is preferred.

  The use ratio of 2-allylphenol and formaldehyde in step 1 is within the range where the molar ratio is 0.50 to 0.95, and it is easy to adjust the ratio of each component in the finally obtained epoxy resin. It is preferable from a certain point, and it is particularly preferable to use in the range of 0.60 to 0.95.

  In addition, after completion | finish of reaction, it is preferable to neutralize or wash with water until the pH value of a reaction mixture will be 4-7. The neutralization treatment and the water washing treatment may be performed according to a conventional method. For example, a basic substance such as sodium hydroxide or potassium hydroxide can be used as a neutralizing agent. After neutralization or water washing treatment, the organic solvent is distilled off under reduced pressure, whereby a novolac phenol resin having an allyl group at the 2-position and the precursors of the compounds (B) and (C). It is possible to suitably obtain a phenol resin containing a specific amount of the phenol compound and giving an epoxy resin containing a predetermined amount of the compounds (B) and (C) at the end of step 2.

<Process 2>
In step 2, 1 to 10 mol of epihalohydrin is added to 1 mol of the novolak type phenol resin obtained in step 1, and 0.9 to 2.0 mol of basic catalyst is added to 1 mol of the novolak type phenol resin. The method of making it react at the temperature of 20-120 degreeC for 0.5 to 10 hours, adding batch or adding gradually is mentioned. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. The solution may be taken out and further separated to remove water and the epihalohydrins are continuously returned to the reaction mixture.

  In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new in industrial production, but the subsequent batches are consumed by the reaction with epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount disappeared. Under the present circumstances, the impurity induced | guided | derived by reaction with epichlorohydrin, water, an organic solvent, etc. may be contained, such as glycidol. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Among these, epichlorohydrin is preferable because it is easily available industrially.

  Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these basic catalysts may be used in the form of an aqueous solution of about 10% to 55% by weight or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

  Subsequently, the reaction product of the epoxidation reaction is washed with water, and unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1% by mass to 3.0% by mass with respect to the epoxy resin used. After completion of the reaction, the generated salt is removed by filtration, washing with water, and a high-purity epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

<Curable resin composition>
The phenol novolac epoxy resin (A) having an allyl group as a substituent on the aromatic ring of the present invention, and the following general formula (1)
Wherein (1), R ¹ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group having 1 to 4 carbon atoms from 1 to 4 carbon atoms, p is 1 to 3 independently Represents an integer. ]
Compound (B) represented, and the following general formula (2)
[In Formula (2), R ² each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Represents an integer. ]
The epoxy resin characterized by containing a total of 0.1% to 0.6% of the compound (C) represented by the formula (GPC) by area ratio in GPC measurement can be used in combination with a curing agent. A curable resin composition can be produced by blending a curing agent with the epoxy resin.

  Examples of the curing agent that can be used here include various known curing agents such as an amine compound, an amide compound, an acid anhydride compound, and a phenol compound.

Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide. And a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine. Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride. Phenol compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, triphenylol methane resin, Tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyphenolic hydroxyl group-containing compound in which phenol nuclei are linked by a bismethylene group), biphenyl Modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified phenol resin (melamine, benzo Polyhydric phenolic hydroxyl group-containing compounds in which phenol nuclei are linked with anamin, etc.), alkoxy group-containing aromatic ring-modified novolak resins (polyhydric phenolic hydroxyl group-containing compounds in which phenol nuclei and alkoxy group-containing aromatic rings are linked with formaldehyde), etc. And a polyhydric phenolic hydroxyl group-containing compound.

  In addition to the epoxy resin described in detail above, the curable resin composition may be used in combination with other thermosetting resins.

  Examples of other thermosetting resins include cyanate ester resins, resins having a benzoxazine structure, maleimide compounds, active ester resins, vinyl benzyl compounds, acrylic compounds, and copolymers of styrene and maleic anhydride. . When the other thermosetting resins described above are used in combination, the amount used is not particularly limited as long as the effects of the present invention are not impaired, but the range is 1 to 50 parts by mass in 100 parts by mass of the thermosetting resin composition. It is preferable that

  Examples of the cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, and phenylene ether type cyanate ester resin. , Naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, triphenylmethane type cyanate Ester resin, tetraphenylethane type cyanate ester resin, Cyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolak type cyanate ester resin, naphthol-cresol co-condensed novolak type Examples include cyanate ester resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type cyanate ester resins, biphenyl-modified novolac-type cyanate ester resins, and anthracene-type cyanate ester resins. These may be used alone or in combination of two or more.

  Among these cyanate ester resins, bisphenol A-type cyanate ester resins, bisphenol F-type cyanate ester resins, bisphenol E-type cyanate ester resins, and polyhydroxynaphthalene-type cyanate ester resins are particularly preferred in that a cured product having excellent heat resistance can be obtained. Naphthalene ether type cyanate ester resin and novolak type cyanate ester resin are preferably used, and dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable in that a cured product having excellent dielectric properties can be obtained.

  The resin having a benzoxazine structure is not particularly limited. For example, a reaction product of bisphenol F, formalin, and aniline (Fa type benzoxazine resin) or a reaction product of diaminodiphenylmethane, formalin, and phenol (P- d-type benzoxazine resin), reaction product of bisphenol A, formalin and aniline, reaction product of dihydroxydiphenyl ether, formalin and aniline, reaction product of diaminodiphenyl ether, formalin and phenol, dicyclopentadiene-phenol addition resin and formalin Reaction product of phenol and aniline, reaction product of phenolphthalein, formalin and aniline, reaction product of diphenyl sulfide, formalin and aniline. These may be used alone or in combination of two or more.

  Examples of the maleimide compound include various compounds represented by any of the following structural formulas (i) to (iii).

(In the formula, R is an m-valent organic group, α and β are each a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and s is an integer of 1 or more.)

(In the formula, R is any one of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, s is an integer of 1 to 3, and t is an average of 0 to 10 repeating units. .)

(In the formula, R is any one of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, s is an integer of 1 to 3, and t is an average of 0 to 10 repeating units. .) These may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular as said active ester resin, Generally ester group with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, is in 1 molecule. A compound having two or more is preferably used. The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or a halide thereof and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or a halide thereof and a phenol compound and / or a naphthol compound is preferred. More preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like, or a halide thereof. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m -Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin , Benzenetriol, dicyclopentadiene-phenol addition resin, and the like.

  Specific examples of the active ester resin include an active ester resin containing a dicyclopentadiene-phenol addition structure, an active ester resin containing a naphthalene structure, an active ester resin that is an acetylated product of phenol novolac, and an activity that is a benzoylated product of phenol novolac. An ester resin or the like is preferable, and an active ester resin including a dicyclopentadiene-phenol addition structure and an active ester resin including a naphthalene structure are more preferable because they are excellent in improving peel strength. More specifically, an active ester resin containing a dicyclopentadiene-phenol addition structure includes a compound represented by the following general formula (iv).

  However, in formula (iv), R is a phenyl group or a naphthyl group, u represents 0 or 1, and n is 0.05-2.5 on the average of a repeating unit. From the viewpoint of reducing the dielectric loss tangent of the cured product of the resin composition and improving the heat resistance, R is preferably a naphthyl group, u is preferably 0, and n is preferably 0.25 to 1.5. .

  Curing proceeds with the curable resin composition of the present invention alone, but a curing accelerator may be used in combination. Curing accelerators include tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride amine complexes such as boron trifluoride and trifluoride monoethylamine complexes; thiodipropion Organic acid compounds such as acids; benzoxazine compounds such as thiodiphenol benzoxazine and sulfonyl benzoxazine; sulfonyl compounds and the like. These may be used alone or in combination of two or more. It is preferable that the addition amount of these catalysts is 0.001-15 mass parts in 100 mass parts of curable resin compositions.

  Moreover, when using for the use as which the high flame retardance is calculated | required by the curable resin composition of this invention, you may mix | blend the non-halogen-type flame retardant which does not contain a halogen atom substantially.

  Examples of the non-halogen flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, an organic metal salt flame retardant, and the like. It is not intended to be used alone, and a plurality of the same type of flame retardants may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  The organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7- Examples thereof include cyclic organic phosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The amount of these phosphorus-based flame retardants is appropriately selected depending on the type of phosphorus-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. In 100 parts by mass of curable resin composition containing all of flame retardant and other fillers and additives, 0.1 to 2.0 parts by mass when red phosphorus is used as a non-halogen flame retardant It is preferable to mix | blend in the range of 0.1 mass part-10.0 mass parts similarly, when using an organophosphorus compound, 0.5 mass part-6.0 mass parts is similarly preferable. It is more preferable to mix in the range.

  Also, when using the phosphorus flame retardant, the phosphorus flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (1) guanylmelamine sulfate, melem sulfate, melam sulfate (2) Co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine, and formaldehyde, (3) (2) A mixture of a co-condensate and a phenol resin such as a phenol formaldehyde condensate, (4) those obtained by further modifying (2) and (3) above with paulownia oil, isomerized linseed oil or the like.

  Examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The compounding amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 10 parts by mass in 100 parts by mass of the curable resin composition containing all of the flame retardant and other fillers and additives, and 0.1 to 5 parts by mass. It is more preferable to mix in the range.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin. The amount of the silicone-based flame retardant is appropriately selected according to the type of the silicone-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable resin composition containing all of the flame retardant and other fillers and additives. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

  Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Examples thereof include chromium oxide, nickel oxide, copper oxide, and tungsten oxide.

  Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Examples of the low-melting-point glass include Shipley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, and P ₂ O _5. Glassy compounds such as —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, and lead borosilicate Can be mentioned.

  The blending amount of the inorganic flame retardant is appropriately selected depending on the kind of the inorganic flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. In 100 parts by mass of the curable resin composition containing all of the flame retardant and other fillers and additives, it is preferably compounded in the range of 0.05 parts by mass to 20 parts by mass, and 0.5 parts by mass to 15 parts by mass. It is more preferable to mix in the range of parts by mass.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound. And the like.

  The amount of the organic metal salt flame retardant is appropriately selected depending on the type of the organic metal salt flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. A curable resin composition containing all of the non-halogen flame retardant and other fillers and additives, for example, in a range of 0.005 parts by mass to 10 parts by mass in 100 parts by mass of the curable resin composition. It is preferable.

  The curable resin composition of this invention can mix | blend an inorganic filler as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably high in consideration of flame retardancy, and is particularly preferably 20% by mass or more with respect to the total mass of the curable resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  In addition to the above, the curable resin composition of the present invention may contain various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.

<Use of curable resin composition>
The curable resin composition of the present invention is a semiconductor encapsulant, a semiconductor device, a prepreg, and a printed circuit board because the obtained cured product is excellent in low thermal expansion and low hygroscopicity and can exhibit high heat resistance. It can be applied to build-up substrates, build-up films, fiber-reinforced composite materials, fiber-reinforced resin molded products, conductive pastes, and the like.

1. Semiconductor encapsulating material As a method for obtaining a semiconductor encapsulating material from the curable resin composition of the present invention, the curable resin composition, the curing accelerator, and a compounding agent such as an inorganic filler are extruded as necessary. Examples thereof include a method of sufficiently melt-mixing until uniform using a machine, kneader, roll or the like. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, nitridation having higher thermal conductivity than fused silica. High filling such as silicon, or fused silica, crystalline silica, alumina, silicon nitride, or the like may be used. As for the filling rate, it is preferable to use an inorganic filler in the range of 30% by mass to 95% by mass per 100 parts by mass of the curable resin composition, and among them, improvement in flame resistance, moisture resistance and solder crack resistance, In order to reduce the expansion coefficient, it is more preferably 70 parts by mass or more, and further preferably 80 parts by mass or more.

2. Semiconductor device As a method for obtaining a semiconductor device from the curable resin composition of the present invention, the semiconductor encapsulating material is cast, or molded using a transfer molding machine, an injection molding machine, or the like, and further at 50 to 200 ° C. The method of heating for 10 hours is mentioned.

3. Prepreg As a method for obtaining a prepreg from the curable resin composition of the present invention, a curable resin composition blended with an organic solvent and varnished is used as a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth). And a glass mat, a glass roving cloth, etc.), followed by heating at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 mass% to 60 mass%.

  Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxy propanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. For example, when a printed circuit board is further produced from a prepreg as described below, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, dimethylformamide, etc. The nonvolatile content is preferably 40% by mass to 80% by mass.

4). Printed Circuit Board As a method for obtaining a printed circuit board from the curable resin composition of the present invention, the prepreg is laminated by a conventional method, and a copper foil is appropriately laminated at 170 to 300 ° C. under a pressure of 1 to 10 MPa. The method of carrying out thermocompression bonding for 10 minutes-3 hours is mentioned.

5). Build-up substrate As a method for obtaining a build-up substrate from the curable resin composition of the present invention, a method through Steps 1 to 3 may be mentioned. In step 1, first, the curable resin composition appropriately blended with rubber, filler, and the like is applied to a circuit board on which a circuit is formed using a spray coating method, a curtain coating method, or the like, and then cured. In step 2, if necessary, after drilling a predetermined through-hole portion or the like on the circuit board coated with the curable resin composition, by treating with a roughening agent and washing the surface with hot water, Unevenness is formed on the substrate, and a metal such as copper is plated. In step 3, the operations of steps 1 and 2 are sequentially repeated as desired to build up a resin insulating layer and a conductor layer having a predetermined circuit pattern alternately to form a build-up substrate. In the step, the through-hole portion is preferably formed after the outermost resin insulating layer is formed. In addition, the build-up board of the present invention is obtained by roughly pressing a resin-coated copper foil obtained by semi-curing the resin composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 300 ° C. It is also possible to produce a build-up substrate by forming the chemical surface and omitting the plating process.

6). Build-up film As a method for obtaining a build-up film from the curable resin composition of the present invention, for example, a curable resin composition is applied on a support film and then dried, and then a resin composition layer is formed on the support film. The method of forming is mentioned. When the curable resin composition of the present invention is used for a build-up film, the film is softened under a lamination temperature condition (usually 70 ° C. to 140 ° C.) in a vacuum laminating method. It is important to show fluidity (resin flow) in which existing via holes or through holes can be filled with resin, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  As a specific method for producing the above-described buildup film, after preparing a curable resin composition that has been varnished with an organic solvent, the composition is applied to the surface of the support film (Y), Further, there is a method in which the organic solvent is dried by heating or hot air blowing to form the layer (X) of the curable resin composition.

  Examples of the organic solvent used herein include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like. Carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and the nonvolatile content is used in a proportion of 30% to 60% by mass. It is preferable.

  In addition, the thickness of the layer (X) of the resin composition to be formed usually needs to be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm. In addition, the layer (X) of the resin composition in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment. Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled after the curable resin composition layer constituting the build-up film is heat-cured, adhesion of dust and the like in the curing step can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

In addition, a multilayer printed circuit board can be manufactured from the buildup film obtained as mentioned above. For example, when the layer (X) of the resin composition is protected by a protective film, after peeling off these layers, one side or both sides of the circuit board so that the layer (X) of the resin composition is in direct contact with the circuit board For example, lamination is performed by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be heated (preheated) as necessary before lamination. The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C. and a pressure bonding pressure of 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ). It is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less.

7). Fiber Reinforced Composite Material As a method for obtaining a fiber reinforced composite material (a sheet-like intermediate material in which a resin is impregnated with a reinforced fiber) from the curable resin composition of the present invention, the components constituting the curable resin composition are uniformly distributed. There is a method in which a varnish is prepared by mixing, and then impregnated into a reinforced substrate made of reinforcing fibers, followed by a polymerization reaction.

  Specifically, the curing temperature at the time of performing the polymerization reaction is preferably in the temperature range of 50 to 250 ° C., in particular, after curing at 50 to 100 ° C. to obtain a tack-free cured product, The treatment is preferably performed at a temperature of 120 to 200 ° C.

  Here, the reinforced fiber may be any of a twisted yarn, an untwisted yarn, or a non-twisted yarn, but an untwisted yarn or a non-twisted yarn is preferable because both the formability and mechanical strength of the fiber-reinforced plastic member are compatible. Furthermore, the form of a reinforced fiber can use what the fiber direction arranged in one direction, and a textile fabric. The woven fabric can be freely selected from plain weaving, satin weaving, and the like according to the site and use. Specifically, since it is excellent in mechanical strength and durability, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like can be mentioned, and two or more of these can be used in combination. Among these, carbon fiber is preferable from the viewpoint that the strength of the molded product is particularly good. As the carbon fiber, various types such as polyacrylonitrile-based, pitch-based, and rayon-based can be used. Among these, a polyacrylonitrile-based one that can easily obtain a high-strength carbon fiber is preferable. Here, the amount of reinforcing fibers used when a reinforced varnish made of reinforcing fibers is impregnated into a fiber-reinforced composite material is such that the volume content of the reinforcing fibers in the fiber-reinforced composite material is 40% to 85%. It is preferable that the amount be in the range.

8). Fiber reinforced resin molded article As a method of obtaining a fiber reinforced molded article (molded article obtained by curing a sheet-like member in which resin is impregnated into reinforced fibers) from the curable resin composition of the present invention, a fiber aggregate is laid on a mold, Using hand lay-up method, spray-up method, male type or female type, in which multiple varnishes are laminated, the base material made of reinforced fiber is piled up while impregnating the varnish, and the pressure acts on the molded product A vacuum bag method in which a flexible mold that can be covered is covered and hermetically sealed is vacuum (reduced pressure) molding, a varnish containing reinforced fibers in advance is formed into a sheet, SMC press method, fiber A prepreg in which reinforcing fibers are impregnated with the varnish is manufactured by an RTM method or the like in which the varnish is injected into a laminated mold in which the varnish is spread, and this is used as a large autoclave. And the method of baking and hardening. The fiber reinforced resin molded product obtained above is a molded product having a reinforced fiber and a cured product of the curable resin composition. Specifically, the amount of the reinforced fiber in the fiber reinforced molded product is: It is preferably in the range of 40% by mass to 70% by mass, and particularly preferably in the range of 50% by mass to 70% by mass from the viewpoint of strength.

9. Conductive paste Examples of a method for obtaining a conductive paste from the curable resin composition of the present invention include a method of dispersing fine conductive particles in the curable resin composition. The conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of fine conductive particles used.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. GPC, ¹³ CNMR, and FD-MS spectrum were measured under the following conditions.

<GPC measurement conditions>
Measuring device: “HLC-8320 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refractometer)
Data processing: “GPC workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodispersed polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC workstation EcoSEC-WorkStation”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

<Measurement conditions for ¹³ C-NMR>
Apparatus: AL-400 manufactured by JEOL Ltd.
Measurement mode: decoupling with reverse gate,
Solvent: deuterated dimethyl sulfoxide,
Pulse angle: 45 ° pulse,
Sample concentration: 30 wt%
Accumulation count: 4000 times.

<Measurement conditions of FD-MS spectrum>
The FD-MS spectrum was measured using a double focusing mass spectrometer “AX505H (FD505H)” manufactured by JEOL Ltd.

Synthesis Example 1 Synthesis of Phenol Resin (a-1) In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 806 parts by mass of 2-allylphenol (6.0 mol) and 16 parts by mass of oxalic acid The mixture was stirred and heated from room temperature to 105 ° C. over 45 minutes. Then, 326 mass parts (4.5 mol) of 42 mass% formalin aqueous solution was dripped over 6 hours. After completion of dropping, the mixture was further stirred at 100 ° C. for 1 hour, and then heated to 180 ° C. in 3 hours. After completion of the reaction, water and unreacted substances remaining in the reaction system were removed under heating and reduced pressure to obtain 727 parts by mass of a phenol resin (a-1) so that the retention time at 170 ° C. or higher was 6 hours. The obtained phenol resin (a-1) had a hydroxyl group equivalent of 154 g / eq.

Synthesis Example 2 Synthesis of Epoxy Resin (A-1) Next, 154 g (hydroxyl equivalent) of the phenol resin (a-1) obtained in Synthesis Example 1 while performing nitrogen gas purging on a flask equipped with a thermometer, a condenser tube, and a stirrer 1.0 g / eq), 555 g (6.0 mol) of epichlorohydrin, and 53 g of n-butanol were charged and dissolved. After the temperature was raised to 50 ° C., 220 g (1.10 mol) of a 20% aqueous sodium hydroxide solution was added over 3 hours, and then further reacted at 50 ° C. for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. Next, 300 g of methyl isobutyl ketone and 50 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Further, 15 g of a 10% by mass aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 100 g of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 185 g of an epoxy resin (A-1). The epoxy equivalent of the obtained epoxy resin was 240 g / eq. The GPC chart of the obtained epoxy resin is shown in FIG. 1, the spectrum of FD-MS is shown in FIG. 2, and the ¹³ C-NMR spectrum is shown in FIG. From FIG. 1, the total area ratio in the GPC measurement of the compounds (B) and (C) in the epoxy resin was 0.36%.

Synthesis Example 3 Synthesis of Phenol Resin (a-2) The amount of 42 mass% formalin aqueous solution was changed to 347 parts by mass (4.8 mol), and the retention time at 170 ° C. or higher after the reaction was completed was 8 hours. The objective phenol resin (a-2) was obtained in the same manner as in Synthesis Example 1 except for the above. The obtained phenol resin (a-2) had a hydroxyl group equivalent of 156 g / eq.

Synthesis Example 4 Synthesis of Epoxy Resin (A-2) 180 g of Epoxy Resin (A-2) was obtained in the same manner as in Synthesis Example 2 except that the phenol resin (a-2) was changed to 155 g (hydroxyl equivalent 1.0 g / eq). Obtained. The epoxy equivalent of the obtained epoxy resin was 244 g / eq. A GPC chart of the obtained epoxy resin is shown in FIG. From FIG. 4, the total area ratio in GPC measurement of the compounds (B) and (C) in the epoxy resin was 0.50%.

Synthesis Example 5 Synthesis of Phenol Resin (a-3) The amount of 42% by mass formalin aqueous solution was changed to 412 parts by mass (5.7 mol) so that the retention time at 170 ° C. or higher after the reaction was 5 hours. The objective phenol resin (a-3) was obtained in the same manner as in Synthesis Example 1 except for the above. The obtained phenol resin (a-3) had a hydroxyl equivalent of 165 g / eq.

Synthesis Example 6 Synthesis of Epoxy Resin (A-3) 189 g of Epoxy Resin (A-3) was obtained in the same manner as in Synthesis Example 2 except that the phenol resin (a-3) was changed to 165 g (hydroxyl equivalent 1.0 g / eq). Obtained. The epoxy equivalent of the obtained epoxy resin was 249 g / eq. The GPC chart of the obtained epoxy resin is shown in FIG. From FIG. 5, the total area ratio in GPC measurement of the compounds (B) and (C) in the epoxy resin was 0.38%.

Comparative Synthesis Example 1
To a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 806 parts by mass of 2-allylphenol (6.0 mol), 16 parts by mass of oxalic acid, 52 parts by mass of a 42% by weight formalin aqueous solution (0 .72 mol) was added and reacted at 100 ° C. for 5 hours. Thereafter, the temperature was raised to 160 ° C. over 3 hours, and moisture and unreacted substances remaining in the reaction system were removed under heating and reduced pressure to obtain a phenol resin. The obtained phenol resin had a hydroxyl group equivalent of 141 g / eq. Next, 141 g (hydroxyl group equivalent: 1.0 g / eq) of the phenol resin obtained above, 555 g (6.0 mol) of epichlorohydrin, n-butanol, while purging a flask equipped with a thermometer, a condenser, and a stirrer with nitrogen gas purge. 53 g was charged and dissolved. After the temperature was raised to 50 ° C., 220 g (1.10 mol) of a 20% aqueous sodium hydroxide solution was added over 3 hours, and then further reacted at 50 ° C. for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. Next, 300 g of methyl isobutyl ketone and 50 g of n-butanol were added to the obtained crude epoxy resin and dissolved. Further, 15 g of a 10% by mass aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 100 g of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy resin (A′-1). The epoxy equivalent of the obtained epoxy resin was 225 g / eq. The total area ratio in GPC measurement of the compounds (B) and (C) in the epoxy resin (A′-1) was 1.1%.

Comparative Synthesis Example 2
A flask equipped with a thermometer, a condenser, and a stirrer was charged with 100 parts by mass of the phenol resin (a-3) obtained in Synthesis Example 5 while purging with nitrogen gas, and kept at 170 ° C. for 10 hours. A large amount was generated and could not be removed.

Examples 1 to 3, Comparative Example 1 <Production of Composition and Cured Product>
After blending the following compounds in the composition shown in Table 1, the intended curable resin composition was prepared by melt kneading for 5 minutes at a temperature of 90 ° C. using two rolls. In addition, the symbol in Table 1 means the following compound.
Epoxy resin A-1: Epoxy resin obtained in Synthesis Example 2 Epoxy resin A-2: Epoxy resin obtained in Synthesis Example 4 Epoxy resin A-3: Epoxy resin obtained in Synthesis Example 6 Epoxy Resin A′-1: Epoxy resin obtained in Comparative Synthesis Example 1 Curing agent TD-2131: Phenol novolac resin Hydroxyl equivalent: 104 g / eq (manufactured by DIC Corporation)
-TPP: Triphenylphosphine-Fused silica: Spherical silica "FB-560" manufactured by Electrochemical Co., Ltd.-Silane coupling agent: γ-glycidoxytriethoxyxysilane "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.-Carnauba Wax: “PEARL WAX No. 1-P” manufactured by Electrochemical Co., Ltd.

Next, what was obtained by pulverizing the curable resin composition obtained above was transferred to a pressure of 70 kg / cm ² , a temperature of 175 ° C., and a time of 180 seconds, φ50 mm × 3 (t) mm. And was further cured at 180 ° C. for 5 hours.

<Measurement of glass transition temperature and thermal modulus>
The molded product produced above was cut into a cured product having a thickness of 0.8 mm and having a width of 5 mm and a length of 54 mm. Using this test piece 1 with a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., Ltd., rectangular tension method: frequency 1 Hz, heating rate 3 ° C./min) The temperature (the tan δ change rate is the largest) was measured as the glass transition temperature, and the storage elastic modulus at 260 ° C. was measured as the thermal elastic modulus.

<Measurement of shrinkage during molding>
Using a transfer molding machine (manufactured by Kotaki Seiki Co., Ltd., KTS-15-1.5C), the curable resin composition was injection molded under conditions of a mold temperature of 150 ° C., a molding pressure of 9.8 MPa, and a curing time of 600 seconds. Thus, a test piece having a length of 110 mm, a width of 12.7 mm, and a thickness of 1.6 mm was produced. Thereafter, the test piece was post-cured at 175 ° C. for 5 hours, the inner diameter size of the mold cavity and the outer diameter size of the test piece at room temperature (25 ° C.) were measured, and the shrinkage rate was calculated by the following formula.
Shrinkage rate (%) = {(inner diameter dimension of mold) − (longitudinal dimension of cured product at 25 ° C.)} / (Inner diameter dimension of mold cavity at 175 ° C.) × 100 (%)
These results are shown in Table 1.

Claims (13)

A phenol novolac type epoxy resin (A) having an allyl group as a substituent on an aromatic ring, which has the following general formula (1)
Wherein (1), R ¹ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group having 1 to 4 carbon atoms from 1 to 4 carbon atoms, p is 1 to 3 independently Represents an integer. ]
Compound (B) represented, and the following general formula (2)
[In Formula (2), R ² each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; Represents an integer. ]
The epoxy resin characterized by containing the compound (C) represented by these by a total area ratio in GPC measurement 0.1 to 0.6%. The phenol novolac epoxy resin (A) is represented by the following general formula (3)
[In Formula (3), each R ³ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and each r independently represents 1 to 3 carbon atoms. An integer is represented, and n is an average of the number of repetitions and is 1 to 10. ]
The epoxy resin according to claim 1, which is represented by   The epoxy resin according to claim 1, wherein an epoxy equivalent is 220 g / eq to 280 g / eq.   A curable resin composition comprising the epoxy resin according to any one of claims 1 to 3 and a curing agent as essential components.   A cured product obtained by curing reaction of the curable resin composition according to claim 4.   The semiconductor sealing material containing the curable resin composition of Claim 4, and an inorganic filler.   A semiconductor device obtained by heat-curing the semiconductor sealing material according to claim 6.   A prepreg which is a semi-cured product of an impregnated substrate having the curable resin composition according to claim 4 and a reinforcing substrate.   A circuit board comprising a plate-shaped shaped product of the curable resin composition according to claim 4 and a copper foil.   A buildup film comprising a cured product of the curable resin composition according to claim 4 and a base film. A fiber-reinforced composite material containing the curable resin composition according to claim 4 and reinforcing fibers. A fiber-reinforced molded article obtained by curing the fiber-reinforced composite material according to claim 11.   A method for producing a phenol novolac-type epoxy resin in which a phenol novolak having an allyl group as a substituent on an aromatic ring is obtained using 2-allylphenol and formaldehyde, and then epoxidized by reaction with epihalohydrin, comprising 2-allyl A method for producing a phenol novolac type epoxy resin, wherein a molar ratio of formaldehyde to phenol is used in a range of 0.50 to 0.95 and is maintained in a range of 170 to 200 ° C for 5 hours or more and 10 hours or less.