JP2020100768A - Xanthene type resin, curable resin composition and its cured product - Google Patents

Abstract

To provide a phenol resin excellent in a balance between flowability in heat hardening and a mold shrinkage ratio, an epoxy resin, a curable composition and its cured product.SOLUTION: There are provided a xanthene type phenol resin represented by formula (1) and a xanthene type epoxy resin. In formula (1), R1, R2 and R3 are alkyl groups or aralkyl groups; l is 0, 1 or 2; m and n are 0 or 1; R4 and R5 each independently are H, and an alkyl group or aralkyl group having 4 to 8 carbon atoms; R6, R7, R8 and R9 are H, and an alkyl group or aryl group; p, q and r are 0 or 1; and s is an integer of 0 to 10.SELECTED DRAWING: Figure 1

Description

The present invention has good fluidity during heat processing, is excellent in low shrinkage characteristics during heat curing, and can be suitably used for semiconductor encapsulating materials and the like, xanthene type epoxy resin, xanthene type epoxy resin, and A curable resin composition containing a resin and a cured product thereof.

A curable resin composition using an epoxy resin and various curing agents is used for adhesives, molding materials, paints, photoresist materials, color developing materials, etc., and also has excellent heat resistance and moisture resistance of the resulting cured product. It is widely used in electrical and electronic fields such as semiconductor encapsulation materials and insulating materials for printed wiring boards because of its excellent properties.

Among these various applications, there is a strong demand for thinness and lightness in the electric and electronic fields, and a wafer level packaging technology is one of the mounting technologies that meet these requirements. The wafer level packaging technology is a packaging technology for manufacturing a semiconductor package by performing resin sealing, rewiring, and electrode formation in a wafer state and dicing into individual pieces. Since the encapsulation resin is used for encapsulation all at once, warpage occurs due to shrinkage during resin curing and a difference in shrinkage amount due to the linear expansion coefficient of the chip and the linear expansion coefficient of the encapsulation resin. Since this warpage significantly lowers the reliability of the package, the sealing resin is required to have a low viscosity and a low shrinkage for the purpose of suppressing the warpage.

As an epoxy resin that can be preferably used as a semiconductor sealing material, an epoxy resin having an allyl group as a substituent on an aromatic ring of a bisphenol skeleton is provided (for example, see Patent Document 1). Alternatively, it is also known that an epoxy resin containing a naphthylene ether skeleton, which may have a substituent on the aromatic ring, is preferably used as a semiconductor encapsulating material (see, for example, Patent Document 2).

In addition, phenol resin may also be used as a curing agent for epoxy resin, and as a phenol resin that can be suitably used as a curing agent for an epoxy resin in electronic materials, particularly in laminated board applications having excellent moisture resistance and solder resistance. For example, there is provided a resin which is a phenol novolac resin containing 25% by mass or more of a trifunctional compound and has a substituent on an aromatic ring of at least one phenol constituting the resin ( See, for example, Patent Document 3).

As described above, by using the epoxy resin or the phenol resin having a substituent on the aromatic ring as the resin component of the curable resin composition, the composition is more than the case of using a general bisphenol type epoxy resin or the phenol novolac resin. Although it is possible to obtain a certain effect on the fluidity of the product and the dimensional stability during curing, it is not possible to satisfy the molding shrinkage rate and high fluidity at the time of heat curing of the resin composition required at a high level in recent years, Further improvements are required.

JP, 2005-000952, A JP, 2016-89096, A JP-A-7-10967

Therefore, the problem to be solved by the present invention, the fluidity during heat curing of a composition containing a phenol resin or an epoxy resin, xanthene type phenol resin excellent in the balance of molding shrinkage, xanthene type epoxy resin, curability The object is to provide a composition and a cured product thereof.

In order to solve the above problems, the present inventors have made extensive studies, and have a substituent on an aromatic ring, and a phenol resin having a xanthene skeleton, or an epoxy resin obtained by glycidylating the same is a resin at the time of heat curing. They have found that they have excellent fluidity and molding shrinkage, and have completed the present invention.

That is, the present invention provides the following general formula (1)

[In formula, R< ¹ >, R< ² >, R< ³ > is respectively independently a C4-C8 alkyl group or an aralkyl group, l is either 0, 1, 2 and m is 0 or 1. And n is 0 or 1 (excluding the case where 1=m=n=0), and R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms or an aralkyl group. And
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, and one of R ⁶ and R ⁷ is an alkyl group or an aryl group, and R ⁸ and R ^{One of 9} is an alkyl group or an aryl group,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
s represents the number of repetitions and is an integer of 0-10. ]
And a curable resin composition containing the same, and a cured product thereof.

Furthermore, the present invention provides the following general formula (2)

[In formula, R< ¹ >, R< ² >, R< ³ > is respectively independently a C4-C8 alkyl group or an aralkyl group, l is either 0, 1, 2 and m is 0 or 1. And n is 0 or 1 (excluding the case where 1=m=n=0), and R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms or an aralkyl group. And
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, and one of R ⁶ and R ⁷ is an alkyl group or an aryl group, and R ⁸ and R ^{One of 9} is an alkyl group or an aryl group,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
G is a glycidyl group, s shows a repeating number, and is an integer of 0-10. ]
The present invention provides a xanthene-type epoxy resin, a curable resin composition containing the same, and a cured product thereof.

According to the present invention, the flowability of the resin composition during heat curing and the molding shrinkage ratio are excellent in the balance of the elastic modulus, and the xanthene-type phenol resin and the xanthene-type epoxy resin, which can be preferably used for the semiconductor sealing material, A curable resin composition, a cured product having the above-mentioned properties, a semiconductor encapsulating material, and the like can be provided.

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

<Phenolic resin>
Hereinafter, the present invention will be described in detail.
The phenol resin of the present invention has the following general formula (1).

[In formula, R< ¹ >, R< ² >, R< ³ > is respectively independently a C4-C8 alkyl group or an aralkyl group, l is either 0, 1, 2 and m is 0 or 1. And n is 0 or 1 (excluding the case where 1=m=n=0), and R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms or an aralkyl group. And
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, and one of R ⁶ and R ⁷ is an alkyl group or an aryl group, and R ⁸ and R ^{One of 9} is an alkyl group or an aryl group,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
s represents the number of repetitions and is an integer of 0-10. ]
It is characterized by being represented by.

The phenol resin of the present invention has at least R ¹ , R ² , and R ^{3 in} the general formula (1), that is, an alkyl group or an aralkyl group having 4 to 8 carbon atoms in one molecule as a substituent on the aromatic ring. I have one. By having such a relatively bulky substituent, it is considered that the crosslinking density during the curing reaction is appropriately adjusted, and the molding shrinkage rate during the heat curing becomes low. The alkyl group is preferably an alkyl group having a branched structure such as t-butyl group, t-amyl group, t-octyl group, and particularly preferably t-butyl group or t-octyl group. The aralkyl group is preferably an aralkyl group having 7 to 15 carbon atoms, and particularly preferably a benzyl group.

Further, the phenol resin of the present invention is a mixture of a plurality of compounds having different s in the general formula (1) and a novolac type phenol resin which does not form a xanthene skeleton, and in particular, the content ratio of s=0 body Is preferably in the range of 50 to 75% in terms of area ratio in GPC measurement, from the viewpoint of improving the fluidity of the curable composition.

The GPC measurement in the present invention is performed under the following conditions, and the area% can be calculated from the obtained chart.

<GPC measurement conditions>
Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation,
Column: Tosoh Co., Ltd. guard column "HXL-L"
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ 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 according to the measurement manual of the “GPC workstation EcoSEC-WorkStation”.
(Polystyrene used)
Tosoh Corporation "A-500"
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
"F-10" manufactured by Tosoh Corporation
Tosoh Corporation "F-20"
"F-40" manufactured by Tosoh Corporation
Tosoh Corporation "F-80"
Tosoh Corporation "F-128"
Sample: 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl)

Further, in the general formula (1), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, and particularly a hydrogen atom or a C 1 to C 4 group. An alkyl group or an aryl group having 6 to 14 carbon atoms is preferable from the viewpoint of easy compatibility between the fluidity of the curable resin composition and the suppression of heat shrinkage during curing. From the viewpoint of easy availability of raw materials when producing this resin, R ⁶ and R ⁸ are preferably benzene rings.

Furthermore, from the viewpoint of good fluidity of the curable resin composition and good curability during heat curing, the hydroxyl equivalent of the phenol resin of the present invention is preferably in the range of 150 to 300 g/eq.

<Epoxy resin>
The epoxy resin of the present invention has the following general formula (2).

[In formula, R< ¹ >, R< ² >, R< ³ > is respectively independently a C4-C8 alkyl group or an aralkyl group, l is either 0, 1, 2 and m is 0 or 1. And n is 0 or 1 (excluding the case where 1=m=n=0), and R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms or an aralkyl group. And
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, and one of R ⁶ and R ⁷ is an alkyl group or an aryl group, and R ⁸ and R ^{One of 9} is an alkyl group or an aryl group,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
G is a glycidyl group, s shows a repeating number, and is an integer of 0-10. ]
It is characterized by being represented by.

The epoxy resin of the present invention has at least R ¹ , R ² , and R ^{3 in} the general formula (2), that is, an alkyl group or an aralkyl group having 4 to 8 carbon atoms in one molecule as a substituent on the aromatic ring. I have one. By having such a relatively bulky substituent, it is considered that the crosslinking density during the curing reaction is appropriately adjusted, and the molding shrinkage rate during the heat curing becomes low. The alkyl group is preferably an alkyl group having a branched structure such as t-butyl group, t-amyl group, t-octyl group, and particularly preferably t-butyl group or t-octyl group. The aralkyl group is preferably an aralkyl group having 7 to 15 carbon atoms, and particularly preferably a benzyl group.

Further, the epoxy resin of the present invention is a mixture of a plurality of compounds having different s in the general formula (2) and a novolac type epoxy resin which does not form a xanthene skeleton, and in particular, the content ratio of s=0 body Is preferably in the range of 30 to 50% in terms of area ratio in GPC measurement, from the viewpoint of improving the fluidity of the curable composition.

The GPC measurement in the present invention is performed under the following conditions, and the area% can be calculated from the obtained chart.

<GPC measurement conditions>
Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation,
Column: Tosoh Co., Ltd. guard column "HXL-L"
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ 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 according to the measurement manual of the “GPC workstation EcoSEC-WorkStation”.
(Polystyrene used)
Tosoh Corporation "A-500"
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
"F-10" manufactured by Tosoh Corporation
Tosoh Corporation "F-20"
"F-40" manufactured by Tosoh Corporation
Tosoh Corporation "F-80"
Tosoh Corporation "F-128"
Sample: 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl)

Further, in the general formula (2), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, and particularly a hydrogen atom or a C 1 to C 4 group. An alkyl group or an aryl group having 6 to 14 carbon atoms is preferable from the viewpoint of easy compatibility between the fluidity of the curable resin composition and the suppression of heat shrinkage during curing. From the viewpoint of easy availability of raw materials when producing this resin, R ⁶ and R ⁸ are preferably benzene rings.

Further, from the viewpoint of good fluidity of the curable resin composition and good curability during heat curing, the epoxy equivalent of the epoxy resin of the present invention is preferably in the range of 300 to 500 g/eq, and The melt viscosity at 150° C. is preferably in the range of 0.1 to 40 dPa·s.

The phenol resin or epoxy resin of the present invention is represented by the following structural formula, for example.

(In the formula, OX represents OH or glycidyl ether.)

<Method for producing phenol resin>
The phenol resin of the present invention uses dihydroxybenzene (I) having an alkyl group having 4 to 8 carbon atoms on an aromatic ring and aldehydes (II) having an alkyl group or an aryl group to undergo intramolecular self-oxidation. A method using a ring closure reaction is preferable.

Examples of the dihydroxybenzene (I) include monoalkyldihydroxybenzenes such as n-butylhydroquinone, n-butylresorcinol, n-butylcatechol, sec-butylhydroquinone, sec-butylresorcinol, sec-butylcatechol, t-butyl. Hydroquinone, t-butylresorcinol, t-butylcatechol, n-hexylhydroquinone, n-hexylresorcinol, 4-octylcatechol and the like can be mentioned. Examples of the dialkyldihydroxybenzene include 3,5-di-t-butylcatechol, 2,5-di-t-butylhydroquinone and the like may be mentioned, and one composed of only one kind may be used, or two or more kinds may be mixed and used. Among these, from the viewpoint of the heat shrinkage ratio of the curable resin composition using the obtained phenolic resin, those having an alkyl group having a bulkier structure are preferable, and availability of raw materials, and the obtained resin It is most preferable to use t-butylcatechol and 3,5-di-t-butylcatechol from the viewpoint of the properties of the composition when cured.

Further, a monohydroxy aromatic compound may be used in combination. Among them, the monocyclic monohydroxy aromatic compounds include phenol, o-cresol, p-cresol, m-cresol, butylphenol, xylenol, nonylphenol, alkylphenols such as octylphenol, phenylphenol, bisphenol A, bisphenol F, bisphenol S. , Amylphenol, pyrogallol, allylphenol, bisphenolfluorenes, and the like, and the polycyclic monohydroxy aromatic compounds include 1-naphthol, 2naphthol, and other phenol compounds used in the synthesis of ordinary phenol resins. You may use together 2 or more types.

Examples of the aldehydes (II) having an alkyl group or an aryl group include formaldehyde, paraaldehyde, benzaldehyde, anisaldehyde, naphthaldehyde, anthraldehyde and the like, and benzaldehyde is used from the viewpoint of easy xanthene formation. preferable. When benzaldehyde is used as a raw material, aralkylation occurs, so that the phenol resin of the present invention can be obtained even when unsubstituted dihydroxybenzene is used as a raw material.

It is preferable to react these phenols and aldehydes in the presence of a basic catalyst with 0.3 to 0.9 mol of aldehydes per mol of phenols. More preferably, the reaction is carried out at 0.4 to 0.8 mol. When the amount of aldehydes is less than 0.3 mol, novolac resin is produced, but the content of xanthene derivative is low, and the amount of unreacted phenols is increased, and the amount of resin produced tends to be small. When the amount of aldehydes exceeds 0.9 mol, the amount of resin produced is advantageous, but gelation tends to occur in the reaction system, and control of the reaction tends to be extremely difficult.

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 in the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. At the time of use, these basic catalysts may be used in the form of an aqueous solution of about 10% by mass to 55% by mass, or may be used in the form of a solid.

The reaction may be carried out in an organic solvent, and examples of usable organic solvents 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 from the viewpoint of work efficiency, for example, is in the range of 10 to 300 parts by mass per 100 parts by mass of the raw material component o-allylphenol. Is preferred.

After the completion of the reaction, it is preferable to carry out neutralization or water washing until the pH value of the reaction mixture reaches 6-8. The neutralization treatment or the water washing treatment may be performed according to a conventional method, and for example, an acidic substance such as sodium monophosphate can be used as a neutralizing agent. After the neutralization or washing with water, the objective phenol resin can be suitably obtained by distilling off the organic solvent under reduced pressure heating.

<Method for producing epoxy resin>
The epoxy resin of the present invention can be obtained by a method of epoxidizing the xanthene-type phenol resin obtained by the above method.

Moreover, you may use together other diphenols in the range which does not impair the effect of this invention.

The method for producing an epoxy resin of the present invention is a method for producing an epoxy resin in which the xanthene-type phenol resin of the present invention is reacted with epihalohydrin to be epoxidized as described above, and the epoxidation method may be a known technique. You can

For example, 1 to 10 mol of epihalohydrin is added to 1 mol of hydroxyl group contained in the xanthene-type phenol resin, and 0.9 to 2.0 mol of basic catalyst is added to 1 mol of hydroxyl group of the raw material all together. Alternatively, there may be mentioned a method of reacting at a temperature of 20 to 120° C. for 0.5 to 10 hours while gradually adding. This basic catalyst may be a solid or an aqueous solution thereof, and when an aqueous solution is used, the basic catalyst is continuously added, and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. Alternatively, a method may be employed in which the water is removed, the water is removed by further liquid separation, and the epihalohydrins are continuously returned to the reaction mixture.

In addition, when performing industrial production, all of the epihalohydrins used for charging are new in the first batch of epoxy resin production, but from the next batch onwards, epihalohydrins recovered from the crude reaction product are consumed in the reaction. It is preferable to use together with a new epihalohydrin corresponding to the amount that disappears. At this time, it may contain impurities such as glycidol which are induced by the reaction of epichlorohydrin with water, an organic solvent or the like. At this time, the epihalohydrin used is not particularly limited, but examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin and the like. Among these, epichlorohydrin is preferable because it is industrially easily available.

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 in the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. At the time of use, these basic catalysts may be used in the form of an aqueous solution of about 10% by mass to 55% by mass, or may be used in the form of a solid. Further, by using the organic solvent together, the reaction rate in the synthesis of the epoxy resin can be increased. Such an organic solvent is not particularly limited, for example, acetone, ketones such as methyl ethyl ketone, methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, alcohols such as tertiary butanol, methyl, methyl. Examples thereof 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 two or more kinds may be appropriately used in combination in order to adjust the polarity.

Subsequently, after washing the reaction product of the above-mentioned epoxidation reaction with water, the unreacted epihalohydrin and the organic solvent used in combination are distilled off by heating under reduced pressure. To obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. Further reaction can be performed by adding an aqueous solution of the substance. 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 produced salt is removed by filtration, washing with water and the like, and the solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain a highly pure epoxy resin.

In particular, in order to obtain the epoxy resin of the present invention, when the xanthene-type phenol resin and epichlorohydrin are reacted with each other, the water concentration in the solvent is set to 5 to 25%, whereby a predetermined epoxy resin can be efficiently obtained. it can.

<Curable resin composition containing xanthene-type phenol resin>
The phenol resin of the present invention can be made into a curable resin composition by using in combination with another compound having a functional group that reacts with a hydroxyl group, that is, a curing agent (X). The curable resin composition can be suitably used for various electric/electronic member applications such as adhesives, paints, photoresists, printed wiring boards, and semiconductor encapsulation materials.

Examples of the curing agent (X) include a melamine compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, a guanamine compound, a glycoluril compound, a urea compound, a resole resin, and an epoxy. Examples thereof include resins, isocyanate compounds, azide compounds, compounds having a double bond such as an alkenyl ether group, acid anhydrides, and oxazoline compounds.

The melamine compound is, for example, hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, or methylol of hexamethylolmelamine. Examples thereof include compounds in which 1 to 6 groups are acyloxymethylated.

The guanamine compound, for example, tetramethylol guanamine, tetramethoxymethyl guanamine, tetramethoxymethyl benzoguanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxy guanamine, tetra Examples thereof include compounds in which 1 to 4 methylol groups of methylolguanamine are acyloxymethylated.

Examples of the glycoluril compound include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis( Hydroxymethyl)glycoluril and the like can be mentioned.

Examples of the urea compound include 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea and 1,1,3,3-tetrakis(methoxymethyl)urea. To be

The resole resin is, for example, an alkylphenol such as phenol, cresol or xylenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A or bisphenol F, a phenolic hydroxyl group-containing compound such as naphthol or dihydroxynaphthalene, and an aldehyde compound are alkaline. Examples thereof include polymers obtained by reacting under catalytic conditions.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, diglycidyloxynaphthalene, naphthol aralkyl type epoxy resin, naphthol- Phenol co-condensed novolak type epoxy resin, naphthol-cresol co-contracted novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl modified novolac type epoxy resin, 1,1-bis(2,7-diglycidyl) (Oxy-1-naphthyl)alkane, naphthylene ether type epoxy resin, triphenylmethane type epoxy resin, phosphorus atom-containing epoxy resin, polyglycidyl ether of a cocondensation product of a phenolic hydroxyl group-containing compound and an alkoxy group-containing aromatic compound, etc. Alternatively, the xanthene-type epoxy resin of the present invention may be used. Among these epoxy resins, tetramethylbiphenol-type epoxy resin, biphenylaralkyl-type epoxy resin, polyhydroxynaphthalene-type epoxy resin, and novolac-type epoxy resin are preferably used in terms of obtaining a cured product having excellent flame retardancy. Dicyclopentadiene-phenol addition reaction type epoxy resin is preferable in that a cured product having excellent dielectric properties can be obtained.

Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidene bisazide, and 4,4'-oxybisazide.

Examples of the compound having a double bond such as the alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether and tetramethylene glycol divinyl ether. , Neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether Etc.

Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and 4,4. Aromatic acid anhydrides such as'-(isopropylidene)diphthalic anhydride and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride Alicyclic carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.

Among these, an epoxy resin is particularly preferable because it provides a curable composition having excellent curability and heat resistance in the cured product.

Furthermore, when using the said epoxy resin, you may mix|blend the hardening|curing agent for epoxy resins.

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

Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative, and examples of the amide compound include dicyandiamide. , A polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, and the like. Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride and methylhexahydro. Examples thereof include phthalic anhydride. As the phenolic compound, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resin), naphthol aralkyl resin, triphenylol methane resin, Tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-convoluted novolac resin, biphenyl modified phenol resin (polyphenolic hydroxyl group-containing compound in which phenol nucleus is linked by bismethylene group), biphenyl Modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified phenol resin (polyphenolic hydroxyl group-containing compound in which phenol nucleus is linked by melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring Examples thereof include polyvalent phenolic hydroxyl group-containing compounds such as modified novolac resins (polyphenolic hydroxyl group-containing compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

<Curable resin composition containing xanthene type epoxy resin>
The xanthene-type epoxy resin of the present invention can be made into a curable resin composition by using together various curing agents (Y) having a group having reactivity with an epoxy group. The curable resin composition can be suitably used for various electric/electronic member applications such as adhesives, paints, photoresists, printed wiring boards, and semiconductor encapsulation materials.

Examples of the curing agent (Y) that can be used here include various known curing agents for epoxy resins such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds.

Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative, and examples of the amide compound include dicyandiamide. , A polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, and the like. Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride and methylhexahydro. Examples thereof include phthalic anhydride. As the phenolic compound, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resin), naphthol aralkyl resin, triphenylol methane resin, Tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-convoluted novolac resin, biphenyl modified phenol resin (polyphenolic hydroxyl group-containing compound in which phenol nucleus is linked by bismethylene group), biphenyl Modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified phenol resin (polyphenolic hydroxyl group-containing compound in which phenol nucleus is linked by melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring Examples thereof include polyvalent phenolic hydroxyl group-containing compounds such as modified novolac resins (polyphenolic hydroxyl group-containing compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde). Further, the xanthene-type phenol resin of the present invention may be used.

Further, the curable resin composition of the present invention can be used in combination with other epoxy resins other than the above-specified epoxy resin within a range that does not impair the effects of the present invention.

Examples of the other epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type. Epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol Examples include condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, biphenyl modified novolac type epoxy resin. Among these epoxy resins, tetramethylbiphenol-type epoxy resin, biphenylaralkyl-type epoxy resin, polyhydroxynaphthalene-type epoxy resin, and novolac-type epoxy resin are preferably used in terms of obtaining a cured product having excellent flame retardancy. Dicyclopentadiene-phenol addition reaction type epoxy resin is preferable in that a cured product having excellent dielectric properties can be obtained. Further, when other epoxy resin is used in combination, the effect of the present invention is that the epoxy resin of the present invention is contained in an amount of 30 to 90 parts by mass with respect to a total of 100 parts by mass of the epoxy resin of the present invention and the other epoxy resin. Is preferable from the viewpoint of easily expressing.

In the curable resin composition of the present invention, the blending amount of the epoxy resin and the curing agent (Y) is such that the epoxy group in the other epoxy resin used in combination with the epoxy resin may be used in view of excellent curability. It is preferable that the total of the active groups in the curing agent (Y) is 0.8 to 1.2 equivalents based on 1 equivalent in total.

<Other ingredients>
In the present invention, other thermosetting resins may be used in combination in both the curable resin composition containing the phenol resin and the curable resin composition containing the epoxy resin.

Examples of other thermosetting resins include cyanate ester resins, resins having a benzoxazine structure, maleimide compounds, active ester resins, vinylbenzyl compounds, acrylic compounds, and copolymers of styrene and maleic anhydride. .. When the other thermosetting resin described above is used in combination, the amount thereof is not particularly limited as long as it does not inhibit the effect of the present invention, but in the range of 1 to 50 parts by mass in 100 parts by mass of the curable resin composition. It is preferable to have.

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, 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, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolac Type cyanate ester resin, naphthol-cresol co-condensed novolac type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resin, biphenyl modified novolac type cyanate ester resin, anthracene type cyanate ester resin and the like. These may be used alone or in combination of two or more.

Among these cyanate ester resins, a bisphenol A type cyanate ester resin, a bisphenol F type cyanate ester resin, a bisphenol E type cyanate ester resin, a polyhydroxynaphthalene type cyanate ester resin is particularly preferable in that a cured product having excellent heat resistance can be obtained. , A naphthylene ether type cyanate ester resin and a novolac type cyanate ester resin are preferably used, and a 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, but 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 And the reaction product of aniline, the reaction product of phenolphthalein, formalin and aniline, the 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 repeating units of 0 to 10. .)

(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 repeating units of 0 to 10. .) These may be used alone or in combination of two or more kinds.

The active ester resin is not particularly limited, but generally, an ester group having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. in one 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. Particularly 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 preferable, 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 More preferable. 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 halides 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, and 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.

As the active ester resin, specifically, an active ester resin containing a dicyclopentadiene-phenol addition structure, an active ester resin containing a naphthalene structure, an active ester resin which is an acetylation product of phenol novolac, and a benzoylation product of phenol novolac. Ester resins and the like are preferable, and among them, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferable because they are excellent in improving the peel strength. Specific examples of the active ester resin containing a dicyclopentadiene-phenol addition structure include compounds represented by the following general formula (iv).

However, in the formula (iv), R is a phenyl group or a naphthyl group, u represents 0 or 1, and n is an average of repeating units of 0.05 to 2.5. From the viewpoint of decreasing 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. ..

Further, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, modified novolak resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (Zyloc resin ), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl modified phenol resin, biphenyl modified naphthol resin, aminotriazine modified phenol resin, and various vinyl polymers may be used in combination.

More specifically, the various novolac resins include, more specifically, a phenolic hydroxyl group-containing compound such as phenol, phenylphenol, resorcinol, biphenyl, bisphenol such as bisphenol A and bisphenol F, naphthol, dihydroxynaphthalene, and an aldehyde compound as an acid catalyst. Examples thereof include polymers obtained by reacting under conditions.

The various vinyl polymers are polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly( Examples thereof include homopolymers of vinyl compounds such as (meth)acrylate and copolymers thereof.

The blending ratio in the case of using these other resins can be arbitrarily set according to the application, but the flowability as the composition of the present invention, and the balance effect of the molding shrinkage ratio at the time of heat curing become more remarkable. From the expression, it is preferable that the amount of the other resin is 0.5 to 100 parts by mass relative to 100 parts by mass of the phenol resin or epoxy resin of the present invention.

A curing accelerator may be used in combination with the curable resin composition of the present invention. As curing accelerators, tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride, boron trifluoride amine complexes such as boron trifluoride monoethylamine complex; thiodipropion Organic acid compounds such as acids; benzoxazine compounds such as thiodiphenolbenzoxazine and sulfonylbenzoxazine; and sulfonyl compounds. These may be used alone or in combination of two or more. The addition amount of these catalysts is preferably in the range of 0.001 to 15 parts by mass in 100 parts by mass of the curable resin composition.

When the curable resin composition of the present invention is used in applications where high flame retardancy is required, a non-halogen flame retardant containing substantially no halogen atom may be added.

Examples of the non-halogen flame retardant include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc., and there is no limitation in using them. The flame retardants may be used alone, or a plurality of flame retardants of the same system may be used, and flame retardants of different systems may be used in combination.

The phosphorus-based flame retardant may be either inorganic or organic. Examples of the inorganic compound include red phosphorus, ammonium monophosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide. ..

The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like, and examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide and 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 thermosetting resins such as phenolic resin, (iii) Thermosetting of phenolic resin or the like on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide or titanium hydroxide A method of double coating treatment with a resin can be used.

Examples of the organophosphorus compound include general-purpose organophosphorus compounds such as phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds, as well as 9,10-dihydro. -9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydrooxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7- Examples thereof include cyclic organophosphorus 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 the phosphorus-based flame retardant compounded is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the resin composition, and the desired degree of flame retardancy. And 100 parts by mass of the resin composition in which all the other fillers and additives are mixed, when red phosphorus is used as the non-halogen flame retardant, it is mixed in the range of 0.1 parts by mass to 2.0 parts by mass. In the case of using an organic phosphorus compound, it is also preferable to mix in the range of 0.1 parts by mass to 10.0 parts by mass, and to mix in the range of 0.5 parts by mass to 6.0 parts by mass. More preferably.

When the phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon and the like may be used in combination with the phosphorus-based flame retardant. Good.

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

The triazine compound is, for example, melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (1) guanyl melamine sulfate, melem sulfate, melam sulfate. Aminotriazine sulfate compounds such as, (2) Phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, and melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine, and formaldehyde, and (3) The above Examples thereof include a mixture of the co-condensate of (2) and a phenol resin such as a phenol-formaldehyde condensate, and (4) those obtained by further modifying (2) and (3) with tung oil, isomerized linseed oil, and the like.

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

The blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. And, in 100 parts by mass of the resin composition in which all the other fillers and additives are mixed, it is preferable to mix in the range of 0.05 to 10 parts by mass, and to mix in the range of 0.1 to 5 parts by mass. More preferably.

When using the nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound or the like may be used together.

The silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin. The blending amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, the other components of the resin composition, and the desired degree of flame retardancy. In addition, it is preferable to add it in a range of 0.05 to 20 parts by mass in 100 parts by mass of the resin composition containing all the other fillers and additives. When using the silicone-based flame retardant, a molybdenum compound, alumina or the like may be used together.

Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, low melting point glass, and the like.

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

The metal oxide is, for example, 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, tungsten oxide and the like.

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

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

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

Examples of the low melting point glass include Sipley (Bokusui Brown Co., Ltd.), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ -B ₂ O ₃ -PbO-MgO-based, _{P-Sn-O-F-based, PbO-V 2 O 5 -TeO} 2 _system, Al ₂ O 3 -H ₂ O system glass-like compounds such as lead borosilicate system Can be mentioned.

The blending amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, the other components of the resin composition, and the desired degree of flame retardancy, for example, a non-halogen flame retardant. And, in 100 parts by mass of the resin composition in which all the other fillers and additives are mixed, it is preferable to mix in a range of 0.05 parts by mass to 20 parts by mass, and a range of 0.5 parts by mass to 15 parts by mass. Is more preferable.

The organometallic salt flame retardant is, for example, ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organocobalt salt compound, organosulfonic acid metal salt, ionic bond or coordination of a metal atom with an aromatic compound or a heterocyclic compound. Examples include compounds having a position bond.

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

The curable resin composition of the present invention may contain an inorganic filler if necessary. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Fused silica is preferably used when the amount of the inorganic filler compounded is particularly large. The fused silica may be used in either a crushed form or a spherical form, but 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 the spherical form. In order to further increase the compounding 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 considering flame retardancy, and particularly preferably 20% by mass or more based on the total mass of the curable resin composition. Further, when it is used for an application such as a conductive paste, a conductive filler such as silver powder or copper powder can be used.

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

<Use of curable resin composition>
The curable resin composition of the present invention should be applied to semiconductor encapsulating materials, semiconductor devices, prepregs, printed circuit boards, build-up boards, build-up films, fiber-reinforced composite materials, fiber-reinforced resin molded products, conductive pastes, etc. You can

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 and a compounding agent such as an inorganic filler are optionally used in an extruder and a kneader. , A roll, etc. may be used to perform sufficient melt mixing until uniform. At that time, fused silica is usually used as the inorganic filler, but when it is used as a high thermal conductive semiconductor encapsulating material for power transistors and power ICs, crystalline silica, alumina, nitride having higher thermal conductivity than fused silica is used. It is preferable to use highly filled silicon or the like, or use fused silica, crystalline silica, alumina, silicon nitride, or the like. The filling rate is preferably 30 parts by mass to 95 parts by mass of the inorganic filler per 100 parts by mass of the curable resin composition, and among them, flame retardancy, moisture resistance and solder crack resistance are improved, and a wire is used. In order to reduce the expansion coefficient, 70 parts by mass or more is more preferable, and 80 parts by mass or more is further preferable.

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 by 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 of obtaining a prepreg from the curable resin composition of the present invention, a curable resin composition containing an organic solvent and varnished is used as a reinforcing base material (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth). , Glass mat, glass roving cloth, etc.) and then heating at a heating temperature, preferably 50 to 170° C., depending on the solvent species used. The mass ratio of the resin composition and the reinforcing base material used at this time is not particularly limited, but it is usually preferable to prepare the resin content in the prepreg to be 20% by mass to 60% by mass.

Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. Although it may be appropriately selected depending on the application, 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 less such as methyl ethyl ketone, acetone, dimethylformamide, It is preferable that the nonvolatile content is 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 prepregs are laminated by a conventional method, copper foils are appropriately laminated, and 170 to 300° C. under a pressure of 1 to 10 MPa. A method of heating and pressure bonding for 10 minutes to 3 hours can be 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 involving steps 1 to 3 can be mentioned. In step 1, first, the curable resin composition in which rubber, filler, and the like are appropriately mixed is applied to a circuit board on which a circuit is formed by a spray coating method, a curtain coating method, or the like, and then cured. In step 2, if necessary, a circuit board coated with the curable resin composition is perforated such as predetermined through holes, treated with a roughening agent, and the surface thereof is washed 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, and the resin insulating layer and the conductor layer having a predetermined circuit pattern are alternately built up to form a buildup substrate. In addition, in the above process, it is preferable to drill the through hole after forming the outermost resin insulating layer. In addition, the build-up substrate of the present invention is obtained by heating and crimping a resin-coated copper foil obtained by semi-curing the resin composition on a copper foil on a circuit-formed wiring substrate at 170 to 300°C. It is also possible to fabricate a build-up substrate by omitting the steps of forming a metallized surface and plating.

6. Build-up film As a method for obtaining a build-up film from the curable resin composition of the present invention, for example, after coating the curable resin composition on a support film, it is dried and a resin composition layer on the support film. And a method of forming. When the curable resin composition of the present invention is used for a build-up film, the film is softened under a temperature condition of laminating in a vacuum laminating method (usually 70°C to 140°C), and is laminated on a circuit board at the same time as laminating the circuit board. It is important to show fluidity (resin flow) capable of filling the resin in the existing via hole or through hole, and it is preferable to mix the above-mentioned components so as to express such characteristics.

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

As a specific method for producing the build-up film described above, after preparing a varnished resin composition by blending an organic solvent, the composition is applied to the surface of a supporting film, and further heated or hot air. Examples thereof include a method of forming a layer of the resin composition by drying the organic solvent by spraying or the like.

Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetic acid esters such as carbitol acetate, cellosolve and butyl carbitol. Carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and the nonvolatile content is 30 to 60% by mass. Preferably.

The thickness of the formed resin composition layer is usually required to be equal to or larger 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. The layer 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 adhering to the surface of the resin composition layer and to prevent scratches.

The support film and the protective film described above include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further separated. Examples include pattern paper and metal foil such as copper foil and aluminum foil. The support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably 25 to 50 μm. Further, the thickness of the protective film is preferably 1 to 40 μm.

The support film is peeled off after being laminated on a circuit board or after forming an insulating layer by heating and curing. If the support film is peeled off after the resin composition layer constituting the build-up film is heat-cured, adhesion of dust or 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.

A multilayer printed circuit board can be manufactured from the build-up film obtained as described above. For example, when the layer of the resin composition is protected by a protective film, after peeling them off, one or both sides of the circuit board are directly contacted with the layer of the resin composition, for example, a vacuum laminating method. Laminate by. The laminating method may be a batch method or a continuous method using rolls. If necessary, the build-up film and the circuit board may be heated (preheated) before laminating. The lamination conditions are preferably a pressure bonding temperature (lamination 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 ). Is preferable, and 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-shaped intermediate material in which a reinforced fiber is impregnated with a resin) from the resin composition of the present invention, each component constituting the resin composition is uniformly mixed and varnished. Is prepared and then impregnated into a reinforcing base material composed of reinforcing fibers, and then a polymerization reaction is carried out to produce the compound.

Specifically, the curing temperature at the time of carrying out such a polymerization reaction is preferably in the temperature range of 50 to 250° C., and particularly, after curing at 50 to 100° C. to obtain a tack-free cured product, It is preferable to perform the treatment under the temperature condition of 120 to 200°C.

Here, the reinforcing fibers may be twisted yarns, untwisted yarns, untwisted yarns, or the like, but untwisted yarns or untwisted yarns are preferable because they have both the moldability and mechanical strength of the fiber-reinforced plastic member. Further, as the form of the reinforcing fiber, a fiber in which the fiber directions are aligned in one direction or a woven fabric can be used. The woven fabric can be freely selected from a plain weave, a satin weave and the like according to the site to be used and the application. Specifically, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like are listed because they are excellent in mechanical strength and durability, and two or more of these can be used in combination. Among these, carbon fibers are preferable from the viewpoint that the strength of the molded product is good, and as such carbon fibers, various types such as polyacrylonitrile-based, pitch-based, and rayon-based can be used. Of these, polyacrylonitrile-based ones, which can easily obtain high-strength carbon fibers, are preferable. Here, the amount of reinforcing fibers used when a reinforced varnish made of reinforcing fibers is impregnated with a varnish to form 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%. The amount is preferably in the range of.

8. Fiber-Reinforced Resin Molded Product As a method for obtaining a fiber-reinforced molded product (molded product obtained by curing a sheet-shaped member impregnated with resin into a reinforcing fiber) from the resin composition of the present invention, a fiber aggregate is spread on a mold and the varnish is used. Using the hand lay-up method, spray-up method, or male/female type in which multiple layers are laminated, stacking them while impregnating the base material made of reinforcing fibers with varnish, and applying pressure to the molded product. A vacuum bag method in which a flexible mold that can be covered and airtightly sealed is vacuum (decompressed) molded, a sheet-shaped varnish containing reinforcing fiber is compressed and molded in a mold, and the fibers are spread. Examples include a method of producing a prepreg in which reinforcing fibers are impregnated with the varnish by the RTM method of injecting the varnish into a mating mold, and baking the prepreg in a large autoclave. The fiber-reinforced resin molded product obtained above is a molded product having a reinforcing fiber and a cured product of the resin composition, and specifically, the amount of the reinforcing fiber in the fiber-reinforced molded product is 40 mass. % To 70% by mass, and particularly 50% to 70% by mass from the viewpoint of strength.

9. Conductive Paste As a method of obtaining a conductive paste from the resin composition of the present invention, for example, a method of dispersing fine conductive particles in the curable resin composition can be mentioned. The conductive paste can be a circuit connecting paste resin composition 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. The GPC was measured under the following conditions.

<GPC measurement conditions>
Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation,
Column: Tosoh Co., Ltd. guard column "HXL-L"
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ 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 according to the measurement manual of the “GPC workstation EcoSEC-WorkStation”.
(Polystyrene used)
Tosoh Corporation "A-500"
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
"F-10" manufactured by Tosoh Corporation
Tosoh Corporation "F-20"
"F-40" manufactured by Tosoh Corporation
Tosoh Corporation "F-80"
Tosoh Corporation "F-128"
Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid content, filtered through a microfilter (50 μl).

< ¹³ C-NMR measurement conditions>
Apparatus: AL-400 manufactured by JEOL Ltd.,
Measurement mode: decoupling with reverse gate,
Solvent: deuterated chloroform,
Pulse angle: 30° pulse,
Sample concentration: 30 wt%,
Total number of times: 4000 times.

<MS measurement conditions>
The MS spectrum was measured using a double focusing mass spectrometer "AX505H (FD505H)" manufactured by JEOL Ltd.

Example 1
A flask equipped with a thermometer, a cooling tube and a stirrer was charged with 166 g (1 mol) of 4-t-butylcatechol, 64 g (0.6 mol) of benzaldehyde and 230 g of xylene while being purged with nitrogen gas. After the temperature was raised to 140° C., 14 g (0.17 mol) of 49 mass% sodium hydroxide aqueous solution was added, and the temperature was raised to 150° C. and reacted for 6 hours. After that, the temperature was raised to 200° C. while removing xylene and water, and the reaction was further performed for 18 hours. After the reaction was completed, 400 g of xylene was added, the mixture was cooled to 80° C., washed with neutralized water, and washed with 200 g of water until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain a phenol resin (1). The hydroxyl equivalent of the obtained phenol resin (1) was 188 g/eq. The GPC chart of the phenol resin (1) is shown in FIG. 1, the ¹³ C-NMR chart is shown in FIG. 2, and the MS spectrum is shown in FIG. The content rate of the substance represented by the following structural formula from GPC was 66%.

Example 2
188 g of phenolic resin (1) obtained in Example 1 (hydroxyl equivalent 1.0 g/eq), 555 g of epichlorohydrin (6.0 mol) while performing nitrogen gas purging on a flask equipped with a thermometer, a cooling tube and a stirrer, 53 g of n-butanol was charged and dissolved. After the temperature was raised to 50° C., 220 g (1.10 mol) of 20 mass% sodium hydroxide aqueous solution was added over 3 hours, and the reaction was further continued at 50° C. for 1 hour. After the reaction was completed, 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 and dissolved in the obtained crude epoxy resin. Further, 15 g of a 10 mass% sodium hydroxide aqueous solution was added to this solution, and the mixture was 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. Then, the system was dehydrated by azeotropic distillation, and after undergoing microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy resin (2). The epoxy equivalent of the obtained epoxy resin was 376 g/eq. The GPC chart of the obtained epoxy resin (2) is shown in FIG. 4, the ¹³ C-NMR spectrum is shown in FIG. 5, and the FD-MS spectrum is shown in FIG. The content rate of the substance represented by the following structural formula from GPC was 48%.

Comparative Synthesis Example 1
In a 1 liter four-necked flask equipped with a stirrer and a heating device, 152 g (1.0 mol) of trimethylhydroquinone was dissolved in a mixed solvent of 500 g of toluene and 200 g of ethylene glycol monoethyl ether. To the solution was added 4.6 g of para-toluenesulfonic acid, 64 g (0.6 mol) of benzaldehyde was added dropwise while paying attention to heat generation, and the mixture was stirred at 100 to 120° C. for 15 hours while distilling off water. Then, the mixture was cooled, the precipitated crystals were separated by filtration, washed repeatedly with water until it became neutral, and then dried to obtain a phenol resin (1′).

Comparative synthesis example 2
An epoxy resin (2′) was obtained in the same manner as in Example 2 except that the phenol resin (1) was changed to 187 g (hydroxyl equivalent 1.0 g/eq). The epoxy equivalent of the obtained epoxy resin was 272 g/eq.

Examples 3 and 4, Comparative Examples 1 and 2
<Preparation of composition and cured product>
The following compounds were compounded in the composition shown in Table 1, and then melt-kneaded at a temperature of 90° C. for 5 minutes using a two-roll mill to prepare a target curable resin composition. The abbreviations in Table 1 mean the following compounds.
Epoxy resin: cresol novolac type epoxy resin “N-655-EXP-S” epoxy equivalent 201 g/eq (manufactured by DIC Corporation)
-Phenol resin: Phenol novolac resin "TD-2131" Hydroxyl equivalent: 104 g/eq (manufactured by DIC Corporation)
-TPP: triphenylphosphine-Fused silica: spherical silica "FB-5602" 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.

<Liquidity>
The curable resin composition was injected into a test mold, and the spiral flow value was measured under conditions of a mold temperature of 150° C., an injection pressure of 70 kg/cm 2, and a curing time of 120 seconds.

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

Claims (13)

The following general formula (1)
[In formula, R< ¹ >, R< ² >, R< ³ > is respectively independently a C4-C8 alkyl group or an aralkyl group, l is either 0, 1, 2 and m is 0 or 1. And n is 0 or 1 (excluding the case where 1=m=n=0), and R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms or an aralkyl group. And
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, and one of R ⁶ and R ⁷ is an alkyl group or an aryl group, and R ⁸ and R ^{One of 9} is an alkyl group or an aryl group,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
s represents the number of repetitions and is an integer of 0-10. ]
A xanthene-type phenol resin represented by: The xanthene-type phenol resin according to claim 1, wherein R ⁶ and R ⁸ in the general formula (1) are benzene rings. The xanthene-type phenol resin according to claim 1 or 2, having a hydroxyl equivalent of 150 to 300 g/eq. The xanthene-type phenol resin according to any one of claims 1 to 3, wherein the content of the compound of s=0 in the general formula (1) is in the range of 50 to 75% in terms of area ratio in GPC measurement. The following general formula (2)
[In formula, R< ¹ >, R< ² >, R< ³ > is respectively independently a C4-C8 alkyl group or an aralkyl group, l is either 0, 1, 2 and m is 0 or 1. And n is 0 or 1 (excluding the case where 1=m=n=0), and R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms or an aralkyl group. And
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, and one of R ⁶ and R ⁷ is an alkyl group or an aryl group, and R ⁸ and R ^{One of 9} is an alkyl group or an aryl group,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
G is a glycidyl group, s shows a repeating number, and is an integer of 0-10. ]
A xanthene-type epoxy resin represented by: The xanthene-type epoxy resin according to claim 5, wherein R ⁶ and R ⁸ in the general formula (2) are benzene rings. The xanthene-type epoxy resin according to claim 5 or 6, having an epoxy equivalent of 300 to 500 g/eq. The xanthene-type epoxy resin according to any one of claims 5 to 7, wherein the content of the compound of s=0 in the general formula (2) is in the range of 30 to 50% in terms of area ratio in GPC measurement. A curable resin composition containing the xanthene-type phenol resin according to any one of claims 1 to 4 and a curing agent (X) as essential components. A curable resin composition comprising the xanthene-type epoxy resin according to any one of claims 5 to 8 and a curing agent (Y) as essential components. A cured product of the curable resin composition according to claim 9. A semiconductor encapsulating material containing the curable resin composition according to claim 9 or 10 and an inorganic filler. A semiconductor device, which is the cured product of the semiconductor encapsulating material according to claim 12.