JP2017061665A - Calixarene compound, composition, method for producing the same, epoxy resin curing agent, epoxy resin composition, laminate, semiconductor sealing material and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide calixarene compounds and compositions having excellent solubility in polar solvent.SOLUTION: The present invention provides a compound represented by formula (1), and a composition comprising the compound (Rand Rindependently represent H, a hydroxy group, a methyl group or a methoxy group; Ris a C1-C18 alkyl group, a phenyl group, a hydroxy phenyl group or a methyl phenyl group; at least two of four Rs are mutually different).SELECTED DRAWING: None

Description

  The present invention relates to a calixarene compound, a composition, a production method thereof, an epoxy resin curing agent, an epoxy resin composition, a laminate, a semiconductor encapsulant, and a semiconductor device.

  Conventionally, an epoxy resin is used for a member constituting a semiconductor device, for example, a sealing portion for sealing a semiconductor, a printed wiring board, and the like. For example, the epoxy resin is dissolved in a solvent together with a curing agent or the like to form a resin varnish. This resin varnish is impregnated into a base material such as glass cloth and dried to obtain a prepreg, and a laminated board obtained by heat-pressing this alone or a plurality of laminated sheets, or a laminated board in which copper foil is laminated on one or both sides thereof (Copper-clad laminate) is used. In general, a polar solvent such as methyl ethyl ketone is used as a solvent when an epoxy resin is used as a resin varnish.

With recent downsizing, thinning, and high performance of electronic devices, from the viewpoints of energy saving, CO ₂ emission reduction, environmental conservation, low power loss, high current and high voltage, high temperature of 200 ° C or higher Silicon carbide (SiC) power devices that can operate are drawing attention. Further, in the manufacture of semiconductor devices used therein, lead-free high melting point solders are increasing from the environmental aspect. Therefore, in order to reduce deformation due to heat during high-temperature operation or high melting point soldering, for example, heat shrinkage and warping due to heat, the members constituting the semiconductor device are strongly required to have improved heat resistance and low thermal expansion. Yes.

  Thus, it has been proposed to use calixarene compounds as curing agents for epoxy resins (Patent Documents 1 to 6). When a calixarene compound is used as the curing agent, a calixarene structure is introduced into the cured product, and physical properties such as heat resistance, low thermal expansion, and high elastic modulus can be imparted to the cured product.

JP-A-2-123126 Japanese Patent Laid-Open No. 3-66724 JP-A-6-136341 JP 2000-264953 A JP 2001-106868 A JP 2010-31089 A

  However, in general, calixarene compounds have low crystallinity and hydrogen bonding properties, and thus have low solubility in polar solvents. Therefore, when this is dissolved in a solvent together with an epoxy resin to form a resin varnish, it is necessary to reduce the solid content concentration. When the solid content concentration is increased, the calixarene compound is precipitated and does not impregnate the substrate well, and the effect of the curing agent is not sufficiently exhibited. However, a decrease in the solid content concentration of the resin varnish causes a decrease in productivity of the laminated board or the like.

This invention is made | formed in view of the said situation, Comprising: It aims at providing the calixarene type compound excellent in the solubility with respect to a polar solvent, a composition, and its manufacturing method.
The present invention provides an epoxy resin curing agent having excellent solubility in a polar solvent, and the resulting cured product is excellent in physical properties such as heat resistance, and an epoxy resin composition, a laminate, a semiconductor encapsulant, and a semiconductor device using the same. The other purpose is to provide.

  As a result of intensive studies, the present inventors have found that the high crystallinity and the high symmetry of the structure of the conventional calixarene compounds cause the low solubility in polar solvents. It was. As a result of further investigation based on this finding, a novel calixarene compound having a specific structure was found.

The present invention has the following aspects.
<1> A calixarene compound represented by the following formula (1).

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a methyl group or a methoxy group, and R ³ is an alkyl group having 1 to 18 carbon atoms, a phenyl group, a hydroxyphenyl group or a methyl group. A phenyl group, at least two of the four R ³ are different from each other.)

<2> A composition comprising the calixarene compound of <1> in a content of 70% by mass or more.
<3> A method for producing the composition according to <2>,
A reaction between polyhydric phenol represented by the following formula (2) and at least two aldehydes selected from the group consisting of a compound represented by the following formula (3) and a multimer thereof, wherein R ³ are different from each other. The manufacturing method of the composition including the process to make.

(In Formula (2), R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a methyl group, or a methoxy group. In Formula (3), R ³ is an alkyl group having 1 to 18 carbon atoms or a phenyl group. , Hydroxyphenyl group or methylphenyl group.)

<4> The method for producing a composition according to <3>, wherein the polyhydric phenol is resorcin, and the at least two aldehydes are paraaldehyde and n-butyraldehyde.
<5> The method for producing a composition according to <3>, wherein the polyhydric phenol is resorcin, and the at least two aldehydes are propionaldehyde and n-butyraldehyde.
<6> The method for producing a composition according to <3>, wherein the polyhydric phenol is resorcin, and the at least two aldehydes are paraaldehyde, propionaldehyde, and n-butyraldehyde.
<7> Among the at least two aldehydes, the ratio of the other aldehydes relative to 1 mol of one aldehyde having the largest amount in terms of the compound represented by the formula (3) is 0.25 to 1. The manufacturing method of the composition in any one of <3>-<6> which is mol.
<8> A curing agent for epoxy resins, comprising the composition of <2>.
<9> An epoxy resin composition comprising an epoxy resin and the curing agent for epoxy resin according to <8>.
<10> A laminate comprising a layer containing a cured product of the epoxy resin composition according to <9>.
<11> A semiconductor encapsulant comprising the epoxy resin composition of <9>.
<12> A semiconductor device comprising a semiconductor sealing portion containing a cured product of the epoxy resin composition according to <9>.

ADVANTAGE OF THE INVENTION According to this invention, the calixarene type compound excellent in the solubility with respect to a polar solvent, a composition, and its manufacturing method can be provided.
In addition, according to the present invention, the epoxy resin curing agent, the epoxy resin composition using the same, the laminate, and the semiconductor encapsulating material, which have excellent solubility in polar solvents and the obtained cured product is excellent in physical properties such as heat resistance In addition, a semiconductor device can be provided.

3 is a chart showing measurement results of ¹³ C-NMR spectrum of Composition A obtained in Example 1. FIG. 4 is a chart showing the measurement results of the FD-MS spectrum of the composition A obtained in Example 1. FIG. 4 is a chart showing the measurement results of the FD-MS spectrum of Composition B obtained in Example 2. FIG. 6 is a chart showing measurement results of FD-MS spectrum of Composition C obtained in Example 3. FIG. 6 is a chart showing measurement results of FD-MS spectrum of Composition D obtained in Comparative Example 1. 6 is a chart showing measurement results of an FD-MS spectrum of a composition E obtained in Comparative Example 2.

<Calixarene compounds>
The calixarene compound of the present invention (hereinafter also referred to as “compound (1)”) is represented by the following formula (1).

（式（１）中、Ｒ^１及びＲ^２はそれぞれ独立に、水素原子、水酸基、メチル基又はメトキシ基であり、Ｒ^３は炭素数１〜１８のアルキル基、フェニル基、ヒドロキシフェニル基又はメチルフェニル基であり、４つのＲ^３のうち少なくとも２つは互いに異なる。）

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a methyl group or a methoxy group, and R ³ is an alkyl group having 1 to 18 carbon atoms, a phenyl group, a hydroxyphenyl group or a methyl group. A phenyl group, at least two of the four R ³ are different from each other.)

In the formula (1), four R ^{1 s} may be the same or different from each other. Further, the four R ^{2 s} may be the same or different from each other.
R ¹ and R ² are each preferably a group other than a hydroxyl group in terms of solubility in a polar solvent, that is, a hydrogen atom, a methyl group or a methoxy group, and a hydroxyl group is preferred in terms of heat resistance.

The carbon number of the alkyl group of R ³ is 1 to 18, 1 to 4 is more preferred. If the carbon number of the alkyl group is not less than the lower limit of the above range, the solubility in a polar solvent is more excellent. When the carbon number of the alkyl group is not more than the upper limit of the above range, the heat resistance is more excellent and the combustibility is lowered. The alkyl group for R ³ may be linear or branched, and is preferably linear. The hydroxyphenyl group of the R ³ hydroxyphenyl group may be one, two or more, and preferably one. The methyl phenyl group of R ³ may have one, two or more methyl groups, and preferably one.
Specific examples of R ³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, A dodecyl group, a phenyl group, 2-hydroxyphenyl group, 4-hydroxyphenyl group, 4-methylphenyl group etc. are mentioned.

In formula (1), at least two of the four R ³ are different from each other. Thereby, the solubility with respect to the polar solvent of a compound (1) is excellent.
Of the four R ^{3 s} , two, three, or four may be different from each other.
Of the four R ³ , the positional relationship between different ones is not particularly limited. Also, if there are identical ones of the four R ^3, positional relationship between identical ones are not particularly limited.
Examples of combinations of R ³ different from each other include, for example, a combination of a methyl group and an n-propyl group, a combination of an ethyl group and an n-propyl group, a combination of a methyl group, an ethyl group and an n-propyl group, and a methyl group and an ethyl group. Combinations of groups, combinations of n-propyl groups and n-butyl groups, combinations of n-butyl groups and pentyl groups, combinations of methyl groups, ethyl groups, n-propyl groups and n-butyl groups, and the like. .
Among the above, it is relatively inexpensive, has good reactivity with the corresponding polyhydric phenols of aldehydes, has better solubility in the polar solvent of the resulting composition, imparts heat resistance and low thermal expansion to the cured product The combination of a methyl group and an n-propyl group, the combination of an ethyl group and an n-propyl group, or the combination of a methyl group, an ethyl group, and an n-propyl group is preferable from the viewpoint of reducing combustibility.

(Function and effect)
The compound (1) of the present invention is superior in solubility in a polar solvent used when an epoxy resin is used as a resin varnish as compared with a general calixarene compound. This is because at least two of the four R ³ are different from each other, so that the crystallinity and the symmetry of the structure are lower than those in the case where the four R ³ are the same. This is thought to be due to relaxation of the bond.
In addition, since the compound (1) of the present invention has a plurality of hydroxyl groups, as a curing agent (crosslinking agent) for a compound having a functional group (epoxy group, carboxyl group, isocyanate group, halide, etc.) that reacts with the hydroxyl group. Can be used. Moreover, by using the composition of the present invention as a curing agent, a calixarene structure can be introduced into the cured product, and physical properties such as heat resistance, low thermal expansion, and high elastic modulus can be imparted.
Moreover, since the compound (1) of this invention is excellent in the solubility with respect to a polar solvent as mentioned above, when using the compound (1) of this invention as a hardening | curing agent for epoxy resins, when using a general calixarene type compound As compared with the above, the solid content concentration of the resin varnish in which the epoxy resin, the curing agent and the like are dissolved in the solvent can be increased. Therefore, productivity of a laminated board etc. manufactured using a resin varnish is favorable.
Moreover, the compound (1) of this invention can be used as a material for manufacturing an epoxy resin. For example, by reacting the compound (1) of the present invention with epichlorohydrin, a part or all of —OH of the compound (1) becomes —OX (where X is a glycidyl group). An epoxy resin containing a compound having a structure can be obtained.

<Composition>
The composition of this invention contains the above-mentioned compound (1).
The compound (1) contained in the composition of the present invention may be one type or two or more types. For example, a plurality of compounds (1) having different types and combinations of R ³ may be included. Even if the types and combinations of R ³ are the same, a plurality of compounds (1) having different numbers of R ³ and different positional relationships among the four R ³ may be included.
The content of the compound (1) in the composition of the present invention is 70% by mass or more, preferably 90% by mass or more, and may be 100% by mass with respect to the total mass of the composition. If content of a compound (1) is more than the lower limit of the said range, the solubility with respect to a polar solvent will be excellent.

The composition of the present invention may further contain other components other than the compound (1).
Examples of other components include by-products that can be produced during the production of compound (1), materials used in the production of compound (1) (polyhydric phenols, aldehydes, etc. described later), and the like. For example, in the production method described later, a calixarene compound in which all four R ³ in the formula (1) are the same can be produced as a by-product.

The weight average molecular weight (Mw) of the composition of the present invention is preferably 500 to 1500, and more preferably 600 to 900.
The weight average molecular weight (Mw) is a standard polystyrene equivalent value measured by gel permeation chromatography (GPC).

  The composition of this invention can be manufactured with the manufacturing method of the composition of this invention mentioned later, for example. However, the method for producing the composition of the present invention is not limited thereto.

(Function and effect)
Since the composition of the present invention contains the compound (1) at a content of 70% by mass or more, it is excellent in solubility in a polar solvent as compared with a general calixarene compound, similarly to the compound (1). Moreover, it can be used as a curing agent for a compound having a functional group that reacts with a hydroxyl group, and by using the composition of the present invention as a curing agent, a calixarene structure is introduced into the cured product, heat resistance, low thermal expansion, Physical properties such as high elastic modulus can be imparted. Moreover, since it is excellent in the solubility with respect to a polar solvent, the solid content density | concentration of the resin varnish which the epoxy resin, the hardening | curing agent etc. melt | dissolved in the solvent can be made high by using the composition of this invention as a hardening | curing agent for epoxy resins. The productivity of laminates manufactured using a resin varnish is good. Moreover, the composition of this invention can be used as a material for manufacturing an epoxy resin.

<Method for producing composition>
The production method of the composition of the present invention includes a polyhydric phenol represented by the following formula (2), a compound represented by the following formula (3) (hereinafter also referred to as “compound (3)”), and a large amount thereof. A step of reacting at least two aldehydes selected from the group consisting of bodies and having different R ³ from each other.
A compound (1) is produced by reacting (condensing) the polyhydric phenol with the at least two aldehydes.

（式（２）中、Ｒ^１及びＲ^２はそれぞれ独立に、水素原子、水酸基、メチル基又はメトキシ基である。式（３）中、Ｒ^３は炭素数１〜１８のアルキル基、フェニル基、ヒドロキシフェニル基又はメチルフェニル基である。）

(In Formula (2), R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a methyl group, or a methoxy group. In Formula (3), R ³ is an alkyl group having 1 to 18 carbon atoms or a phenyl group. , Hydroxyphenyl group or methylphenyl group.)

R ¹ and R ² in the formula (2) correspond to R ¹ and R ² in the formula (1), respectively.
Examples of the polyhydric phenol include resorcin, 2-methylresorcin, 5-methylresorcin, pyrogallol, phloroglucinol, 2-methoxyresorcin, 5-methoxyresorcin and the like.
As the polyhydric phenol, resorcin is preferable because it is relatively inexpensive, has very good reactivity with aldehydes, and easily obtains a calixarene structure.

^{R 3} in the formula (3) corresponds to ^{R 3} in the formula (1).
Examples of the compound (3) include acetaldehyde, propionaldehyde, n-butyraldehyde, benzaldehyde, 2-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, p-tolualdehyde and the like.
Examples of the multimer of compound (3) include paraaldehyde (acetaldehyde trimer). The multimer of compound (3) produces compound (3) by heating in the presence of an acid. For example, when an inorganic acid, an organic acid, or the like is used as a catalyst when a polyhydric phenol and an aldehyde are subjected to a condensation reaction, the compound (3) is produced from a multimer of the compound (3) under the reaction conditions.

As the aldehydes, at least two kinds of R ³ different from each other are used. Thereby, the reaction product includes a compound (1) in which at least two of the four R ³ are different from each other.
One molecule of compound (1) may have four R ³ , but the number of aldehydes to be used is not limited to two, three or four, and may be five or more. In this case, a plurality of compounds (1) having different types of R ³ can be produced. Aldehydes having the same R ³ , such as acetaldehyde and paraaldehyde, are treated as one type.

Examples of the combination of the at least two aldehydes include, for example, a combination of paraaldehyde and n-butyraldehyde, a combination of propionaldehyde and n-butyraldehyde, a combination of paraaldehyde, propionaldehyde and n-butyraldehyde, Combination of methyl group and ethyl group, combination of n-propyl group and n-butyl group, combination of n-butyl group and pentyl group, combination of methyl group, ethyl group, n-propyl group and n-butyl group Etc.
Among the above, it is relatively inexpensive, has good reactivity with polyhydric phenols, has better solubility in the polar solvent of the resulting composition, can impart heat resistance and low thermal expansion to the cured product, and is flammable. In terms of reduction, a combination of paraaldehyde and n-butyraldehyde, a combination of propionaldehyde and n-butyraldehyde, or a combination of paraaldehyde, propionaldehyde and n-butyraldehyde is preferable.

The molar ratio of the at least two aldehydes is not particularly limited, but one of the at least two aldehydes having the largest amount (hereinafter also referred to as “first aldehyde”). It is preferable that the ratio of the other aldehydes with respect to 1 mol is 0.25-1 mol, and 0.5-1 mol is more preferable.
If the ratio of the other aldehydes relative to 1 mol of the first aldehyde is equal to or greater than the lower limit of the above range, when the polyhydric phenol and the aldehyde are reacted, the four R ³ in the formula (1) are It is difficult to produce compounds that are all the same. That is, compound (1) is easy to produce, and the abundance ratio of compound (1) in the reaction product of polyhydric phenol and aldehydes is increased.

Here, the amount of aldehydes (molar amount) is the amount in terms of compound (3), and in the case of multimers, it is a value obtained by multiplying the molar amount of multimers by the polymerization degree of multimers. For example, 1 mol of paraaldehyde is 3 mol in terms of compound (3).
When two or more aldehydes having the largest amount are present, any one of them is the first aldehyde.
When two or more other aldehydes are present, the ratio of the other aldehydes is not the ratio of the total of two or more other aldehydes, but the ratio of each of the two or more other aldehydes.

The molar ratio of the at least two aldehydes to the polyhydric phenol (aldehydes / polyhydric phenol) is preferably 0.50 to 1.20, and more preferably 0.50 to 1.00. If the molar ratio of aldehydes / polyhydric phenol is not less than the lower limit of the range, the yield is good, and if it is not more than the upper limit of the range, it is possible to suppress an increase in cost due to excess aldehydes, Moreover, it is easy to remove excess aldehydes.
In addition, the molar amount of aldehydes here is an amount in terms of compound (3).

The reaction between the polyhydric phenol and the at least two aldehydes can be performed by a conventional method.
The above reaction is preferably performed in the presence of a catalyst from the viewpoint of reaction rate.
The above reaction is preferably performed in a solvent that dissolves the polyhydric phenol and the at least two aldehydes and does not dissolve the compound (1) (hereinafter also referred to as “reaction solvent”). When the reaction is carried out in a reaction solvent, the produced compound (1) can be precipitated in the reaction solvent.
As a method for reacting the polyhydric phenol with the at least two aldehydes, a method in which the polyhydric phenol is dissolved in the reaction solvent and the at least two aldehydes are dropped therein is preferable. Since aldehydes are highly reactive, by-products other than compound (1) are likely to be produced when the entire amount to be reacted is present in the reaction system at one time. By gradually adding aldehydes to the reaction system, generation of by-products can be suppressed. Moreover, since the produced | generated compound (1) precipitates, the reactivity of a compound (1) is low, and reaction with a compound (1) and another component and decomposition | disassembly of a compound (1) do not occur easily. Therefore, the obtained reaction product tends to contain the compound (1) at a content of 70% by mass or more, and the reaction product recovered from the reaction solvent can be used as it is as the composition of the present invention.
A catalyst may be added to the reaction solvent.

  The catalyst is not particularly limited as long as the reaction proceeds, and known catalyst species such as inorganic acids and organic acids can be used. Specific examples include hydrobromic acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, and boron trifluoride.

  1.0-100.0 mass% is preferable with respect to the said polyhydric phenol, and, as for the quantity of a catalyst, 5.0-50.0 mass% is more preferable. If the amount of catalyst is not less than the lower limit of the above range, the reaction rate can be sufficiently increased. If the amount of catalyst is less than or equal to the upper limit of the above range, the reaction does not proceed rapidly and the reaction is easy to control.

The reaction solvent is not particularly limited as long as the compound (1) can be precipitated during the reaction, but water or a hydrocarbon solvent is preferable. Examples of the hydrocarbon solvent include normal hexane, cyclohexane, toluene and the like.
As the reaction solvent, water, normal hexane, and toluene are preferable because they are relatively inexpensive and allow the compound (1) to be easily precipitated.
A reaction solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  The amount of the reaction solvent is not particularly limited as long as the compound (1) can be precipitated during the reaction, but is preferably 50 to 400% by mass and more preferably 100 to 300% by mass with respect to the polyhydric phenol. When the amount of the reaction solvent is not less than the lower limit of the above range, the concentration of the precipitate in the reaction solvent is sufficiently low, and the reaction solvent can be easily stirred. When the amount of the reaction solvent is not more than the upper limit of the above range, the production of by-products other than the compound (1) can be suppressed, and the reaction proceeds sufficiently quickly. Further, an increase in cost due to an increase in the amount of waste liquid can be suppressed.

  The reaction temperature between the polyhydric phenol and the at least two aldehydes is preferably 20 ° C to 150 ° C, more preferably 60 to 100 ° C. When the reaction temperature is equal to or higher than the lower limit of the above range, the reaction is easy to proceed and the molecular weight dispersity of the reaction product is narrowed, so that the composition of the present invention can be easily obtained. Further, the reaction solvent in which the reaction product is precipitated can be easily stirred. If reaction temperature is below the upper limit of the said range, it will be easy to control reaction.

  The dropping time of the at least two aldehydes into the reaction solvent in which the polyhydric phenol is dissolved (the time from the start of dropping until the dropping is finished) is preferably 1 to 20 hours, and 3 to 10 hours. More preferred. When the dropping time is at least the lower limit of the above range, the molecular weight dispersion of the reaction product becomes narrow, and the composition of the present invention can be easily obtained. Further, the reaction solvent in which the reaction product is precipitated can be easily stirred. If the dropping time is not more than the upper limit of the above range, the productivity is good.

  The reaction product precipitated in the reaction solvent can be recovered by a known solid-liquid separation process such as filtration. After recovery, washing, purification, recrystallization, etc. may be performed as necessary.

If the reaction product obtained by the reaction of the polyhydric phenol and the at least two aldehydes contains the compound (1) in a content of 70% by mass or more, it is used as it is as the composition of the present invention. Can do.
The structure of the compound (1) in the reaction product is as follows: ¹³ C-nuclear magnetic resonance analysis (NMR), field desorption mass spectrometry (FD-MS), liquid chromatograph mass spectrometry (LC-MS), time-of-flight mass It can be confirmed by a known analysis method such as analysis (TOF-MS).
The content (purity) of the compound (1) in the reaction product can be confirmed by a known analysis method such as gel permeation chromatography (GPC) or liquid chromatography (LC).

<Curing agent for epoxy resin>
The epoxy resin curing agent of the present invention comprises the above-described composition of the present invention. That is, the compound (1) is contained at a content of 70% by mass or more. The preferable aspect of the hardening | curing agent for epoxy resins of this invention is the same as the preferable aspect of the composition of this invention.

<Epoxy resin composition>
The epoxy resin composition of the present invention contains an epoxy resin and the aforementioned curing agent for epoxy resin of the present invention.
The epoxy resin composition of this invention may further contain other components other than the epoxy resin and the hardening | curing agent for epoxy resins of this invention as needed. Examples of other components include a curing accelerator, a filler (for example, carbon black, glass cloth, silica), a flame retardant, and an additive (wax). In the range which does not impair the effect of this invention, you may further contain other hardening | curing agents other than the hardening | curing agent for epoxy resins of this invention.
The epoxy resin composition of the present invention may contain a solvent, if necessary. For example, when using the epoxy resin composition of this invention for manufacture of a laminated board, it is preferable that a solvent is included. When using the epoxy resin composition of this invention as a semiconductor sealing material, it is preferable not to contain a solvent.

  The epoxy resin is not particularly limited and may be a known epoxy resin, such as a phenol novolac type epoxy resin, an orthocresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenol type epoxy resin, Naphthalene type epoxy resin, anthracene type epoxy resin, naphthol type epoxy resin, xylylene type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, A phosphorus atom containing epoxy resin etc. are mentioned. Any one of these epoxy resins may be used alone, or two or more thereof may be used in combination.

  The curing accelerator is not particularly limited and may be a known curing accelerator, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. Among these, phosphorus compounds, tertiary amines, and imidazoles are preferable because they are more excellent in curability, heat resistance, and electrical properties, and are less likely to deteriorate moisture resistance reliability. Examples of the phosphorus compound include triphenylphosphine. Examples of the tertiary amine include 1,8-diazabicyclo- [5.4.0] undecene. Any one of these curing accelerators may be used alone, or two or more thereof may be used in combination.

  The curing agent for epoxy resin of the present invention may be used in combination with other curing agents. As other curing agents, those known as curing agents used for epoxy resins can be used, and examples thereof include phenol resins such as phenol novolac resins and triphenylmethane type phenol resins, acid anhydrides, and amine resins. .

  The solvent is not particularly limited as long as it can dissolve an epoxy resin, a curing agent, a curing accelerator, and the like, and a polar solvent is typically used. Examples of polar solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N, N-dimethylformamide, N-methyl-2-pyrrolidone, methanol, ethanol, butanol, ethyl acetate, butyl acetate, methyl cellosolve, ethyl diglycol acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran and the like.

  In the epoxy resin composition, the content of the curing agent for epoxy resin of the present invention is the ratio of the epoxy group equivalent of the epoxy resin and the hydroxyl equivalent of the curing agent for epoxy resin of the present invention (epoxy group equivalent / hydroxyl group equivalent). The amount is preferably 0.7 to 1.5. The epoxy group equivalent / hydroxyl group equivalent is more preferably 0.95 to 1.05. When the epoxy group equivalent / hydroxyl group equivalent is within the above range, the resulting cured product has good physical properties. For example, a cured product having high heat resistance, low thermal expansion, and high elastic modulus can be obtained.

As for content of a hardening accelerator, 0.1-5 mass% is preferable with respect to an epoxy resin.
The amount of the solvent is preferably such that the solid content concentration of the epoxy resin composition of the present invention is 20 to 70% by mass, and the amount of the solid content concentration of the epoxy resin composition of the present invention is 40 to 60% by mass. More preferred.

(Function and effect)
Since the epoxy resin composition of the present invention contains the epoxy resin curing agent of the present invention, the resulting cured product has physical properties such as heat resistance, low thermal expansion, and high elastic modulus. Therefore, the cured product of the epoxy resin composition of the present invention is useful as a material constituting, for example, a member of a semiconductor device (printed wiring board, semiconductor sealing portion, etc.).
Moreover, the hardening | curing agent for epoxy resins of this invention is excellent in the solubility with respect to a polar solvent compared with a general calixarene type compound. Therefore, when the epoxy resin composition of the present invention is a varnish in which an epoxy resin, a curing agent for epoxy resin, etc. are dissolved in a polar solvent, compared to a case where a general calixarene compound is used as a curing agent. The solid content concentration can be increased. Such a varnish-like epoxy resin composition is useful, for example, for producing a laminated board.

  The epoxy resin composition of the present invention can be thermally cured to obtain a cured product. As for the heating temperature at the time of making it thermoset, 180 to 220 degreeC is preferable.

<Laminated plate>
The laminated board of this invention may be the same structure as a well-known laminated board except including the hardened | cured material of the epoxy resin composition of this invention as a resin component which comprises a layer.
The laminated board of this invention can be manufactured using a known method using the epoxy resin composition of this invention. For example, a varnish containing a solvent is prepared as the epoxy resin composition of the present invention, the substrate is impregnated with the epoxy resin composition, dried to obtain a prepreg, and the prepreg is used alone or in a plurality of sheets. There is a method in which a metal foil such as a copper foil is further laminated on one side or both sides as necessary, followed by hot pressing. The dried epoxy resin composition is cured by hot pressing, and a layer including the base material and the cured product is formed.
Examples of the substrate include paper, cotton, glass, carbon fiber and the like.

<Semiconductor encapsulant>
The semiconductor sealing material of the present invention may have the same configuration as that of a known sealing material except that the epoxy resin composition of the present invention is included as a constituent resin component.

<Semiconductor device>
The semiconductor device of the present invention may have the same configuration as that of a known semiconductor device, except that the semiconductor encapsulating part includes a cured product of the epoxy resin composition of the present invention.
As a method for forming a semiconductor sealing portion (sealing a semiconductor) using the epoxy resin composition of the present invention, a known method such as a transfer molding method or a compression molding method can be used.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples.
In the following examples, “%” indicates “% by mass” unless otherwise specified.
In each of the following examples, gel permeation chromatography analysis (measurement by GPC method) was performed using HLC8120GPC manufactured by Tosoh Corporation as a GPC measurement apparatus and a column: TSKgel (registered trademark) G3000H + G2000H + G2000H as a column. The hydroxyl equivalent was measured by an acetylation method using acetic anhydride using an automatic titrator (COM-1700S manufactured by Hiranuma Sangyo Co., Ltd.). ¹³ C-nuclear magnetic resonance (NMR) analysis was performed using LA-400 manufactured by JEOL Ltd. Field desorption mass spectrometry (FD-MS) was performed using SX-102A manufactured by JEOL Ltd.

<Example 1>
Reaction of resorcin, paraaldehyde and n-butyraldehyde:
A glass reaction vessel having an internal volume of 1 L equipped with a thermometer, a stirrer, and a cooling tube was charged with 220.0 g of water, 110.1 g (1.0 mol) of resorcin, and 16.5 g of 35% hydrochloric acid, and the temperature was raised to 90 ° C. Thereto, a mixed solution in which 19.8 g (0.15 mol) of paraaldehyde and 32.4 g (0.45 mol) of n-butyraldehyde were mixed in advance was dropped over 6 hours, and then the reaction was performed for 1 hour. During the reaction, precipitates were confirmed in the reaction solution. Next, the reaction solution was neutralized with 30% NaOH and filtered to collect the precipitate. The obtained precipitate was repeatedly washed with water and filtered until the washing water became neutral, and then water was removed by vacuum drying to obtain a composition A.

When GPC measurement was performed on the obtained composition A, the weight average molecular weight (Mw) in terms of standard polystyrene of the composition A was 675, the degree of dispersion (Mw / number average molecular weight (Mn)) was 1.028, and purity. Was 97%. Moreover, the hydroxyl equivalent of the composition A was 76.0 g / eq. Here, the purity is the ratio of the compound corresponding to the compound (1) with respect to the total mass of the composition A, and the same applies to the following.
Moreover, about the composition A, the structural analysis by < ¹³ > C-NMR and FD-MS was implemented. Each result is shown below. FIG. 1 shows a chart showing the measurement result of the ¹³ C-NMR spectrum, and FIG. 2 shows a chart showing the measurement result of the FD-MS spectrum. From these results, it was confirmed that the compound contained in the composition A has a structure represented by the following formula (1-1). The symbols a to j shown at the positions of the carbon atoms in the formula (1-1) correspond to the symbols attached to the carbon in the ¹³ C-NMR data.
¹³ C-NMR (400 MHz, acetone-d ₆ ): δ (ppm) = 152-154 (m, 1.0 C, aromatic C ^a ), 124-128 (m, 1.5 C, aromatic C ^b , C ^c ) , 102-104 (s, 0.5 C, aromatic C ^d ), 32-37 (d, 0.5 C, C ^e , C ^f ), 27-29 (s, 0.25 C, C ⁱ ), 19-23 (D, 0.5 C, C ^g , C ^j ), 13-15 (s, 0.25 C, C ^h ).
FD-MS: Each compound of 545 m / z, 573 m / z, 601 m / z, 629 m / z, and 657 m / z was shown.

<Example 2>
Reaction of resorcin, propionaldehyde and n-butyraldehyde:
A glass reaction vessel having an internal volume of 1 L equipped with a thermometer, a stirrer, and a cooling tube was charged with 220.0 g of water, 110.1 g (1.0 mol) of resorcin, and 16.5 g of 35% hydrochloric acid, and the temperature was raised to 90 ° C. Thereto, a mixed solution in which 26.1 g (0.45 mol) of propionaldehyde and 32.4 g (0.45 mol) of n-butyraldehyde were mixed in advance was dropped over 6 hours, and then the reaction was performed for 1 hour. During the reaction, precipitates were confirmed in the reaction solution. Next, the reaction solution was neutralized with 30% NaOH and filtered to collect the precipitate. The obtained precipitate was repeatedly washed with water and filtered until the washing water became neutral, and then water was removed by vacuum drying to obtain Composition B.
About the obtained composition B, GPC was performed on the conditions similar to Example 1. FIG. As a result, the weight average molecular weight (Mw) of the composition B was 826, the dispersity (Mw / Mn) was 1.099, and the purity was 91%. The hydroxyl equivalent was 80.5 g / eq.
Moreover, about the composition B, the structural analysis was implemented on the conditions similar to Example 1 using FD-MS. The results are shown below. FIG. 3 shows a chart showing the measurement results of the FD-MS spectrum. From this result, it was confirmed that the compound contained in the composition B had a calixarene structure as in Example 1.
FD-MS: Each compound of 601 m / z, 615 m / z, 629 m / z, 643 m / z, and 657 m / z was shown.

<Example 3>
Reaction of resorcin, paraaldehyde, propionaldehyde and n-butyraldehyde:
A glass reaction vessel having an internal volume of 1 L equipped with a thermometer, a stirrer, and a cooling tube was charged with 220.0 g of water, 110.1 g (1.0 mol) of resorcin, and 16.5 g of 35% hydrochloric acid, and the temperature was raised to 90 ° C. A mixed solution in which 13.2 g (0.1 mol) of paraaldehyde, 17.4 g (0.3 mol) of propionaldehyde and 21.6 g (0.3 mol) of n-butyraldehyde were mixed in advance was dropped over 6 hours. Then, the reaction was performed for 1 hour. During the reaction, precipitates were confirmed in the reaction solution. Next, the reaction solution was neutralized with 30% NaOH and filtered to collect the precipitate. The obtained precipitate was repeatedly washed with water and filtered until the washing water became neutral, and then water was removed by vacuum drying to obtain Composition C.
About the obtained composition C, GPC was performed on the conditions similar to Example 1. FIG. As a result, the weight average molecular weight (Mw) of composition C was 686, the dispersity (Mw / Mn) was 1.033, and the purity was 97%. The hydroxyl equivalent was 77.6 g / eq.
Moreover, about the composition C, the structural analysis was implemented on the conditions similar to Example 1 using FD-MS. The results are shown below. FIG. 4 shows a chart showing the measurement results of the FD-MS spectrum. From this result, it was confirmed that the compound contained in the composition C had a calixarene structure as in Example 1.
FD-MS: 545 m / z, 559 m / z, 573 m / z, 587 m / z, 601 m / z, 615 m / z, 629 m / z, 643 m / z, 657 m / z were shown.

<Comparative Example 1>
Reaction of resorcin with paraaldehyde:
A glass reaction vessel having an internal volume of 1 L equipped with a thermometer, a stirrer, and a cooling tube was charged with 220.0 g of water, 110.1 g (1.0 mol) of resorcin, and 16.5 g of 35% hydrochloric acid, and the temperature was raised to 90 ° C. Paraaldehyde 40.0g (0.3mol) was dripped there over 3 hours, and reaction was performed after that for 3 hours. Next, the reaction solution was neutralized with 30% NaOH and filtered to collect the precipitate. The obtained precipitate was repeatedly washed with water and filtered until the washing water became neutral, and then water was removed by vacuum drying to obtain a composition D.
GPC was performed on the obtained composition D under the same conditions as in Example 1. As a result, composition D had a weight average molecular weight (Mw) of 594 and a dispersity (Mw / Mn) of 1.024. The hydroxyl equivalent was 68.5 g / eq.
Moreover, about the composition D, the structural analysis was implemented on the conditions similar to Example 1 using FD-MS. The results are shown below. FIG. 5 shows a chart showing the measurement results of the FD-MS spectrum. From this result, it was confirmed that the compound contained in the composition D had a calixarene structure as in Example 1.
FD-MS: 545 m / z compound was shown.

<Comparative example 2>
Reaction of resorcin with propionaldehyde:
A glass reaction vessel having an internal volume of 1 L equipped with a thermometer, a stirrer, and a cooling tube was charged with 220.0 g of water, 110.1 g (1.0 mol) of resorcin, and 16.5 g of 35% hydrochloric acid, and the temperature was raised to 90 ° C. Propionaldehyde 52.3g (0.9mol) was dripped there over 10 hours, and reaction was performed after that for 3 hours. Next, the reaction solution was neutralized with 30% NaOH and filtered to collect the precipitate. The obtained precipitate was repeatedly washed with water and filtered until the washing water became neutral, and then water was removed by vacuum drying to obtain composition E.
GPC was performed on the obtained composition E under the same conditions as in Example 1. As a result, composition E had a weight average molecular weight (Mw) of 786 and a dispersity (Mw / Mn) of 1.102. The hydroxyl equivalent was 74.0 g / eq.
Moreover, about the composition E, the structural analysis was implemented on the conditions similar to Example 1 using FD-MS. The results are shown below. FIG. 6 shows a chart showing the measurement results of the FD-MS spectrum. From this result, it was confirmed that the compound contained in the composition E had a calixarene structure as in Example 1.
FD-MS: 601 m / z compound was shown.

The solvent solubility of the compositions A to E obtained in Examples 1 to 3 and Comparative Examples 1 to 2 was evaluated by the following method. The results are shown in Table 1.
<Evaluation of solvent solubility>
The composition was dissolved in the solvent shown in Table 1 so that the solid concentration was 30%, and the resulting solution was allowed to stand at 15 ° C. for 1 month in a sealed container. The state of the solution after standing was visually observed, and the solvent solubility was evaluated according to the following criteria.
○ (Good): No precipitate was observed in the solution.
X (Poor): Precipitates were observed in the solution.

The symbols in Table 1 have the following meanings.
ACN: acetone, MEK: methyl ethyl ketone, THF: tetrahydrofuran, PGME: propylene glycol monomethyl ether, DMF: N, N-dimethylformamide, NMP: N-methyl-2-pyrrolidone.

As shown in the above results, the compositions of Examples 1 to 3 had good solubility in any solvent of ACN, MEK, THF, PGME, DMF, and NMP.
On the other hand, the composition of Comparative Example 1 using paraaldehyde alone as aldehydes was poorly soluble in all the above solvents. The composition of Comparative Example 2 using propionaldehyde alone as the aldehydes had poor solubility in all solvents other than PGME.

<Examples 4-6, Comparative Examples 3-4>
[Preparation of epoxy resin composition]
Each component was mixed so that it might become a composition shown in Table 2, and the solution-form epoxy resin composition was prepared.
In Table 2, a phenol novolak resin having a softening point of 120 ° C. was used. As the triphenylmethane type phenol resin, trade name “TPM-100” (softening point 100 ° C.) manufactured by Gunei Chemical Industry Co., Ltd. was used. As the epoxy resin, trade name “YDCN-704” (orthocresol novolac type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. was used. Imidazole is a curing accelerator, and a reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
Moreover, the compounding quantity of an epoxy resin and a hardening | curing agent was set so that the equivalent ratio (epoxy group equivalent / hydroxyl group equivalent) of the epoxy group equivalent in an epoxy resin and the hydroxyl group equivalent in a hardening | curing agent might be set to 1.
The softening point was measured according to JIS K 6910: 2007.

[Preparation of molded product for laminate]
A glass cloth (trade name “WEA7628” manufactured by Nittobo Co., Ltd.) was impregnated with an epoxy resin composition in an amount of about 40% based on the total amount of the prepreg, and air-dried to obtain a prepreg. Thereafter, six prepregs were stacked, semi-cured under conditions of 100 ° C./15 minutes, and subjected to hot pressing under conditions of 130 ° C. and ² kN / m ² using a vacuum heater press device, and 130 ° C. to 180 ° C. Until then, the temperature was raised every 10 ° C./15 minutes under the condition of 20 kN / m ² to produce a molded product. The obtained molded product was post-cured at 180 ° C. for 5 hours to obtain a molded product for a laminate having a thickness of 2.0 mm.

About the obtained molded object for laminated boards, the glass transition temperature, the storage elastic modulus, the thermal decomposition start temperature, and the average linear thermal expansion coefficient were measured with the following method. The results are shown in Table 2.
[Glass transition temperature (Tg), storage modulus]
The molded product for laminate was cut into a size of width 10.0 mm × length 55.0 mm to prepare a test piece. About this test piece, a glass transition temperature (° C.), a storage elastic modulus (MPa) at 30 ° C., and a storage elastic modulus (MPa) at 260 ° C. were respectively measured with a viscoelastic spectrometer (manufactured by Seiko Instruments Inc., DMS 110). It was measured in the range of 30 ° C. to 350 ° C. at a temperature rising rate of 10 ° C./min.
[Pyrolysis start temperature]
About the molded article for laminated boards, the thermogravimetric weight loss was measured in the air atmosphere with the differential thermothermal weight simultaneous measuring apparatus (TG / DTA6300 by Seiko Instruments Inc.), and the thermal decomposition start temperature (degreeC) was calculated | required.
[Average linear thermal expansion coefficient]
A laminate was cut into a size of 2.0 mm wide and 2.0 mm long to prepare a sample. About this sample, using a thermomechanical analyzer (manufactured by Seiko Instruments Inc., TMA 110), the temperature was increased from 30 ° C. to 350 ° C. at a temperature increase rate of 10 ° C./min, and 40 ° C. to 90 ° C. and 160 ° C. The average linear thermal expansion coefficient in each temperature range of ˜200 ° C. was measured.

  As shown in the above results, the laminates obtained from the epoxy resin compositions of Examples 4 to 6 were compared to the laminates obtained from the epoxy resin compositions of Comparative Examples 3 to 4, The glass transition temperature was high, the thermal decomposition starting temperature was high, the average linear thermal expansion coefficient was low, and the storage elastic modulus was high.

The calixarene compound or composition of the present invention is excellent in solubility in a polar solvent.
Further, the calixarene compound or composition of the present invention can be used as a curing agent such as an epoxy resin, and the cured product obtained using the calixarene compound or composition of the present invention as a curing agent is in the structure. Has a calixarene structure, high heat resistance, low thermal expansion and high elastic modulus even at high temperatures.
Therefore, the calixarene compound, composition, epoxy resin composition or cured product thereof of the present invention is extremely useful as a functional material. For example, semiconductor sealing materials, electrical insulating materials, copper-clad laminate resins, resists, electronic component sealing resins, liquid crystal color filter resins, paints, various coating agents, as physically and electrically superior materials It can be used for a wide range of applications such as adhesives, build-up laminate materials, and fiber reinforced plastics (FRP).

Claims (12)

A calixarene compound represented by the following formula (1).

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a methyl group or a methoxy group, and R ³ is an alkyl group having 1 to 18 carbon atoms, a phenyl group, a hydroxyphenyl group or a methyl group. A phenyl group, at least two of the four R ³ are different from each other.)   A composition comprising the calixarene compound according to claim 1 in a content of 70% by mass or more. A method for producing the composition of claim 2, comprising:
A reaction between polyhydric phenol represented by the following formula (2) and at least two aldehydes selected from the group consisting of a compound represented by the following formula (3) and a multimer thereof, wherein R ³ are different from each other. The manufacturing method of the composition including the process to make.

(In Formula (2), R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group, a methyl group, or a methoxy group. In Formula (3), R ³ is an alkyl group having 1 to 18 carbon atoms or a phenyl group. , Hydroxyphenyl group or methylphenyl group.)   The method for producing a composition according to claim 3, wherein the polyhydric phenol is resorcin, and the at least two aldehydes are paraaldehyde and n-butyraldehyde.   The method for producing a composition according to claim 3, wherein the polyhydric phenol is resorcin, and the at least two aldehydes are propionaldehyde and n-butyraldehyde.   The method for producing a composition according to claim 3, wherein the polyhydric phenol is resorcin, and the at least two aldehydes are paraaldehyde, propionaldehyde and n-butyraldehyde.   Among the at least two aldehydes, the ratio of the other aldehydes relative to 1 mol of one aldehyde having the largest amount in terms of the compound represented by the formula (3) is 0.25 to 1 mol. The manufacturing method of the composition as described in any one of Claims 3-6 which exists.   The hardening | curing agent for epoxy resins which consists of a composition of Claim 2.   The epoxy resin composition containing an epoxy resin and the hardening | curing agent for epoxy resins of Claim 8.   A laminated board provided with the layer containing the hardened | cured material of the epoxy resin composition of Claim 9.   The semiconductor sealing material containing the epoxy resin composition of Claim 9.   A semiconductor device provided with the semiconductor sealing part containing the hardened | cured material of the epoxy resin composition of Claim 9.

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