JP2015110695A - Phenolic resin composition, thermosetting resin composition, and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenolic resin composition having excellent flowability, a thermosetting resin composition, and a cured product having excellent heat resistance, moisture resistance, and adhesiveness.SOLUTION: A phenolic resin composition comprises: (A) 30 mass%-80 mass% of phenolic resin having structures represented by formula (I-1)-formula (III-1); and (B) 20 mass%-70 mass% of hydroxyflavan compounds.

Description

  The present invention relates to a phenol resin composition, a thermosetting resin composition, and a cured product.

The thermosetting resin composition combining an epoxy resin (main agent) and a phenol resin (curing agent) is because the cured product of such a thermosetting resin composition is excellent in heat resistance, adhesiveness, electrical insulation, and the like. It is used in various fields. For example, a conductive paste containing a resin composition for printed circuit boards, a resin composition for interlayer insulation materials used for printed circuit boards and resin-coated copper foils, a resin composition for sealing materials for electronic components, resist ink, and a conductive filler , Paints, adhesives, composite materials, etc.
For example, a semiconductor encapsulant such as a resin composition for encapsulant is a cured product (molded product) as compared with the thermosetting resin composition due to increasing needs for downsizing, thinning, and miniaturization of products. ) Further improved heat resistance, moisture resistance, adhesion, reduction of linear expansion coefficient, and the like.
Furthermore, in recent years, with the increasing energy-saving intention for the purpose of global environmental conservation, etc., there has been a demand for higher efficiency of various electrical devices. In addition, due to the tight power situation after the earthquake, further power devices Along with the improvement in efficiency, studies on application of next-generation power devices such as silicon carbide and gallium nitride are ahead of schedule. Since next-generation devices can operate at higher temperatures than conventional silicon, further heat resistance is required for the sealing material.
In response to such a demand, various solutions such as increasing the amount of filler have been studied. As one of the means for solving the problem, there is known a method of increasing the crosslinking density by increasing the number of functional groups of the resin component in the thermosetting resin composition. For example, improvement in heat resistance has been studied by using an epoxy resin or phenol resin having a triphenylmethane structure, or an epoxy resin or phenol resin having a tetrakisphenolethane structure.

As a document showing such means, for example, Patent Document 1 includes, as a main component, an epoxy resin having a triphenylmethane structure and a phenol resin having a triphenylmethane structure, and a part of a crystalline epoxy resin. The invention to be described is described.
For example, Patent Document 2 describes an invention in which a phenol resin containing a phenol resin having a tetrakisphenolethane structure, which is a condensate of phenols and dialdehyde, is used as a curing agent for an epoxy resin.
For example, Patent Document 3 describes an invention of an epoxy resin composition in which a sulfur atom is introduced into a resin skeleton by using a sulfur-containing compound.

Japanese Patent No. 3365725 JP 2001-48959 A JP 2006-273906 A

Increasing the amount of filler in the thermosetting resin composition makes it easier to improve the flame retardancy of the cured product, but on the other hand, the filler and other compounds blended in the thermosetting resin composition There arises a problem that the fluidity is lowered and the moldability of the cured product is deteriorated. Therefore, it is necessary to lower the melt viscosity of the resin component at the same time.
By increasing the number of functional groups of the resin component in the thermosetting resin composition, the heat resistance of the cured product is easily improved, but the fluidity of the resin component tends to decrease as the number of functional groups increases.
Under such circumstances, as disclosed in Patent Documents 1 and 2, methods for achieving both the heat resistance of the cured product and the fluidity of the resin have been studied.

However, although the resin composition obtained by the method disclosed in Patent Document 1 is excellent in fluidity, the heat resistance of the cured product is lowered by the blending of the crystalline epoxy resin.
The phenol resin described in Patent Document 2 imparts fluidity by increasing the ratio of a substance obtained by condensing 3 mol or less of phenols with respect to 1 mol of dialdehyde. Accordingly, although the fluidity is improved, the heat resistance of the cured product is insufficient.
Furthermore, although the epoxy resin composition obtained by the method shown in Patent Document 3 is excellent in adhesiveness with copper, a problem remains in its heat resistance in the environment where next-generation devices are used.

  An object of this invention is to provide the phenol resin composition which is excellent in fluidity | liquidity, and the hardened | cured material which is excellent in heat resistance, moisture resistance, and adhesiveness.

That is, the present invention has the following configuration.
(1) (A) 30% by mass to 80% by mass of a phenol resin having a structure represented by the following formula (I), a structure represented by the following formula (II), and a structure represented by the following formula (III) When,
(B) 20% by mass to 70% by mass of a hydroxyflavan compound represented by the following formula (IV);
A phenolic resin composition comprising:

In formula (I), R ^{1 to} R ³ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group, and a to c are each independently 0 Represents an integer of ~ 3.
When a is 2 or 3, R ¹ may be the same or different.
When b is 2 or 3, R ² may be the same or different.
When c is 2 or 3, R ³ may be the same or different.
In the formula (II), R ⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Wherein (III), R ^m represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group, d represents an integer of 0 to 3. When d is 2 or 3, R ^m may be the same or different.
In the formula (IV), R ⁴ , R ⁷ and R ⁸ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aralkyl group or an aryl group having 7 to 13 carbon atoms. R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or an aryl group.
However, R ⁵ and R ⁶ may be bonded to each other, or R ⁷ and R ⁸ may be bonded to each other to form a ring.
W ¹ , X ¹ , Y ¹ and Z ¹ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyalkyl having 1 to 10 carbon atoms. Represents a group, and the benzene ring to which W ¹ , X ¹ , Y ¹ and Z ¹ are bonded has one or two hydroxyl groups.
W ² , X ² , Y ² and Z ² are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyalkyl having 1 to 10 carbon atoms. Represents a group, and the benzene ring to which W ² , X ² , Y ² and Z ² are bonded has one or two hydroxyl groups.

(2) The phenol resin composition according to (1), wherein the (A) phenol resin has a structure represented by the following formula (V).

In the formula (IV), R ¹¹ , R ²¹ , R ³¹ , R ¹² , R ²² , and R ³² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group A1-c1 and a2-c2 each independently represent an integer of 0-3.
When a1 is 2 or 3, R ¹¹ may be the same or different.
When b1 is 2 or 3, R ²¹ may be the same or different.
When c1 is 2 or 3, R ³¹ may be the same or different.
When a2 is 2 or 3, R ¹² may be the same or different.
When b2 is 2 or 3, R ²² may be the same or different.
When c2 is 2 or 3, R ³² may be the same or different.
R ⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms in total.

(3) The phenol resin composition as described in (1) or (2) whose softening point is 125 degrees C or less.

(4) The (A) phenol resin is obtained by a reaction of a phenol, an aromatic aldehyde, and at least one non-aromatic aldehyde selected from the group consisting of formaldehyde and an aliphatic aldehyde having 2 to 6 carbon atoms. The phenol resin composition according to any one of (1) to (3), which is a product obtained.
(5) The phenol resin composition according to (4), wherein the aromatic aldehyde is orthohydroxybenzaldehyde and the non-aromatic aldehyde is formaldehyde.
(6) The phenol resin composition according to (4) or (5), wherein the reaction is performed in the presence of an acidic catalyst.
(7) The phenol is selected from the group consisting of phenol, cresol, ethylphenol, xylenol, butylphenol, octylphenol, nonylphenol, phenylphenol, cyclohexylphenol, trimethylphenol, bisphenol A, catechol, resorcinol, hydroquinone, naphthol, and pyrogallol. The phenol resin composition according to any one of (4) to (6), which is at least one kind.

(8) The phenol resin composition according to any one of (1) to (7), wherein the (B) hydroxyflavan compound is a reaction product of resorcinol and a ketone compound.
(9) The phenol resin composition according to (8), wherein the ketone compound is acetone.
(10) The phenol resin composition according to any one of (1) to (9), wherein the (B) hydroxyflavan compound is represented by the following formula (iii).

(11) The phenol resin composition according to any one of (1) to (10), wherein the weight average molecular weight of the (A) phenol resin is 280 to 5000.

(12) A thermosetting resin composition comprising the phenol resin composition according to any one of (1) to (11) and an epoxy resin.
(13) The thermosetting resin composition according to (12), wherein the epoxy resin has a weight average molecular weight of 300 to 5,000.
(14) The thermosetting resin composition according to (12) or (13), wherein a hydroxyl group of the phenol resin composition is 0.6 equivalents to 1.2 equivalents with respect to 1.0 equivalent of an epoxy group of the epoxy resin. object.
(15) The thermosetting resin composition according to any one of (12) to (14), comprising a filler.

(16) A cured product obtained by curing the thermosetting resin composition according to any one of (12) to (15).

  The present invention provides a phenol resin composition excellent in fluidity, a thermosetting resin composition excellent in fluidity, and a cured product excellent in heat resistance, moisture resistance, and adhesiveness.

<Phenolic resin composition>
The phenol resin composition of the present invention has (A) a structure represented by the formula (I), a structure represented by the formula (II), and a phenol resin having a structure represented by the formula (III) 30% by mass to 30% by mass. 80% by mass and (B) 20% by mass to 70% by mass of a hydroxyflavan compound represented by the formula (IV).
Hereinafter, the phenol resin composition, thermosetting resin composition, and cured product of the present invention will be described in detail.
In addition, the numerical value range shown using "to" in this specification shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively.
Further, the structure represented by the formula (I) is simply referred to as “structure (I)”, and the structure represented by the formula (II) is simply referred to as “structure (II)”. The structures represented by formula (III), formula (I-1), formula (II-1), etc. described later are also shown.

[(A) Phenolic resin]
The phenol resin composition of the present invention comprises (A) a phenol resin having a structure represented by formula (I), a structure represented by formula (II), and a structure represented by formula (III) (hereinafter referred to as A). 30% by mass to 80% by mass).
Hereinafter, the structure represented by the formula (I) is also referred to as “triphenylmethane structure”.

In formula (I), R ^{1 to} R ³ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group, and a to c are each independently 0 Represents an integer of ~ 3.
When a is 2 or 3, R ¹ may be the same or different.
When b is 2 or 3, R ² may be the same or different.
When c is 2 or 3, R ³ may be the same or different.

In the formula (I), the alkyl group having 1 to 10 carbon atoms represented by R ^{1 to} R ³ is preferably a linear or branched alkyl group, for example, a methyl group, an ethyl group, an i-propyl group, t -A butyl group, n-hexyl group, etc. are mentioned. As for carbon number, it is more preferred that it is 1-5, and it is still more preferred that it is 1-3.
In the formula (I), the alkyl group part of the alkoxy group having 1 to 10 carbon atoms represented by R ^{1 to} R ³ may be linear or branched. For example, methyl group, ethyl Group, i-propyl group, t-butyl group, n-hexyl group and the like. As for carbon number of an alkoxy group, it is more preferable that it is 1-5, and it is still more preferable that it is 1-3.
In the formula (I), each of a to c is preferably independently an integer of 0 to 2, more preferably an integer of 0 or 1, and still more preferably 0.

(A) The phenol resin has a structure represented by the formula (II).
(A) Since the phenol resin has the structure (II) in the molecule, (A) the phenol resin has flexibility, the phenol resin composition has a low softening point and excellent fluidity. Can be obtained.

In the formula (II), R ⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ⁰ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.
The alkyl group represented by R ⁰ may be linear or branched, and may further have a substituent. The total number of carbon atoms including the substituent is 1 to 1. 5.
(A) The phenol resin also has a structure represented by the formula (III).

Wherein (III), R ^m represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group, d represents an integer of 0 to 3. When d is 2 or 3, R ^m may be the same or different.
R ^m has the same meaning as R ¹ in formula (I), and the preferred embodiment is also the same. Moreover, d is synonymous with a in Formula (I), and its preferable aspect is also the same.
Furthermore, the structure (III) is preferably a structure represented by the formula (III-2) [structure (III-2)].

(A) The phenol resin may have a structure in which the structure (I) and the structure (II) or the structure (III) are randomly copolymerized, or a repeating block of the structure (I) and the structure (II) Alternatively, a structure in which the repeating block of the structure (I) and the structure (III) is copolymerized may be used.
(A) The phenol resin may contain structures other than the structure (I), the structure (II), and the structure (III).

The three wavy lines in the formula (I) and the two wavy lines in the formulas (II) and (III) indicate the boundaries of each structure, and other structures are coupled via the coupling portion indicated by the wavy lines. It represents what can be done.
The formula (I) is replaced with the following formula (I-1), the formula (II) is replaced with the following formula (II-1), and the formula (III) is replaced with the following formula (III-1).

R ¹ to R ³ and a~c in formula (I-1) is the same as R ¹ to R ³ and a~c in formula (I), and preferred embodiments are also the same. R ^{0 in} formula (II-1) is the same as R ⁰ in formula (II), and the preferred embodiment is also the same. R ^m and d in formula (III-1) is the same as R ^m and d in formula (III), and their preferred embodiments are also the same.
* 1 to * 3 in the formula (I-1) represent a bond part of the structure (I-1), and * 4 to * 5 in the formula (II-1) represent a bond of the structure (II-1). And * 6 to * 7 in the formula (III-1) represent a bond part of the structure (III-1).
(A) For example, the phenolic resin includes any one or all of * 1 to * 3 of the structure (I-1), * 4 or * 5 of the structure (II-1), or * of the structure (III-1). 6 or * 7 may be bonded.

From the viewpoint of imparting more flexibility to the (A) phenol resin, the (A) phenol resin has * 4 of the structure (II-1) bonded to * 3 of the structure (I-1) in the molecule. It is preferable to have a structure in which any one of * 1 to * 3 of the other structure (I-1) is bonded to * 5 of the structure (II-1). (A) The phenol resin has a structure in which the benzene ring and the benzene ring of the triphenylmethane structure are connected by the structure represented by the formula (II), so that the flexibility of the (A) phenol resin is further increased. The fluidity | liquidity of the phenol resin composition of invention can be improved more.
Specifically, it is preferable that the (A) phenol resin has a structure represented by the following formula (V).

In the formula (IV), R ¹¹ , R ²¹ , R ³¹ , R ¹² , R ²² , and R ³² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group A1-c1 and a2-c2 each independently represent an integer of 0-3.
When a1 is 2 or 3, R ¹¹ may be the same or different.
When b1 is 2 or 3, R ²¹ may be the same or different.
When c1 is 2 or 3, R ³¹ may be the same or different.
When a2 is 2 or 3, R ¹² may be the same or different.
When b2 is 2 or 3, R ²² may be the same or different.
When c2 is 2 or 3, R ³² may be the same or different.
R ⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms in total.

R < ¹¹ >, R <^21> , R <^31> , R < ^{12 >} , R < ²² > and R < ³² > in the formula (V) have the same meanings as R < ¹ > to R < ³ > in the formula (I), and preferred embodiments are also the same.
A1 to c1 and a2 to c2 in the formula (V) have the same meanings as a to c in the formula (I), and preferred embodiments are also the same.
R ⁰ in formula (V) has the same meaning as R ⁰ in formula (II), and the preferred embodiment is also the same.

(A) The structure other than the structure (I), the structure (II), and the structure (III) that can be included in the phenol resin is not particularly limited, and examples thereof include a structure represented by the following formula (I-3). Can be mentioned.
In addition, when * 1 to * 7 of the structure (I-1), the structure (II-1), and the structure (III-1) are the ends of the molecule, hydrogen atoms may be bonded independently. Alternatively, a substituent such as a hydrocarbon group may be bonded.

R ^2, R ³ in the formula (I-3), b, c, * 2 and * 3, R ^2, R ³ in the formula (I-1), b, c, * 2 and * 3 as defined The preferred embodiments are also the same.
R ^{0 in} formula (I-3) has the same meaning as R ⁰ in formula (II-1), and the preferred embodiments are also the same.
(A) The phenol resin has, for example, * 2 or * 3 of structure (I-3), * 4 or * 5 of structure (II-1), or * 6 or * 7 of structure (III-1). It may have a bonded structure.

The component A is obtained by reacting phenols, an aromatic aldehyde, and at least one non-aromatic aldehyde selected from the group consisting of formaldehyde and an aliphatic aldehyde having 2 to 6 carbon atoms in the presence of a sex catalyst. be able to.
The phenols are not particularly limited as long as they have a benzene ring having a hydroxyl group bonded in the molecule, and those used for the production of general phenol resins can be used.
Specific examples of phenols include, for example, phenol, cresol, ethylphenol, xylenol, butylphenol, octylphenol, nonylphenol, phenylphenol, cyclohexylphenol, trimethylphenol, bisphenol A, catechol, resorcinol, hydroquinone, naphthol, pyrogallol and the like. . Phenols may be used alone or in a combination of two or more.
In addition, any isomer may be used as the compound that may have structural isomers such as cresol and ethylphenol. For example, in the case of cresol, any of o-cresol, m-cresol, or p-cresol may be used.
Among these, as phenols, at least one of phenol and cresol is practically preferable.

On the other hand, the aromatic aldehyde to be reacted with phenols is preferably a compound in which a formyl group is directly bonded to an aromatic ring. Examples thereof include hydroxybenzaldehyde and dihydroxybenzaldehyde. An aromatic aldehyde may be used individually by 1 type, and 2 or more types may be mixed and used for it.
When the aromatic aldehyde has a structural isomer, any of the isomers may be used. For example, hydroxy-benzaldehyde may be o-hydroxybenzaldehyde (orthohydroxybenzaldehyde), m-hydroxybenzaldehyde (metahydroxybenzaldehyde), or p-hydroxybenzaldehyde (parahydroxybenzaldehyde). Also good. Of the above isomers, hydroxy-benzaldehyde is preferably o-hydroxybenzaldehyde (orthohydroxybenzaldehyde).
By using hydroxybenzaldehyde as the aromatic aldehyde, (A) the phenol resin has a structure (III-2) in the molecule.

Examples of the non-aromatic aldehyde include formaldehyde, acetaldehyde, paraformaldehyde, propyl aldehyde, butyraldehyde, valeraldehyde, hexyl aldehyde, glyoxal, crotonaldehyde, glutaraldehyde and the like. The said other aldehyde may be used individually by 1 type, and may mix and use 2 or more types.
By using formaldehyde as the non-aromatic aldehyde, the (A) phenol resin has a structure in which R ⁰ in the structure (II) is a hydrogen atom in the molecule.
The amount of the aldehyde used (total of aromatic aldehyde and non-aromatic aldehyde) is 0.2 mol to 1.0 mol, preferably 0.3 mol to 0.9 mol, per 1 mol of the total amount of phenols. It is desirable to use at a molar ratio.
When the amount of aldehyde (the sum of aromatic aldehyde and non-aromatic aldehyde) used is 0.2 mol or more, the phenolic monomer hardly remains and the reaction efficiency tends to be improved. It can suppress that the molecular weight of the phenol resin obtained becomes high because the usage-amount of an aldehyde (total of an aromatic aldehyde and another aldehyde) is 1.0 mol or less.
Hereinafter, aromatic aldehydes and other aldehydes are collectively referred to as “aldehydes”.
The ratio of the aromatic aldehyde in the aldehyde is preferably 20 to 70 mol%, more preferably 30 to 60 mol%.
30-80 mol% is preferable and, as for the ratio of the non-aromatic aldehyde in an aldehyde, More preferably, it is 40-70 mol%. (A) It is desirable to use a non-aromatic aldehyde at a ratio of 0.1 to 0.2 mol with respect to a total of 1 mol of phenols used in the phenol resin.

Any acidic catalyst may be used as long as it is used in the production of a general novolak-type phenol resin, and examples thereof include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and oxalic acid. An acidic catalyst may be used individually by 1 type, and may mix and use 2 or more types.
The amount of the acidic catalyst used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and still more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the phenols. 5 parts by mass.

There is no particular limitation on the method of reacting phenols with aldehyde. For example, phenols, aldehydes and acids are charged and reacted together, or phenols and acids are charged and aldehydes are reacted at a predetermined reaction temperature. The method of adding is mentioned.
At this time, reaction temperature is good to carry out in the range of 30 to 150 degreeC.
When the reaction temperature is 30 ° C. or higher, the progress of the reaction is unlikely to be delayed, and the remaining unreacted phenols can be suppressed. Moreover, the production | generation of a high molecular weight component can be suppressed because reaction temperature is 150 degrees C or less.
There is no restriction | limiting in particular in reaction time, What is necessary is just to adjust with the quantity of aldehyde and a catalyst, and reaction temperature.
In the reaction, an organic solvent may be used.
Examples of such organic solvents include alcohols such as propyl alcohol and butanol, glycols such as ethylene glycol and propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and butylene. Glycol ethers such as glycol monomethyl ether, butylene glycol monoethyl ether, butylene glycol monopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, propyl acetate, butyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Esters such as acetate, ethers such as 1,4-dioxane Etc. are alone, or in combination of two or more can be used.
The organic solvent can be used so that the total amount of phenols and aldehyde is preferably 100 parts by mass to 1,000 parts by mass, and more preferably about 0 to 100 parts by mass. .
After the reaction, the condensed water may be removed by distillation or, if necessary, the remaining catalyst may be removed by washing with water.
Furthermore, unreacted phenols and unreacted aldehydes may be removed by distillation under reduced pressure or steam distillation.
(A) The weight average molecular weight of the phenol resin is preferably 280 to 5000, more preferably 320 to 4000, and more preferably 350 to 4000, from the viewpoint of the balance between fluidity and heat resistance of the thermosetting resin composition. More preferably, it is 3500.
As specific measurement conditions for GPC, for example,
Column: Trade name “KF-801 + KF-802 + KF-802 + KF-803” (Showa Denko, Shodex (registered trademark) series)
Detector: Trade name “RI-71” (manufactured by Showa Denko KK, differential refractometer “Shodex” (registered trademark))
Solvent: tetrahydrofuran flow rate: 1 ml / min.

[(B) Hydroxyflavan compound represented by formula (IV)]
The phenol resin composition of the present invention contains 20% by mass to 70% by mass of (B) a hydroxyflavan compound represented by the formula (IV) (hereinafter also referred to as component B).

In the formula (IV), R ⁴ , R ⁷ and R ⁸ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aralkyl group or an aryl group having 7 to 13 carbon atoms. R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or an aryl group.
However, R ⁵ and R ⁶ may be bonded to each other, or R ⁷ and R ⁸ may be bonded to each other to form a ring.
W ¹ , X ¹ , Y ¹ and Z ¹ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyalkyl having 1 to 10 carbon atoms. Represents a group, and the benzene ring to which W ¹ , X ¹ , Y ¹ and Z ¹ are bonded has one or two hydroxyl groups.
W ² , X ² , Y ² and Z ² are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyalkyl having 1 to 10 carbon atoms. Represents a group, and the benzene ring to which W ² , X ² , Y ² and Z ² are bonded has one or two hydroxyl groups.

In formula (IV), the alkyl group represented by R ^{4 to} R ⁸ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an i-propyl group, Examples thereof include t-butyl group and n-hexyl group. As for carbon number, it is more preferred that it is 1-5, and it is still more preferred that it is 1-3.

In formula (IV), the cycloalkyl group represented by R ^{4 to} R ⁸ preferably has 5 to 10 carbon atoms, and examples thereof include a cyclohexyl group and a cyclooctyl group. As for carbon number, it is more preferred that it is 5-8, and it is still more preferred that it is 6-8.

In the formula (IV), the aralkyl group represented by R ^{4 to} R ⁸ preferably has 7 to 13 carbon atoms, and examples thereof include a phenylmethyl group, a phenylethyl group, and naphthylmethyl. As for carbon number, it is more preferred that it is 7-12, and it is still more preferred that it is 7-11.

In the formula (IV), the aryl group represented by R ^{4 to} R ⁸ preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. As for carbon number, it is more preferred that it is 6-12, and it is still more preferred that it is 6-10.
In the formula (IV), the alkyl group, cycloalkyl group, aralkyl group and aryl group represented by R ^{4 to} R ⁸ may further have a substituent such as an alkyl group or a halogen atom.
Among these, R ⁴ , R ⁷ and R ⁸ are preferably alkyl groups, and R ⁵ and R ⁶ are preferably hydrogen atoms.

Wherein ^{(IV), W 1, X} 1, the alkyl group represented by Y ¹ and Z ¹ and W ^2, X ^2, Y ² and Z ^2, a straight or branched An alkyl group is preferable, and examples thereof include a methyl group, an ethyl group, an i-propyl group, a t-butyl group, and an n-hexyl group. As for carbon number, it is more preferred that it is 1-5, and it is still more preferred that it is 1-3.

Wherein ^{(IV), W 1, X} 1, Y 1 and Z ¹ and W ^2, X ^2, Y ² and the alkyl group moiety of the alkoxy group represented by Z ² can be linear, branched For example, methyl group, ethyl group, i-propyl group, t-butyl group, n-hexyl group and the like can be mentioned. As for carbon number of an alkoxy group, it is more preferable that it is 1-5, and it is still more preferable that it is 1-3.

In Formula (IV), even W ^1, X ^1, Y ¹ and Z ¹ and W ^2, X ^2, alkylene moiety of the hydroxyalkyl group represented by Y ² and Z ² is a linear, branched For example, a heptylene group, octylene, etc. are mentioned.

In formula ^{(IV), W 1, X} 1, Y 1 and Z ¹ and W ^2, represented by X ^2, Y ² and Z ^2, alkyl group, the alkyl group moiety of the alkoxy group, and an alkylene hydroxyalkyl group The group portion may further have a substituent such as an alkyl group or a halogen atom.
Among the ^{above, W 1, X 1, Y} 1 and Z ¹ and W ^2, X ^2, Y ² and Z ² are a hydrogen atom, a hydroxyl group, and the alkyl group is preferably a hydrogen atom and a hydroxyl group are more preferred.

Although the manufacturing method in particular of B component is not restrict | limited, For example, B component can be obtained by making phenols and a ketone compound react under acidity.
The ketone compound is not particularly limited, and examples thereof include acetone and methyl ethyl ketone. Among these, acetone is preferable.
Moreover, the compound shown by following formula (i) is mentioned as phenols which can be used for manufacture of B component.

  In formula (i), W, X, Y and Z are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. The benzene ring represented by formula (i) represents a hydroxyalkyl group and has one or two hydroxyl groups. Further, W, X, Y and Z may be bonded to each other to form a ring.

  In formula (i), the alkyl group represented by W, X, Y and Z is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or i-propyl. Group, t-butyl group, n-hexyl group and the like. As for carbon number, it is more preferred that it is 1-5, and it is still more preferred that it is 1-3.

  In the formula (i), the alkyl group part of the alkoxy group represented by W, X, Y and Z may be linear or branched. For example, a methyl group, an ethyl group, i -Propyl group, t-butyl group, n-hexyl group and the like. As for carbon number of an alkoxy group, it is more preferable that it is 1-5, and it is still more preferable that it is 1-3.

  In formula (i), the alkylene group part of the hydroxyalkyl group represented by W, X, Y and Z may be linear or branched, and examples thereof include a heptylene group and octylene. It is done.

In formula (i), the alkyl group, the alkyl group part of the alkoxy group and the alkylene group part of the hydroxyalkyl group represented by W, X, Y and Z further have a substituent such as an alkyl group or a halogen atom. You may do it.
In addition, when W, X, Y and Z are bonded to each other to form a ring to form a ring, for example, when W is an alkyl group and is an X alkoxy group, they are bonded to each other to form a cycloether. The aspect to form is mentioned.

The compound represented by the formula (i) may be any compound that can be used for the production of a general phenol resin. For example, phenol, orthocresol, metacresol, paracresol, orthoethylphenol, metaethylphenol, Paraethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,5-xylenol, 2,6-xylenol, orthobutylphenol, metabutylphenol, parabutylphenol, orthooctylphenol, metaoctylphenol, para Octylphenol, orthononylphenol, methanonylphenol, paranonylphenol, orthophenylphenol, metaphenylphenol, paraphenylphenol, orthocyclohexylphenol, meta B hexyl phenol, p-cyclohexyl phenol, catechol, resorcinol, 2-methyl resorcinol, 5-methyl resorcinol, and hydroquinone.
As the compound represented by the formula (i), one kind may be used alone, or two or more kinds may be mixed and used. Of these, resorcinol is preferable in terms of excellent reactivity with ketone compounds, particularly acetone.

  The amount of the ketone compound, particularly acetone, is preferably 15 parts by mass to 250 parts by mass, more preferably 25 parts by mass to 150 parts by mass with respect to 100 parts by mass of the phenols.

In the production of the component B, it is preferable to use an acidic catalyst in order to cause the phenol and the ketone compound to react under acidic conditions.
Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, oxalic acid and the like. An acidic catalyst may be used individually by 1 type, and may mix and use 2 or more types. The amount of the acidic catalyst used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and still more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the phenols. 5 parts by mass.

The reaction method of phenols and ketone compounds is not particularly limited. For example, 1) a method in which phenols, ketone compounds, and acidic catalysts are charged and reacted in a lump; 2) phenols and catalysts are charged, and at a predetermined temperature. Examples include a method of reacting by dropping a ketone compound after reacting in advance.
There is no restriction | limiting in particular also in reaction time, What is necessary is just to adjust with the quantity of a ketone compound and a catalyst, and reaction temperature. After the reaction, unreacted ketone compound and condensed water may be removed by distillation, or the product may be washed with water as necessary to remove residual catalyst and unreacted phenols from the product. Further, unreacted phenols may be removed from the product by distillation under reduced pressure or steam distillation.

  (B) The hydroxyflavan compound (component B) represented by the formula (IV) preferably has a structure represented by the following formula (ii), preferably a reaction product of resorcinol and a ketone compound. A structure represented by the formula (iii) is more preferable.

In formula (ii), R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms, h and e represent an integer of 0 to 3, and f and g represent an integer of 1 or 2. Show.
In formula (ii), the alkyl group having 1 to 10 carbon atoms represented by R ⁹ and R ¹⁰ may be linear or branched. For example, a methyl group, an ethyl group, i -Propyl group, t-butyl group, n-hexyl group and the like. As for carbon number, it is more preferred that it is 1-5, and it is still more preferred that it is 1-3.
h and e are each independently preferably 0 or 1, and more preferably 0.
f and g are preferably 1.

  By using resorcinol as the phenol and acetone as the ketone in the reaction between the phenol and the ketone compound, a hydroxyflavan compound having a structure represented by the above formula (iii) is obtained. When the purity of the hydroxyflavan compound having the structure represented by the formula (iii) is high, a crystal having a melting point exceeding 200 ° C. is obtained.

In the phenol resin composition of this invention, 30 mass%-80 mass% of (A) triphenylmethane frame containing phenol resin (A component) is included with respect to the total mass of a phenol resin composition, and (B) Formula (IV) 20% by mass to 70% by mass of a hydroxyflavan compound (component B) represented by
When the content of the B component in the phenol resin composition exceeds 70% by mass, the softening point of the phenol resin composition becomes too high, which is not preferable. On the other hand, when the content of the component B in the phenol resin composition is less than 20% by mass, the water resistance of the cured product of the thermosetting resin composition containing the phenol resin composition and the epoxy resin becomes insufficient, which is preferable. Absent.
When the content of the component A in the phenol resin composition exceeds 80% by mass, the water resistance of the cured product of the thermosetting resin composition becomes insufficient, which is not preferable. Moreover, since the effect which suppresses crystallization of B component will become inadequate when content in the phenol resin composition of A component becomes less than 30 mass%, it is unpreferable.
If the content of component A and component B in the phenol resin composition of the present invention is within the above range, the phenol resin composition further includes a phenol novolak resin, a cresol novolak resin, a phenol aralkyl resin, a biphenyl aralkyl resin, Other phenol resins such as naphthol novolak resin and naphthol aralkyl resin may be contained.

In the phenol resin composition of the present invention, the A component and the B component can be blended separately. However, since the B component has a high melting point and softening point, respectively, the A component and the B component in advance in an organic solvent. After mixing and dissolving, the organic solvent is preferably used after removal.
In that case, the compounding ratio of A component, B component, and other phenol resin is adjusted so that the softening point of the obtained mixture (phenol resin composition) may be 125 degrees C or less.
The phenol resin (A) contained in the phenol resin composition of the present invention has a structure (I), a structure (II), and a structure (III), so that it has excellent flexibility and lowers the softening point of the phenol resin composition. can do. Since the softening point of the phenol resin composition is small (125 ° C. or lower), fluidity can be provided to the phenol resin composition and the thermosetting resin composition containing the phenol resin composition.
The softening point of the phenol resin composition is more preferably 70 ° C. to 120 ° C., further preferably 80 ° C. to 110 ° C., and still more preferably 88 ° C. to 105 ° C.
The phenol resin composition preferably has a melt viscosity at 150 ° C. of 200 mPa · s to 2000 mPa · s, more preferably 250 mPa · s to 1700 mPa · s, and more preferably 280 mPa · s to 1400 mPa · s. More preferably.

<Thermosetting resin composition>
The thermosetting resin composition of the present invention includes a phenol resin composition and an epoxy resin.
That is, the thermosetting resin composition of the present invention comprises (A) a phenol resin having the structure (I), the structure (II), and the structure (III) described above, and (B) the formula (IV) described above. The content of the (A) phenol resin is 30% by mass to 80% by mass with respect to a total of 100% by mass of the (A) phenol resin and (B) the hydroxy flavan compound. And the content of the (B) hydroxyflavan compound is 20% by mass to 70% by mass.
The thermosetting resin composition of the present invention may further contain a filler or the like as necessary.

It does not specifically limit as an epoxy resin which the thermosetting resin composition of this invention can contain, A well-known epoxy resin can be used. Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type Epoxy resins derived from dihydric phenols such as epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane Type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, na Tall novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolak type epoxy resin Examples thereof include an epoxy resin derived from a trivalent or higher valent phenol such as a resin, an epoxy resin modified with an organic phosphorus compound, and the like.
Among these, triphenylmethane type epoxy resin is preferable. Moreover, these epoxy resins may be used independently and may use 2 or more types together.
The weight average molecular weight of the epoxy resin is preferably 300 to 5000, more preferably 400 to 3500, and more preferably 400 to 3000 from the viewpoint of the balance between fluidity and heat resistance of the thermosetting resin composition. More preferably.
As specific measurement conditions for GPC, for example,
Column: Trade name “KF-801 + KF-802 + KF-802 + KF-803” (Showa Denko, Shodex (registered trademark) series)
Detector: Trade name “RI-71” (manufactured by Showa Denko KK, differential refractometer “Shodex” (registered trademark))
Solvent: tetrahydrofuran flow rate: 1 ml / min.

  What is necessary is just to determine the mixing ratio of an epoxy resin and a phenol resin composition from the hydroxyl equivalent of a phenol resin composition with respect to 1.0 equivalent of epoxy groups of an epoxy resin. The hydroxyl group of the phenol resin composition with respect to 1.0 equivalent of the epoxy group of the epoxy resin is preferably in the range of 0.6 equivalents to 1.2 equivalents, more preferably in the range of 0.7 equivalents to 1.1 equivalents. is there.

The total amount of the A component, the B component, and the epoxy resin in the thermosetting resin composition of the present invention is preferably 35% by mass or less, more preferably based on the total mass of the thermosetting resin composition. It is 10 mass%-20 mass%.
The ratio of the total amount of the component A, the component B and the epoxy resin in the total resin contained in the thermosetting resin composition of the present invention is preferably 80% by mass or more with respect to the mass of the total resin. More preferably, it is 90 mass% or more, More preferably, it is 100 mass%.

The thermosetting resin composition of the present invention may contain a curing accelerator as necessary for the purpose of accelerating the curing reaction of the thermosetting resin composition.
Examples of the curing accelerator include imidazole compounds, organic phosphorus compounds, secondary amine compounds, tertiary amine compounds, organic acid metal salts such as tin octylate, Lewis acids, amine complex salts, and the like. . These may be used alone or in combination of two or more.

  Examples of imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-hepta. Decylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4- Examples include methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, and 2-phenyl-4-methylimidazoline.

The imidazole compound may be masked with a masking agent.
Examples of the masking agent include acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, and melamine acrylate.

  Examples of organophosphorus compounds include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, tetra And phenylphosphonium tetraphenylborate.

Secondary amine compounds include morpholine, piperidine, pyrrolidine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dibenzylamine, dicyclohexylamine, N-alkylarylamine, piperazine, diallylamine, thiazoline, thiol. Examples include morpholine.
Examples of the tertiary amine compound include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, and 2,4,6-tris (diaminomethyl) phenol.

  In addition, the thermosetting resin composition of the present invention can be used in various ways such as a thermosetting resin and a thermoplastic resin, a pigment, a silane coupling agent, and a release agent used as a filler and a modifier as necessary. It can contain the compounding agent of.

Among these, for example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, aluminum hydroxide And inorganic fillers such as magnesium hydroxide.
The fused silica can be used in either crushed or spherical shape, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical one. . Furthermore, in order to increase the blending amount of the spherical silica into the thermosetting resin composition, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The desirable range of the blending ratio of the fused silica varies depending on the application and desired characteristics of the thermosetting resin composition. For example, when the thermosetting resin composition is used for semiconductor encapsulant application, the blending ratio of fused silica is higher in view of the linear expansion coefficient and flame retardancy of the cured product of the thermosetting resin composition. Is preferred. Specifically, 65 mass% or more is preferable with respect to the thermosetting resin composition whole quantity, More preferably, it is about 80 mass%-about 90 mass%.
Moreover, when using a thermosetting resin composition for uses, such as an electrically conductive paste and an electrically conductive film, electroconductive fillers, such as silver powder and copper powder, can be used as a filler.

As the thermosetting resin and the thermoplastic resin used as the modifier, various known ones can be used.
Examples of the thermosetting resin and thermoplastic resin include phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether resin, polyphenylene sulfide resin, polyester resin, polystyrene resin, polyethylene terephthalate resin, and the like. Can be used as long as it does not impair the effects of the present invention.

Examples of the silane coupling agent include silane coupling agents such as amino silane compounds, vinyl silane compounds, styrene silane compounds, and methacryl silane compounds.
Examples of the mold release agent include stearic acid, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, and carnauba wax.

  When the thermosetting resin composition of the present invention contains a filler, the total amount of the component A, the component B and the epoxy resin is preferably 35% by mass or less with respect to the total mass of the thermosetting resin composition. Yes, more preferably 10% by mass to 20% by mass.

The thermosetting resin composition of the present invention containing the phenolic resin composition of the present invention having excellent fluidity and the epoxy resin has excellent fluidity, and is cured to have heat resistance, moisture resistance, and adhesion. A cured product having excellent properties can be obtained.
In particular, the thermosetting resin composition of the present invention is a resin composition for an electronic component sealing material, a resin composition for a printed circuit board, a resin composition for an interlayer insulating material used for a printed circuit board and a copper foil with a resin, a conductive material Can be suitably used for conductive pastes, paints, adhesives and composite materials containing a conductive filler. If an inorganic filler is used in the thermosetting resin composition of the present invention, a cured product having excellent flame retardancy can be obtained without using a halogen-based flame retardant. Therefore, the thermosetting resin composition of the present invention is also useful as an environmentally friendly epoxy resin composition.

<Hardened product>
The cured product of the present invention is obtained by curing the thermosetting resin composition of the present invention.
The curing method of the thermosetting resin composition is not particularly limited, and for example, the thermosetting resin composition may be heated under the conditions of a heating temperature of 170 ° C. to 250 ° C. and a heating time of 60 minutes to 20 hours. The heating temperature is more preferably 170 ° C to 220 ° C, and further preferably 170 ° C to 200 ° C. The heating time is more preferably 60 minutes to 10 hours, and still more preferably 90 minutes to 8 hours.

The cured product of the present invention has a high glass transition temperature and is excellent in heat resistance.
Here, the glass transition temperature of the cured product of the present invention is preferably 170 ° C to 250 ° C, more preferably 180 ° C to 240 ° C, and further preferably 190 ° C to 230 ° C.
Moreover, it is preferable that the bending strength measured by the method based on JISK-6911 is 120 MPa-180 MPa, it is more preferable that it is 130 MPa-170 MPa, and the hardened | cured material of this invention is 134 MPa-160 MPa. Is more preferable. The bending strength may be measured, for example, using a test piece having a length of 90 mm, a height of 4 mm, and a width of 10 mm, and a fulcrum distance of 64 mm.

The hardened | cured material of this invention is excellent in the adhesiveness with respect to various members, for example, metals, such as copper.
For example, the cured product obtained by applying and curing the thermosetting resin composition of the present invention on copper has a compressive shear strength measured by a method according to JIS K-6852 of 3.6 MPa or more. Preferably, it is 4.0 MPa or more, more preferably 5.0 MPa or more. The upper limit of the compression shear strength is not particularly limited, but is, for example, 10 MPa.

Even when the cured product of the present invention is placed in a high-temperature and high-humidity environment having a temperature of 121 ° C. and a humidity of 100%, for example, it is difficult to absorb water, so the water absorption rate is low and the moisture resistance is excellent. The water absorption rate of the cured product is calculated from the mass (a) of the cured product before placing the cured product in a high-temperature and high-humidity environment and the mass (b) of the cured product after placing it in a high-temperature and humid environment. It is measured as a mass increase rate [% by mass] of the cured product.
The water absorption rate of the cured product of the present invention when left for 20 hours in an environment of temperature 121 ° C. and humidity 100% is preferably 0.49% by mass or less, and 0.47% by mass or less. Is more preferable, and it is still more preferable that it is 0.44% or less. The smaller the water absorption of the cured product, the better.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In the examples and comparative examples, “%” is based on mass unless otherwise specified.

Synthesis Example 1 (Synthesis of hydroxyflavan compound B)
A flask equipped with a condenser and a stirrer was charged with 100 g of resorcinol, 26 g of acetone, and 0.1 g of paratoluenesulfonic acid, and reacted at 80 ° C. for 2 hours. Next, 78 g of acetone was added to the reaction solution and reacted at 80 ° C. for 5 hours. Subsequently, the product was washed 4 times with 100 g of pure water, and the catalyst and unreacted resorcinol were removed from the product to obtain component b ′. Next, 95 g of acetone was added to the product to dissolve the product, and 220 g of an acetone solution (component b) of hydroxyflavan compound B having a solid content of 50% was obtained.
When the structural formula of the obtained hydroxyflavan compound B was confirmed by ¹ H-NMR, R ⁴ , R ⁷ and R ⁸ in formula (IV) were methyl groups, and R ⁵ , R ⁶ , W ¹ and Y ^1. , Z ¹ , X ² , and Z ² are hydrogen atoms, and X ¹ and X ² are hydroxyl groups, that is, a structure represented by the formula (iii).

Synthesis Example 2 (Synthesis of phenol resin A1 having a triphenylmethane structure)
A flask equipped with a condenser and a stirrer was charged with 100 g of phenol, 19.5 g of orthohydroxybenzaldehyde, 12.9 g of 37% formalin, and 0.1 g of paratoluenesulfonic acid, and reacted at 120 ° C. for 5 hours. The product was then washed 4 times with pure water to remove the catalyst from the product. Next, the distillate was removed from the product under reduced pressure at 180 ° C. and 50 mmHg to obtain 60 g of a reddish brown block phenol resin. 60 g of the obtained phenol resin was dissolved in 60 g of acetone to obtain a phenol resin A1 solution (component a1) having a resin content of 50%.
When the structural formula of the obtained phenol resin A1 was confirmed by ¹ H-NMR, it had the structure (I), the structure (II), and the structure (III-2), and R ^{1 to} R ³ in the formula (I). Is a hydrogen atom, a to c are each 0, and R ⁰ in formula (II) is a hydrogen atom.

Synthesis Example 3 (Synthesis of phenol resin A2 having a triphenylmethane structure)
In Synthesis Example 2, except that 100 g of phenol was changed to 100 g of orthocresol, 19.5 g of orthohydroxybenzaldehyde was changed to 16.9 g, and 12.9 g of 37% formalin was changed to 11.3 g, 58 g of a phenol resin was obtained.
Next, 58 g of the obtained phenol resin was dissolved in 58 g of acetone to obtain a phenol resin A2 solution (component a2) having a resin content of 50%.
When the structural formula of the obtained phenol resin A2 was confirmed by ¹ H-NMR, it had the structure (I), the structure (II), and the structure (III-2), and R ¹ and R ² in the formula (I) And R ³ are a hydrogen atom, a methyl group, and a methyl group, a, b, and c are 0, 1, and 1, respectively, and R ⁰ in formula (II) is a hydrogen atom. I understood it.

Comparative Synthesis Example 1 (Synthesis of phenol resin C)
A flask equipped with a condenser and a stirrer was charged with 100 g of phenol, 65 g of orthohydroxybenzaldehyde, and 1 g of paratoluenesulfonic acid, and reacted at 100 ° C. for 8 hours. Next, the product was washed 4 times with 100 g of pure water to remove the catalyst from the product. Subsequently, the distillate was removed from the product under reduced pressure at 180 ° C. and 50 mmHg to obtain 96 g of phenol resin C (component c ′).
Next, 96 g of the obtained phenol resin C (component c ′) was dissolved in 96 g of acetone to obtain a phenol resin C solution (component c) having a resin content of 50%.
When the structural formula of the obtained phenol resin C was confirmed by ¹ H-NMR, it had a structure (I) and a structure (III-2), and R ^{1 to} R ³ in the formula (I) were each a hydrogen atom. It was found that the structures a to c were 0. Phenol resin C did not have structure (II).

Comparative Synthesis Example 2 (Synthesis of phenol resin D)
A flask equipped with a condenser and a stirrer was charged with 100 g of phenol, 60 g of 37% formalin, and 1 g of oxalic acid, and reacted at 100 ° C. for 5 hours. Thereafter, the distillate was removed from the product under reduced pressure at 180 ° C. and 50 mmHg to obtain 84 g of phenol resin D (component d ′).
Subsequently, 84 g of the obtained phenol resin D (component d ′) was dissolved in 84 g of acetone to obtain a phenol resin D solution (component d) having a resin content of 50%.
When the structural formula of the obtained phenol resin C was confirmed by ¹ H-NMR, it was found that it had a structure (II) and R ⁰ in the formula (II) was a hydrogen atom. The phenol resin D did not have the structure (I) and the structure (III).

  Table 1 shows the raw material compositions used in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 and 2.

Examples 1 to 5 (phenol resin compositions AB1 to AB5)
After mixing component a1 (resin A1 solution) or component a2 (resin A2 solution) and component b (compound B solution) with the composition shown in Table 2, the solvent was removed from the mixture under reduced pressure at 150 ° C. and 50 mmHg. Acetone was distilled off to obtain brown lump-like phenol resin compositions AB1 to AB5 in the yields shown in Table 2. In Table 2, the column “(A) / (B) ratio” indicates the ratio of the resin A1 to the compound B or the ratio of the resin A2 to the compound B as a solid content ratio.

Comparative Examples 1 and 2 (phenolic resin compositions BC and BD)
After mixing component c (resin C solution) or component d (resin D solution) and component b (compound B solution) with the composition shown in Table 2, the product was distilled from the product under a reduced pressure of 150 ° C. and 50 mmHg. The fraction was removed, and the yielded brown lump phenol resin compositions BC and BD shown in Table 2 were obtained. In the column indicated as “(A) / (B) ratio” in Table 2, the ratio of the resin C to the compound B (the ratio indicated by * 1 in Table 2) in Comparative Examples 1 and 2, The ratio of the resin D to the compound B (the ratio indicated by * 2 in Table 2) is shown as a solid content ratio.

Table 2 shows the component compositions and characteristic values of the phenol resin compositions obtained in Examples 1 to 5, Comparative Example 1 and Comparative Example 2.
The analysis method of a phenol resin composition is as follows.

(1) Softening point (° C)
The measurement was performed using a gas phase softening point measuring apparatus EX-719PD manufactured by Elex Scientific. The heating rate was 2.5 ° C./min.
(2) Melt viscosity (mPa · s)
The melt viscosity at 150 ° C. of the phenol resin composition was measured using an ICI viscometer manufactured by Research Equip.
Used cone plate: 19.5φ, for 0-40

  From Table 2, since the phenol resin compositions AB1 to AB5 of the present invention have a low softening point and a low melt viscosity as compared with the phenol resin compositions BC and BD of Comparative Examples 1 and 2, they may be excellent in fluidity. Recognize.

Examples 6-12 and Comparative Examples 3-9
(Preparation of thermosetting resin composition)
The phenol resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 2, and the component a1 (resin A1 solution) and the component a2 (resin A2) obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 2 A thermosetting resin composition was obtained using each of solution, component b ′ (compound B), component c ′ (resin C), and component d ′ (resin D). Specifically, the components shown in the “component (i)” column of Table 3 and the components shown in the “component (ii)” column were melt-kneaded in the following manner with the formulation shown in Table 3, and Example 6 -12 and the thermosetting resin composition of Comparative Examples 3-9 were obtained.
The formulation in Table 3 was performed as follows.
To the amount (10 g) of the epoxy resin shown in Table 3, the components shown in the “Component (i)” column were mixed so that the hydroxyl group / epoxy group (mol) ratio shown in Table 3 was obtained, and 0.1 g of triphenyl was mixed. A resin component was obtained by adding phosphine (curing accelerator). Next, fused silica (inorganic filler, manufactured by Tatsumori Co., Ltd., MSR-2212) is mixed with the obtained resin component so that the content in the thermosetting composition is 80%, and two rolls ( A thermosetting resin composition was prepared by kneading for 5 minutes at 100 ° C. with NS-155 (S-type, manufactured by Nishimura Machinery Co., Ltd.).

(3) Adhesiveness About the obtained thermosetting resin composition, the adhesiveness of the hardened | cured material of a thermosetting resin composition and copper was measured with the following method.
The thermosetting resin composition was applied in the range of 10 mm × 14 mm to the surface of a 10 mm × 26 mm × 8 mm copper block. A block of copper of the same size is stacked so that the uncoated part of this block is exposed, and the thermosetting resin composition is cured by pressing at 180 ° C. for 60 minutes and a pressure of 30 kg / cm ² to obtain a test piece. It was. Using this test piece, the compressive shear strength was measured by a method based on JIS K-6852, and used as an index of the adhesiveness of the cured product of the thermosetting resin composition.

Evaluation of Glass Transition Temperature, Water Absorption Rate, and Bending Strength The obtained thermosetting resin composition was molded by pressing with a mold at 150 ° C. for 30 minutes under a pressure of 30 kg / cm ² . Then, it heated at 180 degreeC for 5 hours, the thermosetting resin composition was hardened, and the test piece was created.
The glass transition temperature, water absorption, and bending strength of the obtained test piece were evaluated by the following methods.
(4) Glass transition temperature (Tg)
Glass transition temperature was measured by TMA method (Thermo Mechanical Analysis method) using SSC / 5200 manufactured by SII. The shape of the test piece was 10 mm long × 4 mm high × 10 mm wide. The heating rate was 10 ° C./min.
(5) Water absorption rate Using a unsaturated high acceleration life test apparatus PC-422R8 manufactured by Hirayama Seisakusho Co., Ltd., the test piece was held at a temperature of 121 ° C. and a humidity of 100% for 20 hours. The mass increase rate (water absorption rate) before and after holding the test piece was measured. The shape of the test piece was 90 mm long × 4 mm high × 10 mm wide. The smaller the mass increase rate, the better the moisture resistance.
(6) Bending strength It measured by the method based on JIS K-6911. The shape of the test piece was 90 mm long × 4 mm high × 10 mm wide, and was measured at a fulcrum distance of 64 mm.
Table 3 shows the measurement results of glass transition temperature, water absorption, and bending strength for Examples 6 to 12 and Comparative Examples 3 to 9.

The details of the components shown in * 1 to * 3 in Table 3 are as follows.
* 1 Made by Mitsubishi Chemical Corporation, triphenylmethane type epoxy resin, trade name 1032H60 (weight average molecular weight 1000)
* 2 Wako Pure Chemical Industries, Ltd. * 3 Tatsumori, trade name MSR-2212

From Table 3, the hardened | cured material of the thermosetting resin composition of Examples 6-12 expresses high adhesiveness and high moisture resistance compared with the hardened | cured material of the thermosetting resin composition of Comparative Examples 3-9. I understood. That is, the adhesiveness of the cured product to copper has an adhesive strength more than twice that of the cured product of the comparative example, and it was found that the adhesiveness is much higher than that of the comparative example. Moreover, it turned out that the hardened | cured material of an Example has moisture resistance lower than the hardened | cured material of a comparative example, and was superior to the comparative example.
Moreover, since the thermosetting resin composition of Examples 6-12 was comprised including the phenol resin composition excellent in the fluidity obtained in Examples 1-5, it was excellent in fluidity | liquidity.
As described above, the cured products of the thermosetting resin compositions of Examples 6 to 12 have heat resistance equivalent to that of the cured products of Comparative Examples 3 to 9, but also moisture resistance and adhesion to metal. outstanding.

  Since the phenol resin composition of the present invention has good fluidity, the thermosetting resin composition of the present invention including the phenol resin composition also has good fluidity. Moreover, the cured product of the thermosetting resin composition of the present invention has good heat resistance, moisture resistance, and adhesion to metal. Therefore, specifically, a resin composition for an electronic component sealing material, a resin composition for a printed circuit board, a resin composition for an interlayer insulating material used for a printed circuit board and a copper foil with resin, a conductive paste (conductive filler) Containment), paints, adhesives and composite materials.

Claims (16)

(A) 30% by mass to 80% by mass of a phenol resin having a structure represented by the following formula (I), a structure represented by the following formula (II), and a structure represented by the following formula (III);
(B) 20% by mass to 70% by mass of a hydroxyflavan compound represented by the following formula (IV);
A phenolic resin composition comprising:

[In Formula (I), R < ¹ > -R < ³ > represents a C1-C10 alkyl group, a C1-C10 alkoxy group, or a hydroxyl group each independently, and a-c are respectively independently, Represents an integer of 0 to 3;
When a is 2 or 3, R ¹ may be the same or different.
When b is 2 or 3, R ² may be the same or different.
When c is 2 or 3, R ³ may be the same or different.
In the formula (II), R ⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Wherein (III), R ^m represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group, d represents an integer of 0 to 3. When d is 2 or 3, R ^m may be the same or different.
In the formula (IV), R ⁴ , R ⁷ and R ⁸ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aralkyl group or an aryl group having 7 to 13 carbon atoms. R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or an aryl group.
However, R ⁵ and R ⁶ may be bonded to each other, or R ⁷ and R ⁸ may be bonded to each other to form a ring.
W ¹ , X ¹ , Y ¹ and Z ¹ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyalkyl having 1 to 10 carbon atoms. Represents a group, and the benzene ring to which W ¹ , X ¹ , Y ¹ and Z ¹ are bonded has one or two hydroxyl groups.
W ² , X ² , Y ² and Z ² are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyalkyl having 1 to 10 carbon atoms. Represents a group, and the benzene ring to which W ² , X ² , Y ² and Z ² are bonded has one or two hydroxyl groups. ] The phenol resin composition according to claim 1, wherein the (A) phenol resin has a structure represented by the following formula (V).

[In Formula (V), R ¹¹ , R ²¹ , R ³¹ , R ¹² , R ²² , and R ³² are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or A hydroxyl group is represented, and a1 to c1 and a2 to c2 each independently represent an integer of 0 to 3.
When a1 is 2 or 3, R ¹¹ may be the same or different.
When b1 is 2 or 3, R ²¹ may be the same or different.
When c1 is 2 or 3, R ³¹ may be the same or different.
When a2 is 2 or 3, R ¹² may be the same or different.
When b2 is 2 or 3, R ²² may be the same or different.
When c2 is 2 or 3, R ³² may be the same or different.
R ⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms in total. ]   The phenol resin composition according to claim 1 or 2, wherein the softening point is 125 ° C or lower.   The product obtained by the reaction of the phenol resin (A) with at least one non-aromatic aldehyde selected from the group consisting of phenols, aromatic aldehydes, formaldehyde and aliphatic aldehydes having 2 to 6 carbon atoms The phenol resin composition according to any one of claims 1 to 3.   The phenol resin composition according to claim 4, wherein the aromatic aldehyde is orthohydroxybenzaldehyde and the non-aromatic aldehyde is formaldehyde.   The phenol resin composition according to claim 4 or 5, wherein the reaction is performed in the presence of an acidic catalyst.   The phenol is at least selected from the group consisting of phenol, cresol, ethylphenol, xylenol, butylphenol, octylphenol, nonylphenol, phenylphenol, cyclohexylphenol, trimethylphenol, bisphenol A, catechol, resorcinol, hydroquinone, naphthol, and pyrogallol. It is 1 type, The phenol resin composition in any one of Claims 4-6.   The phenol resin composition according to claim 1, wherein the (B) hydroxyflavan compound is a reaction product of resorcinol and a ketone compound.   The phenol resin composition according to claim 8, wherein the ketone compound is acetone. The phenol resin composition according to claim 1, wherein the (B) hydroxyflavan compound is represented by the following formula (iii).

  The weight average molecular weight of said (A) phenol resin is 280-5000, The phenol resin composition in any one of Claims 1-10.   The thermosetting resin composition containing the phenol resin composition in any one of Claims 1-11, and an epoxy resin.   The thermosetting resin composition according to claim 12, wherein the epoxy resin has a weight average molecular weight of 300 to 5,000.   The thermosetting resin composition according to claim 12 or 13, wherein a hydroxyl group of the phenol resin composition is 0.6 equivalents to 1.2 equivalents with respect to 1.0 equivalent of an epoxy group of the epoxy resin.   The thermosetting resin composition according to any one of claims 12 to 14, comprising a filler.   Hardened | cured material obtained by hardening | curing the thermosetting resin composition in any one of Claims 12-15.