JP7389967B2 - Phosphorus-containing active ester, curable resin composition, cured product, prepreg, circuit board, build-up film, semiconductor encapsulant, and semiconductor device - Google Patents

Description

The present invention provides a phosphorus-containing active ester, a curable resin composition containing the phosphorus-containing active ester, a cured product obtained from the curable resin composition, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and Related to semiconductor devices.

Epoxy resin compositions containing epoxy resin and its curing agent as essential components exhibit excellent heat resistance and insulation properties in their cured products, and are therefore widely used in electronic component applications such as semiconductors and multilayer printed circuit boards. .

Among these electronic component applications, in the technical field of insulating materials, in recent years, signals have been increasing in speed and frequency in various electronic devices. However, as the speed and frequency of signals become higher, it is becoming difficult to obtain a low dielectric loss tangent while maintaining a sufficiently low dielectric constant.

Patent Document 1 discloses an epoxy resin composition using polyhydric phenols as a curing agent in order to satisfy low dielectric constant and low dielectric loss tangent (low dielectric properties). However, when a cured product formed from an epoxy resin composition that uses polyhydric phenols as a hardening agent is used for applications such as printed circuit boards (copper-clad laminates), it lacks flexibility and Because of problems such as poor adhesion to copper foil, there is a desire to develop an epoxy resin composition that can provide a cured product that maintains low dielectric properties and has good adhesion.

In addition, from the perspective of environmental protection, there is a need to develop non-halogen flame-retardant printed circuit boards (copper-clad laminates). Development of the composition is underway. However, cured products using epoxy resin compositions containing phosphorus-based flame retardants have low flame retardant efficiency, and when added in large amounts, the flame retardant may migrate to the surface of the cured product, causing a bleed-out phenomenon or copper foil There is a need for a reactive phosphorus-based flame retardant that can be incorporated into the cured product through chemical bonds, as it has problems that affect performance, such as reduced adhesion to the cured product (Non-Patent Document 1).

Japanese Patent Application Publication No. 2004-169021

Network Polymer Vol. 36 No. 5 (2015) pp. 232-238

Therefore, the problem to be solved by the present invention is to provide a phosphorus-containing active ester that can exhibit excellent flame retardancy, low dielectric properties, and adhesion in the obtained cured product, and a phosphorus-containing active ester containing the phosphorus-containing active ester. A curable resin composition, a cured product obtained using the curable resin composition, and a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a curable resin composition using the curable resin composition. Its purpose is to provide semiconductor devices and the like.

In order to solve the above problems, the present inventors have made extensive studies and found that by using a specific phosphorus-containing active ester in a curable resin composition, the resulting cured product has excellent flame retardancy and low dielectric properties. The present inventors have discovered that this material exhibits excellent properties and adhesion, and have completed the present invention.

That is, the present invention has a structure in which a residue (A) of a phosphorus-containing polyhydric alcohol compound and a residue (Q) of an aromatic polyhydric carboxylic acid are bonded via an ester bond, and The present invention relates to a phosphorus-containing active ester whose terminal end is capped with a residue (C) of a monovalent aromatic hydroxyl group-containing compound.

［上記一般式（１）中、Ａは、下記一般式（２）～（４）のいずれかで示される構造であり、Ｒは、それぞれ独立して、直鎖又は分岐鎖のアルキレン基であり、Ｑは、芳香族環であり、ｘは、０．１以上の平均繰り返し数であり、ｙは、１以上の平均繰り返し数であり、ｚは、１以上の平均繰り返し数であり、Ａｒは、下記一般式（５）又は（６）で示される構造であり、

上記一般式（２）～（４）中の♯は、上記一般式（１）中のＡと結合する酸素原子との結合部位を表し、上記一般式（５）及び（６）中の＊は、上記一般式（１）中のＡｒと結合する酸素原子との結合部位を表し、ＲｂおよびＲｃは、それぞれ独立して、アルキル基、アルコキシ基、アリル基、アリール基、アリールオキシ基、アラルキル基、又は、ナフチル基であってもよく、ＲｂおよびＲｃが環状構造を形成してもよい。Ｒａは、それぞれ独立して、ハロゲン原子、アルキル基、アリル基、アルコキシ基、アリール基、アラルキル基、又は、ナフチル基のいずれかであり、ｓは、０～７の整数であり、ｔは、０～５の整数である。］ The phosphorus-containing active ester of the present invention is preferably represented by the following general formula (1).

[In the above general formula (1), A is a structure represented by any of the following general formulas (2) to (4), and R is each independently a linear or branched alkylene group. , Q is an aromatic ring, x is an average repeating number of 0.1 or more, y is an average repeating number of 1 or more, z is an average repeating number of 1 or more, and Ar is , has a structure represented by the following general formula (5) or (6),

# in the above general formulas (2) to (4) represents a bonding site with the oxygen atom bonded to A in the above general formula (1), and * in the above general formulas (5) and (6) , represents a bonding site between Ar and the oxygen atom in the above general formula (1), and Rb and Rc each independently represent an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an aralkyl group. , or may be a naphthyl group, and Rb and Rc may form a cyclic structure. Ra is each independently a halogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, an aralkyl group, or a naphthyl group, s is an integer from 0 to 7, and t is It is an integer from 0 to 5. ]

The phosphorus-containing active ester of the present invention preferably has a phosphorus content of 1.8% by mass or more.

The present invention relates to a curable resin composition containing the phosphorus-containing active ester and an epoxy resin.

The present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction.

The present invention relates to a reinforcing base material and a prepreg having a semi-cured product of the curable resin composition impregnated into the reinforcing base material.

The present invention relates to a circuit board obtained by laminating the prepreg and copper foil and molding them under heat and pressure.

The present invention relates to a build-up film containing the curable resin composition.

The present invention relates to a semiconductor encapsulant containing the curable resin composition.

The present invention relates to a semiconductor device including a cured product obtained by heating and curing the semiconductor encapsulant.

According to the present invention, a phosphorus-containing active ester that can exhibit excellent flame retardancy, low dielectric properties, and adhesion in a cured product obtained, a curable resin composition containing the phosphorus-containing active ester, and , to provide a cured product obtained using the curable resin composition, and further to provide a semiconductor encapsulant, a semiconductor device, a prepreg, a circuit board, a build-up film, etc. using the curable resin composition. It is possible and useful.

1 is a GPC chart of the diphenyl isophthalate derivative (A-1) obtained in Synthesis Example 1. 1 is a ¹ H-NMR chart of diphenyl isophthalate derivative (A-1) obtained in Synthesis Example 1. 1 is an FD-MS spectrum chart of diphenyl isophthalate derivative (A-1) obtained in Synthesis Example 1. 1 is a GPC chart of the phosphorus-containing diol (PC-HCA-HQ) obtained in Synthesis Example 2. 13 is a ¹³ C-NMR chart of the phosphorus-containing diol (PC-HCA-HQ) obtained in Synthesis Example 2. 1 is an FD-MS spectrum chart of the phosphorus-containing diol (PC-HCA-HQ) obtained in Synthesis Example 2. 1 is a GPC chart of the phosphorus-containing active ester (B-1) obtained in Example 1. 1 is a ¹³ C-NMR chart of the phosphorus-containing active ester (B-1) obtained in Example 1. 1 is an FD-MS spectrum chart of the phosphorus-containing active ester (B-1) obtained in Example 1. 1 is a GPC chart of the phosphorus-containing diol (EC-HCA-HQ) obtained in Synthesis Example 3. 2 is a GPC chart of the phosphorus-containing active ester (B-2) obtained in Example 2. 1 is a GPC chart of the phosphorus-containing diol (PC-HCA-NQ) obtained in Synthesis Example 4. 3 is a GPC chart of the phosphorus-containing active ester (B-3) obtained in Example 3. 2 is a GPC chart of the phosphorus-containing diol (PC-PPQ) obtained in Synthesis Example 5. 1 is a GPC chart of the phosphorus-containing active ester (B-4) obtained in Example 4. 1 is a GPC chart of intermediate (C-1) obtained in Comparative Synthesis Example 1. 2 is a GPC chart of the phosphorus-containing intermediate (C-2) obtained in Comparative Synthesis Example 2. 1 is a GPC chart of the phosphorus-containing active ester (C-3) obtained in Comparative Example 1.

<Active ester (I)>
The phosphorus-containing active ester of the present invention has a structure in which a residue (A) of a phosphorus-containing polyhydric alcohol compound and a residue (Q) of an aromatic polyhydric carboxylic acid are bonded via an ester bond. , and the end thereof is capped with a residue (C) of a monovalent aromatic hydroxyl group-containing compound.
The phosphorus-containing active ester has an ester bond that suppresses hydroxyl groups generated during curing of the epoxy resin, contains a residue (A) of the phosphorus-containing polyhydric alcohol compound that can become a flexible segment, and further has flame retardant in its structure. Since it contains a phosphorus atom that contributes to properties, a cured product using this phosphorus-containing active ester is useful because it has excellent flame retardancy, flexibility, low dielectric properties, and adhesion.

The phosphorus-containing active ester of the present invention contains the residue (A) of the phosphorus-containing polyhydric alcohol compound, and its valence is preferably 2 to 5, more preferably divalent. . When the valence is two or more, the number of functional groups in the generated active ester is two or more, which is excellent from the viewpoint of curability. Furthermore, the residue (A) of the phosphorus-containing polyhydric alcohol compound includes a phosphorus atom that contributes to flame retardancy in its structure, and at least two or more linear or branched alkylene groups or alkyleneoxy groups. It is preferable to include an aromatic ring bonded to.

The phosphorus-containing active ester of the present invention contains a residue (Q) of the aromatic polycarboxylic acid, and its valence is preferably 2 to 4, more preferably 2. . When the valence is two or more, the number of functional groups in the phosphorus-containing active ester to be produced is two or more, which is excellent from the viewpoint of curability. Further, the aromatic compound is not particularly limited as long as it is a compound having an aromatic ring having a carboxyl group.

The phosphorus-containing active ester of the present invention is a phosphorus-containing active ester whose terminal end is capped with a residue (C) of a monovalent aromatic hydroxyl group-containing compound; The hydroxyl group-containing compound is not particularly limited as long as it has an aromatic ring and one (monovalent) hydroxyl group on the aromatic ring.

In the phosphorus-containing active ester of the present invention, the phosphorus content of the phosphorus-containing polyhydric alcohol compound is preferably 4 to 25% by mass, more preferably 5 to 24% by mass, and more preferably 6 to 23% by mass. It is even more preferable. The above range is preferable because the cured product is excellent in terms of heat resistance and dielectric properties.

In addition, the above-mentioned "residue of a phosphorus-containing polyhydric alcohol compound (A)" in the present invention indicates a group obtained by removing a hydroxyl group from a phosphorus-containing polyhydric alcohol compound, and the above-mentioned "residue of an aromatic polyhydric carboxylic acid" "Group (Q)" refers to a group obtained by removing a carboxyl group from an aromatic polycarboxylic acid, and "Residue (C) of a compound containing a monovalent aromatic hydroxyl group at the terminal" refers to a group obtained by removing a carboxyl group from an aromatic polycarboxylic acid. This refers to a group obtained by removing a hydroxyl group from a hydroxyl group-containing compound. Further, the phosphorus-containing polyhydric alcohol compound may include not only an aliphatic alcohol but also a phosphorus-containing polyhydric alcohol compound containing an aromatic ring.

<Active ester (II)>
The phosphorus-containing active ester of the present invention is preferably represented by the following general formula (1).

In the above general formula (1), A is a structure represented by any of the following general formulas (2) to (4), and R is each independently a linear or branched alkylene group, Q is an aromatic ring, x is an average repeating number of 0.1 or more, y is an average repeating number of 1 or more, z is an average repeating number of 1 or more, and Ar represents the following general formula This is the structure shown in (5) or (6).

# in the above general formulas (2) to (4) represents a bonding site with the oxygen atom bonded to A in the above general formula (1), and * in the above general formulas (5) and (6) , represents a bonding site between Ar and the oxygen atom in the above general formula (1), and Rb and Rc each independently represent an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an aralkyl group. , or may be a naphthyl group, and Rb and Rc may form a cyclic structure. Ra is each independently a halogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, an aralkyl group, or a naphthyl group, s is an integer from 0 to 7, and t is It is preferably an integer from 0 to 5.
The phosphorus-containing active ester has multiple ester bonds and contains linear or branched alkylene groups, so this chain structure has low polarity and forms flexible segments, resulting in flexibility and low dielectric properties. An excellent cured product can be obtained and it is useful.

A in the above general formula (1) is preferably a structure represented by any of the above general formulas (2) to (4), and Rb and Rc in the above general formulas (2) to (4) are , each independently is preferably an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an aralkyl group, or a naphthyl group, and Rb and Rc form a cyclic structure. Good too. Among them, A in the above general formula (1) is 10-(2,5-dihydroxyphenyl)-9,10-dihydro9-oxa-10-phosphaphenanthrene-10-oxide structure, 10-[2- (dihydroxynaphthyl)]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide structure is more preferred. Since the structure contains a phosphorus atom and has a high concentration of aromatic rings, it can contribute to the effect of improving the flame retardance based on the phosphorus-containing active ester, and is therefore preferable. Conventionally known activated esters having an aliphatic cyclic hydrocarbon group in their molecular structures have excellent dielectric properties (low dielectric properties) in the resulting cured products, but they are easily combustible and do not have sufficient heat resistance. However, the phosphorus-containing active ester is useful because it can have both dielectric properties and flame retardancy by introducing a plurality of aromatic rings into its molecular structure. In addition, active esters having a bulky substituent structure, such as the above structure, have a lower concentration of active groups involved in the curing reaction than active esters that do not have a bulky substituent structure. While the heat resistance of phosphorus-containing active esters tends to be poor, the above-mentioned phosphorus-containing activated esters have excellent not only dielectric properties and flame retardance but also heat resistance, and are useful because they can have various performances. .

Each R in the above general formula (1) is preferably a linear or branched alkylene group, and the number of carbon atoms contained in the linear or branched chain is 2 to 16. It is more preferable that the number is 2 to 10. When the number of carbon atoms is within the above range, the phosphorus-containing active ester has excellent compatibility, which is a preferred embodiment.

It is preferable that x in the above general formula (1) has an average repetition number of 0.1 or more. Among these, from the viewpoint of workability and flexibility of the obtained cured product, the average repetition number x is 0.5. It is more preferably from 0.7 to 2.8, and even more preferably from 0.7 to 2.8.

It is preferable that y in the above general formula (1) has an average repeating number of 1 or more, and especially from the viewpoint of workability and flexibility of the obtained cured product, the average repeating number y is 1 to 5. It is more preferable.

It is preferable that z in the above general formula (1) has an average repeating number of 1 or more, and especially from the viewpoint of workability and flexibility of the obtained cured product, the average repeating number z is 1 to 5. It is more preferable.

Q in the above general formula (1) is preferably an aromatic ring, more preferably any aromatic ring such as a benzene ring, a naphthalene ring, or an anthracene ring. From the viewpoint of ease and solubility, a benzene ring is more preferred.

Rb and Rc in the above general formulas (2) to (4) are each independently an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an aralkyl group, or a naphthyl group. Among them, from the viewpoint of physical properties of the obtained cured product and ease of industrial availability, straight chain or cyclic alkyl groups having 2 to 12 carbon atoms, alkoxy groups, allyl groups, aryl groups, or naphthyl groups are preferred. More preferably, it is a group.
In addition, Rb and Rc in the above general formulas (2) to (4) may form a cyclic structure, and from the viewpoint of ease of obtaining industrial raw materials, an alkoxy group, an aryl group, or a naphthyl group may be used. It is more preferable that it has a cyclic structure. Note that Rb and Rc form a cyclic structure here means that Rb and Rc combine to form a cyclic structure, and do not include a structure containing an aromatic ring or an alicyclic structure. It may be formed.

Ar in the above general formula (1) preferably has a structure represented by the above general formula (5) or (6), and Ra in the above general formula (5) or (6) each independently , a halogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, an aralkyl group, or a naphthyl group.Among them, it is preferable to use a halogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, an aralkyl group, or a naphthyl group. From the viewpoint of flexibility, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, an aralkyl group, or a naphthyl group is more preferable.

In the above general formula (5) or (6), s is an integer of 0 to 7, t is preferably an integer of 0 to 5, and s and t are each independently an integer of 0 to 5. It is more preferable that s and t are each independently an integer of 0 to 4 from the viewpoint of reactivity and flexibility of the obtained cured product.

The phosphorus-containing active ester of the present invention (for example, (I) and (II) above) has a function as a curing agent for epoxy resins, etc., has a flexible segment in its structure, and has the phosphorus-containing active ester. Flexibility can be imparted to the cured product obtained by using the ester, which is a preferred embodiment. Furthermore, it is possible to prevent or suppress the generation of hydroxyl groups during the reaction between the phosphorus-containing active ester and the epoxy resin, and is useful because it has excellent low dielectric properties. Furthermore, since the phosphorus-containing active ester has phosphorus atoms incorporated into its structure, it not only has excellent flame retardancy, but also has less bleed-out properties than additive-type phosphorus-based flame retardants used as flame retardants. is suppressed and has excellent adhesion to glass substrates, copper foil, etc., making it useful.

The phosphorus-containing active ester of the present invention is not particularly limited as long as it is an ester compound having the structure shown in either of the above-mentioned phosphorus-containing active esters (I) and (II), but for example, it has two or more carboxyl groups. and/or its acid halide or ester (a) and an aromatic monohydroxy compound (b), with a phosphorus-containing polyol compound (d). The reaction product (compound corresponding to the above-mentioned phosphorus-containing active ester) is preferable. By using the phosphorus-containing active ester, a cured product having a low dielectric loss tangent and excellent flame retardancy, heat resistance, moist heat resistance, and adhesion can be obtained, which is a preferred embodiment. The reason for this is not necessarily clear, but since the obtained phosphorus-containing active ester contains an aryloxycarbonyl group (active ester group) at the end, it exhibits high reactivity with the epoxy group of the epoxy resin described below. The high reactivity makes it possible to prevent or suppress the generation of hydroxyl groups caused by ring opening of epoxy groups, which is a preferred embodiment. In addition, since the phosphorus-containing active ester has no or almost no hydroxyl group in its molecule, hydroxyl groups derived from the phosphorus-containing active ester also exist in the cured product obtained by the reaction of the phosphorus-containing active ester. have no or almost no According to such an active ester, generation of hydroxyl groups during curing can be prevented or suppressed. Generally, it is known that highly polar hydroxyl groups increase the dielectric loss tangent, but the use of the phosphorus-containing active ester makes it possible to achieve a low dielectric loss tangent in the cured product, which is particularly useful.

Moreover, since the phosphorus-containing active ester has two or more ester bonds that have a reactive activity with the epoxy group of the epoxy resin described below, the crosslinking density of the cured product can be increased and the heat resistance can be improved.

The phosphorus-containing active ester of the present invention has a flexible segment such as an alkylene group or an alkyleneoxy group (alkylene ether chain), and has no or almost no hydroxyl group, so it has a low polar structure. A curable resin composition that can exhibit excellent flame retardancy, flexibility, moisture absorption resistance, adhesion to copper foil etc. due to flexibility, and low dielectric properties in the resulting cured product ( For example, an epoxy resin composition containing an epoxy resin), a semiconductor encapsulation material, a semiconductor device, a prepreg, a circuit board, a build-up film, etc. using the above-mentioned curable resin composition can be provided, and a preferred embodiment becomes.

The phosphorus-containing active ester is selected from the softening point of the phosphorus-containing active ester, from the viewpoint of handling properties when preparing a curable resin composition, which will be described later, and a better balance between heat resistance and dielectric properties of the cured product. is preferably 200°C or less, more preferably 180°C or less.

[Aromatic compound having two or more carboxyl groups and/or acid halide or ester thereof (a)]
The aromatic compound having two or more carboxyl groups and/or its acid halide or ester (a) (a compound derived from the residue (Q) of the aromatic polyhydric carboxylic acid) has two or more carboxyl groups. A carboxylic acid having a carboxyl group or a derivative thereof, specifically a carboxylic acid, an acid halide, or an esterified product (hereinafter sometimes referred to as "aromatic compound etc. (a)"). The aromatic compound etc. (a) has two or more carboxyl groups, etc., so that the aromatic monohydroxy compound (b) described below, and the phosphorus-containing polyol compound (d) (hereinafter simply referred to as "compound ( d) (compound derived from the residue (A) of the above-mentioned phosphorus-containing polyhydric alcohol compound), in the structure of the phosphorus-containing active ester. It is possible to form a structure containing both a structural moiety with flexibility and an aryloxycarbonyl structure with epoxy curability at the terminal. active ester groups). Moreover, the obtained phosphorus-containing active ester has an aryloxycarbonyl terminal, and is excellent from the viewpoint of dielectric properties.

The number of carboxyl groups in the aromatic compound (a) is more preferably 2 to 4, and even more preferably 2. By having at least two (two or more) carboxyl groups, the number of functional groups in the generated phosphorus-containing active ester is two or more, which is excellent from the viewpoint of curability.

The aromatic compounds (a) include, but are not particularly limited to, compounds having two or more carboxyl groups in a substituted or unsubstituted aromatic ring. In addition, "carboxyl group etc." refers to carboxyl group; halogenated acyl group such as acyl fluoride group, acyl chloride group, and acyl bromide group; alkyloxycarbonyl group such as methyloxycarbonyl group and ethyloxycarbonyl group; phenyl Examples include aryloxycarbonyl groups such as oxycarbonyl group and naphthyloxycarbonyl group. In addition, when it has a halogenated acyl group, the said aromatic compound is an acid halide, and when it has an alkyloxycarbonyl group or an aryloxycarbonyl group, the said aromatic compound can be an esterified product. Among these, the aromatic compound preferably has a carboxyl group, a halogenated acyl group, or an aryloxycarbonyl group, and more preferably has a carboxyl group, a halogenated acyl group, and a carboxyl group, an acyl chloride group, or an aryloxycarbonyl group. It is more preferable to have an acyl group.

Examples of the aromatic ring include, but are not particularly limited to, monocyclic aromatic rings, condensed aromatic rings, ring-assembled aromatic rings, aromatic rings connected by alkylene chains, and the like.

The aromatic compounds (a) include, but are not particularly limited to, benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, and 2-allyl terephthalic acid; trimellitic acid, 5-allyl trimellitic acid, etc. benzenetricarboxylic acid; naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, Naphthalene dicarboxylic acids such as 3-allylnaphthalene-1,4-dicarboxylic acid and 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acids such as 2,4,5-pyridinetricarboxylic acid; 1,3, Examples include triazinecarboxylic acids such as 5-triazine-2,4,6-tricarboxylic acid; acid halides and esterified products thereof. Among these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferred, and isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid, and 1,3,5-benzenetricarboxylic acid. Trichloride is more preferred, and isophthalic acid chloride, terephthalic acid chloride, and 1,3,5-benzenetricarbonyl trichloride are even more preferred.

Among the above, from the viewpoint of flexibility of the resulting cured product, ease of industrial availability of raw materials, and workability, aromatic compounds in which the aromatic ring is a monocyclic aromatic ring, etc. Aromatic compounds having a group ring are preferable, and benzenedicarboxylic acid, benzenetricarboxylic acid, naphthalene dicarboxylic acid, and acid halides of these are preferable. More preferably, isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 1 , 3,5-benzene and dicarboxylic acid. More preferably, these are acid halides. The above-mentioned aromatic compounds (a) may be used alone or in combination of two or more.

[Aromatic monohydroxy compound (b)]
The aromatic monohydroxy compound (b) used in the present invention (a compound whose terminal is derived from the residue (C) of the monovalent aromatic hydroxyl group-containing compound) is, for example, phenol, o-cresol, m-cresol, Alkylphenols such as p-cresol, 2,4-xylenol, 2,6-xylenol, tert-butylphenol, amylphenol; o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, styrenated phenol, Examples include aralkylphenols such as 4-(α-cumyl)phenol; and naphthol compounds such as 1-naphthol and 2-naphthol. Each of these may be used alone, or two or more types may be used in combination. Among these, o-cresol and naphthol are preferred because they yield a cured product with excellent dielectric properties (low dielectric properties).

The reaction with the aromatic compound etc. (a) and the aromatic monohydroxy compound (b) is not particularly limited, but for example, in the presence of an alkali catalyst at a temperature of 60° C. or lower, 1 to It can be carried out with a reaction time of 24 hours. Examples of the alkali catalyst that can be used here include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, triethylamine, and pyridine. Each of these may be used alone, or two or more types may be used in combination. Among these, sodium hydroxide or potassium hydroxide is preferred because of its high reaction efficiency. Further, these catalysts may be used as a 3 to 30% aqueous solution. Further, at this time, an interlayer transfer catalyst may be used in order to increase reaction efficiency. Examples include alkylammonium salts, crown ethers, and the like. These may be used alone or in combination of two or more.

The above reaction is preferably carried out in an organic solvent because reaction control becomes easy. Examples of organic solvents used here include hydrocarbon solvents such as pentane and hexane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, ether solvents such as diethyl ether and tetrahydrofuran, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether. Examples include acetate ester solvents such as acetate and carbitol acetate, carbitol solvents such as cellosolve and butyl carbitol, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Each of these may be used alone or as a mixed solvent of two or more.

The reaction ratio of the aromatic compound etc. (a) and the aromatic monohydroxy compound (b) can be changed as appropriate depending on the desired molecular design, but in particular, while reducing unreacted terminals, From the viewpoint of reducing surplus reaction raw materials, the aromatic monohydroxy compound (b) is preferably in the range of 1.1 to 5.0 mol per 1 mol of the aromatic compound etc. (a), and 1.5 4.0 mol is more preferable, and 2.0 to 3.0 mol is even more preferable.

After the reaction is completed, when using an aqueous solution in the presence of an alkaline catalyst, the reaction solution is separated by standing to remove the aqueous layer, and the remaining organic layer is washed with water until the aqueous layer is almost neutral (pH 7). A reaction product between the aromatic compound, etc. (a) and the aromatic monohydroxy compound (b), in which the content of inorganic salts that have an adverse effect on insulation properties is reduced by repeating water washing until the inorganic salt content is reduced. A reaction product (c) can be obtained.

[Phosphorus-containing polyol compound (d)]
The phosphorus-containing active ester of the present invention can be produced by reacting the reaction product (c) with the phosphorus-containing polyol compound (d). By using the compound (d), an alkylene group, alkyleneoxy group (alkylene ether chain), etc. derived from the compound (d), which becomes a flexible segment, can be introduced into the structure of the resulting phosphorus-containing active ester. It is possible to impart flexibility to the cured product obtained by using the phosphorus-containing active ester, and furthermore, since a structure with low polarity is introduced, it has excellent low dielectric properties, and is a preferred embodiment. In addition, the phosphorus-containing active ester can prevent or suppress the generation of hydroxyl groups during synthesis, and has excellent low dielectric properties, making it useful.

The number of hydroxyl groups (valence) in the phosphorus-containing polyol compound (d) is preferably 2 to 5, more preferably 2. By having at least two (two or more) carboxyl groups, the number of functional groups in the generated phosphorus-containing active ester is two or more, which is excellent from the viewpoint of curability.

The compound (d) is not particularly limited, but for example, from the viewpoint of flame retardancy, heat resistance, and low dielectric properties, it is represented by any one of the above general formulas (2) to (4). diol compound (d-1) containing the structure (hereinafter sometimes simply referred to as "compound (d-1)"), condensed phosphate ester polyol (d-2) (hereinafter simply referred to as "compound (d-1)"), 2)) and phosphorus-containing polyester polyol (d-3) (hereinafter sometimes simply referred to as "compound (d-3)") are preferably used, for example, the following: A compound having a structure as shown in general formula (7) can be exemplified. In addition, A, R, y, and z in the following general formula (7) are the same as each in the said general formula (1).

Examples of the compound (d-1) include compounds represented by the following general formulas (8) to (12).

In addition, Rw, Rx, Ry, and Rz in the following general formulas (8) to (12) are each independently preferably hydrogen or an alkyl group, and from the viewpoint of industrial availability. From the above, hydrogen or an alkyl group having 1 to 4 carbon atoms is more preferable. These compounds (d-1) may be used alone or in combination of two or more.

The method for producing the compound (d-1) includes preparing a compound having two or more phenol hydroxyl groups in the presence of a compound having an epoxy group such as ethylene oxide, propylene oxide, or butylene oxide, or a carbonate such as ethylene carbonate, propylene carbonate, or butylene carbonate. It is obtained by heating and stirring a phosphorus-containing compound (e) (hereinafter sometimes simply referred to as "compound (e)") and a base catalyst. Examples of the base catalyst used include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, triethylamine, pyridine, diazabicycloundecene, diazabicyclononene, and triphenyl. Examples include phosphine. These may be used alone or in combination of two or more. Among these, diazabicycloundecene, diazabicyclononene, and triphenylphosphine are preferred because of their high reaction efficiency. Although the above reaction is not particularly limited, it may be performed without an organic solvent or in an organic solvent. Examples of organic solvents used here include hydrocarbon solvents such as pentane and hexane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, ether solvents such as diethyl ether and tetrahydrofuran, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol. Acetate ester solvents such as monomethyl ether acetate and carbitol acetate, carbitol solvents such as cellosolve and butyl carbitol, aromatic hydrocarbon solvents such as toluene and xylene, amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Examples include solvents. Each of these may be used alone or as a mixed solvent of two or more. The reaction conditions are not particularly limited, but, for example, the compound (d-1) can be obtained by stirring and reacting for 1 to 24 hours at a temperature of 50 to 250°C.

As the compound (e), a commercially available compound may be used. Commercially available products include, for example, HCA-HQ (10-(2,5-dihydroxyphenyl)-9,10-dihydro9-oxa-10-phosphaphenanthrene-10-oxide) manufactured by Sanko Co., Ltd., and HCA=NQ (10-[2-(dihydroxynaphthyl)]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), CPHO-HQ (1,4-cyclooctyl) manufactured by Nippon Chemical Industry Co., Ltd. A mixture of lenephosphonyl-1,4-hydroquinone and 1,5-cyclooctylenephosphonyl-1,4-hydroquinone), and the like.

Examples of the compound (d-2) include polyphosphoric ester polyols obtained by condensing phosphoric acid, phosphorous acid, phosphoric esters, etc., and alkylene polyols.

The compound (d-3) includes phosphorus-containing dicarboxylic acid monomers such as HCA-maleic acid adduct, HCA-citraconic acid adduct, and HCA-itaconic acid adduct (trade name M-ACID, manufactured by Sanko Co., Ltd.). and a phosphorus-containing polyester polyol condensate having a hydroxyl group end (product name: M-ESTER, ME-P8, manufactured by Sanko Co., Ltd.), which is obtained by condensing an alkylene polyol compound.

By reacting the reaction product (c) with the compound (d), a transesterification reaction occurs, and the phosphorus-containing active ester of the present invention can be obtained. As for the reaction conditions, for example, the phosphorus-containing active ester can be obtained by stirring and reacting for 1 to 24 hours at a temperature of 50 to 250°C. In addition, the reaction can be carried out by adding an alkali catalyst, especially an amine catalyst (alkyl amine such as triethylamine, triphenylamine, aryl amine, condensed ring amine such as DBU, DBN, heterocyclic amine such as imidazole, pyridine, etc.). can be promoted. After completion of the reaction, in order to remove the excess aromatic monohydroxy compound (b), high-purity phosphorus-containing Active esters can be obtained.

In the above reaction, the same solvent as used in the reaction of the aromatic compound etc. (a) and the aromatic monohydroxy compound (b) can be used.

The reaction ratio of the reaction product (c) and the compound (d) can be changed as appropriate depending on the desired molecular design, but among them, phosphorus-containing active esters with better workability and flexibility are used. Therefore, the hydroxyl equivalent of the compound (d) is preferably in the range of 0.1 to 0.9 mol, and 0.2 to 0.8 mol per equivalent of the active ester equivalent of the reaction product (c). More preferably, 0.3 to 0.8 mol is even more preferable.

The phosphorus content (phosphorus content) in the phosphorus-containing active ester is preferably 1.8% by mass or more, from the viewpoint of flame retardancy and low dielectric loss tangent of the obtained cured product, and 1.8 to 25% by mass. %, and even more preferably 1.9 to 24% by mass.

The functional group equivalent of the phosphorus-containing active ester of the present invention is, when the total number of aromatic ester groups in the phosphorus-containing active ester structure is taken as the number of functional groups of the phosphorus-containing active ester, the phosphorus-containing active ester has excellent curability, low dielectric constant, and dielectric loss tangent. (low dielectric properties), it is preferably in the range of 160 to 1,500 g/eq, more preferably in the range of 180 to 1,200 g/eq, and more preferably in the range of 200 to 1,000 g/eq. Even more preferred.

The number average molecular weight (Mn) of the phosphorus-containing active ester of the present invention is preferably from 320 to 3,000, more preferably from 360 to 2,400. It is preferable that the number average molecular weight (Mn) is 320 or more because the dielectric loss tangent is excellent. On the other hand, it is preferable that the number average molecular weight (Mn) is 3000 or less because it has excellent moldability.

<Curable resin composition>
The curable resin composition of the present invention preferably contains the phosphorus-containing active ester and an epoxy resin.

[Epoxy resin]
The epoxy resin is not particularly limited, but is preferably a curable resin that contains two or more epoxy groups in its molecule and can be cured by forming a crosslinked network with the epoxy groups.

The epoxy resin is not particularly limited, but includes phenol novolak epoxy resin, cresol novolac epoxy resin, α-naphthol novolac epoxy resin, β-naphthol novolac epoxy resin, bisphenol A novolak epoxy resin, biphenyl novolac epoxy resin. Novolak type epoxy resin such as resin;
Aralkyl type epoxy resins such as phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, phenol biphenylaralkyl type epoxy resins;
Bisphenol A epoxy resin, bisphenol AP epoxy resin, bisphenol AF epoxy resin, bisphenol B epoxy resin, bisphenol BP epoxy resin, bisphenol C epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S bisphenol type epoxy resin such as type epoxy resin, tetrabromobisphenol A type epoxy resin;
Biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton;
Naphthalene type epoxy resin;
Binaphthol type epoxy resin; Binaphthyl type epoxy resin;
Dicyclopentadiene type epoxy resin such as dicyclopentadiene phenol type epoxy resin;
Glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane type epoxy resins, triglycidyl-p-aminophenol type epoxy resins, glycidylamine type epoxy resins of diaminodiphenylsulfone;
Diglycidyl ester type epoxy resins such as 2,6-naphthalene dicarboxylic acid diglycidyl ester type epoxy resins and hexahydrophthalic anhydride glycidyl ester type epoxy resins;
Examples include benzopyran type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran.
Among these epoxy resins, so-called glycidyl ether type epoxy resins obtained by epoxidizing a phenol compound are preferred, and among these, novolac type epoxy resins, aralkyl type epoxy resins, and dicyclopentadiene type epoxy resins are preferred because of their dielectric properties. It is more preferable from the viewpoint of

In addition, the above-mentioned epoxy resins may be used alone or in combination of two or more types.

The epoxy equivalent of the epoxy resin is preferably 120 to 400 g/eq, more preferably 150 to 300 g/eq. When the epoxy equivalent of the epoxy resin is 120 g/eq or more, it is preferable because the dielectric properties of the resulting cured product are better. On the other hand, when the epoxy equivalent of the epoxy resin is 400 g/eq or less, the heat resistance of the resulting cured product improves. This is preferable because it has an excellent balance between properties and dielectric loss tangent.

The softening point of the epoxy resin is preferably 20 to 200°C, more preferably 40 to 150°C. It is preferable that the softening point of the epoxy resin is 20° C. or higher, since it also has fast curing properties. On the other hand, it is preferable that the softening point of the epoxy resin is 200° C. or lower because it has excellent moldability.

The functional group equivalent ratio (phosphorus-containing active ester/epoxy resin) of the usage amount of the phosphorus-containing active ester to the usage amount of the epoxy resin is preferably 0.2 to 2, and preferably 0.4 to 1.5. It is more preferable that there be. It is preferable that the functional group equivalent ratio is 0.2 or more because the resulting cured product can have a lower dielectric loss tangent and higher flexibility. If the functional group equivalent ratio exceeds 2, heat resistance and curability will decrease, so it is preferable to use within the above range.

In addition to the phosphorus-containing active ester and epoxy resin, the curable resin composition of the present invention may further contain other curing agents, other resins, solvents, additives, etc., within a range that does not impair the effects of the present invention. May contain.

[Other hardening agents]
In the curable resin composition of the present invention, other curing agents may be used in combination with the phosphorus-containing active ester.

Examples of the other curing agents include, but are not particularly limited to, amine curing agents, acid anhydride curing agents, phenolic resin curing agents, and the like.

The amine curing agent is not particularly limited, but includes diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylene diamine (DPDA), diethylaminopropylamine (DEAPA), and N-aminoethyl. Aliphatic amines such as piperazine, menzendiamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N,-dimethylpiperazine, triethylenediamine; m-xylene diamine (XDA), methanephenylene diamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethyl) Examples include aromatic amines such as (aminomethyl) phenol.

Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerol tris trimellitate, maleic anhydride, tetrahydrophthalic anhydride, Methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, Examples include methylcyclohexenedicarboxylic anhydride.

Examples of the phenolic resin curing agent include phenol novolak resin, cresol novolak resin, naphthol novolac resin, bisphenol novolak resin, biphenyl novolak resin, dicyclopentadiene-phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, and triphenol methane type resin. , tetraphenolethane type resin, aminotriazine modified phenol resin, and the like.

The other curing agents mentioned above may be used alone or in combination of two or more.

[Other resins]
The curable resin composition of the present invention may contain other resins in addition to the epoxy resin. In addition, in this specification, "other resin" means resin other than epoxy resin.

Specific examples of the other resins include, but are not particularly limited to, maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolac resins, and cyanate esters. Examples include resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallylbisphenol and triallyl isocyanurate, polyphosphoric acid esters, and phosphoric acid ester-carbonate copolymers. These other resins may be used alone or in combination of two or more.

[solvent]
The curable resin composition of the present invention may be prepared without a solvent or may contain a solvent. The solvent has a function of adjusting the viscosity of the curable resin composition.

Specific examples of the solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl. Ester solvents such as ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, etc. Examples include aromatic hydrocarbons, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

The amount of the solvent used is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the curable resin composition. It is preferable that the amount of the solvent used is 10% by mass or more because the handling property is excellent. On the other hand, it is preferable from the economic point of view that the amount of solvent used is 90% by mass or less.

[Additive]
The curable resin composition of the present invention may contain additives. Examples of the additives include curing accelerators, flame retardants, fillers, and the like.

(hardening accelerator)
Examples of the curing accelerator (curing catalyst) include, but are not limited to, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, and the like.

Examples of the phosphorus curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organic phosphite compounds such as trimethylphosphite and triethylphosphite; ethyltriphenyl; Phosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, Examples include phosphonium salts such as butylphenylphosphonium dicyanamide and tetrabutylphosphonium decanoate.

Examples of the amine curing accelerator include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5, Examples thereof include 4,0]-undecene-7 (DBU) and 1,5-diazabicyclo[4,3,0]-nonene-5 (DBN).

Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl. -4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2 -Methyl-3-benzylimidazolium chloride, 2-methylimidazoline and the like.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1, 5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide , 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and the like.

Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1 -dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, and the like.

Among the above-mentioned curing accelerators, it is preferable to use 2-ethyl-4-methylimidazole and N,N-dimethyl-4-aminopyridine (DMAP).

In addition, the above-mentioned curing accelerators may be used alone or in combination of two or more types.

The amount of the curing accelerator used can be adjusted as appropriate to obtain the desired curability, but it is 0.01 to 5 parts by weight based on 100 parts by weight of the total mixture of the epoxy resin and the phosphorus-containing active ester. The amount is preferably 0.1 to 3 parts by mass, and more preferably 0.1 to 3 parts by mass. It is preferable that the amount of the curing accelerator used is 0.01 part by mass or more, since the curing properties are excellent. On the other hand, it is preferable that the amount of the curing accelerator used is 5 parts by mass or less because the insulation reliability is excellent.

(Flame retardants)
The curable resin composition of the present invention uses a phosphorus-containing active ester that contributes to flame retardancy, but a flame retardant can be used separately as long as it does not impair the performance of the present invention. Examples of the flame retardant include, but are not particularly limited to, inorganic phosphorus flame retardants, organic phosphorus flame retardants, halogen flame retardants, and the like.

Examples of the inorganic phosphorus flame retardant include, but are not limited to, red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphoric acid amides.

The organic phosphorus flame retardant is not particularly limited, but includes methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, and bis(2-ethylhexyl). Phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl ) Phosphoric acid esters such as methacrylate acid phosphate; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine such as diphenylphosphine oxide; 10-(2,5-dihydroxyphenyl)-10H- 9-Oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphos Phosphorus-containing phenols such as phenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, and 1,5-cyclooctylenephosphinyl-1,4-phenyldiol ;9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10 -(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic phosphorus compounds; the phosphoric acid ester, the diphenylphosphine, the phosphorus-containing phenol, and an epoxy resin or Examples include compounds obtained by reacting with aldehyde compounds and phenol compounds.

The halogen flame retardant is not particularly limited, but includes brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A, bis(dibromopropyl ether), 1,2-bis(tetrabromophthalimide)ethane, 2 , 4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, and tetrabromophthalic acid. Note that when used in non-halogen flame retardant printed circuit boards (copper-clad laminates), etc., it is preferable not to use the halogen-based flame retardant.

The above flame retardants may be used alone or in combination of two or more.

The amount of the flame retardant used is preferably 0 to 50 parts by weight, more preferably 0 to 30 parts by weight, based on 100 parts by weight of the epoxy resin. It is preferable that the amount of flame retardant used is 50 parts by mass or less because flame retardancy can be imparted while maintaining dielectric properties, adhesiveness, etc.

(filler)
Examples of fillers include organic fillers and inorganic fillers. The organic filler has a function of improving elongation, a function of improving mechanical strength, etc. Inorganic fillers have functions such as reducing the coefficient of thermal expansion and imparting flame retardancy.

The organic filler is not particularly limited, but includes polyamide particles and the like.

The inorganic filler is not particularly limited, but includes silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitride. Boron, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate , calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black and the like. Among these, it is preferable to use silica. At this time, as the silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be used.

Further, the filler may be surface-treated if necessary. At this time, surface treatment agents that can be used include, but are not particularly limited to, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc. A ring agent or the like may be used. Specific examples of surface treatment agents include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and hexamethyldimethoxysilane. Examples include silazane.

In addition, the above-mentioned fillers may be used alone or in combination of two or more types.

The amount of the filler used is preferably 0.5 to 95 parts by weight, more preferably 5 to 80 parts by weight, based on 100 parts by weight of the epoxy resin. It is preferable that the amount of the filler used is 0.5 parts by mass or more because the effect of the filler can be sufficiently imparted. On the other hand, the amount of filler used is preferably 95 parts by mass or less so as not to increase the viscosity of the blend and impair moldability.

<Cured product>
The present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction. Since the phosphorus-containing active ester itself has a low dielectric loss tangent, the cured product obtained from the curable resin composition containing the phosphorus-containing active ester also has a low dielectric loss tangent. This is a preferred embodiment because it can exhibit flame retardancy, flexibility, adhesion to metals such as copper foil, and low dielectric properties due to flexibility.

As a method for obtaining a cured product obtained by subjecting the curable resin composition to a curing reaction, for example, the heating temperature during heating curing is not particularly limited, but is 100 to 300°C, and the heating time is 1 to 24°C. Preferably it is time.

<Applications of curable resin composition>
Applications for which the above curable resin composition is used include printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulation materials for build-up boards, insulating materials for circuit boards such as build-up adhesive films, and resin injection materials. Examples include mold materials, adhesives, semiconductor sealing materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up substrates, fiber-reinforced composite materials, and molded products obtained by curing the above-mentioned composite materials. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and build-up adhesive films are used for so-called electronic component embedded substrates in which passive components such as capacitors and active components such as IC chips are embedded within the substrate. It can be used as an insulating material. Furthermore, among the above, the curable resin composition of the present invention is suitable for semiconductor encapsulation by taking advantage of the properties that the cured product has excellent flame retardancy, flexibility, adhesion, low dielectric properties, heat resistance, etc. Preferably used for materials, semiconductor devices, prepregs, flexible wiring boards, circuit boards, build-up films, build-up boards, multilayer printed wiring boards, fiber-reinforced composite materials, and molded products obtained by curing the composite materials. . Below, a method for producing the semiconductor encapsulating material and the like from a curable resin composition will be explained.

1. Semiconductor encapsulation material The present invention relates to a semiconductor encapsulation material containing the curable resin composition. As a method for obtaining a semiconductor encapsulating material from the above curable resin composition, the above curable resin composition and compounding agents such as a curing accelerator and an inorganic filler are mixed as necessary in an extruder, a kneader, Examples include a method of sufficiently melting and mixing using a roll or the like until the mixture becomes uniform. At that time, fused silica is usually used as the inorganic filler, but when used as a highly thermally conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, nitride, etc., which have higher thermal conductivity than fused silica, It is preferable to use highly filled silicon or the like, or use fused silica, crystalline silica, alumina, silicon nitride, or the like. It is preferable to use the inorganic filler in a range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition. In order to reduce the amount, the amount is more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.

2. TECHNICAL FIELD The present invention relates to a semiconductor device including a cured product obtained by heating and curing the semiconductor sealing material. A method for obtaining a semiconductor device from the above-mentioned curable resin composition is to mold the above-mentioned semiconductor encapsulating material by casting, using a transfer molding machine, an injection molding machine, etc., and then molding the semiconductor device at 50 to 200°C for 2 to 10 hours. A method of heating for a while is mentioned.

3. Prepreg The present invention relates to a reinforcing base material and a prepreg having a semi-cured product of the curable resin composition impregnated into the reinforcing base material. A method for obtaining a prepreg from the above curable resin composition is to apply a curable resin composition prepared as a varnish by blending the following organic solvent to a reinforcing base material (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass Examples of methods include impregnating a mat, glass roving cloth, etc.) and then heating at a heating temperature depending on the type of solvent used, preferably 50 to 170°C. The mass ratio of the resin composition and the reinforcing base material used at this time is not particularly limited, but it is usually preferable to prepare the prepreg so that the resin content is 20 to 60 mass%.

Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethyl formamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc., and their selection and appropriate usage amount are Although it can be selected as appropriate depending on the application, for example, when further manufacturing a printed circuit board from prepreg as described below, it is preferable to use a polar solvent with a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, or dimethyl formamide. , it is preferable to use the non-volatile content in a proportion of 40 to 80% by mass.

4. TECHNICAL FIELD The present invention relates to a circuit board obtained by laminating the prepreg and copper foil and molding them under heat and pressure. As a method for obtaining a printed circuit board from the above curable resin composition, the above prepregs are laminated by a conventional method, copper foil is layered as appropriate, and the mixture is heated at 170 to 300° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa. , and heat compression bonding methods.

5. Flexible Wiring Board As a method for manufacturing a flexible wiring board from the above-mentioned curable resin composition, a method comprising the following three steps may be used. The first step is to apply a curable resin composition containing an active ester, an epoxy resin, and an organic solvent to an electrically insulating film using a coating machine such as a reverse roll coater or a comma coater. Step 2 is to heat the electrically insulating film coated with the curable resin composition using a heating machine at 60 to 170°C for 1 to 15 minutes to volatilize the solvent from the electrically insulating film and cure it. The third step is to B-stage the curable resin composition, and the third step is to apply a metal foil to the adhesive using a heating roll or the like on the electrically insulating film in which the curable resin composition has been B-staged. This is a process of thermocompression bonding (compression pressure is preferably 2 to 200 N/cm, and compression temperature is preferably 40 to 200° C.). If sufficient adhesion performance is obtained by going through the above three steps, you can finish here, but if complete adhesion performance is required, an additional 1 to 24 hours at 100 to 200°C may be used. It is preferable to post-cure with. The thickness of the curable resin composition film after final curing is preferably in the range of 5 to 100 μm.

6. Build-up Board A method for manufacturing a build-up board from the above-mentioned curable resin composition includes a method comprising the following three steps. The first step is a step of applying the above-mentioned curable resin composition suitably blended with rubber, filler, etc. to the circuit board on which the circuit has been formed using a spray coating method, curtain coating method, etc., and then curing it. In the second step, after drilling predetermined through-holes as necessary, the surface is treated with a roughening agent, and the surface is washed with hot water to form unevenness, and then the surface is made of metal such as copper. The third step is a step of sequentially repeating such operations as desired to alternately build up and form a resin insulating layer and a conductor layer of a predetermined circuit pattern. Note that it is preferable that the through-hole portion be formed after the outermost resin insulating layer is formed. The first step can be carried out not only by solution coating as described above, but also by laminating a build-up film that has been coated to a desired thickness and dried. In addition, the build-up board of the present invention can be produced by heat-pressing a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil at 170 to 250°C onto a wiring board on which a circuit has been formed. It is also possible to manufacture a build-up board by omitting the steps of forming a chemically coated surface and plating.

7. Build-up film The present invention relates to a build-up film containing the curable resin composition. As a method for manufacturing the build-up film of the present invention, the above-mentioned curable resin composition is applied onto a support film to form a curable resin composition layer to form an adhesive film for a multilayer printed wiring board. Examples include methods of manufacturing.

When producing a build-up film from a curable resin composition, the film softens under the lamination temperature conditions (usually 70 to 140°C) in the vacuum lamination method, and simultaneously laminates the circuit board and fills the via holes present in the circuit board. Alternatively, it is important that the resin exhibits fluidity (resin flow) that allows resin filling in the through-hole, and it is preferable to mix the above-mentioned components so as to exhibit such characteristics.

Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to allow resin filling within this range. . Note that when laminating both sides of the circuit board, it is desirable that about 1/2 of the through holes be filled.

Specifically, the method for manufacturing the adhesive film described above includes preparing the varnish-like curable resin composition, applying this varnish-like composition to the surface of the support film (Y), and further heating. Alternatively, it can be produced by drying the organic solvent by blowing hot air or the like to form a composition layer (X) made of a curable resin composition.

The thickness of the composition layer (X) to be formed is usually preferably greater than the thickness of the conductor layer. Since the thickness of a conductor layer included in a circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably in the range of 10 to 100 μm.

In addition, the composition layer (X) in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and from scratching it.

The support film and protective film described above are made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate, polycarbonate, polyimide, and even release materials. Examples include paper patterns and metal foils such as copper foil and aluminum foil. Note that the support film and the protective film may be subjected to a release treatment in addition to mud treatment and corona treatment.

The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, preferably 25 to 50 μm. Further, the thickness of the protective film is preferably 1 to 40 μm.

The support film (Y) described above is peeled off after being laminated onto the circuit board or after forming an insulating layer by heating and curing. If the support film (Y) is peeled off after the adhesive film is cured by heating, it is possible to prevent dust and the like from adhering to the adhesive film during the curing process. When peeling is performed after curing, the support film is usually subjected to a release treatment in advance.

8. Multilayer Printed Wiring Board A multilayer printed wiring board can also be manufactured using the film obtained as described above. A method for producing such a multilayer printed wiring board is, for example, when the composition layer (X) is protected with a protective film, after peeling off these, the composition layer (X) is directly attached to the circuit board. The substrate is laminated on one or both sides by, for example, a vacuum lamination method. The lamination method may be a batch method or a continuous method using rolls. Furthermore, the adhesive film and the circuit board may be heated (preheated) if necessary before laminating.

The lamination conditions are as follows: the pressure bonding temperature is preferably 70 to 140°C, and the pressure is preferably 1 to 11 kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ). It is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less.

9. Fiber-reinforced composite material The method for producing a fiber-reinforced composite material from the above-mentioned curable resin composition involves uniformly mixing each component constituting the curable resin composition to prepare a varnish, which is then mixed with reinforcing fibers. It can be manufactured by impregnating a reinforcing base material and then subjecting it to a polymerization reaction.

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

Here, the reinforcing fibers may be twisted yarns, untwisted yarns, untwisted yarns, or the like, but untwisted yarns and untwisted yarns are preferable because they achieve both moldability and mechanical strength of the fiber-reinforced plastic member. Furthermore, the reinforcing fibers can be in the form of one in which the fibers are aligned in one direction or a woven fabric. Fabrics can be freely selected from plain weave, satin weave, etc. depending on the part and purpose of use. Specifically, since they have excellent mechanical strength and durability, carbon fibers, glass fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers, etc. can be used, and two or more of these can also be used in combination. Among these, carbon fibers are particularly preferred since they provide good strength to the molded product, and various carbon fibers such as polyacrylonitrile-based, pitch-based, and rayon-based carbon fibers can be used. Among these, polyacrylonitrile-based materials are preferred because they can easily yield high-strength carbon fibers. Here, the amount of reinforcing fiber used when making a fiber-reinforced composite material by impregnating a reinforcing base material made of reinforcing fibers with varnish is such that the volume content of reinforcing fibers in the fiber-reinforced composite material is 40 to 85%. The amount is preferably within a range.

10. Fiber-reinforced resin molded products Methods for producing fiber-reinforced resin molded products from the above-mentioned curable resin composition include the hand lay-up method, the spray-up method in which fiber aggregate is laid in a mold, and the above-mentioned varnish is laminated in multiple layers. Using either a mold or a female mold, the base material made of reinforcing fibers is impregnated with varnish and stacked and molded, covered with a flexible mold that can apply pressure to the molded product, sealed airtight, and then vacuumed ( Reinforcement is achieved by the vacuum bag method, which involves molding (under reduced pressure), the SMC press method, which compresses and molds a sheet of varnish containing reinforcing fibers in a mold, and the RTM method, which injects the varnish into a mold lined with fibers. Examples include a method in which a prepreg is produced by impregnating fibers with the above varnish, and the prepreg is baked and hardened in a large autoclave. The fiber-reinforced resin molded product obtained above is a molded product containing reinforcing fibers and a cured product of the curable resin composition, and specifically, the amount of reinforcing fibers in the fiber-reinforced resin molded product is , preferably in the range of 40 to 70% by mass, and particularly preferably in the range of 50 to 70% by mass from the viewpoint of strength.

11. Others Although the method for producing semiconductor sealing materials and the like has been described above, other cured products can also be produced from the curable resin composition. Other methods for producing the cured product may be based on general curing methods for curable resin compositions. For example, the heating temperature conditions may be appropriately selected depending on the type of curing agent to be combined, the intended use, and the like.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified. In addition, GPC measurement, ¹ H-NMR measurement, ¹³ C-NMR measurement, FD-MS spectrum measurement, softening point, and phosphorus content are calculated based on the conditions shown below and the calculation formula shown below. did.

<GPC measurement>
Measured using the following measuring equipment and measurement conditions, and used in the synthesis of isophthalic acid diphenyl derivatives, phosphorus-containing diols, phosphorus-containing active esters, and phosphorus-containing active esters obtained in the synthesis examples and examples shown below. GPC charts of the intermediate and the target compound were obtained. From the results of the GPC chart, it was confirmed that the target product was produced from the decrease and disappearance of the raw material peak.
Measuring device: “HLC-8320 GPC” manufactured by Tosoh Corporation
Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation "TSK-GEL G4000HXL"
Detector: RI (differential refractometer)
Data processing: “GPC Workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40℃
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml/min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of the above-mentioned "GPC Workstation EcoSEC-WorkStation".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: 1.0 mass in terms of solid content of diphenyl isophthalate derivatives, phosphorus-containing diols, phosphorus-containing active esters, and intermediates used in the synthesis of phosphorus-containing active esters obtained in the synthesis examples and examples shown below. % tetrahydrofuran solution filtered through a microfilter (50 μl) was used.

< ^1H -NMR measurement>
¹ H-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE
Magnetic field strength: 600MHz
Total number of times: 32 times Solvent: DMSO-d6
Sample concentration: 30% by mass
From the results of the ¹ H-NMR chart, a peak derived from the target product could be confirmed, and it was confirmed that the target product was obtained in each reaction.

< ^13C -NMR measurement>
^13C -NMR: “JNM-ECA600” manufactured by JEOL RESONANCE
Magnetic field strength: 150MHz
Total number of times: 320 times Solvent: DMSO-d6
Sample concentration: 30% by mass
From the results of the ¹³ C-NMR chart, a peak derived from the target product could be confirmed, and it was confirmed that the target product was obtained in each reaction.

<FD-MS spectrum measurement>
The FD-MS spectrum was measured using the following measurement device and measurement conditions.
Measuring device: JMS-T100GC AccuTOF
Measurement conditions Measurement range: m/z = 4.00 to 2000.00
Rate of change: 51.2mA/min
Final current value: 45mA
Cathode voltage: -10kV
Recording interval: 0.07sec
From the results of the FD-MS spectrum, a peak derived from the target product could be confirmed, confirming that the target product was obtained in each reaction.

<Softening point>
Measured according to JIS K7234.

<Theoretical phosphorus content>
Theoretical phosphorus content (%) = 100 x [amount of phosphorus-containing raw material (mass parts) x (phosphorus content of phosphorus-containing raw material (mass %)/100)] / (phosphorus synthesized using phosphorus-containing raw materials Theoretical yield of contained compounds)
In addition, for the phosphorus content of the phosphorus-containing raw material, when a commercial product was used, the product catalog value was used.
The phosphorus-containing compound refers to a phosphorus-containing diol, a phosphorus-containing active ester, and a phosphorus-containing intermediate used in Examples and Comparative Examples.

Synthesis Example 1: Synthesis of diphenyl isophthalate derivative (A-1) 864.0 g (8.0 mol) of o-cresol and toluene were placed in a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. 4140.0 g was charged, and the system was replaced with nitrogen under reduced pressure to dissolve it. Next, 808 g of isophthalic acid chloride (number of moles of acid chloride group: 4.0 mol) was charged, and the system was replaced with nitrogen under reduced pressure to dissolve it. Thereafter, 2.07 g of tetrabutylammonium bromide (hereinafter referred to as "TBAB") was dissolved, the inside of the system was controlled at 60°C or less while purging with nitrogen gas, and 1648.0 g of a 20% aqueous sodium hydroxide solution was added over 3 hours. dripped. Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Furthermore, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water and toluene were removed by dehydration in a decanter and solvent removal to obtain a crystalline compound diphenyl isophthalate derivative (A-1). The active ester equivalent of the obtained diphenyl isophthalate derivative (A-1) was 173 g/eq based on the charging ratio. FIG. 1 shows the GPC chart of the obtained diphenyl isophthalate derivative (A-1), FIG. 2 shows ^{the 1} H-NMR chart, and FIG. 3 shows the FD-MS spectrum chart.

Synthesis Example 2: Synthesis of phosphorus-containing diol: PC-HCA-HQ
10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- was placed in a flask equipped with a thermometer, dropping funnel, condenser tube, fractionator tube, and stirrer. 200.0 g of oxide (manufactured by Sanko Co., Ltd., product name: HCA-HQ), 156.4 g of propylene carbonate, and 1.07 g of triphenylphosphine (hereinafter referred to as TPP) were charged, the temperature was raised to 190°C, and the reaction was carried out until the reaction was completed. In this way, a phosphorus-containing diol (PC-HCA-HQ) was obtained. The theoretical phosphorus content (content) of the obtained phosphorus-containing diol (PC-HCA-HQ) was 7.06% by mass, and the hydroxyl equivalent was 253 g/eq. FIG. 4 shows the GPC chart of the obtained PC-HCA-HQ, FIG. 5 shows the ¹³ C-NMR chart, and FIG. 6 shows the FD-MS spectrum chart.

Example 1: Synthesis of phosphorus-containing active ester (B-1) The diphenyl ophthalate derivative A-1 obtained in Synthesis Example 1 was placed in a flask equipped with a thermometer, dropping funnel, condenser tube, fractionator tube, and stirrer. 137.0 g of phosphorus-containing diol PC-HCA-HQ obtained in Synthesis Example 2, and 0.24 g of diazabicycloundecene (hereinafter abbreviated as "DBU") as a catalyst were charged. The temperature was raised to ℃ and allowed to react for 3 hours. Thereafter, the reaction was further carried out while o-cresol was removed by vacuum distillation to obtain phosphorus-containing active ester (B-1). The theoretical phosphorus content (content) of the obtained phosphorus-containing active ester (B-1) is 3.63% by mass, the functional group equivalent calculated from the charging ratio is 486 g / eq, and the softening point is 110 ° C. Met. FIG. 7 shows the GPC chart of the obtained active ester (B-1), FIG. 8 shows the ¹³ C-NMR chart, and FIG. 9 shows the FD-MS spectrum chart.

Synthesis Example 3: Synthesis of phosphorus-containing diol: EC-HCA-HQ
200 g of HCA-HQ, 199.5 g of ethylene carbonate, and 0.96 g of TPP were placed in an eggplant flask equipped with a stirrer, and the mixture was stirred at 180°C until the reaction was completed in an oil bath equipped with a thermometer. -HQ) was obtained. The theoretical phosphorus content (content) of the obtained phosphorus-containing diol (EC-HCA-HQ) was 7.34% by mass, and the hydroxyl equivalent was 227 g/eq. FIG. 10 shows a GPC chart of the obtained phosphorus-containing diol.

Example 2: Synthesis of phosphorus-containing active ester (B-2) In Example 1, 60.0 g of EC-HCA-HQ and 91 g of diphenyl isophthalate derivative (A-1) were added in place of PC-HCA-HQ. A phosphorus-containing active ester (B-2) was obtained by carrying out the same operation as in Example 1 except that DBU was changed to 0.7g and 0.15g. The theoretical phosphorus content (content) of the obtained phosphorus-containing active ester (B-2) is 3.58% by mass, the functional group equivalent calculated from the charging ratio is 465 g / eq, and the softening point is 99 ° C. Met. FIG. 11 shows a GPC chart of the obtained phosphorus-containing active ester (B-2).

Synthesis Example 4: Synthesis of phosphorus-containing diol: PC-HCA-NQ
In Synthesis Example 3, 10-[2-(dihydroxynaphthyl)]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., A phosphorus-containing diol (PC-HCA-NQ) was obtained by carrying out the same operation as in Synthesis Example 3, except that the product name: HCA=NQ), 68.2 g of ethylene carbonate, and 0.50 g of DBU were changed. The theoretical phosphorus content (content) of the obtained phosphorus-containing diol (PC-HCA-NQ) was 5.95% by mass, the hydroxyl equivalent was 245 g/eq, and the softening point was 116°C. FIG. 12 shows a GPC chart of the obtained phosphorus-containing diol.

Example 3: Synthesis of phosphorus-containing active ester (B-3) In Example 1, 71.5 g of PC-HCA-NQ and 100 g of diphenyl isophthalate derivative (A-1) were added instead of PC-HCA-HQ. A phosphorus-containing active ester (B-3) was obtained by carrying out the same operation as in Example 1, except that 0.9 g and DBU were changed to 0.34 g, and 0.17 g of 4-dimethylaminopyridine (hereinafter referred to as DMAP) was added. Ta. The theoretical phosphorus content (content) of the obtained phosphorus-containing active ester (B-3) was 3.03% by mass, and the functional group equivalent calculated from the charging ratio was 484 g/eq. FIG. 13 shows a GPC chart of the obtained phosphorus-containing active ester (B-3).

Synthesis Example 5: Phosphorus-containing diol: PC-PPQ
In Synthesis Example 2, HCA-HQ was replaced with 100.0 g of diphenylphosphinylhydroquinone (manufactured by Hokuko Sangyo Co., Ltd., trade name: PPQ (registered trademark)), 72.4 g of propylene carbonate, and 0.52 g of TPP. Except for this, the same operation as in Synthesis Example 2 was performed to obtain a phosphorus-containing diol (PC-PPQ).The theoretical phosphorus content (content) of the obtained phosphorus-containing diol (PC-PPQ) was 7.05% by mass. The hydroxyl equivalent was 208 g/eq, and the softening point was 99° C. FIG. 14 shows a GPC chart of the obtained phosphorus-containing diol.

Example 4: Synthesis of phosphorus-containing active ester (B-4) In Example 1, instead of PC-HCA-HQ, 70.0 g of PC-PPQ, 116.5 g of diphenyl isophthalate derivative A-1, and DBU A phosphorus-containing active ester (B-4) was obtained by carrying out the same operation as in Example 1, except that the amount was changed to 1.86 g. The theoretical phosphorus content (content) of the obtained phosphorus-containing active ester (B-4) was 3.28% by mass, and the functional group equivalent calculated from the charging ratio was 447 g/eq. FIG. 15 shows a GPC chart of the obtained phosphorus-containing active ester (B-4).

Comparative Synthesis Example 1: Synthesis of Intermediate (C-1) A polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl group equivalent: 165 g) was placed in a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. /eq, softening point: 85° C.) and 1,184 g of toluene were charged, and the system was replaced with nitrogen under reduced pressure to dissolve them. Next, 101 g of isophthalic acid chloride was charged, and then 0.59 g of TBAB was charged, and while purging with nitrogen gas, the inside of the system was controlled at 60° C. or lower, and 206 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. . Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Furthermore, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration in a decanter, and then toluene was removed by dehydration under reduced pressure to obtain intermediate (C-1). FIG. 16 shows a GPC chart of the obtained intermediate (C-1).

Comparative Synthesis Example 2: Synthesis of phosphorus-containing intermediate (C-2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene- was placed in a flask equipped with a thermometer, cooling tube, fractionation tube, and stirrer. 77.0 g of 10-oxide, 48.5 g of p-anisaldehyde, and 197.5 g of intermediate (C-1) were charged, heated to 90° C., and stirred while blowing nitrogen. Thereafter, the temperature was raised to 180°C and stirred for 5 hours, and then the temperature was further raised to 190°C and stirred for 9 hours. Water was removed from the reaction mixture under heating and reduced pressure to obtain a phosphorus-containing intermediate (C-2). The theoretical phosphorus content (content) of the obtained phosphorus-containing intermediate was 3.49% by mass. FIG. 17 shows a GPC chart of the obtained phosphorus-containing intermediate (C-2).

Comparative Example 1: Synthesis of phosphorus-containing active ester (C-3) 193.8 g of phosphorus-containing intermediate (C-2) and methyl were placed in a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. 678.0 g of isobutyl ketone was charged, and the system was replaced with nitrogen under reduced pressure to dissolve it. Next, after charging 42.2 g of benzoic acid chloride, 0.56 g of TBAB was charged, the inside of the system was controlled at 60°C or lower while performing nitrogen gas purging, and 78 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. . Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was left to separate and the aqueous layer was removed. Furthermore, water was added to the methyl isobutyl ketone layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration in a decanter, and then methyl isobutyl ketone was removed by dehydration under reduced pressure to obtain a phosphorus-containing active ester (C-3). The theoretical phosphorus content (content) of the obtained phosphorus-containing active ester (C-3) was 3.01% by mass. A GPC chart of the obtained phosphorus-containing active ester (C-3) is shown in FIG.

Examples 5 to 8 and Comparative Example 2
<Preparation of curable resin composition>
As an epoxy resin, "EPICLON HP-7200H-75M" manufactured by DIC Corporation (epoxy resin of polyaddition reaction product of dicyclopentadiene and phenol, epoxy equivalent: 276 g/eq) was used, and as a curing agent, the above-mentioned phosphorus obtained by synthesis was used. The active esters contained were blended in the proportions shown in Table 1 below, and the final nonvolatile content (N. A curable resin composition was prepared by blending methyl ethyl ketone so that V.) was 58% by mass.

Comparative example 3
<Preparation of curable resin composition>
As the epoxy resin, "HP-7200H-75M" manufactured by DIC Corporation (epoxy resin of polyaddition reaction product of dicyclopentadiene and phenol, epoxy equivalent: 276 g/eq), as curing agent "EPICLON HPC-8000-65T" manufactured by DIC Corporation. '', each was blended in the proportions shown in Table 1 below, DMAP was added as a curing catalyst, and methyl ethyl ketone was blended so that the final nonvolatile content (N.V.) was 58% by mass to form a curable resin composition. was prepared.

Comparative example 4
<Preparation of curable resin composition>
As the epoxy resin, "EPICLON EXA-9726" manufactured by DIC Corporation (phosphorus-containing epoxy resin, epoxy equivalent: 494 g/eq); as a curing agent, "EPICLON HPC-8000-65T" manufactured by DIC Corporation; the proportions shown in Table 1 below. DMAP was added as a curing catalyst, and methyl ethyl ketone was added so that the final nonvolatile content (N.V.) was 58% by mass to prepare a curable resin composition.

<Laminated board production conditions>
Using the curable resin composition obtained above, a laminate was produced under the following conditions, and various evaluation tests were conducted using the methods described below.
Base material: Nittobo Co., Ltd., glass cloth "#2116" (210 x 280 mm)
Copper foil: JX Nippon Mining Co., Ltd. "JTCSLC foil" (18μm)
Number of plies: 6
Curing conditions: 200℃, 29kg/ ^cm2 for 1.5 hours Plate thickness after molding: 0.8mm

<Measurement of dielectric properties (permittivity and dielectric loss tangent)>
In accordance with JIS-C-6481, the impedance material analyzer "HP4291B" manufactured by Agilent Technologies Co., Ltd. was used to measure the 1 GHz of the test piece after it was completely dried and stored in a room at 23 ° C. and 50% humidity for 24 hours, and The dielectric constant (Dk) and dielectric loss tangent (Df) at 10 GHz were measured. The results are shown in Table 2.

The dielectric constant (Dk) is preferably 4.80 or less, more preferably 4.50 or less at both 1 GHz and 10 GHz. Further, the dielectric loss tangent (Df) is preferably 0.0100 or less, more preferably 0.0095 or less at both 1 GHz and 10 GHz. It is preferable that the dielectric constant and the dielectric loss tangent are low, since it is possible to cope with higher speed and higher frequency signals.

<Copper foil adhesion (peel strength)>
In accordance with JIS-6911, the laminate obtained above was cut into a size of 10 mm in width and 200 mm in length, and this was used as a test piece to measure the peel strength of the copper foil and evaluate the adhesion. The results are shown in Table 2.

The peel strength is preferably 0.8 kN/m or more, more preferably 0.90 kN/m. If it is within the above range, the adhesion between the base material and the copper foil can be sufficiently ensured, which is preferable.

<Interlayer adhesion (interlayer peel strength)>
In accordance with JIS-6911, the copper foil-coated laminate obtained above was cut into a size of 10 mm in width and 200 mm in length, and this was used as a test piece to measure the adhesion between the layers. The results are shown in Table 2.

The interlayer peel strength is preferably 1.00 kN/m or more, more preferably 1.20 kN/m or more.

<Flame retardancy evaluation>
A combustion test was conducted using five test pieces in accordance with the UL-94 test method. The results are shown in Table 2.

注）硬化性樹脂組成物（溶剤を含まない有効成分中）中のリン含有率(質量％)は、原料の仕込み量、及び、前記理論リン含有率に基づき、計算した。また、「測定不可」とは、強度が大きく、測定できなかったことを示し、実用上問題はなく、銅箔への密着性や、積層体間の密着性が高いことを意味する。

Note) The phosphorus content (% by mass) in the curable resin composition (in the active ingredient not containing the solvent) was calculated based on the amount of raw materials charged and the theoretical phosphorus content. Moreover, "unmeasurable" indicates that the strength was too large to be measured, and it means that there is no practical problem and the adhesion to copper foil and the adhesion between the laminates are high.

From the evaluation results in Table 2 above, it was confirmed that the use of the desired phosphorus-containing active ester provided excellent flame retardancy, low dielectric properties (especially low dielectric loss tangent), and adhesion in all Examples. did it. On the other hand, in the comparative example, since the desired phosphorus-containing active ester was not used, it was confirmed that all the characteristics could not be satisfied at the same time.

The curable resin composition containing the phosphorus-containing active ester of the present invention has excellent flame retardancy, low dielectric properties, and adhesion, and therefore can be suitably used for electronic components, etc. In particular, it can be suitably used for semiconductor encapsulants, semiconductor devices, prepregs, flexible wiring boards, circuit boards, build-up films, build-up substrates, fiber-reinforced composite materials, molded products, and the like.

Claims (10)

An aromatic compound having a structure in which a residue of a phosphorus-containing polyhydric alcohol compound (A) and a residue of an aromatic polyhydric carboxylic acid (Q) are bonded via an ester bond, and the terminal is monovalent. A phosphorus-containing active ester characterized by being capped with a residue (C) of a compound containing a hydroxyl group. The phosphorus-containing active ester according to claim 1, which is represented by the following general formula (1).

[In the above general formula (1), A is a structure represented by any of the following general formulas (2) to (4), and R is each independently a linear or branched alkylene group. , Q is an aromatic ring, x is an average repeating number of 0.1 or more, y is an average repeating number of 1 or more, z is an average repeating number of 1 or more, and Ar is , has a structure represented by the following general formula (5) or (6),

# in the above general formulas (2) to (4) represents a bonding site with the oxygen atom bonded to A in the above general formula (1), and * in the above general formulas (5) and (6) , represents a bonding site between Ar and the oxygen atom in the above general formula (1), and Rb and Rc each independently represent an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an aralkyl group. , or may be a naphthyl group, and Rb and Rc may form a cyclic structure. Ra is each independently a halogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, an aralkyl group, or a naphthyl group, s is an integer from 0 to 7, and t is It is an integer from 0 to 5. ] The phosphorus-containing active ester according to claim 1 or 2, wherein the phosphorus content is 1.8% by mass or more. A curable resin composition comprising the phosphorus-containing active ester according to any one of claims 1 to 3 and an epoxy resin. A cured product obtained by subjecting the curable resin composition according to claim 4 to a curing reaction. A prepreg comprising a reinforcing base material and a semi-cured product of the curable resin composition according to claim 4 impregnated into the reinforcing base material. A circuit board characterized in that it is obtained by laminating the prepreg according to claim 6 and copper foil and molding them under heat and pressure. A build-up film comprising the curable resin composition according to claim 4. A semiconductor encapsulant comprising the curable resin composition according to claim 4. A semiconductor device comprising a cured product obtained by heating and curing the semiconductor sealing material according to claim 9.

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