JP2022001612A - Phosphorous-containing active ester, curable resin composition, cured material, prepreg, circuit board, build-up film, semiconductor sealant, and semiconductor device - Google Patents

Abstract

To provide a phosphorous-containing active ester capable of developing excellent fire retardancy, low dielectric property, and adhesiveness in an obtained cured material, a curable resin composition containing the phosphorous-containing active ester, and a cured material obtained by using the curable resin composition, furthermore, a semiconductor sealant using the curable resin composition, a semiconductor device, a prepreg, a circuit board, and a build-up film.SOLUTION: The present invention relates to a phosphorous-containing active ester characterized by having a structure in which a residue (A) of a phosphorous-containing polyvalent alcohol compound and a residual (Q) of aromatic polyvalent carboxylic acid are bonded via an ester bond, and a terminal is sealed by a residual (C) of a monovalent aromatic hydroxyl group-containing compound.SELECTED DRAWING: None

Description

The present invention relates to 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 the like. Regarding semiconductor devices.

Epoxy resin compositions containing epoxy resins and their curing agents as essential components are widely used in electronic component applications such as semiconductors and multilayer printed circuit boards because they exhibit excellent heat resistance and insulating properties in the cured products. ..

Among these applications for electronic components, in the technical field of insulating materials, the speed and frequency of signals in various electronic devices have been increasing in recent years. However, as the speed and frequency of signals increase, 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 property). However, when a cured product formed from an epoxy resin composition using polyhydric phenols as a curing agent is used for applications such as printed circuit boards (copper-clad laminates), it lacks flexibility and is caused by flexibility. Since it has problems such as inferior adhesion to copper foil, it is desired to develop an epoxy resin composition capable of obtaining a cured product having low dielectric properties and adhesion.

Further, from the viewpoint of environmental protection, the development of a non-halogen flame retardant printed circuit board (copper-clad laminated board) is required, and an epoxy resin obtained by adding a phosphorus-based flame retardant widely used as a flame retardant to an epoxy resin composition. The development of the composition is in progress. However, the cured product using the epoxy resin composition to which the phosphorus-based flame retardant is added has a low flame retardant efficiency, and when a large amount is added, a bleed-out phenomenon occurs in which the flame retardant is transferred to the surface of the cured product, and the copper foil Since it has a problem of affecting the performance such as a decrease in adhesion to the cured product, a reactive phosphorus flame retardant incorporated into a cured product by a chemical bond is required (Non-Patent Document 1).

Japanese Unexamined Patent Publication No. 2004-169821

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

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

As a result of diligent studies to solve the above problems, the present inventor has obtained a cured product having excellent flame retardancy and low dielectric constant by using a specific phosphorus-containing active ester in the curable resin composition. We have found that the properties and adhesion are exhibited, and have completed the present invention.

That is, the present invention has a structure in which the residue (A) of the phosphorus-containing polyhydric alcohol compound and the residue (Q) of the aromatic polyvalent carboxylic acid are bonded via an ester bond, and The present invention relates to a phosphorus-containing active ester characterized in that the terminal is sealed 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 an independently linear or branched alkylene group. , Q is an aromatic ring, x is an average number of repetitions of 0.1 or more, y is an average number of repetitions of 1 or more, z is an average number of repetitions of 1 or more, and Ar is an average number of repetitions. , The structure represented by the following general formula (5) or (6).

# In the general formulas (2) to (4) represents a bond site between A and an oxygen atom in the general formula (1), and * in the general formulas (5) and (6) is. Represents the bonding site between Ar and the oxygen atom bonded in the above general formula (1), and Rb and Rc independently represent an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, and an aralkyl group. , Or it may be a naphthyl group, and Rb and Rc may form a cyclic structure. Ra is independently any of 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 of 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 prepreg having a reinforcing base material and a semi-cured product of the curable resin composition impregnated in the reinforcing base material.

The present invention relates to a circuit board obtained by laminating the prepreg and copper foil and heat-pressing molding.

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 containing a cured product obtained by heating and curing the semiconductor encapsulant.

According to the present invention, a phosphorus-containing active ester capable of exhibiting excellent flame retardancy, low dielectric properties, and adhesion in the obtained cured product, a curable resin composition containing the phosphorus-containing active ester, and a curable resin composition. Provided are a cured product obtained by using the curable resin composition, and further, a semiconductor encapsulant, a semiconductor device, a prepreg, a circuit board, a build-up film, and the like using the curable resin composition. Can be useful.

6 is a GPC chart of the isophthalic acid diphenyl derivative (A-1) obtained in Synthesis Example 1. ^{6 is a 1} H-NMR chart of the isophthalic acid diphenyl derivative (A-1) obtained in Synthesis Example 1. 6 is an FD-MS spectrum chart of the isophthalic acid diphenyl derivative (A-1) obtained in Synthesis Example 1. 6 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. 6 is an FD-MS spectrum chart of the phosphorus-containing diol (PC-HCA-HQ) obtained in Synthesis Example 2. 6 is a GPC chart of the phosphorus-containing active ester (B-1) obtained in Example 1. ^{13 is} a 13 C-NMR chart of the phosphorus-containing active ester (B-1) obtained in Example 1. 6 is an FD-MS spectrum chart of the phosphorus-containing active ester (B-1) obtained in Example 1. 6 is a GPC chart of the phosphorus-containing diol (EC-HCA-HQ) obtained in Synthesis Example 3. 6 is a GPC chart of the phosphorus-containing active ester (B-2) obtained in Example 2. 6 is a GPC chart of the phosphorus-containing diol (PC-HCA-NQ) obtained in Synthesis Example 4. 6 is a GPC chart of the phosphorus-containing active ester (B-3) obtained in Example 3. 6 is a GPC chart of the phosphorus-containing diol (PC-PPQ) obtained in Synthesis Example 5. 6 is a GPC chart of the phosphorus-containing active ester (B-4) obtained in Example 4. 6 is a GPC chart of the intermediate (C-1) obtained in Comparative Synthesis Example 1. 3 is a GPC chart of the phosphorus-containing intermediate (C-2) obtained in Comparative Synthesis Example 2. 6 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 polyvalent carboxylic acid are bonded via an ester bond. Moreover, the terminal is sealed with the residue (C) of the 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 the residue (A) of the phosphorus-containing polyhydric alcohol compound that can be a flexible segment, and further has flame retardant properties in the structure. Since it contains a phosphorus atom that contributes to the property, a cured product using this phosphorus-containing active ester is excellent in flame retardancy, flexibility, low dielectric property, and adhesion, and is useful.

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 valent, more preferably divalent. .. When the valence is divalent or more, the number of functional groups of the active ester produced is 2 or more, which is excellent from the viewpoint of curability. The residue (A) of the phosphorus-containing polyhydric alcohol compound contains a phosphorus atom that contributes to flame retardancy in the structure, and has at least two linear or branched alkylene groups or alkyleneoxy groups. It preferably contains an aromatic ring that binds to.

The phosphorus-containing active ester of the present invention contains the residue (Q) of the aromatic polyvalent carboxylic acid, and its valence is preferably 2 to 4 valent, and more preferably divalent. .. When the valence is divalent or more, the number of functional groups of the phosphorus-containing active ester produced is 2 or more, which is excellent from the viewpoint of curability. Further, the aromatic 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 is sealed with the residue (C) of the monovalent aromatic hydroxyl group-containing compound, but the terminal is monovalent aromatic. The hydroxyl group-containing compound is not particularly limited as long as it has an aromatic ring and has one hydroxyl group (monovalent) 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 6 to 23% by mass. It is more preferable to have it. The above range is preferable because it is excellent in terms of heat resistance and dielectric properties of the cured product.

The "residue (A) of the phosphorus-containing polyhydric alcohol compound" in the present invention indicates a group obtained by removing the hydroxyl group from the phosphorus-containing polyhydric alcohol compound, and is the residue of the "aromatic polyvalent carboxylic acid". "Group (Q)" indicates a group obtained by removing a carboxyl group from an aromatic polyvalent carboxylic acid, and "residue (C) of an aromatic hydroxyl group-containing compound having a monovalent terminal" is aromatic. It shows 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 an independently linear or branched alkylene group. Q is an aromatic ring, x is an average number of repetitions of 0.1 or more, y is an average number of repetitions of 1 or more, z is an average number of repetitions of 1 or more, and Ar is the following general formula. It is the structure shown in (5) or (6).

# In the general formulas (2) to (4) represents a bond site between A and an oxygen atom in the general formula (1), and * in the general formulas (5) and (6) is. Represents the bonding site between Ar and the oxygen atom bonded in the above general formula (1), and Rb and Rc independently represent an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, and an aralkyl group. , Or it may be a naphthyl group, and Rb and Rc may form a cyclic structure. Ra is independently any of 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 of 0 to 7, and t is. It is preferably an integer of 0-5.
Since the phosphorus-containing active ester has a plurality of ester bonds and contains a linear or branched alkylene group, this chain structure has low polarity and constitutes a flexible segment, so that it has flexibility and low dielectric properties. An excellent cured product can be obtained, which is useful.

It is preferable that A in the general formula (1) has a structure represented by any of the general formulas (2) to (4), and Rb and Rc in the general formulas (2) to (4) are , Independently, preferably one of 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. May be good. Among them, A in the above general formula (1) has a 10- (2,5-dihydroxyphenyl) -9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide structure and a 10- [2- [2- (Dihydroxynaphthyl)] It is more preferable to have a -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide structure. Since the structure contains a phosphorus atom and has a high aromatic ring concentration, it can contribute to the effect of improving the flame retardancy based on the phosphorus-containing active ester, which is preferable. Active esters having an aliphatic cyclic hydrocarbon group in a conventionally known molecular structure are excellent in dielectric properties (low dielectric properties) in the obtained cured product, but are easy to burn and have insufficient heat resistance. Therefore, 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 the molecular structure. Further, since the active ester having a bulky substituent structure as described above has a lower concentration of active groups involved in the curing reaction than the active ester having no bulky substituent structure, it is a cured product. The phosphorus-containing active ester tends to be inferior in heat resistance, but the phosphorus-containing active ester has not only dielectric properties and flame retardancy but also excellent heat resistance, and is useful because it can have various performances. ..

It is preferable that R in the general formula (1) is independently 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 preferably 2 to 10 and even more preferably 2 to 10. When the number of carbon atoms is within the above range, a phosphorus-containing active ester having excellent compatibility is obtained, which is a preferable embodiment.

In the general formula (1), x is preferably an average number of repetitions of 0.1 or more, and above all, from the viewpoint of workability and flexibility of the obtained cured product, the average number of repetitions x is 0.5. It is more preferably to 3 and even more preferably 0.7 to 2.8.

In the general formula (1), y is preferably an average number of repetitions of 1 or more, and above all, the average number of repetitions y is 1 to 5 from the viewpoint of workability and flexibility of the obtained cured product. Is more preferable.

The z in the general formula (1) is preferably an average number of repetitions of 1 or more, and above all, the average number of repetitions z is 1 to 5 from the viewpoint of workability and flexibility of the obtained cured product. Is more preferable.

The Q in the general formula (1) is preferably an aromatic ring, more preferably an aromatic ring of any one of a benzene ring, a naphthalene ring, and an anthracene ring, and above all, an industrial raw material can be obtained. From the viewpoint of ease and solubility, a benzene ring is more preferable.

Rb and Rc in the above general formulas (2) to (4) are independently any of an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an aralkyl group, or a naphthyl group. It is preferable, and above all, from the viewpoint of physical properties of the obtained cured product and industrial availability, a linear or cyclic alkyl group having 2 to 12 carbon atoms, an alkoxy group, an allyl group, an aryl group, or a naphthyl is preferable. It is more preferable that it is a group.
Further, Rb and Rc in the above general formulas (2) to (4) may form a cyclic structure, and an alkoxy group, an aryl group, or a naphthyl group may be used from the viewpoint of easy availability of industrial raw materials. It is more preferable to have an annular structure. Here, the fact that Rb and Rc form a cyclic structure means that a cyclic structure is formed by binding Rb and Rc, and a structure including an aromatic ring or an alicyclic structure can be used. It may be formed.

Ar in the general formula (1) preferably has a structure represented by the general formula (5) or (6), and Ra in the general formula (5) or (6) is independent of each other. , Halogen atom, alkyl group, allyl group, alkoxy group, aryl group, aralkyl group, or naphthyl group, among which dielectric properties (low dielectric properties), workability and the obtained cured product. 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 general formula (5) or (6), s is preferably an integer of 0 to 7, t is preferably an integer of 0 to 5, and s and t are independently 0 to 5, respectively. It is more preferable that s and t are integers of 0 to 4, respectively, 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 such as an epoxy resin, has a flexible segment in its structure, and has the phosphorus-containing activity. Flexibility can be imparted to the cured product obtained by using the ester, which is a preferable embodiment. Further, 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 it is excellent in low dielectric property and is useful. Furthermore, since the phosphorus-containing active ester incorporates a phosphorus atom in its structure, it not only has excellent flame retardancy, but also bleeds out from the additive-type phosphorus-based flame retardant used as a flame retardant. Is suppressed, and it is useful because of its excellent adhesion to glass substrates and copper foil.

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 any of the above-mentioned phosphorus-containing active esters (I) and (II), but for example, two or more carboxyl groups. A phosphorus-containing polyol compound (d) is obtained by reacting a reaction product (c) of an aromatic compound and / or an acid halide or esterified product (a) thereof with an aromatic monohydroxy compound (b). The reaction product (compound corresponding to the above phosphorus-containing active ester) is preferably used. By using the phosphorus-containing active ester, a cured product having a low dielectric loss tangent and more excellent flame retardancy, heat resistance, moisture heat resistance, and adhesion can be obtained, which is a preferable embodiment. The reason is not always clear, but the obtained phosphorus-containing active ester contains an aryloxycarbonyl group (active ester group) at the terminal, and therefore exhibits high reactivity with the epoxy group of the epoxy resin described later. Due to the high reactivity, the generation of hydroxyl groups generated by the ring opening of the epoxy group can be prevented or suppressed, which is a preferable embodiment. Further, since the phosphorus-containing active ester has no or almost no hydroxyl group in the molecule, the hydroxyl group derived from the phosphorus-containing active ester is also contained in the cured product obtained by the reaction of the phosphorus-containing active ester. Or almost none. According to such an active ester, it is possible to prevent or suppress the generation of hydroxyl groups during curing. Generally, it is known that a hydroxyl group having a high polarity increases the dielectric loss tangent, but by using the phosphorus-containing active ester, a low dielectric loss tangent can be realized in a cured product, which is particularly useful.

Further, since the phosphorus-containing active ester has two or more ester bonds having a reaction activity with the epoxy group of the epoxy resin described later, the crosslink 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 alkylene oxy group (alkylene ether chain), and has a structure having low polarity because it has no or almost no hydroxyl group. A curable resin composition capable of exhibiting excellent flame retardancy, flexibility, moisture absorption resistance, adhesion to copper foil, etc. due to flexibility, and low dielectric property in the obtained cured product ( For example, an epoxy resin composition containing an epoxy resin), and further, a semiconductor encapsulating material using the curable resin composition, a semiconductor device, a prepreg, a circuit board, a build-up film, and the like can be provided, which is a preferable embodiment. Will be.

The phosphorus-containing active ester has a softening point from the viewpoint of excellent balance between handleability when prepared as a curable resin composition described later, heat resistance of the cured product, and dielectric properties. Is preferably 200 ° C. or lower, and more preferably 180 ° C. or lower.

[Aromatic compounds having two or more carboxyl groups and / or their acid halides or esters (a)]
The aromatic compound having two or more carboxyl groups and / or an acid halide or esterified product (a) thereof (a compound derived from the residue (Q) of the aromatic polyvalent carboxylic acid) has two or more. A carboxylic acid having a carboxyl group or a derivative thereof, specifically, a carboxylic acid, an acid halide, or an esterified product (hereinafter, may be referred to as "aromatic compound or the like (a)"). The aromatic compound and the like (a) have two or more carboxyl groups and the like, so that the aromatic monohydroxy compound (b) described later and the phosphorus-containing polyol compound (d) (hereinafter, simply "compound (hereinafter, simply" compound (hereinafter, "compound") are used. It may be referred to as "d)".) Derived from the compound (d) in the structure of the phosphorus-containing active ester by reacting with (a compound derived from the residue (A) of the phosphorus-containing polyhydric alcohol compound). A structure containing both a flexible structural moiety and an aryloxycarbonyl structure having epoxy curability at the terminal can be formed, and the ester structure having high reaction activity in the structure of the phosphorus-containing active ester ( Active ester group) can be formed. Further, 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 or the like (a) is more preferably 2 to 4, and even more preferably 2. When the number of carboxyl groups is at least 2 (2 or more), the number of functional groups of the phosphorus-containing active ester to be produced is 2 or more, which is excellent from the viewpoint of curability.

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

The aromatic ring is not particularly limited, and examples thereof include a monocyclic aromatic ring, a condensed aromatic ring, a ring-aggregated aromatic ring, and an aromatic ring linked by an alkylene chain.

The aromatic compound or the like (a) is not particularly limited, but is a benzenedicarboxylic acid such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, 2-allylterephthalic acid; trimellitic acid, 5-allyltrimellitic acid and the like. Benzintricarboxylic 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, Naphthalenedicarboxylic 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. Triazine carboxylic acids such as 5-triazine-2,4,6-tricarboxylic acid; examples thereof include acid halides and esterified acids thereof. Of these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferable, and isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid, and 1,3,5-benzenetricarbonyl. It is more preferably trichloride, more preferably isophthalic acid chloride, terephthalic acid chloride, and even more preferably 1,3,5-benzenetricarbonyltrichloride.

Of the above, from the viewpoints of flexibility of the obtained cured product, industrial availability of raw materials, and workability, an aromatic ring such as an aromatic compound in which the aromatic ring is a monocyclic aromatic ring has a condensed ring fragrance. It is preferably an aromatic compound or the like which is a group ring, preferably a benzenedicarboxylic acid, a benzenetricarboxylic acid, a naphthalenedicarboxylic acid, or an acid halide thereof, and preferably a benzenedicarboxylic acid, a naphthalenedicarboxylic acid, or an acid halide thereof. 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 acids These acid halides are more preferred. The above-mentioned aromatic compound or the like (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 derived from the residue (C) of the aromatic hydroxyl group-containing compound having a monovalent terminal) is, for example, phenol, o-cresol, m-cresol, and the like. Alkylphenols such as p-cresol, 2,4-xylenol, 2,6-xylenol, tertiary butylphenol, amylphenol; o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, styrenated phenol, Aralkylphenols such as 4- (α-cumyl) phenol; naphthol compounds such as 1-naphthol and 2-naphthol can be mentioned. These may be used alone or in combination of two or more. Of these, o-cresol and naphthol are preferable because a cured product having excellent dielectric properties (low dielectric properties) can be obtained.

The reaction with the aromatic compound or the like (a) and the aromatic monohydroxy compound (b) is not particularly limited, but is, for example, 1 to 1 in the presence of an alkaline catalyst under a temperature condition of 60 ° C. or lower. It can be carried out with a reaction time of 24 hours. Examples of the alkaline catalyst that can be used here include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, triethylamine, pyridine and the like. These may be used alone or in combination of two or more. Among these, sodium hydroxide or potassium hydroxide is preferable because of its high reaction efficiency. Further, these catalysts may be used as a 3 to 30% aqueous solution. At this time, a phase transfer catalyst may be used in order to increase the reaction efficiency. For example, an alkylammonium salt, a crown ether and the like can be mentioned. These may be used alone or in combination of two or more.

The above reaction is preferably carried out in an organic solvent because the reaction can be easily controlled. The organic solvent used here is, for example, a hydrocarbon solvent such as pentane or hexane, a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone, an ether solvent such as diethyl ether or tetrahydrofuran, ethyl acetate, butyl acetate, cellosolve acetate or propylene glycol monomethyl ether. Examples thereof include acetate 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 kinds.

The reaction ratios of the aromatic compound and the like (a) and the aromatic monohydroxy compound (b) can be appropriately changed according to the desired molecular design, but among them, while reducing the unreacted ends. From the viewpoint of reducing excess reaction raw materials, the aromatic monohydroxy compound (b) is preferably in the range of 1.1 to 5.0 mol, preferably 1.5 to 1 mol of the aromatic compound or the like (a). ~ 4.0 mol is more preferable, and 2.0 to 3.0 mol is even more preferable.

After completion of the reaction, when using an aqueous solution in the presence of an alkaline catalyst, the reaction solution is statically separated to remove the aqueous layer, the remaining organic layer is washed with water, and the aqueous layer is almost neutral (pH 7). The reaction product with the aromatic compound and the like (a) and the aromatic monohydroxy compound (b) in which the content of the inorganic salt having an adverse effect on the insulating property is reduced by repeating washing with water until the degree becomes). The reaction product (c) is 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, an alkyleneoxy group (alkylene ether chain) derived from the compound (d), which is a flexible segment, is introduced into the structure of the obtained phosphorus-containing active ester. It is possible to impart flexibility to the cured product obtained by using the phosphorus-containing active ester, and further, since a structure having a low polarity is introduced, the low dielectric property is excellent, which is a preferable embodiment. In addition, the phosphorus-containing active ester can prevent or suppress the generation of hydroxyl groups during synthesis, and is excellent in low dielectric properties and is useful.

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

The compound (d) is not particularly limited, but is represented by any of the above general formulas (2) to (4) from the viewpoints of flame retardancy, heat resistance, low dielectric property and the like. A diol compound (d-1) containing a structure (hereinafter, may be simply referred to as “compound (d-1)”), a condensed phosphoric acid ester-based polyol (d-2) (hereinafter, simply “compound (d−”). 2) ”), phosphorus-containing polyester polyol (d-3) (hereinafter, may be simply referred to as“ compound (d-3) ”) and the like are preferably used, for example, the following. A compound having a structure as shown in the 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 above general formula (1).

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

It is preferable that Rw, Rx, Ry, and Rz in the following general formulas (8) to (12) are independently hydrogen or alkyl groups, respectively, from the viewpoint of industrial availability. Therefore, 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.

As a method for producing the compound (d-1), it has two or more phenol hydroxyl groups in the presence of compounds having an epoxy group such as ethylene oxide, propylene oxide and butylene oxide and carbonates such as ethylene carbonate, propylene carbonate and butylene carbonate. It is obtained by heating and stirring a phosphorus-containing compound (e) (hereinafter, may be 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 hydrogencarbonate, potassium hydrogencarbonate, triethylamine, pyridine, diazabicycloundecene, diazabicyclononen, and triphenyl. Hosphin and the like can be mentioned. These may be used alone or in combination of two or more. Among these, diazabicycloundecene, diazabicyclononene, and triphenylphosphine are preferable because of their high reaction efficiency. The above reaction is not particularly limited, but may be carried out without an organic solvent or may be carried out in an organic solvent. The organic solvent used here is, for example, a hydrocarbon solvent such as pentane or hexane, a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone, an ether solvent such as diethyl ether or tetrahydrofuran, ethyl acetate, butyl acetate, cellosolve acetate or 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, dimethylformamide, dimethylacetamide, amides such as N-methylpyrrolidone. Examples include system solvents. Each of these may be used alone or as a mixed solvent of two or more kinds. The reaction conditions are not particularly limited, but the compound (d-1) can be obtained, for example, by stirring and reacting for 1 to 24 hours under a temperature condition 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-dihydro-9-oxa-10-phosphophenanthrene-10-oxide) manufactured by Sanko Co., Ltd. and HCA = NQ. (10- [2- (dihydroxynaphthyl)]-9,10-dihydro-9-oxa-10-phospphaphenanthrene-10-oxide), CPHO-HQ (1,4-cycloocty) manufactured by Nippon Kagaku Kogyo Co., Ltd. Examples thereof include a mixture of renphosphonyl-1,4-hydroquinone and 1,5-cyclooctylenephosphonyl-1,4-hydroquinone).

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

Examples of the compound (d-3) include 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.). Examples thereof include phosphorus-containing polyester polyol condensates having a hydroxyl group terminal (trade names: M-ESTER, ME-P8, manufactured by Sanko Co., Ltd.) 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 the reaction conditions, for example, a phosphorus-containing active ester can be obtained by stirring and reacting for 1 to 24 hours under a temperature condition of 50 to 250 ° C. Further, an alkali catalyst, particularly an amine-based catalyst (alkylamine such as triethylamine, triphenylamine and the like, condensed ring amine such as arylamine, DBU, DBN, and heterocyclic amine such as imidazole and pyridine) is added to react. Can be promoted. After completion of the reaction, in order to remove the excess aromatic monohydroxy compound (b), high-purity phosphorus is contained by distillation under atmospheric pressure and reduced pressure (for example, 0.9 to 0.01 atm). An active ester can be obtained.

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

The reaction ratios of the reaction product (c) and the compound (d) can be appropriately changed according to the desired molecular design, and among them, a phosphorus-containing active ester having more excellent workability and flexibility. Therefore, the hydroxyl equivalent of the compound (d) is preferably in the range of 0.1 to 0.9 mol, preferably 0.2 to 0.8 mol, with respect to 1 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 to 25% by mass, preferably 1.8% by mass or more, from the viewpoint of flame retardancy of the obtained cured product or the like and low dielectric loss tangent. %, More preferably 1.9 to 24% by mass.

The functional group equivalent of the phosphorus-containing active ester of the present invention is excellent in curability, has a low dielectric constant, and has a dielectric constant tangent when the total number of aromatic ester groups contained in the phosphorus-containing active ester structure is taken as the number of functional groups of the phosphorus-containing active ester. Since a cured product having (low dielectric properties) can be obtained, the range is preferably 160 to 1500 g / eq, more preferably 180 to 1200 g / eq, and 200 to 1000 g / eq. Is even more preferable.

The number average molecular weight (Mn) of the phosphorus-containing active ester of the present invention is preferably 320 to 3000, more preferably 360 to 2400. When the number average molecular weight (Mn) is 320 or more, it is preferable because the dielectric loss tangent is excellent. On the other hand, when the number average molecular weight (Mn) is 3000 or less, it is preferable because the moldability is excellent.

<Curable resin composition>
The curable resin composition of the present invention preferably contains the phosphorus-containing active ester and the 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 the molecule and can be cured by forming a crosslinked network with the epoxy groups.

The epoxy resin is not particularly limited, but is not particularly limited, but is phenol novolac type epoxy resin, cresol novolac type epoxy resin, α-naphthol novolac type epoxy resin, β-naphthol novolac type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl novolac type epoxy. Novolac type epoxy resin such as resin;
Phenolic aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin and other aralkyl type epoxy resins;
Bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S Bisphenol type epoxy resin such as type epoxy resin, tetrabromobisphenol A type epoxy resin;
Biphenyl type epoxy resin such as biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, epoxy resin having biphenyl skeleton and diglycidyl oxybenzene skeleton;
Naphthalene type epoxy resin;
Vinaftor type epoxy resin; Vinaftil type epoxy resin;
Dicyclopentadiene type epoxy resin such as dicyclopentadiene phenol type epoxy resin;
Glycidylamine type epoxy resin such as tetraglycidyldiaminodiphenylmethane type epoxy resin, triglycidyl-p-aminophenol type epoxy resin, and diaminodiphenylsulfone glycidylamine type epoxy resin;
Diglycidyl ester type epoxy resin such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resin and glycidyl ester type epoxy resin of hexahydrophthalic anhydride;
Examples thereof include benzopyran type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran.
Among these epoxy resins, the so-called glycidyl ether type epoxy resin obtained by epoxidizing a phenol compound is preferable, and among them, the novolak type epoxy resin, the aralkyl type epoxy resin, and the dicyclopentadiene type epoxy resin have dielectric properties. It is more preferable from the viewpoint of.

The above-mentioned epoxy resin may be used alone or in combination of two or more.

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 it is excellent in the dielectric property of the obtained cured product. On the other hand, when the epoxy equivalent of the epoxy resin is 400 g / eq or less, the heat resistance of the obtained cured product is good. It 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. When the softening point of the epoxy resin is 20 ° C. or higher, it is preferable because it can also have quick curing property. On the other hand, when the softening point of the epoxy resin is 200 ° C. or lower, it is preferable because the moldability is excellent.

The functional group equivalent ratio (phosphorus-containing active ester / epoxy resin) of the amount of the phosphorus-containing active ester used to the amount of the epoxy resin used is preferably 0.2 to 2, preferably 0.4 to 1.5. It is more preferable to have. When the functional group equivalent ratio is 0.2 or more, the obtained cured product can have lower dielectric loss tangent and higher flexibility, which is preferable. When the functional group equivalent ratio exceeds 2, heat resistance and curability are lowered, so that 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 further contains other curing agents, other resins, solvents, additives and the like as long as the effects of the present invention are not impaired. It may be included.

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

The other curing agent is not particularly limited, and examples thereof include an amine curing agent, an acid anhydride curing agent, and a phenol resin curing agent.

The amine curing agent is not particularly limited, but is diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diproprenzamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethyl. Aliper amines such as piperazine, mensendiamine (MDA), isopholonediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N, N, -dimethylpiperazine, triethylenediamine; m-xylenediamine (XDA), methanephenylenediamine (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 acid anhydride, ethylene glycol bistrimeritate, glycerol tristrimeritate, maleic anhydride, and tetrahydrophthalic anhydride. Methyltetrahydrochloride phthalic acid, endomethylenetetrahydrochloride phthalic acid, methylendomethylenetetrahydrochloride phthalic acid, methylbutenyltetrahydrochloride phthalic acid, dodecenyl succinic anhydride, hexahydrochloride phthalic acid, methylhexahydrohydride phthalic acid, succinic anhydride, Methylcyclohexene dicarboxylic acid anhydride and the like can be mentioned.

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

The above-mentioned other curing agents 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 a resin other than an epoxy resin.

Specific examples of the other resins are not particularly limited, but are limited to maleimide resin, bismaleimide resin, polymaleimide resin, polyphenylene ether resin, polyimide resin, cyanate ester resin, benzoxazine resin, triazine-containing cresol novolak resin, and cyanate ester. Examples thereof include resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallyl bisphenol and triallyl isocyanurate, polyphosphate esters, phosphate ester-carbonate copolymers and the like. 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 and the like.

Specific examples of the solvent are not particularly limited, but are 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-based solvents such as ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol, toluene, xylene, ethylbenzene, mecitylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and the like. Examples thereof include amide-based solvents such as aromatic hydrocarbons, dimethylformamides, dimethylacetamides, 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. When the amount of the solvent used is 10% by mass or more, it is preferable because the handling property is excellent. On the other hand, when the amount of the solvent used is 90% by mass or less, it is preferable from the viewpoint of economy.

[Additive]
The curable resin composition of the present invention may contain an additive. Examples of the additive include a curing accelerator, a flame retardant, a filler and the like.

(Hardening accelerator)
The curing accelerator (curing catalyst) is not particularly limited, and examples thereof include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a urea-based curing accelerator.

Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatrilphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine; organic phosphine compounds such as trimethylphosphine and triethylphosphine; ethyltriphenyl. Phosphornium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-trilborate, triphenylphosphine triphenylboran, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium disianamide, Examples thereof include phosphonium salts such as butylphenylphosphonium dicyanamide and tetrabutylphosphonium decanoate.

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 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-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2 -Methyl-3-benzylimidazolium chloride, 2-methylimidazoline and the like can be mentioned.

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] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-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, and 3- (4-chlorophenyl) -1,1. -Dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea and the like can be mentioned.

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

The above-mentioned curing accelerator may be used alone or in combination of two or more.

The amount of the curing accelerator used can be appropriately adjusted to obtain the desired curability, but is 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the mixture of the epoxy resin and the phosphorus-containing active ester. It is preferably 0.1 to 3 parts by mass, and more preferably 0.1 to 3 parts by mass. When the amount of the curing accelerator used is 0.01 parts by mass or more, it is preferable because the curing property is excellent. On the other hand, when the amount of the curing accelerator used is 5 parts by mass or less, it is preferable 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 separately used as long as the performance of the present invention is not impaired. The flame retardant is not particularly limited, and examples thereof include an inorganic phosphorus flame retardant, an organic phosphorus flame retardant, and a halogen flame retardant.

The inorganic phosphorus-based flame retardant is not particularly limited, and examples thereof include red phosphorus; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphoric acid amide.

The organophosphorus flame retardant is not particularly limited, but is limited to methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, and bis (2-ethylhexyl). Phosphates, Monoisodecyl Acid Phosphates, Lauryl Acid Phosphates, Tridecyl Acid Phosphates, Stearyl Acid Phosphates, Isostearyl Acid Phosphates, Oleyl Acid Phosphates, Butyl Pyrophosphates, Tetracosyl Acid Phosphates, Ethylene Glycol Acid Phosphates, (2-Hydroxyethyl) ) Phosphoric acid esters such as methacrylate acid phosphate; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide and the like diphenylphosphine; 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 compounds such as phenyl-1,4-dioxynaphthalin, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, 1,5-cyclooctylenephosphinyl-1,4-phenyldiol 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10 -Cyclic phosphorus compounds such as (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; the phosphoric acid ester, the diphenylphosphine, the phosphorus-containing phenol, and epoxy resins. Examples thereof include aldehyde compounds and compounds obtained by reacting with phenol compounds.

The halogen-based flame retardant is not particularly limited, but is limited to 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, tetrabromophthalic acid and the like. When used for a non-halogen flame retardant printed circuit board (copper-clad laminated board) or the like, it is preferable not to use the halogen-based flame retardant.

The above-mentioned 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 mass, more preferably 0 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin. When the amount of the flame retardant used is 50 parts by mass or less, flame retardancy can be imparted while maintaining the dielectric properties and adhesion, which is preferable.

(filler)
Examples of the filler include an organic filler and an inorganic filler. The organic filler has a function of improving elongation, a function of improving mechanical strength, and the like. The inorganic filler has functions such as reduction of the coefficient of thermal expansion and imparting flame retardancy.

The organic filler is not particularly limited, and examples thereof include polyamide particles.

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

Further, the filler may be surface-treated if necessary. At this time, the surface treatment agent that can be used is not particularly limited, but is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based cup. Ring agents and the like can be used. Specific examples of the surface treatment agent include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and hexamethyldi. Silazan and the like can be mentioned.

The above-mentioned filler may be used alone or in combination of two or more.

The amount of the filler used is preferably 0.5 to 95 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the epoxy resin. When the amount of the filler used is 0.5 parts by mass or more, the effect of the filler can be sufficiently imparted, which is preferable. On the other hand, the amount of the filler used is preferably 95 parts by mass or less so that the viscosity of the formulation becomes high and the moldability is not impaired.

<Curing 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, and the obtained cured product has a low dielectric loss tangent. It is a preferable embodiment because it can exhibit flame retardancy, flexibility, adhesion to a metal such as copper foil due to flexibility, and low dielectric property.

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

<Use of curable resin composition>
Applications in which the above curable resin composition is used include printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up boards, insulating materials for circuit boards such as adhesive films for build-up, and resin injection. Examples thereof include mold materials, adhesives, semiconductor encapsulant materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up substrates, fiber-reinforced composite materials, and molded products obtained by curing the composite materials. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and adhesive films for build-up are for so-called electronic component built-in boards in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. Can be used as an insulating material. Further, among the above, the curable resin composition of the present invention is semiconductor-sealed by taking advantage of the characteristics that the cured product has excellent flame retardancy, flexibility, adhesion, low dielectric property, heat resistance, and the like. It is preferably used for materials, semiconductor devices, prepregs, flexible wiring boards, circuit boards, and build-up films, build-up boards, multilayer printed wiring boards, fiber-reinforced composite materials, and molded products obtained by curing the composite materials. .. Hereinafter, a method for producing the semiconductor encapsulating material or the like from the curable resin composition will be described.

1. 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 curable resin composition, an extruder, a feeder, or a compounding agent such as the curable resin composition, a curing accelerator, and an inorganic filler is used as necessary. Examples thereof include a method of sufficiently melting and mixing until the mixture becomes uniform using a roll or the like. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and silicon nitride having higher thermal conductivity than fused silica are used. It is preferable to increase the filling of silicon or the like, or to use fused silica, crystalline silica, alumina, silicon nitride or the like. It is preferable to use an inorganic filler in the range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition, and above all, improvement of flame retardancy, moisture resistance and solder crack resistance, and a coefficient of linear expansion. 70 parts by mass or more is more preferable, and 80 parts by mass or more is further preferable.

2. 2. Semiconductor device The present invention relates to a semiconductor device containing a cured product obtained by heating and curing the semiconductor encapsulant. As a method for obtaining a semiconductor device from the curable resin composition, the semiconductor encapsulant material is cast or molded using a transfer molding machine, an injection molding machine, or the like, and further at 50 to 200 ° C. for 2 to 10 hours. In the meantime, there is a method of heating.

3. 3. Prepreg The present invention relates to a prepreg having a reinforcing base material and a semi-cured product of the curable resin composition impregnated in the reinforcing base material. As a method for obtaining a prepreg from the curable resin composition, a curable resin composition varnished by blending the following organic solvent is used as a reinforcing base material (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass). A method obtained by impregnating a mat, a glass roving cloth, etc.) and then heating at a heating temperature according to the solvent type used, preferably 50 to 170 ° C. can be mentioned. The mass ratio of the resin composition and the reinforcing base material used at this time is not particularly limited, but it is usually preferable to prepare the resin composition in the prepreg so as to have a mass ratio of 20 to 60% by mass.

Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like. It can be appropriately selected depending on the application, but for example, when further producing a printed circuit board from prepylene as described below, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, or dimethylformamide. , It is preferable to use the non-volatile content at a ratio of 40 to 80% by mass.

4. Circuit board The present invention relates to a circuit board obtained by laminating the prepreg and copper foil and heat-pressing molding. As a method for obtaining a printed circuit board from the curable resin composition, the prepregs are laminated by a conventional method, copper foils are appropriately laminated, and the pressure is 170 to 300 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa. , A method of heat-bonding can be mentioned.

5. Flexible wiring board As a method for manufacturing a flexible wiring board from the curable resin composition, there is a method manufactured by a method consisting of the following three steps. The first step is a step of applying 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. In the second step, the electrically insulating film coated with the curable resin composition is heated at 60 to 170 ° C. for 1 to 15 minutes using a heater, and the solvent is volatilized from the electrically insulating film to cure the film. The third step is to B-stage the sex resin composition, and the third step is to use a heating roll or the like on an electrically insulating film in which the curable resin composition is B-staged, and to use a metal foil as an adhesive. Is a step of thermal crimping (preferably a crimping pressure of 2 to 200 N / cm and a crimping temperature of 40 to 200 ° C.). If sufficient adhesive performance can be obtained by going through the above three steps, it may be finished here, but if complete adhesive performance is required, the condition is further at 100 to 200 ° C. for 1 to 24 hours. It is preferable to post-cure with. The thickness of the curable resin composition film after the final curing is preferably in the range of 5 to 100 μm.

6. Build-up substrate As a method for producing a build-up substrate from the above-mentioned curable resin composition, a method comprising the following three steps can be mentioned. The first step is a step of applying the above-mentioned curable resin composition appropriately containing rubber, filler and the like to a circuit substrate on which a circuit is formed by using a spray coating method, a curtain coating method, or the like, and then curing the curable resin composition. In the second step, after that, if necessary, a predetermined through hole portion or the like is drilled, treated with a roughening agent, and the surface thereof is washed with hot water to form irregularities, and a metal such as copper is formed. The third step is a step of sequentially repeating such an operation as desired to alternately build up and form a resin insulating layer and a conductor layer having a predetermined circuit pattern. It is preferable that the through-hole portion is drilled after the resin insulating layer of the outermost layer is formed. In addition to the above-mentioned solution coating, the first step can also be performed by laminating a build-up film that has been previously coated to a desired thickness and dried. Further, the build-up substrate of the present invention is coarsely formed by heat-pressing a copper foil with a resin, which is a semi-cured resin composition on a copper foil, onto a wiring board on which a circuit is formed at 170 to 250 ° C. It is also possible to manufacture a build-up substrate by forming a chemical surface and omitting the plating process.

7. Build-up film The present invention relates to a build-up film containing the curable resin composition. As a method for producing the build-up film of the present invention, the 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. The manufacturing method can be mentioned.

When a build-up film is produced from a curable resin composition, the film is softened under the temperature conditions of laminating (usually 70 to 140 ° C.) in the vacuum laminating method, and the via holes existing in the circuit board are present at the same time as laminating the circuit board. Alternatively, it is important to show fluidity (resin flow) capable of filling the through hole with the resin, and it is preferable to add each of the above 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 enable resin filling in this range. .. When laminating both sides of a circuit board, it is desirable to fill about 1/2 of the through holes.

Specifically, in the method for producing the above-mentioned adhesive film, after preparing the above-mentioned curable resin composition in the form of a varnish, the varnish-like composition is applied to the surface of the support film (Y) and further heated. Alternatively, it can be produced by drying an 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 equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

The composition layer (X) in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches.

The above-mentioned support film and protective film include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples include metal foils such as patterns, copper foils, and aluminum foils. The support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment.

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

The above-mentioned support film (Y) is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat-cured, it is possible to prevent dust and the like from adhering in the curing step. When peeling after curing, the support film is usually subjected to a mold release treatment in advance.

8. Multi-layer printed wiring board It is also possible to manufacture a multi-layer printed wiring board using the film obtained as described above. In the method of manufacturing such a multilayer printed wiring board, for example, when the composition layer (X) is protected by a protective film, the composition layer (X) is directly attached to the circuit board after peeling off the protective film. It is laminated on one side or both sides of the above, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be preheated if necessary before laminating.

The laminating conditions were preferably a crimping temperature (laminating temperature) of 70 to 140 ° C. and a crimping pressure of 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ). , It is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less.

9. Fiber-reinforced composite material As a method for producing a fiber-reinforced composite material from the curable resin composition, a varnish is prepared by uniformly mixing each component constituting the curable resin composition, and then the varnish is composed of reinforced fibers. It can be produced by impregnating a reinforced base material and then reacting with a polymerization reaction.

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

Here, the reinforcing fiber may be twisted yarn, untwisted yarn, untwisted yarn, or the like, but untwisted yarn or untwisted yarn is preferable because it has both formability and mechanical strength of the fiber-reinforced plastic member. Further, as the form of the reinforcing fiber, a fiber whose fiber direction is aligned in one direction or a woven fabric can be used. For woven fabrics, plain weaves, satin weaves, and the like can be freely selected according to the part to be used and the intended use. Specific examples thereof include carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like because of their excellent mechanical strength and durability, and two or more of these can be used in combination. Among these, carbon fiber is particularly preferable from the viewpoint of improving the strength of the molded product, and various carbon fibers such as polyacrylonitrile-based, pitch-based, and rayon-based can be used. Of these, polyacrylonitrile-based ones, which can easily obtain high-strength carbon fibers, are preferable. Here, the amount of the reinforcing fiber used when the varnish is impregnated into the reinforcing base material made of the reinforcing fiber to form a fiber-reinforced composite material is such that the volume content of the reinforcing fiber in the fiber-reinforced composite material is 40 to 85%. The amount is preferably in the range.

10. Fiber-reinforced resin molded product As a method for producing a fiber-reinforced resin molded product from the curable resin composition, a hand lay-up method, a spray-up method, or a male method in which a fiber aggregate is laid on a mold and the varnish is laminated in multiple layers. Using either a mold or a female mold, the base material made of reinforced fibers is impregnated with varnish and molded, and a flexible mold that can apply pressure to the molded product is put on and the airtightly sealed one is vacuumed. (Reduced pressure) Reinforced by the vacuum bag method for molding, the SMC press method in which a varnish containing reinforcing fibers is preliminarily made into a sheet and compression molded with a mold, and the RTM method in which the varnish is injected into a combined mold in which fibers are spread. Examples thereof include a method of producing a prepreg in which fibers are impregnated with the above varnish and baking the prepreg with a large autoclave. The fiber-reinforced resin molded product obtained above is a molded product having a reinforcing fiber and a cured product of a curable resin composition. Specifically, the amount of the reinforcing fiber in the fiber-reinforced resin molded product is , 40 to 70% by mass, and particularly preferably 50 to 70% by mass from the viewpoint of strength.

11. Others Although the method for producing a semiconductor encapsulating material or the like has been described above, other cured products can also be produced from the curable resin composition. As another method for producing a cured product, it can be produced by complying with a general curing method for a curable resin composition. For example, the heating temperature conditions may be appropriately selected depending on the type and application of the curing agent to be combined.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but in the following, "part" and "%" are based on mass unless otherwise specified. The 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 formula shown below. did.

<GPC measurement>
Measured using the following measuring device and measurement conditions, and used during the synthesis of the isophthalate diphenyl derivative, phosphorus-containing diol, phosphorus-containing active ester, and phosphorus-containing active ester obtained in the following synthesis examples and examples. GPC charts of intermediates and compounds of interest 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 + Tosoh Corporation Made by "TSK-GEL G4000HXL"
Detector: RI (Differential Refractometer)
Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene 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 the isophthalic acid diphenyl derivative, phosphorus-containing diol, phosphorus-containing active ester, and intermediate used in the synthesis of the phosphorus-containing active ester obtained in the synthesis examples and examples shown below. A solution obtained by filtering the% tetrahydrofuran solution with a microfilter (50 μl) was used.

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

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

<FD-MS spectrum measurement>
The FD-MS spectrum was measured using the following measuring device and measuring conditions.
Measuring device: JMS-T100GC AccuTOF
Measurement conditions Measurement range: m / z = 4.00 to 2000.0
Rate of change: 51.2mA / min
Final current value: 45mA
Cathode voltage: -10kV
Recording interval: 0.07 sec
From the results of the FD-MS spectrum, it was confirmed that the peak derived from the target product was confirmed, and that the target product was obtained in each reaction.

<Softening point>
Measured according to JIS K7234.

<Theoretical phosphorus content>
Theoretical phosphorus content (%) = 100 x [Phosphorus-containing raw material charged (parts by mass) x (Phosphorus content of phosphorus-containing raw material (mass%) / 100)] / (Phosphorus synthesized using phosphorus-containing raw material Theoretical yield of contained compound)
For the phosphorus content of the phosphorus-containing raw material, the product catalog value was used when the product 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) o-cresol 864.0 g (8.0 mol) and toluene were placed in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer. 4140.0 g was charged, and the inside of the system was replaced with reduced pressure toluene to dissolve it. Next, 808 g of isophthalic acid chloride (number of moles of acid chloride group: 4.0 mol) was charged, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve it. Then, 2.07 g of tetrabutylammonium bromide (hereinafter referred to as "TBAB") was dissolved, and the inside of the system was controlled to 60 ° C. or lower while purging with nitrogen gas, and 1648.0 g of a 20% sodium hydroxide aqueous solution was applied over 3 hours. And dropped. Then, stirring was continued for 1.0 hour under this condition. After completion of the reaction, the solution was statically separated and the aqueous layer was removed. Further, water was added to the toluene layer in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes, and the solution was allowed to stand and separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, water and toluene were removed by decanter dehydration and solvent removal to obtain a diphenyl isophthalate derivative (A-1) which is a crystalline compound. The active ester equivalent of the obtained isophthalic acid diphenyl derivative (A-1) was 173 g / eq from the charging ratio. The GPC chart of the diphenyl derivative (A-1) obtained in FIG. 1 is shown in FIG. 2, the ¹ H-NMR chart is shown in FIG. 2, and the FD-MS spectrum chart is shown in FIG.

Synthesis Example 2: Synthesis of phosphorus-containing diol: PC-HCA-HQ
In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Add 200.0 g of oxide (manufactured by Sanko Co., Ltd., trade name: HCA-HQ), 156.4 g of propylene carbonate and 1.07 g of triphenylphosphine (hereinafter TPP), heat the temperature to 190 ° C., and react until the reaction is completed. To obtain a phosphorus-containing diol (PC-HCA-HQ). The theoretical phosphorus content (content) of the obtained phosphorus-containing diol (PC-HCA-HQ) was 7.06% by mass, and the hydroxyl group equivalent was 253 g / eq. The GPC chart of the obtained PC-HCA-HQ is shown in FIG. 4, the ¹³ C-NMR chart is shown in FIG. 5, and the FD-MS spectrum chart is shown in FIG.

Example 1: Synthesis of phosphorus-containing active ester (B-1) The diphenyl derivative A-1 irophthalate obtained in Synthesis Example 1 was placed in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer. 137.0 g, 100.0 g of the 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, and 190. The temperature was raised to ° C. and the reaction was carried out for 3 hours. Then, the phosphorus-containing active ester (B-1) was obtained by further reacting while removing o-cresol by vacuum distillation. 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. The GPC chart of the active ester (B-1) obtained in FIG. 7 is shown, the ¹³ C-NMR chart is shown in FIG. 8, and the FD-MS spectrum chart is shown in FIG.

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 charged in an eggplant flask equipped with a stirrer, and the mixture was stirred at 180 ° C. in an oil bath equipped with a thermometer until the reaction was completed, and a phosphorus-containing diol (EC-HCA) was added. -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 group 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) For Example 1, instead of PC-HCA-HQ, EC-HCA-HQ 60.0 g and isophthalic acid diphenyl derivative (A-1) were 91. The same operation as in Example 1 was carried out except that the amount was changed to 0.7 g and DBU was changed to 0.15 g, to obtain a phosphorus-containing active ester (B-2). 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
For Synthesis Example 3, instead of HCA-HQ, 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 performing the same operation as in Synthesis Example 3 except that the trade name: HCA = NQ), ethylene carbonate 68.2 g, and DBU were changed to 0.50 g. The theoretical phosphorus content (content) of the obtained phosphorus-containing diol (PC-HCA-NQ) was 5.95% by mass, the hydroxyl group 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 place of PC-HCA-HQ, 71.5 g of PC-HCA-NQ and 100 isophthalic acid diphenyl derivative (A-1) were added to Example 1. The same operation as in Example 1 was carried out except that 0.9 g and DBU were changed to 0.34 g and 0.17 g of 4-dimethylaminopyridine (hereinafter DMAP) was added to obtain a phosphorus-containing active ester (B-3). rice field. 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
Diphenylphosphinyl hydroquinone (manufactured by Hokuko Sangyo Co., Ltd., trade name: PPQ (trademark registration) 100.0 g, propylene carbonate 72.4 g, TPP 0.52 g) was changed to Synthesis Example 2 in place of HCA-HQ. A phosphorus-containing diol (PC-PPQ) was obtained by performing the same operation as in Synthesis Example 2. The theoretical phosphorus content (content) of the obtained phosphorus-containing diol (PC-PPQ) was 7.05% by mass. The hydroxyl group equivalent was 208 g / eq, and the softening point was 99 ° C.. FIG. 14 shows the GPC chart of the obtained phosphorus-containing diol.

Example 4: Synthesis of phosphorus-containing active ester (B-4) For Example 1, instead of PC-HCA-HQ, 70.0 g of PC-PPQ, 116.5 g of isophthalic acid diphenyl derivative A-1, and DBU. Was changed to 1.86 g, and the same operation as in Example 1 was carried out to obtain a phosphorus-containing active ester (B-4). 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 double addition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g) was placed in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer. (/ Eq, softening point 85 ° C.) 330 g and 1184 g of toluene were charged, and the inside of the system was replaced with reduced pressure nitrogen to dissolve it. Next, 101 g of isophthalic acid chloride was charged, then 0.59 g of TBAB was charged, and the inside of the system was controlled to 60 ° C. or lower while performing nitrogen gas purging, and 206 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. .. Then, stirring was continued for 1.0 hour under this condition. After completion of the reaction, the solution was statically separated and the aqueous layer was removed. Further, water was added to the toluene layer in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes, and the solution was allowed to stand and separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, water was removed by decanter dehydration, and then toluene was removed by vacuum dehydration to obtain an 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) In a flask equipped with a thermometer, a cooling tube, a fractionation tube, and a stirrer, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- 77.0 g of 10-oxide, 48.5 g of p-anisaldehyde, and 197.5 g of the intermediate (C-1) were charged, the temperature was raised to 90 ° C., and the mixture was stirred while blowing nitrogen. Then, the temperature was raised to 180 ° C. and stirred for 5 hours, then 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, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer. 678.0 g of isobutyl ketone was charged, and the inside of 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 to 60 ° C. or lower while performing nitrogen gas purging, and 78 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. .. Then, stirring was continued for 1.0 hour under this condition. After completion of the reaction, the aqueous layer was removed by static separation. Further, water was added to the methyl isobutyl ketone layer in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes, and the solution was allowed to stand and separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, water was removed by decanter dehydration, and then methyl isobutyl ketone was removed by vacuum dehydration 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. The 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 Co., Ltd. (epoxy resin of a heavy addition reaction product of dicyclopentadiene and phenol, epoxy equivalent 276 g / eq), and the phosphorus obtained by synthesizing as a curing agent. The contained active esters were blended in the proportions shown in Table 1 below, and N, N-dimethylaminopyridine (DMAP) was used as the curing catalyst (curing accelerator), or the final non-volatile component (N. A curable resin composition was prepared by blending a methyl ethyl ketone so that V.) was 58% by mass.

Comparative Example 3
<Preparation of curable resin composition>
As an epoxy resin, "HP-7200H-75M" manufactured by DIC Corporation (epoxy resin of a heavy addition reaction product of dicyclopentadiene and phenol, epoxy equivalent 276 g / eq), and as a curing agent, "EPICLON HPC-8000-65T" manufactured by DIC Corporation. , Each of which is blended in the proportions shown in Table 1 below, DMAP is added as a curing catalyst, and methyl ethyl ketone is blended so that the final non-volatile content (NV) is 58% by mass to form a curable resin composition. Was prepared.

Comparative Example 4
<Preparation of curable resin composition>
As an 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 ratio shown in Table 1 below. DMAP was added as a curing catalyst, and methyl ethyl ketone was added so that the final non-volatile content (NV) was 58% by mass to prepare a curable resin composition.

<Conditions for manufacturing laminated boards>
Using the obtained curable resin composition, a laminated board was prepared under the following conditions, and various evaluation tests were performed by the method described later.
Base material: Glass cloth "# 2116" (210 x 280 mm) manufactured by Nitto Boseki Co., Ltd.
Copper foil: "JTC SLC foil" manufactured by JX Nippon Mining & Metals Co., Ltd. (18 μm)
Number of plies: 6
Curing conditions: 200 ° C, 29 kg / cm ² for 1.5 hours After molding Plate thickness: 0.8 mm

<Measurement of dielectric properties (dielectric constant and dielectric loss tangent)>
1 GHz of the test piece after being stored in a room at 23 ° C and 50% humidity after absolute drying by the impedance material analyzer "HP4291B" manufactured by Agilent Technologies Co., Ltd. for 24 hours in accordance with JIS-C-6481, and The permittivity (Dk) and the 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 either 1 GHz or 10 GHz. The dielectric loss tangent (Df) is preferably 0.0100 or less, more preferably 0.0095 or less, at either 1 GHz or 10 GHz. Since the dielectric constant and the dielectric loss tangent are low, it is possible to cope with high speed and high frequency of the signal, which is preferable.

<Copper foil adhesion (peel strength)>
According to JIS-6911, the laminated board obtained above was cut into a size of 10 mm in width and 200 mm in length, and the peel strength of the copper foil was measured using this as a test piece to evaluate the adhesion. The results are shown in Table 2.

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

<Interlayer adhesion (delamination strength)>
According to JIS-6911, the obtained laminated board with copper foil was cut into a size of 10 mm in width and 200 mm in length, and the adhesion between layers was measured using this as a test piece. The results are shown in Table 2.

The delamination strength is preferably 1.00 kN / m or more, and more preferably 1.20 kN / m or more.

<Flame retardance 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 containing no solvent) was calculated based on the amount of the raw material charged and the theoretical phosphorus content. Further, "unmeasurable" means that the strength is high and the measurement cannot be performed, there is no problem in practical use, and the adhesion to the copper foil and the adhesion between the laminated bodies are high.

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

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

Claims (10)

The residue (A) of the phosphorus-containing polyhydric alcohol compound and the residue (Q) of the aromatic polyvalent carboxylic acid have a structure in which they are bonded via an ester bond, and the terminal is a monovalent fragrance. A phosphorus-containing active ester characterized by being sealed with the residue (C) of the group hydroxyl group-containing compound. 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 an independently linear or branched alkylene group. , Q is an aromatic ring, x is an average number of repetitions of 0.1 or more, y is an average number of repetitions of 1 or more, z is an average number of repetitions of 1 or more, and Ar is an average number of repetitions. , The structure represented by the following general formula (5) or (6).

# In the general formulas (2) to (4) represents a bond site between A and an oxygen atom in the general formula (1), and * in the general formulas (5) and (6) is. Represents the bonding site between Ar and the oxygen atom bonded in the above general formula (1), and Rb and Rc independently represent an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, and an aralkyl group. , Or it may be a naphthyl group, and Rb and Rc may form a cyclic structure. Ra is independently any of 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 of 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, which is impregnated with the reinforcing base material. A circuit board obtained by laminating the prepreg and the copper foil according to claim 6 and heat-pressing molding. 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 heat-curing the semiconductor encapsulant according to claim 9.

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