JP2019044077A - Phosphorus-containing epoxy resin, method for producing the same, epoxy resin composition, and cured product thereof - Google Patents

Abstract

To provide a phosphorus-containing epoxy resin having excellent adhesiveness, heat resistance, and flame retardancy, and an epoxy resin composition thereof.SOLUTION: A phosphorus-containing epoxy resin has a structural site represented by a formula (b). (Ar is an aromatic ring group; Z is a phosphorus-containing group represented by a specific formula).SELECTED DRAWING: None

Description

  The present invention relates to an epoxy resin composition for producing a copper-clad laminate, a film material, a copper foil with resin and the like used for an electronic circuit board, and a sealing material, a molding material, a casting material, an adhesive and an electrical insulation used for electronic components. The present invention relates to a phosphorus-containing epoxy resin useful as a coating material or the like, a method for producing the same, an epoxy resin composition using the resin, and a cured product.

  In recent years, in the flame retardancy of electronic devices, the flame retardancy by halogen containing compounds represented by the conventional brominated epoxy resin for the purpose of suppression of toxic gas generated at the time of combustion from the consideration to environmental impact reduction. From the above, halogen-free flame retarding aimed at achieving flame retardancy by phosphorus compounds has already been established, and generally it is widely used and recognized as a phosphorus flame retardant epoxy resin.

  As a specific representative example of such a flame-retardant epoxy resin, proposals have been made to apply a phosphorus compound as disclosed in Patent Documents 1 to 4. Patent Document 1 discloses 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO-HQ) and epoxy resins. A thermosetting resin obtained by reacting at a predetermined molar ratio is disclosed. Further, Patent Document 2 briefly describes a method for producing diphenylphosphinyl hydroquinone, and discloses an epoxy resin having two or more epoxy groups and a phosphorus-containing epoxy resin formed by reacting this diphenyl phosphinyl hydroquinone. There is. Patent Document 3 discloses a method for producing a flame retardant epoxy resin in which an epoxy resin, a phosphine compound having an aromatic group on a phosphorus atom, and a quinone compound are reacted in the presence of an organic solvent. Patent Document 4 discloses a phosphorus-containing epoxy resin obtained by reacting a phosphorus-containing polyhydric phenol compound and an epoxy resin, and a phosphorus-containing flame retardant epoxy resin composition.

Patent Document 5 discloses 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO) and 1,4-benzoquinone (hereinafter referred to as BQ) and / or 1,4 -A step of obtaining a reaction composition by controlling naphthoquinone (hereinafter referred to as NQ) by controlling the total water content in the reaction system to be 0.3% by mass or less based on the total amount of DOPO used in the reaction 1 and Step 2 of reacting with a bisphenol A epoxy resin and / or a bisphenol F epoxy resin without purification of the reaction composition obtained in step 1 to produce a phosphorus-containing flame retardant bisphenol epoxy resin Methods are disclosed.
Here, a phosphorus-containing epoxy resin is produced after reaction of a quinone compound with a phosphorus compound such as DOPO or diphenyl phosphine oxide to form a bifunctional phenol compound, which is then reacted with epoxy resins. doing. All of these are naturally free of flame retardancy by the above-mentioned phosphorus compound as a halogen-free treatment considering the influence on the environment, but the crosslinking of the cured product is performed so as not to impair the heat resistance after curing of the phosphorus-containing epoxy resin. The method is described as being used in the form of the above bifunctional phenolic compound in order to increase the density.

  On the other hand, about the bifunctional phenol compound which added these DOPO, the influence of the by-product produced | generated in the synthetic | combination process is described in the patent documents 6-7. In Patent Document 6, DOPO and NQ undergo a reaction in which the content of by-products is reduced in an inert solvent having a dielectric constant of 10 or less, and then this reaction composition is ethylene glycol, propylene glycol, diethylene glycol, cyclohexanone, benzyl alcohol, acetate ester. And a method of dissolving in a solvent selected from benzoic acid esters and performing recrystallization purification. In this document, impurities and moisture are removed by enhancing the crystallinity of the bifunctional phenol compound to which DOPO is added to improve the heat resistance against solder, which is a problem, but the recrystallization step in the purification is a printed circuit board etc. These phosphorus-containing resins are poorly soluble in solvents such as methyl ethyl ketone generally used in the preparation of varnishes for producing prepregs, and they are difficult to precipitate crystals. Improper impregnation to glass cloth due to the influence, deterioration of properties in terms of mechanical characteristics and heat resistance after substrate molding, uniform flame resistance, etc. are concerned. In addition, since the melting start temperature of these crystals is a high temperature of 280 ° C. or higher, curing defects occur under the pressing temperature conditions on general printed circuit boards at around 200 ° C., and the target heat resistance, flame resistance, etc. It is also considered that the characteristic can not be obtained. For these reasons, the polyfunctional phenol compound in which a phosphorus compound such as DOPO is added to a quinone compound is not purified after the reaction, and the method of handling as a phosphorus-containing epoxy resin reacted with an epoxy resin is economically advantageous. is there.

  Patent Document 7 refers to by-products in producing a phosphorus-containing phenolic compound. It describes about the content which can suppress the remarkable hardening delay in the case of hardening reaction by specifying content of this by-product when making an epoxy resin and this phosphorus containing phenol compound react and handling as a phosphorus containing epoxy resin. And even if the content of this by-product is small, the influence on inhibiting the curability is very large, and it is described that the control of the content is important.

  However, the phosphorus-containing epoxy resin of the present invention as well as the phosphorus compound used in the production thereof is not mentioned in any of the documents, and the production conditions of the phosphorus compound and the effect thereof are not found.

JP 04-11662 A JP 05-214070 A JP, 2000-309624, A Unexamined-Japanese-Patent No. 2002-265562 JP, 2006-342217, A JP, 2013-43910, A International Publication 2009/060987

  Phosphorus-containing epoxy resin which exhibits excellent flame retardancy without reducing heat resistance of the cured product as flame retardant formulation of non-halogen epoxy resin cured product, and epoxy resin composition using the phosphorus-containing epoxy resin To provide goods.

  The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, a phosphorus-containing phenolic compound which is obtained by reacting a phosphorus compound typified by DOPO with a quinone compound has hitherto been known. An epoxy resin composition using a phosphorus-containing epoxy resin obtained by reacting a phosphorus-containing phenol compound with a polyfunctional epoxy resin, which has excellent flame retardancy compared to a phenol compound, is a cured product thereof In addition to the excellent flame retardancy, it has been found that the properties such as the solder reflowability are improved due to the improvement of the heat resistance and the decrease of the water absorption, and the present invention has been completed.

That is, the present invention is a phosphorus-containing epoxy resin characterized by having a structural portion (hereinafter referred to as a structural portion b) represented by the following formula (b).

Here, Ar represents an aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring, and these aromatic ring groups are alkyl groups having 1 to 8 carbon atoms and 1 to 8 carbon atoms. Alkoxy group, cycloalkyl group having 5 to 8 carbon atoms, aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 11 carbon atoms, aryloxy group having 6 to 10 carbon atoms, or aralkyloxy having 7 to 11 carbon atoms It may have any of the groups as a substituent.
Z is a phosphorus-containing group represented by the following formula (a).

ここで、Ｒ^１、Ｒ^２はそれぞれ独立に、ヘテロ原子を有してもよい炭素数１〜２０の炭化水素基を示し、直鎖状、分岐鎖状、又は環状であってもよく、また、Ｒ^１とＲ^２が結合し、環状構造部位となっていてもよい。ｎ１、ｎ２はそれぞれ独立に、０又は１である。

Here, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, and may be linear, branched or cyclic, or And R ¹ and R ² may combine to form a cyclic structure site. n1 and n2 are each independently 0 or 1.

ここで、Ａｒ及びＺは式（ｂ）のＡｒ及びＺとそれぞれ同義である。 The phosphorus-containing epoxy resin can further have a structural site (hereinafter referred to as structural site c) represented by the following formula (c).

Here, Ar and Z are respectively synonymous with Ar and Z of Formula (b).

  Moreover, this invention is a phosphorus containing epoxy resin which has a structure represented by a following formula (b1), and can have a structure represented by a following formula (c1).

Here, Ar and Z are respectively synonymous with Ar and Z of Formula (b). E is an organic group represented by -R ³ -A ¹ , -R ³ -is a linking group generated by the reaction of an epoxy group of a polyfunctional epoxy resin and a hydroxyl group, and A ¹ is a residue of the polyfunctional epoxy resin Group having at least one mole of an epoxy group or an epoxy derivative group thereof per one mole of A ¹ , wherein at least a portion is an epoxy group, and in the epoxy derivative group, the phosphorus-containing group Z and the hydroxyl group are Ar It is a group which arises from the phenol compound which has a bonded structure, and an epoxy group, E of Formula (b1) and Formula (c1) may be shared with E of other Formula (b1) or Formula (c1). Y is a hydrogen atom or E.

ここで、Ａｒ及びＺは式（ｂ）のＡｒ及びＺとそれぞれ同義である。 The above-mentioned phosphorus-containing epoxy resin is obtained by reacting the hydroxyl group of phosphorus-containing phenol compound (1) represented by the following formula (1) with the epoxy group of the polyfunctional epoxy resin.

Here, Ar and Z are respectively synonymous with Ar and Z of Formula (b).

  Further, according to the present invention, there is provided a reactive agent (x) comprising a compound having a functional group reactive with an epoxy group containing the phosphorus-containing phenol compound (1) represented by the above formula (1) as an essential component, and a polyfunctional epoxy It is a method for producing a phosphorus-containing epoxy resin, which comprises reacting with a resin (y).

（ここで、Ａｒ、Ｚは式（１）のＡｒ及びＺとそれぞれと同義である。） The reactive agent (x) contains a phosphorus compound (p) having a functional group reactive with an epoxy group, and this phosphorus compound (p) is represented by the phosphorus-containing phenol compound (1) and the following formula (2) The phosphorus-containing phenol compound (2) is preferably contained, and the content of the phosphorus-containing phenol compound (1) is preferably 0.1 to 35% by mass of the phosphorus compound (p). More preferably, it is 0.5-30 mass%, More preferably, it is 1.0-25 mass%.

(Here, Ar and Z are respectively synonymous with Ar and Z of Formula (1).)

ここで、Ｒ^１、Ｒ^２、ｎ１、及びｎ２は式（ａ）のＲ^１、Ｒ^２、ｎ１、及びｎ２とそれぞれ同義である。
上記反応剤（ｘ）が、リン化合物（ｐ）以外のエポキシ基と反応性の官能基を有する化合物（ｘ１）を含むこともできる。 In the above method for producing a phosphorus-containing epoxy resin, 0.10 or more moles of quinone compound (q) relative to 1 mole of phosphorus compound (3) represented by the following formula (3) is used as the phosphorus compound (p). It is obtained by reacting at 100 to 200 ° C. in an organic solvent having a water content of 0.05 to 0.5 mol with respect to 1 mol of phosphorus compound (3). Good thing.

^{Wherein, R 1, R 2, n1} , and n2 are the same meanings as ^{R 1, R 2, n1,} and n2 of formula (a).
The reactive agent (x) may also include a compound (x1) having a functional group reactive with an epoxy group other than the phosphorus compound (p).

  The present invention is also an epoxy resin composition comprising the above-mentioned phosphorus-containing epoxy resin and a curing agent for epoxy resin. The present invention is also a circuit board material, a sealing material, or a casting material obtained using this epoxy resin composition. Further, the present invention is a cured product obtained by curing the epoxy resin composition.

  The cured product using the phosphorus-containing epoxy resin of the present invention is significantly improved in flame retardancy as compared with a cured product using a phosphorus-containing epoxy resin obtained from a conventional phosphorus compound. That is, since the phosphorus content, which is the purpose of imparting flame retardancy, can be suppressed to a low level, the epoxy equivalent showing the number of functional groups in the epoxy resin can be kept low, thereby greatly improving the heat resistance of the cured product. Can. At the same time, lowering the water content can be achieved by lowering the phosphorus content, and a phosphorus-containing epoxy resin and an electronic circuit board material excellent in thermal stability such as solder reflowability of a cured product such as a laminate are provided. be able to.

15 is a GPC chart of the phosphorus-containing epoxy resin obtained in Example 11. 15 is a chart of FT-IR of the phosphorus-containing epoxy resin obtained in Example 11. 6 is a chart of the HPLC of the phosphorus compound obtained in Synthesis Example 1. 7 is a chart of NMR of a phosphorus compound obtained in Synthesis Example 2.

  The phosphorus-containing epoxy resin of the present invention has a structural site b represented by the above formula (b). And this structural part b is introduce | transduced in phosphorus containing epoxy resin by making a phosphorus containing phenol compound (1) and an epoxy resin react.

In Formula (b), Ar represents a tetravalent aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring. The aromatic ring group may be composed only of a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring, and may have a substituent.
The substituent in the case of having a substituent is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, To 11 aralkyl group, an aryloxy group having 6 to 10 carbon atoms, or an aralkyloxy group having 7 to 11 carbon atoms, and when the substituent has an aromatic ring, the aromatic ring is further an alkyl group or an alkoxy group Etc. may be substituted.

  For example, examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, hexyl group, etc. Examples of the group include a cyclohexyl group and the like, and examples of the aryl group having 6 to 10 carbon atoms or aryloxy group include a phenyl group, a tolyl group, a naphthyl group, a methoxyphenyl group, an ethoxyphenyl group, a phenoxy group, a naphthyloxy group and the like And examples of the aralkyl group having 7 to 11 carbon atoms or the aralkyloxy group include a benzyl group, a phenethyl group, a 1-phenylethyl group, a benzyloxy group, and a naphthylmethyloxy group.

  Preferred examples of Ar include a benzene ring group, a methyl group-substituted benzene ring group, a 1-phenylethyl group-substituted benzene ring group, a naphthalene ring group, a methyl group-substituted naphthalene ring group, and a 1-phenylethyl group-substituted naphthalene ring group. Here, the benzene ring group is a group generated by removing four H (hydrogen atoms) from the benzene ring, the naphthalene ring group is a group generated by removing four H from the naphthalene ring, and the position excluding H is It is not limited.

Z is a phosphorus-containing group represented by the above formula (a).
In formula (a), R ¹ and R ² each represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, which may be different or identical, and is linear or branched, It may be annular. Also, R ¹ and R ² may be combined to form a cyclic structure. In particular, an aromatic ring group such as a benzene ring is preferred. When R ¹ and R ² are an aromatic ring group, as a substituent, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, 6 to 10 carbon atoms And an aralkyl group having 7 to 11 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an aralkyloxy group having 7 to 11 carbon atoms. As a hetero atom, an oxygen atom etc. are illustrated and this can be contained between carbon which comprises a hydrocarbon chain or a hydrocarbon ring.

  n1 and n2 are 0 or 1 and independent of each other.

  In the present specification, in the formulas (a) to (c), (a1), (a2), (b1), (c1) and (1) to (6), common symbols are used unless otherwise noted. It is synonymous.

  The phosphorus-containing group represented by the above formula (a) is preferably one represented by the following formula (a1) or (a2).

In formulas (a1) and (a2), R ⁴ and R ⁵ each independently represent a hydrocarbon group having 1 to 11 carbon atoms, and specifically, methyl group, ethyl group, tert-butyl group, cyclohexyl Groups, phenyl group, tolyl group and benzyl group are mentioned, and methyl group, phenyl group and benzyl group are preferable. m1 is each independently an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1. m2 is respectively independently the integer of 0-5, 0-2 are preferable and 0 or 1 are more preferable.

  As another preferable example of the phosphorus containing group represented by Formula (a), the phosphorus containing group represented by following formula (a3)-(a12) is mentioned.

  100-1500 are preferable, as for the epoxy equivalent (g / eq.) Of the phosphorus containing epoxy resin of this invention, 160-1200 are more preferable, 200-800 are still more preferable, and 250-700 are especially preferable. If the epoxy equivalent is low, the introduction of the phosphorus structure is small and the flame retardancy may be deteriorated. When the epoxy equivalent is high, the molecular chain becomes longer than necessary, which may increase adverse effects such as deterioration of solvent solubility and increase of resin viscosity. Or, there are many addition reaction sites with epoxy groups and less epoxy groups. Therefore, since the crosslink density of the cured product becomes low, the elastic modulus may decrease at the temperature of the solder reflow, which may cause a serious problem in use. However, when it is used as a reactive flame retardant, the upper limit of the epoxy equivalent does not have to be particularly considered since only one epoxy group is required.

  Moreover, when using it as a flame retardant simply, since a flame retardance will be exhibited even if there are few usage-amounts, if a phosphorus content rate is high, it is preferable. However, 0.5-15 mass% is preferable as phosphorus in phosphorus containing epoxy resin in the case of using in the state with the effect as an epoxy resin, and 1-8 mass% is more preferable, and 1 0.5 to 6.0% by mass is more preferable, and 2.0 to 3.5% by mass is particularly preferable. If the phosphorus content is low, the flame retardancy may be deteriorated. If the phosphorus content is high, there is a possibility that adverse effects such as deterioration in solvent solubility and moisture absorption resistance and increase in resin viscosity may increase due to the effect of improving flame retardancy. Therefore, it is effective to manage the upper limit.

  The phosphorus-containing epoxy resin of the present invention has improved flame retardancy and heat resistance when the phosphorus content is the same as compared with a phosphorus-containing epoxy resin having no structural site b. It is impossible to quantify the structural site b in the phosphorus-containing epoxy resin, and the characterization is also quite difficult. For example, after isolation of only low molecular weight components in the phosphorus-containing epoxy resin, the presence can be confirmed by analysis such as NMR, but such isolation requires an operation such as separation. Briefly, since the reaction between the hydroxyl group and the epoxy group contained in the phosphorus compound used as the raw material proceeds almost quantitatively, the phosphorus compound used as the raw material is analyzed and the phosphorus-containing phenolic compound contained (1) It can be calculated from the amount of As a side note, there is a method of measuring the remaining amount of the phosphorus-containing phenol compound (1) in the phosphorus-containing epoxy resin. The phosphorus-containing phenol compound (1) is essential for the introduction of the structural site b, and under normal reaction conditions, the phosphorus-containing phenol compound (1) may remain although in a small amount. By confirming the remaining phosphorus-containing phenol compound (1), it can be determined whether it is the phosphorus-containing epoxy resin of the present invention having the structural site b. Specifically, it is judged whether or not the lowest detection sensitivity is detected by high performance liquid chromatography (HPLC) measurement under measurement conditions of 0.01% by mass. The content of the structural portion b in the phosphorus-containing epoxy resin is preferably 0.01 to 60% by mass, more preferably 0.1 to 50% by mass, still more preferably 1.0 to 40% by mass, and particularly preferably 10 to 30% by mass preferable.

The phosphorus-containing epoxy resin of the present invention has the above structural site b, and preferably further has a structural site c. The entire structure including these structural parts b and c is a structure represented by the above formula (b1), or the above formula (b1) and the formula (c1). E in the formulas (b1) and (c1) is an organic group represented by -R ³ -A ¹ , and -R ³ -is a linking group generated by the reaction of an epoxy group of a polyfunctional epoxy resin and a hydroxyl group A ¹ is a residue of a multifunctional epoxy resin and has one or more moles of an epoxy group or its epoxy derivative group per mole of A ¹ , wherein at least a portion is an epoxy group, the above epoxy The derivative group is a group derived from a phenol compound having a structure in which a phosphorus-containing group Z and a hydroxyl group are bonded to Ar and an epoxy group. And E of Formula (b1) and Formula (c1) can be shared with E of other Formula (b1) or Formula (c1).

The hydroxyl group of the phosphorus compound used as the raw material reacts with the epoxy group of the epoxy resin to form a linking group R ³ and bonds the two. The linking group R ³ is determined by the type of epoxy resin. When the epoxy resin is glycidyl ether or glycidyl ester, -R ³ -A ¹ is represented by -CH ₂ -CH (OH) -CH ₂ -O-A ¹ , and in the case of glycidyl amine, -CH _{2- CH (OH) -CH 2 -N-} a 1 is represented, in the case of polyvinyl arene polyoxide becomes represented by ^{_{-CH 2 -CH (OH) -A 1}} . Moreover, when an epoxy resin is alicyclic like a celloxide, it becomes what is represented by a following formula (E1). Since the reaction mechanism of the hydroxyl group and the epoxy group of various epoxy resins is well known, it is possible to understand the linking group R ³ from the reaction formulas described above and below.

A ¹ is a residue of a multifunctional epoxy resin, one of its epoxy groups is used to form the linking group R ³ and the other epoxy groups remain unreacted or used as a raw material It reacts with the phosphorus compound to form an epoxy derivative. That is, the phosphorus compound is for a phenolic compound having the structure phosphorus-containing group Z and the hydroxyl group is bonded to Ar, and a hydroxyl group of the phosphorus compound, and the epoxy group of the polyfunctional epoxy resin to form a linking group R ³ by reacting The epoxy derivative is a structure in which the polyfunctional epoxy resin is bonded to Ar of the phosphorus compound through a linking group R ³ . The phosphorus compound to be an epoxy derivative group may be a phosphorus compound of the formula (1) or a phosphorus compound of the formula (2), and as a result, the structural part b and the structural part c are simultaneously obtained. be able to. And, since A ¹ can further have a linking group R ³ , E containing A ¹ can also be E of formula (b 1) or E of formula (c 1) and can be shared it can. And to share the Ar of formula (b1) and Ar ^b, when the Ar of formula (c1) was Ar ^c, refers to as a structure such as Ar b -E-Ar ^c, which is the formula (b1 And both the expression (c1) are satisfied. That is, the structures of Formula (b1) and Formula (c1) may exist separately, or may share E and be present in one molecule as described above. And since Formula (b1) and Formula (c1) are also resin, in E, a plurality of Formula (b), Formula (c), or both structural parts via another E or linking group R ³ Can have a linked structure, as well as the residue site E ′ corresponding to E can be internalized.

A ¹ or more moles of an epoxy group or an epoxy derivative group thereof per 1 mole of Al, wherein at least a portion is an epoxy group. As a result of having a plurality of epoxy groups, the polyfunctional epoxy resin can be crosslinked to simultaneously have the structural part b and the structural part c in one molecule. However, since it is an epoxy resin, it has an epoxy group necessary to satisfy the above epoxy equivalent. Details of A ¹ can be understood from the specific examples and reaction formulas of the phosphorus-containing epoxy resin of the present invention described later.

  The phosphorus-containing epoxy resin of the present invention is obtained by reacting the hydroxyl group of the phosphorus compound represented by the above formula (1) with the epoxy group of the epoxy resin.

The manufacturing method of the phosphorus containing epoxy resin of this invention is demonstrated.
The method for producing the phosphorus-containing epoxy resin of the present invention is not unique to the present invention, and a reaction agent (x) essentially comprising the phosphorus-containing phenol compound (1) is reacted with the polyfunctional epoxy resin (y). Just do it. For example, known and commonly used methods such as the method described in JP-A-11-279258 or the advance method which is a reaction method of a phenol compound and an epoxy resin can be used.

The reactive agent (x) is composed of one or two or more compounds having a functional group capable of reacting with an epoxy group, and as a compound having a functional group reactive with the epoxy group, a phosphorus compound containing phosphorus (p And the compound (x1) which does not contain phosphorus. The reactive agent (x) essentially contains the phosphorus compound (p), and the compound (x1) can optionally be contained, and the reactive agent (x) or the phosphorus compound (p) contains the phosphorus-containing phenolic compound (1) Is an essential ingredient.
The phosphorus-containing phenol compound (1) is used as a phosphorus compound (p) containing another phosphorus-containing phenol compound such as phosphorus-containing phenol compound (2) or another phosphorus compound having a functional group reactive with an epoxy group be able to. The phosphorus-containing phenol compound (1) is obtained by the reaction described later, but is usually obtained as a reaction mixture containing by-products and unreacted materials. Such a reaction mixture, or a partially purified mixture thereof is excellent as a phosphorus compound (p). The reactive agent (x) can include a compound (x1) having a functional group that reacts with an epoxy group other than the phosphorus compound (p).
The phosphorus compound (p) may be the phosphorus-containing phenol compound (1) alone, or may be a mixture with other phosphorus compounds having a functional group reactive with an epoxy group. The phosphorus-containing phenol compound (1) has better heat resistance and flame retardancy than the phosphorus-containing phenol compound (2) and the phosphorus compound (3) conventionally known as flame retardants. The reason is considered as follows. The phosphorus-containing phenol compound (1) and the phosphorus-containing phenol compound (2) are uniformly incorporated into the entire cured product because they are bifunctional, but the phosphorus-containing phenol compound (1) is more likely to be phosphorus than the phosphorus-containing phenol compound (2). It is considered that the flame retardancy is improved because the char formation of the cured product is far more favored because the atoms are unevenly distributed. Moreover, since phosphorus compound (3) is monofunctional, and phosphorus containing phenol compound (1) is bifunctional, it is thought that the heat resistance of hardened | cured material improves.

The phosphorus-containing phenol compound (1) used in the present invention is 0.1 mol or more and less than 1.0 mol of the phosphorus compound (3) and the quinone compound (q) relative to 1 mol of the phosphorus compound (3). The quinone compound (q) is charged so as to be in the range, and the reaction is performed at 100 to 200 ° C. in an organic solvent in which 0.05 to 0.5 mol of water is present relative to 1 mol of the phosphorus compound (3). It is obtained by The reaction is preferably carried out at reflux.
An example of this reaction formula is shown in the following reaction formula (5). The reaction formula (5) exemplifies the formation of the phosphorus-containing phenol compound (1) obtained by the reaction of the phosphorus compound (3) and the quinone compound (q), but the phosphorus-containing phenol compound (2) or The phosphorus compound (4) is also exemplified, and this is an example in which the raw material phosphorus compound (3) remains as an impurity. In addition, Z in ZH is a phosphorus containing group represented by Formula (a).

ここで、Ａｒ及びＺは、式（１）のＡｒ及びＺとそれぞれ同義である。［Ａｒ］は下記反応式（６）が成立する芳香族環基である。

Here, Ar and Z are respectively synonymous with Ar and Z of Formula (1). [Ar] is an aromatic ring group which satisfies the following reaction formula (6).

ここで、Ａｒは、式（１）のＡｒと同義である。

Here, Ar is synonymous with Ar of Formula (1).

  When the above reaction formula (5) is shown as an example using DOPO (3-1) and NQ (q) as specific compounds, it becomes the following reaction formula (5-1).

  By selecting the phosphorus compound (3) and the quinone compound (q) as raw materials as the phosphorus-containing phenol compound (1), it is possible to use, for example, the following formulas (1-2) to ( Although the phosphorus compound represented by 1-5) is mentioned, it is not limited to these.

  The phosphorus-containing phenol compound (1) has, for example, three isomers when the quinone compound is BQ, and nine isomers when NQ. Among these isomers, preferred are phosphorus compounds (1 ') having a phosphorus-containing group Z at the 2-position and 3-position with respect to the 1- and 4-position hydroxyl groups. Although the phosphorus compound represented by following formula (1'-1)-(1'-5) will be mentioned if a preferable phosphorus compound (1 ') is illustrated, It is not limited to these.

  The phosphorus compound (p) may be one obtained by isolating the phosphorus-containing phenol compound (1), but the reaction mixture in a state in which the by-products shown in the above reaction formula are mixed, or the by-products contained in this reaction mixture In order to reduce the concentration, it is possible to use the concentrate after performing purification operations such as extraction, washing, recrystallization, distillation and the like. In addition, it may be a mixture of the isolated or concentrated phosphorus-containing phenol compound (1) and another phosphorus compound such as the phosphorus-containing phenol compound (2). The phosphorus compound (4) is preferably removed because it adversely affects the curability as disclosed in Patent Document 7.

Since many complex steps are required to isolate the phosphorus-containing phenol compound (1), industrially it can be used in a state of being mixed with the phosphorus-containing phenol compound (2) and the phosphorus compound (3) preferable. In this case, since the flame retardancy is slightly inferior to the case of using the phosphorus-containing phenol compound (1) alone, it is preferable to use it so as to slightly increase the phosphorus content in the composition.
In this case, the content of the phosphorus-containing phenol compound (1) is preferably 0.1 to 35% by mass of the phosphorus compound (p). More preferably, it is 0.5-30 mass%, More preferably, it is 1.0-25 mass%. If it is 0.1 mass% or more with respect to the phosphorus compound (p) which does not contain a phosphorus containing phenol compound (1) at all, the improvement effect of a flame retardance is recognized. In addition, the higher the upper limit, the higher the improvement effect of the flame retardancy is, but when the actual reaction is taken into consideration, it is controlled to about 35% by mass from the viewpoint of suppressing by-produced impurities such as phosphorus compound (4). It is preferable to do.

  In the reaction shown in the reaction formula (5), a competition reaction occurs between the phosphorus-containing phenol compound (1) and the phosphorus-containing phenol compound (2) and the phosphorus compound (4) by-produced. In order to increase the yield of the phosphorus-containing phenol compound (1), it is preferable to increase the molar ratio of the quinone compound (q) to the phosphorus compound (3). The quinone compound (q) is in the range of 0.1 mol to less than 1.0 mol, preferably 0.2 mol to 0.99 mol, and more preferably 0 per 1 mol of the phosphorus compound (3). It is not less than 25 mol and not more than 0.85 mol, and more preferably not less than 0.3 mol and not more than 0.9 mol. When the molar ratio is low, the reactivity of the phosphorus compound (3) with respect to the quinone compound (q) is extremely high, so the reaction is completed early and it becomes difficult to form the phosphorus-containing phenol compound (1).

  When the molar ratio is less than 0.10, the amount of the quinone compound (q) used is small, and the remaining of the phosphorus compound (3) is more than the formation of the phosphorus-containing phenol compound (1) or the phosphorus-containing phenol compound (2) Quantity increases. Therefore, when it is used as it is as a modifier of the phosphorus-containing epoxy resin, the sealing structure site of the terminal epoxy group by the phosphorus compound (3) increases and the crosslinking point is lowered, so that the heat resistance as a cured product is lowered. . In addition, in order to reduce the phosphorus compound (3), a purification step is required, and at the same time a large loss occurs, which is industrially disadvantageous and not preferable.

  On the other hand, when the reaction molar ratio is 1.0 or more, although it is effective for the formation of the phosphorus-containing phenol compound (1), the unreacted quinone compound (q) easily remains and the washing step after the reaction Mandatory, industrially disadvantageous and undesirable.

  Besides the above molar ratio, the reaction temperature affects the formation of the phosphorus-containing phenolic compound (1). The reaction temperature is preferably 100 to 200 ° C., and more preferably azeotropically with water at that temperature. Therefore, it is preferable to use the organic solvent which can maintain reflux temperature at 100-200 degreeC. Since the reflux temperature is lowered by water, the boiling point is preferably elevated, more preferably 100 to 220 ° C., and still more preferably 110 to 180 ° C. In addition, as long as the reflux temperature can be maintained, an organic solvent having a low boiling point may be used in combination. In addition, when using it as a modifier of phosphorus containing epoxy resin as it is after the synthesis | combination of phosphorus containing phenol compound (1), if an organic solvent with a very high boiling point is used, since it becomes difficult to remove the used organic solvent, it is unpreferable. . In that case, the organic solvent which can maintain reflux temperature at 100-160 degreeC is preferable, and the organic solvent whose boiling point is 100-160 degreeC is more preferable. Moreover, as a kind of organic solvent, although the ketone type organic solvent reactive with a phosphorus compound (3) is not suitable, it will not be specifically limited if it is other organic solvents which satisfy | fill the said conditions.

  Examples of the organic solvent that can be used include alcohols such as 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, 1,3-butanediol, isopropyl alcohol, and acetic acid Acetic acid esters such as butyl, methoxybutyl acetate, cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, benzyl alcohol acetate, and benzoic acid esters such as methyl benzoate and ethyl benzoate, Cellosolves such as methyl cellosolve, cellosolve and butyl cellosolve, carbitols such as methyl carbitol and butyl carbitol, and dimethoxydiethylene glycol Ethers such as ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, N, N-dimethylformamide, N, Amides such as N-dimethyl acetamide, dimethyl sulfoxide, acetonitrile, N-methyl pyrrolidone and the like can be mentioned, but it is not limited thereto. These organic solvents may be used alone or in combination of two or more.

  In addition, the water content in the reaction system is also important in order to promote the formation of the phosphorus-containing phenolic compound (1). It is effective to adjust the water content in the range of 0.05 to 0.5 mol with respect to 1 mol of the raw material phosphorus compound (3). Although the factor that promotes the formation of this phosphorus-containing phenol compound (1) is not yet clarified at present, the reaction mechanism is as follows: to the carbon adjacent to the C = O group of quinone compound (q), the phosphorus compound It is inferred that two addition reactions occur almost simultaneously by partial hydrogen bonding between two molecules of a phosphorus compound having good affinity for water when reacting and binding. As for the water content with respect to 1 mol of raw material phosphorus compounds (3), 0.1-0.5 mol is more preferable, and 0.2-0.4 mol is still more preferable.

  The quinone compound (q) used in the above reaction can be used without problems as long as its purity is 90% or more as an industrial product. If the purity is less than this, the properties as a cured product of the phosphorus-containing epoxy resin are adversely affected, and the durability in oven heat resistance and solder reflow characteristics is reduced. The preferred purity is 96% or more, and the more preferred purity is 98% or more. Because of their harmful effects, these quinone compounds (q) may be sold in advance in the hydrated state from the manufacturer for prevention of scattering. In this case, the reaction needs to be adjusted in advance in consideration of the amount of water in the quinone compound (q). These quinone compounds (q) may be used alone or in combination of two or more.

  When Ar in the formula (1) is a benzene ring as the quinone compound (q), for example, benzoquinone, methyl-benzoquinone, ethyl-benzoquinone, butyl-benzoquinone, dimethyl-benzoquinone, diethyl-benzoquinone, dibutyl-benzoquinone, Examples include, but are not limited to, methyl-isopropyl-benzoquinone, diethoxy-benzoquinone, methyl-methoxy-benzoquinone, phenyl-benzoquinone, tolyl-benzoquinone, ethoxy-phenyl-benzoquinone, diphenyl-benzoquinone and the like.

  When Ar in the formula (1) is a naphthalene ring, for example, naphthoquinone, methyl-naphthoquinone, cyclohexyl-naphthoquinone, methoxy-naphthoquinone, ethoxy-naphthoquinone, dimethyl-naphthoquinone, dimethyl-isopropyl-naphthoquinone, methyl-methoxy-naphthoquinone And the like, but not limited thereto.

  When Ar in the formula (1) is an anthracene ring, examples thereof include, but are not limited to, anthraquinone, methyl-anthraquinone, ethyl-anthraquinone, methoxy-anthraquinone, dimethoxy-anthraquinone, diphenoxy-anthraquinone and the like. is not.

  When Ar in the formula (1) is a phenanthrene ring, examples thereof include phenanthrenequinone, methyl-phenanthrenequinone, isopropyl-phenanthrenequinone, methoxy-phenanthrenequinone, butoxy-naphthoquinone, dimethoxy-phenanthrenequinone and the like. It is not limited to

  Examples of phosphorus compounds (3) as raw materials used in the above reaction include dimethyl phosphine oxide, diethyl phosphine oxide, dibutyl phosphine oxide, diphenyl phosphine oxide, dibenzyl phosphine oxide, cyclooctylene phosphine oxide, tolyl phosphine oxide, bis ( Methoxyphenyl) phosphine oxide, etc., phenyl phenyl phosphinate, ethyl phenyl phosphinate, tolyl tolyl phosphinate, benzyl benzyl phosphinate etc., DOPO, 8-methyl-9, 10-dihydro-9-oxa-10-phospha Phenanthrene-10-oxide, 8-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-phenyl-9,10-dihydro-9-oxa 10-phosphaphenanthrene-10-oxide, 2,6,8-tri-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dicyclohexyl-9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like, diphenyl phosphonate, dithiol phosphonate, dibenzyl phosphonate, 5,5-dimethyl-1,3,2-dioxaphosphorinane and the like can be mentioned. However, it is not limited to these. These phosphorus compounds (3) may be used alone or in combination of two or more.

  In the production method of the present invention, as the polyfunctional epoxy resin (y) to be used, it is preferable to use one having two or more, preferably three or more epoxy groups in the molecule. Specific examples thereof include polyglycidyl ether compounds, polyglycidyl amine compounds, polyglycidyl ester compounds, alicyclic epoxy resins, and other modified epoxy resins, but are not limited thereto. These epoxy resins may be used alone, or two or more of the same epoxy resins may be used in combination, or epoxy resins of different systems may be used in combination. Among these epoxy resins, a phenol novolac epoxy resin is particularly preferable in view of cost, heat resistance, flame resistance and the like from the viewpoint of excellent versatility.

  Specific examples of polyglycidyl ether compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, biphenol type epoxy resin, hydroquinone type epoxy resin, bisphenol fluorene type epoxy resin, naphthalene diol Epoxy resin, bisphenol S epoxy resin, diphenyl sulfide epoxy resin, diphenyl ether epoxy resin, resorcinol epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, alkyl novolac epoxy resin, styrenated phenol novolac epoxy Resin, bisphenol novolac epoxy resin, naphthol novolac epoxy resin, β-naphthol alcohol Epoxy type epoxy resin, naphthalenediol aralkyl type epoxy resin, α-naphthol aralkyl type epoxy resin, biphenylaralkylphenol type epoxy resin, trihydroxyphenylmethane type epoxy resin, tetrahydroxyphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, Although an alkylene glycol type epoxy resin, an aliphatic cyclic epoxy resin, etc. are mentioned, it is not limited to these.

  Specific examples of polyglycidyl amine compounds include diaminodiphenylmethane epoxy resin, metaxylene diamine epoxy resin, 1,3-bisaminomethylcyclohexane epoxy resin, isocyanurate epoxy resin, aniline epoxy resin, hydantoin epoxy resin. Although an epoxy resin, an aminophenol type epoxy resin, etc. are mentioned, it is not limited to these.

  Specific examples of the polyglycidyl ester compound include, but are not limited to, dimer acid epoxy resins, hexahydrophthalic acid epoxy resins and trimellitic acid epoxy resins.

  Examples of the alicyclic epoxy resin include, but are not limited to, aliphatic cyclic epoxy resins such as Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd.) and the like.

  As other modified epoxy resin, specifically, urethane modified epoxy resin, oxazolidone ring containing epoxy resin, epoxy modified polybutadiene rubber derivative, CTBN modified epoxy resin, polyvinylarene polyoxide (for example, divinyl benzene dioxide, trivinyl naphthalene trioxide Oxides, etc.), phosphorus-containing epoxy resins, etc. may be mentioned, but not limited thereto.

  The reaction of the phosphorus-containing phenol compound (1) with the polyfunctional epoxy resin (y) is specifically exemplified. When using a phenol novolac epoxy resin represented by the following formula (y-1) as the epoxy resin and the above formula (1-1) as the phosphorus-containing phenol compound, as one example, the following formula (7-1) The phosphorus containing epoxy resin represented by these is obtained. This is an example in which two phenol novolac epoxy resins and one phosphorus-containing phenol compound (1) of the formula (1-1) are reacted.

ここで、Ｇはグリシジル基を示す。ｋ１及びｋ２は繰り返し数で１以上の数である。

Here, G represents a glycidyl group. k1 and k2 are 1 or more in repetition number.

  When a phenol novolac epoxy resin represented by the following formula (y-1) is used as the epoxy resin and the above formulas (1-1) and the formula (3-1) are used as the phosphorus compound, the following formula is an example. The phosphorus-containing epoxy resin represented by (7-2) is obtained. This is an example in which two phenol novolac epoxy resins, one phosphorus-containing phenol compound (1) of the formula (1-1) and one or more phosphorus compounds (3) of the formula (3-1) are reacted. It is.

ここで、Ｇはグリシジル基を示す。ｋ１、ｋ２、ｋ５及びｋ８は繰り返し数で１以上の数である。ｋ３、ｋ４、ｋ６及びｋ７は繰り返し数で０以上の数であり、各ｋ５個のｋ３とｋ４の総和はｋ１であり、各ｋ８個あるｋ６とｋ７の総和はｋ２であり、ｋ５個のｋ３及びｋ８個のｋ６の内少なくとも１つは１以上の数である。

Here, G represents a glycidyl group. k1, k2, k5 and k8 are 1 or more in repetition number. k3, k4, k6 and k7 are 0 or more in repetition number, the sum of each of k5 k3 and k4 is k1, and the sum of each k8 k6 and k7 is k2, k5 k3 And at least one of k8 and k6 is one or more.

  When a glycidyl amine type epoxy resin represented by the following formula (y-2) is used as the epoxy resin and the above formula (1-1) is used as the phosphorus compound, the table is represented by the following formula (8-1) as an example. The resulting phosphorus-containing epoxy resin is obtained.

ここで、Ｇはグリシジル基を示す。

Here, G represents a glycidyl group.

  When a glycidyl ester type epoxy resin represented by the following formula (y-3) is used as the epoxy resin, and the above formula (1-1) is used as the phosphorus compound, the table is represented by the following formula (9-1) as an example. The resulting phosphorus-containing epoxy resin is obtained.

ここで、Ｇはグリシジル基を示す。

Here, G represents a glycidyl group.

  When an alicyclic epoxy resin represented by the following formula (y-4) is used as the epoxy resin, and the above formula (1-1) is used as the phosphorus compound, the table is represented by the following formula (10-1) as an example. The resulting phosphorus-containing epoxy resin is obtained.

  When an epoxy resin is a polyvinylarene polyoxide represented by the following formula (y-5) and the above formula (1-1) is used as a phosphorus compound, it is represented by the following formula (11-1) as an example. Phosphorus-containing epoxy resin is obtained.

  Reactive agent (x) is an epoxy equivalent, a molecular weight, etc. by using various epoxy resin modifiers as needed as a compound (x1) which has a functional group which reacts with epoxy groups other than phosphorus compound (p). It can also be adjusted. Examples of various epoxy resin modifiers include, but are not limited to, phenol compounds, amine compounds, and carboxylic acids. These epoxy resin modifiers may be used alone, or two or more kinds of epoxy resin modifiers of the same system may be used in combination, or epoxy resin modifiers of different systems may be used in combination. 30 parts by mass or less is preferable, 100 parts by mass or less is more preferable, 20 parts by mass or less is more preferable, and 10 parts by mass or less is still more preferable.

  Specific examples of the phenol compound include monophenol compounds such as nonylphenol, tert-butylphenol, phenylphenol and naphthol, bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol A, tetrabutyl bisphenol A, bisphenol F and dimethyl bisphenol F, tetramethylbisphenol F, bis (4-hydroxyphenyl) sulfone, dimethylbisphenol S, tetramethylbisphenol S, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-methyl-4- 4 Hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,4-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 2,2-bis (4-hydro) Ciphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bisphenol fluorene, biscresol fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, tetramethylbisphenol Z, 4, 4 '-(3,3,5-trimethylcyclohexylidene) bisphenol, dihydroxydiphenyl sulfide, 4,4'-thiobis (3-methyl-6-tert-butylphenol), dihydroxydiphenyl ether, dihydroxybenzophenone, dihydroxydiphenyl sulfide, dihydroxy Bisphenols such as stilbenes, biphenol, dimethylbiphenol, diethylbiphenol, di-tert-butylbiphenol, tetramethylbiphenol etc. Diphenols and dihydroxybenzenes such as hydroquinone, methylhydroquinone, dimethylhydroquinone, dibutylhydroquinone, methoxyhydroquinone, catechol, methyl catechol, dimethyl catechol, methoxy catechol, methoxy catechol, resorcinol, methyl resorcinol, hexyl resorcinol, dimethyl resorcinol, methoxy resorcinol, dihydroxy Polyhydroxynaphthalenes such as naphthalene, dihydroxymethyl naphthalene, trihydroxy naphthalene, tetrahydroxy naphthalene, etc., phenol novolak resin, cresol novolak resin, bisphenol A novolac resin, trishydroxyphenylmethane novolak resin, styrenated phenol novolac resin, naphthol novolak resin , Naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, etc. phenols and / or condensation products of naphthols and aldehydes, aromatic hydrocarbon formaldehyde resin-modified phenolic resin, phenol aralkyl resin, naphthol Condensates of phenols such as aralkyl resin and / or naphthols with xylylene glycol and / or xylylene dihalide, reaction products of phenols such as dicyclopentadiene phenol resin and / or naphthols and dicyclopentadiene, , Condensation products of phenols and / or naphthols with isopropenylacetophenone, phenols such as biphenyl-modified phenol resin, biphenyl-modified naphthol resin and / or naphthols, and biphenyl-based condensing agent Of various compounds such as phenol compounds such as condensates of amino acid derivatives, amino triazine modified phenolic resin (polyhydric phenol compound in which phenol nucleus is linked with melamine, benzoguanamine etc), terpene phenolic resin, heavy oil modified phenolic resin And polyfunctional phenol resins obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde and glyoxal, and these polyfunctional phenol resins are nucleus-substituted with substituents such as alkyl group, alkoxy group, aryl group and the like And the like, but not limited thereto.

  As raw materials of these polyfunctional phenol compounds, phenol, cresol, xylenol, butylphenol, octylphenol, amylphenol, nonylphenol, trimethylphenol, phenylphenol and the like can be mentioned. The naphthols include 1-naphthol and 2-naphthol. In addition, although not strictly naphthol, naphthanols also include naphthalenediols such as 1,4-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol and 2,7-naphthalenediol. Aldehydes include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipinaldehyde, pimerin aldehyde, sebacin aldehyde, acrolein, crotonaldehyde, and salicylic acid. Aldehyde, phthalaldehyde, hydroxybenzaldehyde and the like can be mentioned. Examples of the biphenyl condensing agent include bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, bis (chloromethyl) biphenyl and the like.

  Specific examples of the amine compound include diethylenetriamine, triethylenetetramine, cyclohexanediamine, isophoronediamine, aniline, phenylenediamine, toluidine, xylidine, naphthylamine, methylnaphthaleneamine, xylylenediamine, toluenediamine, diethyltoluenediamine, diaminodiphenylmethane Dimethyldiaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenyl ketone, diaminodiphenyl sulfide, diaminodiphenyl sulfone, bis (aminophenyl) fluorene, diaminodiphenylether, diaminobenzanilide, diaminobiphenyl, dimethyldiaminobiphenyl, tetramethylbenzidine, Biphenyl tetraamine, bis Minophenyl anthracene, bisamino phenoxy benzene, bis amino phenoxy phenyl ether, bis amino phenoxy biphenyl, bis amino phenoxy phenyl sulfone, bis amino phenoxy phenyl propane, diamino naphthalene, methyl naphthalene diamine, tetrahydro naphthalene diamine, decahydro naphthalene diamine, diamino bi Although naphthalene etc. are mentioned, it is not limited to these.

  Specific examples of the carboxylic acid include monocarboxylic acids such as acetic acid, lauric acid and benzoic acid, succinic acid, adipic acid, sebacic acid, dimer acid, hydrogenated dimer acid, cyclohexanedicarboxylic acid, phthalic acid and isophthalic acid. And polyvalent carboxylic acids such as terephthalic acid, methylphthalic acid, methylisophthalic acid, methylterephthalic acid, α-carboxyphenylacetic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, binaphthalenedicarboxylic acid and trimellitic acid. It is not limited.

  In the method for producing a phosphorus-containing epoxy resin of the present invention, the molar ratio of the reactant (x) to the polyfunctional epoxy resin (y) is a functional group (phenolic hydroxyl group) reactive with the epoxy group possessed by the reactant (x) The equivalent ratio of the epoxy group in the multifunctional epoxy resin (y) and the like is preferably in the range of 1: 0.5 to 2.0.

  As this reaction temperature, 100-200 degreeC is preferable and 120-180 degreeC is more preferable. If the rate of this reaction is slow, a catalyst can be used to measure productivity improvement as needed.

  Specific examples of the catalyst that can be used include phosphines such as triphenylphosphine, tritolylphosphine, trixylyl phosphine, tris (para-methoxyphenyl) phosphine, tris (dimethoxyphenyl) phosphine, tris (tert-butoxyphenyl) phosphine and the like. And quaternary phosphonium salts such as n-butyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, tetraphenylphosphonium bromide, 2-methylimidazole, 2-ethyl-4-methylimidazole, Imidazoles such as 2-phenylimidazole, quaternary ammonium salts such as tetramethyl ammonium chloride and tetraethyl ammonium bromide, triethylamine, benzyl It is known conventional catalysts such as tertiary amines such as dimethylamine, and the like, but not limited thereto. These catalysts may be used alone, or two or more types of catalysts of the same system may be used in combination, or catalysts of different systems may be used in combination. The amount of these catalysts used is preferably 0.002 to 2 parts by mass, more preferably 0.003 to 1 parts by mass, and still more preferably 0.005 to 0. 100 parts by mass of the reactant (x). 5 parts by mass is more preferred. When the amount used is large, reaction control is difficult, and there is a possibility that a phosphorus-containing epoxy resin having a stable viscosity can not be obtained. Furthermore, the storage stability of the epoxy resin composition of the present invention may be adversely affected.

  Moreover, you may use the non-reactive organic solvent as needed. Specifically, hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone And ethyl ether, isopropyl ether, butyl ether, diisoamyl ether, methyl phenyl ether, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane, methyl furan, tetrahydrofuran, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, methyl ethyl carbitol Etc., methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate Esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and diethyl oxalate; and amides such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide Lactones such as γ-butyrolactone, sulfoxides such as dimethyl sulfoxide, ureas such as tetramethyl urea, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene and the like Examples include, but are not limited to, halogenated hydrocarbons. These non-reactive organic solvents may be used alone or in combination of two or more. 1-900 mass parts is preferable with respect to 100 mass parts of epoxy resins, and, as for the usage-amount of these solvent, 5-100 mass parts is more preferable.

  The reaction mixture containing phosphorus compound (3) and quinone compound (q) is reacted to obtain a reaction mixture containing the phosphorus-containing phenol compound (1) of the present invention, and the obtained reaction mixture is not removed from the system, Furthermore, a phosphorus-containing epoxy resin of the present invention can be obtained by adding a polyfunctional epoxy resin (y) and, if necessary, a compound (x1) having a functional group that reacts with an epoxy group other than the phosphorus compound (p). You may get it. In addition, the reaction mixture may be purified, and one or more products or unreacted materials as shown in the reaction formula (5) may be concentrated together with the phosphorus-containing phenol compound (1).

  The reaction time is about 1 to 10 hours, preferably until the functional group of the epoxy group and the hydroxyl group of the phosphorus compound are almost eliminated. Moreover, in order to provide characteristics, such as viscosity reduction, according to a condition, you may make the reaction rate into 60 to 95% with the manufacturing method of Unexamined-Japanese-Patent No. 2012-172079. After completion of the reaction, if necessary, the solvent and the like are removed to obtain the phosphorus-containing epoxy resin of the present invention.

Next, the epoxy resin composition of the present invention will be described.
The epoxy resin composition of the present invention contains a phosphorus-containing epoxy resin and a curing agent for epoxy resin.

  The curing agent for the epoxy resin is not particularly limited as long as it cures the epoxy resin, and a phenol curing agent, an acid anhydride curing agent, an amine curing agent, a hydrazide curing agent, an active ester curing agent, Curing agents for epoxy resins such as phosphorus-containing curing agents can be used. These curing agents may be used alone, or two or more of the same curing agents may be used in combination, or curing agents of different systems may be used in combination. Among these, dicyandiamide and a phenolic curing agent are preferred.

  In the epoxy resin composition, the amount of the curing agent for epoxy resin used is such that the amount of active hydrogen groups of the curing agent for epoxy resin is 0.2 to 1.5 moles with respect to 1 mole of the epoxy group of the epoxy resin. . If the amount of active hydrogen group is less than 0.2 mol or more than 1.5 mol with respect to 1 mol of epoxy group, curing may be incomplete and good cured physical properties may not be obtained. A preferred range is 0.3 to 1.5 moles, a more preferred range is 0.5 to 1.5 moles, and a further preferred range is 0.8 to 1.2 moles. For example, when a phenol type curing agent, an amine type curing agent or an active ester type curing agent is used, an equimolar amount of active hydrogen group is mixed with an epoxy group, and an epoxy group is used when an acid anhydride type curing agent is used. The acid anhydride group is blended in an amount of 0.5 to 1.2 moles, preferably 0.6 to 1.0 moles, per mole.

The term "active hydrogen group" as used herein refers to a functional group having active hydrogen reactive with an epoxy group (a functional group having latent active hydrogen that generates active hydrogen upon hydrolysis etc., or a functional group exhibiting an equivalent curing action) And specifically includes an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group and the like. Regarding the active hydrogen group, a carboxyl group (-COOH) or a phenolic hydroxyl group (-OH) is one mole, an amino group (-NH ₂₎ is calculated to 2 moles. Moreover, when an active hydrogen group is not clear, an active hydrogen equivalent can be calculated | required by measurement. For example, the active hydrogen equivalent of the used curing agent is obtained by reacting a monoepoxy resin having a known epoxy equivalent such as phenyl glycidyl ether with a curing agent having an unknown active hydrogen equivalent and measuring the amount of the monoepoxy resin consumed. You can ask for

  As a phenol type hardening agent, the polyfunctional phenol compound which can be used as said various epoxy resin modifiers is mentioned.

  Among these phenol-based curing agents, those containing a large amount of aromatic skeleton in the molecular structure are preferable. For example, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin And naphthol novolac resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenolic resin, biphenyl-modified naphthol resin, aminotriazine-modified phenolic resin.

  In addition, benzoxazine compounds which are ring-opened upon heating to be phenol compounds are also useful as curing agents. Specific examples thereof include bisphenol F type and bisphenol S type benzoxazine compounds and the like, but are not limited thereto.

  Specific examples of the acid anhydride curing agent include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, hydrogenated trimellate Acid anhydride, methyl nadic anhydride, succinic anhydride, maleic anhydride etc., 4,4'-oxydiphthalic anhydride, 4,4'-biphthalic anhydride, pyromellitic anhydride, hydrogenated pyromellitic anhydride 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofurfuryl) -3 -Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,6 , 4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and the like, but not limited thereto.

  Examples of amine curing agents include amine compounds that can be used as the above various epoxy resin modifiers. In addition, amine compounds such as 2,4,6-tris (dimethylaminomethyl) phenol, dimer diamine, dicyandiamide and its derivatives, and polyamide amines which are condensates of acids such as dimer acid and polyamines And the like, but not limited thereto.

  Specific examples of the hydrazide curing agent include, but are not limited to, adipic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, and the like.

  Examples of active ester curing agents include reaction products of polyfunctional phenol compounds and aromatic carboxylic acids as described in Japanese Patent No. 5152445, and commercially available products include Epiclon HPC-8000-65T (DIC Corporation And the like, but is not limited thereto.

  Specific examples of other curing agents include phosphine compounds such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, n-butyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide and ethyltriphenylphosphonium Phosphonium salts such as iodide and tetraphenylphosphonium bromide; and imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole And imidazole salts which are salts of imidazoles with trimellitic acid, isocyanuric acid, boric acid, etc., tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium chloride Hydroxide, triethylmethyl ammonium chloride, tetraethyl ammonium chloride, tetraethyl ammonium bromide, tetraethyl ammonium iodide, tetrapropyl ammonium hydroxide, tetrapropyl ammonium chloride, tetrapropyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium Quaternary ammonium salts such as iodide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride, phenyltrimethylammonium chloride, salts of diazabicyclo compounds, salts of diazabicyclo compounds with phenol compounds, etc., boron trifluoride and amines or ether compounds Complex compounds with Um salts, and the like, but not limited thereto.

  A hardening accelerator can be used for the epoxy resin composition as needed. Examples of the curing accelerator include, but are not limited to, imidazole derivatives, tertiary amines, phosphorus compounds such as phosphines, metal compounds, Lewis acids, amine complexes and the like. These curing accelerators may be used alone or in combination of two or more.

  The imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton. For example, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, 2,4- Alkyl substituted imidazole compounds such as dimethylimidazole and 2-heptadecylimidazole; 2-phenylimidazole; 2-phenyl-4-methylimidazole; 1-benzyl-2-methylimidazole; 1-benzyl-2-ethylimidazole; Aryl groups such as benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, etc. Contain ring structures such as and aralkyl groups That imidazole compounds substituted with a hydrocarbon group, and the like, but is not limited thereto.

  As tertiary amines, for example, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo [5.4.0] -7-undecene ( Although DBU etc. are mentioned, it is not limited to these.

  Examples of phosphines include, but are not limited to, triphenyl phosphine, tricyclohexyl phosphine, triphenyl phosphine triphenyl borane and the like.

  Examples of the metal compound include, but are not limited to, tin octylate and the like.

  As an amine complex salt, for example, boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, boron trifluoride chlorophenylamine complex, boron trifluoride benzylamine complex, boron trifluoride Although an aniline complex or boron trifluoride complexes, such as mixtures thereof, etc. are mentioned, it is not limited to these.

  Among these curing accelerators, when used as a build-up material application or circuit board application, 2-dimethylaminopyridine, 4-dimethylaminopyridine or the like from the viewpoint of being excellent in heat resistance, dielectric properties, solder resistance, etc. Imidazoles are preferred. Moreover, when using it as a semiconductor sealing material use, a triphenyl phosphine and DBU are preferable from the point which is excellent in curability, heat resistance, an electrical property, moisture-reliability etc.

  Although the compounding quantity of a hardening accelerator may be suitably selected according to the intended purpose, 0.01-15 mass parts is used as needed with respect to 100 mass parts of epoxy resin components in an epoxy resin composition. Ru. Preferably it is 0.01-10 mass parts, More preferably, it is 0.05-8 mass parts, More preferably, it is 0.1-5 mass parts. By using a curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

  For the purpose of improving the flame retardancy of the cured product obtained, various non-halogen flame retardants substantially free of halogen atoms can be used in combination with the epoxy resin composition, as long as the reliability is not reduced. Examples of non-halogen flame retardants that can be used include phosphorus flame retardants (phosphorus compounds as flame retardants), nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc. . These non-halogen flame retardants are not limited at all in use, and may be used alone or in combination of two or more flame retardants of the same system, and may be used in combination of flame retardants of different systems. It is also possible.

  The phosphorus-containing additive may be either an inorganic phosphorus compound or an organic phosphorus compound. Examples of inorganic phosphorus compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, ammonium phosphates such as ammonium triphosphate and ammonium polyphosphate, and nitrogen-containing inorganic phosphorus compounds such as phosphoric acid amide. Although it is not limited to these.

  Further, it is preferable that red phosphorus is subjected to surface treatment for the purpose of preventing hydrolysis and the like, and as the surface treatment method, for example, (1) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, hydroxide Method of coating with an inorganic compound such as titanium, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof, (2) inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and phenol Method of coating with a mixture of thermosetting resin such as resin, (3) Thermosetting resin such as phenol resin on a film of inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide Although the method etc. which carry out double coating processing etc. are mentioned by these, it is not limited to these.

  Examples of the organic phosphorus compounds include general-purpose organic phosphorus compounds such as phosphoric acid ester compounds, condensed phosphoric acid esters, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, and phosphorane compounds, nitrogen-containing organic phosphorus compounds, In addition to metal salts of phosphinic acid, etc., phosphorus compounds (for example, DOPO, diphenylphosphine oxide etc.) having an active hydrogen group directly linked to a phosphorus atom, and phosphorus-containing phenol compounds (for example, DOPO-HQ, 10- (2, 7- Dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO-NQ), 2-diphenylphosphinyl hydroquinone, 2-diphenylphosphinyl-1,4-naphthalenediol 1,4-Cyclooctylenephosphinyl-1,4 Organophosphorus compounds such as phenyldiol and 1,5-cyclooctyrenephosphinyl-1,4-phenyldiol, and derivatives obtained by reacting such organophosphorus compounds with compounds such as epoxy resin and phenol resin are listed. Although it is not limited to these.

  Moreover, as a reactive phosphorus compound used for the phosphorus containing epoxy resin which can be used together, or a phosphorus containing hardening agent, the phosphorus containing phenol compound (1) used as a raw material of the phosphorus containing epoxy resin of this invention, and the same formula The phosphorus-containing phenol compound (2) and the phosphorus compound (3) having the phosphorus-containing group position represented by (a) are preferable.

  Examples of phosphorus-containing epoxy resins that can be used in combination include Epototh FX-305, FX-289B, TX-1320A, TX-1328 (above, manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), etc. Absent.

  The epoxy equivalent of the phosphorus containing epoxy resin which can be used together is preferably 200 to 800, more preferably 300 to 780, and still more preferably 400 to 760. The phosphorus content is preferably 0.5 to 6% by mass, more preferably 2 to 5.5% by mass, and still more preferably 3 to 5% by mass.

  As the phosphorus-containing curing agent, in addition to the above-mentioned phosphorus-containing phenol compounds, a phosphorus-containing group represented by the formula (a) can be produced by a production method as shown in JP-A-2008-501063 or JP-A 4548547. A phosphorus-containing phenol compound can be obtained by reacting an aldehyde with a phenol compound having a phosphorus compound. In this case, the phosphorus compound having a phosphorus-containing group represented by the formula (a) is incorporated into the molecule by condensation addition via an aldehyde to the aromatic ring of the phenol compound. Moreover, phosphorus-containing activity can be obtained from the phosphorus compound phenol compound having a phosphorus-containing group represented by the formula (a) by further reacting an aromatic carboxylic acid by a production method as shown in JP-A-2013-185002. An ester compound can be obtained. In addition, a phosphorus-containing benzoxazine compound having a phosphorus-containing group represented by formula (a) can be obtained by the production method as shown in WO2008 / 010429.

  The compounding quantity of the phosphorus base flame retardant to be used together is suitably selected by the kind and phosphorus content of a phosphorus base flame retardant, the component of an epoxy resin composition, and the extent of desired flame retardance. When the phosphorus-based flame retardant is a reactive phosphorus compound, that is, a phosphorus compound having an active hydrogen group such as phosphorus compound (3), a phosphorus-containing epoxy resin or a phosphorus-containing curing agent, an epoxy resin, a curing agent for epoxy resin, The content of phosphorus is preferably 0.2 to 6% by mass, with respect to the solid content (nonvolatile content) in the epoxy resin composition containing all of the flame retardant and other fillers, additives, etc., and 0.4 to 4 % By mass is more preferable, 0.5 to 3.5% by mass is further preferable, and 0.6 to 3.3% by mass is particularly preferable. If the phosphorus content is low, it may be difficult to ensure flame retardancy, and if it is too high, the heat resistance may be adversely affected. In addition, not only the phosphorus content of the phosphorus flame retardant which can be used together but the phosphorus content of the phosphorus containing epoxy resin of this invention is contained in the phosphorus content in the epoxy resin composition said here.

  The compounding amount when the phosphorus-based flame retardant used in combination is an additive system is in the range of 0.1 to 2 parts by mass in the case of using red phosphorus in 100 parts by mass of solid content (nonvolatile content) in the epoxy resin composition. It is preferable to mix | blend, when using an organophosphorus compound, it is preferable to mix | blend in the range of 0.1-10 mass parts similarly, and it is preferable to mix | blend in the range of 0.5-6 mass parts especially.

  In the epoxy resin composition of the present invention, for example, hydrotalcite, magnesium hydroxide, a boron compound, zirconium oxide, calcium carbonate, zinc molybdate and the like may be used in combination as a flame retardant auxiliary.

  In the present invention, it is preferable to use a phosphorus-based flame retardant as the flame retardant to be used in combination, but the flame retardants described below can also be used in combination.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine and the like, and triazine compounds, cyanuric acid compounds and isocyanuric acid compounds are preferable. Although the compounding quantity of a nitrogen-type flame retardant is suitably selected by the kind of nitrogen-type flame retardant, the other component of an epoxy resin composition, and the extent of desired flame retardance, for example, in an epoxy resin composition It is preferable to mix | blend in the range of 0.05-10 mass parts in 100 mass parts of solid content (non volatile matter), and it is preferable to mix | blend in the range of 0.1-5 mass parts especially. Moreover, when using a nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include, but are not limited to, silicone oil, silicone rubber and silicone resin. Although the compounding quantity of a silicone type flame retardant is suitably selected by the kind of silicone type flame retardant, the other component of an epoxy resin composition, and the extent of the desired flame retardance, for example, in an epoxy resin composition It is preferable to mix | blend in 0.05-20 mass parts in 100 mass parts of solid content (nonvolatile content). Moreover, when using a silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of inorganic flame retardants include, but are not limited to, metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, low melting point glasses, and the like. Although the compounding quantity of an inorganic type flame retardant is suitably selected by the kind of inorganic type flame retardant, the other component of an epoxy resin composition, and the extent of desired flame retardance, it is for epoxy resin, an epoxy resin, for example It is preferable to blend in a range of 0.05 to 20 parts by mass in 100 parts by mass of solid content (nonvolatile content) in the epoxy resin composition containing all of a curing agent, a flame retardant and other fillers, additives and the like. It is preferable to mix | blend in the range of 0.5-15 mass parts especially.

  As the organic metal salt flame retardant, for example, ferrocene, acetylacetonato metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound are ionically bonded or arranged Although the compound etc. which were attached are mentioned, it is not limited to these. Although the compounding quantity of the organic metal salt type flame retardant is suitably selected by the kind of organic metal salt type flame retardant, the other component of an epoxy resin composition, and the extent of desired flame retardance, for example, an epoxy resin In the range of 0.005 to 10 parts by mass in 100 parts by mass of the solid content (non-volatile matter) of the epoxy resin composition containing all of curing agents for epoxy resins, flame retardants and other fillers, additives and the like Is preferred.

  In the epoxy resin composition, an organic solvent or a reactive diluent can be used for viscosity adjustment.

  Examples of the organic solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and ethers such as ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether and triethylene glycol dimethyl ether And ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyl diglycol Alcohol such as pine oil, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate Acetic esters such as ethyl diglycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, benzyl alcohol acetate, benzoic esters such as methyl benzoate and ethyl benzoate, and cellosolves such as methyl cellosolve, cellosolve and butyl cellosolve And carbitols such as methyl carbitol, carbitol and butyl carbitol, aromatic hydrocarbons such as benzene, toluene and xylene, dimethyl sulfoxide, acetonitrile, N-methyl pyrrolidone and the like. It is not limited.

  Examples of reactive diluents include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether , Difunctional glycidyl ethers such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane Polyglycidyl ether, trimethylolethane polyglycidyl ether, pentaerythritol polyglycidyl ether Polyfunctional glycidyl ethers or, or glycidyl esters such as neodecanoic acid glycidyl ester, phenyl diglycidyl amine, although glycidyl amines such as tolyl diglycidyl amines, but not limited thereto.

  These organic solvents or reactive diluents are preferably used singly or as a mixture of two or more, at 90% by mass or less as a non-volatile component, and the appropriate type and amount used are appropriately selected depending on the application. For example, in printed wiring board applications, polar solvents such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol and the like having a boiling point of 160 ° C. or less are preferable. For adhesive film applications, it is preferable to use, for example, ketones, acetic acid esters, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. And preferably 30 to 60% by mass.

  In the epoxy resin composition, if necessary, a filler, a thermoplastic resin, a thermosetting resin other than an epoxy resin, a silane coupling agent, an antioxidant, a mold release agent, an extinction agent, as long as the properties are not impaired. Other additives such as a foaming agent, an emulsifying agent, a thixotropic agent, a leveling agent, and a pigment can be blended.

  As the filler, for example, fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, clay, calcium carbonate, magnesium carbonate, barium carbonate, Inorganic fillers such as zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, carbon, etc., carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester Examples thereof include fibrous fillers such as fibers, cellulose fibers, aramid fibers and ceramic fibers, and particulate rubbers. Among these, those which do not decompose or dissolve are preferable due to the oxidizing compound such as an aqueous solution of permanganate used for surface roughening treatment of a cured product, and in particular, fine particles of fused silica and crystalline silica are easily obtained. preferable. Moreover, it is preferable to use a fused silica, when making the compounding quantity of a filler especially large. Although fused silica can be used either in a crushed or spherical shape, it is more preferable to use mainly spherical ones in order to suppress the increase in melt viscosity of the molding material while increasing the blending amount of fused silica. . In order to further increase the content of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. The filler may be treated with a silane coupling agent or an organic acid such as stearic acid. Generally, the reason for using a filler is the effect of improving the impact resistance of the cured product, and the low linear expansion of the cured product. When a metal hydroxide such as aluminum hydroxide, boehmite or magnesium hydroxide is used, it acts as a flame retardant auxiliary and has an effect of improving the flame retardancy. When used for applications such as conductive paste, conductive fillers such as silver powder and copper powder can be used.

  The blending amount of the filler is preferably large in consideration of the low linear expansion of the cured product and the flame retardancy. 1-90 mass% is preferable with respect to solid content (non volatile matter) in an epoxy resin composition, 5-80 mass% is more preferable, 10-60 mass% is still more preferable. If the compounding amount is too large, the adhesion required for laminate applications may be lowered, and the cured product may be brittle, and sufficient mechanical properties may not be obtained. In addition, when the amount is small, there is a possibility that the effect of mixing the filler, such as improvement of the impact resistance of the cured product, may not be obtained.

  Moreover, 0.05-1.5 micrometers is preferable and, as for the average particle diameter of an inorganic filler, 0.1-1 micrometer is more preferable. If the average particle diameter of the inorganic filler is in this range, the flowability of the epoxy resin composition can be maintained well. The average particle size can be measured by a particle size distribution measuring apparatus.

  Blending a thermoplastic resin is particularly effective when the epoxy resin composition is formed into a sheet or film. As a thermoplastic resin, for example, phenoxy resin, polyurethane resin, polyester resin, polyolefin resin (polyethylene resin, polypropylene resin, etc.), polystyrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), vinyl chloride resin, polyvinyl acetate resin, polymethyl methacrylate resin, polycarbonate resin, polyacetal resin, cyclic polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyamideimide resin, polytetrafluoroethylene resin, polyether Imide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether sulfone resin, polysulfone resin, polyether ether ketone resin, polyphenyle Sulfide resins, polyvinyl formal resins and the like, but not limited thereto. A phenoxy resin is preferable in terms of compatibility with the epoxy resin, and a polyphenylene ether resin or a modified polyphenylene ether resin is preferable in terms of low dielectric characteristics.

  Other additives include, for example, thermosetting resins other than epoxy resins such as phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, diallyl phthalate resin, thermosetting polyimide, quinacridone, azo Organic pigments such as phthalocyanine pigments, inorganic pigments such as titanium oxide, metal foil pigments and rust preventive pigments, UV absorbers such as hindered amines, benzotriazoles and benzophenones, hindered phenols and phosphorus pigments , Antioxidants such as sulfur and hydrazide, coupling agents such as silane and titanium, release agents such as stearic acid, palmitic acid, zinc stearate and calcium stearate, leveling agents, rheology control agents, Additives such as pigment dispersants, repelling inhibitors, antifoaming agents and the like can be mentioned. The blending amount of these other additives is preferably in the range of 0.01 to 20% by mass with respect to the solid content (nonvolatile content) in the epoxy resin composition.

  The epoxy resin composition of the present invention can be cured by the same method as a known epoxy resin composition to obtain the cured product of the present invention. As a method for obtaining a cured product, the same method as a known epoxy resin composition can be taken, and casting, pouring, potting, dipping, drip coating, transfer molding, compression molding, resin sheet, resin attached A method is preferably used such as forming a copper foil, a prepreg, etc., and laminating and heating / pressure curing to form a laminate. The curing temperature at that time is usually in the range of 100 to 300 ° C., and the curing time is usually on the order of 10 minutes to 5 hours.

  The epoxy resin composition of the present invention is obtained by uniformly mixing the above-mentioned components. The epoxy resin, the curing agent for epoxy resin, and, if necessary, the epoxy resin composition blended with various additives can be easily made into a cured product by the same method as the conventionally known method. Examples of the cured product include molded and cured products such as laminates, cast products, molded products, adhesive layers, insulating layers and films.

  Examples of applications in which the epoxy resin composition is used include circuit board materials, sealing materials, casting materials, conductive pastes, adhesives, and the like. Materials for circuit boards include prepregs, resin sheets, metal foils with resins, resin compositions for printed wiring boards and flexible wiring boards, insulating materials for circuit boards such as interlayer insulation materials for buildup boards, adhesive films for buildup And resist inks.

  Among these various uses, so-called electronic component embedded substrates in which passive components such as capacitors and active components such as IC chips are embedded in a substrate for printed wiring board materials, insulating materials for circuit boards, and adhesive films for buildup It can be used as an insulating material for Among these, circuit boards such as printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for buildup boards, etc. from the characteristics such as high flame retardancy, high heat resistance, low dielectric characteristics, and solvent solubility It is preferable to use for material for board | plates and semiconductor sealing material.

  When making an epoxy resin composition into plate shape, such as a laminate, as a filler to be used, a fibrous thing is preferable at points, such as dimensional stability and flexural strength, and glass cloth, glass mat, glass roving cloth Is more preferred.

  The epoxy resin composition can be impregnated into a fibrous reinforcing substrate to prepare a prepreg used in a printed wiring board or the like. As the fibrous reinforcing substrate, woven or non-woven fabric of inorganic fibers such as glass, organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, aromatic polyamide resin, etc. can be used. It is not limited to this.

  It does not specifically limit as a method to manufacture a prepreg from an epoxy resin composition, For example, resin which mix | blended the organic solvent with the varnish-like epoxy resin composition containing the said organic solvent further, and adjusted it to appropriate viscosity A varnish is prepared, and the resin varnish is impregnated into the above-mentioned fibrous base material, followed by heating and drying to semi-cure (B-stage) resin components. The heating temperature is preferably 50 to 200 ° C., more preferably 100 to 170 ° C., depending on the type of the organic solvent used. The heating time is adjusted depending on the type of the organic solvent used and the curability of the prepreg, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes. Under the present circumstances, although it does not specifically limit as a mass ratio of the epoxy resin composition to be used and a reinforcement base material, Usually, it is preferable to adjust so that the resin part in a prepreg will be 20-80 mass%.

  The epoxy resin composition of the present invention can be used after being formed into a sheet or film. In this case, it is possible to form a sheet or a film using a conventionally known method.

  The method for producing the resin sheet is not particularly limited. For example, using a coating machine such as a reverse roll coater, a comma coater, a die coater or the like on the supporting base film which does not dissolve in the resin varnish. After coating, the resin component is obtained by B-staging by heating and drying. In addition, if necessary, another supporting base film is overlaid on the coated surface (adhesive layer) as a protective film, and drying is performed to obtain an adhesive sheet having a release layer on both sides of the adhesive layer.

  Examples of the supporting base film include metal foils such as copper foils, polyolefin films such as polyethylene films and polypropylene films, polyester films such as polyethylene terephthalate films, polycarbonate films, silicone films, polyimide films and the like. For example, a polyethylene terephthalate film which is free from defects, excellent in dimensional accuracy and excellent in cost is preferable. In addition, metal foils, particularly copper foils, in which multilayering of the laminate is easy are preferable. The thickness of the supporting base film is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm, because it has strength as a support and is less likely to cause lamination failure.

  The thickness of the protective film is not particularly limited, but generally 5 to 50 μm. In addition, in order to peel off the shape | molded adhesive sheet easily, it is preferable to surface-treat with a mold release agent beforehand.

  Moreover, 5-200 micrometers is preferable in the thickness after drying, and, as for the thickness which apply | coats a resin varnish, 5-100 micrometers is more preferable.

  The heating temperature is preferably 50 to 200 ° C., more preferably 100 to 170 ° C., depending on the type of the organic solvent used. The heating time is adjusted depending on the type of the organic solvent used and the curability of the prepreg, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes.

  The resin sheet thus obtained is usually an insulating adhesive sheet having an insulating property, but the conductive adhesive sheet is obtained by mixing an epoxy resin composition with metal having conductivity and fine particles coated with metal. You can also get it. The support base film is peeled off after laminating on a circuit board or after heat curing to form an insulating layer. If the support base film is peeled off after the adhesive sheet is heated and cured, it is possible to prevent the adhesion of dust and the like in the curing step. Here, the insulating adhesive sheet is also an insulating sheet.

  The metal foil with a resin obtained by the said phosphorus containing epoxy resin composition is demonstrated. As the metal foil, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel and the like can be used. It is preferable to use a metal foil of 9 to 70 μm in thickness. It does not specifically limit as a flame retardant resin composition which comprises a phosphorus containing epoxy resin, and a method of manufacturing metal foil with resin from metal foil, For example, the said phosphorus containing epoxy resin composition is carried out to one surface of the said metal foil A resin varnish having its viscosity adjusted with a solvent is applied using a roll coater or the like, and then dried by heating to semi-cure the resin component (B-staging) to form a resin layer. When semi-curing the resin component, for example, it can be dried by heating at 100 to 200 ° C. for 1 to 40 minutes. Here, as for the thickness of the resin part of metal foil with resin, it is desirable to form in 5-110 micrometers.

  In addition, in order to cure the prepreg and the insulating adhesive sheet, it is possible to use a method of curing a laminate in general when producing a printed wiring board, but it is not limited thereto.

  For example, in the case of forming a laminate using a prepreg, one or more prepregs are laminated, a metal foil is disposed on one side or both sides to construct a laminate, and the laminate is pressurized and heated. Thus, the prepreg can be cured and integrated to obtain a laminate. Here, as the metal foil, a metal foil of copper, aluminum, brass, nickel, etc. alone, an alloy, or a composite can be used.

  The conditions for heating and pressing the laminate may be appropriately adjusted and heated and pressurized under the conditions for curing of the epoxy resin composition, but if the amount of pressure applied is too low, bubbles will appear inside the resulting laminate. As it may remain and electrical characteristics may be degraded, it is desirable to apply pressure under conditions that satisfy moldability. 160-250 degreeC is preferable and, as for heating temperature, 170-220 degreeC is more preferable. 0.5-10 Mpa is preferable and, as for a pressurization pressure, 1-5 Mpa is more preferable. The heating and pressurizing time is preferably 10 minutes to 4 hours, and more preferably 40 minutes to 3 hours. If the heating temperature is low, the curing reaction may not proceed sufficiently, and if the temperature is high, thermal decomposition of the cured product may occur. If the applied pressure is low, air bubbles may remain inside the obtained laminate, and the electrical properties may be degraded. If the applied pressure is high, the resin may flow before curing, and a laminate having a desired thickness may not be obtained. There is a fear. In addition, if the heating and pressing time is short, the curing reaction may not proceed sufficiently, and if it is long, thermal decomposition of the cured product may occur.

  Furthermore, a multilayer board can be produced by using the single-layer laminated board obtained in this manner as an inner layer material. In this case, first, the laminated board is subjected to circuit formation by an additive method or a subtractive method, and the formed circuit surface is treated with an acid solution and subjected to a blackening treatment to obtain an inner layer material. An insulating layer is formed of a prepreg, a resin sheet, an insulating adhesive sheet, or a metal foil with resin on one side or both sides of a circuit forming surface of this inner layer material, and a conductor layer is formed on the surface of the insulating layer. It forms.

  Moreover, when forming an insulating layer using a prepreg, what laminated one or several sheets of prepreg is arrange | positioned on the circuit formation surface of inner layer material, metal foil is arrange | positioned further on the outer side, and a laminated body Form Then, the laminate is heated and pressurized to be integrally molded, whereby the cured product of the prepreg is formed as an insulating layer, and the metal foil on the outside thereof is formed as a conductor layer. Here, as metal foil, the thing similar to what was used for the laminated board used as an inner-layer material can be used. The heat and pressure molding can be performed under the same conditions as the molding of the inner layer material. The printed wiring board can be molded by further forming via holes and circuits on the surface of the multilayer laminate molded in this manner by the additive method or the subtractive method. Further, by repeating the above-described method using the printed wiring board as an inner layer material, a multilayer board of further layers can be formed.

  For example, when forming an insulating layer with an insulation adhesion sheet, an insulation adhesion sheet is arrange | positioned on the circuit formation surface of several sheets of inner layer material, and a laminated body is formed. Alternatively, an insulating adhesive sheet is disposed between the circuit forming surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressurized to be integrally molded, thereby forming a cured product of the insulating adhesive sheet as an insulating layer and forming a multilayer of the inner layer material. Alternatively, a cured product of the insulating adhesive sheet is formed as an insulating layer between the inner layer material and the metal foil which is a conductor layer. Here, as metal foil, the thing similar to what was used for the laminated board used as an inner-layer material can be used. The heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.

  When an epoxy resin composition is applied to a laminate to form an insulating layer, the epoxy resin composition is preferably applied to a thickness of 5 to 100 μm and then at 100 to 200 ° C., preferably 150 to 200 ° C. The sheet is heated and dried for 1 to 120 minutes, preferably 30 to 90 minutes. It is generally formed by a method called casting method. The thickness after drying is desirably 5 to 150 μm, preferably 5 to 80 μm. The viscosity of the epoxy resin composition is preferably in the range of 10 to 40000 mPa · s at 25 ° C., and more preferably 200 to 30000 mPa · s, because sufficient film thickness can be obtained and coating unevenness and streaks are less likely to occur. It is. A printed wiring board can be formed by further forming via holes and forming circuits by the additive method or the subtractive method on the surface of the multilayer laminate thus formed. Further, by repeating the above-described method using the printed wiring board as an inner layer material, it is possible to form a multi-layered laminated board.

  As a sealing material obtained using the epoxy resin composition of the present invention, there are a tape-shaped semiconductor chip, a potting type liquid sealing, an underfill, a semiconductor interlayer insulating film, etc. It can be used for For example, for semiconductor package molding, the epoxy resin composition is cast or molded using a transfer molding machine, an injection molding machine or the like, and further heated at 50 to 200 ° C. for 2 to 10 hours. The method to obtain is mentioned.

  In order to prepare the epoxy resin composition for a semiconductor sealing material, it is added to the epoxy resin composition as needed, such as an inorganic filler, a compounding agent such as an inorganic filler, a coupling agent, a releasing agent, etc. After pre-mixing the agent, an extruder, a kneader, a roll or the like may be used to sufficiently melt and mix until uniform. In that case, although silica is usually used as an inorganic filler, in that case, it is preferable to mix | blend an inorganic filler in the ratio used as 70-95 mass% in an epoxy resin composition.

When the epoxy resin composition thus obtained is used as a tape-like sealing material, it is heated to prepare a semi-cured sheet, and after forming a sealing material tape, this sealing material tape May be placed on a semiconductor chip, softened by heating to 100 to 150.degree. C., and molded, and may be completely cured at 170 to 250.degree.
Moreover, when using as a potting type liquid sealing material, after melt | dissolving the obtained epoxy resin composition in a solvent as needed, it is sufficient to apply on a semiconductor chip or an electronic component, and to harden it directly. .

  The epoxy resin composition of the present invention can also be used as a resist ink. In this case, the epoxy resin composition is mixed with a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent, and further a pigment, talc, and a filler are added to the composition for a resist ink. Then, the composition is applied on a print substrate by a screen printing method, and then cured as a resist ink. The curing temperature at this time is preferably in the range of about 20 to 250 ° C.

  The epoxy resin composition of the present invention was prepared, and the cured product was evaluated by heat curing. As a result, a phosphorus-containing epoxy obtained from a reactive agent (x) containing a phosphorus-containing phenolic compound (1) and a polyfunctional epoxy resin (y) The resin has better flame retardancy as compared to a phosphorus-containing epoxy resin obtained from a phosphorus compound or the like not containing the phosphorus-containing phenol compound (1). Therefore, in a laminate having a necessary and sufficient amount of phosphorus, the heat resistance and the water absorption are improved, and therefore, it is useful in a laminate used under more severe conditions.

The present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to these as long as the gist of the invention is not exceeded. Unless otherwise noted, "parts" represents parts by mass, and "%" represents mass%.
The analysis method and the measurement method are shown below.

(1) Epoxy equivalent: Measured in accordance with JIS K7236 standard, and the unit was represented by "g / eq.".
(2) Softening point: Measured according to JIS K7234 standard, ring and ball method. Specifically, an automatic softening point apparatus (ASP-MG4 manufactured by Meitec Co., Ltd.) was used.
(3) Phosphorus content rate: The phosphorus content rate in a phosphorus containing epoxy resin added sulfuric acid, hydrochloric acid, and perchloric acid to a sample, heated and wet-ashed, and made all the phosphorus atoms into ortho phosphoric acid. The metavanadate and molybdate were reacted in a sulfuric acid solution, and the absorbance at 420 nm of the resulting phosphovanad molybdate complex was measured, and the phosphorus atom content determined by the calibration curve prepared in advance was expressed in mass%. Moreover, the phosphorus content rate of the epoxy resin composition (laminated board) was represented as content with respect to the resin part (solid content) of a laminated board. Here, the resin component (solid content) of the laminate corresponds to the organic component (epoxy resin, curing agent for epoxy resin, phosphorus compound, etc.) excluding the solvent among the components blended in the epoxy resin composition. Say
(4) Copper foil peel strength and interlayer adhesion strength: Measured under an atmosphere of 25 ° C. according to JIS C6481, 5.7. The interlaminar adhesion was measured between the seventh and eighth layers.
(5) Glass transition temperature (Tg): IPC-TM-650 2.4.25. c · DSC · Tgm (A tangent to a glass state and a rubber state when measured under a temperature rising condition of 20 ° C / min with a differential scanning calorimeter (EXSTA16000 DSC6200, manufactured by Hitachi High-Tech Science Co., Ltd.) according to the c standard The temperature at the middle temperature of the mutation curve is shown.
(6) Flame retardance: It evaluated by the perpendicular method according to UL94. Evaluation was described by V-0, V-1, and V-2. In addition, when a test piece is a film form, it described by VTM-0, VTM-1, and VTM-2. However, what was completely burned was noted as x.
(7) Relative dielectric constant and dielectric loss tangent: Using a material analyzer (manufactured by AGILENT Technologies) according to IPC-TM-650 2.5.5.9 standard, the relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz are obtained by the capacitance method. I asked.
(8) GPC (gel permeation chromatography) measurement: A column (manufactured by Tosoh Corp., HLC-8220GPC) with columns (manufactured by Tosoh Corp., TSKgel G4000H _XL , TSKgel G3000H _XL , TSKgel G2000H _XL ) in series is used. The column temperature was 40 ° C. In addition, tetrahydrofuran (THF) was used as an eluent, and a flow rate of 1 mL / min was used, and a detector used a differential refractometer. A 0.1 g sample was dissolved in 10 mL of THF, and 50 μL of a sample filtered with a microfilter was used as a measurement sample. Data processing used Tosoh Corp. GPC-8020 model II version 6.00.
(9) FT-IR: The absorbance at a wavenumber of 400 to 4000 cm ^-1 was measured by total reflection measurement (ATR method) of a Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X) .
(10) HPLC measurement: A column (manufactured by Sigma Aldrich, Ascentis C18, 4.6 mmφ × 250 mm L) was used for the main body (Agilent Technology, Agilent-HP1100), and the column temperature was 40 ° C. In addition, as an eluent, 10 mM ammonium acetate aqueous solution / acetonitrile / THF = 55 / 22.5 / 22.5 (volume ratio) was used, and the flow rate was 1 mL / min. The detector used was a UV detector (detection wavelength: 280 nm). A 0.4 g sample was dissolved in 10 mL of 10 mM aqueous ammonium acetate solution, and 5 μL was injected for measurement.
(11) NMR: Fourier transform nuclear magnetic resonance apparatus (JNM-ECA400, manufactured by Nippon Denshi Co., Ltd.) was used to measure ¹ H liquid at room temperature using THF-d8 as a solvent.

Synthesis example 1
200 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PMA), 108 parts of DOPO, and 4.2 parts of water in a reaction apparatus equipped with a stirrer, a thermometer, a nitrogen blowing pipe, and a cooling pipe The molar ratio of DOPO was 0.23), and it was completely dissolved by raising the temperature to 70 ° C. under a nitrogen atmosphere. Thereto, 78.9 parts of 1,4-naphthoquinone (NQ) (molar ratio of NQ / DOPO = 0.999) was charged over 30 minutes. After completion of the charging, the temperature was raised to 145 ° C. at which refluxing started, and the reaction was continued for 2 hours while maintaining the reflux temperature. After completion of the reaction, the reaction product was cooled to 25 ° C. and suction filtered to obtain a reaction product as a filter cake. 150 parts of the reaction product and 750 parts of PMA were charged, heated and mixed, cooled to 25 ° C., and suction-filtered twice to obtain a reaction product as a filter cake to obtain a phosphorus compound (p0).

  The HPLC chart of the obtained phosphorus compound is shown in FIG. In FIG. 3, the component corresponding to the phosphorus-containing phenol compound (1) in (p0) is the peak group (a), and the remaining raw material phosphorus compound (3): DOPO is the peak (c) and was by-produced Phosphorus-containing phenolic compound (2): DOPO-NQ is a peak (b), and a by-produced phosphorus compound (4) is a peak (d). The phosphorus-containing phenol compound (1) is represented by the above formula (1-1), DOPO-NQ is represented by the above (1-2), and the phosphorus compound (4) is represented by the above formula (1-4). Be done.

Synthesis example 2
Into the same apparatus as in Synthesis Example 1, 15 parts of the phosphorus compound (p0) obtained in Synthesis Example 1 and 200 parts of benzyl acetate were charged and completely dissolved by raising the temperature to 200 ° C. under a nitrogen atmosphere. The mixture was cooled to room temperature and allowed to stand for 1 day, and the formed precipitate (1) was separated by suction filtration. The filtrate was poured into 39% aqueous methanol, and the precipitate formed was separated by suction filtration, and the phosphorus-containing phenol compound (1) was isolated as a filter cake. The NMR chart is shown in FIG.

Synthesis example 3
In an apparatus similar to Synthesis Example 1, 15 parts of the precipitate (1) obtained in Synthesis Example 2 and 200 parts of benzyl acetate were charged, and completely dissolved by raising the temperature to 200 ° C. under a nitrogen atmosphere. The mixture was cooled to room temperature, allowed to stand for 1 day, and recrystallized to isolate phosphorus-containing phenol compound (2): DOPO-NQ.

Synthesis example 4
The phosphorus compound (p0) obtained in Synthesis Example 1 was separated by HPLC to isolate the by-produced phosphorus compound (4).

  The description of the abbreviations used in Examples and Comparative Examples is as follows.

[Phosphorus compound]
(P1): phosphorus-containing phenolic compound (1) isolated in Synthesis Example 2
DOPO-NQ: Phosphorus-containing Phenolic Compound Isolated in Synthesis Example 3 (2)
DOPO: 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (active hydrogen equivalent 216, phosphorus content 14.3%)
(P4): phosphorus compound isolated in Synthesis Example 4 (4)
DPPO: diphenyl phosphine oxide (active hydrogen equivalent 202, phosphorus content 15.3%)

[Quinone compound]
NQ: 1,4-naphthoquinone (reagent, purity 99%)
BQ: para-benzoquinone (reagent, purity 99%)

[Epoxy resin]
YDPN-638: Phenolic novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epototo YDPN-638, epoxy equivalent 176)
YDF-170: bisphenol F-type liquid epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epotote YDF-170, epoxy equivalent: 167)
ESN-485: Naphthol aralkyl type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epotote ESN-485, epoxy equivalent 296)
YDG-414: 4-functional epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epototh YDG-414, epoxy equivalent weight 187)
DCPD-E: Dicyclopentadiene / phenol co-condensed epoxy resin (manufactured by Kokuto Chemical Co., Ltd., KDCP-130, epoxy equivalent 254)

[Phenolic compound]
BPA: Bisphenol A (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., phenolic hydroxyl equivalent 114)

[catalyst]
TPP: triphenylphosphine (reagent)
TDMPP: Tris (2,6-dimethoxyphenyl) phosphine (reagent)

[Hardener]
PN: Phenolic novolak resin (manufactured by Showa Denko KK, Shonol BRG-557, softening point 80 ° C., phenolic hydroxyl group equivalent 105)
GK-5855P: aromatic modified novolak resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., GK-5855P, phenolic hydroxyl equivalent 230)
DCPD-P: Dicyclopentadiene / phenol co-condensation resin (Gunei Chemical Co., Ltd., GDP 9140, phenolic hydroxyl equivalent 196)
DICY: Dicyandiamide (manufactured by Nippon Carbide Industries Co., Ltd., DIHARD, active hydrogen equivalent 21)
MTHPA: 3 or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride (manufactured by Hitachi Chemical Co., Ltd., HN-2200, acid anhydride equivalent 166)

[Hardening accelerator]
2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., Cuazole 2E4MZ)

[Others]
YP-50S: bisphenol A type phenoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Phenotote YP-50S, weight average molecular weight = 40000)
BMB: Alumina monohydrate (manufactured by Kawai Lime Industry Co., Ltd., BMB, average particle diameter 1.5 μm)
CMC12: crystalline silica (manufactured by Ryumori Co., Ltd., Crystallite CMC-12, average particle diameter 5 μm)
PX-200: aromatic condensed phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd., PX-200, phosphorus content 9%)

Example 1
In an apparatus similar to Synthesis Example 1, 805 parts of YDPN-638, 100 parts of YDF-170, 95 parts of (p1) and 0.1 parts of TPP are charged, and the temperature is raised to 150 ° C. in a nitrogen atmosphere, The reaction was continued for 3 hours while maintaining the reaction temperature of 150 to 155 ° C. to obtain a phosphorus-containing epoxy resin (Resin 1). The epoxy equivalent and the phosphorus content of the obtained phosphorus-containing epoxy resin were measured. The measurement results are shown in Table 1.

Example 2
In a similar apparatus to Example 1, 835 parts of YDPN-638, 95 parts of (p1), 70 parts of DOPO, 0.1 parts of TPP are charged, and the temperature is raised to 150 ° C. under a nitrogen atmosphere, The reaction was continued for 3 hours while maintaining a reaction temperature of 155 ° C. to obtain a phosphorus-containing epoxy resin (Resin 2).

Example 3
In the same apparatus as in Example 1, 835 parts of ESN-485, 95 parts of (p1), 70 parts of DOPO, and 0.1 parts of TPP are charged, and the temperature is raised to 150 ° C. under a nitrogen atmosphere, The reaction was continued for 3 hours while maintaining a reaction temperature of 155 ° C. to obtain a phosphorus-containing epoxy resin (Resin 3).

Example 4
In the same apparatus as in Example 1, 835 parts of YDG-414, 95 parts of (p1), 70 parts of DOPO, and 0.1 parts of TPP are charged, and the temperature is raised to 150 ° C. under a nitrogen atmosphere. The reaction was continued for 3 hours while maintaining a reaction temperature of 155 ° C. to obtain a phosphorus-containing epoxy resin (Resin 4).

Example 5
In a similar apparatus to Example 1, 762 parts of YDF-170, 238 parts of (p1) and 0.3 parts of TPP are charged, heated to 150 ° C. under a nitrogen atmosphere, and the reaction temperature of 150 to 155 ° C. The reaction was continued for 3 hours while maintaining the above to obtain a phosphorus-containing epoxy resin (Resin 5).

Example 6
In an apparatus similar to Example 1, 714 parts of YDF-170, 286 parts of (p1) and 0.5 parts of TPP are charged, and the temperature is raised to 150 ° C. under a nitrogen atmosphere, and the reaction temperature of 150-155 ° C. The reaction was continued for 3 hours while maintaining the above to obtain a phosphorus-containing epoxy resin (Resin 6).

Example 7
In a similar apparatus to Example 1, 639 parts of YDF-170, 3 parts of (p1), 358 parts of DOPO-NQ and 0.5 parts of TDMPP are charged, and heated to 150 ° C. in a nitrogen atmosphere, The reaction was continued for 3 hours while maintaining the reaction temperature of 150 to 155 ° C. to obtain a phosphorus-containing epoxy resin (Resin 7).

Example 8
In a similar apparatus to Example 1, 690 parts of YDPN-638, 10 parts of (p1), 200 parts of DOPO, 100 parts of BPA, and 0.4 parts of TPP are charged, and the temperature is raised to 150 ° C. in a nitrogen atmosphere. Then, the reaction was continued for 3 hours while maintaining the reaction temperature of 150 to 155 ° C. to obtain a phosphorus-containing epoxy resin (Resin 8).

Example 9
In an apparatus similar to Example 1, 690 parts of YDPN-638, 100 parts of YDF-170, 0.5 parts of (p1), 209.5 parts of DOPO, 0.4 parts of TPP are charged, and they are under a nitrogen atmosphere. The temperature was raised to 150 ° C., and the reaction was continued for 3 hours while maintaining the reaction temperature of 150 to 155 ° C. to obtain a phosphorus-containing epoxy resin (Resin 9).

Example 10
In the same apparatus as in Example 1, 238 parts of YDPN-638, 190 parts of YDF-170, 310 parts of (p1), 262 parts of DOPO, 0.5 parts of TPP are charged, and heated to 150 ° C. in a nitrogen atmosphere. The temperature was raised, and the reaction was continued for 3 hours while maintaining the reaction temperature of 150 to 155 ° C. to obtain a phosphorus-containing epoxy resin (Resin 10).

Example 11
In an apparatus similar to Synthesis Example 1, 175 parts of DOPO, 90 parts of NQ (molar ratio of NQ / DOPO = 0.70), 4.7 parts of water (molar ratio of water / DOPO = 0.33), 409 parts of PMA were charged, and the temperature was raised to 145 ° C. at which reflux was started under nitrogen atmosphere, and the reaction was continued for 2 hours while maintaining the reflux state. As a result of collecting the contents and measuring it by HPLC, the content of (p1) was 35 parts.
Next, 515 parts of YDPN-638 and 220 parts of YDF-170 are charged in this content, PMA is removed by distillation under reduced pressure, 0.5 parts of TDMPP is charged, and a reaction temperature of 160 to 165 ° C. is maintained. The reaction was continued for 3 hours to obtain a phosphorus-containing epoxy resin (Resin 11).
The GPC measurement chart is shown in FIG. The ordinate represents the signal strength. The FT-IR measurement chart is shown in FIG. The vertical axis shows the transmittance.

Example 12
In an apparatus similar to Synthesis Example 1, 210 parts of DOPO, 38 parts of NQ (molar ratio of NQ / DOPO = 0.25), 2.0 parts of water (molar ratio of water / DOPO = 0.11), 490 parts of xylene were charged, and the temperature was raised to 142 ° C. at which reflux starts under a nitrogen atmosphere, and the reaction was continued for 2 hours while maintaining the reflux state. As a result of collecting the contents and measuring it by HPLC, the content of (p1) was 5 parts.
Next, 752 parts of YDPN-638 were charged in this content, xylene was removed by distillation under reduced pressure, 0.5 parts of TPP was charged, and the reaction was continued for 3 hours while maintaining the reaction temperature of 155 to 160 ° C. Thus, a phosphorus-containing epoxy resin (resin 12) was obtained.

Example 13
In an apparatus similar to Synthesis Example 1, 62 parts of DOPO, 38 parts of NQ (molar ratio of NQ / DOPO = 0.84), 2.0 parts of water (molar ratio of water / DOPO = 0.39), After 490 parts of toluene was charged, the temperature was raised to 109 ° C. at which refluxing was started under a nitrogen atmosphere, reaction was continued for 3 hours while maintaining the reflux state, and 148 parts of DOPO was added and uniformly stirred. As a result of collecting the contents and measuring it by HPLC, the content of (p1) was 17 parts.
Next, 752 parts of YDPN-638 were added to the contents, toluene was removed by distillation under reduced pressure, 0.5 parts of TPP was added, and the reaction was continued for 3 hours while maintaining the reaction temperature of 155 to 160 ° C. And a phosphorus-containing epoxy resin (resin 13).

Comparative Example 1
In a similar apparatus to Example 1, 780 parts of YDPN-638, 100 parts of YDF-170, 120 parts of DOPO-NQ, 0.1 parts of TPP are charged, and the temperature is raised to 150 ° C. in a nitrogen atmosphere, The reaction was continued for 3 hours while maintaining the reaction temperature of 150 to 155 ° C. to obtain a phosphorus-containing epoxy resin (Resin H1).

Comparative example 2
In an apparatus similar to Example 1, 830 parts of YDPN-638, 100 parts of YDF-170, 70 parts of DOPO, 0.1 parts of TPP are charged, and the temperature is raised to 150 ° C. under a nitrogen atmosphere, The reaction was continued for 3 hours while maintaining a reaction temperature of 155 ° C. to obtain a phosphorus-containing epoxy resin (resin H2).

Comparative example 3
In a similar apparatus to Example 1, 780 parts of YDPN-638, 100 parts of YDF-170, 120 parts of (p4) and 0.1 parts of TPP are charged, and the temperature is raised to 150 ° C. in a nitrogen atmosphere, The reaction was continued for 3 hours while maintaining a reaction temperature of 150 to 155 ° C. to obtain a phosphorus-containing epoxy resin (resin H3).

Comparative example 4
In the same apparatus as in Example 1, 860 parts of YDPN-638, 140 parts of DOPO, and 0.1 parts of TPP are charged, and the temperature is raised to 150 ° C. under a nitrogen atmosphere to maintain a reaction temperature of 150 to 155 ° C. While continuing the reaction for 3 hours, a phosphorus-containing epoxy resin (resin H4) was obtained.

Comparative example 5
In an apparatus similar to Example 1, 639 parts of YDF-170, 361 parts of DOPO-NQ and 0.3 parts of TPP are charged, and the temperature is raised to 150 ° C. under a nitrogen atmosphere, and the reaction temperature of 150-155 ° C. The reaction was continued for 3 hours while maintaining the above to obtain a phosphorus-containing epoxy resin (Resin H5).

Comparative example 6
In a similar apparatus to Example 1, 690 parts of YDPN-638, 210 parts of DOPO, 100 parts of BPA, and 0.5 parts of TDMPP are charged, heated to 150 ° C. in a nitrogen atmosphere, and 150-155 ° C. The reaction was continued for 3 hours while maintaining the reaction temperature of to obtain a phosphorus-containing epoxy resin (resin H6).

Comparative example 7
In an apparatus similar to Example 1, 690 parts of YDPN-638, 100 parts of YDF-170, 210 parts of DOPO, 0.4 parts of TPP are charged, and the temperature is raised to 150 ° C. under a nitrogen atmosphere, The reaction was continued for 3 hours while maintaining a reaction temperature of 155 ° C. to obtain a phosphorus-containing epoxy resin (Resin H7).

Comparative Example 8
In a similar apparatus to Example 1, 471 parts of YDPN-638, 529 parts of DOPO and 0.5 parts of TPP are charged, and the temperature is raised to 150 ° C. under a nitrogen atmosphere to maintain a reaction temperature of 150 to 155 ° C. While continuing the reaction for 3 hours, a phosphorus-containing epoxy resin (Resin H8) was obtained.

Comparative Example 9
In an apparatus similar to Synthesis Example 1, 210 parts of DOPO, 38 parts of NQ (molar ratio of NQ / DOPO = 0.25), 2.0 parts of water (molar ratio of water / DOPO = 0.11), 490 parts of toluene were charged, the temperature was raised to 80 ° C. under a nitrogen atmosphere, and the reaction was continued for 4 hours while maintaining 80 ° C. As a result of collecting the contents and measuring by HPLC, (p1) could not be detected.
Next, 752 parts of YDPN-638 were added to the contents, toluene was removed by distillation under reduced pressure, 0.5 parts of TPP was added, and the reaction was continued for 3 hours while maintaining the reaction temperature of 155 to 160 ° C. And a phosphorus-containing epoxy resin (resin H9).

The same tests as in Example 1 were conducted on the resins 2 to 13 and H1 to H9 obtained in Examples 2 to 13 and Comparative Examples 1 to 9.
Table 1 shows the measurement results of the epoxy equivalents and the phosphorus content of the resins 1 to 13 and H1 to H9 obtained in Examples 1 to 13 and Comparative Examples 1 to 9. In addition, b1 content rate in a table | surface is content rate (%) of the structural site represented by following formula (1'-1b) in phosphorus containing epoxy resin, and the preparation amount of a phosphorus containing phenol compound (1), It calculated | required by calculation from the measurement result of HPLC, and the residual amount of phosphorus containing phenol compound (1).

Example 14
In an apparatus similar to Synthesis Example 1, 210 parts of DOPO, 94 parts of BQ (molar ratio of BQ / DOPO = 0.90), 3.4 parts of water (molar ratio of water / DOPO = 0.19), 490 parts of PMA was charged, the temperature was raised to 145 ° C. at which reflux was started under nitrogen atmosphere, and the reaction was continued for 2 hours while maintaining the reflux state. As a result of collecting the contents and measuring by HPLC, the content of the phosphorus-containing phenol compound (1) represented by the above formula (1-2) was 51 parts.
Then, 70 parts of YDPN-638 and 626 parts of YDF-170 are charged in the contents, PMA is removed by distillation under reduced pressure, 0.5 parts of TDMPP is charged, and the reaction temperature of 160 to 165 ° C. is maintained. The reaction was continued for 3 hours to obtain a phosphorus-containing epoxy resin (Resin 14).

Comparative example 10
In an apparatus similar to Synthesis Example 1, 210 parts of DOPO, 94 parts of BQ (molar ratio of BQ / DOPO = 0.90), 490 parts of toluene without using water, reflux starts under nitrogen atmosphere The temperature was raised to 109 ° C., and the reaction was continued for 3 hours while maintaining the reflux state. As a result of collecting the contents and measuring it by HPLC, the phosphorus compound represented by the above formula (2-1) could not be detected.
Next, 70 parts of YDPN-638 and 626 parts of YDF-170 are charged in the contents, toluene is removed by distillation under reduced pressure, and then 0.5 parts of TDMPP are charged, while maintaining the reaction temperature of 160 to 165 ° C. The reaction was continued for 3 hours to obtain a phosphorus-containing epoxy resin (resin H10).

  About the resin 14 and H10 obtained in Example 14 and Comparative Example 10, the measurement result of the epoxy equivalent carried out similarly to Example 1 and a phosphorus content is shown. In addition, b2 content rate in a table | surface is a content rate of the structure site | part represented by following formula (1-2b) in phosphorus containing epoxy resin.

Example 15
In an apparatus similar to Synthesis Example 1, 196 parts of DPPO, 77 parts of NQ (molar ratio of NQ / DPPO = 0.50), 4.0 parts of water (molar ratio of water / DPPO = 0.23), 450 parts of PMA were charged, and the temperature was raised to 145 ° C. at which reflux was started under a nitrogen atmosphere, and the reaction was continued for 2 hours while maintaining the reflux state. As a result of collecting the contents and measuring by HPLC, the content of the phosphorus-containing phenol compound (1) represented by the above formula (1-3) was 23 parts.
Next, 509 parts of YDPN-638 and 218 parts of YDF-170 are charged in this content, PMA is removed by distillation under reduced pressure, 0.5 parts of TDMPP is charged, and a reaction temperature of 160 to 165 ° C. is maintained. The reaction was continued for 3 hours to obtain a phosphorus-containing epoxy resin (Resin 15).

Example 16
In an apparatus similar to Synthesis Example 1, 196 parts of DPPO, 77 parts of NQ (molar ratio of NQ / DPPO = 0.50), and 8.0 parts of water (molar ratio of water / DPPO = 0.46), 450 parts of toluene were charged, and the temperature was raised to 108 ° C. at which reflux was started under a nitrogen atmosphere, and the reaction was continued for 3 hours while maintaining the reflux state. As a result of collecting the contents and measuring by HPLC, the content of the phosphorus-containing phenol compound (1) represented by the above formula (3-1) was 17 parts.
Next, 509 parts of YDPN-638 and 218 parts of YDF-170 are charged into the contents, toluene is removed by distillation under reduced pressure, and then 0.5 parts of TDMPP are charged, maintaining a reaction temperature of 160 to 165 ° C. The reaction was continued for 3 hours to obtain a phosphorus-containing epoxy resin (resin 16).

Comparative example 11
In an apparatus similar to Synthesis Example 1, 196 parts of DPPO, 23 parts of NQ (molar ratio of NQ / DPPO = 0.15), and 0.7 parts of water (molar ratio of water / DPPO = 0.04), 450 parts of toluene were charged, the temperature was raised to 109 ° C. at which reflux was started under a nitrogen atmosphere, and the reaction was continued for 3 hours while maintaining the reflux state. As a result of collecting the contents and measuring by HPLC, the phosphorus compound represented by the above formula (3-1) could not be detected.
Next, 546 parts of YDPN-638 and 234 parts of YDF-170 are charged in this content, and after removing toluene by distillation under reduced pressure, 0.5 parts of TDMPP are charged and the reaction temperature of 160 to 165 ° C. is maintained. The reaction was continued for 3 hours to obtain a phosphorus-containing epoxy resin (resin H11).

  The results of measurement of the epoxy equivalent and the phosphorus content of the resins 15, 16 and H11 obtained in Examples 15, 16 and Comparative Example 11 are shown in Table 3. In addition, b3 content rate in a table | surface is a content rate of the structure site | part represented by following formula (1-3b) in phosphorus containing epoxy resin.

  Examples 11 to 16 and Comparative Examples 9 to 11 are examples in which, after synthesizing the phosphorus compound, the phosphorus compound is continuously reacted with the epoxy resin without taking it out of the reaction system to obtain a phosphorus-containing epoxy resin. Table 4 shows the results of HPLC measurement of the phosphorus compound before charging the epoxy resin. The numbers given to the phosphorus compounds correspond to the numbers given to the phosphorus compounds shown in the reaction formula (5-1).

Example 17
100 parts of Resin 1 as a phosphorus-containing epoxy resin, 5.0 parts of DICY as a curing agent, 0.1 parts of 2E4MZ as a curing accelerator, methyl ethyl ketone (hereinafter referred to as MEK), propylene glycol monomethyl ether (hereinafter referred to as PGM) In addition, it melt | dissolves in the mixed solvent adjusted with N, N- dimethylformamide (it describes as DMF hereafter), and the epoxy resin composition varnish of 50% of a non volatile matter was obtained.

  The obtained epoxy resin composition varnish was impregnated into a glass cloth (WEA 2116, 0.1 mm thick, manufactured by Nitto Boseki Co., Ltd.). The impregnated glass cloth was dried in a hot air circulating oven at 150 ° C. for 10 minutes to obtain a prepreg. 8 pieces of the obtained prepreg and copper foil (3EC-III made by Mitsui Mining & Smelting Co., Ltd., thickness 35 μm) are piled up and down, and 2MPa vacuum press is performed under the temperature condition of 130 ° C × 15 minutes + 170 ° C × 70 minutes , 1 mm thick laminated plate was obtained. The copper foil portion of the obtained laminate was removed by immersion in an etching solution, washed and dried, and then cut into a size of 127 mm × 12.7 mm to obtain a test piece for flame resistance measurement. The phosphorus content of the epoxy resin composition, the copper foil peel strength of the laminate, the interlayer adhesion, the glass transition temperature (Tg) and the flame retardancy results are shown in Table 5.

Comparative Examples 12-14
An epoxy resin composition varnish is obtained in the same manner as in Example 17 according to the composition of Table 5, except that the resins H1 to H3 obtained in Comparative Examples 1 to 3 are used as the resin, and further, a laminate, flame retardancy A test piece for measurement was obtained. The same test as in Example 17 was conducted, and the results are shown in Table 5. In the table, (parts) of DICY and 2E4MZ are compounding amounts, which are amounts relative to 100 parts of resin.

Examples 18 to 20 and Comparative Example 15
Epoxy resin composition varnish was prepared in the same manner as in Example 17 according to the composition of Table 6, except that Resins 2 to 4 obtained in Examples 2 to 4 and the resin H4 obtained in Comparative Example 4 were used as the resin. Further, a laminate and a test piece for flame retardancy measurement were obtained. The same test as in Example 17 was conducted, and the results are shown in Table 6. In the table, (parts) of DICY and 2E4MZ have the same meaning as in Table 5.

  Examples 17 to 20 (Comparative Examples 12 to 15) are examples in which the phosphorus-containing phenol compound (1) was used alone. Example 17 (comparative examples 12 to 14) is a comparison where the phosphorus content of the phosphorus-containing epoxy resin is 1.0%, and examples 18 to 20 (comparative example 15) are phosphorus of the phosphorus-containing epoxy resin It is a comparison in the case of a content rate of 2.0%. In either case, the flame retardancy of the laminate using the phosphorus-containing epoxy resin of the present invention was improved.

Examples 21 to 23 and Comparative Example 16
An epoxy resin composition varnish was prepared in the same manner as in Example 17 according to the composition of Table 7, except that the resins 5 to 7 obtained in Examples 5 to 7 and the resin H5 obtained in Comparative Example 5 were used as the resin. Further, a laminate and a test piece for flame retardancy measurement were obtained. The same test as in Example 17 was conducted, and the results are shown in Table 7. In the table, (parts) of DICY and 2E4MZ are compounding amounts, which are amounts relative to 100 parts of resin.

  In Examples 21 to 23 (Comparative Example 16), a linear phosphorus-containing epoxy resin reacted with a bifunctional epoxy resin using the phosphorus-containing phenol compound (1) or DOPO-NQ as the phosphorus compound, and It is a system using DICY as an agent. In Comparative Example 16 in which DOPO-NQ was used alone, although the flame retardancy was satisfactory, the heat resistance was insufficient. In Example 22, the phosphorus-containing phenol compound (1) was used alone, and the heat resistance was improved. Moreover, although Example 23 only used phosphorus-containing phenol compound (1) in combination with 3% of DOPO-NQ, the heat resistance of the laminate was improved. Example 21 is an example using phosphorus-containing phenol compound (1) alone and using a phosphorus-containing epoxy resin having a phosphorus content reduced by 3% to 2.5%. The sex was good.

Examples 24 to 25 and Comparative Example 17
An epoxy resin composition varnish was prepared in the same manner as in Example 17 according to the composition of Table 8, except that Resins 6 to 7 obtained in Examples 6 to 7 and the resin H5 obtained in Comparative Example 5 were used as the resin. Further, a laminate and a test piece for flame retardancy measurement were obtained. The same test as in Example 17 was conducted, and the results are shown in Table 8. In the table, (parts) of YDPN-638, PN and 2E4MZ are compounding amounts, which are amounts relative to 40 parts of resin.

Examples 24 to 25 (Comparative Example 17) are linear phosphorus-containing epoxy resins reacted with a bifunctional epoxy resin using phosphorus-containing phenol compound (1) or DOPO-NQ as a phosphorus compound, In addition to the phosphorus-containing epoxy resin, a phenol novolac epoxy resin is used in combination, and PN is used as a curing agent. This is an example in which the blending amount of the phosphorus-containing epoxy resin is small and the phosphorus content of the epoxy resin composition is low. The heat resistance was insufficient in Comparative Example 16 in which DOPO-NQ was used alone. Example 25 only used phosphorus-containing phenol compound (1) in combination with 3% of DOPO-NQ, but the flame retardancy of the laminate was satisfactory and the heat resistance was also improved. Moreover, although Example 24 is an example which used not DOPO-NQ but phosphorus containing phenol compound (1) independently, the flame retardance and heat resistance were favorable.
From the results of Tables 7 and 8, it is understood that the phosphorus-containing phenol compound (1) has a large effect of improving the flame retardancy and the heat resistance when it is made to be a phosphorus-containing epoxy resin as compared to DOPO-NQ.

Examples 26-27 and Comparative Examples 18-19
An epoxy resin was prepared in the same manner as in Example 17 according to the composition of Table 9, except that the resins 8 to 9 obtained in Examples 8 to 9 and the resins H6 to H7 obtained in Comparative Examples 6 to 7 were used as the resin. A composition varnish was obtained, and a laminate and a test piece for flame resistance measurement were further obtained. The same test as in Example 17 was conducted, and the results are shown in Table 9. In the table, (parts) of PN and 2E4MZ are compounding amounts, and are amounts relative to 100 parts of resin.

  In Examples 26 to 27 (Comparative Examples 18 to 19), a phosphorus-containing epoxy resin reacted with a phenol novolac epoxy resin using phosphorus-containing phenol compound (1) or DOPO as a phosphorus compound, and PN as a curing agent It is the used system. The example is an example in which a small amount of phosphorus-containing phenol compound (1) is used in combination with DOPO. The flame retardancy and heat resistance of the laminate using the obtained phosphorus-containing epoxy resin were improved only by using a small amount of the phosphorus-containing phenol compound (1) in combination.

Examples 28-31 and Comparative Examples 20-21
Epoxy resin composition in the same manner as in Example 17 according to the composition of Table 10, except that resins 11 to 14 obtained in Examples 11 to 14 and resins H9 to H10 obtained in Comparative Examples 9 to 10 were used as resins. A product varnish was obtained, and a laminate and a test piece for flame resistance measurement were further obtained. The same test as in Example 17 was conducted, and the results are shown in Table 10. In the table, (parts) of KDCP130, PN and 2E4MZ are compounding amounts, which are amounts relative to 100 parts of resin.

Examples 32 to 34 and Comparative Examples 22 to 24
An epoxy resin composition varnish was prepared in the same manner as in Example 17 according to the composition of Table 11, except that the resins 15 to 16 obtained in Examples 15 to 16 and the resin H11 obtained in Comparative Example 11 were used as the resin. Further, a laminate and a test piece for flame retardancy measurement were obtained. The same test as in Example 17 was conducted, and the results are shown in Table 11. In addition, (part) of DCPD-P, GK5855P, and 2E4MZ is a compounding quantity in a table | surface, and it is the quantity with respect to 100 parts of resin.

  Examples 32 to 34 (Comparative Examples 22 to 24) are examples in which a phenolic curing agent other than PN is used. There was no difference in dielectric properties, and the flame retardancy, heat resistance and adhesion of the laminate were improved.

Example 35
100 parts of resin 13 as phosphorus-containing epoxy resin, 3.2 parts of DICY as curing agent, 0.2 parts of 2E4MZ as curing accelerator, 95 parts of YP-50S as other components, and 39 parts of BMB It melt | dissolved in the mixed solvent adjusted with MEK, PGM, and DMF, and obtained the epoxy resin composition varnish of 50% of a non volatile matter.

  The obtained epoxy resin composition varnish was applied onto a separator film (polyimide film) using a roll coater, and dried in an oven at 130 ° C. for 10 minutes to obtain a resin film having a thickness of 60 μm. The resin film was peeled off from the separator film, and the resin film was further cured in an oven at 200 ° C. for 120 minutes to obtain a cured film. The cured film was cut into a size of 200 mm × 50 mm to obtain a test piece for flame resistance measurement. The Tg and flame retardancy results of the cured film are shown in Table 12.

Example 36 and Comparative Examples 25 to 26
An epoxy resin composition varnish was obtained in the same manner as in Example 35 according to the composition of Table 12, except that the resin 10 obtained in Example 10 and the resins H8 to H9 obtained in Comparative Examples 8 to 9 were used as the resin. Further, a cured film and a test piece for flame resistance measurement were obtained. The same test as in Example 35 was conducted and the results are shown in Table 12. In addition, (part) of YDPN-638, YP-50S, DICY, 2E4MZ, BMB, and PX-200 is a compounding quantity in a table | surface, and it is the quantity with respect to 100 parts of resin.

Comparative example 27
An epoxy resin composition varnish was obtained in the same manner as in Example 35 according to the formulation of Table 12 except that 81 parts of PX-200 was used as a flame retardant, without using a phosphorus-containing epoxy resin, to obtain a cured film, A test piece for flame resistance measurement was obtained. The same test as in Example 35 was conducted and the results are shown in Table 12.

  Examples 35-36 (Comparative Examples 25-27) are examples when it is set as a cured film. Even in this case, the flame retardancy and heat resistance were improved.

Example 37
100 parts of resin 10 as phosphorus-containing epoxy resin, 100 parts of YDF-170, 106 parts of MTHPA as curing agent, 0.5 parts of 2E4MZ as curing accelerator, 160 parts of CMC 12 as other components, 80 ° C. The mixture was stirred and homogenized while heating to obtain an epoxy resin composition. The obtained epoxy resin composition was defoamed, cast in a mold, and cured at a temperature of 150 ° C. for 120 minutes to obtain a 2 mm-thick cured product. After demolding, the cured product was further post-cured in an oven at 200 ° C. for 120 minutes. The resulting cured product was cut into a size of 127 mm × 12.7 mm to obtain a test piece for flame resistance measurement. The results of Tg and flame retardancy of the cured product are shown in Table 13.

Comparative Examples 28-29
An epoxy resin composition was obtained in the same manner as in Example 37, except that the resin H8 obtained in Comparative Example 8 was used as a resin, in accordance with the composition of Table 13, to obtain a cured product and a test piece for flame retardancy measurement. The The same test as in Example 37 was conducted, and the results are shown in Table 13. In the table, (parts) of YDF-170, MTHPA, 2E4MZ, CMC12 and PX-200 are compounding amounts, which are the amount relative to 100 parts of resin.

  Example 37 (comparative examples 28 to 29) is an example when a cured product (casting product) is used. Even in this case, the flame retardancy and heat resistance were improved.

The phosphorus-containing epoxy resin and the phosphorus-containing epoxy resin composition of the present invention can be used for circuit board materials, sealing materials, casting materials, conductive pastes, adhesives and the like, and in particular, high flame retardancy and high heat resistance Materials for circuit boards (laminated boards) such as printed wiring board materials requiring various properties such as low dielectric properties and solvent solubility, resin compositions for flexible wiring boards, interlayer insulating materials for buildup boards, and semiconductor encapsulation Useful for materials.

Claims (13)

The phosphorus containing epoxy resin characterized by having a structure site | part represented by following formula (b).

Here, Ar represents an aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring, and these aromatic ring groups are alkyl groups having 1 to 8 carbon atoms and 1 to 8 carbon atoms. Alkoxy group, cycloalkyl group having 5 to 8 carbon atoms, aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 11 carbon atoms, aryloxy group having 6 to 10 carbon atoms, or aralkyloxy having 7 to 11 carbon atoms It may have a group as a substituent. Z is a phosphorus-containing group represented by the following formula (a).

Here, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, and may be linear, branched or cyclic, or , R ¹ and R ² may combine to form a cyclic structure. n1 and n2 are each independently 0 or 1. The phosphorus containing epoxy resin of Claim 1 which further has a structure site | part represented by following formula (c).

Here, Ar and Z are respectively synonymous with Ar and Z of Formula (b). The phosphorus-containing compound according to claim 1 or 2, characterized by having a structure represented by the following formula (b1), or a structure represented by the following formula (b1) and a structure represented by the following formula (c1) Epoxy resin.

Here, Ar and Z are respectively synonymous with Ar and Z of Formula (b). E is an organic group represented by -R ³ -A ¹ , -R ³ -is a linking group generated by the reaction of an epoxy group of a polyfunctional epoxy resin and a hydroxyl group, and A ¹ is a residue of the polyfunctional epoxy resin Group having at least one mole of an epoxy group or an epoxy derivative group thereof per mole of A ¹ , wherein at least a portion is an epoxy group, and the epoxy derivative group has a structure in which Z and a hydroxyl group are bonded to Ar And E in the formula (b1) and the formula (c1) may be shared with E in the other formula (b1) or the formula (c1). Y is a hydrogen atom or E. It is obtained by making the hydroxyl group of phosphorus containing phenol compound (1) represented by following formula (1), and the epoxy group of an epoxy resin react, The phosphorus containing epoxy resin of Claim 1 or 3 characterized by the above-mentioned.

Here, Ar and Z are respectively synonymous with Ar and Z of Formula (b). A reactive agent (x) comprising a compound having a functional group having reactivity with an epoxy group containing the phosphorus-containing phenol compound (1) represented by the following formula (1) as an essential component, and a polyfunctional epoxy resin (y) The manufacturing method of the phosphorus containing epoxy resin characterized by making it react.

Here, Ar represents an aromatic ring group selected from a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring, and these aromatic ring groups are alkyl groups having 1 to 8 carbon atoms and 1 to 8 carbon atoms. Alkoxy group, cycloalkyl group having 5 to 8 carbon atoms, aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 11 carbon atoms, aryloxy group having 6 to 10 carbon atoms, or aralkyloxy having 7 to 11 carbon atoms It may have a group as a substituent. Z is a phosphorus-containing group represented by the following formula (a).

Here, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, and may be linear, branched or cyclic, or R ¹ and R ² may combine to form a cyclic structure. n1 and n2 are each independently 0 or 1. The reactive agent (x) contains a phosphorus compound (p) having a functional group reactive with an epoxy group, and the phosphorus compound (p) is represented by the phosphorus-containing phenol compound (1) and the following formula (2) The method for producing a phosphorus-containing epoxy resin according to claim 5, comprising the phosphorus-containing phenol compound (2), wherein the content of the phosphorus-containing phenol compound (1) is 0.1 to 35% by mass of the phosphorus compound (p).

Here, Ar and Z are respectively synonymous with Ar and Z of Formula (1). The phosphorus compound (p) is charged so as to be 0.10 mol or more and less than 1.0 mol of the quinone compound (q) relative to 1 mol of the phosphorus compound (3) represented by the following formula (3) (3) The phosphorus-containing epoxy resin according to claim 6, which is obtained by reacting at 100 to 200 ° C. in an organic solvent having a water content of 0.05 to 0.5 mol per 1 mol. Manufacturing method.

^{Wherein, R 1, R 2, n1} , and n2 are the same meanings as ^{R 1, R 2, n1,} and n2 of formula (a).   The method for producing a phosphorus-containing epoxy resin according to claim 5 or 6, wherein the reactive agent (x) contains a compound (x1) having a functional group reactive with an epoxy group other than the phosphorus compound (p).   The epoxy resin composition containing the phosphorus containing epoxy resin in any one of Claims 1-4, and the hardening | curing agent for epoxy resins.   The material for circuit boards obtained using the epoxy resin composition of Claim 9.   The sealing material obtained using the epoxy resin composition of Claim 9.   The casting material obtained using the epoxy resin composition of Claim 9. A cured product obtained by curing the epoxy resin composition according to claim 9.

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