JP2013040284A - Curable resin composition, cured product thereof, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition achieving excellent flame retardancy, heat resistance, low dielectric constant, and a low dielectric loss tangent in a cured product thereof.SOLUTION: The curable resin composition contains a cyanate ester resin (A) that has a resin structure expressed by the following structural formula (1) and a curing accelerator (B) as essential components.

Description

  The present invention is excellent in flame retardancy, heat resistance, low dielectric constant and low dielectric loss tangent of the resulting cured product, and can be suitably used for printed wiring boards, semiconductor encapsulants, paints, casting applications, etc. The present invention relates to a composition, a cured product thereof, and a printed wiring board.

  In recent years, frequencies used in fields such as the electronics industry, communications, and computers are shifting to high frequency regions such as the gigahertz band, and resins used for insulating layers such as electrical laminates used in such high frequency regions. The material is required to have a low dielectric constant and a low dielectric loss tangent.

  As a resin material having such characteristics, a cyanate ester resin can impart high heat resistance and excellent dielectric properties to a cured product by a triazine ring generated during thermosetting. Have been widely used in electronic components, electronic component fields, composite material matrices, and the like.

  In particular, in the use of printed circuit boards for electric circuits, in recent years, the frequency used is shifting to a high frequency region such as the gigahertz band, and in recent years, high melting point solder that does not use lead due to environmental regulations. This lead-free solder has a higher operating temperature than conventional eutectic solder by about 20 to 40 ° C, and thus further improvements in heat resistance and dielectric properties are required. ing.

  In the field of printed wiring board materials, it is necessary to impart flame retardancy from the viewpoint of ensuring safety against fire, and halogen flame retardants such as bromine and antimony compounds have been used in combination. However, in recent environmental and safety initiatives, environmentally and flame-resistant flame retardants that do not use halogen-based flame retardants that may cause dioxins and do not use antimony compounds that are suspected of carcinogenicity. There is a strong demand for the development of a conversion method.

  As a method for obtaining flame retardancy with a non-halogen thermosetting resin composition, for example, a bifunctional cyanate ester resin typified by 2,2-bis (4-cyanatophenyl) propane is used. Disclosed is a technique using a phosphorus atom-containing cyanate ester resin modified with 2,5-dihydroxyphenyl) -6H-dibenzo [c, e] [1,2] oxaphosphorine-6-oxide (hereinafter, HCA-HQ). (See Patent Document 1 below).

  However, the composition described in Patent Document 1 reacts the hydroxyl group of HCA-HQ, which is a phosphorus atom-containing cyanate ester resin, with a cyanate group that is a cross-linking point in the phosphorus atom-containing cyanate ester resin. The cross-linking density of the cured product decreased, and the heat resistance of the cured product was lowered accordingly, which did not satisfy the recently required level of heat resistance.

JP 2004-182816 A

  Therefore, the problem to be solved by the present invention is a curable resin composition that achieves excellent flame retardancy, heat resistance, low dielectric constant, and low dielectric loss tangent in the cured product, the cured product, and their performance. It is providing the printed wiring board which combines.

  As a result of intensive investigations to solve the above problems, the present inventors have determined that a phosphorus atom-containing phenol oligomer obtained by reacting and oligomerizing a phosphorus atom-containing compound represented by HCA and an o-hydroxybenzaldehyde compound is cyanidated. When a cyanate ester resin obtained by acid esterification was used, the cured product was found to exhibit excellent heat resistance and dielectric properties, and the present invention was completed.

  That is, the present invention provides the following structural formula (1)

（式中、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein X represents the following structural formula (x1) or (x2)

で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、又は前記構造式（ｘ１）若しくは（ｘ２）であり、ｎは繰り返し単位で１以上の整数であり、また、前記構造式（ｘ１）又は（ｘ２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基である。）で表される樹脂構造を有するシアン酸エステル樹脂（Ａ）、及び硬化促進剤（Ｂ）を必須成分とすることを特徴とする硬化性樹脂組成物に関する。

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , An alkoxy group having 1 to 4 carbon atoms, a phenyl group, or the structural formula (x1) or (x2), n is a repeating unit and is an integer of 1 or more, and the structural formula (x1) or ( In x2), R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. It is related with the curable resin composition characterized by making the cyanate ester resin (A) which has the resin structure represented by this, and a hardening accelerator (B) into an essential component.

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

  The present invention can be obtained by further impregnating the curable resin composition with a varnished resin composition by further blending an organic solvent (E) into a reinforcing base material and stacking the copper foil on the thermocompression bonding. The present invention relates to a printed wiring board.

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which implement | achieves the heat resistance excellent in the hardened | cured material, a low dielectric constant, and a low dielectric loss tangent, the hardened | cured material, and the printed wiring board which combined these performance can be provided.

Hereinafter, the present invention will be described in detail.
The cyanate ester resin (A) used in the present invention has the following structural formula (1):

（式中、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein X represents the following structural formula (x1) or (x2)

で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、又は前記構造式（ｘ１）若しくは（ｘ２）であり、ｎは繰り返し単位で１以上の整数であり、また、前記構造式（ｘ１）又は（ｘ２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基である。）で表される樹脂構造を有するものである。

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , An alkoxy group having 1 to 4 carbon atoms, a phenyl group, or the structural formula (x1) or (x2), n is a repeating unit and is an integer of 1 or more, and the structural formula (x1) or ( In x2), R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. ).

  Thus, the cyanate ester resin (A) has the following structural formula (2) in the structural formula (1).

（式中、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein X represents the following structural formula (x1) or (x2)

で表される構造部位であり、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、又は前記構造式（ｘ１）若しくは（ｘ２）を表す。）で表される構造部位を繰り返し単位として有することから、硬化した状態において難燃性に優れ、かつ、高ガラス転移温度を有し、更に耐熱剥離性に優れたものとなる。

R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or the structural formula (x1) or (x2). Represent. ) As a repeating unit, it is excellent in flame retardancy in a cured state, has a high glass transition temperature, and is further excellent in heat-resistant peelability.

  Here, specific examples of the structural portion represented in the structural formula (2) include those represented by the following structural formulas (2-1) to (2-10).

  In the present invention, X in the structural formula (1) is selected from the structural formula (x1) and the structural formula (x2), and may be the structural formula (x1) particularly from the viewpoint of flame retardancy. Therefore, among the structural sites represented by the structural formula (2), the structural formulas (2-1), (2-2), (2-3) corresponding to the structural formula (x1), (2-4) and (2-9) are preferable.

  In the structural formula (1), Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2), and these coexist in the phosphorus atom-containing oligomer. May be. In the present invention, Y is preferably a hydrogen atom or a structural moiety represented by the structural formula (x1) or (x2) from the viewpoint of solvent solubility and heat resistance, and particularly from the viewpoint of flame retardancy. It is preferable that it is Formula (x1).

  In the cyanate ester resin (A), as described above, the content of the component in which n is 2 or more in the above structural formula (1) is in the range of 5 to 90% on the basis of the peak area in GPC measurement. It is preferable from the viewpoint that the solubility of the cyanate ester resin (A) in an organic solvent and the flame retardancy of the cured product are remarkably excellent.

  Here, the content of the component having n of 2 or more in the structural formula (1) refers to the ratio of the peak area of less than 36.0 minutes in the GPC chart measured under the following conditions.

<GPC measurement conditions>
4) GPC: The measurement conditions are as follows.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

  In the present invention, when the content of the component having n of 2 or more is 5% or more on the basis of the peak area in GPC measurement, the solvent solubility is good. On the other hand, when the content is 90% or less, the flow during melting Or fluidity when made into a varnish. Here, the other component is a component having n = 1, and therefore, in the phosphorus atom-containing oligomer of the present invention, the component having n = 1 is 95 to 10% on the basis of the peak area in GPC measurement. In the present invention, a component having n of 2 or more from the viewpoint of exhibiting excellent heat resistance in a cured product, in particular, high glass transition point and excellent performance in T288 test while maintaining the above-mentioned solvent solubility and fluidity. Is preferably in the range where the content of components having n is 1 is 60-25%.

  Further, specifically, the content of the component where n is 1 is 95 to 10%, the content of the component where n is 2 is 3 to 50%, and the content of the component where n is 3 or more is 1 to 45. % Is preferable from the viewpoint of solvent solubility, in particular, the content of the component where n is 1 is 60 to 25%, the content of the component where n is 2 is 10 to 45%, and n is 3 or more. The component content is preferably 10 to 40% from the viewpoint that the balance of solvent solubility, fluidity, and heat resistance becomes remarkable.

  As described above, Y in the structural formula (1) is preferably the structural formula (x1). Therefore, in the structural formula (1), Y is the structural formula (x1), and n Is preferably a phosphorus atom-containing oligomer having a content of 2 or more components of 40 to 75% and a content of n of 1 of 60 to 25% from the viewpoint of flame retardancy and heat resistance. In (1), Y is the structural formula (x1), the content of the component in which n is 1 is 95 to 10%, the content of the component in which n is 2 is 3 to 50%, and n is 3 or more A phosphorus atom-containing oligomer having a content of 1 to 45% is preferable from the viewpoint of excellent flame retardancy, heat resistance, and solvent solubility. In particular, Y is the structural formula (x1), and n is The content of component 1 is 60 to 25%, the content of component 2 is 10 to 45%, and n is 3 or more. Phosphorus atom-containing oligomer flame retardant component content of of 10 to 40% solvent solubility, flowability, and most preferable from the viewpoint of excellent balance between heat resistance.

  Moreover, it is preferable from the point of a flame retardance that above-mentioned cyanate ester resin (A) is the range whose phosphorus atom content rate in this resin is 9-12 mass%. The phosphorus atom content is a value measured according to “JIS standard K010246”.

  As the cyanate ester resin (A) described in detail above, those obtained by the following production method are preferable from the viewpoint of excellent solubility in organic solvents and excellent heat resistance of the cured product.

  That is, the following structural formula (a1-1) or (a1-2)

（式中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表される化合物（ａ１）と、
下記構造式（ａ２）

(Wherein R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group) a1)
The following structural formula (a2)

（式中、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表す。）
で表される化合物（ａ２）とを反応させてリン原子含有オリゴマーを得（工程１）、次いで、得られたリン原子含有オリゴマーに、ハロゲン化シアンを反応させる（工程２）方法が挙げられる。
ここで、工程１の反応を詳述すれば、具体的には、下記構造式（ａ１−１）又は（ａ１−２）

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group.)
And a compound (a2) represented by formula (1) to obtain a phosphorus atom-containing oligomer (step 1), and then reacting the resulting phosphorus atom-containing oligomer with cyanogen halide (step 2).
Here, if the reaction of step 1 is described in detail, specifically, the following structural formula (a1-1) or (a1-2)

（式中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表される化合物（ａ１）と、
下記構造式（ａ２）

(Wherein R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group) a1)
The following structural formula (a2)

（式中、Ｒ^６は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表す。）
で表される化合物（ａ２）とを、モル比［化合物（ａ１）／化合物（ａ２）］が０．０１／１．０〜０．９９／１．０となる割合で配合し、酸触媒の存在下、８０〜１８０℃で反応を行い、次いで、前記化合物（ａ２）の仕込み量に対して、モル基準で合計１．０１〜３．０倍量となる前記化合物（ａ１）を加え、１２０〜２００℃にて反応を行うことにより中間体であるリン原子含有オリゴマーを製造することができる。

(In the formula, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group.)
The compound (a2) represented by formula (I) is blended at a molar ratio of [compound (a1) / compound (a2)] of 0.01 / 1.0 to 0.99 / 1.0. The reaction is carried out at 80 to 180 ° C. in the presence, and then the compound (a1) is added in a total amount of 1.01 to 3.0 times on a molar basis with respect to the charged amount of the compound (a2), and 120 By carrying out the reaction at ˜200 ° C., an intermediate phosphorus atom-containing oligomer can be produced.

Here, as the alkyl group having 1 to 5 carbon atoms constituting R ² , R ³ , R ⁴ , R ⁵ in the structural formula (a1-1) or (a1-2), a methyl group, ethyl Group, n-propyl group, i-propyl group, t-butyl group, and the compound (a1) used in the present invention is one in which all of R ² , R ³ , R ⁴ , and R ⁵ are hydrogen atoms. Is preferable from the viewpoint of flame retardancy. Further, the compound (a1) preferably has the structural formula (a1-1) from the viewpoint that the cured product is excellent in flame retardancy. On the other hand, R ¹ in the structural formula (a2) in the compound (a2) includes a methyl group, an ethyl group, an n-propyl group, a methoxy group, etc., but the reactivity with the compound (a1) and the cured product From the viewpoint of excellent flame retardancy, R ¹ is preferably a hydrogen atom.

  Examples of catalysts that can be used in Step 1 include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Lewis acids such as The amount used is preferably in the range of 0.1 to 5.0% by mass with respect to the total weight of the charged raw materials from the viewpoint of preventing a decrease in electrical insulation of the cured product.

  In the reaction, since the compound (a2) is in a liquid state, it can be used as an organic solvent, but another organic solvent may be used from the viewpoint of improving workability and the like. Here, examples of the organic solvent used include non-ketone organic solvents such as alcohol-based organic solvents and hydrocarbon-based organic solvents. Specifically, examples of the alcohol-based organic solvent include propylene glycol monomethyl ether. Examples of the hydrocarbon organic solvent include toluene, xylene and the like.

  After completion of the reaction, a phosphorus atom-containing oligomer represented by the following structural formula (1 ') can be obtained by drying under reduced pressure.

（式中、Ｘは下記構造式（ｘ１）又は（ｘ２）

(Wherein X represents the following structural formula (x1) or (x2)

で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、Ｒ^１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、又は前記構造式（ｘ１）若しくは（ｘ２）であり、ｎは繰り返し単位で１以上の整数であり、また、前記構造式（ｘ１）又は（ｘ２）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基である。）で表されるリン原子含有オリゴマーを得ることができる。

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , An alkoxy group having 1 to 4 carbon atoms, a phenyl group, or the structural formula (x1) or (x2), n is a repeating unit and is an integer of 1 or more, and the structural formula (x1) or ( In x2), R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. The phosphorus atom containing oligomer represented by this can be obtained.

  Subsequently, the target cyanate ester resin (A) can be obtained by reacting the phosphorus atom-containing oligomer and cyanogen halide in step 2. Specifically, for example, cyanogen halide can be used in a ratio of 1.05 mol to 1.5 mol with respect to 1 mol of the phenolic hydroxyl group in the phosphorus atom-containing oligomer and reacted.

  Here, examples of the cyanogen halide include cyanogen chloride and cyanogen bromide. The above reaction is preferably performed in the presence of a basic catalyst from the viewpoint of good reactivity. Examples of the basic catalyst used here include tertiary amines such as triethylamine and trimethylamine; sodium hydroxide and the like And basic substances such as alkali metal hydroxides such as potassium hydroxide.

  In the above reaction, the reaction is preferably performed in the presence of an organic solvent. Examples of the organic solvent used in this case include aromatic solvents such as benzene, toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.

  After carrying out the reaction under the above conditions, an appropriate amount of water is added to the reaction solution to dissolve the produced salt. Thereafter, washing with water is repeated to remove the generated salt in the system, and further purification is performed by dehydration or filtration, and the organic solvent is removed by distillation to obtain the intended cyanate ester resin (A).

  The cyanate ester resin (A) thus obtained has a cyanate group equivalent in the cyanate ester resin (A) of 300 to 800 g / eq. Is preferably in the range of heat resistance, low dielectric constant, and low dielectric loss tangent, particularly 305 to 550 g / eq. It is preferable to be in the range.

  Specific examples of the curing catalyst (B) used in the present invention include phenols, amines, Lewis acids, tertiary sulfonium salts, quaternary ammonium salts, quaternary phosphonium salts, and epoxy group-containing compounds. It is done. Among these, nonylphenol, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, copper, lead, tin, manganese, nickel, iron, zinc, cobalt and other carboxylates, titanium tetra-n- Butoxide and its polymer, pentadionate salts such as copper, nickel and cobalt, tetrabutylammonium bromide, tetrabutylphosphonium chloride and zinc octylate are highly compatible with the cyanate ester resin (A) during the reaction. Is preferable for smoothly proceeding. Moreover, an epoxy compound is particularly preferable from the viewpoint of a fast reaction rate.

  It is preferable that the usage-amount of the said curing catalyst (B) is 0.001-1.00 mass part per 100 mass parts of cyanate ester resin (A), for example.

  The curable resin composition according to claim 1, further comprising a bismaleimide (C) in addition to the cyanate ester resin (A) and the curing accelerator (B).

The maleimide (C) which is a preferred embodiment of the thermosetting resin (C) of the present invention is not particularly limited as long as it is a compound having two or more maleimide groups in one molecule. Specific examples thereof include N-aliphatic maleimides such as N-cyclohexylmaleimide, N-methylmaleimide, Nn-butylmaleimide, N-hexylmaleimide, N-tert-butylmaleimide; N-phenylmaleimide, N N-aromatic maleimides such as-(P-methylphenyl) maleimide and N-benzylmaleimide; 4,4'-diphenylmethane bismaleimide, 4,4'-diphenylsulfone bismaleimide, m-phenylenebismaleimide,
Bis (3-methyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl) And bismaleimides such as -4-maleimidophenyl) methane and bis (3,5-diethyl-4-maleimidophenyl) methane.

  Among these, bismaleimides are preferable from the viewpoint that the heat resistance of the cured product is particularly good. In particular, 4,4′-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis ( 3-Ethyl-5-methyl-4-maleimidophenyl) methane and bis (3,5-diethyl-4-maleimidophenyl) methane are preferred.

  When using the said maleimide (C), a hardening accelerator can be used as needed. Examples of the curing accelerator that can be used here include amine compounds, phenol compounds, acid anhydrides, imidazoles, and organic metal salts.

  In the curable resin composition of the present invention, in addition to the cyanate ester resin (A) and the curing catalyst (B), or the cyanate ester resin (A), the curing catalyst (B), and maleimide (C In addition, it is preferable to use an epoxy resin (D) in combination.

  The epoxy resin (D) used here is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A, etc. Novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol- Phenolic co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde resin modified pheno Le resin type epoxy resin, a biphenyl novolak type epoxy resins.

  Among these, phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins, naphthol novolak type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolacs. Type epoxy resin, crystalline biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, xanthene type epoxy resin, alkoxy group-containing aromatic ring-modified novolak type epoxy resin (formaldehyde glycidyl group-containing aromatic ring and alkoxy group-containing aromatic ring Are particularly preferable in that a cured product having excellent heat resistance can be obtained.

Moreover, when using an epoxy resin (D), you may use together the hardening | curing agent for epoxy resins. Specifically, the curing agent for epoxy resin used here includes diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, guanidine derivatives, etc. as amine compounds. Examples of the amide compound include dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, and examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, and pyrophilic anhydride. Mellitic acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin (Zyrock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol Novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked by bismethylene groups), biphenyl-modified naphthol resin (phenol nuclei in bismethylene groups are Polyvalent naphthol compound), aminotriazine modified phenolic resin (melamine, benzoguanamine, etc.) Products) and alkoxy group-containing aromatic ring-modified novolak resins (polyphenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

  When using an epoxy resin (D), a hardening accelerator can also be suitably used together with the curable resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.

  In particular, when the curable resin composition of the present invention described in detail above is used as a varnish for a printed wiring board, it is preferable to blend an organic solvent (E) in addition to the above components. Examples of the organic solvent (E) that can be used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The proper amount used can be appropriately selected depending on the application. For example, in a printed wiring board application, a polar solvent having a boiling point of 160 ° C. or less such as methyl ethyl ketone, acetone, dimethylformamide, etc. It is preferable to use at a ratio of 80% by mass. On the other hand, in build-up adhesive film applications, examples of organic solvents (E) include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetic acid such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Esters, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and non-volatile content is 30 to 60 mass. It is preferable to use it at a ratio of%.

  The thermosetting resin composition is a non-halogen flame retardant that substantially does not contain a halogen atom in order to exert flame retardancy, for example, in the field of printed wiring boards, as long as the reliability is not lowered. May be blended.

  Examples of the non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. The flame retardants may be used alone or in combination, and a plurality of flame retardants of the same system may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7- Examples thereof include cyclic organophosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. In 100 parts by mass of curable resin composition containing all of halogen-based flame retardant and other fillers and additives, 0.1 to 2.0 parts by mass of red phosphorus is used as a non-halogen flame retardant. It is preferable to mix in the range, and when using an organophosphorus compound, it is preferably mixed in the range of 0.1 to 10.0 parts by mass, particularly in the range of 0.5 to 6.0 parts by mass. It is preferable to do.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenolic resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) and (iii) with paulownia oil, isomerized linseed oil, etc. It is.

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The compounding amount of the nitrogen-based flame retardant is appropriately selected according to the type of the nitrogen-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, It is preferable to mix in the range of 0.05 to 10 parts by mass in 100 parts by mass of the curable resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix | blend in the range of 1-5 mass parts.

  Moreover, when using the said 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 silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  The amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix | blend in 5-15 mass parts.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organic metal salt flame retardant is appropriately selected depending on the type of the organic metal salt flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. In 100 parts by mass of the curable resin composition in which all of epoxy resin, curing agent, non-halogen flame retardant and other fillers and additives are blended, it is preferably blended in the range of 0.005 to 10 parts by mass. .

  An inorganic filler can be mix | blended with the curable resin composition of this invention as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 20% by mass or more with respect to the total amount of the curable resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, can be added to the curable resin composition of this invention as needed.

  The curable resin composition of the present invention can be obtained by uniformly mixing the above-described components. The curable resin composition of the present invention in which the epoxy resin of the present invention, a curing agent, and further, if necessary, a curing accelerator are blended can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Applications for which the curable resin composition of the present invention is used include printed wiring board materials, resin casting materials, adhesives, interlayer insulation materials for build-up substrates, and adhesive films for build-ups. Among these various applications, in printed circuit boards, insulating materials for electronic circuit boards, and adhesive films for build-up, passive parts such as capacitors and active parts such as IC chips are embedded in so-called electronic parts. It can be used as an insulating material for a substrate. Among these, it is preferable to use for the printed wiring board material and the adhesive film for buildup from the characteristics, such as high heat resistance, low thermal expansibility, and solvent solubility.

  Here, in order to produce a printed circuit board from the curable resin composition of the present invention, the varnish-like curable resin composition containing the organic solvent (E) is further blended with the organic solvent (E) to obtain a varnish. A method of impregnating a reinforced resin composition into a reinforcing base material and stacking a copper foil to heat-press is mentioned. Examples of the reinforcing substrate that can be used here include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. If this method is described in further detail, first, the varnish-like curable resin composition is heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C., thereby being a prepreg which is a cured product. Get. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Next, the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately stacked, and then subjected to thermocompression bonding at a pressure of 1 to 10 MPa at 170 to 250 ° C. for 10 minutes to 3 hours, A desired printed circuit board can be obtained.

    When the curable resin composition of the present invention is used as a conductive paste, for example, a method of dispersing fine conductive particles in the curable resin composition to obtain a composition for anisotropic conductive film, liquid at room temperature And a paste resin composition for circuit connection and an anisotropic conductive adhesive.

  As a method for obtaining an interlayer insulating material for a build-up substrate from the curable resin composition of the present invention, for example, the curable resin composition appropriately blended with rubber, filler, etc., spray coating method on a wiring board on which a circuit is formed, After applying using a curtain coating method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  The method for producing an adhesive film for buildup from the curable resin composition of the present invention is, for example, a multilayer printed wiring board in which the curable resin composition of the present invention is applied on a support film to form a resin composition layer. And an adhesive film for use.

  When the curable resin composition of the present invention is used for a build-up adhesive film, the adhesive film is softened under the temperature condition of the laminate in the vacuum laminating method (usually 70 ° C. to 140 ° C.), and simultaneously with the lamination of the circuit board, It is important to show fluidity (resin flow) that allows resin filling in via holes or through holes present in a circuit board, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like curable resin composition of the present invention, coating the varnish-like composition on the surface of the support film (Y), Further, it can be produced by drying the organic solvent by heating or blowing hot air to form the layer (X) of the curable resin composition.

  The thickness of the formed layer (X) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

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

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (X) is protected by a protective film, after peeling these layers ( X) is laminated on one side or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

  The lamination conditions are such that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 104 N / m 2), and the air pressure is 20 mmHg (26 It is preferable to laminate under a reduced pressure of 0.7 hPa or less.

  The method for obtaining the cured product of the present invention may be based on a general curing method for a curable resin composition, but for example, the heating temperature condition may be appropriately selected depending on the kind of curing agent to be combined and the use. However, what is necessary is just to heat the composition obtained by the said method in the temperature range about 20-250 degreeC.

  Further, in the present invention, by using an acid group-containing radical polymerizable resin obtained by modifying an acid anhydride to the reaction product of the cyanate ester resin (A) and epoxy acrylate and a polymerizable monomer, It can be set as a development type resist ink composition.

As the epoxy acrylate, specifically, any epoxy acrylate obtained by reacting the epoxy resin (D) exemplified with (meth) acrylic acid can be used. Examples of the acid anhydride used here include maleic anhydride, succinic anhydride, itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydro Phthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, 3- Butenyl-5,6-dimethyltetrahydrophthalic anhydride, 3,6-endomethylene-tetrahydrophthalic anhydride, 7-methyl-3,6-endomethylenetetrahydrophthalic anhydride,
Aliphatic acid anhydrides such as benzophenone tetracarboxylic anhydride; phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, etc. Of the aromatic acid anhydride.

  Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. The melt viscosity at 150 ° C. and GPC, NMR and MS spectra were measured under the following conditions.

Examples will be described specifically with reference to comparative examples. The melt viscosity at 180 ° C., softening point, phosphorus content, GPC measurement, NMR, and MS spectrum were measured under the following conditions.
1) Melt viscosity at 180 ° C .: in accordance with ASTM D4287 2) Softening point measurement method: JIS K7234
3) Phosphorus content measurement method: compliant with JIS K0102-46

4) GPC: The measurement conditions are as follows.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

5) NMR: JEOL JNM-ECA500 nuclear magnetic resonance apparatus Magnetic field strength: 500 MHz
Pulse width: 3.25 μsec
Integration count: 8000 times Solvent: DMSO-d6
Sample concentration: 30% by mass

6) MS: Shimazu Biotech AXIMA-TOF2
Measurement mode: linear
Integration frequency: 50 times Sample composition: sample / DHBA / NaTFA / THF = 9.4 mg / 104.7 mg / 6.3 mg / 1 ml
The component ratio of n = 2 or more was calculated based on the peak area of less than 36.0 minutes on the GPC chart.

Synthesis Example 1 [Synthesis of phosphorus atom-containing oligomer (A-1)]
In a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 122 g (1.0 mol) of 2-hydroxybenzaldehyde and 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide (hereinafter abbreviated as “HCA”) 151.2 g (0.7 mol) and oxalic acid 2.23 g (0.019 mol) were charged, and the temperature was raised to 120 ° C. and reacted for 1 hour. . Next, 172.8 g (0.8 mol) of HCA was added, and the temperature was raised to 180 ° C. and reacted for 3 hours. Next, water is removed under reduced pressure by heating, and the following structural formula

で表される構造単位を有するリン原子含有オリゴマー（Ａ−１）４１０ｇを得た。得られたリン原子含有オリゴマーの軟化点は１３８℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１８０℃）は６６ｄＰａ・ｓ、水酸基当量は４２８ｇ／ｅｑ．リン含有量１０．５％であり、ｎ＝２以上の成分比率は４９．０％であった。

The phosphorus atom containing oligomer (A-1) 410g which has a structural unit represented by these was obtained. The resulting phosphorus atom-containing oligomer had a softening point of 138 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 180 ° C.) of 66 dPa · s, and a hydroxyl group equivalent of 428 g / eq. The phosphorus content was 10.5%, and the component ratio of n = 2 or more was 49.0%.

Synthesis Example 2 [Synthesis of phosphorus atom-containing oligomer (A-2)]
In a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 122 g (1.0 mol) of o-hydroxybenzaldehyde, 108 g (0.5 mol) of HCA, and 2.23 g of oxalic acid ( 0.019 mol) was added, and the temperature was raised to 120 ° C. and reacted for 1 hour. Next, 216 g (1.0 mol) of HCA was added, the temperature was raised to 180 ° C., and the reaction was allowed to proceed for 3 hours. Next, water is removed under heating and reduced pressure, and the following structural formula:

で表される構造単位を有するリン原子含有オリゴマー（Ａ−２）４１５ｇを得た。これの軟化点は１３０℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１８０℃）は７２ｄＰａ・ｓ、水酸基当量は４３０ｇ／ｅｑ．リン含有量１０．５質量％であり、ｎ＝２以上の成分比率は４４．７％であった。

The phosphorus atom containing oligomer (A-2) which has a structural unit represented by 415g was obtained. The softening point is 130 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 180 ° C.) is 72 dPa · s, and the hydroxyl group equivalent is 430 g / eq. The phosphorus content was 10.5% by mass, and the component ratio of n = 2 or more was 44.7%.

Synthesis Example 3 [Synthesis of phosphorus atom-containing oligomer (A-3)]
In a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 122 g (1.0 mol) of o-hydroxybenzaldehyde, 129.6 g (0.6 mol) of HCA, and oxalic acid 3. 81 g (0.032 mol) was charged, and the temperature was raised to 120 ° C. and reacted for 1 hour. Next, 129.6 g (0.6 mol) of HCA was added, the temperature was raised to 180 ° C., and the reaction was carried out for 3 hours. Next, water is removed under heating and reduced pressure, and the following structural formula:

で表される構造単位を有するリン原子含有オリゴマー（Ａ−３）４１５ｇを得た。これの軟化点は１５０℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１８０℃）は１０５ｄＰａ・ｓ、水酸基当量は３６３．２ｇ／ｅｑ．リン含有量９．９質量％であり、ｎ＝２以上の成分比率は６６．２％であった。

415 g of a phosphorus atom-containing oligomer (A-3) having a structural unit represented by The softening point is 150 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 180 ° C.) is 105 dPa · s, and the hydroxyl group equivalent is 363.2 g / eq. The phosphorus content was 9.9% by mass, and the component ratio of n = 2 or more was 66.2%.

Synthesis Example 4 [Synthesis of cyanate ester resin (B-1)]
While flowing nitrogen gas through a four-necked flask equipped with a dropping funnel, thermometer, stirring device, heating device, and cooling reflux tube, 106 g (1.0 mol) of cyanogen bromide and 214 g of phenol resin (A-1) (0 0.5 mol) was dissolved in 1000 g of acetone, and then cooled to -3 ° C. Next, 111 g (1.1 mol) of triethylamine was charged into the dropping funnel and added dropwise at a rate such that the temperature inside the flask did not exceed 10 ° C. while stirring. After completion of the dropwise addition, the mixture was stirred at a temperature of 10 ° C. or lower for 2 hours, and the resulting precipitate was removed by filtration, and then poured into a large amount of water and reprecipitated. This was extracted with methylene chloride and washed with water to obtain 200 g of cyanate ester resin (B-1). The IR spectrum of this compound showed an absorption of 2264 cm ⁻¹ (cyanate group), no absorption of a hydroxyl group, and MS spectra showed peaks of 561, 906, and 1251.

で表される目的のシアン酸エステル樹脂（Ｂ−１）であることが確認された。
得られたシアン酸エステル樹脂のリン含有量は９．９％であった。

It was confirmed that it was the target cyanate ester resin (B-1) represented by.
The phosphorus content of the obtained cyanate ester resin was 9.9%.

で表わされるシアン酸エステル樹脂（Ｂ−２）２０２ｇを得た。得られたシアン酸エステル樹脂のリン含有量は９．９％であった。 Synthesis Example 5 [Synthesis of cyanate ester resin (B-2)]
In Synthesis Example 4, the following structural formula was obtained in the same manner as in Example 1, except that 215 g of phenol resin (A-2) was used instead of phenol resin (A-1).

202 g of a cyanate ester resin (B-2) represented by The phosphorus content of the obtained cyanate ester resin was 9.9%.

で表わされるシアン酸エステル樹脂（Ｂ−３）１７８ｇを得た。得られたシアン酸エステル樹脂のリン含有量は９．３％であった。 Synthesis Example 6 [Synthesis of cyanate ester resin (B-3)]
In Synthesis Example 4, the following structural formula was obtained in the same manner as in Example 1 except that 181.5 g of phenol resin (A-3) was used instead of phenol resin (A-1).

178 g of a cyanate ester resin (B-3) represented by The phosphorus content of the obtained cyanate ester resin was 9.3%.

Comparative Synthesis Example 1
110 g of toluene, 110 g of bisphenol A cyanate ester resin (BA-200 made by LONZA), 6- (2,5-dihydroxy) in a four-necked flask equipped with a dropping funnel, thermometer, stirring device, heating device, and cooling reflux tube 20.7 g of phenyl) -6H-dibenzo [c, e] [1,2] oxaphosphorin-6-oxide (hereinafter abbreviated as HCA-HQ) and 0.11 g of 17% toluene solution of manganese naphthenate were added. By reacting at 105 ° C. for 4 hours, 230 g of a toluene solution of cyanate ester resin (B-4) (nonvolatile content: 54%) was obtained.

Examples 1 to 3, Comparative Examples 1 and 2
LONZA BA-200 (bisphenol A type cyanate ester resin) is used as the cyanate ester resin and zinc octylate is used as the curing accelerator, and the composition shown in Table 1 is used. The press is used at a temperature of 200 ° C. for 10 minutes. After molding, it was prepared by post-curing at a temperature of 200 ° C. for 5 hours. The heat resistance, dielectric constant, and dielectric loss tangent were measured by the following methods, and the results are shown in Table 1.

[Physical property test conditions]
<Heat resistance (glass transition temperature)>
Using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Rheometric, rectangular tension method; frequency 1 Hz, heating rate 3 ° C./min), the elastic modulus change is maximized (tan δ change rate is the highest). The (large) temperature was evaluated as the glass transition temperature.

<Measurement of dielectric constant and dissipation factor>
In accordance with JIS-C-6481, the dielectric material at 1 GHz of the test piece after being stored in an indoor room at 23 ° C. and 50% humidity for 24 hours after absolutely dry using an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, Inc. The rate and dielectric loss tangent were measured.

Examples 4 to 6, Comparative Examples 3 and 4
In accordance with the composition shown in Table 2 below, a cyanate ester resin was charged into a four-necked flask equipped with a stirrer, a heating device, and a cooling reflux tube, and heated and stirred at 150 ° C. for 10 hours while flowing nitrogen gas. A varnish containing a cyanate ester prepolymer having a triazine skeleton formed by 35% by mole of an ester group was synthesized. 0.1 parts by mass of zinc octylate is added to 100 parts by mass of the varnish, impregnated into a glass cloth, dried at 100 ° C. for 5 minutes, and then heat-treated at 150 ° C. for 10 minutes to obtain a resin content of 50% by mass. A prepreg was obtained. Seven prepregs were stacked, and two electrolytic copper foils having a thickness of 18 μm were placed on both sides of the prepreg, and heated and pressurized with a hot press machine to obtain a double-sided copper-clad laminate having a thickness of 1.6 mm. The pressing conditions at this time were 180 ° C. for 2 hours and the pressure was 20 kg / cm ² . After this laminate was after-cured at 220 ° C. for 2 hours, the copper foil was removed by etching to prepare a sample for measuring the properties of the laminate. Table 2 shows values of glass transition temperature (DMA), flame retardancy, and dielectric properties (1 GHz).

[Physical property test conditions]
<Heat resistance (glass transition temperature)>
Using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Rheometric, rectangular tension method; frequency 1 Hz, heating rate 3 ° C./min), the elastic modulus change is maximized (tan δ change rate is the highest). The (large) temperature was evaluated as the glass transition temperature.
<Measurement of dielectric constant and dissipation factor>
In accordance with JIS-C-6481, the dielectric material at 1 GHz of the test piece after being stored in an indoor room at 23 ° C. and 50% humidity for 24 hours after absolutely dry using an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, Inc. The rate and dielectric loss tangent were measured.
<Flame retardance test>
The test method conforms to the UL-94 vertical test.

Claims (8)

The following structural formula (1)

(Wherein X represents the following structural formula (x1) or (x2)

Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , An alkoxy group having 1 to 4 carbon atoms, a phenyl group, or the structural formula (x1) or (x2), n is a repeating unit and is an integer of 1 or more, and the structural formula (x1) or ( In x2), R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. A curable resin composition comprising a cyanate ester resin (A) having a resin structure represented by formula (A) and a curing accelerator (B) as essential components. 2. The cyanate ester resin (A) according to claim 1, wherein the content of the component having n of 2 or more in the structural formula (1) is in the range of 5 to 90% on the basis of the peak area in GPC measurement. Curable resin composition. The cyanate ester resin (A) has the following structural formula (a1-1) or (a1-2)

(Wherein R ² , R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group) a1)
The following structural formula (a2)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group.)
The curable resin composition according to claim 1, which is a cyanate ester of a phosphorus atom-containing oligomer obtained by reacting with the compound (a2) represented by formula (1). The curable resin composition according to claim 1, further comprising a bismaleimide (C) in addition to the cyanate ester resin (A) and the curing accelerator (B). A curable resin composition further comprising an epoxy resin (D) in addition to the cyanate ester resin (A) and the curing accelerator (B). A curable resin composition comprising, as essential components, an acid group-containing radical polymerizable resin obtained by modifying an acid anhydride into a reaction product of the cyanate ester resin (A) and an epoxy acrylate, and a polymerizable monomer. Hardened | cured material formed by carrying out hardening reaction of the curable resin composition as described in any one of Claims 1-6. A resin composition obtained by further blending an organic solvent (E) with the composition according to any one of claims 1 to 6 to make a varnish impregnated into a reinforcing base material, and hot-pressing the copper foil. Printed wiring board obtained by