JP6579309B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition. Furthermore, the present invention provides a composition for an insulating layer containing the composition, a sheet-like laminate material containing the composition, a multilayer printed wiring board comprising an insulating layer obtained by curing the curable composition in the composition, The present invention relates to a semiconductor device including the multilayer printed wiring board.

2. Description of the Related Art In recent years, electronic devices have been reduced in size and performance, and in multilayer printed wiring boards, build-up layers have been multilayered, and miniaturization and high density of wiring have been demanded. In order to pursue miniaturization of wiring and the like, various performances are also required for insulating layers for multilayer printed wiring boards.
For example, Patent Document 1 discloses performance such as tackiness when a curable resin composition containing a specific vinyl compound and a high molecular weight polymer having a weight average molecular weight of 10,000 or more as an essential component is processed into a curable film. It is disclosed that it can be improved (see claim 1, paragraph number 0004, etc.). However, Patent Document 1 does not disclose that the curable resin composition contains a phosphonate compound. Moreover, patent document 1 does not examine the peel strength and linear thermal expansion coefficient of the hardened | cured material which hardened the curable resin composition.
On the other hand, the insulating layer is required to be able to achieve sufficient peel strength, low linear thermal expansion coefficient, and low dielectric loss tangent. However, when trying to achieve low dielectric loss tangent, the peel strength tends to be weakened. Therefore, it is difficult to design a cured product satisfying these performances at the same time.

JP 2006-83364 A

The present invention relates to a composition capable of preparing a cured product having sufficient peel strength and capable of achieving a low linear thermal expansion coefficient and a low dielectric loss tangent.
Moreover, this invention relates to the composition suitable for preparation of the insulating layer of a multilayer printed wiring board.
Furthermore, this invention relates to the semiconductor device containing the insulating layer of the said multilayer printed wiring board.

As a result of intensive studies to solve the above problems, the present inventors have (1) a phosphonate compound having one or more ethylenically unsaturated bonds in the molecule, and (2) two or more ethylenically unsaturated groups in the molecule. A composition containing a radically polymerizable compound having a saturated bond and one or more aromatic hydrocarbons or alicyclic hydrocarbons, and (3) an inorganic filler has been described above while maintaining sufficient peel strength. The present inventors have found that a cured product capable of achieving a low linear thermal expansion coefficient and a low dielectric loss tangent can be provided, and the present invention has been completed.
That is, the present invention includes the following aspects.

[1]
(1) A phosphonate compound having one or more ethylenically unsaturated bonds in the molecule,
(2) a radically polymerizable compound having two or more ethylenically unsaturated bonds and one or more aromatic hydrocarbons or alicyclic hydrocarbons in the molecule;
and,
(3) A composition comprising an inorganic filler, wherein (1) component and (2) component are different compounds.

[2] The composition according to [1], wherein the component (1) is represented by the following formula (I).
[In the formula (I), R ₄₁ and R ₄₂ are each independently an alkyl group or an aryl group, and X is represented by the following formula (X-1) or the following formula (X-2). ]

[In the formulas (X-1) and (X-2), R _{35 to} R ₄₀ are each independently hydrogen, an alkyl group, or an aryl group. ]

[3] The composition according to [2], wherein in formula (I), R ₄₁ and R ₄₂ are each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group.

[4] In Formula (I), X is represented by Formula (X-1), and in Formula (X-1), R _{35 to} R ₃₇ are hydrogen, according to [2] or [3] above Composition.

[5] (1) When the non-volatile component of the composition excluding the component is 100% by mass, the component (1) is any one of [1] to [4], wherein the component is 3-45% by mass. Composition.

[6] When the nonvolatile component of the composition is 100% by mass, the total of (1) component and (2) component is 1 to 70% by mass, in any one of [1] to [5] above The composition as described.

[7] The composition according to any one of [1] to [6], wherein the inorganic filler of component (3) is silica.

[8] The inorganic filler as component (3) is surface-treated with a silane coupling agent having one or more functional groups selected from acrylic, methacrylic, styryl, amino, epoxy, and vinyl, [1] -Composition of any one of [7].

[9] Any one of [1] to [7], wherein the inorganic filler of component (3) is surface-treated with an aminosilane coupling agent, a vinylsilane coupling agent, or a styrylsilane coupling agent. The composition according to item.

[10] The composition according to any one of [1] to [9] above, wherein the component (3) is 30 to 80% by mass when the nonvolatile component of the composition is 100% by mass.

[11] The composition according to any one of [1] to [10], wherein the component (2) is a radical polymerizable compound represented by the following formula (II).
[In Formula (II), R _{1 to} R ₆ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and A is a divalent group containing an aromatic hydrocarbon or an alicyclic hydrocarbon. ]

[12] The composition according to [11], wherein A is represented by the following formula (A-1), (A-2), (A-3) or (A-4) in formula (II): .

[In the formulas (A-1) and (A-2), B is a divalent group containing an aromatic hydrocarbon or an alicyclic hydrocarbon. In the formula (A-1), E ₁ and E ₂ are Each independently represents an alkylene group or an alkyleneoxy group. ]
[In Formula (A-3), D is the following Formula (D-1). ]
[In Formula (D-1), R _{7 to} R ₁₄ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, or a phenyl group, and a and b are integers of 0 to 100 in which at least one is not 0. , B is a divalent group containing an aromatic hydrocarbon or alicyclic hydrocarbon. ]
[In Formula (A-4), B is a divalent group containing an aromatic hydrocarbon or an alicyclic hydrocarbon, and E ₄ and E ₅ are each independently an alkylene group or an alkyleneoxy group. ]

[13] In the formulas (A-1), (A-2), (D-1) and (A-4), B is represented by any one of the following formulas (B-1) to (B-6). The composition according to [12] above.





[In the formulas (B-1) to (B-5), R _{15 to} R ₃₄ and R _{43 to} R ₅₀ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, or a phenyl group. ), E is an alkylene group or an alkyleneoxy group. ]

[14] A radically polymerizable compound in which the structural units represented by the formulas (III) to (V) are randomly polymerized, wherein the component (2) includes at least two structural units represented by the formula (V). The composition according to any one of [1] to [10].


[In the formulas (III) to (V), X is hydrogen or an alkyl group having 6 or less carbon atoms. In the formula (IV), R ₅₁ is an alkyl group or a hydroxyalkyl group. , R ₅₂ is a group containing an ethylenically unsaturated bond and an aromatic hydrocarbon or alicyclic hydrocarbon. ]

[15] The composition according to [14], wherein the formula (V) is represented by the formula (VI).

[16] A composition for an insulating layer of a multilayer printed wiring board, comprising the composition according to any one of [1] to [15].

[17] A sheet-like laminated material comprising the composition according to any one of [1] to [16].

[18] A cured product obtained by heat-curing the composition according to any one of [1] to [16] or the sheet-shaped laminated material according to [17], Hardened | cured material whose dielectric loss tangent is 0.005 or less.

[19] A cured product obtained by heat-curing the composition according to any one of [1] to [16] or the sheet-shaped laminated material according to [17], Hardened | cured material whose linear thermal expansion coefficient is 40 ppm / degrees C or less.

[20] A cured product obtained by heat-curing the composition according to any one of [1] to [16] or the sheet-shaped laminated material according to [17], Hardened | cured material whose glass transition temperature is 170 degreeC or more.

[21] An insulating layer obtained by thermosetting the composition according to any one of [1] to [16] or the sheet-like laminated material according to [17]. , Multilayer printed wiring board.

[22] A semiconductor device comprising the multilayer printed wiring board according to [21].

  The present invention can provide a composition capable of preparing a cured product having sufficient peel strength and capable of achieving a low linear thermal expansion coefficient and a low dielectric loss tangent. Moreover, this invention can provide the composition suitable for preparation of the insulating layer of a multilayer printed wiring board. Furthermore, the present invention can provide a semiconductor device including the insulating layer of the multilayer printed wiring board.

[Composition]
The composition which is one embodiment of the present invention comprises (1) a phosphonate compound having one or more ethylenically unsaturated bonds in the molecule, (2) two or more ethylenically unsaturated bonds in the molecule, and 1 A composition comprising a radically polymerizable compound having one or more aromatic hydrocarbons or alicyclic hydrocarbons, (3) an inorganic filler, and optionally (4) other components. Hereinafter, each component contained in the composition of the present invention will be described in detail.

(1) Phosphonate compound having one or more ethylenically unsaturated bonds in the molecule (1) The component (1) which can be used in the present invention is at least one ethylenically unsaturated bond to the phosphorus atom of the compound having a phosphonate skeleton. It is a compound to which a group having a bond is bonded. Preferred phosphonate compounds have the structure of formula (I)

In formula (I), R ₄₁ and R ₄₂ are each independently an alkyl group or an aryl group, and X is represented by the following formula (X-1) or the following formula (X-2).

In the formulas (X-1) and (X-2), R _{35 to} R ₄₀ are each independently hydrogen, an alkyl group, or an aryl group.

The alkyl group of the present invention may be linear or branched. Carbon number of this alkyl group becomes like this. Preferably it is 1-20, More preferably, it is 1-14, More preferably, it is 1-12, More preferably, it is 1-6, Most preferably, it is 1-3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. And decyl group.
The aryl group of the present invention is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms of the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

R ₄₁ and R ₄₂ are preferably each independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a phenyl group, or naphthyl. And an anthracenyl group, more preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, and most preferably selected from a methyl group, an ethyl group, or a phenyl group.

R ₃₅ , R ₃₆ and R ₃₇ are preferably each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 24 carbon atoms, more preferably hydrogen, 1 to 6 carbon atoms. An alkyl group and a phenyl group;
More preferably, at least one of R ₃₆ and R ₃₇ is hydrogen.

R _{35 to} R ₄₀ are preferably each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and more preferably hydrogen.

As the component (A), compounds represented by the following formulas (8) to (21) are particularly preferable.













These compounds are available from, for example, Katayama Chemical Co., Ltd.

  Of these, compounds represented by the formulas (8), (9) and (10) are preferred.

  In the composition of the present invention, from the viewpoint of lowering the dielectric loss tangent of the cured product obtained from the composition, when the nonvolatile component of the composition excluding the component (3) is 100% by mass, the phosphonate compound as the component (1) The content of is preferably 3 to 45% by mass, more preferably 5 to 40% by mass, and still more preferably 5 to 36% by mass.

(2) Radical polymerizable compound having two or more ethylenically unsaturated bonds and one or more aromatic hydrocarbons or alicyclic hydrocarbons in the molecule (2) The component (2) that can be used in the present invention includes two components. It is a radically polymerizable compound having the above ethylenically unsaturated bond as a radically polymerizable group. The component (2) is a compound different from the component (1). In the present specification, the radical polymerizable compound includes a resin having two or more ethylenically unsaturated bonds as a curable group. Since an ethylenically unsaturated bond does not generate a hydroxyl group by polymerization, a cured resin having a low dielectric loss tangent can be obtained.
The component (2) that can be used in the present invention is preferably a radical polymerizable compound represented by the following formula (II).

In formula (II), R _{1 to} R ₆ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably 2 to 3 carbon atoms. R ₁ , R ₂ , R ₅ and R ₆ are preferably hydrogen. R ₃ and R ₄ are preferably hydrogen or a methyl group.

  In the formula (II), A is a divalent group containing an aromatic hydrocarbon or an alicyclic hydrocarbon. A is preferably a divalent group represented by the following formula (A-1), (A-2), (A-3) or (A-4).

In the formulas (A-1) and (A-2), B is a divalent group containing an aromatic hydrocarbon or alicyclic hydrocarbon, and E ₁ and E ₂ are each independently an alkylene group or an alkyleneoxy group. It is.

E ₁ and E ₂ are preferably an alkylene group or alkyleneoxy group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, preferably a methylene group, an ethylene group, a propylene group, an isopropylene group, or a polymethyleneoxy group. And a polyethyleneoxy group, more preferably a methylene group, an isopropylene group, and a polyethyleneoxy group having 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms.

In formula (A-3), D is the following formula (D-1).
In formula (D-1), R _{7 to} R ₁₄ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, preferably 1 to 3 alkyl groups, or a phenyl group, preferably hydrogen or a methyl group. In particular, R ₇ , R ₈ , R ₁₃ and R ₁₄ are more preferably methyl groups. a and b are integers of 0 to 100, at least one of which is not 0, preferably 3 to 80, more preferably 5 to 50, and B includes an aromatic hydrocarbon or an alicyclic hydrocarbon. It is a divalent group.

In formula (A-4), B is a divalent group containing an aromatic hydrocarbon or alicyclic hydrocarbon, and E ₄ and E ₅ are each independently an alkylene group or an alkyleneoxy group.

B is a divalent group containing an aromatic hydrocarbon or an alicyclic hydrocarbon, and is an arylene group, heteroarylene group, cycloalkylene group, bridged ring (for example, an adamantyl group, norbornyl group, methylnorbornyl group) ) -Like hydrocarbon group, divalent aromatic hydrocarbon group such as a bridged ring and a monocyclic (for example, cycloheptane ring, cyclohexane ring) or polycyclic (for example, decahydronaphthalene ring) or aliphatic group A cyclic hydrocarbon group; a group in which a divalent aromatic hydrocarbon or alicyclic hydrocarbon is bonded to an oxygen atom, an alkylene group or an alkyleneoxy group to form a divalent group as a whole; a monovalent aromatic carbon A group containing a hydrogen group or an alicyclic hydrocarbon group in a pendant form.
Preferably, an arylene group, a cycloalkylene group, a bridged cyclic hydrocarbon group, a group in which a bridged ring and a monocyclic or polycyclic ring are condensed, and a group in which the arylene group is bonded to an oxygen atom, an alkylene group, or an alkyleneoxy group. It is done.

More preferable B includes the following formulas (B-1) to (B-6).





In formulas (B-1) to (B-5), R _{15 to} R ₃₄ and R _{43 to} R ₅₀ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, or a phenyl group, more preferably hydrogen or It is a methyl group. In formula (B-3), E represents an alkylene group or an alkyleneoxy group. Preferred E is the same as E ₁ or E _{2 in} (A-1).

More specifically, as the component (2), any one compound represented by the following formulas (23) to (31) is more preferable.
(23)
In the formula (23), R _{1 to} R ₆ , B, a, and b are the same as described above.

As the commercially available radically polymerizable compound of component (2), styrene-modified polyphenylene ether resin (“OPE-2St” manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 1200, equivalent to general formula (23), B (B-1), R _{1 to} R ₆ are hydrogen, a is 5 to 50, and b is 5 to 50), xylenol diallyl ether (“YL7776 (number average molecular weight 331)” manufactured by Mitsubishi Chemical Corporation) Dimethylol-tricyclodecane diacrylate (manufactured by Kyoei Chemical Co., Ltd., “DCP-A”, number average molecular weight 304, equivalent to general formula (25)), dimethylol-tricyclodecane dimethacrylate (Kyoei Chemical Co., Ltd., “DCP-M”, number average molecular weight 318, equivalent to general formula (26)), bisphenol AEO addition diacrylate, bisphenol A O-added dimethacrylate (equivalent to general formula (27) to (29) manufactured by Kyoei Chemical Co., Ltd.)), orthophthalic acid diallyl ester (manufactured by Daiso Co., Ltd., “Daiso Dup (registered trademark) monomer (number average molecular weight 246.3)” ) ", General formula (30) equivalent), isophthalic acid diallyl ester (" Daiso Dup (registered trademark) 100 monomer (number average molecular weight 246.3) "manufactured by Daiso Corporation), general formula (31) equivalent), etc. It is done.

Other preferable radically polymerizable compounds of component (2) include polymers having a number average molecular weight of 30000 or less, preferably 12000 to 25000, in which structural units represented by formulas (III) to (V) are randomly polymerized. Can be mentioned. The polymer includes at least two structural units represented by the formula (V).


In formulas (III) to (V), X is hydrogen or an alkyl group having 6 or less carbon atoms, preferably 1 to 3 carbon atoms, preferably hydrogen or a methyl group. In formula (IV), R ₅₁ is an alkyl group or a hydroxyalkyl group. In the formula (V), R ₅₂ contains an ethylenically unsaturated bond and an aromatic hydrocarbon or alicyclic hydrocarbon. Formula (V) is preferably represented by Formula (VI).
Polymers in which the structural units represented by the formulas (III), (IV) and (VI) are randomly polymerized are commercially available as acrylic oligomers ("Cyclomer P Z230AA" manufactured by Daicel Chemical Industries, Ltd.). )), Carboxylic acid group-containing acrylic oligomers ("Cyclomer P Z251", "Cyclomer P Z254F" manufactured by Daicel Chemical Industries, Ltd.) and the like.

The number average molecular weight of the radically polymerizable compound is 30000 or less from the viewpoint of preventing volatilization during drying of the resin varnish prepared from the composition of the present invention and preventing the melt viscosity of the composition from excessively increasing. Preferably, it is in the range of 100-28000, more preferably in the range of 200-25000. In addition, the number average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.
In the composition of the present invention, from the viewpoint of improving the compatibility of the composition, when the nonvolatile component of the composition is 100% by mass, the content of the radical polymerizable compound as the component (2) is 1 to 65% by mass. Is preferable, 5 to 65% is more preferable, and 10 to 65% by mass is even more preferable.

  The composition of this invention can reduce the linear thermal expansion coefficient of the hardened | cured material formed from a composition by including a radically polymerizable compound.

  In the composition of the present invention, the radically polymerizable compound as the component (2) may be used alone or in combination of two or more.

  The composition of this invention can form the hardened | cured material which has sufficient peel strength with the combination of (1) component and (2) component. When the nonvolatile component is 100% by mass, the total content of the component (1) and the component (2) is preferably 1 to 70% by mass, more preferably 5 to 70%, and even more preferably 10 to 70% by mass.

(3) Inorganic filler The composition of this invention can reduce the dielectric loss tangent and linear thermal expansion coefficient of the hardened | cured material formed from a composition by containing an inorganic filler further. Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica is preferable. In addition, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and mesoporous silica is preferable, and fused silica is more preferable. Further, the silica is preferably spherical. These may be used alone or in combination of two or more. Examples of commercially available spherical fused silica include “SOC2”, “SOC1”, and “SOC4” manufactured by Admatechs Corporation.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less, from the viewpoint of forming fine wiring on the insulating layer. 7 μm or less is even more preferable. On the other hand, when the composition is a varnish, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, and more preferably 0.1 μm or more from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing. Is more preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used.

  The content of the inorganic filler is not particularly limited, but when the nonvolatile component of the resin composition is 100% by mass from the viewpoint of reducing the dielectric loss tangent and preventing the flexibility of the film form. 30 to 80% by mass, preferably 40 to 75% by mass, more preferably 45 to 70% by mass.

  The inorganic filler may be surface-treated with a silane coupling agent having one or more functional groups selected from acrylic, methacrylic, styryl, amino, epoxy, and vinyl. For example, inorganic fillers include aminosilane coupling agents, ureidosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, vinylsilane coupling agents, and styrylsilane cups. Surface treatment with a surface treatment agent such as a ring agent, an acrylate silane coupling agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, an organosilazane compound, a titanate coupling agent, etc. Improved ones are preferred. These may be used alone or in combination of two or more.

  Specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane Aminosilane coupling agents such as N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3-ureidopropyltriethoxysilane, etc. Ureidosilane coupling agent, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane Epoxysilane coupling agents such as glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyl Mercaptosilane-based coupling agents such as dimethoxysilane, 11-mercaptoundecyltrimethoxysilane, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane, t- Silane coupling agents such as butyltrimethoxysilane, vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane Coupling agents, styrylsilane coupling agents such as p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltri Acrylate silane coupling agents such as ethoxysilane and 3-methacryloxypropyldiethoxysilane, isocyanate silane coupling agents such as 3-isocyanatopropyltrimethoxysilane, bis (triethoxysilylpropyl) disulfide, bis (triethoxysilyl) Propyl) tetrasulfide silane coupling agents such as tetrasulfide, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexafe Nildisilazane, trisilazane, cyclotrisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldi Silazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1, Organosilazane compounds such as 3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane, tetra-n -Butyl titanate dimer, titania -I-propoxyoctylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ) Ethylene titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetra Octyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) Sphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tridodecylbenzenesulfonyl titanate And titanate coupling agents such as isopropyltris (dioctylpyrophosphate) titanate and isopropyltri (N-amidoethyl / aminoethyl) titanate. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM1403" manufactured by Shin-Etsu Chemical Co., Ltd. (P-styryltrimethoxysilane) and the like. Among these, when the inorganic filler is surface-treated with an aminosilane coupling agent, a vinylsilane coupling agent or a styrylsilane coupling agent, it is excellent in reducing the dielectric loss tangent, and is preferable.

(4) Other components In the resin composition of the present invention, in addition to the components described above, as other components, a curing agent, a thermosetting resin, a thermoplastic resin, a polymerization initiator, a curing accelerator, an organic filler, Organic solvents, thickeners, antifoaming agents, adhesion-imparting agents, colorants, additives, and the like can be appropriately blended. These other components can be used by mixing at least one, for example, two or more.
(I) Curing agent The curing agent used in the present invention is not particularly limited, and examples thereof include an active ester type curing agent, a cyanate ester type curing agent, a phenol type curing agent, and a benzoxazine type curing agent, and surface roughness. From the viewpoint of further reducing the resistance and the dielectric loss tangent, it is preferable to use an active ester type curing agent and / or a cyanate ester type curing agent, and it is more preferable to use an active ester type curing agent. These may be used alone or in combination of two or more.

  The active ester type curing agent is not particularly limited, but generally an ester group having high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, heterocyclic hydroxy compound ester or the like in one molecule. A compound having two or more in the above is preferably used. The active ester type curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.

  In particular, from the viewpoint of improving heat resistance, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadiene type diphenol, phenol novolac and the like. The active ester type curing agent includes an active ester type curing agent having a dicyclopentadiene type diphenol structure, an active ester type curing agent having a naphthalene structure, an active ester type curing agent which is an acetylated product of phenol novolac, and benzoyl of phenol novolac. An active ester type curing agent that is a chemical compound is preferable, and an active ester type curing agent that includes a dicyclopentadiene type diphenol structure and an active ester type curing agent that includes a naphthalene structure are more preferable in that it is excellent in improving peel strength. An active ester type curing agent containing a dicyclopentadiene type diphenol structure is more preferred.

As the active ester type curing agent, an active ester type curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used. Specifically, as an active ester type curing agent containing a dicyclopentadiene type diphenol structure, EXB9451, EXB9460, EXB9460S-65T, HPC-8000, HPC-8000-65T (manufactured by DIC Corporation, active group equivalent of about 223) , HPC8000L-65M (manufactured by DIC Corporation, MEK solution having a non-volatile content of 65% by mass with an active group equivalent of about 220), EXB9416-70BK (manufactured by DIC Corporation, active group equivalent) as an active ester type curing agent containing a naphthalene structure About 274), DC808 (manufactured by Mitsubishi Chemical Co., Ltd., active group equivalent: about 149) as an active ester type curing agent that is an acetylated product of phenol novolak, and YLH1026 (Mitsubishi Chemical) as an active ester type curing agent that is a benzoylated product of phenol novolak. Co., Ltd., active group equivalent of about 200 , YLH1030 (Mitsubishi Chemical Co., Ltd., active group equivalent about 201), YLH1048 (Mitsubishi Chemical Co., Ltd., active group equivalent about 245), and the like.
Particularly preferred active ester resins are those represented by the following general formula (32):
(Wherein m is 0 or 1, and n is an average value of 0.25 to 1.5, preferably 0.4 to 1.2), and a dicyclopentadiene type diphenol structure represented by And a resin compound each having an X-group and an XO-group (wherein X is an optionally substituted phenyl group or naphthyl group) at the terminal. The weight average molecular weight of the active ester resin is preferably 1500 to 4000, and more preferably 2000 to 3000.
A particularly preferred active ester resin has a dicyclopentadiene type diphenol structure represented by the following formula (33), and has an X-group and an XO-group (where X may have a substituent). HPC-8000, which is an active ester resin each having a good naphthyl group) and a weight average molecular weight of about 2700.

(In the formula, m is 0 or 1, and n is 0.4 to 1.2 as an average value)

Although there is no restriction | limiting in particular as a cyanate ester type hardening | curing agent, A novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening | curing agent, dicyclopentadiene type cyanate ester type hardening | curing agent, bisphenol type (bisphenol A type, bisphenol) Fate, bisphenol S type, etc.) cyanate ester type curing agents, and prepolymers in which these are partially triazines. Although the weight average molecular weight of a cyanate ester type hardening | curing agent is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. Specific examples of the cyanate ester type curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3, Bifunctional cyanate resins such as 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether , Phenol novolac, Examples thereof include polyfunctional cyanate resins derived from sol novolac, dicyclopentadiene structure-containing phenol resins, prepolymers in which these cyanate resins are partially triazines, and these may be used alone or in combination of two or more. Examples of commercially available cyanate ester resins include phenol novolac polyfunctional cyanate ester resins (manufactured by Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), and some or all of bisphenol A dicyanate are triazines and trimers. The prepolymer (Lonza Japan Co., Ltd. product, BA230, cyanate equivalent 232), dicyclopentadiene structure containing cyanate ester resin (Lonza Japan Co., Ltd. product, DT-4000, DT-7000) etc. are mentioned.
The structural formula of PT30, which is a preferred cyanate ester type curing agent, is as follows.

[In formula, n shows arbitrary numbers (preferably 0-20, more preferably 1-10) as an average value. ]

  The phenol type curing agent is not particularly limited, but a biphenyl type curing agent, a naphthalene type curing agent, a phenol novolac type curing agent, a naphthylene ether type curing agent, and a triazine skeleton-containing phenol type curing agent are preferable. Specifically, biphenyl type curing agents MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei Co., Ltd.), naphthalene type curing agents NHN, CBN, GPH (Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Nippon Steel Chemical Co., Ltd.), EXB9500 (manufactured by DIC Corporation), phenol novolac type curing agent TD2090 (manufactured by DIC Corporation), Examples include naphthylene ether type curing agents EXB-6000 (manufactured by DIC Corporation), triazine skeleton-containing phenol type curing agents LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Corporation), and the like.

  Although there is no restriction | limiting in particular as a benzoxazine type hardening | curing agent, As a specific example, Fa, Pd (made by Shikoku Kasei Co., Ltd.), HFB2006M (made by Showa Polymer Co., Ltd.), etc. are mentioned.

  In the composition of the present invention, from the viewpoint of reducing the dielectric loss tangent of a cured product formed from the composition, when the nonvolatile component in the composition is 100% by mass, the content of the curing agent is 1 to 30% by mass. Is preferable, 2-20 mass% is more preferable, and 3-10 mass% is still more preferable.

(Ii) Thermosetting resin As a thermosetting resin which can be used by this invention, an epoxy resin is mentioned, for example. Among them, examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, and naphthol type epoxy. Resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, butadiene Structured epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethyl Lumpur type epoxy resins, and halogenated epoxy resins. These may be used alone or in combination of two or more.

Among these, from the viewpoint of improving peel strength while reducing surface roughness, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene It is preferable to use one or more selected from ether type epoxy resins, glycidyl ester type epoxy resins and anthracene type epoxy resins. Specifically, for example, bisphenol A type epoxy resin (“Epicoat 828EL”, “YL980” manufactured by Mitsubishi Chemical Corporation),) fluorinated bisphenol A type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation), Bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Corporation), naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D”, “HP4032SS”, “EXA4032SS” manufactured by DIC Corporation), Naphthalene-type tetrafunctional epoxy resins (“HP4700” and “HP4710” manufactured by DIC Corporation), naphthol-type epoxy resins (“ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd.), and epoxy resins having a biphenyl structure (Nipponization) “NC3000H”, “NC3000L”, “NC310” manufactured by Yakuhin Co., Ltd. 0 ”,“ YX4000 ”,“ YX4000H ”,“ YX4000HK ”,“ YL6121 ”) manufactured by Mitsubishi Chemical Corporation, anthracene type epoxy resin (“ YX8800 ”manufactured by Mitsubishi Chemical Corporation), naphthylene ether type epoxy resin (DIC) “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3”), glycidyl ester type epoxy resin (“EX711”, “EX721” manufactured by Nagase ChemteX Corp.) Examples thereof include “R540” manufactured by Printec Co., Ltd. Biphenyl type epoxy resins are particularly preferable because they exhibit low roughness and high peel strength.
The structural formula of NC3000L which is a preferred epoxy resin is as follows.
Moreover, the structural formula of EXA4032SS which is another preferable epoxy resin is as follows.
In the composition of the present invention, from the viewpoint of improving the mechanical strength and water resistance of a cured product formed from the composition, when the nonvolatile component in the composition is 100% by mass, the content of the epoxy resin is 1 to 1. 30 mass% is preferable, 2-20 mass% is more preferable, and 3-10 mass% is still more preferable.

(Iii) Thermoplastic resin Examples of the thermoplastic resin that can be used in the present invention include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, cycloolefin polymer, polyacrylate resin, and polysulfone. Examples thereof include phenoxy resin and polyacrylate resin. These may be used alone or in combination of two or more. The polystyrene-reduced weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 1,000,000, more preferably in the range of 10,000 to 80,000, and still more preferably in the range of 20,000 to 500,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin can be measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve. When the thermoplastic resin is a phenoxy resin, the epoxy equivalent of the phenoxy resin is, for example, 10,000 to 20000 (g / equivalent).

(Iv) Polymerization initiator A polymerization initiator can be used in order to cure a radically polymerizable compound efficiently. The type of the polymerization initiator is not particularly limited, but cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydro Examples of the radical generator include peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, and 2,3-dimethyl-2,3-diphenylbutane. These may be used alone or in combination of two or more. Preferable polymerization initiators include dialkyl peroxide organic peroxides (“Perhexin 25B” manufactured by NOF Corporation, and cyclic peroxide organic peroxides (“TRIGONOX 311” manufactured by Kayaku Akzo Corporation)). be able to.
Although content in particular when mix | blending a polymerization initiator is not restrict | limited, When the non-volatile component in a composition is 100 mass%, 0.1-3 mass% is preferable, and 0.2-2 mass% is more. preferable. Within this range, an increase in dielectric loss tangent can be prevented.

(V) Curing accelerator Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and guanidine-based curing accelerators.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. (5, 4, 0) -undecene and the like.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6 -[2 -Methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s -Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H- Pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, - adduct of an imidazole compound and an imidazole compound and an epoxy resin of the phenyl imidazoline, and the like.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like.

  A hardening accelerator may be used individually by 1 type, or may be used in combination of 2 or more type. When the composition contains an epoxy resin, the content of the curing accelerator in the curable composition of the present invention is 0.00 when the total amount of nonvolatile components of the epoxy resin and the curing agent is 100% by mass. It is preferable to use within the range of 05 mass% to 3 mass%.

Examples of the organic filler that can be used in the present invention include silicon powder, nylon powder, fluorine powder, and rubber particles.
Examples of organic solvents that can be used in the present invention include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetates such as carbitol acetate, cellosolve, Examples thereof include carbitols such as butyl carbitol, aromatic hydrocarbons such as solvent naphtha, toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
Examples of the thickener that can be used in the present invention include olben, benton and the like.
Examples of antifoaming agents that can be used in the present invention include silicone antifoaming agents, fluorine antifoaming agents, and polymer antifoaming agents.
Examples of the adhesion-imparting agent that can be used in the present invention include imidazole-based, thiazole-based, triazole-based, and silane coupling agents.
Examples of the colorant that can be used in the present invention include phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, and carbon black.

  The composition containing each of the above components has a phosphorus content of 0.2 to 5% by mass, preferably 0.5 to 4% by mass, when the nonvolatile component of the composition excluding the inorganic filler is 100% by mass. %, More preferably 0.5 to 3% by mass. If the phosphorus content is 0.2% by mass or more, it is preferable because sufficient flame retardancy can be exhibited. If the phosphorus content is 5% by mass or less, the glass transition temperature may be increased. This is preferable because the linear thermal expansion coefficient can be lowered.

[Preparation of composition]
The composition of the present invention is appropriately mixed with the above components, and if necessary, by kneading means such as a triple roll, ball mill, bead mill, sand mill, or by stirring means such as a high-speed rotating mixer, super mixer, planetary mixer, etc. It can be prepared by kneading or mixing. Moreover, it can also prepare as a resin varnish by adding the organic solvent mentioned above.

In the composition of the present invention, a cured product capable of achieving a low linear thermal expansion coefficient, a low dielectric loss tangent, and a high glass transition temperature can be formed. Therefore, in the production of a multilayer printed wiring board, the insulating layer of the multilayer printed wiring board It can be suitably used as a composition for use. Furthermore, it can be suitably used as a composition (that is, a composition for interlayer insulation) used for build-up layers and for forming a conductor layer by plating.
Although it does not specifically limit as a form of the composition of this invention, It can apply to sheet-like laminated materials, such as an adhesive film and a prepreg, and a circuit board (a laminated board use, a multilayer printed wiring board use, etc.). Although the composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, it is generally preferred industrially to be used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. The softening point of the composition is preferably 40 to 150 ° C. from the viewpoint of the laminate property of the sheet-like laminated material.

[Multilayer printed wiring board]
The composition of the present invention can be used as a composition for an insulating layer of a multilayer printed wiring board. The multilayer printed wiring board which can be used by this invention is a multilayer printed wiring board containing the insulating layer obtained by thermosetting the composition and sheet-like laminated material of this invention.
Here, when the composition contains an epoxy resin, the thermosetting conditions may be appropriately selected according to the type and content of the epoxy resin. For example, the curing temperature is 90 to 220 ° C., preferably 160. The curing time is 10 minutes to 180 minutes, preferably 20 to 120 minutes. In addition, thermosetting may be performed in two stages.

[Sheet laminated material]
The sheet-like laminated material used in the present invention is a sheet-like material before curing, in which the composition is layered. The sheet-like laminated material is obtained by a method known to those skilled in the art, for example, by dissolving the composition in the organic solvent described above, and polymerizing the monomers in the composition when the composition does not contain a resin, Prepare and apply this resin varnish to the support using a die coater, etc., and further dry the organic solvent by heating or blowing hot air, etc., to form a resin composition layer (sheet-like laminated material) on the support Can be produced as a sheet-like laminated material with a support. Moreover, a sheet-like laminated material can also be made into a prepreg by impregnating and drying a resin varnish on a sheet-like reinforcing base material such as glass cloth by a hot melt method or a solvent method. In addition, a sheet-like laminated material with a support may be referred to as an adhesive film.

The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do.
Although the thickness of the obtained sheet-like laminated material (resin composition layer) is not particularly limited, for example, a range of 1 to 150 μm is preferable, a range of 2 to 100 μm is more preferable, a range of 3 to 70 μm is further preferable, and 5 A range of ˜50 μm is particularly preferred.
The sheet-like laminated material may have a plurality of resin composition layers, may have a support on one side of the resin composition layer, and have a protective film on the other side. Also good.

[Support]
Examples of the support that can be used in the present invention include plastic films and metal foils. Specifically, as a plastic film, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, acrylic, cyclic polyolefin, triacetyl cellulose, polyether sulfide , Polyether ketone, polyimide and the like. Among these, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and a polyethylene terephthalate film that is inexpensive and easily available is particularly preferable.
Examples of the metal foil include copper foil and aluminum foil.

From the viewpoint of versatility, a plastic film is preferable. When a plastic film is used, it is preferable to use a support whose surface in contact with the layer containing the composition is release-treated in order to improve the peelability. The release agent used for the release treatment is not particularly limited as long as the layer containing the composition can be peeled off from the support. For example, silicon release agent, alkyd resin release agent, polyolefin resin, urethane Examples thereof include resins and fluororesins. In addition, you may use the plastic film with a release layer marketed as a support body by which the mold release process was carried out, As a preferable thing, for example, it has a release layer which has an alkyd resin type release agent as a main component. Examples thereof include PET 501010, SK-1, AL-5, and AL-7 (manufactured by Lintec Corporation), which are PET films. The plastic film may be subjected to mat treatment or corona treatment, and a release layer may be formed on the treated surface. On the other hand, the metal foil can be removed by an etching solution, or the metal foil may be used as a conductor layer without being removed.
Although the thickness of a support body is not specifically limited, The range of 0.5-150 micrometers is preferable, The range of 20-50 micrometers is more preferable, The range of 25-45 micrometers is further more preferable.
The protective film that can be used in the present invention may be provided for the purpose of preventing adhesion of dust and the like to the layer containing the composition. As the protective film, a plastic film similar to the support can be used. The protective film may be subjected to a surface treatment such as a mud treatment or a corona treatment, or may be subjected to a mold release treatment similar to the above. 3-30 micrometers is preferable and, as for the thickness of a protective film, 5-20 micrometers is more preferable.

[Multilayer printed wiring board using sheet-like laminated material]
Next, an example of a method for producing a multilayer printed wiring board using the sheet-like laminated material produced as described above will be described.
First, a sheet-like laminated material is laminated (laminated) on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when the sheet-like laminate material has a protective film, after removing the protective film, the sheet-like laminate material and the circuit board are preheated as necessary, and the sheet-like laminate material is pressurized and Laminate to circuit board while heating. In the sheet-like laminated material of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure is reduced to an air pressure of 20 mmHg (26.7 hPa) or less for about 10 to 120 seconds, and then the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., pressure bonding pressure. (Lamination pressure) is preferably 0.1 to 1.5 MPa, more preferably 0.5 to 1.2 MPa, and pressure bonding time (laminating time) is preferably 5 to 180 seconds. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.
Then, after cooling to near room temperature (25 ° C.), if the support is peeled off, the support is peeled off, and the resin composition is thermally cured to form a cured product, thereby forming an insulating layer on the circuit board. Can do. The heat curing conditions may be appropriately selected according to the type and content of the resin component in the resin composition. For example, the curing temperature is 100 to 220 ° C., preferably 160 ° C. to 210 ° C., and the curing time. Is carried out by heating for 20 to 180 minutes, preferably 30 to 120 minutes. In addition, thermosetting may be performed in two stages. After the insulating layer is formed, if the support is not peeled before curing, it can be peeled off here if necessary.

  Moreover, a sheet-like laminated material can also be laminated | stacked on the single side | surface or both surfaces of a circuit board using a vacuum press machine. The lamination process for heating and pressurizing under reduced pressure can be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support side. The pressing conditions are 70 to 250 ° C., preferably 100 to 230 ° C., and the degree of vacuum is usually 0.01 MPa or less, preferably 0.001 MPa or less, and the pressing pressure is in the range of 0.5 to 4 MPa. The pressing time is preferably 30 to 150 minutes. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin. For example, the first stage press has a temperature in the range of 70 to 150 ° C. and the press pressure is in the range of 0.1 to 1.5 MPa. The second stage press has a temperature in the range of 150 to 200 ° C. and the pressure is 0.5 to 4 MPa. It is preferable to perform in the range. The time for each stage is preferably 20 to 120 minutes. Thus, an insulating layer can be formed on a circuit board by thermosetting the resin composition layer. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

Next, a via hole or a through hole may be formed by drilling the insulating layer formed on the circuit board. For example, the drilling can be performed by a known method such as drilling, laser, or plasma, or a combination of these methods if necessary, but drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common. Is the method. If the support is not peeled off before drilling, it will be peeled off here.
Next, the above-described roughening treatment is performed on the surface of the insulating layer, and a conductor layer can be formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is done. As a pattern formation method thereafter, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. By repeating the above-described series of steps a plurality of times, a multilayer in which build-up layers are stacked in multiple stages It becomes a printed wiring board. In the present invention, since it has low roughness and high peel, it can be suitably used as a build-up layer of a multilayer printed wiring board.

Here, the dielectric loss tangent (ASTM D2520) of the cured product formed from the composition of the present invention to be the insulating layer is 0.006 as measured by a cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. In the following, it is preferably 0.0055 or less, more preferably 0.005 or less. This reduces power consumption loss.
The linear thermal expansion coefficient (JIS K7197) of the cured product formed from the composition of the present invention is preferably 40 ppm / ° C. or less, as measured by an average linear thermal expansion coefficient of 25 to 150 ° C., and is 38 ppm / It is more preferable that the temperature is not higher than ° C, and it is more preferable that the temperature is not higher than 36 ppm / ° C. Although there is no restriction | limiting in particular in a lower limit, Generally it will be 4 ppm / degrees C or more. Thereby, distortion with an insulating layer and a conductor layer (wiring) can be prevented, and a highly reliable multilayer printed wiring board can be obtained.
The glass transition temperature (JIS K7121) of the cured product formed from the composition of the present invention is 170 ° C or higher, preferably 175, as measured by a tensile load method under a load of 200 mN and a temperature increase rate of 2 ° C / min. It is appropriate that the temperature is at least 180 ° C, more preferably at least 180 ° C, at least 190 ° C and at least 200 ° C. Thereby, a substrate with high heat resistance can be obtained.

[Semiconductor device]
A semiconductor device can be manufactured by using the multilayer printed wiring board manufactured as described above. A semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of a multilayer printed wiring board that can be used in the present invention. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. Moreover, as long as it conduct | electrically_connects, it may be a part of conductor layers, or other conductive parts, such as a connector. The “semiconductor chip” is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

<Measurement method / Evaluation method>
<Creation of cured product>
The resin varnishes obtained in the examples and comparative examples were dried on a PET film (“PET501010”, 50 μm thickness, manufactured by Lintec Corporation) and the thickness of the resin composition layer after drying was 40 μm. Then, it was uniformly coated with a die coater and dried at 80 to 100 ° C. (average 90 ° C.) for 5 minutes. Then, it heat-processed for 90 minutes at 200 degreeC in nitrogen atmosphere, and obtained the hardened | cured material film (thickness 40 micrometers) by peeling from a support body.

<Measurement of dielectric loss tangent>
The cured product film (thickness 40 μm) obtained above was cut into a length of 80 mm and a width of 2 mm to obtain an evaluation sample. The dielectric loss tangent of this evaluation sample was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method (JIS C2565) using an HP 8362B apparatus manufactured by Agilent Technologies. Two test pieces were measured, and the average value was calculated.

<Measurement of linear thermal expansion coefficient>
The cured product film (thickness 40 μm) obtained above is cut into a test piece having a width of about 5 mm and a length of about 15 mm, and is stretched using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Corporation). Thermomechanical analysis was performed by a weighting method (JIS K7197) . After the test piece was mounted on the apparatus, the measurement was performed twice continuously under the conditions of a load of 1 g, a heating rate of 5 ° C./min, and 30 ° C. to 250 ° C. The average linear thermal expansion coefficient (ppm / ° C.) from 25 ° C. to 150 ° C. in the second measurement was calculated.
The linear thermal expansion coefficient was set to ○ when it was 40 ppm / ° C or less, and x when it exceeded 40 ppm / ° C.

<Measurement of glass transition temperature>
The cured film was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile load method using a dynamic viscoelasticity measuring apparatus (EXSTAR6000 (SII Nanotechnology Co., Ltd.)). After mounting the test piece on the device, the measurement was performed twice continuously under the measurement conditions of a load of 200 mN and a heating rate of 2 ° C./min.Glass transition from the point that the slope of the dimensional change signal in the second measurement changes. The temperature (° C.) was calculated.

<Measurement of peel strength (peel strength) of plated conductor layer>
(Creation of adhesive film)
Resin composition after drying resin varnishes obtained in Examples and Comparative Examples on copper foil (JXUT-III, thickness 2um, with carrier copper foil, Ra = 250nm) manufactured by JX Nippon Mining & Metals Co., Ltd. It applied uniformly with the die coater so that the thickness of a physical layer might be 40 micrometers, and it dried for 5 minutes at 80-100 degreeC (average 90 degreeC).

(Inner layer circuit board ground treatment)
Glass cloth base epoxy resin double-sided copper-clad laminate with inner layer circuit (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works Ltd. R5715ES) 1 μm on both sides of Mec CZ8100 The copper surface was roughened by etching.

(Lamination of adhesive film)
The said adhesive film was laminated on both surfaces of the inner-layer circuit board using the batch type vacuum pressurization laminator MVLP-500 (brand name by Meiki Co., Ltd.). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.

(Curing resin composition)
The laminated adhesive film was cured under a curing condition of 200 ° C. for 60 minutes to form an insulating layer, and then the carrier copper foil was peeled from the adhesive film.

(Copper plating treatment)
In order to form a circuit on the surface of the insulating layer, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 25 μm.

(Measurement of peel strength (peel strength) of plated conductor layer)
Make a notch of width 10mm and length 100mm in the conductor layer of the circuit board, peel off one end and grasp it with a gripping tool (TSE Co., Ltd., Autocom type testing machine AC-50CSL) at room temperature The load (kgf / cm) when peeling 35 mm in the vertical direction at a speed of 50 mm / min was measured.
The case where the adhesion strength was less than 0.30 kgf / cm was evaluated as x, the case where the adhesion strength was 0.30 kgf / cm or more and less than 0.40 kgf / cm, and the case where it was 0.40 kgf / cm or more.

(Peeling strength after environmental resistance test (HAST) (Measurement of peel strength)
After performing an accelerated environment test for 100 hours under the conditions of 130 ° C. and 85% RH on a circuit board that has been subjected to copper plating treatment using a highly accelerated life test apparatus PM422 (manufactured by Enomoto Kasei Co., Ltd.) Make a notch of width 10mm and length 100mm in the conductor layer of the circuit board, peel off one end and grasp it with a gripping tool (TSE Co., Ltd., Autocom type testing machine AC-50CSL) at room temperature The load (kgf / cm) when peeling 35 mm in the vertical direction at a speed of 50 mm / min was measured.
The case where the adhesion strength was less than 0.30 kgf / cm was evaluated as x, the case where the adhesion strength was 0.30 kgf / cm or more and less than 0.40 kgf / cm, and the case where it was 0.40 kgf / cm or more.

In the examples, “parts” representing amounts indicate “parts by mass”.
Example 1
125 parts of toluene solution of styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.” non-volatile content 64.4 wt%), polymerization initiator (“Trigonox” manufactured by Kayaku Akzo Co., Ltd.) 311 "), 1 part phosphonate compound (" K-1 "dimethyl vinyl phosphonate, molecular weight 130.09 g / mol, manufactured by Katayama Chemical Co., Ltd.), 5 parts, spherical silica (average particle size 0.5 µm, Admatechs Co., Ltd.) 130 parts of “SOC4” (with aminophenylsilane treatment) manufactured by MEK were mixed with 15 parts of MEK and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

(Example 2)
A resin varnish was prepared in the same manner as in Example 1 except that the toluene solution of the styrene-modified polyphenylene ether resin was 117 parts and the phosphonate compound was 10 parts.

(Example 3)
A resin varnish was prepared in the same manner as in Example 1 except that 86 parts of a toluene solution of a styrene-modified polyphenylene ether resin and 86 parts of a phosphonate compound were used.

Example 4
Toluene solution of styrene-modified polyphenylene ether resin ("OPE-2St (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.", nonvolatile content 64.4 wt%) 102 parts, polymerization initiator ("Trigonox" manufactured by Kayaku Akzo Co., Ltd.) 311 "), 1 part, phosphonate compound (" V-2 "diethyl vinylphosphonate, molecular weight 164.14 g / mol, manufactured by Katayama Chemical Co., Ltd.) 20 parts, spherical silica (average particle size 0.5 μm, Admatechs Co., Ltd.) 130 parts of “SOC4” (with aminophenylsilane treatment) manufactured by MEK were mixed with 15 parts of MEK and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

(Example 5)
Toluene solution of styrene-modified polyphenylene ether resin ("OPE-2St (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.", nonvolatile content 64.4 wt%) 102 parts, polymerization initiator ("Trigonox" manufactured by Kayaku Akzo Co., Ltd.) 311 ”), 1 part, phosphonate compound (“ V-3 ”diphenylvinylphosphonate, molecular weight 260.22 g / mol) manufactured by Katayama Chemical Co., Ltd., spherical silica (average particle size 0.5 μm, Admatechs Co., Ltd.) 130 parts of “SOC4” (with aminophenylsilane treatment) manufactured by MEK were mixed with 15 parts of MEK and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

(Example 6)
Toluene solution of styrene-modified polyphenylene ether resin ("OPE-2St (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.", nonvolatile content 64.4 wt%) 102 parts, bixylenol diallyl ether resin (manufactured by Mitsubishi Chemical Corporation) YL7776 (number average molecular weight 331) ") 5 parts, polymerization initiator (" Trigonox 311 "manufactured by Kayaku Akzo Co., Ltd.), phosphonate compound (" V-1 "dimethyl vinyl phosphonate manufactured by Katayama Chemical Co., Ltd.), 15 parts of molecular weight 130.09 g / mol), spherical silica (average particle diameter 0.5 μm, 130 parts of “SOC4” (with aminophenylsilane treatment) manufactured by Admatechs Co., Ltd. are mixed with 15 parts of MEK, and uniformly mixed with a high-speed rotary mixer To obtain a resin varnish.

(Example 7)
Toluene solution of styrene-modified polyphenylene ether resin (OPE-2St (number average molecular weight 1200), nonvolatile content 64.4 wt%, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 102 parts, dimethylol-tricyclodecane diacrylate (Kyoeisha Chemical Co., Ltd.) Manufactured by “DCP-A”), 5 parts by polymerization initiator (“Trigonox 311” manufactured by Kayaku Akzo Co., Ltd.), phosphonate compound (“V-1” dimethylvinylphosphonate manufactured by Katayama Chemical Co., Ltd., molecular weight) 130.09 g / mol), 15 parts of spherical silica (average particle size of 0.5 μm, 130 parts of “SOC4” (with aminophenylsilane treatment) manufactured by Admatechs Co., Ltd. are mixed with 15 parts of MEK, and uniformly mixed with a high-speed rotary mixer. A resin varnish was prepared by dispersing.

(Example 8)
102 parts of toluene solution of styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200)” nonvolatile content 64.4 wt% manufactured by Mitsubishi Gas Chemical Co., Ltd.), dimethylol-tricyclodecane dimethacrylate (Kyoeisha Chemical Co., Ltd.) , DCP-M ") 5 parts, polymerization initiator (" Trigonox 311 "manufactured by Kayaku Akzo Co., Ltd.), phosphonate compound (" V-1 "dimethyl vinyl phosphonate manufactured by Katayama Chemical Co., Ltd., molecular weight 130) .09 g / mol), 15 parts of spherical silica (average particle size 0.5 μm, 130 parts of “SOC4” (with aminophenylsilane treatment) manufactured by Admatechs Co., Ltd. are mixed with 15 parts of MEK and uniformly dispersed with a high-speed rotary mixer. Thus, a resin varnish was produced.

Example 9
102 parts of toluene solution of styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.” non-volatile content 64.4 wt%), acrylic oligomer (manufactured by Daicel Chemical Industries, Ltd. Mer PZ230AA "Nonvolatile content 53 wt%" 6 parts, biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent of about 288), polymerization initiator (Kayaku Akzo Co., Ltd. "Trigonox" 311 "), 1 part, phosphonate compound (" K-1 "dimethyl vinyl phosphonate, molecular weight 130.09 g / mol, manufactured by Katayama Chemical Co., Ltd.), 15 parts, spherical silica (average particle size 0.5 μm, Admatechs Co., Ltd.) “SOC4” (with aminophenylsilane treatment) 130 parts made by mixing with 15 parts MEK, Uniformly dispersed in the server, to prepare a resin varnish.

(Example 10)
60 parts of a toluene solution of a styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.”, nonvolatile content 64.4 wt%), carboxylic acid group-containing acrylic oligomer (Daicel Chemical Industries, Ltd.) 20 parts of “Cyclomer P Z251” nonvolatile content 45 wt%), 20 parts of carboxylic acid group-containing acrylic oligomer (manufactured by Daicel Chemical Industries, Ltd., “Cyclomer P Z254F” nonvolatile content 55 wt%), fluorinated bisphenol A type 12 parts of epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 243), 1 part of polymerization initiator (“Trigonox 311” manufactured by Kayaku Akzo Co., Ltd.), phosphonate compound (manufactured by Katayama Chemical Co., Ltd.) V-1 "dimethyl vinyl phosphonate, molecular weight 130.09 g / mol) 15 parts, spherical Ca (average particle size 0.5 [mu] m, 130 parts Co. Admatechs Ltd., "SOC4" (with aminophenyl silanized) were mixed in MEK15 parts was uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

(Example 11)
Toluene solution of styrene-modified polyphenylene ether resin ("OPE-2St (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.", nonvolatile content 64.4 wt%) 102 parts, polymerization initiator ("Trigonox" manufactured by Kayaku Akzo Co., Ltd.) 311 "), 1 part, phosphonate compound (Katayama Chemical Co., Ltd." V-1 "dimethyl vinyl phosphonate, molecular weight 130.09 g / mol), 20 parts, spherical silica (average particle size 0.5 μm, Admatechs Co., Ltd.) “SOC4” (with aminophenylsilane treatment) 172 parts, biphenyl aralkyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 288), active ester curing agent (manufactured by DIC Corporation “ HPC8000L-65M ", MEK solution having a non-volatile content of 65% by mass with an active group equivalent of about 220), 20 parts, curing accelerator 3 parts (4-dimethylaminopyridine (DMAP), MEK solution containing 5% by mass of non-volatile components) were mixed with 15 parts of MEK and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

Example 12
Toluene solution of styrene-modified polyphenylene ether resin ("OPE-2St (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.", nonvolatile content 64.4 wt%) 102 parts, polymerization initiator ("Trigonox" manufactured by Kayaku Akzo Co., Ltd.) 311 "), 1 part, phosphonate compound (Katayama Chemical Co., Ltd." V-1 "dimethyl vinyl phosphonate, molecular weight 130.09 g / mol), 20 parts, spherical silica (average particle size 0.5 μm, Admatechs Co., Ltd.) "SOC4" (with aminophenylsilane treatment) 175 parts, naphthalene type epoxy resin (DIC Corporation "EXA4032SS") 15 parts, cyanate ester type curing agent (Lonza Corporation "PT30") 15 parts, curing 2 parts of accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 5% by mass of non-volatile components) in MEK1 Mixed section, and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

(Comparative Example 1)
133 parts of a toluene solution of styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.”, nonvolatile content 64.4 wt%), 133 parts of polymerization initiator (“Trigonox manufactured by Kayaku Akzo Co., Ltd.) 311 ”), 1 part of spherical silica (average particle size 0.5 μm, 130 parts of“ SOC4 ”(with aminophenylsilane treatment) manufactured by Admatechs Co., Ltd. are mixed with 15 parts of MEK, and uniformly dispersed with a high-speed rotating mixer. A resin varnish was prepared.

(Comparative Example 2)
117 parts of a toluene solution of a styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.”, nonvolatile content 64.4 wt%), 117 parts, cyclic phosphorus compound (“PSS-” manufactured by Otsuka Chemical Co., Ltd.) 100 ”) 10 parts, polymerization initiator (“ Trigonox 311 ”manufactured by Kayaku Akzo Co., Ltd.), spherical silica (average particle size 0.5 μm,“ SOC4 ”manufactured by Admatechs Co., Ltd. (with aminophenylsilane treatment) ) 130 parts, uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish, the structural formula of SPS-100 is as follows.

(Comparative Example 3)
117 parts of a toluene solution of styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.”, nonvolatile content 64.4 wt%), 117 parts, phosphonate compound (V-5 manufactured by Katayama Chemical Co., Ltd.) ”9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, molecular weight 242.21 g / mol)), 20 parts of MEK solution with a non-volatile content of 50%, polymerization initiator (Kayaku Akzo Co., Ltd.) "Trigonox 311" 1 part, spherical silica (average particle size 0.5μm, 130 parts "SOC4" (with aminophenylsilane treatment) manufactured by Admatechs Co., Ltd. are mixed with 15 parts MEK, and uniformly mixed with a high-speed rotary mixer A resin varnish was prepared by dispersing, and “V-5” 9, 10-dihydro-9-oxa-10-phosphaphenanthrene. The structural formula of 10-oxide is as follows.

Claims (21)

A composition for an insulating layer of a multilayer printed wiring board,
(1) A phosphonate compound having one or more ethylenically unsaturated bonds in the molecule,
(2) a radically polymerizable compound having two or more ethylenically unsaturated bonds and one or more aromatic hydrocarbons or alicyclic hydrocarbons in the molecule;
and,
(3) A composition comprising an inorganic filler, wherein (1) component and (2) component are different compounds. (1) The composition according to claim 1, wherein the component is represented by the following formula (I).
[In the formula (I), R ₄₁ and R ₄₂ are each independently an alkyl group or an aryl group, and X is represented by the following formula (X-1) or the following formula (X-2). ]

[In the formulas (X-1) and (X-2), R _{35 to} R ₄₀ are each independently hydrogen, an alkyl group, or an aryl group. ] The composition according to claim 2, wherein R ₄₁ and R _{42 in the} formula (I) are each independently an alkyl group having 1 to 3 carbon atoms or a phenyl group. 4. The composition according to claim 2, wherein X is represented by formula (X-1) in formula (I), and R _{35 to} R ₃₇ are hydrogen in formula (X-1).   (3) The composition according to any one of claims 1 to 4, wherein the component (1) is 3 to 45 mass% when the nonvolatile component of the composition excluding the component is 100 mass%.   The composition of any one of Claims 1-5 whose sum total of (1) component and (2) component is 1-70 mass% when the non-volatile component of a composition is 100 mass%.   (3) The composition of any one of Claims 1-6 whose inorganic filler of a component is a silica.   The inorganic filler as component (3) is surface-treated with a silane coupling agent having one or more functional groups selected from acrylic, methacrylic, styryl, amino, epoxy, and vinyl. The composition according to claim 1.   The composition according to any one of claims 1 to 7, wherein the inorganic filler as the component (3) is surface-treated with an aminosilane coupling agent, a vinylsilane coupling agent, or a styrylsilane coupling agent. .   The composition of any one of Claims 1-9 whose (3) component is 30-80 mass% when the non-volatile component of a composition is 100 mass%. (2) The composition of any one of Claims 1-10 whose component is a radically polymerizable compound represented by following formula (II).
[In Formula (II), R _{1 to} R ₆ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and A is a divalent group containing an aromatic hydrocarbon or an alicyclic hydrocarbon. ] The composition according to claim 11, wherein A is represented by the following formula (A-1), (A-2), (A-3) or (A-4) in formula (II).

[In the formulas (A-1) and (A-2), B is a divalent group containing an aromatic hydrocarbon or an alicyclic hydrocarbon. In the formula (A-1), E ₁ and E ₂ are Each independently represents an alkylene group or an alkyleneoxy group. ]
[In Formula (A-3), D is the following Formula (D-1). ]
[In Formula (D-1), R _{7 to} R ₁₄ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, or a phenyl group, and a and b are integers of 0 to 100 in which at least one is not 0. , B is a divalent group containing an aromatic hydrocarbon or alicyclic hydrocarbon. ]
[In Formula (A-4), B is a divalent group containing an aromatic hydrocarbon or an alicyclic hydrocarbon, and E ₄ and E ₅ are each independently an alkylene group or an alkyleneoxy group. ] In formulas (A-1), (A-2), (D-1) and (A-4), B is represented by any one of the following formulas (B-1) to (B-6). Item 13. The composition according to Item 12.





[In the formulas (B-1) to (B-5), R _{15 to} R ₃₄ and R _{43 to} R ₅₀ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, or a phenyl group. ), E is an alkylene group or an alkyleneoxy group. ] (2) The component is a radically polymerizable compound in which structural units represented by formulas (III) to (V) are randomly polymerized, including at least two structural units represented by formula (V) Item 11. The composition according to any one of Items 1 to 10.


[In the formulas (III) to (V), X is hydrogen or an alkyl group having 6 or less carbon atoms. In the formula (IV), R ₅₁ is an alkyl group or a hydroxyalkyl group. , R ₅₂ is a group containing an ethylenically unsaturated bond and an aromatic hydrocarbon or alicyclic hydrocarbon. ] The composition according to claim 14, wherein formula (V) is represented by formula (VI).
A sheet-like laminated material comprising the composition according to any one of claims 1 to 15 . A cured product obtained by thermally curing the composition according to any one of claims 1 to 15 or the sheet-shaped laminated material according to claim 16 , wherein a dielectric loss tangent of the cured product is 0.005 or less. A cured product. A cured product obtained by thermosetting the composition according to any one of claims 1 to 15 or the sheet-shaped laminated material according to claim 16 , wherein the linear thermal expansion coefficient of the cured product is 40 ppm / Cured product having a temperature of ℃ or less. A cured product obtained by thermosetting the composition according to any one of claims 1 to 15 or the sheet-like laminated material according to claim 16 , wherein the glass transition temperature of the cured product is 170 ° C or higher. A cured product. A multilayer printed wiring board comprising an insulating layer obtained by thermosetting the composition according to any one of claims 1 to 15 or the sheet-like laminated material according to claim 16 . 21. A semiconductor device comprising the multilayer printed wiring board according to claim 20 .