JP5245253B2 - Resin composition, insulating resin sheet with film or metal foil, multilayer printed wiring board, and semiconductor device - Google Patents

Description

  The present invention relates to a resin composition, an insulating resin sheet with a film or a metal foil, a multilayer printed wiring board, and a semiconductor device.

  A cured product of an insulating resin composition typified by an epoxy resin is excellent in mechanical characteristics, electrical characteristics, chemical characteristics, and the like, and is used in a wide range of applications such as electrical and electronic equipment parts. These thermosetting resin compositions are often imparted with flame retardancy to ensure safety against fire.

One method for making an insulating resin composition flame-retardant is a method using a halogen-containing compound such as a brominated epoxy resin (see, for example, Patent Document 1).
However, although halogen-containing compounds can impart a high degree of flame retardancy, for example, brominated aromatic compounds not only generate corrosive bromine and hydrogen bromide by thermal decomposition, but also decompose in the presence of oxygen. In some cases, highly toxic polybromodibenzofuran or polybromodibenzooxine may be produced. And disposal of obsolete waste containing bromine is extremely difficult. For these reasons, flame retardants that replace halogen-containing compounds have been studied.

  Examples of the flame retardant technology that does not use a halogen-containing compound include a method using a phosphorus-containing compound such as a phosphine oxide compound (for example, see Patent Documents 2 to 4), and a method using aluminum hydroxide (for example, Patent Document). 5).

In recent years, with the demand for higher functionality of electronic devices, electronic components have been densely integrated and mounted with high density, and multilayer printed wiring boards and the like for high density mounting used for these have conventionally been used. In addition, applications for miniaturization and high density are also expanding. In order to enable use in these applications, it is important to reduce the thermal expansion and connection reliability of the multilayer printed wiring board (see, for example, Patent Document 6).

JP 2000-212249 A JP 2001-254001 A JP 2004-0697968 A JP-A-11-124489 Japanese Patent Laid-Open No. 2005-20692 JP 2005-7783 A

  The present invention is excellent in laser via processability when used in an insulating resin composition of a multilayer printed wiring board used in electronic equipment, and in the thermal shock test such as a thermal cycle test, the via connection portion and the conductor circuit layer are peeled off. Alternatively, a multilayer printed wiring board that has high insulation reliability even in a high temperature and high humidity environment without cracks in the insulating resin layer, has flame retardancy, and can be formed with high density and high multilayers. Provided are an insulating resin composition that can be produced, an insulating resin sheet with a film or a metal foil, a multilayer printed wiring board, and a semiconductor device using the same.

Such an object is achieved by the present invention described in the following (1) to (1 5 ).
(1) An insulating resin composition used for forming an insulating resin layer of a multilayer printed wiring board, wherein a linear expansion coefficient of a cured product of the insulating resin composition is 6 ppm / ° C. or more and 50 ppm / ° C. or less at 25 ° C. And
(A) metal hydroxide,
(B) an epoxy resin containing a novolac-type epoxy resin and substantially not halogenated,
(C) contains an ultraviolet absorber,
And (a) the metal ionic impurity contained in the metal hydroxide is 500 ppm or less, (a) the metal hydroxide is aluminum hydroxide, and the metal ionic impurity is sodium ion,
The content of the metal hydroxide (a) is 1% by weight or more and 50% by weight or less of the insulating resin composition,
Wherein (c) UV absorbers Ri der content the insulating resin composition 2.00 wt% 0.01 wt% or more of the total weight a compound having a coumarin structure,
The insulating resin layer comprising the insulating resin composition is used for an insulating resin sheet with a film or metal foil formed on a film or metal foil,
The multilayer printed wiring board, Ru said der those insulating resin layer formed by heat and pressure molding are superposed on the inner layer circuit pattern is formed faces of the inner layer circuit board of the film with or metal foil with an insulating resin sheet An insulating resin composition characterized by that.
(2) The said insulating resin composition is an insulating resin composition as described in (1) containing resin which has film forming property whose weight average molecular weight is 1.0 * 10 < ³ > -1.0 * 10 < ⁵ >.
(3) The insulating resin composition according to (1) or (2), wherein the insulating resin composition contains an inorganic filler other than (d) a metal hydroxide.
(4) The ultraviolet absorber (c) has at least one absorption peak in a wavelength region of 200 nm or more and 300 nm or less in a photoelectric spectrophotometer measurement, any one of (1) to (3) The insulating resin composition as described in 2.
(5) The insulating resin composition according to any one of (1) to (4), wherein a weight reduction rate at 300 ° C. of the insulating resin composition is 15% or less.
(6) The insulating resin composition according to any one of (1) to (5), wherein the (a) metal hydroxide has an average particle size of 0.1 μm to 5 μm.
(7) The insulating resin composition according to any one of (1) to (6), wherein the weight reduction rate at 300 ° C. of the (a) metal hydroxide is 20% by weight or more and 40% by weight or less.
( 8) The insulating resin composition according to any one of (3) to ( 7 ), wherein the inorganic filler other than (d) the metal hydroxide is a metal oxide.
( 9 ) The insulating resin composition according to ( 8 ), wherein the metal oxide is fused silica.
(1 0 ) An insulating resin sheet with a film or a metal foil formed by forming an insulating resin layer made of the insulating resin composition according to any one of (1 0 ) (1) to ( 9 ) on a film or a metal foil.
(1 1 ) The insulating resin sheet with a film or with a metal foil according to (1 0 ), wherein the insulating resin layer contains a fiber base material.
(1 2 ) The insulating resin sheet with film or metal foil according to (11) , wherein the fiber base material is glass fiber.
(1 3 ) The insulating resin sheet with a film or with a metal foil according to (11) , wherein the fiber base material is an organic fiber.
(1 4 ) The insulating resin layer of the insulating resin sheet with film or metal foil according to any one of (1 4 ) (1 0 ) to (1 3 ) is superimposed on the surface of the inner circuit board on which the inner circuit pattern is formed. A multilayer printed wiring board formed by heating and pressing.
(1 5 ) A semiconductor device comprising a semiconductor element mounted on the multilayer printed wiring board according to (1 4 ).

  The insulating resin composition, the insulating resin sheet with a film or metal foil of the present invention can achieve flame retardancy without using a halogen-containing compound or a phosphorus-containing compound, and is superior to conventional ones. In addition, it is possible to obtain a multilayer printed wiring board and a semiconductor device that can exhibit laser via processability, thermal shock resistance, and insulation reliability.

  The insulating resin composition, the insulating resin sheet with film or metal foil, the multilayer printed wiring board, and the semiconductor device of the present invention will be described in detail below.

  The linear expansion coefficient of the cured product of the insulating resin composition of the present invention (hereinafter sometimes simply referred to as “cured product”) is 6 ppm / ° C. or more and 50 ppm / ° C. or less at 25 ° C. Thereby, when the cured product is used as a multilayer printed wiring board or a semiconductor device, it is possible to suppress the peeling of the conductor circuit layer or the occurrence of cracks in the insulating resin layer in a thermal shock test such as a thermal cycle test. Moreover, the curvature of the board | substrate at the time of press molding or solder reflow can also be suppressed. The linear expansion coefficient is not particularly limited, but is preferably 8 ppm / ° C. or more and 40 ppm / ° C. or less, more preferably 10 ppm / ° C. or more and 30 ppm / ° C. or less, and further preferably 12 ppm / ° C. or more and 20 ppm / ° C. or less. Thereby, the said effect | action can be expressed effectively.

  If the linear expansion coefficient is less than the lower limit value, depending on the thickness of the substrate, it may not be possible to suppress warpage of the substrate during press molding or solder reflow due to mismatch of linear expansion with the conductor circuit. Also, if the above upper limit is exceeded, there is a risk of warping of the substrate during press molding or solder reflow due to mismatch of linear expansion with the conductor circuit, and via connection in thermal shock tests such as thermal cycle tests There is a possibility that peeling of a portion or a conductor circuit layer or generation of a crack in an insulating resin layer cannot be suppressed.

  The linear expansion coefficient of the cured product depends on the type of resin, the resin content, the type of filler, and the amount of filler. In the present invention, the linear expansion coefficient can be arbitrarily set by adjusting the selection of the resin, the content of the selected resin, and (a) the content of the metal hydroxide or the selected inorganic filler.

Although the hardened | cured material of this invention is not specifically limited, The weight decreasing rate in 300 degreeC is 15% or less. Thereby, when a hardened | cured material is used for a multilayer printed wiring board or a semiconductor device, the solder heat resistance after moisture absorption can be improved. The weight reduction rate is preferably 10% or less. Thereby, the said effect | action can be expressed effectively.
The weight reduction rate was determined by raising the temperature of the sample from 30 ° C. to 500 ° C. at 10 ° C./min by TG-DTA (differential thermogravimetric simultaneous measurement), and tracking the weight change of the sample ((30 It was set as the value calculated | required by the sample weight of (degreeC)-(sample weight of 300 degreeC) / (sample weight of 30 degreeC) x100.

The (a) metal hydroxide used in the insulating resin composition of the present invention has a concentration of metal ionic impurities contained in the (a) metal hydroxide of 500 ppm or less. As a result, when the cured product is used in a multilayer printed wiring board or a semiconductor device, high insulation reliability can be maintained even if it is processed under high temperature and high humidity such as HAST test and PCT test. Further, although not particularly limited, the concentration of the metal ionic impurity is preferably 400 ppm or less, more preferably 300 ppm or less, and further preferably 200 ppm or less. Thereby, the said effect | action can be expressed effectively.
If the upper limit is exceeded, insulation reliability may be impaired.
The concentration of the metal ionic impurities is determined by: (a) treating the metal hydroxide in pure water at 80 ° C. for 24 hours, extracting the metal ions in pure water, and then ICP-MS (inductively coupled plasma ion source mass spectrometer) ) And measured.

  The metal ionic impurities contained in the metal hydroxide (a) used in the insulating resin composition of the present invention include thium ions, sodium ions, potassium ions, rubidium ions, cesium ions, francium ions, beryllium ions, calcium ions, strontium ions. And at least one selected from the group consisting of barium ions, zinc ions, tin ions, and lead ions. Among these, sodium ions and potassium ions are particularly preferable. If these concentrations are within the above range, when the cured product is used for a multilayer printed wiring board or a semiconductor device, it retains high insulation reliability even when processed under high temperature and high humidity such as HAST test and PCT test. Can do.

  Although the average particle diameter of (a) metal hydroxide used for the insulating resin composition of the present invention is not particularly limited, it is preferably 0.1 μm or more and 10 μm or less. This makes it easy to adjust the viscosity of the varnish made of the insulating resin composition and the minimum melt viscosity when the insulating resin composition is B-staged, and has good moldability during heating and pressurization and good embedding of the inner layer circuit board. It becomes. Furthermore, the resin surface roughness when the surface of the B-staged or cured insulating resin composition is roughened by chemical and / or physical treatment can be adjusted. The average particle diameter can be measured by, for example, a particle size distribution meter (manufactured by HORIBA, LA-500).

The average particle diameter of the (a) metal hydroxide is preferably 0.1 μm or more and 8 μm or less, more preferably 0.1 μm or more and 5 μm or less, and particularly preferably 0.1 μm or more and 3 μm or less. Thereby, the said effect | action can be expressed effectively.
(A) If the average particle size of the metal hydroxide is less than the lower limit, the viscosity of the varnish made of the insulating resin composition becomes high, so that it becomes difficult to apply the varnish to the film, and the insulating resin with film or metal foil Production of the sheet becomes difficult. Further, since the minimum melt viscosity when the insulating resin composition is B-staged is increased, the moldability during heating and pressurization and the embedding property of the inner layer circuit board are lowered. When the upper limit is exceeded, the resin surface roughness increases when the surface of the insulating resin layer made of the B-staged or cured insulating resin composition is roughened by chemical and / or physical treatment. Or the insulation reliability is reduced.

  The (a) metal hydroxide is not particularly limited, but the (a) metal hydroxide having a monodisperse average particle diameter can be used, or the (a) metal hydroxide having a polydisperse average particle diameter can be used. Can be used. Further, monodispersed and / or polydispersed hydroxides having an average particle diameter of one type or two or more types can be used in combination.

  The surface roughness when the surface of the insulating resin layer made of the insulating resin composition is roughened is not particularly limited, but the arithmetic average roughness (Ra) is preferably 1 μm or less. Thereby, when it is used for a high frequency circuit board, the influence on the signal propagation speed of the conductor circuit can be reduced.

The weight reduction rate of the (a) metal hydroxide at 300 ° C. is preferably 20% by weight or more and 40% by weight or less. Thereby, a flame retardance can be provided, without impairing heat resistance. If the weight reduction rate is less than the lower limit, it is difficult to sufficiently exhibit flame retardancy, and if it exceeds the upper limit, heat resistance may be deteriorated.
The weight reduction rate was determined by raising the temperature of the sample from 30 ° C. to 500 ° C. at 10 ° C./min by TG-DTA (differential thermogravimetric simultaneous measurement), and tracking the weight change of the sample ((30 (Sample weight at 0 ° C.) − (Sample weight at 300 ° C.)) / (Sample weight at 30 ° C.) × 100).

  Although content of said (a) metal hydroxide is not specifically limited, It is preferable that they are 1 weight% or more and 50 weight% or less with respect to the whole insulating resin composition. Thereby, a flame retardance can be provided, without impairing heat resistance. The content is further preferably 2% by weight to 45% by weight, more preferably 5% by weight to 40% by weight, and particularly preferably 10% by weight to 30% by weight. Thereby, the said effect | action can be expressed effectively. If the content is less than the lower limit, the flame-retardant effect may not be sufficiently obtained, and if the content exceeds the upper limit, the heat resistance may be reduced.

  The (a) metal hydroxide is preferably at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide, gallium hydroxide, and zirconyl hydroxide. Thereby, a flame retardance can be provided. Among these, aluminum hydroxide is particularly preferable. Thereby, a flame retardance can be provided, without impairing heat resistance.

The (b) epoxy resin used in the insulating resin composition of the present invention includes a novolac type epoxy resin. Thereby, the crosslinking density of the hardened | cured material of this insulating resin composition can be increased, and high flame retardance and heat resistance can be provided.
Examples of the novolak type epoxy resin include a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, and a bisphenol A novolak type epoxy resin. Among these, a cresol novolac type epoxy resin is preferable. Thereby, in addition to the said effect, the water absorption rate of hardened | cured material can be reduced and the moisture resistance in a high-humidity environment can be improved.

Although content of the said novolak-type epoxy resin is not specifically limited, It is preferable that it is 60 to 90 weight% of the whole epoxy resin. More preferably, it is 65 to 75% by weight. Thereby, the said effect | action can be expressed effectively.
If the content of the novolac epoxy resin is less than the lower limit, the effect of improving the heat resistance may not be sufficient. Moreover, when the upper limit is exceeded, the cured product when B-staged is hardened, the handling property of the B-staged film or metal foil-attached insulating resin sheet is reduced, and the resin powder falls when cut, There is a fear of resin cracking when wound on the branch pipe.

The insulating resin composition of the present invention can use an epoxy resin in addition to the (b) novolac type epoxy resin. Examples of the epoxy resin used in combination include bisphenol A type epoxy resin and bisphenol F type epoxy resin.
Here, when liquid bisphenol A type epoxy resin and bisphenol F type epoxy resin are used in combination, the impregnation property to the fiber base material can be improved. Moreover, when solid bisphenol A type epoxy resin and bisphenol F type epoxy resin are used in combination, adhesion to copper foil can be improved.

The epoxy resin used in the insulating resin composition of the present invention is not halogenated.
Thereby, flame retardancy can be imparted substantially without using a halogen compound, and the occurrence of corrosive and toxic components due to halogen can be eliminated during thermal decomposition of the cured product.

The ultraviolet absorber (c) used in the insulating resin composition of the present invention is not particularly limited, but preferably has at least one absorption peak in a wavelength region of 200 nm to 300 nm in photoelectric spectrophotometer measurement. As a result, productivity and via connection reliability when processing vias with a UV laser can be improved, and the occurrence of delamination at the bottom of the via can be suppressed. In addition, the absorption peak can measure ultraviolet region absorption with the photoelectric spectrophotometer for the sample which put the solution which contains 5 mg of ultraviolet absorbers in 100 ml of methanol solvent in the cell whose sample optical path length is 1 cm, for example.

Examples of the ultraviolet absorber include 4,4′-bisdiethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (5- (chloro-2′-). Hydroxy-3 'tert-butyl-5' methylphenyl) -benzotriazole, 1,1 ', 2,2'-tetrakis (4-glycidylphenyl) ethane, 2,2dimethoxy-1,2diphenylethane-1-one 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 7-diethylamino-4-methylcoumarin, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,4) Trimethyl benzoyl) - can be exemplified phenyl phosphine oxide and the like.
Among these, 4,4′-bisdiethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (5- (chloro-2′-hydroxy-3 ′) tert-butyl-5′methylphenyl) -benzotriazole, coumarin, 4-hydroxycoumarin, 7-diethylamino-4-methylcoumarin, 1,1 ′, 2,2′-tetrakis (4-glycidylphenyl) ethane At least one kind is preferable, and particularly, coumarin having a coumarin structure, 4-hydroxycoumarin, and 7-diethylamino-4-methylcoumarin are preferable, whereby insulation with a film or metal foil using the above insulating resin composition is preferable. Improves via processability of resin sheets with UV lasers and affects bonding reliability Able to form a shape of a via which does not adversely.

  The content of the ultraviolet absorber is not particularly limited, but is preferably 0.01% by weight or more and 2.00% by weight or less, and particularly preferably 0.05% by weight or more and 1.50% by weight or less of the entire insulating resin composition. . When the content of the ultraviolet absorber is less than the lower limit, the effect of improving the UV laser processability and the connection reliability may be lowered. Also, delamination may occur at the bottom of the via. When the upper limit is exceeded, moisture-absorbing solder heat resistance may decrease.

  The insulating resin composition of the present invention preferably contains a resin having film-forming properties. This further improves the film-forming properties and handling properties when manufacturing an insulating resin sheet with a film or a metal foil, and when the insulating resin sheet with a film or a metal foil is cut, the resin powder falls off and is wound around a branch pipe. Resin cracking when taken can be prevented.

Examples of the resin having a film forming property include phenoxy resins, bisphenol F resins, olefin resins, and the like. One of these, including derivatives thereof, can be used alone, or two or more having different weight average molecular weights are used in combination, or one or two or more thereof and a prepolymer thereof are used in combination. You can also.
Among these, a phenoxy resin is preferable. Thereby, heat resistance and a flame retardance can be improved.

    The phenoxy resin is not particularly limited. For example, a phenoxy resin having a bisphenol A skeleton, a phenoxy resin having a bisphenol F skeleton, a phenoxy resin having a bisphenol S skeleton, and bisphenol M (4,4 ′-(1,3- Phenoxy resin having phenylenediisopridiene) bisphenol) skeleton, phenoxy resin having bisphenol P (4,4 ′-(1,4) -phenylenediisopridiene) bisphenol) skeleton, bisphenol Z (4,4′- A phenoxy resin having a bisphenol skeleton, a phenoxy resin having a novolak skeleton, a phenoxy resin having an anthracene skeleton, a phenoxy resin having a fluorene skeleton, and a dicyclopentadiene skeleton. To phenoxy resins, phenoxy resins having a norbornene skeleton, phenoxy resins having a naphthalene skeleton, phenoxy resins having a biphenyl skeleton include phenoxy resins having an adamantane skeleton. A structure having a plurality of types of skeletons can be used, and phenoxy resins having different ratios of the skeletons can be used. Furthermore, a plurality of types of phenoxy resins having different skeletons can be used, a plurality of types of phenoxy resins having different weight average molecular weights can be used, or prepolymers thereof can be used together.

Among these, a phenoxy resin having a biphenyl skeleton and a bisphenol S skeleton can be used. Thereby, the glass transition temperature can be increased due to the rigidity of the biphenyl skeleton, and the adhesion of the plated metal when the multilayer printed wiring board is manufactured can be improved by the bisphenol S skeleton.
Alternatively, a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton can be used. Thereby, the adhesiveness to an inner-layer circuit board can be improved at the time of manufacture of a multilayer printed wiring board. Further, the phenoxy resin having the biphenyl skeleton and the bisphenol S skeleton and the phenoxy resin having the bisphenol A skeleton and the bisphenol F skeleton may be used in combination.

The molecular weight of the resin having the film-forming property is not particularly limited, but the weight average molecular weight is preferably 1.0 × 10 ^{3 to} 1.0 × 10 ⁵ . More preferably from ^{1.0 × 10 4 ~6.0 × 10 4} .
If the weight average molecular weight of the resin having film-forming properties is less than the lower limit, the effect of improving the film-forming properties may not be sufficient. On the other hand, if the upper limit is exceeded, the solubility of the resin having film-forming properties may be lowered. By setting the weight average molecular weight of the resin having film-forming properties within the above range, it is possible to achieve an excellent balance of these characteristics.

Although content of resin which has film forming property is not specifically limited, It is preferable that it is 1-20 weight% of the whole insulating resin composition. More preferably, it is 2 to 10% by weight.
When the content of the film-forming resin is less than the lower limit, the effect of improving the film-forming property may not be sufficient. On the other hand, when the upper limit is exceeded, the linear expansion coefficient may increase and the low thermal expansion property may decrease. By making content of resin which has film forming property into the said range, it can be excellent in the balance of these characteristics.

The resin having film-forming properties used in the insulating resin composition of the present invention is not halogenated.
Thereby, flame retardancy can be imparted substantially without using a halogen compound, and the occurrence of corrosive and toxic components due to halogen can be eliminated during thermal decomposition of the cured product.

The insulating resin composition of the present invention preferably contains (d) an inorganic filler other than the metal hydroxide (hereinafter sometimes simply referred to as “(d) inorganic filler”). Thereby, low thermal expansibility and a flame retardance can be provided. Although content of the said inorganic filler is not specifically limited, It is preferable that it is 5 to 70 weight% with respect to the whole insulating resin composition. Further, it is preferably 10% by weight or more and 60% by weight or less, more preferably 15% by weight or more and 50% by weight or less. Thereby, the said effect | action can be expressed effectively. If the content is less than the lower limit, the effects of low thermal expansion and flame retardancy may not be sufficiently obtained, and if the content exceeds the upper limit, the moldability during heating and pressurization may be reduced.
Examples of the inorganic filler (d) include silicates such as talc, fired clay, unfired clay, mica and glass, oxides such as titanium oxide, alumina, silica, and fused silica, calcium carbonate, magnesium carbonate, and hydrotalc. Carbonate such as site, sulfate or sulfite such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, etc. borate, aluminum nitride, Examples thereof include nitrides such as boron nitride, silicon nitride, and carbon nitride, and titanates such as strontium titanate and barium titanate. One of these can be used alone, or two or more can be used in combination.

  The (d) inorganic filler of the present invention is particularly preferably a metal oxide. Thereby, low thermal expansibility and a flame retardance can be provided, without impairing heat resistance. Further, the metal oxide is preferably silica, and fused silica is preferable in that it has excellent low thermal expansion. Thereby, the said effect | action can be expressed effectively. The shape is crushed and spherical, but for example, spherical silica is used to lower the melt viscosity of the insulating resin composition in order to ensure the impregnation of the fiber base material, etc. Is done.

The average particle diameter of the (d) inorganic filler is not particularly limited, but is preferably 5.0 μm or less, and particularly preferably 0.1 to 2.0 μm. (D) Since the viscosity of a varnish will become it high that the particle size of an inorganic filler is less than the said lower limit, it may affect workability | operativity at the time of insulation resin sheet preparation with a film or metal foil. When the upper limit is exceeded, phenomena such as sedimentation of the inorganic filler may occur in the varnish.
This average particle diameter can be measured, for example, by a particle size distribution meter (manufactured by HORIBA, LA-500).

  Further, the (d) inorganic filler is not particularly limited, but the (d) inorganic filler having a monodisperse average particle diameter can be used, or the (d) inorganic filler having a polydisperse average particle diameter can be used. be able to. Furthermore, one type or two or more types of (d) inorganic fillers having an average particle size of monodisperse and / or polydisperse may be used in combination.

The insulating resin composition is not particularly limited, but it is preferable to use a coupling agent. The coupling agent improves the wettability of the interface between the insulating resin layer in the insulating resin composition and the (a) metal hydroxide and the (d) inorganic filler. On the other hand, insulating resin or the like, (a) metal hydroxide, and (d) inorganic filler can be uniformly fixed to improve heat resistance, particularly solder heat resistance after moisture absorption.
The coupling agent can be used without particular limitation as long as it is usually used. Specific examples include an epoxy silane coupling agent, a cationic silane coupling agent, an amino silane coupling agent, a titanate coupling agent, a molybdic acid coupling agent, and a silicone oil type coupling agent. One type including derivatives can be used alone, or two or more types including these derivatives can be used in combination. Thereby, (a) wettability with the interface of a metal hydroxide and an inorganic filler can be made high, and thereby heat resistance can be improved more.

  The amount of the coupling agent added is not particularly limited because it depends on the specific surface area of the (a) metal hydroxide and the inorganic filler, but (a) 100 parts by weight of the total of the metal hydroxide and the inorganic filler. The amount is preferably 0.05 to 3.00% by weight, particularly preferably 0.10 to 2.00% by weight. If the content is less than the lower limit (a) the metal hydroxide and the inorganic filler cannot be sufficiently covered, the effect of improving heat resistance may be reduced. If the content exceeds the upper limit, the reaction is affected. The bending strength and the like may be reduced.

  The insulating resin composition may use a curing accelerator as necessary. A well-known thing can be used for the said hardening accelerator. For example, tertiary amines such as triethylamine, tributylamine, diazabicyclo [2,2,2] octane, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-methylimidazole, Imidazoles such as 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5-dihydroxyimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, phenol, bisphenol A, nonylphenol, etc. Examples thereof include phenolic compounds, acetic acid, benzoic acid, salicylic acid, organic acids such as p-toluenesulfonic acid, and the like, or mixtures thereof. One of these can be used alone, including derivatives thereof, or two or more of these can be used in combination.

  Although content of the said hardening accelerator is not specifically limited, 0.05 to 5.00 weight% of the whole said insulating resin composition is preferable, and 0.20 to 2.00 weight% is especially preferable. If the content is less than the lower limit, the effect of promoting curing may not appear, and if the content exceeds the upper limit, the storage stability of the insulating resin sheet with a film or metal foil may deteriorate.

The insulating resin composition may be a polyimide resin, polyamideimide resin, polyphenylene oxide resin, polyethersulfone resin, polyester resin, polyethylene resin, polystyrene resin or other thermoplastic resin, styrene-butadiene copolymer, styrene, if necessary. -Thermoplastic elastomers such as polystyrene-based thermoplastic elastomers such as isoprene copolymers, polyolefin-based thermoplastic elastomers, polyamide-based elastomers, and polyester-based elastomers, and diene-based materials such as polybutadiene, epoxy-modified polybutadiene, acrylic-modified polybutadiene, and methacryl-modified polybutadiene An elastomer may be used in combination.
In addition, the insulating resin composition may contain additives other than the above components such as pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, and ion scavengers as necessary. May be added.

Next, an insulating resin sheet with a film or metal foil will be described.
The insulating resin sheet with a film or metal foil of the present invention is formed by forming an insulating resin layer composed of the insulating resin composition on a film or metal foil.

Here, the method for forming the insulating resin composition on the film or the metal foil is not particularly limited. For example, the resin varnish is prepared by dissolving and dispersing the insulating resin composition in a solvent or the like, and various coating apparatuses. The method of drying after coating a resin varnish on a film or a metal foil using a spray, or the method of drying after spray-coating the resin varnish on a film or a metal foil with a spray device.
Among these, the method of drying after coating a resin varnish on a substrate using various coaters such as a comma coater and a die coater is preferable. Thereby, an insulating resin sheet with a film or metal foil having a uniform insulating resin layer thickness without voids can be efficiently produced.

  Moreover, an insulating resin sheet with a film containing a fiber base material or a metal foil can be produced by laminating a fiber base material on a film or a metal foil when coating.

The solvent used in the resin varnish preferably exhibits good solubility with respect to the resin component in the insulating resin composition, but a poor solvent may be used as long as it does not adversely affect the resin varnish. Examples of the solvent exhibiting good solubility include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve and carbitol.
Although solid content in the said resin varnish is not specifically limited, 30 to 80 weight% is preferable and 40 to 70 weight% is especially preferable.

  In the insulating resin sheet with a film or metal foil of the present invention, the thickness of the insulating resin layer composed of the insulating resin composition is not particularly limited, but is preferably 5 to 100 μm. More preferably, it is 10-80 micrometers. Thereby, when manufacturing a multilayer printed wiring board using this insulating resin sheet with a film or metal foil, it can be filled and formed with irregularities of the inner layer circuit, and a suitable insulating resin layer thickness is ensured. In addition, when the insulating resin sheet with a film or metal foil is cut, it is possible to suppress the occurrence of cracking of the insulating resin layer and to reduce the falling off of the insulating resin layer.

The insulating resin sheet with a film or metal foil of the present invention can contain a fiber substrate in the insulating resin layer. Thereby, the intensity | strength of the insulating resin layer after hardening can go up and a linear expansion coefficient can be made small.
The fiber base material used in the present invention includes glass fiber base materials such as glass woven fabric and glass nonwoven fabric, polyamide resin fibers, aromatic polyamide resin fibers, polyamide resin fibers such as wholly aromatic polyamide resin fibers, polyester resin fibers, and aromatics. Synthetic fiber base material, craft made of woven or non-woven fabric mainly composed of polyester resin fiber such as aromatic polyester resin fiber, wholly aromatic polyester resin fiber, polyimide resin fiber, polybenzoxazole fiber, fluororesin fiber Examples thereof include organic fiber base materials such as paper base materials such as paper, cotton linter paper, and mixed paper of linter and kraft pulp. Among these, a glass fiber base material is preferable. Thereby, the intensity | strength of an insulating resin sheet with a film or a metal foil can go up, and it can also reduce water absorption. Moreover, the linear expansion coefficient of an insulating resin sheet with a film or a metal foil can be reduced.

The film used for the insulating resin sheet with a film or metal foil of the present invention is not particularly limited. For example, a thermoplastic resin having heat resistance such as a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, a fluorine resin, or a polyimide resin. Resin films can be used, and metal foils are, for example, copper and / or copper-based alloys, aluminum and / or aluminum-based alloys, iron and / or iron-based alloys, silver and / or silver-based alloys, gold and gold Metal foils such as zinc alloys, zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys can be used.
Although the thickness of the said film or metal foil is not specifically limited, When the thing of 10-100 micrometers is used, the handleability at the time of manufacturing an insulating resin sheet with a film or metal foil is preferable.
In manufacturing the insulating resin sheet with a film or metal foil of the present invention, it is preferable that the unevenness on the surface of the insulating film to be bonded to the insulating resin layer is as small as possible. Thereby, the effect | action of this invention can be expressed effectively.

Next, the multilayer printed wiring board using the insulating resin sheet with a film or metal foil of the present invention will be described.
The multilayer printed wiring board is formed by superposing the insulating resin sheet with film or metal foil on the surface of the inner circuit board on which the inner circuit pattern is formed, and heating and pressing.
Specifically, the insulating resin layer side of the present invention and the surface on which the inner layer circuit pattern of the inner layer circuit board is formed are combined and vacuum heated and pressed using a vacuum pressurizing laminator device, etc. It can be obtained by heat-curing with a drying device or the like.
The conditions for heat and pressure molding here are not particularly limited, but for example, it can be carried out at a temperature of 60 to 160 ° C. and a pressure of 0.2 to 3.0 MPa. Moreover, it is although it does not specifically limit as conditions to heat-harden, If an example is given, it can implement in temperature 140-240 degreeC and time 30-120 minutes.
Alternatively, the insulating resin of the insulating resin sheet with a film or metal foil according to the present invention is obtained by superimposing the insulating resin sheet on the surface of the inner circuit board on which the inner circuit pattern is formed, and heating and pressing using a flat plate press or the like. be able to. Here, the conditions for heat and pressure molding are not particularly limited, but for example, it can be carried out at a temperature of 140 to 240 ° C. and a pressure of 1 to 4 MPa.
The inner layer circuit board used when obtaining the multilayer printed wiring board is formed by, for example, forming a predetermined conductor circuit on both surfaces of a copper clad laminate by etching or the like, and roughening the conductor circuit portion by blackening or the like. What was processed can be used conveniently.

  When an insulating resin sheet with a film is used, the multilayer printed wiring board obtained above is further roughened with an oxidizing agent such as permanganate or dichromate after removing the film. After the treatment, a new conductive wiring circuit can be formed by metal plating. The insulating resin layer formed from the insulating resin composition of the present invention can form a large number of fine uneven shapes with high uniformity in the roughening treatment step, and the insulating resin layer surface has high smoothness. Therefore, a fine wiring circuit can be formed with high accuracy.

When the insulating resin sheet with metal foil is used, the multilayer printed wiring board obtained above can form a conductive wiring circuit by etching.

Next, the semiconductor device will be described.
A conductor circuit or the like normally performed on the multilayer printed wiring board was formed, a semiconductor element was mounted, and a predetermined processing was performed to manufacture a semiconductor device.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this. The blending was performed with the aim of obtaining a previously predicted linear expansion coefficient.

Example 1
(1) Adjustment of resin varnish Cresol novolak type epoxy resin (“Epiclon N-690”, epoxy equivalent 210, manufactured by Dainippon Ink & Chemicals, Inc.) 34.00 parts by weight, bisphenol A type epoxy resin (1) (“Epiclon”) 850 ", epoxy equivalent 190, manufactured by Dainippon Ink & Chemicals, Inc.) 8.00 parts by weight, bisphenol A type epoxy resin (2) (" Epiclon 7050 ", epoxy equivalent 1900, manufactured by Dainippon Ink & Chemicals, Inc.) 4 0.000 parts by weight, phenoxy resin (“YX-8100”, weight average molecular weight 30000, manufactured by Japan Epoxy Resin Co., Ltd.) 2.00 parts by weight, UV absorber (“7-diethylamino-4-methylcoumarin”, Sigma-Aldrich Japan 0.05 parts by weight, curing accelerator (2-ethyl-4-) (Tilimidazole) 1.00 parts by weight and epoxysilane type coupling agent (A-187, manufactured by GE Toshiba Silicone Co., Ltd.) 0.95 parts by weight in methyl ethyl ketone at room temperature and washed (1) (Aluminum hydroxide, HP-360, average particle size of 2.7 μm, metal ion impurity (sodium ion) concentration of 10 ppm, weight reduction rate of 300 ° C., 25%, Showa Denko KK) 10.00 parts by weight, inorganic filling 40.00 parts by weight of a material (spherical fused silica, SO-25R, average particle size 0.5 μm, manufactured by Admatex Co., Ltd.) was added and stirred for 10 minutes using a high-speed stirrer to obtain a resin varnish. . Concentrations of metal ion impurities were: (a) metal hydroxide was treated in pure water at 80 ° C. for 24 hours, and after extracting metal ions into pure water, sodium ions were measured by ICP-MS. Hereinafter, the measurement was performed in the same manner unless otherwise specified.

(2) Production of insulating resin sheet with film The resin varnish obtained as described above is formed on one side of a PET (polyethylene terephthalate) film having a thickness of 25 μm, and the thickness of the insulating resin layer after drying using a comma coater device is 60 μm. This was coated so as to be and dried for 10 minutes with a drying apparatus at 160 ° C. to produce an insulating resin sheet with a film.

(3) Confirmation of linear expansion coefficient of cured product of insulating resin composition Two sheets of the insulating resin sheet with film obtained above were prepared, and the insulating resin layer surface of the insulating resin sheet with film was placed inside, and the vacuum pressure type Using a laminator device, vacuum heating and pressure molding is performed at a temperature of 100 ° C. and a pressure of 1 MPa, and then heat curing is performed at 170 ° C. for 60 minutes in a hot air drying device, the film is removed and the thickness of the insulating resin layer is 120 μm. An insulating resin layer was obtained. A test piece of 4 mm × 40 mm was cut out from the obtained insulating resin layer, and the linear expansion coefficient at 25 ° C. was measured under a pulling condition of 5 ° C./min using TMA. As a result, the linear expansion coefficient of the cured product at 25 ° C. was 26 ppm, which was confirmed to be 6 ppm / ° C. or more and 50 ppm / ° C. or less.

(4) Production of Insulating Resin Sheet with Metal Foil The resin varnish obtained above was applied to one side of a 12 μm thick copper foil (“F2WS-12”, 12 μm thick, manufactured by Furukawa Circuit Foil Co., Ltd.). Using an apparatus, coating was performed so that the thickness of the insulating resin layer after drying was 60 μm, and this was dried with a drying apparatus at 160 ° C. for 10 minutes to produce an insulating resin sheet with copper foil.

(5) Fabrication of multilayer printed wiring board Overlaid on the front and back of the inner layer circuit board on which the predetermined inner layer circuit pattern is formed on both sides, with the insulating resin layer surface of the insulating resin sheet with film or copper foil obtained above inside Then, this is vacuum-pressed and molded at a temperature of 100 ° C. and a pressure of 1 MPa using a vacuum pressurizing laminator device, and then heated and cured at 170 ° C. for 60 minutes in a hot air drying device to obtain a multilayer printed wiring board. Obtained.
In addition, the following were used as the inner layer circuit board.
-Insulating layer: Halogen-free FR-4 material, thickness 0.4mm
Conductor layer: copper foil thickness 18 μm, L / S = 120/180 μm, clearance holes 1 mmφ, 3 mmφ, slit 2 mm

(6) Manufacture of semiconductor device Using a multilayer printed wiring board made of the insulating resin sheet with copper foil, a conductor circuit is formed by etching, PSR-4000 AUS703 manufactured by Taiyo Ink Manufacturing Co., Ltd. is printed, and the semiconductor Exposure, development, and thermosetting are performed using a predetermined mask manufactured so that a 50 mm × 50 mm semiconductor device can be obtained so that the element mounting pad and the like are exposed, and the solder resist layer thickness on the circuit is It formed so that it might become 12 micrometers.
Next, the electroless nickel plating layer 3 μm was formed on the circuit layer exposed from the solder resist layer, and the electroless gold plating layer 0.1 μm was further formed thereon.
The obtained multilayer printed wiring board was cut into a size of 50 mm × 50 mm, semiconductor elements of a size of 15 mm × 15 mm were joined with a flip chip bonder and a reflow furnace, and a semiconductor device was fabricated by filling the underfill.

(Example 2)
Except for 30.00 parts by weight of cresol novolac type epoxy resin, 1.00 parts by weight of phenoxy resin, 5.00 parts by weight of washed metal hydroxide (1), and 50.00 parts by weight of inorganic filler. In the same manner as in Example 1, an insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of an insulating resin composition is 20 ppm and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 3)
25.00 parts by weight of cresol novolac type epoxy resin, 6.00 parts by weight of bisphenol A type epoxy resin (1), 3.00 parts by weight of bisphenol A type epoxy resin (2), washed metal hydroxide (1 ) And 2.00 parts by weight of inorganic filler, and an insulating resin sheet with a film or copper foil, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions is 17 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

Example 4
19.00 parts by weight of cresol novolac type epoxy resin, 5.00 parts by weight of bisphenol A type epoxy resin (1), 2.00 parts by weight of bisphenol A type epoxy resin (2), and 1.00 parts by weight of phenoxy resin Insulating resin sheet with film or copper foil, multilayer printed wiring, as in Example 1, except that the washed metal hydroxide (1) was 1.00 parts by weight and the inorganic filler was 70.00 parts by weight A plate and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of an insulating resin composition is 10 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 5)
17.00 parts by weight of cresol novolac type epoxy resin, 3.00 parts by weight of bisphenol A type epoxy resin (1), 2.00 parts by weight of bisphenol A type epoxy resin (2), and 1.00 parts by weight of phenoxy resin Insulating resin sheet with film or copper foil, multilayer printed wiring, as in Example 1, except that the washed metal hydroxide (1) was 5.00 parts by weight and the inorganic filler was 70.00 parts by weight A plate and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of an insulating resin composition is 8 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 6)
12.00 parts by weight of cresol novolac type epoxy resin, 3.00 parts by weight of bisphenol A type epoxy resin (1), 2.00 parts by weight of bisphenol A type epoxy resin (2), and 1.00 parts by weight of phenoxy resin Insulating resin sheet with film or with copper foil as in Example 1 except that the ultraviolet absorber was 0.01 parts by weight, the coupling agent was 0.99 parts by weight, and the inorganic filler was 70.00 parts by weight. A multilayer printed wiring board and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions is 6 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 7)
36.00 parts by weight of cresol novolac type epoxy resin, 9.50 parts by weight of bisphenol A type epoxy resin (1), 5.00 parts by weight of bisphenol A type epoxy resin (2), and 1.00 parts by weight of phenoxy resin , Except that the ultraviolet absorber was 2.00 parts by weight, the coupling agent was 0.50 parts by weight, the washed metal hydroxide (1) was 30.00 parts by weight, and the inorganic filler was 15.00 parts by weight. In the same manner as in Example 1, an insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of an insulating resin composition is 30 ppm and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 8)
36.00 parts by weight of cresol novolac type epoxy resin, 0.50 parts by weight of bisphenol A type epoxy resin (1), 5.00 parts by weight of bisphenol A type epoxy resin (2), and 10.00 parts by weight of phenoxy resin , Except that the ultraviolet absorber was 2.00 parts by weight, the coupling agent was 0.50 parts by weight, the washed metal hydroxide (1) was 30.00 parts by weight, and the inorganic filler was 15.00 parts by weight. In the same manner as in Example 1, an insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of an insulating resin composition is 37 ppm and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

Example 9
31.00 parts by weight of cresol novolac type epoxy resin, 0.00 part by weight of bisphenol A type epoxy resin (1), 0.50 part by weight of bisphenol A type epoxy resin (2), and 20.00 parts by weight of phenoxy resin , Except that the ultraviolet absorber was 2.00 parts by weight, the coupling agent was 0.50 parts by weight, the washed metal hydroxide (1) was 30.00 parts by weight, and the inorganic filler was 15.00 parts by weight. In the same manner as in Example 1, an insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions is 44 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 10)
36.00 parts by weight of cresol novolac type epoxy resin, 5.50 parts by weight of bisphenol A type epoxy resin (1), 5.00 parts by weight of bisphenol A type epoxy resin (2), and 5.00 parts by weight of phenoxy resin , Except that the ultraviolet absorber was 2.00 parts by weight, the coupling agent was 0.50 parts by weight, the washed metal hydroxide (1) was 30.00 parts by weight, and the inorganic filler was 15.00 parts by weight. In the same manner as in Example 1, an insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were produced. In addition, the linear expansion coefficient of the hardened | cured material which consists of an insulating resin composition was 33 ppm, and confirmed that it was 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 11)
1.00 parts by weight of phenoxy resin, 1.50 parts by weight of ultraviolet absorber, 0.50 parts by weight of coupling agent, 40.00 parts by weight of washed metal hydroxide (1), and 10 inorganic fillers An insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the amount was 0.000 part by weight. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions is 35 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 12)
28.00 parts by weight of cresol novolac type epoxy resin, 5.00 parts by weight of bisphenol A type epoxy resin (2), 45.00 parts by weight of washed metal hydroxide (1), and 10.00 parts of inorganic filler An insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the weight part was used. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions is 40 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 13)
28.00 parts by weight of cresol novolac type epoxy resin, 9.00 parts by weight of bisphenol A type epoxy resin (1), 5.00 parts by weight of bisphenol A type epoxy resin (2), and 1.00 parts by weight of phenoxy resin Insulating resin sheet with film or copper foil, multilayer printed wiring, as in Example 1, except that the washed metal hydroxide (1) was 50.00 parts by weight and the inorganic filler was 5.00 parts by weight A plate and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of an insulating resin composition is 50 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 14)
Example 1 except that 36.00 parts by weight of the cresol novolac type epoxy resin, 7.00 parts by weight of the bisphenol A type epoxy resin (1), and 3.00 parts by weight of the bisphenol A type epoxy resin (2) are used. Similarly, an insulating resin sheet with a film or copper foil, a multilayer printed wiring board, and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions is 26 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 15)
Example 1 except that the cresol novolac type epoxy resin was 29.00 parts by weight, the bisphenol A type epoxy resin (1) was 11.00 parts by weight, and the bisphenol A type epoxy resin (2) was 6.00 parts by weight. Similarly, an insulating resin sheet with a film or copper foil, a multilayer printed wiring board, and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of an insulating resin composition is 30 ppm and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 16)
Washed metal hydroxide (2) instead of washed metal hydroxide (1) (aluminum hydroxide, HP-32, average particle size 8.0 μm, metal ion impurity (sodium ion) concentration 200 ppm, 300 ° C. An insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the weight reduction rate of 30%, manufactured by Showa Denko KK was 10.00 parts by weight. . In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions is 26 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 17)
Washed metal hydroxide (3) instead of washed metal hydroxide (1) (aluminum hydroxide, HP-42M, average particle size 1.0 μm, metal ion impurity (sodium ion) concentration 400 ppm, 300 ° C. An insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the weight reduction rate of 30%, manufactured by Showa Denko KK was 10.00 parts by weight. . In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions is 26 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 18)
Washed metal hydroxide (4) instead of washed metal hydroxide (1) (aluminum hydroxide, HP-43M, average particle size 0.6 μm, metal ionic impurity (sodium ion) concentration 500 ppm, 300 ° C. An insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the weight reduction rate of 30%, manufactured by Showa Denko KK was 10.00 parts by weight. . In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions is 26 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 19)
Washed metal hydroxide (5) instead of washed metal hydroxide (1) (aluminum hydroxide, HS-320, average particle size 10.0 μm, metal ionic impurity (sodium ion) concentration 20 ppm, 300 ° C. An insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were prepared in the same manner as in Example 1 except that the weight reduction rate of 25%, made by Showa Denko KK was 10.00 parts by weight. . In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions is 26 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Example 20)
Example 1 except that phenol novolac epoxy resin (“Epiclon N-770”, epoxy equivalent 190, manufactured by Dainippon Ink & Chemicals, Inc.) was changed to 34.00 parts by weight instead of cresol novolac epoxy resin. An insulating resin sheet with a film or copper foil, a multilayer printed wiring board, and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of an insulating resin composition is 29 ppm and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Comparative Example 1)
44.00 parts by weight of cresol novolac type epoxy resin, 18.00 parts by weight of bisphenol A type epoxy resin (1), 14.00 parts by weight of bisphenol A type epoxy resin (2), washed metal hydroxide (1 ) Was 20.00 parts by weight, and an insulating resin sheet with a film or a copper foil, a multilayer printed wiring board, and a semiconductor device were produced in the same manner as in Example 1 except that the inorganic filler was not blended. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of an insulating resin composition is 59 ppm and is outside the range of 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Comparative Example 2)
44 parts by weight of cresol novolac type epoxy resin, 0.00 part by weight of bisphenol A type epoxy resin (1), 30 parts by weight of phenoxy resin, 0.00 part by weight of UV absorber, 1.00 weight of coupling agent Parts, 20 parts by weight of the washed metal hydroxide (1), and an insulating resin sheet with a film or copper foil, multilayer printed wiring board, semiconductor as in Example 1 except that no inorganic filler was added A device was made. In addition, the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions was 65 ppm, and confirmed that it was outside the range of 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Comparative Example 3)
44.00 parts by weight of cresol novolac type epoxy resin, 19.50 parts by weight of bisphenol A type epoxy resin (1), 10.00 parts by weight of bisphenol A type epoxy resin (2), and 0.00 part by weight of phenoxy resin , Except that the ultraviolet absorber was 5.00 parts by weight, the coupling agent was 0.50 parts by weight, the washed metal hydroxide (1) was 20.00 parts by weight, and no inorganic filler was added. In the same manner as in Example 1, an insulating resin sheet with a film or copper foil, a multilayer printed wiring board, and a semiconductor device were produced. In addition, the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions was 54 ppm, and confirmed that it was outside the range of 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Comparative Example 4)
36 parts by weight of cresol novolac type epoxy resin, 10 parts by weight of bisphenol A type epoxy resin (1), 5 parts by weight of bisphenol A type epoxy resin (2), unwashed instead of washed metal hydroxide (1) Metal hydroxide (6) (aluminum hydroxide, HP-42I, average particle size 1.0 μm, metal ion impurity (sodium ion) concentration 2800 ppm, weight reduction rate of 300 ° C., 25%, manufactured by Showa Denko KK) In the same manner as in Example 1, an insulating resin sheet with a film or with a copper foil, a multilayer printed wiring board, and a semiconductor device were prepared except that 30.00 parts by weight and 15.00 parts by weight of an inorganic filler were used. In addition, the linear expansion coefficient of the hardened | cured material which consists of an insulating resin composition was 33 ppm, and confirmed that it was 6 ppm / degrees C or more and 50 ppm / degrees C or less.

(Comparative Example 5)
57 parts by weight of a cresol novolac type epoxy resin, 16.00 parts by weight of a bisphenol A type epoxy resin (1), 7.00 parts by weight of a bisphenol A type epoxy resin (2), a curing accelerator (2-ethyl-4- Methylimidazole) with 2.00 parts by weight, inorganic filler with 15.00 parts by weight, and with washed metal hydroxide (1) not added, with film or with copper foil as in Example 1. An insulating resin sheet, a multilayer printed wiring board, and a semiconductor device were produced. In addition, it was confirmed that the linear expansion coefficient of the hardened | cured material which consists of insulating resin compositions is 48 ppm, and is 6 ppm / degrees C or more and 50 ppm / degrees C or less.

The characteristics of the resin compositions obtained in Examples and Comparative Examples, insulating resin sheets with films or copper foils, multilayer printed wiring boards, and semiconductor devices were evaluated. The results are shown in Tables 1 and 2.

The evaluation method is as follows.

1. Thermal shock test The semiconductor device manufactured in the above example was processed in Fluorinert for 1000 cycles at −55 ° C. for 10 minutes, 125 ° C. for 10 minutes, and −55 ° C. for 10 minutes, and no cracks occurred in the test piece. I confirmed.
○: No crack occurrence ×: Crack occurrence

2. Warpage of the substrate The warpage of the substrate was measured using the semiconductor device manufactured in the above example.

3. Insulation reliability test A multilayer printed wiring board made of an insulating resin sheet with a film or copper foil prepared in the above example was prepared, treated for 1000 h under the conditions of 85 ° C., 85% RH, and applied voltage of 50 V, and multilayered at 100 V The insulation resistance between the insulating resin layers of the printed wiring board was measured.
○: 1.0 × 10 ¹⁰ Ω or more ×: 1.0 × 10 ¹⁰ Ω or less

4). Press formability Inner layer circuit copper thickness 35μm, 20mm diameter uncladding pattern on the top and bottom of the test substrate, one each of the above-mentioned insulating resin sheets with film, 18μm copper foil overlap, pressure 4MPa After heating and pressing at a temperature of 200 ° C. for 2 hours, the entire surface of the copper foil was etched to confirm whether there was any press-molding void.
○: No forming void ×: With forming void

5. Arithmetic surface roughness: Ra
Using the multilayer printed wiring board produced in the above example, desmearing was performed under conditions of swelling: 80 ° C., 5 minutes, roughening: 80 ° C., 10 minutes, neutralization: 40 ° C., 5 minutes, and Ra of the substrate was measured. did.

6). Glass transition temperature A 10 mm × 60 mm test piece was cut out from a 120 μm-thick insulating resin layer produced by measuring the linear expansion coefficient, and 3 ° C./mm using a dynamic viscoelasticity measuring apparatus (DMA983, manufactured by TA Instruments). The temperature was raised in minutes, and the peak position of tan δ was taken as the glass transition temperature.

7. Weight reduction rate From the 120 μm thick insulating resin layer produced by measuring the linear expansion coefficient, the cured product of the insulating resin composition is scraped off, and the temperature is increased from 30 ° C. to 500 ° C. at a rate of 10 ° C./min using TG-DTA. The weight reduction rate (%) was calculated from ((30 ° C. cured product weight) − (300 ° C. cured product weight)) / (30 ° C. cured product weight) × 100).

8). Flame Retardancy Test According to UL-94 standard, a 1 mm thick test piece was measured by the vertical method.

9. Water absorption rate A test piece of 50 mm × 50 mm was cut out from a 120 μm-thick insulating resin layer produced by measuring the linear expansion coefficient, and measured according to JIS C 6481.

10. Peel strength It measured based on JIS C 6481 using the multilayer printed wiring board produced in the said Example.

11. Moisture-absorbing solder heat resistance Cut out to 50 mm × 50 mm from the multilayer printed wiring board prepared in the above example, and half-etched according to JIS C 6481 to create a test piece. After being treated with a pressure cooker at 121 ° C. for 2 hours, it was floated in a solder bath at 260 ° C. with the copper foil face down, and the presence or absence of appearance abnormality after 120 seconds was examined.
○: No abnormality ×: There is swelling

12 Powdered Insulation Resin Sheet with a 80 μm thick film was cut using a push cutter at room temperature of 25 ° C. to confirm the presence or absence of powdered insulation resin.
○: Resin powdering is low and there are no practical problems ×: Resin powdering is many and there are practical problems

13. Via Plating Workability Using the multilayer printed wiring board produced in the above example, via drilling with a UV laser with a wavelength of 266 nm was performed, and after plating, the via cross section was observed with a scanning electron microscope.
○: Good via plating property ×: Poor via plating property, poor connection

14 Delamination Using a double-sided copper-clad multilayer printed wiring board with a thickness of 0.6 mm, via drilling was performed with a UV laser with a wavelength of 266 nm, and the bottom of the via was observed with a scanning electron microscope.
○: No delamination occurred ×: Delamination occurred

As is clear from Tables 1 and 2, the linear expansion coefficient of the cured product was controlled to 6 ppm / ° C. or more and 50 ppm / ° C. or less at 25 ° C., and (a) Example in which the metal ionic impurities of the metal hydroxide were small. Nos. 1 to 20 all had good results in insulation reliability, flame retardancy, moisture absorption heat resistance, via plating processability, and delamination.
On the other hand, in Comparative Example 1 where the linear expansion coefficient of the cured product was as large as 59 ppm, cracks and blisters were generated in the thermal shock test and the hygroscopic solder heat resistance test, and the flame retardancy was also lowered.
In Comparative Example 2 where the linear expansion coefficient of the cured product was as large as 65 ppm, cracks were generated due to thermal shock, flame retardancy was reduced, and moisture absorption resistance and solder heat resistance were also reduced. Further, since it does not contain an ultraviolet absorber, the plating processability of vias and the occurrence of delamination occurred, and the working efficiency during UV laser processing was reduced.
In Comparative Example 3, where the linear expansion coefficient of the cured product was as large as 54 ppm, cracks occurred due to thermal shock, flame retardancy decreased, and moisture absorption resistance and solder heat resistance also decreased. Moreover, powdering of the insulating resin occurred, and the handling property of the insulating resin sheet with a film was lowered.
In Comparative Example 4, the concentration of metal ionic impurities in the metal hydroxide was high, the insulation resistance decreased in the insulation reliability test, and appearance abnormality occurred in the heat-absorbing solder heat resistance. Moreover, since the comparative example 5 did not contain (a) metal hydroxide and there was little content of an inorganic filler, a flame retardance fell remarkably.

  The insulating resin composition of the present invention is suitably used for an insulating resin sheet with a film or a copper foil, a multilayer printed wiring board using the insulating resin sheet with a film or a copper foil, and a semiconductor device comprising the multilayer printed wiring board. However, since it has excellent reliability such as flame retardancy, solder resistance, insulation reliability, thermal shock resistance, etc., the power of in-vehicle electronic component devices such as fuel cell vehicles and hybrid vehicles It can also be used for a resin portion used for protecting a chip of an electronic component for driving a motor used in an electronic device or a hybrid vehicle.

Claims (15)

An insulating resin composition used for forming an insulating resin layer of a multilayer printed wiring board, wherein a linear expansion coefficient of a cured product of the insulating resin composition is 6 ppm / ° C. or more and 50 ppm / ° C. or less at 25 ° C.
(A) metal hydroxide,
(B) an epoxy resin containing a novolac-type epoxy resin and substantially not halogenated,
(C) contains an ultraviolet absorber,
And (a) the metal ionic impurity contained in the metal hydroxide is 500 ppm or less, (a) the metal hydroxide is aluminum hydroxide, and the metal ionic impurity is sodium ion,
The content of the metal hydroxide (a) is 1% by weight or more and 50% by weight or less of the insulating resin composition,
Wherein (c) UV absorbers Ri der content the insulating resin composition 2.00 wt% 0.01 wt% or more of the total weight a compound having a coumarin structure,
The insulating resin layer comprising the insulating resin composition is used for an insulating resin sheet with a film or metal foil formed on a film or metal foil,
The multilayer printed wiring board, Ru said der those insulating resin layer formed by heat and pressure molding are superposed on the inner layer circuit pattern is formed faces of the inner layer circuit board of the film with or metal foil with an insulating resin sheet An insulating resin composition characterized by that. The said insulating resin composition is an insulating resin composition of Claim 1 containing resin which has film forming property whose weight average molecular weight is 1.0 * 10 < ³ > -1.0 * 10 < ⁵ >. The insulating resin composition according to claim 1, wherein the insulating resin composition contains (d) an inorganic filler other than a metal hydroxide. The insulating resin according to any one of claims 1 to 3, wherein the ultraviolet absorber (c) has at least one absorption peak in a wavelength region of 200 nm to 300 nm in photoelectric spectrophotometer measurement. Composition. The insulating resin composition according to any one of claims 1 to 4, wherein a weight reduction rate of the insulating resin composition at 300 ° C is 15% or less. The insulating resin composition according to any one of claims 1 to 5, wherein an average particle diameter of the metal hydroxide (a) is 0.1 µm or more and 5 µm or less. The insulating resin composition according to any one of claims 1 to 6, wherein a weight reduction rate of the metal hydroxide (a) at 300 ° C is 20 wt% or more and 40 wt% or less. The insulating resin composition according to any one of claims 3 to 7 , wherein the inorganic filler other than (d) the metal hydroxide is a metal oxide. The insulating resin composition according to claim 8 , wherein the metal oxide is fused silica. Claims 1 to 9 or the insulating resin layer made of an insulating resin composition according to one, with a film or a metal foil with an insulating resin sheet obtained by forming a film or a metal foil. The insulating resin layer with a film or a metal foil with an insulating resin sheet according to claim 1 0 comprising a fibrous base material. The fiber base material, a film with or metal foil with an insulating resin sheet according to claim 1 1, which is a glass fiber. The fiber base material, a film with or metal foil with an insulating resin sheet according to claim 1 1 is an organic fiber. Claim 1 0 with a film or heat pressure molded inner layer circuit pattern is superimposed on the formed surface of the metal foil with an insulating resin sheet of the insulating resin layer an inner layer circuit board according to any one of 1 3 A multilayer printed wiring board. Semiconductor device comprising a semiconductor element mounted on the multilayer printed wiring board according to claim 1 4.