JP2008101062A - Resin composition, prepreg, laminated plate and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulation resin composition having a high insulation reliability in the case of using it as the insulation resin composition of a laminated plate, having flame retardance and capable of performing a high density, highly multiple-layered molding, and a prepreg, laminated plate and a semiconductor device by using the same. <P>SOLUTION: This insulation resin composition is characterized by having ≥6 and ≤50 ppm/°C linear expansion coefficient at 25°C, containing (a) a metal hydroxide having ≥10 and ≤500 ppm concentration of metal ionic impurities and (b) a novolac type epoxy resin and also containing a not substantially halogenated epoxy resin. The prepreg is characterized by using the above insulation resin composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition, a prepreg, a laminate, 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, along with demands for higher functionality of electronic devices, electronic components have been densely integrated and mounted with high density, and the number of high-density mounting compatible laminates used for these components has increased. As a result, applications for miniaturization and high density are also expanding. In order to be usable in these applications, low thermal expansion and connection reliability of the laminated plate are important (for example, see 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, when used in an insulating resin composition of a laminated board used in electronic equipment, has low thermal expansion, high temperature and high humidity, and does not cause peeling or cracking of a conductor circuit layer by a thermal shock test such as a thermal cycle test. Insulating resin composition capable of producing a laminated board that has high insulation reliability even under the environment of the above, flame retardancy, and capable of high density and high multilayer molding, and a prepreg, laminated board, And a semiconductor device.

Such an object is achieved by the present invention described in the following (1) to (15).
(1) An insulating resin composition used for forming a sheet-like prepreg by impregnating a fiber base material, wherein a linear expansion coefficient of a cured product of the insulating resin composition is 6 ppm / ° C. or more and 50 ppm at 25 ° C. / ° C or less,
(A) a metal hydroxide having a concentration of metal ionic impurities of 500 ppm or less,
(B) An insulating resin composition comprising a novolac type epoxy resin and an epoxy resin which is not substantially halogenated.
(2) The insulating resin composition according to (1), wherein the insulating resin composition contains an inorganic filler other than (c) a metal hydroxide.
(3) The insulating resin composition according to (1) or (2), wherein a weight reduction rate at 300 ° C. of the insulating resin composition is 15% or less.
(4) The insulating resin composition according to any one of (1) to (3), wherein (a) the metal hydroxide has an average particle size of 0.1 μm to 10 μm.
(5) The insulating resin composition according to any one of (1) to (4), 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. object.
(6) The insulating resin composition as a whole, wherein the content of the (a) metal hydroxide is 1% by weight or more and 50% by weight or less. Insulating resin composition.
(7) The metal ionic impurities contained in the metal hydroxide (a) are lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, francium ion, beryllium ion, calcium ion, strontium ion, barium ion. The insulating resin composition according to any one of (1) to (6), which is at least one selected from the group consisting of zinc ions, tin ions, and lead ions.
(8) The insulating resin according to any one of (1) to (7), wherein the metal hydroxide (a) is selected from the group consisting of magnesium hydroxide, aluminum hydroxide, gallium hydroxide, and zirconyl hydroxide. Composition.
(9) The insulating resin composition according to any one of (2) to (8), wherein the inorganic filler other than (c) the metal hydroxide is a metal oxide.
(10) The insulating resin composition according to (9), wherein the metal oxide is fused silica.
(11) A prepreg obtained by impregnating a fiber base material with the insulating resin composition according to any one of (1) to (10).
(12) The prepreg according to (11), wherein the fiber base material is made of glass fiber.
(13) The prepreg according to (11), wherein the fiber base material is made of an organic fiber.
(14) A laminate comprising one or more of the prepregs according to any one of (11) to (13) which are stacked and heated and pressed.
(15) A semiconductor device comprising a chip mounted on the laminate according to (14).

The insulating resin composition and prepreg of the present invention can achieve flame retardancy without using a halogen-containing compound and a phosphorus-containing compound, and have superior low thermal expansion and insulation reliability compared to conventional ones. Thus, a laminated plate and a semiconductor device can be obtained.

  The insulating resin composition, prepreg, laminate and 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 a hardened material is used for a laminated board or a semiconductor device, peeling of a conductor circuit layer and generation of cracks can be suppressed 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. In addition, if the upper limit is exceeded, this also causes a linear expansion mismatch with the conductor circuit, which causes warpage of the circuit board during press molding or solder reflow, and peeling or cracking of the conductor circuit layer in a thermal shock test such as a thermal cycle test. There is a risk that the generation cannot be suppressed.

The linear expansion coefficient of the cured product of the insulating resin composition depends on the type of resin, the content of the resin, 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 the insulating resin composition 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 laminated 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. Thereby, when using hardened | cured material for a laminated board and a semiconductor device, high insulation reliability can be hold | maintained even if it processes under high temperature and high humidity, such as a HAST test and a 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: (a) after treating the metal hydroxide in pure water at 80 ° C. for 24 hours and extracting the metal ions in pure water, 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 ion, sodium ion, potassium ion, rubidium ion, cesium ion, francium ion, beryllium ion, calcium ion, and strontium. It is desirable that there be at least one selected from the group consisting of ions, barium ions, zinc ions, tin ions, and lead ions. Of these, sodium ions and potassium ions are particularly desirable. If these concentrations are within the above ranges, high insulation reliability can be maintained even when the cured product is used in a laminated plate or a semiconductor device even if it is processed under high temperature and high humidity such as HAST test or PCT test. .

  Although the average particle diameter of (a) metal hydroxide used by the insulating resin composition of this invention is not specifically limited, It is preferable that they are 0.1 micrometer or more and 10 micrometers 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) When the average particle diameter 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 impregnate the fiber base material, and it becomes difficult to produce the prepreg. 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 when the surface of the film sheet made of the B-staged or cured insulating resin composition is roughened by chemical and / or physical treatment may increase. Insulation reliability may be 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 film sheet made of the insulating resin composition is roughened is not particularly limited, but Ra (arithmetic mean roughness) 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 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.

  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.

The content of the novolac type epoxy resin is not particularly limited, but is preferably 60 to 90% by weight of the entire 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 said upper limit is exceeded, hardened | cured material will become hard and drill workability and punching workability may fall.

In the insulating resin composition of the present invention, an epoxy resin can be used in combination with the 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 insulating resin composition of the present invention preferably contains (c) an inorganic filler other than the metal hydroxide (hereinafter sometimes simply referred to as “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 include silicates such as talc, calcined clay, unfired clay, mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, calcium carbonate, magnesium carbonate, hydrotalcite and the like. Carbonates, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, aluminum nitride, boron nitride And nitrides such as silicon nitride and carbon nitride, and titanates such as strontium titanate and barium titanate. As the inorganic filler, one of these can be used alone, or two or more can be used in combination.

  The 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. Furthermore, the metal oxide is preferably silica, and fused silica (particularly spherical fused silica) is preferred in that it has excellent low thermal expansibility. 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 inorganic filler is not particularly limited, but is preferably 5.0 μm or less, and particularly preferably 0.1 to 2.0 μm. If the particle size of the inorganic filler is less than the lower limit, the viscosity of the varnish becomes high, which may affect the workability during prepreg production. 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).

  The inorganic filler is not particularly limited, and an inorganic filler having a monodispersed average particle diameter can be used, and an inorganic filler having a polydispersed average particle diameter can be used. Furthermore, one type or two or more types of 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 in the insulating resin composition and the (a) metal hydroxide and the inorganic filler, thereby insulating the fiber base material. (A) The metal hydroxide and the inorganic filler can be uniformly fixed to improve heat resistance, particularly solder heat resistance after moisture absorption.
As the coupling agent, any commonly used one can be used. Specifically, an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, and a silicone oil type coupling. It is preferable to use one or more coupling agents selected from among the agents. 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% by weight, more preferably 0.1 to 2% 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.

  A curing accelerator may be used in the insulating resin composition as necessary. A well-known thing can be used as 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. As the curing accelerator, one kind including these derivatives can be used alone, or two or more kinds including these derivatives can be used in combination.

  Although content of the said hardening accelerator is not specifically limited, 0.05 to 5 weight% of the whole said insulating resin composition is preferable, and 0.2 to 2 weight% is especially preferable. When the content is less than the lower limit, the effect of promoting curing may not appear, and when the content exceeds the upper limit, the storability of the prepreg may deteriorate.

In the insulating resin composition, a phenoxy resin, polyimide resin, polyamideimide resin, polyphenylene oxide resin, polyethersulfone resin, polyester resin, polyethylene resin, polystyrene resin or other thermoplastic resin, styrene-butadiene copolymer, styrene-isoprene. Polystyrene thermoplastic elastomers such as copolymers, thermoplastic elastomers such as polyolefin thermoplastic elastomers, polyamide elastomers, polyester elastomers, and other diene elastomers such as polybutadiene, epoxy modified polybutadiene, acrylic modified polybutadiene, and methacrylic modified polybutadiene. You may use together.
In addition, if necessary, additives other than the above components such as pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, and ion scavengers may be added to the insulating resin composition. A thing may be added.

Next, the prepreg will be described.
The prepreg of the present invention is obtained by impregnating a fiber base material with the above-described insulating resin composition. Thereby, a prepreg suitable for manufacturing a printed wiring board excellent in various characteristics such as dielectric characteristics, mechanical and electrical connection reliability under high temperature and high humidity can be obtained.

  As the fiber base material used in the present invention, 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, Synthetic fiber substrate, kraft paper, cotton linter composed of woven or non-woven fabric mainly composed of aromatic polyester resin fiber, polyester resin fiber such as wholly aromatic polyester resin fiber, polyimide resin fiber, fluororesin fiber, etc. Examples thereof include organic fiber base materials such as paper base materials mainly composed of paper, mixed paper of linter and kraft pulp, and the like. Among these, a glass fiber base material is preferable. Thereby, the intensity | strength of a prepreg can go up and water absorption can be made low. In addition, the linear expansion coefficient of the prepreg can be reduced.

  Examples of the method of impregnating the fiber base material with the insulating resin composition obtained in the present invention include a method of preparing a resin varnish using the insulating resin composition of the present invention and immersing the fiber base material in the resin varnish, Examples thereof include a coating method using a coater and a spraying method. Among these, the method of immersing the fiber base material in the resin varnish is preferable. Thereby, the impregnation property of the insulating resin composition with respect to the fiber base material can be improved. In addition, when a fiber base material is immersed in a resin varnish, a normal impregnation coating equipment can be used.

The solvent used in the resin varnish desirably has good solubility in 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.
The nonvolatile content concentration in the resin varnish is not particularly limited, but is preferably 40 to 80% by weight, and particularly preferably 50 to 65% by weight. Thereby, the viscosity of a resin varnish can be adjusted to a suitable range, and the impregnation property to a fiber base material can be improved further. A prepreg can be obtained by impregnating the fibrous base material with the insulating resin composition and drying at a predetermined temperature, for example, 80 to 200 ° C.

Next, a laminated board is demonstrated.
The laminate of the present invention is formed by molding at least one prepreg described above. Thereby, the laminated board excellent in the dielectric property and the mechanical and electrical connection reliability in high temperature and high humidity can be obtained.
In the case of a single prepreg, a metal foil or film is stacked on both upper and lower surfaces or one surface. Two or more prepregs can be laminated. When two or more prepregs are laminated, a metal foil or film is laminated on the outermost upper and lower surfaces or one surface of the laminated prepreg. Next, a laminate can be obtained by heating and pressurizing a laminate of a prepreg and a metal foil. Although the temperature to heat is not specifically limited, 120-220 degreeC is preferable and especially 150-200 degreeC is preferable. Moreover, the pressure to pressurize is not particularly limited, but is preferably 2 to 5 MPa, and particularly preferably 2.5 to 4 MPa.

Examples of the metal constituting the metal foil include copper and copper alloys, aluminum and aluminum alloys, silver and silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, tin and tin. Alloy, iron, iron alloy and the like.
Examples of the film include polyethylene, polypropylene, polyethylene terephthalate, polyimide, and fluorine resin.

Next, the semiconductor device will be described.
A conductor circuit or the like normally performed on the laminated plate 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 parts by weight, bisphenol A type epoxy resin (1)
("Epiclon 850", epoxy equivalent 190, manufactured by Dainippon Ink & Chemicals, Inc.) 10 parts by weight, bisphenol A type epoxy resin (2) ("Epiclon 7050", epoxy equivalent 1900, manufactured by Dainippon Ink & Chemicals, Inc.) 4 parts by weight, 1 part by weight of a curing accelerator (2-ethyl-4-methylimidazole), and 1 part by weight of an epoxysilane coupling agent (A-187, manufactured by GE Toshiba Silicone Co., Ltd.) were dissolved in methyl ethyl ketone at room temperature. Washed metal hydroxide (1) (aluminum hydroxide, HP-360, average particle size of 2.7 μm, metal ionic impurity (sodium ion) concentration of 10 ppm, weight reduction rate of 300 ° C., 25%, Showa Denko KK 10 parts by weight, inorganic filler (spherical fused silica, SO-25R, average particle size 0.5 μm, Adma Co., Ltd.) 40 parts by weight of Tex Co.) 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) Manufacture of prepreg The above-mentioned resin varnish is impregnated into a glass woven fabric (thickness 94 μm, manufactured by Nitto Boseki Co., Ltd., WEA-2116), dried in a heating furnace at 150 ° C. for 2 minutes, and the varnish solid content in the prepreg is reduced. About 50 parts by weight of prepreg was obtained.

(3) Manufacture of laminated board A predetermined number of the above-mentioned prepregs were stacked, 18 μm copper foils were stacked on both sides, and heat-pressed at a pressure of 4 MPa and a temperature of 200 ° C. for 2 hours to obtain a double-sided copper-clad laminate. .

(4) Manufacture of semiconductor device A predetermined circuit wiring is formed on the above-mentioned double-sided copper-clad laminate having a size of 50 mm × 50 mm, and a semiconductor element having a thickness of 0.75 mm and a size of 15 mm × 15 mm is applied to a flip chip bonder and a reflow furnace. The semiconductor device was fabricated by bonding and filling with underfill.

(Example 2)
Except for 30 parts by weight of cresol novolac type epoxy resin, 9 parts by weight of bisphenol A type epoxy resin (1), 5 parts by weight of washed metal hydroxide (1), and 50 parts by weight of inorganic filler. Prepared in the same manner as in Example 1.

(Example 3)
25 parts by weight of cresol novolac type epoxy resin, 8 parts by weight of bisphenol A type epoxy resin (1), 3 parts by weight of bisphenol A type epoxy resin (2), 2 parts by weight of washed metal hydroxide (1), It was produced in the same manner as in Example 1 except that the inorganic filler was changed to 60 parts by weight.

Example 4
19 parts by weight of cresol novolac type epoxy resin, 6 parts by weight of bisphenol A type epoxy resin (1), 2 parts by weight of bisphenol A type epoxy resin (2), 1 part by weight of washed metal hydroxide (1), It was produced in the same manner as in Example 1 except that the inorganic filler was 70 parts by weight.

(Example 5)
17 parts by weight of cresol novolac type epoxy resin, 4 parts by weight of bisphenol A type epoxy resin (1), 2 parts by weight of bisphenol A type epoxy resin (2), 5 parts by weight of washed metal hydroxide (1), It was produced in the same manner as in Example 1 except that the inorganic filler was 70 parts by weight.

(Example 6)
Example except that cresol novolac type epoxy resin was 12 parts by weight, bisphenol A type epoxy resin (1) was 4 parts by weight, bisphenol A type epoxy resin (2) was 2 parts by weight, and inorganic filler was 70 parts by weight. 1 was produced.

(Example 7)
36 parts by weight of cresol novolac type epoxy resin, 12 parts by weight of bisphenol A type epoxy resin (1), 5 parts by weight of bisphenol A type epoxy resin (2), 30 parts by weight of washed metal hydroxide (1), It was produced in the same manner as in Example 1 except that the inorganic filler was changed to 15 parts by weight.

(Example 8)
This was prepared in the same manner as in Example 1 except that the washed metal hydroxide (1) was 40 parts by weight and the inorganic filler was 10 parts by weight.

Example 9
Except for 28 parts by weight of cresol novolac type epoxy resin, 5 parts by weight of bisphenol A type epoxy resin (2), 45 parts by weight of washed metal hydroxide (1), and 10 parts by weight of inorganic filler. Prepared in the same manner as in Example 1.

(Example 10)
Except for 28 parts by weight of cresol novolac type epoxy resin, 5 parts by weight of bisphenol A type epoxy resin (2), 50 parts by weight of washed metal hydroxide (1), and 5 parts by weight of inorganic filler. Prepared in the same manner as in Example 1.

(Example 11)
This was prepared in the same manner as in Example 1 except that 36 parts by weight of the cresol novolac type epoxy resin, 9 parts by weight of the bisphenol A type epoxy resin (1), and 3 parts by weight of the bisphenol A type epoxy resin (2) were used.

(Example 12)
It was prepared in the same manner as in Example 1 except that 29 parts by weight of the cresol novolac type epoxy resin, 13 parts by weight of the bisphenol A type epoxy resin (1), and 6 parts by weight of the bisphenol A type epoxy resin (2) were used.

(Example 13)
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. This was prepared in the same manner as in Example 1 except that the weight reduction rate of 30% of Showa Denko KK was 10 parts by weight.

(Example 14)
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. This was prepared in the same manner as in Example 1 except that the weight reduction rate of 30% of Showa Denko KK was 10 parts by weight.

(Example 15)
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. This was prepared in the same manner as in Example 1 except that the weight reduction rate of 30% of Showa Denko KK was 10 parts by weight.

(Example 16)
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. This was prepared in the same manner as in Example 1 except that the weight reduction rate of 25%, manufactured by Showa Denko KK was 10 parts by weight.

(Example 17)
Prepared in the same manner as in Example 1 except that 34 parts by weight of phenol novolac epoxy resin (“Epiclon N-770”, epoxy equivalent 190, manufactured by Dainippon Ink & Chemicals, Inc.) was used instead of cresol novolac epoxy resin. did.

(Comparative Example 1)
44 parts by weight of cresol novolac type epoxy resin, 20 parts by weight of bisphenol A type epoxy resin (1), 14 parts by weight of bisphenol A type epoxy resin (2), and 20 parts by weight of washed metal hydroxide (1) This was prepared in the same manner as in Example 1 except that the inorganic filler was not blended.

(Comparative Example 2)
36 parts by weight of cresol novolac type epoxy resin, 12 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) Was prepared in the same manner as in Example 1 except that 30 parts by weight and 15 parts by weight of the inorganic filler were used.

(Comparative Example 3)
57 parts by weight of a cresol novolac type epoxy resin, 18 parts by weight of a bisphenol A type epoxy resin (1), 7 parts by weight of a bisphenol A type epoxy resin (2), and a curing accelerator (2-ethyl-4-methylimidazole) It was produced in the same manner as in Example 1 except that 2 parts by weight and 15 parts by weight of the inorganic filler were used and the washed metal hydroxide (1) was not blended.

The properties of the resin compositions, prepregs, laminates, and semiconductor devices obtained in the examples and comparative examples were evaluated. The results are shown in Tables 1 and 2.

The evaluation method is as follows.

1. A copper foil of a double-sided copper clad laminate having a linear expansion coefficient thickness of 1.2 mm was etched on the entire surface, and a 2 mm × 2 mm test piece was cut out from the obtained laminate, and 25 ° C./minute using TMA. The linear expansion coefficient in the thickness direction (Z direction) at ° C. was measured, and it was confirmed that the expected linear expansion coefficient was obtained.

2. A test piece of a semiconductor device was manufactured using a double-sided copper clad laminate having a thermal shock test thickness of 0.8 mm. The obtained test piece was treated for 1000 cycles in Fluorinert with -55 ° C for 10 minutes, 125 ° C for 10 minutes, and -55 ° C for 10 minutes as one cycle, and it was confirmed whether or not cracks occurred in the test piece.
○: No crack occurrence ×: Crack occurrence

3. Substrate Warpage A semiconductor device was fabricated using a double-sided copper clad laminate having a thickness of 0.4 mm, and the warpage of the substrate was measured.
Insulation reliability test On a double-sided copper clad laminate with a thickness of 0.4 mm, a mechanical drill is used to open a through hole with a diameter of 0.4 mm and a distance between walls of 0.4 mm, and then plating and circuit wiring are formed. The film was treated for 1000 h under the conditions of ° C., 85% RH and applied voltage of 50V, and the insulation resistance was measured at 100V.
○: 1.0 × 10 ¹⁰ Ω or more ×: 1.0 × 10 ¹⁰ Ω or less

4). Press formability One layer of the above prepreg and 18 μm copper foil are stacked on top and bottom of a test substrate having a pattern in which inner layer circuit copper has a thickness of 35 μm and 20 mm diameter unclad are arranged, pressure 4 MPa, temperature 200 ° C. After 2 hours heating and pressure forming, the entire surface of the copper foil was etched to confirm that there was no press molding void.
○: No forming void ×: With forming void

5. Arithmetic surface roughness: Ra
After etching the copper foil of a double-sided copper clad laminate with a thickness of 0.6 mm, desmearing is performed under conditions of swelling: 80 ° C., 5 minutes, roughening: 80 ° C., 10 minutes, neutralization: 40 ° C., 5 minutes. The Ra of the substrate was measured.

6). Glass transition temperature A copper foil of a double-sided copper-clad laminate with a thickness of 0.6 mm is entirely etched, and a 10 mm × 60 mm test piece is cut out from the obtained laminate, and a dynamic viscoelasticity measuring device (DMA983, TA instrument) Was used, and the peak position of tan δ was defined as the glass transition temperature.

7). Weight reduction rate After etching the entire surface of the copper foil of the double-sided copper-clad laminate, the cured product of the insulating resin composition is scraped off, and the temperature is raised from 30 ° C. to 500 ° C. at a rate of 10 ° C./min using TG-DTA. 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. A double-sided copper-clad laminate having a water absorption rate of 0.2 mm was entirely etched, and a 50 mm × 50 mm test piece was cut out from the obtained laminate and measured according to JIS C 6481.

10. Peel strength A double-sided copper clad laminate having a thickness of 0.6 mm was measured in accordance with JIS C 6481.

11. A test piece was prepared by cutting a double-sided copper-clad laminate having a heat-absorbing solder heat-resistant thickness of 0.2 mm into 50 mm × 50 mm and performing half-surface etching according to JIS C 6481. 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 ×: Fluffy

As is clear from Tables 1 and 2, Examples 1 to 17 have a low linear expansion coefficient of the cured product of the insulating resin composition, and (a) an epoxy resin containing a metal hydroxide and a novolac type epoxy resin, and An insulating resin composition of the present invention containing an inorganic filler, and a prepreg, a laminate and a semiconductor device using the same.
Examples 1 to 17 all had good results in insulation reliability, flame retardancy, and moisture absorption heat resistance.
On the other hand, Comparative Example 1 does not contain an inorganic filler, and since the content of novolac-type epoxy with respect to the epoxy resin is small, the coefficient of linear expansion increases, and cracks and blisters are observed in the thermal shock test and moisture absorption solder heat test. Occurred.
In Comparative Example 2, the concentration of metal ionic impurities in the metal hydroxide was high, and the insulation resistance decreased in the insulation reliability test.
Moreover, since the comparative example 3 did not contain (a) metal hydroxide and there was little content of an inorganic filler, a flame retardance fell.

  The insulating resin composition of the present invention can be suitably used for a prepreg, a laminate using the prepreg, and a semiconductor device comprising the laminate, but in addition, flame retardancy, solder resistance, insulation reliability, heat Excellent in impact and other reliability, so it can be used to protect automotive electronic component devices such as power electronics devices such as fuel cell vehicles and hybrid vehicles, and motor drive electronic component chips used in hybrid vehicles. It is also possible to use for the resin part to be used.

Claims (15)

An insulating resin composition used for impregnating a fiber base material to form a sheet-like prepreg, 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) a metal hydroxide having a concentration of metal ionic impurities of 500 ppm or less,
(B) An insulating resin composition comprising a novolac type epoxy resin and an epoxy resin which is not substantially halogenated. The insulating resin composition according to claim 1, wherein the insulating resin composition contains an inorganic filler other than (c) a metal hydroxide. The insulating resin composition according to claim 1 or 2, wherein a weight reduction rate at 300 ° C of the insulating resin composition is 15% or less. The insulating resin composition according to any one of claims 1 to 3, wherein the average particle diameter of the (a) metal hydroxide is 0.1 µm or more and 10 µm or less. 5. The insulating resin composition according to claim 1, wherein (a) the weight reduction rate of the metal hydroxide at 300 ° C. is 20 wt% or more and 40 wt% or less. The insulating resin composition according to any one of claims 1 to 5, wherein the content of the (a) metal hydroxide is 1 wt% or more and 50 wt% or less as the whole insulating resin composition. . The metal ionic impurities contained in the metal hydroxide (a) are lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, francium ion, beryllium ion, calcium ion, strontium ion, barium ion, zinc ion. The insulating resin composition according to claim 1, wherein the insulating resin composition is at least one selected from the group consisting of tin ions and lead ions. The insulating resin composition according to any one of claims 1 to 7, wherein the metal hydroxide (a) is selected from the group consisting of magnesium hydroxide, aluminum hydroxide, gallium hydroxide, and zirconyl hydroxide. The insulating resin composition according to any one of claims 2 to 8, wherein the inorganic filler other than (c) the metal hydroxide is a metal oxide. The insulating resin composition according to claim 9, wherein the metal oxide is fused silica. A prepreg obtained by impregnating a fiber base material with the insulating resin composition according to any one of claims 1 to 10. The prepreg according to claim 11, wherein the fiber substrate is made of glass fiber. The prepreg according to claim 11, wherein the fiber substrate is made of an organic fiber. A laminate comprising one or more of the prepregs according to any one of claims 11 to 13 laminated and heated and pressed. A semiconductor device comprising a semiconductor element mounted on the laminate according to claim 14.