JP2011099072A - Resin composition, insulating layer, prepreg, laminate, print wiring board and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low elastic, low thermal expandable, and low hygroscopic resin composition, and to provide insulating layers, prepregs, laminates, print wiring boards and semiconductor devices each provided with low elasticity, low thermal expansion, and low hygroscopicity by using the resin composition. <P>SOLUTION: The resin composition contains (A) a thermosetting resin and (B) particles having vacancies inside. The incorporation of the particles having vacancies inside (B) provides the resin composition with low elasticity, low thermal expansion, and low hygroscopicity. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition excellent in low elasticity and low thermal expansion. The present invention also relates to an insulating layer, a prepreg, a laminated board, a printed wiring board, and a semiconductor device using the resin composition.

  In the field of semiconductors, a trend of shifting from conventional surface mounting to area mounting is progressing due to progress in high-density mounting technology, and new packages such as BGA and CSP are appearing and increasing. Therefore, the rigid substrate for interposers has been attracting more attention than before.

  Further, in recent years, along with demands for higher functionality of electronic devices, electronic components have been integrated with higher density and further mounted with higher density. For this reason, printed wiring boards and the like for high-density mounting used for these are becoming smaller and higher in density than ever before. Along with this, since the printed wiring board is required to be thin, warping of the substrate has become a problem. In order to suppress this, increasing the elasticity of printed wiring board materials has been studied (for example, see Patent Document 1). However, with the increase in elasticity of materials, there has been a problem that cracks are likely to occur under severe conditions such as high temperature and high humidity.

  On the other hand, in order to improve the crack resistance, a printed circuit board material having low elasticity and high heat resistance has been studied (for example, see Patent Document 2). However, as described above, warpage is likely to occur with a decrease in the elastic modulus of the substrate. Therefore, when the printed wiring board material is made low elastic, it is necessary to have low thermal expansion.

JP 2004-231847 A JP 2006-22309 A

The present invention is to provide a resin composition excellent in low elasticity, low thermal expansibility and low hygroscopicity.
Another object of the present invention is to provide an insulating layer, a prepreg, a laminate, a printed wiring board, and a semiconductor device that are excellent in low elasticity, low thermal expansion, and low hygroscopicity by using the resin composition.

Such an object is achieved by the present inventions (1) to (13) below.
(1) A resin composition comprising a thermosetting resin (A) and particles (B) having pores therein.
(2) The resin composition according to (1), wherein the particles (B) having pores therein are those in which the periphery of the porous particles (B1) is covered with a coating layer (B2).
(3) The resin composition according to (2), wherein the porous particle (B1) is an inorganic compound.
(4) The resin composition according to (3), wherein the inorganic compound is silica.
(5) The resin composition according to any one of (2) to (4), wherein the coating layer (B2) is an inorganic compound.
(6) The resin composition according to any one of (2) to (5), wherein the coating layer (B2) is an organosilicon compound and / or a polymer thereof.
(7) The thermosetting resin (A) includes at least one selected from the group consisting of an epoxy resin, a cyanate ester resin, and a phenol resin, according to any one of (1) to (6). Resin composition.
(8) An insulating layer obtained by thermosetting the resin composition according to any one of (1) to (7).
(9) A prepreg obtained by impregnating a base material with the resin composition according to any one of (1) to (7).
(10) A laminate obtained by superposing one or more prepregs according to (9) above, placing a metal foil on at least one outer surface, and heat-pressing the laminate. .
(11) A printed wiring board obtained by using the insulating layer according to (8).
(12) A printed wiring board obtained by using the laminated board according to (10).
(13) A semiconductor device obtained by using the printed wiring board according to (11) or (12).

According to the present invention, it is possible to provide a resin composition excellent in low elasticity, low thermal expansibility, and low hygroscopicity.
In addition, by using the resin composition, it is possible to provide an insulating layer, a prepreg, a laminated board, a printed wiring board, and a semiconductor device that are excellent in low elasticity, low thermal expansion, and low hygroscopicity.

  Hereinafter, the resin composition, insulating layer, prepreg, laminate, printed wiring board and semiconductor device of the present invention will be described.

The resin composition of the present invention comprises a thermosetting resin (A) and particles (B) having pores therein.
The insulating layer of the present invention is obtained by thermosetting the resin composition.
Moreover, the prepreg of the present invention is characterized by comprising the resin composition.
In addition, the laminated board of the present invention is obtained by stacking one or two or more of the prepregs, placing a metal foil on at least one outer surface, and heating and pressing.
Moreover, the printed wiring board of the present invention is obtained using the insulating layer.
The semiconductor device of the present invention is obtained using the printed wiring board.

  First, the resin composition will be described. The resin composition includes a thermosetting resin (A) and particles (B) having pores therein.

The thermosetting resin (A) is not particularly limited. For example, epoxy resin, cyanate ester resin, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, phenol resin, unsaturated polyester resin, polyimide, polyurethane Resins having a triazine ring such as maleic resin, melamine resin, urea resin and epoxy acrylate, unsaturated polyester resin, bismaleimide resin, polyurethane resin, diallyl phthalate resin, silicone resin, resin having benzoxazine ring and cyanate resin Can be mentioned. Among these, since the thermosetting resin (A) is excellent in heat resistance, electrical characteristics, and cost, it is at least one selected from the group consisting of epoxy resins, cyanate ester resins, and phenol resins. It is particularly preferred.
One of these can be used alone, or two or more having different weight average molecular weights can be used in combination, or one or two or more of these prepolymers can be used in combination.

Among these thermosetting resins (A), the epoxy resin has high heat resistance, is excellent in insulation and insulation reliability, and is inexpensive, as widely used as a laminated board material. This is preferable.
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, and bisphenol Z type epoxy resin. Bisphenol type epoxy resins, phenol novolac type epoxy resins, cresol novolac epoxy resins and other novolac type epoxy resins, biphenyl type epoxy resins, xylylene type epoxy resins, biphenyl aralkyl type epoxy resins and other aryl alkylene type epoxy resins, naphthalene type epoxy resins , Anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamanta Type epoxy resins, fluorene type epoxy resins and the like.
One of these can be used alone, or two or more having different weight average molecular weights can be used in combination, or one or two or more of these prepolymers can be used in combination.

Among these thermosetting resins (A), the cyanate ester resin can reduce the thermal expansion coefficient of the insulating layer, and further, the electrical characteristics of the insulating layer (low dielectric constant, low dielectric loss tangent). It is preferable because of excellent mechanical strength.
The cyanate ester resin can be obtained, for example, by reacting a halogenated cyanide compound with a phenol and prepolymerizing it by a method such as heating as necessary. Specific examples include bisphenol type cyanate resins such as novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, and tetramethylbisphenol F type cyanate resin. Among these, novolac type cyanate resin is preferable. Thereby, the heat resistance improvement by a crosslinking density increase and flame retardance, such as a resin composition, can be improved. This is because the novolac-type cyanate resin forms a triazine ring after the curing reaction. Furthermore, it is considered that novolak-type cyanate resin has a high benzene ring ratio due to its structure and is easily carbonized. Furthermore, even when the insulating layer has a thickness of 0.5 mm or less, excellent rigidity can be imparted to the manufactured insulating layer. In particular, since the rigidity during heating is excellent, the reliability when mounting a semiconductor element is also particularly excellent.

  As said novolak-type cyanate resin, what is shown by following formula (1) can be used, for example.

  The average repeating unit n of the novolak cyanate resin represented by the formula (1) is not particularly limited, but is preferably 1 to 10, and particularly preferably 2 to 7. When the average repeating unit n is less than the lower limit, the novolak cyanate resin has low heat resistance, and the low-mer may be desorbed and volatilized during heating. Moreover, when average repeating unit n exceeds the said upper limit, melt viscosity will become high too much, and when it uses for a prepreg, a moldability may fall.

Although the weight average molecular weight of the cyanate ester resin is not particularly limited, a weight average molecular weight of 500 to 4,500 is preferable, and 600 to 3,000 is particularly preferable. When the prepreg is produced when the weight average molecular weight is less than the lower limit, tackiness may occur, and when the prepregs come into contact with each other, they may adhere to each other or transfer of the resin may occur. In addition, when the weight average molecular weight exceeds the upper limit, the reaction becomes too fast, and when used in an insulating layer, molding defects may occur or the interlayer peel strength may be lowered.
The weight average molecular weight of the cyanate ester resin or the like can be measured by, for example, GPC (gel permeation chromatography, standard substance: converted to polystyrene).

  Further, although not particularly limited, the cyanate ester resin can be used alone or in combination of two or more having different weight average molecular weights, or one or two or more prepolymers thereof. Can also be used together.

  Although content of the said cyanate ester resin is not specifically limited, 5-50 weight part of the said resin composition or the said resin layer is preferable, and 20-40 weight part is especially preferable. When the content is less than the lower limit, it may be difficult to form a prepreg, and when the content exceeds the upper limit, the strength of the prepreg or the resin layer may be reduced.

  Among these thermosetting resins (A), a phenol resin is preferable because heat resistance and punchability are improved. The phenol resin is not particularly limited, and examples of the phenol resin include novolac-type phenol resins, resol-type phenol resins, and arylalkylene-type phenol resins. Among these, arylalkylene type phenol resins are preferable. Thereby, heat resistance can be improved further. Examples of the aryl alkylene type phenol resin include a xylylene type phenol resin and a biphenyl dimethylene type phenol resin. A biphenyl dimethylene type phenol resin can be shown, for example by following formula (2).

  Although n of the biphenyl dimethylene type | mold phenol resin shown by Formula (2) is not specifically limited, 1-12 are preferable and 2-8 are especially preferable. If it is less than this, the heat resistance may decrease. Moreover, when more than this, since compatibility with other resin falls and workability | operativity may worsen, it is unpreferable. The combination of the aforementioned cyanate resin and / or prepolymer thereof (particularly a novolac type cyanate resin) and an arylalkylene type phenol resin can control the crosslink density and improve the adhesion between the metal and the resin.

   Although content of the said phenol resin is not specifically limited, 1 to 55 weight% of the whole resin composition is preferable, and 5 to 40 weight% is especially preferable. When the phenol resin is less than the lower limit value, the heat resistance may be lowered, and when the upper limit value is exceeded, the characteristics of low thermal expansion may be impaired. The weight average molecular weight of the phenol resin is not particularly limited, but a weight average molecular weight of 400 to 18,000 is preferable, and 500 to 15,000 is particularly preferable. If the weight average molecular weight is less than the lower limit, problems such as tackiness may occur in the prepreg, and if the upper limit is exceeded, the impregnation property to the base material is reduced during preparation of the prepreg, and a uniform product is obtained. Problems such as inability to occur.

  The resin composition includes particles (B) having pores therein. As a result, the voids in the particles (B) having voids therein also increase the porosity of the resin composition. Therefore, an insulating layer, a prepreg, a laminate, and a printed wiring obtained using the resin composition Low elasticity can be imparted to the plate. The shape of the particle (B) having pores in the inside is not particularly limited. For example, the particle having a hollow inside and the periphery of the porous particle (B1) are covered with the coating layer (B2). Particles and the like. Among these, particles in which the periphery of the porous particles (B1) is covered with the coating layer (B2) are particularly preferable. Thereby, since the adsorption | suction of the water to the inside of a void | hole of the particle | grains (B) which have a void | hole in the said inside can be prevented by a coating layer (B2), the hygroscopic property of the said resin composition can be reduced more. Furthermore, heat resistance can be improved. Moreover, the compressive strength of the resin composition can be reduced. Specifically, when processing such as drilling and cutting the molded product of the resin composition, particles can be easily crushed by having pores inside, so that drillability, cutting processing Insulating layers, prepregs, laminates and printed wiring boards having excellent properties can be obtained.

  The shape of the porous particles (B1) is not particularly limited, but is formed by agglomerating particles of porous material, particles of fibrous material, fine particles of non-uniform shape / size, template agent And particles having a plurality of pores formed on the surface and inside thereof by removing the template agent by firing or the like. Among these, in order to give low elasticity to the molded article of the resin composition, particles formed by agglomerating fine particles having non-uniform shapes and sizes are particularly preferable.

  The material of the porous particles (B1) is not particularly limited, and examples thereof include organic compounds such as carbon fiber, carbon nanotube, and graphite, and inorganic compounds such as talc, alumina, glass, silica, and aluminum hydroxide. Among these, since the flame retardancy is high, an inorganic compound is particularly preferable. Furthermore, silica is particularly preferable because of its low thermal expansion.

  Although it does not specifically limit as said coating layer (B2), Organic compounds, such as rubber | gum and a polymer, an organic silicon compound and / or its polymer, inorganic compounds, such as titanium, an alumina, a silica, etc. are mentioned. Among these, since the flame retardancy is high, an inorganic compound is more preferable. Furthermore, when the material of the porous particles (B1) is silica, from the point of high affinity and high adhesion with the porous particles (B1), or high workability at the time of coating, Organosilicon compounds and / or polymers thereof are particularly preferred.

  The coating layer (B2) has a nonporous surface by adding an organosilicon compound in a solvent, coating the porous particles (B1) with an organosilicon compound and / or a polymer thereof, and firing the resultant. By using such a laminated plate, a laminate having high insulation reliability and low thermal expansion can be produced.

The average particle diameter of the particles (B) having pores therein is not particularly limited, but is preferably 0.01 to 8 μm, particularly preferably 0.2 to 3 μm. If the particle diameter of the particles (B) having pores in the interior is smaller than the lower limit, the viscosity of the varnish becomes high, which may affect the workability at the time of preparing the prepreg. Moreover, when higher than the said upper limit, phenomena, such as sedimentation of the particle | grains (B) which have a void | hole inside the said varnish, will arise, and it is not desirable.
Further, spherical fused silica having an average particle size of 5 μm or less is preferable, and spherical fused silica having an average particle size of 2 μm or less is particularly preferable. Thereby, the filling property of the particles (B) having pores in the interior can be improved.

  The content of the particles (B) having pores therein is preferably 10 to 75% by weight, particularly preferably 15 to 70% by weight, based on the entire resin composition. When the particles (B) having pores in the interior are within the above range, the resin composition can be imparted with low thermal expansion and low hygroscopicity. In addition, although not particularly limited, the particles (B) having pores in the interior can be used alone or in combination of two or more different types of particles (B) having pores in the interior. Alternatively, it may be used in combination with particles that do not have pores inside.

  In the resin composition of this invention, additives, such as a coupling agent and a hardening accelerator, can be added in the range which does not impair a characteristic as needed.

Next, the insulating layer will be described.
The insulating layer of the present invention is not particularly limited, and examples thereof include built-up, prepreg, resin-attached carrier material, cured film, protective film, insulating film, resin-attached carrier material, and an insulating layer of a printed wiring board described later. These insulating layers can be produced by impregnating or applying the resin composition to a substrate.

Next, the prepreg will be described.
The prepreg of the present invention is obtained by impregnating a base material with the resin composition. Thereby, the prepreg excellent in heat resistance, low expansibility, and a flame retardance can be obtained.
Examples of the base material include glass fiber base materials such as glass woven fabric, glass non-woven fabric, and glass paper, woven fabric and non-woven fabric made of synthetic fibers such as paper, aramid, polyester, aromatic polyester, and fluororesin, and metal fibers. Woven fabrics, nonwoven fabrics, mats and the like made of carbon fibers, mineral fibers, and the like. These substrates may be used alone or in combination. Among these, since the rigidity and dimensional stability of a prepreg can be improved, a glass fiber base material is preferable.

  Examples of the method for impregnating the base material with the resin composition include a method of immersing the base material in a resin varnish, a method of applying with various coaters, and a spraying method. Among these, since the impregnation property of the resin composition with respect to the base material can be improved, a method of immersing the base material in the resin varnish is preferable. In addition, when a 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 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, cyclopentanone, cyclohexanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
The solid content of the resin varnish is not particularly limited, but the solid content of the resin composition is preferably 30 to 80% by weight, and particularly preferably 40 to 70% by weight. Thereby, the impregnation property to the base material of the resin varnish can be improved.
A prepreg can be obtained by impregnating the base material with the resin composition and drying at a predetermined temperature, for example, 90 to 180 ° C.

Next, a laminated board is demonstrated.
The laminate of the present invention is obtained by heating and pressing the above prepreg. Thereby, the laminated board excellent in heat resistance and low thermal expansibility can be obtained. When one prepreg is used, the metal foil is overlapped on both the 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 heat-pressing 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. Although the pressure to pressurize is not particularly limited, it is preferably 1.5 to 5 MPa, and particularly preferably 2 to 4 MPa.
Further, if necessary, post-curing can be performed at a temperature of 150 to 300 ° C. with a high-temperature soot.

  The metal foil is not particularly limited. For example, copper and copper-based alloy, aluminum and aluminum-based alloy, silver and silver-based alloy, gold and gold-based alloy, zinc and zinc-based alloy, nickel and nickel-based alloy, tin and tin And metal foils such as iron alloys, iron and iron alloys. Among these, copper and copper-based alloys are particularly preferable because of excellent dielectric characteristics and cost.

Next, the printed wiring board of the present invention will be described.
The printed wiring board of this invention uses the said insulating layer and the said prepreg for an insulating layer. Moreover, the printed wiring board of this invention uses the laminated board as described above for an inner layer circuit board. The case where the said laminated board is used as an inner-layer circuit board is demonstrated.
A circuit is formed on one side or both sides of the laminated board to be the inner circuit board. In some cases, through holes can be formed by drilling or laser processing, and electrical connection on both sides can be achieved by plating or the like. Moreover, a multilayer printed wiring board can be obtained by superposing a commercially available resin sheet or the prepreg on the inner layer circuit board and performing heat and pressure molding.
Specifically, the insulating layer side of the resin sheet and the inner layer circuit board are combined, vacuum-pressed using a pressure-pressing laminator, etc., and then the insulating layer is heat-cured with a hot-air dryer or the like. Can be obtained. Although it does not specifically limit as conditions to heat-press form here, If an example is given, it can implement at the temperature of 60-160 degreeC, and the pressure of 0.2-3 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.

  Further, the prepreg can be obtained by superimposing the prepreg on the inner circuit board and heating and pressing it with a flat plate press or the like. Although it does not specifically limit as conditions to heat-press form here, For example, it can implement at the temperature of 140-240 degreeC, and the pressure of 1-4 MPa. In the heat and pressure forming by such a flat plate press apparatus or the like, the insulating layer is heat-cured simultaneously with the heat and pressure forming.

  The method for producing the printed wiring board includes a step of continuously laminating the resin sheet or prepreg on the surface of the inner layer circuit board on which the inner layer circuit pattern is formed, and a step of forming a conductor circuit layer by a semi-additive method. .

Curing of the insulating layer formed from the resin sheet or the prepreg may be left in a semi-cured state in order to facilitate the subsequent laser irradiation and removal of the resin residue and improve desmearing properties. In addition, the first insulating layer is partially cured (semi-cured) by heating at a temperature lower than the normal heating temperature, and one or more insulating layers are further formed on the insulating layer to form a semi-cured insulating layer. By heat-curing again to such an extent that there is no practical problem, the adhesion between the insulating layer and between the insulating layer and the circuit can be improved. In this case, the semi-curing temperature is preferably 80 to 200 ° C, more preferably 100 to 180 ° C. In the next step, laser is irradiated to form an opening in the insulating layer, but it is necessary to peel off the substrate before that. There is no particular problem with the peeling of the base material either after the insulating layer is formed, before heat curing, or after heat curing.
The inner layer circuit board used when obtaining the printed wiring board is preferably, for example, one in which a predetermined conductor circuit is formed by etching or the like on both surfaces of a copper clad laminate and the conductor circuit portion is blackened. Can be used.

  Next, the insulating layer is irradiated with laser to form an opening. As the laser, an excimer laser, a UV laser, a carbon dioxide laser, or the like can be used.

  Resin residues after laser irradiation are preferably removed with an oxidizing agent such as permanganate or dichromate. Further, the surface of the smooth insulating layer can be simultaneously roughened, and the adhesion of the conductive wiring circuit formed by subsequent metal plating can be improved.

Next, an outer layer circuit is formed. The outer layer circuit is formed by connecting the insulating resin layers by metal plating and forming an outer layer circuit pattern by etching. A printed wiring board can be obtained in the same manner as when a resin sheet or prepreg is used.
When a resin sheet having a metal foil or a prepreg is used, a circuit may be formed by etching for use as a conductor circuit without peeling off the metal foil. In that case, if an insulating resin sheet with a base material using a thick copper foil is used, it becomes difficult to make a fine pitch in subsequent circuit pattern formation, so use an ultrathin copper foil of 1 to 5 μm, or 12 to 18 μm. In some cases, the copper foil is half-etched to a thickness of 1 to 5 μm by etching.

  Further, an insulating layer may be laminated and a circuit may be formed in the same manner as described above. However, a solder resist is formed on the outermost layer after the circuit is formed in designing the printed wiring board. The method for forming the solder resist is not particularly limited. For example, a method of laminating (laminating) a dry film type solder resist, forming by exposure and development, or forming a printed liquid resist by exposure and development It is done by the method to do. In addition, when using the obtained printed wiring board for a semiconductor device, in order to mount a semiconductor element, the electrode part for a connection is provided. The connecting electrode portion can be appropriately coated with a metal film such as gold plating, nickel plating, or solder plating. A printed wiring board can be manufactured by such a method.

Next, a semiconductor device manufactured using the printed wiring board of the present invention will be described.
Although the manufacturing method of a semiconductor device is not specifically limited, For example, the said printed wiring board is used and a printed wiring board and a semiconductor element are connected via a solder bump. A method for connecting a semiconductor element and a printed wiring board is to use a flip chip bonder or the like to align a connection electrode portion on a substrate and a metal bump of a semiconductor element, and then a heating device such as an IR reflow device or a hot plate The solder bumps are heated to the melting point or higher by using, and the printed wiring board and the solder bumps are fused and connected. In order to improve connection reliability, a metal layer having a relatively low melting point, such as solder paste, may be formed in advance on the connection electrode portion on the printed wiring board. Prior to this joining step, the connectivity can also be improved by applying a flux to the solder bumps and / or the surface layer of the connection electrode portion on the printed wiring board.

  Next, a liquid sealing resin is filled between the printed wiring board and the semiconductor element to obtain a semiconductor device.

Example 1
(1) Preparation of resin varnish 25 parts by weight (hereinafter abbreviated as “part”) of novolak-type cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30), bisphenol A-type cyanate resin (AroCy B Epoxy Co., Ltd., AroCy B-) 30) 25 parts, 1 part of an epoxy silane coupling agent (manufactured by Nihon Unicar Co., Ltd., A-187) and 1 part of catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2MZ) are dissolved in methyl ethyl ketone at room temperature and porous as a filler. 48 parts of silica (P15C, manufactured by JGC Catalysts & Chemicals Co., Ltd.) was added and stirred for 10 minutes using a high-speed stirrer to obtain a resin varnish.
(2) Preparation of prepreg The resin varnish was impregnated into a glass woven fabric (thickness 200 μm, manufactured by Nitto Boseki Co., Ltd., WEA-7628), dried in a heating furnace at 120 ° C. for 2 minutes, and varnish solids (resin in prepreg And a component occupying about 50% of silica were obtained.

(3) Production of laminated plate A predetermined number of the prepregs are laminated, 18 μm copper foils are laminated on both sides, and a laminated plate having copper foils on both sides is obtained by heating and pressing at a pressure of 4 MPa and a temperature of 200 ° C. for 2 hours. It was.

(4) Manufacture of printed wiring board Using a laminated board having copper foil on both sides, after drilling with a drilling machine, conducting conduction between upper and lower copper foils by electroless plating and etching the copper foils on both sides Thus, inner layer circuits were formed on both sides. (L (conductor circuit width) / S (conductor circuit width) = 120/180 μm, clearance holes 1 mmφ, 3 mmφ, slit 2 mm) Next, a chemical solution containing hydrogen peroxide and sulfuric acid as main components in the inner layer circuit (Asahi Denka Kogyo) Unevenness was formed by a roughening treatment by spraying Tech Co., Ltd. (Tech SO-G).

  Next, a commercially available resin film (also referred to as a build-up material) (Ajinomoto Fine Techno Co., ABF GX-13, thickness 40 μm) is laminated on the inner circuit using a vacuum laminator, temperature 170 ° C., time 60 minutes. Heat-cured to obtain a laminate.

  Thereafter, an opening portion (blind via hole) of φ60 μm was formed on the prepreg of the laminate obtained above using a carbonic acid laser device, and a swelling liquid (Swelling Dip Securigant P, manufactured by Atotech Japan Co., Ltd.) at 70 ° C. ) For 5 minutes, and further immersed in an aqueous solution of potassium permanganate at 80 ° C. (manufactured by Atotech Japan, Concentrate Compact CP) for 15 minutes, followed by neutralization and roughening treatment. Next, after passing through degreasing, catalyst application, and activation steps, an electroless copper plating film was formed with a power supply layer of about 0.5 μm. Next, a 25 μm thick UV-sensitive dry film (AQ-2558 manufactured by Asahi Kasei Co., Ltd.) is bonded to the surface of the power supply layer with a hot roll laminator, and a chromium having a pattern with a minimum line width / line spacing of 20/20 μm is drawn. Using a vapor deposition mask (manufactured by Towa Process Co., Ltd.), the position was adjusted, exposure was performed with an exposure apparatus (UX-1100SM-AJN01 manufactured by USHIO INC.), And development was performed with a sodium carbonate aqueous solution to form a plating resist.

Next, electrolytic copper plating (81-HL, manufactured by Okuno Pharmaceutical Co., Ltd.) was performed at 3 A / dm ² for 30 minutes using the power feeding layer as an electrode to form a copper wiring having a thickness of about 25 μm. Here, the plating resist was peeled off using a two-stage peeling machine. Each chemical solution is mainly composed of monoethanolamine solution (R-100 manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the first stage alkaline aqueous solution layer, and potassium permanganate and sodium hydroxide as the main ingredients in the second stage oxidizing resin etchant. An aqueous solution of acidic amine (Mc. Dicer 9279, manufactured by Nihon McDermid Co., Ltd.) was used for neutralization.

  Then, the power feeding layer was immersed in an ammonium persulfate aqueous solution (AD-485 manufactured by Meltex Co., Ltd.) to remove it by etching and ensure insulation between the wirings. Next, the insulating layer was finally cured at a temperature of 200 ° C. for 60 minutes, and finally a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) was formed on the circuit surface to obtain a printed wiring board.

(5) Manufacture of Semiconductor Device The multilayer printed wiring board was used by cutting the connection electrode portion subjected to nickel gold plating corresponding to the solder bump arrangement of the semiconductor element into a size of 50 mm × 50 mm. . A semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 0.8 mm) has a solder bump formed of a eutectic of Sn / Pb composition, and a circuit protective film of the semiconductor element is a positive photosensitive resin (Sumitomo Bakelite). What was formed by company CRC-8300) was used. In assembling the semiconductor device, first, a flux material was uniformly applied to the solder bumps by a transfer method, and then mounted on a multilayer printed wiring board by thermocompression bonding using a flip chip bonder device.
Next, after solder bumps were melt-bonded in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The curing condition of the liquid sealing resin was a temperature of 150 ° C. and 120 minutes.

(Example 2)
Example 1 was repeated except that a resin varnish described below was used.
Novolac type cyanate resin (Lonza Japan Co., Ltd., Primaset PT-60) 25 parts, biphenyl alkylene type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000SH) 25 parts, epoxy silane type coupling agent (Nippon Unicar Corporation) 1 part of a company, A-187) and 1 part of a catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2MZ) are dissolved in methyl ethyl ketone at room temperature, and 28 parts of porous silica (manufactured by JGC Catalysts and Chemicals, L15C) as a filler 20 parts of aluminum hydroxide (manufactured by Showa Denko KK, HP-350) was added and stirred for 10 minutes using a high-speed stirrer to obtain a resin varnish.

(Example 3)
Example 1 was repeated except that a resin varnish described below was used.
29 parts of novolak type cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30), 19 parts of novolak type epoxy resin (Dainippon Ink and Chemicals, Epicron N-775), epoxy silane type coupling agent (Japan) Unicar Co., Ltd., A-187) 1 part and catalyst (Shikoku Kasei Kogyo Co., Ltd., 2MZ) 1 part are dissolved in methyl ethyl ketone at room temperature, and silica particles (admatechs Co., Ltd., SO-32R) 40 are used as fillers. Part and 10 parts of porous silica (manufactured by JGC Catalysts & Chemicals Co., Ltd., N15C) were added and stirred for 10 minutes using a high speed stirrer to obtain a resin varnish.

(Comparative Example 1)
Example 1 was repeated except that a resin varnish described below was used.
19 parts of novolak type cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30), 19 parts of bisphenol A type cyanate resin (AroCy B-30, manufactured by Asahi Kasei Epoxy Co., Ltd.), epoxy silane type coupling agent (Nippon Unicar Corporation) 1 part of a company, A-187) and 1 part of a catalyst (manufactured by Shikoku Chemicals Co., Ltd., 2MZ) are dissolved in methyl ethyl ketone at room temperature, and 60 parts of silica particles (SFP-10X, manufactured by Denki Kagaku Kogyo Co., Ltd.) are used as a filler. Was added and stirred for 10 minutes using a high-speed stirrer to obtain a resin varnish.

(Comparative Example 2)
Example 1 was repeated except that a resin varnish described below was used.
19 parts of novolak type cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30), 19 parts of bisphenol A type cyanate resin (AroCy B-30, manufactured by Asahi Kasei Epoxy Co., Ltd.), epoxy silane type coupling agent (Nippon Unicar Corporation) 1 part of a company, A-187) and 1 part of a catalyst (manufactured by Shikoku Chemicals Co., Ltd., 2MZ) are dissolved in methyl ethyl ketone at room temperature, and 60 parts of silica particles (manufactured by Admatechs Co., Ltd., SO-32R) are used as a filler. The mixture was added and stirred for 10 minutes using a high-speed stirrer to obtain a resin varnish.

(Comparative Example 3)
Example 1 was repeated except that a resin varnish described below was used.
19 parts of novolac type cyanate resin (Lonza Japan Co., Ltd., Primaset PT-60), 19 parts biphenyl alkylene type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000SH), epoxy silane type coupling agent (Nihon Unicar Corporation) 1 part of a company, A-187) and 1 part of a catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2MZ) are dissolved in methyl ethyl ketone at room temperature, and 40 parts of silica particles (manufactured by Admatechs Co., Ltd., SO-32R) and 20 parts of aluminum hydroxide (manufactured by Showa Denko KK, HP-350) was added and stirred for 10 minutes using a high-speed stirrer to obtain a resin varnish.

(Comparative Example 4)
Example 1 was repeated except that a resin varnish described below was used.
23 parts of novolak type cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30), 15 parts of novolak type epoxy resin (Dainippon Ink and Chemicals, Epicron N-775), epoxy silane type coupling agent (Japan) Unicar Co., Ltd., A-187) 1 part and catalyst (Shikoku Kasei Kogyo Co., Ltd., 2MZ) 1 part are dissolved in methyl ethyl ketone at room temperature, and silica particles (admatechs Co., Ltd., SO-32R) 40 are used as fillers. Part and 20 parts of aluminum hydroxide (manufactured by Showa Denko KK, HP-350) were added and stirred for 10 minutes using a high-speed stirrer to obtain a resin varnish.

The evaluation method of the obtained laminated board is shown to (1)-(4).
(1) Coefficient of linear expansion A laminated board having a copper foil on both sides with a thickness of 1.2 mm is etched on the entire surface, a 2 mm × 2 mm test piece is cut out from the obtained laminated board, and the thickness direction (Z direction) is obtained using TMA. The linear expansion coefficient was measured at 5 ° C./min.

(2) Moisture-absorbing solder heat resistance A test piece was prepared by cutting 50 mm × 50 mm from a laminate having copper foil on both sides with a thickness of 0.6 mm and performing half-side etching according to JIS 6481. After processing with a 125 ° C. pressure cooker, the copper foil surface was floated down in a 260 ° C. solder bath, and the processing time for blistering after 180 seconds was measured.

(3) Elastic modulus The entire copper foil of the laminate having copper foil on both sides was etched, a 2 mm × 2 mm test piece was cut out from the obtained laminate, and 3 ° C./day using DMA 983 manufactured by TA Instruments. The temperature was raised in minutes and the dynamic viscoelasticity measurement was performed.

(4) Drilling process A laminated board with copper foil on both sides with a thickness of 0.6 mm is drilled at 160,000 revolutions, 4000 shots using a 0.2 mmφ drill, the apex area of the drill before drilling, and after drilling The area of the drill wear part was measured by comparing with the apex area of the drill.

Evaluation methods of the obtained semiconductor device are shown in (5) and (6).
(5) Warpage of semiconductor device during heating The semiconductor device (50 mm × 50 mm) obtained above was evaluated for warpage of the entire PKG when heated at 260 ° C. The measurement range was 48 mm × 48 mm in the substrate.

(6) TCT bias test of semiconductor device The semiconductor device (50 mm × 50 mm) obtained above was subjected to a temperature cycle test in which the temperature was maintained at −55 ° C. to 150 ° C. for 30 minutes. The determination was made when the sample whose conduction resistance increased by 10% was judged as NG, and finished when all the five samples became NG.

  These evaluation results are shown in Table 1.

The resins in the table are shown in detail below.
1) Primaset PT-30 (Novolac type cyanate resin, number average molecular weight of about 380): Lonza Japan Co., Ltd. 2) Primaset PT-60 (Novolac type cyanate resin, number average molecular weight of about 560): Lonza Japan Co., Ltd. 3) AroCy B-30 (bisphenol A type cyanate resin): Asahi Kasei Epoxy Co., Ltd. 4) NC-3000SH (biphenyl alkylene type epoxy resin, epoxy equivalent 290): Nippon Kayaku Co., Ltd. 5) Epicron N-775 (Novolac type epoxy) Resin, epoxy equivalent 190): Dainippon Ink & Chemicals, Inc. 6) SFP-10X (spherical fused silica, average particle size 0.3 μm): Denki Kagaku Kogyo Co., Ltd. 7) SO-32R (spherical fused silica, average) (Particle diameter 1.5 μm): manufactured by Admatechs Co., Ltd. ) P15C (porous silica): JGC Catalysts & Chemicals 9) L15C (porous silica): JGC Catalysts & Chemicals 10) N15C (porous silica): JGC Catalysts & Chemicals 11) HP-350 ( Aluminum hydroxide): Showa Denko Co., Ltd. 12) A-187 (epoxysilane type coupling agent): Nippon Unicar Co., Ltd. 13) 2MZ (2-methylimidazole): Shikoku Kasei Kogyo Co., Ltd.

  In Examples 1 to 3, the obtained laminates are excellent in low elasticity and low thermal expansion. Therefore, the obtained semiconductor device has a small warpage when heated at 260 ° C. due to the low elasticity, and the obtained semiconductor device has a small stress accumulation due to the low elasticity and low thermal expansion. The results are shown. Moreover, the obtained laminated board is excellent also in moisture absorption solder heat resistance.

  The resin composition according to the present invention has low elasticity, low thermal expansibility, and low hygroscopicity, and is suitably used for a substrate used in a semiconductor device requiring miniaturization, high-density wiring, and high reliability. be able to.

Claims (13)

  A resin composition comprising a thermosetting resin (A) and particles (B) having pores therein.   The resin composition according to claim 1, wherein the particles (B) having pores therein are those in which the periphery of the porous particles (B1) is covered with a coating layer (B2).   The resin composition according to claim 2, wherein the porous particles (B1) are an inorganic compound.   The resin composition according to claim 3, wherein the inorganic compound is silica.   The resin composition according to any one of claims 2 to 4, wherein the coating layer (B2) is an inorganic compound.   The resin composition according to any one of claims 2 to 5, wherein the coating layer (B2) is an organosilicon compound and / or a polymer thereof.   The resin composition according to any one of claims 1 to 6, wherein the thermosetting resin (A) contains at least one selected from the group consisting of an epoxy resin, a cyanate ester resin, and a phenol resin.   An insulating layer obtained by thermosetting the resin composition according to claim 1.   A prepreg obtained by impregnating a base material with the resin composition according to claim 1. A laminate obtained by stacking one or more prepregs according to claim 9, placing a metal foil on at least one outer surface, and heat-pressing the laminate.   A printed wiring board obtained using the insulating layer according to claim 8.   A printed wiring board obtained by using the laminated board according to claim 10.   A semiconductor device obtained using the printed wiring board according to claim 11.