JP5167853B2 - Liquid resin composition and semiconductor device - Google Patents

Description

  The present invention relates to a liquid resin composition and a semiconductor device manufactured using the same.

  In recent years, there has been a remarkable progress in higher functionality, smaller size, and lighter weight of mobile phones, personal digital assistants, DVCs (digital video cameras), and there has been a strong demand for higher functionality, smaller size, and lighter weight of semiconductor packages. ing. Therefore, a plurality of semiconductor elements having different functions or a plurality of semiconductor elements having the same function are mounted in one semiconductor package for enhancing the function of the semiconductor package, and the size of the semiconductor element and the size of the semiconductor package are reduced in size and weight. Attempts have been made to bring this as close as possible. For this reason, the thickness of the semiconductor element has been further reduced, and the distance between the semiconductor element and the wire bond pad on the support such as a metal lead frame or an organic substrate has become increasingly closer.

In the conventional die attach process in the semiconductor assembly process, a liquid die attach material is applied to the support, and the semiconductor element is bonded to the support by mounting after heating the semiconductor element at room temperature. The problem of adhesion of die attach material to wire bond pads, and the problem of contamination due to bleed of the die attach material (a phenomenon in which only the liquid component of the die attach material is transmitted by capillary action) are becoming ignorable.
Therefore, instead of using a liquid die attach material, a film die attach material is used. After the film die attach material is attached to a support, a semiconductor element is mounted while heating. A method for mounting a semiconductor element with a die attach material obtained by pasting on a dicing sheet after being attached to a dicing sheet in a state where the touch material is attached to a support while heating, a die attach film having a dicing sheet function For example, a method of mounting a semiconductor element with a die attach material obtained by pasting a semiconductor wafer and mounting it on a support while heating is employed. (For example, see Patent Documents 1 and 2.)

However, the film-like die attach material has a problem that it is necessary to prepare films corresponding to the size of the semiconductor element to be used and the thickness of the die attach material, and the product type management becomes complicated.
Therefore, a method of forming a die attach material layer on a support substrate by printing, drying and semi-curing, and using it as a substitute for a film material has been performed. It is desirable that the die attach material used in such applications is tack-free at room temperature from the surface of automatic transfer of the semiconductor element mounting process after drying and semi-curing, and further from the mounting of the semiconductor element to the adhesive curing process. Sufficient adhesion strength (semiconductor element holding force) is required to prevent the semiconductor element from being removed due to the bending of the intermediate substrate, and the necessity thereof is extremely large at present when the organic substrate tends to be thinned. In addition, as the use of lead-flow solder rapidly spreads as part of environmental measures, there is a strong demand for improved solder crack resistance, and stress relaxation during solder processing is indispensable as a required characteristic of die attach materials. ing. However, it has been difficult to realize a material having a high semiconductor element holding power while being tack-free at room temperature, and having a low elastic modulus and excellent reliability such as solder crack resistance in a die attach material for printing.
JP 2002-294177 A JP 2003-347321 A

The present invention relates to a liquid resin composition in which a resin composition layer can be formed on a support by printing, and is tack-free at room temperature after drying, or drying and semi-curing the liquid resin composition, and then a semiconductor An object of the present invention is to provide a liquid resin composition excellent in reliability of the semiconductor element after mounting the element, having excellent resilience such as low elasticity after soldering and excellent resistance to solder cracks, and a semiconductor device manufactured using the liquid resin composition.

Such an object is achieved by the present invention described in the following [1] to [6].
[1] A liquid resin composition for forming a resin composition layer on a support by printing and adhering a semiconductor element to the support, the epoxy resin having two or more epoxy groups in one molecule (A) A curing agent (B) having two or more phenolic hydroxyl groups in one molecule, a solvent (C), and a filler (D) are contained, and a dicyclopentadiene skeleton is used as the epoxy resin (A). look-containing epoxy resin (A1) and liquid epoxy resin (A2) having a boiling point of the solvent (C) is at 210 ° C. or higher 250 ° C. or less, the liquid resin composition 100 the content of the solvent (C) excluding the solvent A liquid resin composition, which is 0.5 to 70 parts by weight with respect to parts by weight .
[2] The liquid resin composition as described in the above item [1], wherein the epoxy resin (A1) having a dicyclopentadiene skeleton is an epoxy resin represented by the general formula (1).

（式（１）中のｎは、０または１〜３の整数を示す。）

(N in the formula (1) represents 0 or an integer of 1 to 3)

[3] The liquid resin composition as described in the above item [1], wherein the liquid epoxy resin (A2) is an epoxy resin having a molecular weight of 200 to 3000.
[4] The content of the liquid epoxy resin (A2) with respect to 100 parts by weight of the epoxy resin (A1) having a dicyclopentadiene skeleton is 50 parts by weight or more and 1500 parts by weight or less [1] The liquid resin composition according to item.
[5] The liquid resin composition according to [1] or [2], wherein the curing agent (B) is a curing agent represented by the following general formula (2).

（式（２）中のｎは、０または１〜６の整数を示す。）

(N in the formula (2) represents 0 or an integer of 1 to 6)

[6] A semiconductor device manufactured using the liquid resin composition according to any one of [1] to [5].

According to the present invention, a liquid resin composition capable of forming a resin composition layer on a support by printing, which is tack-free at room temperature after drying, or drying and semi-curing the liquid resin composition, and thereafter It is possible to provide a liquid resin composition having excellent reliability, such as excellent semiconductor element holding power after mounting a semiconductor element, low elasticity and excellent solder crack resistance after curing. Moreover, according to the present invention, it is possible to provide a semiconductor device having excellent reliability such as excellent solder crack resistance.

  The liquid resin composition of the present invention comprises an epoxy resin (A) having two or more epoxy groups in one molecule, a curing agent (B) having two or more phenolic hydroxyl groups in one molecule, and a solvent (C). And a liquid resin composition for adhering a semiconductor element containing a filler (D) to a support, the epoxy resin (A) having an epoxy resin (A1) having a dicyclopentadiene skeleton and a liquid epoxy resin ( A2) is a liquid resin composition.

  The liquid resin composition of the present invention is formed by printing and drying and semi-curing to form a resin composition layer on a support, then mounting a semiconductor element, and then curing the resin composition layer. A liquid resin composition for adhering a semiconductor element to a support. The liquid resin composition of the present invention is excellent in printability at the time of printing, is tack-free when dried or dried and semi-cured, has excellent semiconductor element mounting properties, and has low elasticity after curing. It is a liquid resin composition having high reliability such as excellent solder crack resistance. This resin composition layer can be used as a die attach material or a heat radiation member adhesive for adhering a semiconductor element to a support. Here, examples of the support to which the semiconductor element is bonded include a printed circuit board such as a lead frame, an organic substrate, and a flexible substrate, and a heat radiating member such as a heat spreader and a heat sink.

  The liquid resin composition of the present invention contains an epoxy resin (A) having two or more epoxy groups in one molecule (hereinafter also referred to as an epoxy resin (A)). And the liquid resin composition of this invention contains the epoxy resin (A1) which has a dicyclopentadiene frame | skeleton, and a liquid epoxy resin (A2) as an epoxy resin (A). That is, in the liquid resin composition of the present invention, the epoxy resin (A) is a combination of an epoxy resin (A1) having a dicyclopentadiene skeleton and a liquid epoxy resin (A2), or a dicyclopentadiene skeleton. The epoxy resin (A1) having liquid, the liquid epoxy resin (A2), and an epoxy resin having two or more epoxy groups in another molecule.

  The epoxy resin (A1) having a dicyclopentadiene skeleton used in the liquid resin composition of the present invention has two or more epoxy groups in one molecule and one or more dicyclopentadiene skeletons in the molecule. The epoxy resin is not particularly limited as long as it has an epoxy resin. And as an epoxy resin (A1) which has a dicyclopentadiene frame | skeleton, the epoxy resin represented by following formula (1) is preferable.

（式（１）中のｎは、０または１〜３の整数を示す。）

(N in the formula (1) represents 0 or an integer of 1 to 3)

  Since the softening point of the epoxy resin (A1) represented by the formula (1) is 55 ° C. or higher, the effect of tack-free after drying and semi-curing is increased, which is preferable. Since the epoxy resin (A1) represented by the formula (1) has a dicyclopentadiene skeleton, the water absorption rate and elastic modulus of the cured product can be lowered, so that the effect of increasing the reliability is enhanced.

The liquid epoxy resin (A2) used in the present invention is not particularly limited as long as it is liquid at 25 ° C. and further has two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, 1,6-hexanediol type epoxy resin and the like can be mentioned. Preferred are bisphenol A type epoxy resin and bisphenol F type epoxy resin. As a liquid, a softening point is 25 degrees C or less.
The molecular weight of the liquid epoxy resin (A2) is preferably 200 to 3000, and particularly preferably 250 to 2000.

  In the liquid resin composition of the present invention, by using the epoxy resin (A1) having the dicyclopentadiene skeleton and the liquid epoxy resin (A2) as the epoxy resin (A), when dry and semi-cured, It is tack-free, has excellent semiconductor element holding power, has low elasticity after curing, and is excellent in solder crack resistance, so that reliability is increased.

The content of the liquid epoxy resin (A2) is preferably 50 parts by weight or more and 1500 parts by weight or less, particularly preferably 100 parts by weight or more, with respect to 100 parts by weight of the epoxy resin (A1) having a dicyclopentadiene skeleton. 900 parts by weight or less. When the content of the liquid epoxy resin (A2) is within the above range, it is tack-free when dried and semi-cured, has excellent semiconductor element holding power, has low elasticity after curing, and has no solder crack resistance. The effect of high reliability is improved because of its superiority. On the other hand, if the content of the liquid epoxy resin (A2) is less than the above range, the semiconductor element holding power tends to be difficult to develop, and if it is more than the above range, tack at room temperature tends to occur.
The liquid resin composition of the present invention has two or more in one molecule other than the epoxy resin (A1) having the dicyclopentadiene skeleton and the liquid epoxy resin (A2) as long as the properties are not impaired. Epoxy resins having an epoxy group (hereinafter also referred to as other epoxy resins (A3)), for example, phenol novolac type epoxy resins, cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, and other triphenyl resins. An epoxy resin having a phenylmethine skeleton, an epoxy resin having an anthracene skeleton, or the like may be included.

  In the liquid resin composition of the present invention, the epoxy resin (A1) having the dicyclopentadiene skeleton with respect to the total content of the epoxy resin composition (A) having two or more epoxy groups in one molecule and the liquid epoxy The content ratio ((A1 + A2) / A) of the resin (A2) is preferably 0.8 to 1, particularly preferably 0.85 to 1. The total content of the epoxy resin composition (A) means that the liquid resin composition of the present invention has an epoxy resin (A1) having a dicyclopentadiene skeleton and a liquid epoxy resin (A2) as the epoxy resin (A). ) Only, the content is (A1) + (A2), and the epoxy resin (A) is an epoxy resin (A1) having a dicyclopentadiene skeleton, a liquid epoxy resin (A2), and another epoxy. When the resin (A3) is contained, the content is (A1) + (A2) + (A3).

The curing agent (B) having two or more phenolic hydroxyl groups in one molecule used in the liquid resin composition of the present invention (hereinafter, also referred to as curing agent (B)) is a cured epoxy resin (A). For example, bisphenols such as bisphenol A, bisphenol F, and bisphenol S, phenol novolac, cresol novolac, etc., a compound obtained by reacting phenol or its derivative with formaldehyde, phenol or its derivative and benzaldehyde. And the like, compounds having a phenol aralkyl type phenol resin, biphenyl aralkyl type phenol resin, other compounds having a naphthalene skeleton, compounds having an anthracene skeleton, and having two or more phenolic hydroxyl groups in one molecule. Especially, as a hardening | curing agent (B), a solid hardening | curing agent is preferable at normal temperature (20-30 degreeC). Further, the curing agent (B) may be used in combination of plural kinds. As the solid curing agent (B) at room temperature (20 to 30 ° C.), a curing agent having a softening point of 55 ° C. or higher is preferable. Moreover, as a hardening | curing agent (B), a phenol novolak, a phenol aralkyl type phenol resin, a biphenyl aralkyl type phenol resin, bisphenol F, etc. are mentioned, Preferably it is a phenol aralkyl type phenol resin. In addition, even when the softening point of the curing agent (B) is high, when mixed with an epoxy resin, the softening point of the mixture is lowered. Therefore, the curing agent (B) has no problem even if the softening point is, for example, about 150 ° C. It is possible to use.

  The ratio of the epoxy resin (A) having two or more epoxy groups in one molecule and the curing agent (B) having two or more phenolic hydroxyl groups in one molecule is such that the phenolic hydroxyl group is based on the epoxy group 1. It is preferably 0.7 to 1.3. A more desirable ratio is 0.9 to 1.2 in terms of phenolic hydroxyl group with respect to epoxy group 1.

The solvent (C) used in the present invention is a solvent having a boiling point of 200 ° C. or higher and 260 ° C. or lower, and is not particularly limited as long as it can dissolve the epoxy resin (A) and the curing agent (B). When the boiling point of the solvent is lower than 200 ° C., thickening due to the volatilization of the solvent is likely to occur during printing, and printing defects such as uneven thickness and fading tend to occur. Further, when the boiling point of the solvent is higher than 260 ° C., there is a possibility that the solvent evaporates for a long time at the time of drying and semi-curing, or the residual solvent increases to cause tack at room temperature and void at the time of curing. .
If the solubility of the epoxy resin (A) and the curing agent (B) in the solvent (C) is good, the surface of the resin composition layer after printing or drying and semi-curing becomes smooth, and the inclination of the semiconductor element when the semiconductor element is mounted And voids are less likely to occur.
Such a solvent (C) is not particularly limited as long as the solubility of the epoxy resin (A) and the curing agent (B) to be used is sufficient, but a halogen-based solvent is not preferable because it is used for semiconductors. Further, a solvent that deteriorates the storage stability of the liquid resin composition, such as an amine-based solvent containing a primary amine and a secondary amine, is also not preferable. Solvents (C) that can be used are as follows, and these can be used alone or in combination.

Examples of the solvent (C) include ethyl benzoate, propyl benzoate, butyl benzoate, γ-butyrolactone, dibutyl oxalate, dimethyl maleate, diethyl maleate, ethylene glycol monobutyrate, propylene carbonate, and N-methylpyrrolidone. 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethyl glycol monomethyl ether, dipropylene glycol, tripropylene glycol monomethyl ether, methyl salicylate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Etc. Particularly preferred solvents are those having a boiling point of 210 ° C. or more and 250 ° C. or less, and particularly preferred are ethyl benzoate, propyl benzoate, butyl benzoate, γ-butyrolactone, dibutyl oxalate, diethyl maleate, ethylene Examples thereof include glycol monobutyric acid ester, propylene carbonate, diethylene glycol, diethylene glycol monobutyl ether, triethyl glycol monomethyl ether, dipropylene glycol, tripropylene glycol monomethyl ether, methyl salicylate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

Furthermore, the liquid resin composition of the present invention may contain a filler (D). Examples of the filler (D) used in the present invention include organic fillers such as organic silicone and urethane particles, and inorganic fillers such as silica and calcium carbonate, and are mainly used for adjusting workability. For this reason, it will not specifically limit if it functions as a workability adjustment material of a liquid resin composition.
The average particle size of the filler (D) used in the present invention is preferably 5 μm or less. When the average particle size of the filler (D) is 5 μm or less, the surface of the resin composition layer becomes smooth after drying and semi-curing, and voids due to air entrainment are less likely to occur when a semiconductor element is mounted.

  The content of the filler (D) is preferably 5 to 150 parts by weight, particularly preferably 15 to 80 parts by weight, based on 100 parts by weight of the total of the epoxy resin (A) and the curing agent (B). Since the content of the filler (D) is within the above range, the viscosity becomes suitable for printing and the surface of the resin composition layer after drying and semi-curing becomes smooth.

  Furthermore, the liquid resin composition of the present invention can contain a coupling agent, a leveling agent, an antifoaming agent, a surfactant and the like as necessary.

In the liquid resin composition of the present invention, the content of each component relative to the liquid resin composition excluding the solvent (liquid resin composition-solvent (C)) is the same as the liquid resin composition excluding the solvent (liquid resin composition-solvent ( C)) The epoxy resin (A) is preferably 20 to 80 parts by weight, particularly preferably 30 to 65 parts by weight, and the curing agent (B) is preferably 5 to 60 parts by weight with respect to 100 parts by weight. The amount of the filler (D) is preferably 5 to 70 parts by weight, particularly preferably 10 to 40 parts by weight.
The content of the solvent (C) is preferably 0.5 to 70 parts by weight, particularly preferably 10 parts per 100 parts by weight of the liquid resin composition excluding the solvent (liquid resin composition-solvent (C)). -45 parts by weight.

  In addition, the viscosity of the liquid resin composition of the present invention is preferably 10 Pa · s to 600 Pa · s, particularly preferably 20 Pa · s to 300 Pa · s. When the viscosity of the liquid resin composition is in the above range, a resin composition layer having a stable thickness after printing can be obtained. Further, it has good printability even in continuous printing. Here, the value of the viscosity is a value measured at 25 ° C. and 2.5 rpm using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., 3 ° cone).

Here, the manufacturing method of a liquid resin composition can be manufactured by, for example, pre-mixing each component, kneading using three rolls, and degassing under vacuum.
Hereinafter, an example of a semiconductor device manufactured using the liquid resin composition of the present invention will be described. However, it is not limited to this.

  The liquid resin composition of the present invention is used by printing on a support such as a support substrate on which a semiconductor element is mounted. Here, the support substrate is a printed circuit board such as a lead frame, an organic substrate, or a flexible substrate, and a semiconductor element is mounted on the organic substrate and electrically connected by a gold wire, but the semiconductor element is mounted. The support substrate may be a semiconductor element itself or another substrate. As a printing method of the liquid resin composition, screen printing, stencil printing, and the like are possible, but printing (coating) is preferably performed by a stencil printing method using a stencil mask from the viewpoint of surface smoothness. The stencil printing method can be performed by a known method. Alternatively, a liquid resin composition printed on a semiconductor wafer and then cut into semiconductor elements may be used.

The support substrate on which the liquid resin composition is printed is dried and semi-cured by using an oven or a hot platen. The temperature at the time of drying and semi-curing is preferably 80 ° C. or higher in order to complete within 120 minutes from the viewpoint of productivity. Moreover, in order to prevent the curvature of the support substrate before sealing, the temperature at the time of drying and semi-curing is preferably 150 ° C. or less, and more preferably 120 ° C. or less. In the present invention, dry semi-curing means that the liquid resin composition after printing is evaporated by heating the liquid resin composition at a predetermined temperature, or the solvent (C C) is evaporated, and a part thereof is cured to the extent that it does not hinder the mounting and adhesion of the semiconductor element in the subsequent process.

  A support substrate formed with a resin composition layer (hereinafter referred to as a resin composition layer) obtained by drying and semi-curing a liquid resin composition is usually set on a die bonder and picked up (support substrates one by one from the top) Step of taking) After the transfer to the heater block, the semiconductor element is mounted in a heated state. At this time, it is necessary to be picked up one by one from the support substrate set in piles, but if there is a tack in the resin composition layer, the overlapped support substrates adhere to each other, and cannot be picked up one by one. Or there exists a possibility that it may adhere to the back surface of the support substrate which a part of resin composition layer accumulated. For this reason, it is preferable that a resin composition layer does not have a tack | tuck at room temperature (20-30 degreeC).

  Specifically, the liquid resin composition was printed on a support substrate with a squeegee load of 2 kg and a squeegee speed of 20 mm / s using a 50 μm thick stencil mask and a 27 cm long urethane squeegee, and a dryer at 100 ° C. ± 5 ° C. Among them, the resin composition layer obtained by heat treatment for 80 ± 3 minutes preferably has a tack force at 25 ° C. of 0.05 N or less, which is an index of stickiness. The tack force is measured using a tack force measuring machine (manufactured by RHESCA) at a probe descending speed (Immersion Speed) of 30 mm / min, a test speed of 600 mm / min, a contact load (Preload) of 0.2 N, and a contact holding time (Press Time) of 1.0. This is a value measured with a probe of 5.1 mmΦ (SUS304).

  After mounting the semiconductor element on the support substrate on which the resin composition layer is formed, the resin composition layer is cured and then electrically connected with a gold wire. The temperature for curing the resin composition layer is preferably 200 ° C. or less, more preferably 180 ° C. or less, and particularly preferably 160 ° C. or less in consideration of the warp of the support substrate and the decomposition temperature of the resin composition layer.

After electrical connection is made in this manner, resin sealing is performed, and when a lead frame is used as the support substrate, lead processing, exterior plating, or the like is performed as necessary to obtain a semiconductor device. When an organic substrate is used as the support substrate, a solder ball attachment or the like is performed as necessary to obtain a semiconductor device.
Hereinafter, although the present invention is explained using an example, the present invention is not limited to these.

[Liquid resin composition]
-Liquid resin composition A
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight Dicyclopentadiene type epoxy resin (softening point 60 ° C., epoxy equivalent 265)
(Epoxy resin of formula (1) wherein n is an integer of 0 to 3) 7.4 parts by weight Bisphenol A type epoxy resin (molecular weight 700, liquid at 25 ° C., epoxy equivalent 350) 29.8 parts by weight Phenol aralkyl resin ( Softening point 65 ° C., hydroxyl group equivalent 175) 19.8 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition A.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

-Liquid resin composition B
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight Dicyclopentadiene type epoxy resin (softening point 60 ° C., epoxy equivalent 265)
(Epoxy resin of formula (1) where n is an integer of 0 to 3) 18.0 parts by weight Bisphenol A type epoxy resin (molecular weight 700, liquid at 25 ° C., epoxy equivalent 350) 18.0 parts by weight Phenol aralkyl resin ( Softening point 65 ° C., hydroxyl group equivalent 175) 20.9 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition B.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

・ Liquid resin composition C
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight Dicyclopentadiene type epoxy resin (softening point 60 ° C., epoxy equivalent 265)
(Epoxy resin of formula (1) wherein n is an integer of 0 to 3) 3.8 parts by weight Bisphenol A type epoxy resin (molecular weight 700, liquid at 25 ° C., epoxy equivalent 350) 33.9 parts by weight Phenol aralkyl resin ( Softening point 65 ° C., hydroxyl group equivalent 175) 19.4 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition C.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

・ Liquid resin composition D
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight

Dicyclopentadiene type epoxy resin (softening point 60 ° C., epoxy equivalent 265)
(Epoxy resin of formula (1) where n is an integer of 0 to 3) 21.5 parts by weight Bisphenol A type epoxy resin (molecular weight 700, liquid at 25 ° C., epoxy equivalent 350) 14.3 parts by weight Phenol aralkyl resin ( Softening point 65 ° C., hydroxyl group equivalent 175) 21.3 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition D.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

・ Liquid resin composition E
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight Dicyclopentadiene type epoxy resin (softening point 60 ° C., epoxy equivalent 265)
(Epoxy resin of formula (1) where n is an integer of 0 to 3) 2.6 parts by weight Bisphenol A type epoxy resin (molecular weight 700, liquid at 25 ° C., epoxy equivalent 350) 35.1 parts by weight Phenol aralkyl resin ( Softening point 65 ° C., hydroxyl group equivalent 175) 19.3 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition E.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

・ Liquid resin composition F
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight

Dicyclopentadiene type epoxy resin (softening point 60 ° C., epoxy equivalent 265)
(Epoxy resin of formula (1) where n is an integer of 0 to 3) 5.8 parts by weight Bisphenol F type epoxy resin (molecular weight 310, liquid at 25 ° C., epoxy equivalent 165) 23.3 parts by weight Phenol aralkyl resin ( Softening point 65 ° C., hydroxyl group equivalent 175) 27.9 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition F.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

・ Liquid resin composition G
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight Dicyclopentadiene type epoxy resin (softening point 60 ° C., epoxy equivalent 265)
(Epoxy resin of formula (1) where n is an integer of 0 to 3) 5.4 parts by weight Naphthalene type epoxy resin (molecular weight 270, liquid at 25 ° C., epoxy equivalent 140) 21.4 parts by weight Phenol aralkyl resin (softening Point 65 ° C., hydroxyl group equivalent 175) 30.3 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition G.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

・ Liquid resin composition H
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight Dicyclopentadiene type epoxy resin (softening point 60 ° C., epoxy equivalent 265)
(Epoxy resin of formula (1) where n is an integer of 0 to 3) 3.7 parts by weight Orthocresol novolac type epoxy resin (softening point 70 ° C., epoxy equivalent 210)
3.7 parts by weight Bisphenol A type epoxy resin (molecular weight 700, liquid at 25 ° C., epoxy equivalent 350) 29.5 parts by weight Phenol aralkyl resin (softening point 65 ° C., hydroxyl group equivalent 175) 20.2 parts by weight It mix | blended with the separable flask and the brown transparent varnish was obtained by stirring at 80 degreeC for 2 hours. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition H.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

・ Liquid resin composition I
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight

Dicyclopentadiene type epoxy resin (softening point 60 ° C., epoxy equivalent 265)
(Epoxy resin of formula (1) where n is an integer of 0 to 3) 3.7 parts by weight Phenol aralkyl type epoxy resin (softening point 52 ° C., epoxy equivalent 238)
3.7 parts by weight Bisphenol A type epoxy resin (molecular weight 700, liquid at 25 ° C., epoxy equivalent 350) 29.6 parts by weight Phenol aralkyl resin (softening point 65 ° C., hydroxyl group equivalent 175) 20.0 parts by weight It mix | blended with the separable flask and the brown transparent varnish was obtained by stirring at 80 degreeC for 2 hours. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition I.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

・ Liquid resin composition J
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight

Dicyclopentadiene type epoxy resin (softening point 60 ° C., epoxy equivalent 265)
(Epoxy resin of formula (1) wherein n is an integer of 0 to 3) 8.7 parts by weight Bisphenol A type epoxy resin (molecular weight 700, liquid at 25 ° C., epoxy equivalent 350) 34.7 parts by weight Phenol novolac resin ( Softening point 110 ° C., hydroxyl group equivalent 104) 13.7 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition J.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

・ Liquid resin composition K
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight

Dicyclopentadiene type epoxy resin (softening point 60 ° C., epoxy equivalent 265)
(Epoxy resin of formula (1) where n is an integer of 0 to 3) 34.4 parts by weight

Phenol aralkyl resin (softening point 65 ° C., hydroxyl group equivalent 175) 22.7 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition K.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

・ Liquid resin composition L
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight Bisphenol A type epoxy resin (molecular weight 700, liquid at 25 ° C., epoxy equivalent 350) 38.1 parts by weight Phenol aralkyl resin (softening point 65 ° C., hydroxyl group equivalent 175) 19.0 parts by weight It mix | blended with the separable flask and the brown transparent varnish was obtained by stirring at 80 degreeC for 2 hours. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition L.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

・ Liquid resin composition M
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
23.5 parts by weight Phenol aralkyl type epoxy resin (softening point 52 ° C., epoxy equivalent 238)
39.7 parts by weight Phenol novolac resin (softening point 110 ° C., hydroxyl group equivalent 104) 17.3 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition M.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator 0.2 parts by weight Aerosil R805 (manufactured by DEGUSSA) 5.8 parts by weight Organic filler having an average particle diameter of 2 μm (KMP-590, Shin-Etsu Chemical Co., Ltd.) Made by Co., Ltd.)
13.2 parts by weight

The liquid resin compositions A to M described above were used as substrates for BOC (Board On Chip) type semiconductor devices, that is, BT (bismaleimide-triazine) resin substrates (resist: PSR4000AUS308 (manufactured by Taiyo Ink Manufacturing Co., Ltd.)), thickness 0 .56 mm). The squeegee moving speed and squeegee load were adjusted so that the thickness of the used stencil mask was 50 μm, and the printed thickness was 35 μm ± 5 after drying and semi-curing. This was heat-treated at 100 ° C. for 80 minutes to obtain a semiconductor support substrate on which a resin composition layer was formed by drying and semi-curing the liquid resin composition. For printing, a metal squeegee (stainless steel type, length 27 cm) is used for the printing device (Toray Engineering, VE500), the load is about 20 N, and the squeegee moving speed is 40 mm / s.
I went there.

  Moreover, said liquid resin composition A-M was printed by the thickness of 50 micrometers on the slide glass. This was heat-treated at 100 ° C. for 80 minutes to obtain a slide glass having a resin composition layer formed by drying and semi-curing the liquid resin composition.

[Example 1]
The following tests were performed using a semiconductor element supporting substrate on which a resin composition layer produced using the liquid resin composition A was formed and a slide glass on which a resin composition layer was formed.
[Tacking test]
Using the slide glass on which the resin composition layer was formed, the tack force on the surface of the resin composition layer at room temperature was measured. Measurement is performed with a tack force measuring machine (manufactured by RHESCA), probe lowering speed (immersion speed) 30 mm / min, test speed 600 mm / min, contact load (preceding load) 0.2 N, contact holding time (pressing time) 1.0. Second, the probe was 5.1 mmφ (SUS304).

[Three-point bending strength (semiconductor element holding power)]
The semiconductor element support substrate on which the resin composition layer is formed is singulated, and a 6 × 6 mm semiconductor element is heated to 100 ° C. with a die bonder on the support substrate at a heating temperature of 100 ° C., a bond load of 3.0 N, and a bond time of 10 seconds. After mounting, both ends of the semiconductor element mounting support substrate were fixed, and the strength until the semiconductor element peeled when pressed with a push-pull gauge from the surface opposite to the semiconductor element mounting surface was measured.

[Elastic modulus]
Using the above liquid resin composition A, a 4 × 20 × 0.1 mm film-like test piece was prepared (curing conditions: 150 ° C. for 60 minutes), and in a tensile mode using a dynamic viscoelasticity measuring machine (DMA). Measurements were made. The measurement conditions were a measurement range of −100 to 330 ° C., a temperature rising rate of 5 ° C./min, a frequency of 10 Hz, and a load of 100 mN.

[Moisture resistance test]
A semiconductor prepared by cutting a simulated semiconductor wafer (Phase 8 manufactured by Hitachi ULSI Co., Ltd.) with a circuit surface side protected with polyimide resin (CRC-8800 manufactured by Sumitomo Bakelite Co., Ltd.) to 10.5 × 5 mm using an auto die bonder. Resin composition of BT resin substrate, which is a semiconductor support substrate (substrate for BOC type semiconductor device) in which the resin composition layer is formed on the surface on the polyimide resin side under the mounting condition of 100 ° C. for 8 seconds and a load of 300 g. It was mounted toward the layer and an electrical connection was made with a gold wire. This was molded at 175 ° C. for 90 seconds with a semiconductor sealing material (EME-G700 manufactured by Sumitomo Bakelite Co., Ltd.) and post-cured for 4 hours to obtain a 12.3 × 8.3 mm size semiconductor device (BOC type semiconductor) The device was separated. Using this semiconductor device, drying (125 ° C. for 20 hours), moisture absorption treatment (85 ° C. relative humidity 60% 168 hours, and 85 ° C. relative humidity 85% 168 hours), reflow soldering treatment (maximum temperature 255 to 260 ° C., 20 A second soldering test was performed three times continuously). The moisture absorption treatment condition of 85 ° C. and relative humidity of 60% is 168 hours for JEDEC level 2, and the moisture absorption treatment condition of 85 ° C. and relative humidity of 60% for 168 hours is JEDEC level 1. The test was conducted at n = 10, and internal defects were observed through transmission using an ultrasonic flaw detector 5 MHz probe. The number of semiconductor devices having internal peeling or cracks was counted as defective.
The results are shown in Table 1.

[Examples 2 to 10]
Using the printing resin compositions B to J, a semiconductor support substrate on which a resin composition layer was formed and a slide glass on which the resin composition layer was formed were prepared and tested in the same manner as in Example 1.

[Comparative Examples 1-3]
Using the printing resin compositions K to M, a semiconductor support substrate on which a resin composition layer was formed and a slide glass on which the resin composition layer was formed were prepared and tested in the same manner as in Example 1.

  By using the liquid resin composition of the present invention, a low-elasticity liquid resin composition that is tack-free at room temperature after drying and semi-curing and then has excellent semiconductor element holding power after mounting a semiconductor element, and a liquid resin composition produced using the same The semiconductor device is excellent in reliability such as solder crack resistance.

Claims (6)

A liquid resin composition for forming a resin composition layer on a support by printing and adhering a semiconductor element to the support, the epoxy resin having two or more epoxy groups in one molecule (A) , curing agent having two or more phenolic hydroxyl groups in the molecule (B), a solvent (C), and a filler (D), wherein as the epoxy resin (a), the epoxy resin having a dicyclopentadiene skeleton (A1) and viewed contains a liquid epoxy resin (A2), the boiling point of the solvent (C) is at 210 ° C. or higher 250 ° C. or less, in 100 parts by weight of liquid resin composition, excluding content of the solvent of the solvent (C) A liquid resin composition characterized by being 0.5 to 70 parts by weight . The liquid resin composition according to claim 1, wherein the epoxy resin (A1) having a dicyclopentadiene skeleton is an epoxy resin represented by the general formula (1).

(N in the formula (1) represents 0 or an integer of 1 to 3) The liquid resin composition according to claim 1, wherein the liquid epoxy resin (A2) is an epoxy resin having a molecular weight of 200 to 3000.   2. The liquid according to claim 1, wherein the content of the liquid epoxy resin (A2) with respect to 100 parts by weight of the epoxy resin (A1) having the dicyclopentadiene skeleton is 50 parts by weight or more and 1500 parts by weight or less. Resin composition. The liquid resin composition according to claim 1 or 2, wherein the curing agent (B) is a curing agent represented by the following general formula (2).

(N in the formula (2) represents 0 or an integer of 1 to 6) A semiconductor device manufactured using the liquid resin composition according to claim 1.