CN114773780A

CN114773780A - Resin composition, resin paste, cured product, semiconductor chip package, and semiconductor device

Info

Publication number: CN114773780A
Application number: CN202210059849.0A
Authority: CN
Inventors: 阪内启之; 佐佐木成; 胁坂安晃
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2021-01-22
Filing date: 2022-01-19
Publication date: 2022-07-22
Also published as: TW202244158A; JP2022113053A; KR20220106701A

Abstract

The invention provides a resin composition or a resin paste which can obtain a cured product with suppressed generation of warpage and excellent mechanical properties; a cured product, a semiconductor chip package and a semiconductor device formed by using the resin composition or the resin paste. The resin composition of the present invention is a resin composition containing (a) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein when the resin composition is cured by a curing method comprising the following compression molding step and post-curing step, the obtained cured product exhibits a void ratio in the range of 0.002% to 2%, where the void ratio is an area ratio (%) of void regions in an SEM cross-sectional image of the cured product. < compression Molding step > A step of placing a resin composition so as to bond to a silicon wafer, and then compression molding the resulting material under a pressure of 15 tons and at a temperature of 130 ℃ for 10 minutes to obtain a compression molded article of the resin composition having a thickness of 300 μm bonded to the silicon wafer < postcuring step > A step of heating the obtained compression molded article of the resin composition under a nitrogen atmosphere at a temperature of 150 ℃ for 1 hour to obtain a cured product.

Description

Resin composition, resin paste, cured product, semiconductor chip package, and semiconductor device

Technical Field

The present invention relates to a resin composition, and particularly to a resin paste. Further, the present invention relates to a cured product, a semiconductor chip package and a semiconductor device, each of which is formed using the resin composition or the resin paste.

Background

In recent years, there has been an increasing demand for small and highly functional electronic devices such as smartphones and tablet personal computer devices, and accordingly, higher functionality has been demanded for insulating materials for semiconductor chip packaging used for these small electronic devices. As such an insulating material, an insulating material formed by curing a resin composition is known (for example, patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2004-137370.

Disclosure of Invention

Problems to be solved by the invention

In recent years, in the production of semiconductor chip packages, a cured product which is suppressed in the occurrence of warpage and has excellent mechanical properties has been required for a resin composition for forming an insulating layer.

The invention provides: a resin composition or a resin paste which can provide a cured product having excellent mechanical properties while suppressing the occurrence of warpage; a cured product, a semiconductor chip package and a semiconductor device formed by using the resin composition or the resin paste.

Means for solving the problems

The present inventors have made extensive studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by a resin composition containing (a) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and a grease composition which gives a cured product having voids in an amount within a specific range, and have completed the present invention.

That is, the present invention includes the following;

[1] a resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,

when the resin composition is cured by a curing method comprising a compression molding step and a post-curing step, the obtained cured product has a porosity of 0.002% to 2%,

the porosity is the area ratio (%) of the void region in the SEM cross-sectional image of the cured product,

< compression Molding Process >

A step of disposing the resin composition so as to bond to the silicon wafer, and then subjecting the resultant to compression molding under conditions of a pressure of 15 tons, a temperature of 130 ℃ and 10 minutes to obtain a compression-molded article of the resin composition having a thickness of 300 μm bonded to the silicon wafer,

< post-curing Process >

Heating the obtained compression-molded resin composition in a nitrogen atmosphere at 150 ℃ for 1 hour to obtain a cured product;

[2] the resin composition according to [1], wherein the void ratio is obtained as follows: calculating an area ratio (%) of a void region obtained as a void image to an observation region having a thickness direction size of 1000 pixels × an in-plane direction size of 1000 pixels in an SEM sectional image having a magnification of 27000 times;

[3] the resin composition according to [1] or [2], wherein the porosity is an arithmetic average of area ratios (%) of void regions obtained with respect to an SEM sectional image of a cured product at 50 points;

[4] the resin composition according to any one of [1] to [3], wherein the compression molding step includes the following steps (c1) to (c4) in order:

(c1) a step of disposing a silicon wafer and a resin composition in a metal mold (gold mold) having a release film attached thereto;

(c2) a step of clamping the mold within 90 seconds after the resin composition is prepared, and bonding the silicon wafer and the resin composition;

(c3) a step of reducing the pressure in the metal mold to a reduced pressure within a range of 0 to 0.7 torr; and

(c4) a step of obtaining a compression-molded article of a resin composition having a thickness of 300 μm bonded to a silicon wafer by compression-molding under conditions of a pressure of 15 tons, a temperature of 130 ℃ and 10 minutes;

[5] the resin composition according to any one of [1] to [4], wherein the post-curing step sequentially includes the following steps (p1) to (p 2):

(p1) a step of putting the compression-molded resin composition taken out of the mold into an oven set to a temperature of 150 ℃ and 1atm in a nitrogen atmosphere, and waiting for 1 hour to obtain a cured product; and

(p2) a step of taking out the cured product from the oven within 120 seconds after the step (p1) and cooling the cured product at normal temperature and pressure;

[6] the resin composition according to any one of [1] to [5], wherein a resin void ratio indicating an area ratio of a void region in a resin component region obtained by excluding a void region in a region drawn with an outer shape region of (C) an inorganic filler out of void regions obtained as void images by image analysis with respect to the observation region is in a range of 0.002% to 2%;

[7] the resin composition according to any one of [1] to [6], wherein the component (C) is 30% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass;

[8] the resin composition according to any one of [1] to [7], wherein the component (A) comprises (A-1) a liquid epoxy resin;

[9] the resin composition according to any one of [1] to [8], which comprises (E-1) a silane coupling agent, the silane coupling agent being a single species;

[10] the resin composition according to any one of [1] to [8], which comprises (E-1) a silane coupling agent, wherein the silane coupling agent is of a plurality of types;

[11] the resin composition according to any one of [1] to [10], wherein the content of the solvent is 3% by mass or less, assuming that the nonvolatile component in the resin composition is 100% by mass;

[12] the resin composition according to any one of [1] to [11], wherein the viscosity at 25 ℃ measured with an E-type viscometer is in the range of 1Pa · s to 1000Pa · s;

[13] the resin composition according to any one of [1] to [12], wherein a value of a dielectric constant (Dk) of a cured product is less than 3.6;

[14] the resin composition according to any one of [1] to [13], wherein a value of a dielectric loss tangent (Df) of a cured product is less than 0.03;

[15] the resin composition according to any one of [1] to [14], wherein a fracture point strength of a cured product is more than 45 MPa;

[16] the resin composition according to any one of [1] to [15], wherein a degree of curing of the cured product is 95% or more;

[17] the resin composition according to any one of [1] to [16], which is used for forming an insulating layer of a semiconductor chip package;

[18] the resin composition according to any one of [1] to [17], which is used for a rewiring-forming layer;

[19] a resin paste comprising the resin composition according to any one of [1] to [18 ];

[20] a cured product of the resin composition according to any one of claims [1] to [18] or the resin paste according to [19 ];

[21] a cured product of a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the cured product has a porosity in the range of 0.002% to 2%, and the porosity is an area ratio (%) of void regions in an SEM sectional image of the cured product;

[22] a semiconductor chip package comprising an insulating layer formed of the resin composition according to any one of [1] to [18] or the cured product of the resin paste according to [19], or an insulating layer formed of the cured product according to [20] or [21 ];

[23] the semiconductor chip package according to [22], wherein the insulating layer is a rewiring-forming layer;

[24] the semiconductor chip package according to [22] or [23], which is a Fan-out (Fan-out) type package;

[25] a semiconductor device comprising the semiconductor chip package according to any one of [22] to [24 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a resin composition or a resin paste which can provide a cured product that is suppressed in the occurrence of warpage and has excellent mechanical properties; a cured product, a semiconductor chip package and a semiconductor device formed by using the resin composition or the resin paste.

Brief description of the drawings

Fig. 1 is a cross-sectional view schematically showing a configuration of a fan-out WLP as an example of a semiconductor chip package according to an embodiment of the present invention;

FIG. 2 is a photograph of an SEM cross-sectional image of a cured product of example 8 shown in analytical software;

fig. 3 is a photograph showing a state in which the void region is colored red in the SEM cross-sectional image of fig. 2.

Detailed Description

The following describes embodiments and examples of the present invention in detail. The present invention is not limited to the following embodiments and examples, and may be modified and practiced without departing from the scope of the appended claims and their equivalents.

[ resin composition ]

The resin composition of the present invention is characterized by containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and giving a cured product having voids in an amount within a specific range.

Specifically, when the resin composition of the present invention is cured by a curing method including the following compression molding step and post-curing step, the obtained cured product exhibits a porosity in the range of 0.002% to 2%;

< compression Molding Process >

A step of disposing the resin composition so as to bond to the silicon wafer, and then subjecting the resultant to compression molding under conditions of a pressure of 15 tons, a temperature of 130 ℃ and 10 minutes to obtain a compression-molded article of the resin composition having a thickness of 300 μm bonded to the silicon wafer

< post-curing Process >

And heating the resulting compression-molded resin composition in a nitrogen atmosphere at a temperature of 150 ℃ for 1 hour to obtain a cured product.

The "porosity" used as an index of the amount of voids in a cured product represents the area ratio (%) of voids in a cross section of the cured product, and in the present invention, it is represented by the area ratio (%) of void regions in an SEM cross-sectional image of the cured product. Here, it is also considered that the amount of voids contained in the cured product is evaluated in terms of volume ratio (%), but the present inventors found that: the porosity in terms of area ratio (%) allows the composition of the resin composition, which exhibits the effects of the present invention of providing a cured product having excellent mechanical properties with suppressed occurrence of warpage, to be evaluated and defined easily and with high accuracy.

In the calculation of the porosity, the area ratio (%) of the void region may be calculated for the entire SEM cross-sectional image, or the area ratio (%) of the void region may be calculated for a specific region in the SEM cross-sectional image, preferably an observation region having a predetermined size or more, more preferably a specific size. From the viewpoint of high-precision evaluation and predetermined porosity (hereinafter, referred to as "high-precision evaluation and predetermined porosity" in the same sense) in association with the achievement of the effects of the present invention, it is preferable to calculate the area ratio (%) of the void region (preferable size of the observation region, as described later) for the observation region having a predetermined size or more, preferably a specific size, in the SEM cross-sectional image.

The SEM cross-sectional image may be an SEM image of a vertical cross-section of a cured product of the resin composition, or an SEM image of a cross-section of a cured product of the resin composition. The longitudinal section means a section including a dimension in the thickness direction. The longitudinal section may be a section along a direction perpendicular to a principal surface of a cured product of the resin composition, or a section along a direction perpendicular to a plane of a member (for example, a silicon wafer) having the plane when the member is bonded to the cured product of the resin composition with the plane. The cross section is a cross section perpendicular to the longitudinal section, that is, a cross section parallel to the in-plane direction. The cross section may be a section parallel to the principal surface of the cured product of the resin composition, or may be a section parallel to the plane of a member (e.g., a silicon wafer) having a plane when the member is bonded to the cured product of the resin composition with the plane. From the viewpoint of facilitating the cross-sectional exposure (cross-section し), the SEM cross-sectional image is preferably a vertical cross-sectional SEM image of a cured product of the resin composition.

From the viewpoint of highly accurate evaluation and specification of the porosity, it is preferable to previously specify the magnification at the time of SEM observation and the size of the observation area of the SEM cross-sectional image. For example, the magnification in SEM observation is preferably 20000 times or more, more preferably 25000 times or more, 26000 times or more, or 27000 times or more, and the size of the observation region of the SEM cross-sectional image is preferably 800 pixels or more, more preferably 900 pixels or more, or 1000 pixels or more in terms of the number of pixels. From the viewpoint of highly accurate evaluation and specification of the porosity, the upper limit of the magnification in SEM observation is preferably 50000 times or less, more preferably 49000 times or less, 48000 times or less, or 47000 times or less, and the upper limit of the size of the observation region of the SEM cross-sectional image is not particularly limited in calculating the area ratio (%) of the void region, and is preferably 1300 pixels or less, more preferably 1200 pixels or less, or 1100 pixels or less in terms of the number of pixels. In a preferred embodiment, the porosity is obtained by performing image analysis on an observation region of 1000 pixels square (1000 pixels in the thickness direction size 1000 pixels × 1000 pixels in the in-plane direction size) in an SEM cross-sectional image of the cured product at magnification 27000 times, and calculating the area ratio (%) of the void region obtained as the void image with respect to the observation region.

From the viewpoint of highly accurate evaluation and specification of the porosity, it is preferable to use an arithmetic average of the porosities calculated for a plurality of SEM sectional images and observation regions as the porosity. Therefore, in a preferred embodiment, the void ratio is an arithmetic average of the area ratios (%) of void regions obtained for an SEM cross-sectional image at 50 points of the cured product.

Typically, the porosity can be measured by the method described in the section for measuring the porosity of a cured product described later. When an SEM cross-sectional image at 50 points of the cured product is obtained, it is preferable that cross-sections of a plurality of test pieces of a single sample are exposed (cross-sections of vertical cross-sections are exposed). Moreover, the cross-sectional exposure (preferably, the cross-sectional exposure in the vertical cross-section) may be performed a plurality of times for 1 test piece.

The compression molding step and the post-curing step performed when preparing a cured product sample for obtaining the porosity will be described below.

< compression Molding Process >

In the compression molding step, the resin composition was disposed so as to bond to the silicon wafer, and then compression molding was performed under conditions of a pressure of 15 tons, a temperature of 130 ℃ and 10 minutes to obtain a compression-molded article of the resin composition having a thickness of 300 μm bonded to the silicon wafer.

The compression molding step may be carried out by any device including a metal mold as long as the silicon wafer and the resin composition are compression molded under the above conditions to give a compression molded article of the resin composition bonded to the silicon wafer. For example, the compression molding step may be performed by a compression molding machine including a pair of separable metal molds.

As the pair of metal molds, it is preferable that the silicon wafer be disposed in either one of a metal mold located below in the vertical direction and a metal mold located above in the same vertical direction. In one embodiment, the compression molding step is performed by using a compression molding machine including a pair of separable molds, a silicon wafer is disposed in the mold positioned vertically below, and the resin composition is disposed between the mold positioned vertically above and the silicon wafer. In another embodiment, the compression molding step is performed by using a compression molding machine including a pair of separable molds, the silicon wafer is disposed in the mold positioned vertically above, and the resin composition is disposed between the mold positioned vertically below and the silicon wafer. The silicon wafer and the resin composition may be disposed separately, or the silicon wafer and the resin composition may be disposed in contact with each other. That is, the positional relationship between the silicon wafer and the resin composition may be such that the silicon wafer is disposed above the resin composition or the resin composition is disposed above the silicon wafer, as long as both are disposed so as to be capable of bonding.

The silicon wafer and the resin composition are preferably arranged in a mold having an interior previously heated to 130 ℃. The temperature for heating the metal mold was set to 130 ℃, but the inside of the metal mold may be heated so as to allow variation within a range of +5 ℃ during or before the compression molding step.

In the compression molding step, it is preferable that the pressure is set to 15 tons quickly after the start of pressing, for example, within 60 seconds. The time may be measured by setting the pressing start point to a time when the mold clamping operation is started or a time when the distance separating the pair of molds starts to be narrowed. The mold clamping operation is preferably started quickly. The 10 minutes, which is one of the conditions of the compression molding step, is usually a time period after the resin composition is exposed to a temperature of 130 ℃, but is preferably an elapsed time after the pressure reaches 15 tons.

The silicon wafer is not limited as long as it has a size that gives a cured product of the resin composition capable of measuring the porosity, but in the compression molding step, for example, the thickness: 775 μm, diameter: a 12 inch silicon wafer was placed in a metal mold. When it is necessary to remove the compression-molded article of the resin composition from the silicon wafer, it is preferable to subject the silicon wafer to a mold release treatment in advance.

The thickness of the compression molded article of the resin composition is 300 μm, but it is not necessarily strictly 300 μm, and in the compression molding step, compression molding may be performed so as to allow variation in the thickness of the compression molded article of the resin composition within a range of ± 5 μm.

From the viewpoint of highly accurate evaluation and defining the porosity, the compression molding step particularly preferably includes the following steps (c1) to (c4) in order:

(c1) disposing a silicon wafer and a resin composition in a mold having a release film attached thereto;

(c2) a step of clamping the mold within 90 seconds after the setting of the resin composition to bond the silicon wafer and the resin composition;

(c4) and a step of compression molding under conditions of a pressure of 15 tons, a temperature of 130 ℃ and 10 minutes to obtain a compression molded article of the resin composition having a thickness of 300 μm bonded to the silicon wafer. The compression molding step including the steps (c1) to (c4) in this order is also referred to as a "standardized compression molding step".

In the standardized compression molding step, the silicon wafer and the resin composition are arranged in the step (c1) as described above, and in one embodiment, the compression molding step is performed using a compression molding machine including a pair of separable molds, and the silicon wafer is provided on the surface of the mold positioned vertically downward. Other embodiments are as previously described.

As the release film used in the step (c1), a commercially available product which has not been subjected to embossing (embossing) or the like, specifically, a commercially available product which has been mirror-polished can be used from the viewpoint of obtaining a cured product of the resin composition having a uniform thickness of 300 μm. Such a commercially available product is manufactured by AGC corporation "アフレックス (registered trademark) 50N390 NT" (mirror finish).

In the step (c2), the mold is closed within 90 seconds after the resin composition is set, and the silicon wafer is bonded to the resin composition. In the case where the compression molding process is performed using a compression molding machine including a pair of separable dies, the start of mold clamping means that the distance between the pair of dies is reduced.

In the step (c3), the reduced pressure level is a vacuum level at which the reduced pressure is obtained. The degree of pressure reduction is preferably in the range of 0 to 0.7torr, and in one embodiment, 0.2 torr.

The step (c4) is the same as the step described in the compression molding step, and therefore, the description thereof is omitted.

The standardized compression molding step is not limited as long as the steps (c1) to (c4) are included in this order, and typically, the compression molding step described in the examples described below can be employed as the standardized compression molding step.

< post-curing Process >

In the post-curing step, the compression-molded article of the obtained resin composition was heated at 150 ℃ for 1 hour in a nitrogen atmosphere to obtain a cured product.

From the viewpoint of highly accurate evaluation and defining the porosity, it is particularly preferable that the post-curing step comprises the following steps (p1) to (p2) in order:

(p1) a step of charging the compression-molded resin composition taken out of the mold into an oven set to a temperature of 150 ℃ and 1atm in a nitrogen atmosphere, and waiting for 1 hour to elapse to obtain a cured product; and

(p2) the step of taking out the cured product from the oven within 120 seconds after the step (p1) and cooling the cured product in a normal temperature and pressure environment. The post-curing step including the steps (p1) to (p2) in this order is also referred to as a "standardized post-curing step".

In the post-curing step, it is preferable that the oven be preliminarily set to a nitrogen atmosphere, a temperature of 150 ℃ and a pressure of 1atm before the step (p1), whereby the compression-molded resin composition can be rapidly charged into the oven in the step (p 1). Further, the compressed molded body of the resin composition charged into the oven may have a silicon wafer.

In the step (p2), in order to avoid the continuation of the undesired heating in the step (p1), the cured product may be quickly taken out of the oven, and therefore, the time is within the predetermined 120 seconds, preferably within 110 seconds, more preferably within 100 seconds. The cured product taken out of the oven can be allowed to cool in an environment of normal temperature and pressure, for example, an environment of 1 atmosphere + -1 atmosphere and a temperature of 23 deg.C + -5 deg.C, preferably an environment of 1 atmosphere + -0.5 atmosphere and a temperature of 23 deg.C + -5 deg.C. The humidity in the environment is preferably 40-60%, for example 50%. In this step, it is preferable to confirm that the surface temperature of the cured product reaches 23 ℃, but it can be considered that the temperature reaches room temperature after a predetermined time (for example, 6 hours) has elapsed.

The thickness of the cured product (resin composition layer) obtained through the step (p2) is preferably less than. + -. 5%, more preferably within the range of 300. mu. m. + -. 5 μm, of the thickness before post-curing. When the degree of curing of the same cured product (resin composition layer) is measured by differential scanning calorimetry using a differential scanning calorimetry apparatus ("DSC 7020" manufactured by hitachi High-Tech Science), the post-curing step is preferably performed so that the degree of curing becomes 95% or more, more preferably 96% or more.

The standardized post-curing step is not limited as long as the above-described steps (p1) to (p2) are included in this order, and typically, a post-curing step described in examples described later can be employed as the standardized post-curing step.

The cured product to be evaluated for the porosity is preferably subjected to the compression molding step and the post-curing step so that the degree of curing thereof becomes 95% or more, more preferably 96% or more. The degree of curing can be measured by differential scanning calorimetry using a differential scanning calorimetry apparatus ("DSC 7020" manufactured by Hitachi High-Tech Science Co., Ltd.).

The resin composition of the present invention has a porosity of 0.002% to 2% in a cured product thereof. Thus, the resin composition of the present invention can provide a cured product that is suppressed in warpage and has excellent mechanical properties. In addition, the resin composition of the present invention, which exhibits a porosity after curing in the range of 0.002% to 2%, tends to give a cured product excellent in dielectric characteristics.

From the viewpoint of obtaining a cured product in which the occurrence of warpage is more suppressed, the porosity is preferably 0.002% or more, more preferably 0.0025% or more, and still more preferably 0.003% or more. From the viewpoint of obtaining a cured product having more excellent mechanical properties, the void ratio is preferably 2% or less, more preferably 1.95% or less, and still more preferably 1.9% or less.

In place of the above porosity or in addition to the above porosity, the following resin porosity is also preferably evaluated. The resin porosity indicates an area ratio (%) of a void region in a resin component region to the observation region, the void region being obtained by image analysis, excluding void regions in a region depicted by an outer shape region of the inorganic filler (C) described later, out of void regions in the void image obtained as the void image. Unless otherwise stated, the resin component means a component other than (C) the inorganic filler among nonvolatile components in the resin composition, and the resin component region means a region other than the inorganic filler region in a cured product of the resin composition. When the compression molding step and the post-curing step are performed using a resin composition containing a solid inorganic filler as the inorganic filler, which is an inorganic filler substantially free from inclusion voids, the void ratio and the resin void ratio can generally be the same value. In this case, the resin porosity is preferably in the range of 0.002% to 2% as in the case of the above porosity.

When the compression molding step and the post-curing step are performed using a resin composition containing an inorganic filler (so-called hollow filler) containing voids therein as the inorganic filler, the resin void ratio does not count voids in the inorganic filler, and therefore generally exhibits a value smaller than the void ratio. In this case, the resin porosity is preferably in the range of 0.0025% to 1.95%, more preferably in the range of 0.003% to 1.9%. However, from the viewpoint of improving the accuracy of measurement of the void ratio, it is preferable not to use a hollow filler as the inorganic filler, and from the viewpoint described above, even when the resin composition contains a hollow filler, the content is more preferably less than 0.005% by mass, still more preferably 0.003% by mass or less, and particularly preferably 0.001% by mass or less, when the nonvolatile component of the resin composition is 100% by mass.

[ composition of the resin composition ]

The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler. The resin composition of the present invention may contain components other than the component (A), the component (B) and the component (C), for example, (D) a curing accelerator, (E-1) a silane coupling agent, (E-2) a reactive component, (E-3) a non-reactive additive, other additives and a solvent, as long as the resin composition satisfies the above range of the porosity after curing. Among them, the components constituting the resin composition differ in the presence or absence of an influence on the generation of voids and in the degree thereof, and the degree of the influence on the generation of voids is increased or weakened even by the combination of the components. Hereinafter, a preferred composition of the resin composition when the above-mentioned range of the void ratio is satisfied after curing is described, but the preferred type and preferred content range vary depending on the combination of the components. The kind (combination) and content of the components constituting the resin composition are not limited to the specific kinds and ranges shown below as long as the porosity after curing is within the above range.

[ (A) epoxy resin ]

The resin composition of the present invention comprises (a) an epoxy resin. (A) The epoxy resin means a resin having an epoxy group.

Examples of the epoxy resin (a) include a biscresol (bixylenol) type epoxy resin, a bisphenol a type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; bisphenol AF type epoxy resin; dicyclopentadiene type epoxy resins; a trisphenol type epoxy resin; phenol novolac (phenol novolac) type epoxy resins; glycidyl amine type epoxy resins; glycidyl ester type epoxy resins; cresol novolac (cresol novolac) type epoxy resins; biphenyl type epoxy resin; a linear aliphatic epoxy resin; an epoxy resin having a butadiene structure; a cycloaliphatic epoxy resin; a cycloaliphatic epoxy resin having an ester skeleton; heterocyclic epoxy resins; epoxy resins containing spiro rings; a cyclohexane type epoxy resin; cyclohexane dimethanol type epoxy resins; a trihydroxymethyl-type epoxy resin; tetraphenylethane-type epoxy resins; epoxy resins having a condensed ring skeleton such as naphthylene ether type epoxy resins, t-butyl catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, naphthol novolac (naphtholac) type epoxy resins, and the like; isocyanurate type epoxy resins; an epoxy resin having an alkyleneoxy skeleton and a butadiene skeleton; an epoxy resin containing a fluorene structure; and the like. (A) The epoxy resin may be used alone or in combination of two or more.

The epoxy resin (a) may contain an epoxy resin having an aromatic structure, from the viewpoint of obtaining a cured product having excellent heat resistance. Aromatic structures refer to chemical structures generally defined as aromatic, and also include polycyclic aromatic and aromatic heterocycles. Examples of the epoxy resin having an aromatic structure include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, t-butyl catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy resin, glycidylamine type epoxy resin having an aromatic structure, glycidyl ester type epoxy resin having an aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, epoxy resin having a butadiene structure having an aromatic structure, alicyclic epoxy resin having an aromatic structure, heterocyclic type epoxy resin, A spiro ring-containing epoxy resin having an aromatic structure, a cyclohexane dimethanol type epoxy resin having an aromatic structure, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin having an aromatic structure, a tetraphenylethane type epoxy resin having an aromatic structure, and the like.

Among the epoxy resins having an aromatic structure, epoxy resins having a condensed ring structure are preferably used from the viewpoint of obtaining a cured product having excellent heat resistance. Examples of the condensed ring in the epoxy resin having a condensed ring structure include naphthalene rings, anthracene rings, phenanthrene rings, and the like, and naphthalene rings are particularly preferable. Therefore, (a) the epoxy resin preferably contains a naphthalene type epoxy resin containing a naphthalene ring structure. The amount of the naphthalene type epoxy resin is preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, more preferably 50% by mass or less, further preferably 40% by mass or less, further preferably 30% by mass or less, based on 100% by mass of the total amount of the epoxy resin (A).

The epoxy resin (a) may include a glycidylamine type epoxy resin from the viewpoint of improving the heat resistance and metal adhesion of the cured product.

(A) The epoxy resin may include an epoxy resin having a butadiene structure.

In the resin composition, the epoxy resin (a) is preferably an epoxy resin having 2 or more epoxy groups in 1 molecule. The proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, based on 100% by mass of the nonvolatile component of the epoxy resin (a).

The epoxy resin includes an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "liquid epoxy resin") and an epoxy resin which is solid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "solid epoxy resin"). In the resin composition of the present embodiment, the epoxy resin may contain only the (a-1) liquid epoxy resin, only the (a-2) solid epoxy resin, or a combination of the liquid epoxy resin and the solid epoxy resin, but it is preferable to contain at least the liquid epoxy resin.

The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.

The liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, an epoxy resin having a butadiene structure, an epoxy resin containing an alkyleneoxy skeleton and a butadiene skeleton, an epoxy resin containing a fluorene structure, or a dicyclopentadiene type epoxy resin. Among them, bisphenol a type epoxy resins, bisphenol F type epoxy resins, naphthalene type epoxy resins, glycidylamine type epoxy resins, alicyclic epoxy resins having an ester skeleton, epoxy resins having a butadiene structure, epoxy resins containing an alkyleneoxy skeleton and a butadiene skeleton, epoxy resins containing a fluorene structure, and dicyclopentadiene type epoxy resins are particularly preferable.

Specific examples of the liquid epoxy resin include "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene type epoxy resin) manufactured by DIC corporation; "828 US", "828 EL", "jER 828 EL", "825", "EPIKOTE 828 EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi chemical company; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630", "630 LSD" and "604" (glycidyl amine type epoxy resins) manufactured by Mitsubishi chemical company; "ED-523T" (Glycirol type epoxy resin) manufactured by ADEKA corporation; "EP-3950L" and "EP-3980S" (glycidylamine-type epoxy resins) manufactured by ADEKA; EP-4088S (dicyclopentadiene type epoxy resin) manufactured by ADEKA corporation; "ZX 1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon iron chemical Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "EX-991L" (epoxy resin having alkyleneoxy skeleton) "and" EX-992L "(epoxy resin having polyether) manufactured by Nagase ChemteX; "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Dailuo corporation; "PB-3600" manufactured by Daxylonite, JP-100 "and JP-200" manufactured by Nippon Caoda (a butadiene-structured epoxy resin); "ZX 1658" and "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) manufactured by Nippon iron chemical materials Co., Ltd.; "EG-280" (epoxy resin containing fluorene structure) manufactured by osaka gas chemical company; and the like.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.

As the solid epoxy resin, preferred are a biscresol (bixylenol) type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol a type epoxy resin, a bisphenol AF type epoxy resin, and a tetraphenylethane type epoxy resin.

Specific examples of the solid epoxy resin include "HP 4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200", "HP-7200 HH" and "HP-7200H" (dicyclopentadiene type epoxy resins) manufactured by DIC corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" and "HP 6000" (naphthylene ether type epoxy resins) manufactured by DIC corporation; EPPN-502H (a trisphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H", "NC 3000L" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical and pharmaceutical company; ESN475V (naphthol type epoxy resin) manufactured by Nippon iron chemical Co., Ltd; ESN485 (naphthol novolac type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "YX 4000H", "YX 4000", "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical company; "YX 4000 HK" (bisphenol type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; "YX 7700" (novolac-type epoxy resin containing a xylene structure) manufactured by mitsubishi chemical corporation; PG-100 and CG-500 manufactured by Osaka gas chemical company; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 1010" (solid bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation, and the like.

The amount of the liquid epoxy resin (A-1) is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, particularly preferably 100% by mass, based on 100% by mass of the total amount of the epoxy resin (A).

(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5000g/eq, more preferably 50g/eq to 3000g/eq, still more preferably 80g/eq to 2000g/eq, and still more preferably 110g/eq to 1000g/eq. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 200 to 3000, further preferably 400 to 1500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

The amount of the epoxy resin (A) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, particularly preferably 1.5% by mass or more, further preferably 45% by mass or less, further preferably 40% by mass or less, particularly preferably 30% by mass or less, based on 100% by mass of the nonvolatile matter in the resin composition.

The amount of the epoxy resin (A) is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, further preferably 80% by mass or less, further preferably 70% by mass or less, particularly preferably 60% by mass or less, based on 100% by mass of the resin component in the resin composition. The resin component in the resin composition means, unless otherwise specified, a component other than (C) the inorganic filler among nonvolatile components in the resin composition.

[ (B) curing agent ]

The resin composition of the present invention contains (B) a curing agent. (B) The curing agent generally has a function of reacting with the (a) epoxy resin to cure the resin composition. Examples of the curing agent (B) include an active ester curing agent, a phenol curing agent, a benzoxazine curing agent, a carbodiimide curing agent, an acid anhydride curing agent, an amine curing agent, and a cyanate curing agent. In one embodiment, at least one selected from the group consisting of an acid anhydride-based curing agent, an amine-based curing agent, and a phenol-based curing agent may be used as the (B) curing agent. When an acid anhydride-based curing agent, an amine-based curing agent or a phenol-based curing agent is used, warpage of a cured product can be generally suppressed. One curing agent may be used alone, or two or more curing agents may be used in combination. As the curing agent (B), at least one selected from the group consisting of a liquid curing agent (B-1) and a solid curing agent (B-2) can be used, and it is preferable to use a liquid curing agent (B-1). In one embodiment, (B) the curing agent is formed of (B-1) a liquid curing agent. "liquid curing agent" means a curing agent that is liquid at a temperature of 20 ℃, and "solid curing agent" means a curing agent that is solid at a temperature of 20 ℃.

Examples of the acid anhydride-based curing agent include a curing agent having 1 or more acid anhydride groups in 1 molecule, and preferably 2 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic anhydride, 3,3'-4,4' -diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5, and polymer type acid anhydrides such as 9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (trimellitic anhydride ester), and styrene-maleic acid resins obtained by copolymerizing styrene and maleic acid. Examples of commercially available products of acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA" and "OSA" manufactured by Nissan chemical and physical Co., Ltd.; "YH 306" and "YH 307" manufactured by Mitsubishi chemical corporation; HN-2200 and HN-5500 manufactured by Hitachi chemical Co.

Examples of the amine-based curing agent include those having 1 or more, preferably 2 or more, amino groups in 1 molecule. Specific examples thereof include aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines, and among them, aromatic amines are preferred. The amine-based curing agent is preferably a primary or secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4 '-methylenebis (2, 6-dimethylaniline), diphenyldiaminosulfone, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4 '-diaminodiphenyl ether, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dihydroxybiphenylamine, 2-bis (3-amino-4-hydroxyphenyl) propane, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethanediamine, and, 2, 2-bis (4-aminophenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone and the like. As the amine-based curing agent, commercially available products are used, and examples thereof include "SEIKACIURE-S" manufactured by SEIKA corporation, "KAYABOND C-200S" manufactured by Nippon Kagaku corporation, "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S", "EPICURE W" manufactured by Mitsubishi chemical corporation, and "DTDA" manufactured by Sumitomo refining corporation.

Examples of the phenol-based curing agent include those having 1 or more, preferably 2 or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or naphthalene ring in 1 molecule. Among them, compounds having a hydroxyl group bonded to a benzene ring are preferred. In addition, a phenol-based curing agent having a phenolic structure (novolac structure) is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Particularly, a phenol novolak curing agent having a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.

Specific examples of the phenolic curing agent include "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000H" manufactured by Kogyo Co., Ltd; "NHN", "CBN" and "GPH" manufactured by Nippon chemical Co., Ltd; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165", manufactured by DIC; GDP-6115L, GDP-6115H, ELPC75, manufactured by Rongche chemical Co., Ltd; "2, 2-Diallylbisphenol A" manufactured by Sigma-Aldrich Co.

(B) The active group equivalent of the curing agent is preferably 50 g/eq.3000 g/eq, more preferably 100 g/eq.1000 g/eq, still more preferably 100 g/eq.500 g/eq, and particularly preferably 100 g/eq.300 g/eq. The reactive group equivalent means the mass of the curing agent per 1 equivalent of the reactive group.

The amount of the curing agent (B) is preferably determined so that the number of active groups is determined in accordance with the number of epoxy groups of the epoxy resin (A). For example, when the number of epoxy groups in the epoxy resin (A) is 1, the number of active groups in the curing agent (B) is preferably at least 0.1, more preferably at least 0.3, still more preferably at least 0.5, yet more preferably at most 5.0, yet more preferably at most 4.0, still more preferably at most 3.0. Here, "the number of epoxy groups of the (a) epoxy resin" represents a total value of all values obtained by dividing the mass of nonvolatile components of the (a) epoxy resin present in the resin composition by the epoxy equivalent weight. The term "the number of active groups of the (B) curing agent" means a total value of all the values obtained by dividing the mass of nonvolatile components of the (B) curing agent present in the resin composition by the equivalent of the active groups.

The amount of the curing agent (B) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1.0% by mass or more, further preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass or less, based on 100% by mass of the nonvolatile matter in the resin composition.

[ (C) inorganic Filler Material ]

The resin composition of the present invention contains (C) an inorganic filler. The cured product of the resin composition containing (C) an inorganic filler can generally reduce the thermal expansion coefficient.

As the inorganic filler, an inorganic compound is used. Examples of the inorganic filler include: silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate zirconate, barium zirconate, zirconium phosphate, zirconium phosphotungstate phosphate, and the like. Among them, silica and alumina are suitable, and silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as the silica, spherical silica is preferable. (C) The inorganic filler may be used alone or in combination of two or more.

As the inorganic filler (C), one or more selected from a solid inorganic filler and a hollow inorganic filler can be used. "solid inorganic filler" means an inorganic filler substantially free of voids or pores, and "hollow inorganic filler" means an inorganic filler having voids or pores enclosed therein. In one embodiment, (C) the inorganic filler material is formed of a solid inorganic filler material.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the average particle size of the inorganic filler (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, more preferably 5 μm or less, more preferably 4.5 μm or less, still more preferably 4.1 μm or less.

(C) The average particle diameter of the component can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size is measured as an average particle size. As the measurement sample, a sample obtained by weighing 100mg of the inorganic filler and 10g of methyl ethyl ketone in a vial and dispersing them by ultrasonic waves for 10 minutes can be used. For the measurement sample, the volume-based particle size distribution of the inorganic filler (C) was measured in a flow cell (flow cell) using a laser diffraction type particle size distribution measuring apparatus with the wavelengths of the light source used set to blue and red, and the average particle size was calculated from the obtained particle size distribution as the median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Ltd.

(C) The specific surface area of the inorganic filler is preferably 1m²More than g, preferably 1.5m²More preferably 2 m/g or more²More than g, particularly preferably 3m²More than g. The upper limit is not particularly limited, but is preferably 60m²Less than 50 m/g²Less than or equal to 40 m/g²The ratio of the carbon atoms to the carbon atoms is below g. The specific surface area can be obtained by: according to the BET method, nitrogen gas was adsorbed on the surface of the sample using a specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountech), and the specific surface area was calculated by the BET multipoint method.

Examples of commercially available products of the inorganic filler (C) include "SP 60-05", "SP 507-05", "ST 7010-2" manufactured by Nippon iron chemical Co., Ltd; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by Yadama corporation; "SILFIL (シルフィル) NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N" manufactured by Deshan company; "SC 2500 SQ", "SO-C4", "SO-C2", "SO-C1", "SO-C5", "SO-C6", "FE 9 series", "FEB series", "FED series" manufactured by Yatoma corporation; "DAW-03", "DAW-10", "FB-105 FD", "UFP-30" manufactured by DENKA corporation, and the like. Commercially available products can be pulverized, mixed, classified, or a combination thereof so as to have the above particle size distribution, and can be used by adjusting the particle size distribution to an appropriate one.

The inorganic filler (C) may be treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilicon azane compounds, titanate coupling agents, and the like. The surface treatment agent may be used alone or in combination of two or more kinds.

Examples of commercially available surface-treating agents include "KBM 403" (3-glycidoxypropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd., "KBM 803" (3-mercaptopropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd., "KBE 903" (3-aminopropyltriethoxysilane) manufactured by shin-Etsu chemical Co., Ltd., "KBM 903" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by shin-Etsu chemical Co., Ltd., "KBM 103" (phenyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd., "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by shin-Etsu chemical Co., Ltd., "KBM-7103" (3,3, 3-trifluoropropyltrimethoxysilane), and the like.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2to 5 parts by mass of the surface treatment agent, more preferably 0.2to 3 parts by mass of the surface treatment agent, and still more preferably 0.3 to 2 parts by mass of the surface treatment agent.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02mg/m²Above, preferably 0.1mg/m²The above, more preferably 0.2mg/m²As described above. On the other hand, from the viewpoint of suppressing the increase in melt viscosity of the resin composition, it is preferably 1mg/m²The concentration is preferably 0.8mg/m or less²More preferably 0.5mg/m or less²The following.

The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after surface treatment is subjected to a cleaning treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, a sufficient amount of MEK was added as a solvent to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning was performed at 25 ℃ for 5 minutes. After removing the supernatant liquid and drying the solid components, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd., can be used.

(C) The amount of the inorganic filler is not particularly limited, and from the viewpoint of increasing the void ratio in the resin component region of the cured product, the amount of the (C) inorganic filler is 30 mass% or more, preferably 40 mass% or more, more preferably 50 mass% or more, further more preferably more than 50 mass%, with respect to 100 mass% of the nonvolatile component in the resin composition, and may be 70 mass% or more, 75 mass% or more, or 76 mass% or more. (C) The amount of the inorganic filler is not particularly limited, and may be 96% by mass or less, 95% by mass or less, 94% by mass or less, or 93% by mass or less with respect to 100% by mass of nonvolatile components in the resin composition. The cured product of the resin composition containing the inorganic filler (C) in an amount within such a range can effectively reduce the thermal expansion coefficient.

[ (D) curing Accelerator ]

The resin composition of the present invention may further contain (D) a curing accelerator as an optional component. The curing accelerator (D) can effectively adjust the curing time of the resin composition.

Examples of the curing accelerator (D) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, imidazole-based curing accelerators are preferred. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5,4,0) -undecene, 1, 8-diazabicyclo [5,4,0] undecene-7, 4-dimethylaminopyridine, and 2,4, 6-tris (dimethylaminomethyl) phenol, and 4-dimethylaminopyridine and 1, 8-diazabicyclo (5,4,0) -undecene are preferred.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-methylimidazole, 1, 2-benzyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-methylimidazole, and the like, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [ 2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [ 2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [ 2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [ 2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanuric acid adduct, and mixtures thereof, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, imidazole compounds such as 2-methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi chemical corporation, "Curezol 2 MZ", "2E 4 MZ", "Cl 1Z", "Cl 1Z-CN", "Cl 1Z-CNS", "Cl 1Z-A", "2 MZ-OK", "2 MA-OK-PW" and "2 PHZ" manufactured by Mitsubishi chemical corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like, dicyandiamide, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene is preferred.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

(D) The amount of the curing accelerator is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, further preferably 5% by mass or less, further preferably 4% by mass or less, further preferably 3% by mass or less, based on 100% by mass of nonvolatile components in the resin composition.

[ (E-1) silane coupling agent ]

The resin composition of the present invention may further contain (E-1) a silane coupling agent as an optional component. However, when a silane coupling agent is used as a surface treatment agent for an inorganic filler, the inorganic filler treated with the surface treatment agent is classified as the component (C) described above. By containing a silane coupling agent as the (E-1) component, the bonding of the resin component and the inorganic filler can be expected.

Examples of the silane coupling agent include an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, an alkoxysilane compound, an organosilazane compound, and a titanate coupling agent. Among them, epoxy silane-based coupling agents containing an epoxy group and mercapto silane-based coupling agents containing a mercapto group are preferred, and epoxy silane-based coupling agents are particularly preferred. The silane coupling agent may be used alone or in combination of two or more. In one embodiment, a single type of silane coupling agent is contained as the (E-1) component. In another embodiment, a plurality of types, for example, 2 types of silane coupling agents are contained as the component (E-1). The resin composition of the present invention preferably contains a plurality of types of silane coupling agents, and preferably contains a plurality of types of silane coupling agents in combination with the silane coupling agent used as the component (C) surface treatment agent and the silane coupling agent used as the component (E-1).

As the silane coupling agent, for example, commercially available products can be used. Examples of commercially available silane coupling agents include "KBM 403" (3-glycidoxypropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM 803" (3-mercaptopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBE 903" (3-aminopropyltriethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "SZ-31" (hexamethyldisilazane) available from shin-Etsu chemical Co., Ltd, "KBM 103" (phenyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM-4803" (long-chain epoxy-type silane coupling agent) available from shin-Etsu chemical Co., Ltd, "KBM-7103" (3,3, 3-trifluoropropyltrimethoxysilane), KBM503 (3-methacryloxypropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, KBM5783 manufactured by shin-Etsu chemical industries, and the like.

The amount of the (E-1) silane coupling agent is 0% by mass or more, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, and 10% by mass or less, 5% by mass or less, or 3% by mass or less, based on 100% by mass of nonvolatile components in the resin composition.

The amount of (E-1) the silane coupling agent is 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, 15% by mass or less, 10% by mass or less, or 5% by mass or less, relative to 100% by mass of the resin component in the resin composition.

[ (E-2) reactive component ]

The resin composition of the present invention may further contain (E-2) a reactive component as an optional component. (A) The component (B), the component (D) and the component (E-1) are excluded from the component (E-2). The component (E-2) has a reactive functional group and is a component which can be expected to react with the component (A) and/or the component (E-2). The reactive functional group may be a functional group that exhibits reactivity by heating or light irradiation. By including the component (E-2) in the resin composition, the component (E-2) can be inserted into the crosslinked structure formed by the component (A). The component (E-2) may be used singly or in combination of two or more.

Examples of the reactive functional group include-OH and-NH₂and-COOH. However, compounds containing an epoxy group as a reactive functional group are classified as component (a). Further, the reactive functional group may be a group having an ethylenic unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include compounds having a radical polymerizable group such as a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, a maleoyl group, a vinylphenyl group, a styryl group, a cinnamoyl group, and a maleimido group (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl group).

Examples of the component (E-2) include (E-2-1) a radical polymerizable compound and (E-2-2) a polyether skeleton-containing compound having a reactive functional group.

[ (E-2-1) radically polymerizable Compound ]

The resin composition of the present invention may further contain (E-2-1) a radical polymerizable compound as an optional component.

As the radical polymerizable compound (E-2-1), a compound having an ethylenically unsaturated bond can be used. Examples of the (E-2-1) radically polymerizable compound include compounds having a radically polymerizable group such as a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, a maleoyl group, a vinylphenyl group, a styryl group, a cinnamoyl group, and a maleimido group (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl group). The radical polymerizable compound (E-2-1) may be used singly or in combination of two or more kinds.

Specific examples of the (E-2-1) radical polymerizable compound include (meth) acrylic radical polymerizable compounds having 1 or 2 or more acryloyl groups and/or methacryloyl groups; a styrene-based radical polymerizable compound having 1 or 2 or more vinyl groups directly bonded to an aromatic carbon atom; an allyl radical polymerizable compound having 1 or 2 or more allyl groups; a maleimide-based radical polymerizable compound having 1 or 2 or more maleimide groups; and so on. Among them, a (meth) acrylic radical polymerizable compound is preferred.

The (E-2-1) radical polymerizable compound preferably contains a polyoxyalkylene (polyalkylene oxide) structure. By using the (E-2-1) radically polymerizable compound having a polyoxyalkylene structure, the flexibility of a cured product of the resin composition can be improved.

The polyoxyalkylene structure can be represented by formula (1): - (R)^fO)_n-represents. In formula (1), n generally represents an integer of 2 or more. The integer n is preferably 4 or more, more preferably 9 or more, further preferably 11 or more, usually 101 or less, preferably 90 or less, further preferably 68 or less, further preferably 65 or less. In the formula (1), R^fEach independently represents an alkylene group which may have a substituent. The number of carbon atoms of the alkylene group is preferably 1 or more, more preferably 2 or more, further preferably 6 or less, further preferably 5 or less, further preferably 4 or less, further preferably 3 or less, particularly preferably 2. Examples of the substituent optionally contained in the alkylene group include a halogen atom, -OH, an alkoxy group, a primary substituentOr secondary amino, aryl, -NH₂、-CN、-COOH、-C(O)H、-NO₂And so on. However, the alkyl group is preferably unsubstituted. Specific examples of the polyoxyalkylene structure include a polyoxyethylene structure, a polyoxypropylene structure, a polyoxyn-butylene structure, a poly (oxyethylene-co-oxypropylene) structure, a poly (oxyethylene-ran-oxypropylene) structure, a poly (oxyethylene-alt-oxypropylene) structure, and a poly (oxyethylene-block-oxypropylene) structure.

(E-2-1) the number of polyoxyalkylene structures contained in 1 molecule of the radical polymerizable compound may be 1, or may be 2 or more. The number of polyoxyalkylene structures contained in 1 molecule of the (E-2-1) radically polymerizable compound is preferably at least 2, more preferably at least 4, still more preferably at least 9, particularly preferably at least 11, preferably at most 101, more preferably at most 90, still more preferably at most 68, particularly preferably at most 65. (E-2-1) when the radical polymerizable compound contains 2 or more polyoxyalkylene structures in 1 molecule, these polyoxyalkylene structures may be the same as or different from each other.

Examples of commercially available products of (E-2-1) radically polymerizable compounds having a polyoxyalkylene structure include monofunctional acrylates "AM-90G", "AM-130G" and "AMP-20 GY", manufactured by Ninghamu chemical industries, Ltd.; 2-functional acrylates "A-1000", "A-B1206 PE", "A-BPE-20", "A-BPE-30"; monofunctional methacrylates "M-20G", "M-40G", "M-90G", "M-130G", "M-230G"; and 2-functional methacrylates "23G", "BPE-900", "BPE-1300N", "1206 PE". Further, examples of the other compounds include "Light ester BC", "Light ester 041 MA", "Light acrylate EC-A", and "Light acrylate EHDG-AT", manufactured by Kyoeisha chemical Co., Ltd.; "FA-023M" manufactured by Hitachi chemical Co., Ltd.; "BLEMMER (registered trademark) PME-4000", "BLEMMER (registered trademark) 50 POEO-800B", "BLEMMER (registered trademark) PLE-200", "BLEMMER (registered trademark) PLE-1300", "BLEMMER (registered trademark) PSE-1300", "BLEMMER (registered trademark) 43 PAPE-600B", "BLEMMER (registered trademark) ANP-300", manufactured by Nikko oil Co., Ltd. In one embodiment, "M-130G" or "BPE-1300N" can be used as the (E-2-1) radically polymerizable compound having a polyoxyalkylene structure.

(E-2-1) the equivalent weight of the ethylenically unsaturated bond in the radically polymerizable compound is preferably 20 g/eq.about 3000g/eq, more preferably 50 g/eq.about 2500g/eq, still more preferably 70 g/eq.about 2000g/eq, particularly preferably 90 g/eq.about 1500g/eq. The ethylenic unsaturated bond equivalent is the mass of the radical polymerizable compound per 1 equivalent of the ethylenic unsaturated bond.

(E-2-1) the weight average molecular weight (Mw) of the radical polymerizable compound is preferably 150 or more, more preferably 250 or more, further preferably 400 or more, preferably 40000 or less, further preferably 10000 or less, further preferably 5000 or less, particularly preferably 3000 or less.

The amount of the (E-2-1) radical polymerizable compound is 0% by mass or more, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, and 15% by mass or less, 10% by mass or less, or 8% by mass or less, relative to 100% by mass of nonvolatile components in the resin composition.

The amount of the (E-2-1) radical polymerizable compound is 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, and 25% by mass or less, 20% by mass or less, or 15% by mass or less, relative to 100% by mass of the resin component in the resin composition.

[ (E-2-2) Compound having reactive functional group and polyether skeleton-containing Compound ]

The resin composition of the present invention may further contain (E-2-2) a polyether skeleton-containing compound having a reactive functional group as an optional component. The warpage of the cured product of the resin composition can be suppressed by (E-2-2) the polyether skeleton-containing compound having a reactive functional group. (E-2-2) the polyether skeleton-containing compound having a reactive functional group may be used singly or in combination of two or more.

(E-2-2) the polyether skeleton-containing compound having a reactive functional group means a polymer compound having a polyether skeleton. The polyether skeleton-containing compound having a reactive functional group (E-2-2) does not contain the above-mentioned components (A) to (E-2-1). The polyether skeleton contained in the polyether skeleton-containing compound having a reactive functional group (E-2-2) is preferably a polyoxyalkylene skeleton composed of at least one monomer unit selected from the group consisting of an ethylene oxide unit and a propylene oxide unit. Therefore, (E-2-2) the polyether skeleton-containing compound having a reactive functional group preferably does not contain: a polyether skeleton comprising a monomer unit having 4 or more carbon atoms such as a butylene oxide unit and a phenylene oxide unit. Further, (E-2-2) the polyether skeleton-containing compound having a reactive functional group may contain a hydroxyl group as the reactive functional group.

(E-2-2) the polyether skeleton-containing compound having a reactive functional group may have an organosilicon (silicone) skeleton. Examples of the silicone skeleton include polydialkylsiloxane skeletons such as polydimethylsiloxane skeletons; polydiarylsiloxane backbones such as polydiphenylsiloxane backbones; polyalkylaryl siloxane skeletons such as polymethylphenylsiloxane skeletons; a polydialkyl-diarylsiloxane skeleton such as a polydimethyl-diphenylsiloxane skeleton; a polydialkyl-alkylaryl siloxane backbone such as a polydimethyl-methylphenyl siloxane backbone; polydiaryl-alkylaryl siloxane backbone such as polydiphenyl-methylphenyl siloxane backbone, etc., preferably polydialkylsiloxane backbone, particularly preferably polydimethylsiloxane backbone. Examples of the silicone skeleton-containing (E-2-2) polyether skeleton-containing compound include polyoxyalkylene-modified silicones, alkyl etherified polyoxyalkylene-modified silicones (polyoxyalkylene-modified silicones wherein at least a part of the terminal end of the polyether skeleton is an alkoxy group), and the like.

(E-2-2) the polyether skeleton-containing compound having a reactive functional group may contain a polyester skeleton. The polyester skeleton is preferably an aliphatic polyester skeleton. The hydrocarbon chain included in the aliphatic polyester skeleton may be linear or branched, but is preferably branched. The number of carbon atoms contained in the polyester skeleton may be, for example, 4 to 16. The polyester skeleton may be derived from a polycarboxylic acid, a lactone, or an anhydride thereof, and therefore the (E-2-2) polyether skeleton-containing compound having a reactive functional group, which contains a polyester skeleton, may have a carboxyl group at the end of the molecule, and preferably has a hydroxyl group as a reactive functional group at the end of the molecule.

Examples of the polyether skeleton-containing compound having a reactive functional group (E-2-2) include linear polyoxyalkylene glycols (linear polyalkylene glycols) such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; polyoxyalkylene glycols (polyalkylene glycols) such as polyoxyalkylene glycols (multi-chain polyalkylene glycols) of multi-chain type such as polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene trimethylolpropane ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxyethylene pentaerythritol ether, polyoxypropylene pentaerythritol ether, polyoxyethylene sorbitol (polyoxyyethylene sorbitol), polyoxypropylene sorbitol, and polyoxyethylene polyoxypropylene sorbitol; polyoxyalkylene alkyl ethers such as polyoxyethylene monoalkyl ethers, polyoxyethylene dialkyl ethers, polyoxypropylene monoalkyl ethers, polyoxypropylene dialkyl ethers, polyoxyethylene polyoxypropylene monoalkyl ethers, and polyoxyethylene polyoxypropylene dialkyl ethers; polyoxyalkylene esters (including acetate, propionate, butyrate, (meth) acrylate, and the like) such as polyoxyethylene monoester, polyoxyethylene diester, polypropylene glycol monoester, polypropylene glycol diester, polyoxyethylene polyoxypropylene monoester, and polyoxyethylene polyoxypropylene diester; polyoxyalkylene alkyl ether esters (including acetate, propionate, butyrate, (meth) acrylate, and the like) such as polyoxyethylene monoester, polyoxyethylene diester, polyoxypropylene monoester, polyoxypropylene diester, polyoxyethylene polyoxypropylene monoester, polyoxyethylene polyoxypropylene diester, polyoxyethylene alkyl ether ester, polyoxypropylene alkyl ether ester, and polyoxyethylene polyoxypropylene alkyl ether ester; polyoxyalkylene alkylamines such as polyoxyethylene alkylamine, polyoxypropylene alkylamine, and polyoxyethylene polyoxypropylene alkylamine; polyoxyalkylene alkylamides such as polyoxyethylene alkylamides, polyoxypropylene alkylamides and polyoxyethylene polyoxypropylene alkylamides; polyoxyalkylene-modified silicones such as polyoxyethylene polydimethylsiloxane (polyoxyethylenedimeticone), polyoxypropylene polydimethylsiloxane, polyoxyethylene polydimethylsiloxy (siloxy) alkylpolydimethylsiloxane, polyoxypropylene polydimethylsiloxyalkylpolydimethylsiloxane, and polyoxyethylene polyoxypropylene polydimethylsiloxyalkylpolydimethylsiloxane; an alkyl etherified polyoxyalkylene modified silicone (a polyoxyalkylene modified silicone in which at least a part of the terminal of the polyether skeleton is an alkoxy group), such as polyoxyethylene alkyl ether polydimethylsiloxane, polyoxypropylene alkyl ether polydimethylsiloxane, polyoxyethylene polyoxypropylene alkyl ether polydimethylsiloxane, and polyoxyethylene polyoxypropylene alkyl ether polydimethylsiloxane (a polyoxyalkylene modified silicone in which at least a part of the terminal of the polyether skeleton is an alkoxy group), and the like.

The number average molecular weight of the polyether skeleton-containing compound having a reactive functional group (E-2-2) is preferably 500 to 40000, more preferably 500 to 20000, and further preferably 500 to 10000. The weight average molecular weight of the (E-2-2) polyether skeleton-containing compound is preferably 500 to 40000, more preferably 500 to 20000, and further preferably 500 to 10000. The number average molecular weight and the weight average molecular weight can be measured as values converted to polystyrene by a Gel Permeation Chromatography (GPC) method.

(E-2-2) the polyether skeleton-containing compound having a reactive functional group is preferably in a liquid state at 25 ℃. (E-2-2) the viscosity at 25 ℃ of the polyether skeleton-containing compound having a reactive functional group is preferably 100000 mPas or less, more preferably 50000 mPas or less, further preferably 30000 mPas or less, further preferably 10000 mPas or less, further preferably 5000 mPas or less, further preferably 4000 mPas or less, further preferably 3000 mPas or less, further preferably 2000 mPas or less, particularly preferably 1500 mPas or less. The lower limit of the viscosity at 25 ℃ of the polyether skeleton-containing compound having a reactive functional group (E-2-2) is preferably 10 mPas or more, more preferably 20 mPas or more, further preferably 30 mPas or more, further preferably 40 mPas or more, particularly preferably 50 mPas or more. The viscosity may be measured by a B-type viscometer (mPas).

Examples of commercially available products of (E-2-2) the polyether skeleton-containing compound having a reactive functional group include "PLONON # 102", "PLONON # 104", "PLONON # 201", "PLONON # 202B", "PLONON # 204", "PLONON # 208", "UNILUBE 70 DP-600B" and "UNILUBE 70 DP-950B" (polyoxyethylene polyoxypropylene glycol); "Pluronic (プルロニック) (registered trade mark)" L-23 "," Pluronic L-31 "," Pluronic L-44 "," Pluronic L-61 "," ADEKA Pluronic L-62 "," Pluronic L-64 "," Pluronic L-71 "," Pluronic L-72 "," Pluronic L-101 "," Pluronic L-121 "," Pluronic P-84 "," Pluronic P-85 "," Pluronic P-103 "," Pluronic F-68 "," Pluronic F-88 "," Pluronic F-108 "," Pluronic 25R-1 "," Pluronic 25R-2 "," Pluronic 17R-3 "and" Pluronic 17R-4 "(polyoxyethylene polyoxypropylene glycol) manufactured by ADEKA company; "KF-6011", "KF-6011P", "KF-6012", "KF-6013", "KF-6015", "KF-6016", "KF-6017P", "KF-6043", "KF-6004", "KF 351A", "KF 352A", "KF 353", "KF 354L", "KF 355A", "KF 615A", "KF 945", "KF-640", "KF-642", "KF-643", "KF-644", "KF-6020", "KF-6204", "X22-4515", "KF-6028P", "KF-6038", "KF-6048" and "KF-6025" (polyoxyalkylene modified silicone) manufactured by shin-Etsu silicone Co., Ltd. As the polyether skeleton-containing compound having a reactive functional group (E-2-2), a polyether polyol synthesized by the synthesis of < reactive component E2E ("polyether polyol a") described later or a modified product thereof can be used.

The amount of the polyether skeleton-containing compound having a reactive functional group (E-2-2) is 0% by mass or more, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, and 15% by mass or less, 10% by mass or less, or 8% by mass or less, based on 100% by mass of nonvolatile components in the resin composition.

The amount of the (E-2-2) polyether skeleton-containing compound having a reactive functional group is 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, and 25% by mass or less, 20% by mass or less, or 15% by mass or less, relative to 100% by mass of the resin component in the resin composition.

[ (E-3) non-reactive additive ]

The resin composition of the present invention may further comprise (E-3) a non-reactive additive as an optional component. The component (C), the component (E-2) and optional additives described later are excluded from the component (E-3). The component (E-3) is an additive component which has no reactive functional group at the terminal or side chain unlike the component (E-2) and is not expected to react with the component (A) and/or the component (E-2). However, the component (E-3) allows a reaction with other components to occur at a site other than the terminal or side chain. A typical example of the (E-3) component is a high molecular weight component. The high molecular weight component may act as a plasticizer. As the component (E-3), commercially available products such as butadiene homopolymers "B-1000", "B-2000" and "B-3000" manufactured by Nippon Caoda corporation can be mentioned. The component (E-3) may be used singly or in combination of two or more.

The number average molecular weight of the component (E-3) is preferably 500 to 40000, more preferably 500 to 20000, and still more preferably 500 to 10000. The weight average molecular weight of the component (E-3) is preferably 500 to 40000, more preferably 500 to 20000, and still more preferably 500 to 10000. The number average molecular weight and the weight average molecular weight can be measured as values in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

The component (E-3) is in a liquid state at 25 ℃ or the viscosity of the component (E-3) at 45 ℃ is preferably 100000 mPas or less, more preferably 50000 mPas or less, further preferably 30000 mPas or less, further preferably 10000 mPas or less, further preferably 5000 mPas or less, further preferably 4000 mPas or less, further preferably 3000 mPas or less, further preferably 2000 mPas or less, particularly preferably 1500 mPas or less or 500 mPas or less. The lower limit of the viscosity at 25 ℃ of (E-2-2) the polyether skeleton-containing compound having a reactive functional group is preferably at least 0.5 mPas, more preferably at least 1 mPas, still more preferably at least 2 mPas, yet more preferably at least 3 mPas, particularly preferably at least 4 mPas. The viscosity may be measured by a B-type viscometer (mPas).

The amount of the component (E-3) is not limited as long as the porosity of the cured product of the resin composition falls within the above range, but is 0 mass% or more, 0.01 mass% or more, 0.05 mass% or more, or 0.1 mass% or more, and 15 mass% or less, 10 mass% or less, or 8 mass% or less with respect to 100 mass% of the nonvolatile components in the resin composition, and preferably 4 mass% or less from the viewpoint of obtaining a cured product excellent in mechanical strength.

The amount of the component (E-3) is not limited as long as the porosity of the cured product of the resin composition is within the above range, and is preferably 0 mass% or more, 0.01 mass% or more, 0.1 mass% or more, or 0.2 mass% or more, based on 100 mass% of the resin component in the resin composition, and 25 mass% or less, 20 mass% or less, or 15 mass% or less, from the viewpoint of obtaining a cured product excellent in mechanical strength.

[ (F) radical polymerization initiator ]

The resin composition of the present invention may further contain (F) a radical polymerization initiator as an optional component. As the radical polymerization initiator (F), a thermal polymerization initiator which generates free radicals (free radials) upon heating is preferred. When the resin composition contains (E-2-1) a radical polymerizable compound, the resin composition usually contains (F) a radical polymerization initiator. (F) One kind of radical polymerization initiator may be used alone, or two or more kinds may be used in combination.

Examples of the radical polymerization initiator (F) include peroxide-based radical polymerization initiators and azo-based radical polymerization initiators. Among them, peroxide-based radical polymerization initiators are preferred.

Examples of the peroxide-based radical polymerization initiator include: hydrogen peroxide compounds such as 1,1,3, 3-tetramethylbutylhydroperoxide; dialkyl peroxide compounds such as t-butylcumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, dicumyl peroxide, 1, 4-bis (1-t-butylperoxy-1-methylethyl) benzene, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) -3-hexyne (ヘキシン); diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis (4-t-butylcyclohexyl) peroxydicarbonate; peroxy ester compounds such as t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyneodecanoate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxylaurate, 1-dimethylpropyl 2-ethylperoxyhexanoate, t-butyl 3,5, 5-trimethylperoxyhexanoate, t-butyl peroxy-2-ethylhexyl monocarbonate, and t-butyl peroxymaleate; and the like.

Examples of the azo radical polymerization initiator include: 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 1' -azobis (cyclohexane-1-carbonitrile), 1- [ (1-cyano-1-methylethyl) azo ] formamide, 2-phenylazo-4-methoxy-2, 4-dimethyl-valeronitrile and the like; 2,2 '-azobis [ 2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl ] propionamide ], 2' -azobis [ 2-methyl-N- [1, 1-bis (hydroxymethyl) ethyl ] propionamide ], 2 '-azobis [ 2-methyl-N- [2- (1-hydroxybutyl) ] -propionamide ], 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) -propionamide ], 2 '-azobis (2-methylpropionamide) dihydrate, 2' -azobis [ N- (2-propenyl) -2-methylpropionamide ], 2, azoamide compounds such as 2 '-azobis (N-butyl-2-methylpropionamide) and 2,2' -azobis (N-cyclohexyl-2-methylpropionamide); alkyl azo compounds such as 2,2 '-azobis (2,4, 4-trimethylpentane) and 2,2' -azobis (2-methylpropane); and the like.

(F) The radical polymerization initiator is preferably a substance having a medium-temperature activity. Specifically, (F) the radical polymerization initiator is preferably one having a 10-hour half-life temperature T10 (. degree. C.) in a specific low temperature range. The 10-hour half-life temperature T10 is preferably 50 to 110 ℃, more preferably 50 to 100 ℃, and further preferably 50 to 80 ℃. Examples of commercially available products of such a radical polymerization initiator (F) include "LUPEROX 531M 80" manufactured by Arkema Fuji Co., Ltd, "PERHEXYL (registered trademark) O" manufactured by Nichikura oil Co., Ltd, and "MAIB" manufactured by Fuji film and Wako pure chemical industries, Ltd.

The amount of the (F) radical polymerization initiator is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.05% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less, based on 100% by mass of the nonvolatile matter in the resin composition.

[ (G) other additives ]

The resin composition of the present invention may further contain an optional additive as an optional nonvolatile component in addition to the above-mentioned components (a) to (F). Examples of such additives include organic fillers such as rubber particles, polyamide fine particles, and silicone particles; thermoplastic resins such as polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, and polyester resins; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, and the like; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as Benton and montmorillonite; defoaming agents such as silicone defoaming agents, acrylic defoaming agents, fluorine defoaming agents, and vinyl resin defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improving agents such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants; flame retardants such as phosphorus flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen flame retardants (e.g., melamine sulfate), halogen flame retardants, and inorganic flame retardants (e.g., antimony trioxide). The additive can be used alone in 1 kind, also can be used in any ratio combination of 2 or more. In one embodiment, the resin composition contains a hollow organic filler as the organic filler. However, from the viewpoint of improving the measurement accuracy of the void ratio, it is preferable not to use a hollow organic filler as the organic filler, and from the viewpoint described above, even when the hollow organic filler is contained in the resin composition, the content thereof is more preferably less than 0.005 mass%, still more preferably 0.003 mass% or less, particularly preferably 0.001 mass% or less, when the nonvolatile component of the resin composition is 100 mass%.

[ (H) solvent ]

The resin composition of the present invention may further contain (H) an arbitrary solvent as a volatile component. Examples of the solvent (H) include organic solvents. One solvent may be used alone, or two or more solvents may be used in combination at an arbitrary ratio. The smaller the amount of the solvent, the better. The content of the solvent is preferably 3% by mass or less, more preferably 1% by mass or less, further preferably 0.5% by mass or less, further preferably 0.1% by mass or less, further preferably 0.01% by mass or less, and particularly preferably not contained (0% by mass), as a volatile component, when the nonvolatile component in the resin composition is taken as 100% by mass.

[ method for producing resin composition ]

The resin composition of the present invention can be produced by, for example, mixing the above components. The above components may be partially or entirely mixed at the same time, or may be mixed sequentially. The temperature may be set as appropriate during the mixing of the components, and thus the heating and/or cooling may be performed temporarily or constantly. In addition, stirring or shaking may be performed during the mixing of the components.

[ Properties of the resin composition ]

Generally, the resin composition is thermosetting. Therefore, a cured product can be obtained by curing the resin composition by heat. The porosity (area%) of the cured product is in the range of 0.002% to 2%, preferably 0.0025% to 1.95%, more preferably 0.003% to 1.9%, as described above. Thereby, it is possible to provide: a resin composition or a resin paste which can give a cured product with suppressed occurrence of warpage and excellent mechanical properties; a cured product, a semiconductor chip package and a semiconductor device formed by using the resin composition or the resin paste.

The resin composition is preferably in the form of a paste. Such a paste-like resin composition (hereinafter also referred to as "resin paste") can be easily molded by compression molding (compression mold). The viscosity at 25 ℃ of the paste-like resin composition may be in the range of 1 pas to 1000 pas, preferably in the range of 20 pas to 900 pas, more preferably in the range of 50 pas to 800 pas. The viscosity can be measured at 25 ℃ using an E-type viscometer.

The resin composition of the present invention tends to have a small value of dielectric constant (Dk) of a cured product thereof. Specifically, the value of the dielectric constant (Dk) tends to be less than 3.6, preferably 3.5 or less, more preferably less than 3.5. This provides a cured product having excellent dielectric properties. The lower limit of the dielectric constant (Dk) may be 1.0 or more or 2.0 or more. The resin composition of the present invention tends to have a small value of dielectric loss tangent (Df) of a cured product thereof. Specifically, there is a tendency for the value of the dielectric loss tangent (Df) to be less than 0.03, preferably less than 0.025, more preferably less than 0.02, and may be less than 0.01, less than 0.008, less than 0.006, or less than 0.005. This provides a cured product having excellent dielectric properties. The lower limit of the dielectric loss tangent (Df) may be 0.0001 or more. The resin composition of the present invention tends to have a dielectric constant (Dk) value of less than 3.6, preferably 3.5 or less, more preferably less than 3.5 in a cured product thereof, and a dielectric loss tangent (Df) value of less than 0.03, preferably less than 0.025, more preferably less than 0.02 in the same cured product thereof. This provides a cured product having excellent dielectric properties. The dielectric loss tangent and the relative permittivity can be measured by the methods described later. The test piece for measuring the dielectric loss tangent and the relative dielectric constant can be prepared by the method and the curing conditions described later.

The resin composition of the present invention tends to have a warpage of less than 2000. mu.m (2mm), preferably 1950. mu.m or less, more preferably 1900. mu.m or less, still more preferably 1850. mu.m or less, in a cured product having a thickness of 300. mu.m. The amount of warpage can be measured by the method described in the following examples. Thus, the resin composition of the present invention can provide a cured product in which the occurrence of warpage is suppressed. The warpage amount can be measured by the method described later. The test piece for measuring the amount of warpage can be prepared by the method and curing conditions described later.

The resin composition of the present invention tends to have a breaking point strength of a cured product of the resin composition of the present invention of more than 45MPa, preferably 50MPa or more, more preferably 55MPa or more. The resin composition of the present invention shows a tendency that the cured product thereof has a breaking point strength of less than 110MPa, preferably 108MPa or less, more preferably 106MPa or less. The breaking point strength can be measured by the method described in the column of examples described later. Thus, the resin composition of the present invention can provide a cured product having excellent mechanical strength. The breaking point strength can be measured by the method described later. The test piece for measuring the breaking point strength can be prepared by the method and the curing conditions described later.

[ use of resin composition ]

The resin composition of the present invention can be preferably used as a resin composition (sealing resin composition) for sealing electronic devices such as organic EL devices and semiconductors, and particularly preferably used as a resin composition (semiconductor sealing resin composition) for sealing semiconductors, and more preferably used as a resin composition (semiconductor chip sealing resin composition) for sealing semiconductor chips. The resin composition can be used as a resin composition for insulation purposes for an insulating layer in addition to sealing purposes. For example, the resin composition can be preferably used as a resin composition for forming an insulating layer of a semiconductor chip package, for example, a resin composition for a rewiring forming layer (a resin composition for an insulating layer of a semiconductor chip package, a resin composition for a rewiring forming layer), and a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) (a resin composition for an insulating layer of a circuit board).

As described above, the resin composition of the present invention can be used as a material for forming a sealing layer or an insulating layer of a semiconductor chip package. Examples of the semiconductor chip Package include an FC-CSP, an MIS-BGA Package, an ETS-BGA Package, a fan-out WLP (Wafer Level Package), a fan-in WLP, a fan-out PLP (Panel Level Package), and a fan-in PLP.

The resin composition can be used as an underfill material, for example, a material for MUF (Molding underfill) used after a semiconductor chip is attached to a substrate.

Further, the resin composition can be used in a wide range of applications using resin compositions such as resin sheets, sheet-like laminates such as prepregs, solder resists, die-bonding materials, hole-filling resins, and component-embedding resins.

[ resin sheet ]

The resin sheet according to one embodiment of the present invention includes at least a support, and a resin composition layer provided on the support, and if necessary, a protective film. The resin composition layer is a layer containing the resin composition of the present invention. The thickness of the resin composition layer and the thickness of the cured product layer obtained by curing the resin composition layer are arbitrary. The resin sheet can be produced, for example, by a known method, and the material used as the support can be selected arbitrarily.

The use of the resin sheet is the same as that of the resin composition of the present invention described above. Examples of packages using applicable circuit boards include FC-CSP, MIS-BGA, and ETS-BGA packages. Examples of applicable semiconductor chip packages include fan-out WLP, fan-in WLP, fan-out PLP, and fan-in PLP. Further, the resin sheet may be used as a material of the MUF used after the semiconductor chip is connected to the substrate. Further, the resin sheet can be used for other wide-ranging applications requiring high insulation reliability.

[ Circuit Board ]

The circuit board according to one embodiment of the present invention may contain a cured product of the resin composition of the present invention. The circuit board can be manufactured by a known method, for example, and the material used as the base material and the conductor layer that can be formed on the base material can be selected arbitrarily.

In the production of a circuit board, after a base material is prepared, a resin composition layer, for example, a resin composition layer containing the resin composition of the present invention is formed on the base material by a known method. For example, the resin composition layer may be formed by compression molding. In the compression molding method, a base material and a resin composition are usually placed in a mold, and a resin composition layer is formed on the base material by applying pressure and, if necessary, heating to the resin composition in the mold.

The specific operation of the compression molding method can be performed, for example, in the following manner. An upper mold and a lower mold were prepared as molds for compression molding. Further, the resin composition is coated on the substrate. The base material coated with the resin composition is mounted on a lower die. Then, the upper mold and the lower mold are closed, and heat and pressure are applied to the resin composition to perform compression molding.

Further, the specific operation of the compression molding method can be performed, for example, as follows. An upper mold and a lower mold were prepared as molds for compression molding. The resin composition is placed on a lower mold. Further, the base material and, if necessary, a release film are attached to the upper mold. Then, the upper mold and the lower mold are closed so that the resin composition placed on the lower mold contacts the base material attached to the upper mold, and heat and pressure are applied to the closed mold to perform compression molding.

The molding conditions vary depending on the composition of the resin composition of the present invention, and appropriate conditions can be adopted to achieve good sealing. For example, the temperature of the mold at the time of molding is preferably 70 ℃ or higher, more preferably 80 ℃ or higher, particularly preferably 90 ℃ or higher, and preferably 200 ℃ or lower. The pressure applied during molding is preferably 1MPa or more, more preferably 3MPa or more, particularly preferably 5MPa or more, preferably 50MPa or less, more preferably 30MPa or less, particularly preferably 20MPa or less. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 3 minutes or more, preferably 100 minutes or less, more preferably 90 minutes or less, and in one embodiment, may be 60 minutes or less, 30 minutes or less, or 20 minutes or less. Generally, after the resin composition layer is formed, the mold is removed. The removal of the mold may be performed before or after the thermosetting of the resin composition layer.

After the resin composition layer is formed on the base material, the resin composition layer is thermally cured (post-cured) to form a cured product layer. The heat curing conditions of the resin composition layer may vary depending on the kind of the resin composition, but the curing temperature is usually in the range of 120 to 240 ℃ (preferably in the range of 150 to 220 ℃, more preferably in the range of 170 to 200 ℃), and the curing time is usually in the range of 5 to 120 minutes (preferably in the range of 10 to 100 minutes, more preferably in the range of 15 to 90 minutes).

Before the resin composition layer is thermally cured, a preliminary heat treatment of heating at a temperature lower than the curing temperature may be performed on the resin composition layer. For example, before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature of usually 50 ℃ or higher and less than 120 ℃ (preferably 60 ℃ or higher and 110 ℃ or lower, more preferably 70 ℃ or higher and 100 ℃ or lower) for usually 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

As described above, a circuit board having a cured product layer formed from a cured product of the resin composition of the present invention can be produced. The method for manufacturing the circuit board may further include any process.

[ semiconductor chip Package ]

A semiconductor chip package according to one embodiment of the present invention includes a cured product of the resin composition of the present invention. Examples of the semiconductor chip package include the following packages.

A semiconductor chip package according to a first example includes the circuit board and a semiconductor chip mounted on the circuit board. The semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit substrate.

As for the bonding condition between the circuit board and the semiconductor chip, any condition that the terminal electrode of the semiconductor chip and the circuit wiring of the circuit board can be conductively connected can be adopted. For example, conditions used in flip-chip mounting of a semiconductor chip may be employed. Further, for example, the semiconductor chip and the circuit board may be bonded to each other via an insulating adhesive.

As an example of the bonding method, a method of pressure-bonding a semiconductor chip to a circuit board is given. The pressure bonding temperature is usually in the range of 120 to 240 ℃ (preferably 130 to 200 ℃, more preferably 140 to 180 ℃) and the pressure bonding time is usually in the range of 1 to 60 seconds (preferably 5 to 30 seconds) as the pressure bonding conditions.

In addition, as another example of the bonding method, a method of bonding a semiconductor chip to a circuit board by reflow soldering is given. The reflow soldering conditions may be in the range of 120 ℃ to 300 ℃.

After the semiconductor chip is bonded to the circuit substrate, the semiconductor chip may be filled with a mold underfill material. As the molding underfill material, the above-described resin composition can be used.

The semiconductor chip package according to the second example includes a semiconductor chip and a cured product of the resin composition of the present invention sealing the semiconductor chip. In such a semiconductor chip package, a cured product of the resin composition of the present invention generally functions as a sealing layer. As the semiconductor chip package according to the second example, a fan-out type WLP is exemplified.

Fig. 1 is a cross-sectional view schematically showing a configuration of a fan-out WLP as an example of a semiconductor chip package according to the present embodiment. As shown in fig. 1, for example, a semiconductor chip package 100 as a fan-out WLP includes: a semiconductor chip 110; a sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110; a rewiring formation layer 130 as an insulating layer provided on a surface of the semiconductor chip 110 on the side opposite to the sealing layer 120; a rewiring layer 140 as a conductor layer; a solder resist layer 150; and a bump 160.

The method for manufacturing the semiconductor chip package comprises the following steps:

(A) a step of laminating a temporary fixing film on the base material,

(B) a step of temporarily fixing the semiconductor chip to the temporary fixing film,

(C) a step of forming a sealing layer on the semiconductor chip,

(D) a step of peeling the base material and the temporary fixing film from the semiconductor chip,

(E) a step of forming a rewiring formation layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled,

(F) a step of forming a rewiring layer as a conductor layer on the rewiring formation layer, and

(G) and forming a solder resist layer on the rewiring layer. In addition, the method of manufacturing a semiconductor chip package may further include:

(H) and a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages and singulating the individual semiconductor chip packages.

(Process (A))

The step (a) is a step of laminating a temporary fixing film on a base material. The lamination conditions of the base material and the temporary fixing film may be the same as those of the base material and the resin sheet in the method for manufacturing the circuit board.

Examples of the substrate include: a silicon wafer; a glass wafer; a glass substrate; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel Sheet (SPCC); substrates such as FR-4 substrates obtained by impregnating glass fibers with an epoxy resin or the like and thermally curing the resin; and a substrate made of bismaleimide triazine resin such as BT resin.

As the temporary securing film, any material that can be peeled off from the semiconductor chip and can temporarily secure the semiconductor chip can be used. Examples of commercially available products include "REVALPHA" manufactured by ritonary electric corporation.

(Process (B))

The step (B) is a step of temporarily fixing the semiconductor chip to the temporary fixing film. The temporary fixing of the semiconductor chip can be performed by using a flip chip bonder (flip chip bonder), a die bonder (die bonder), or the like. The layout (layout) and the number of semiconductor chips to be arranged may be appropriately set according to the shape and size of the temporary fixing film, the number of production processes of a target semiconductor chip package, and the like, and for example, the semiconductor chips may be arranged in a matrix of a plurality of rows and a plurality of columns to be temporarily fixed.

(Process (C))

The step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer can be formed by curing the resin composition of the present invention. The sealing layer is generally formed by a method including the following steps: forming a resin composition layer on a semiconductor chip; and a step of forming a cured material layer as a sealing layer by thermally curing the resin composition layer. The formation of the resin composition layer on the semiconductor chip can be performed, for example, by the same method as the method for forming the resin composition layer on the substrate described in the above [ circuit substrate ] except that the semiconductor chip is used instead of the substrate.

After a resin composition layer is formed on a semiconductor chip, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. Thus, the semiconductor chip is sealed with the cured product of the resin composition of the present invention. The conditions for the heat curing of the resin composition layer may be the same as those for the heat curing of the resin composition layer in the method for producing a circuit substrate. Further, the resin composition layer may be subjected to a preliminary heat treatment of heating at a temperature lower than the curing temperature before the resin composition layer is thermally cured. The process conditions of the preliminary heating process may be the same as those of the preliminary heating process in the manufacturing method of the circuit substrate.

(Process (D))

The step (D) is a step of peeling the base material and the temporary securing film from the semiconductor chip. The peeling method is preferably selected according to the material of the temporary fixing film. Examples of the peeling method include a method in which the temporary fixing film is heated, foamed, or expanded to be peeled. Further, as a peeling method, for example, a method of irradiating ultraviolet rays to the temporary fixing film through the base material to lower the adhesive force of the temporary fixing film and peeling the film is exemplified.

In the method of peeling the temporary fixing film by heating, foaming or expanding, the heating condition is usuallyHeating at 100-250 deg.c for 1 sec-90 sec or 5 min-15 min. In the method of peeling the temporary fixing film by irradiating the temporary fixing film with ultraviolet rays to lower the adhesive strength, the irradiation dose of the ultraviolet rays is usually 10mJ/cm²～1000mJ/cm²。

When the base material and the temporary securing film are peeled off from the semiconductor chip as described above, the surface of the sealing layer is exposed. The method of manufacturing a semiconductor chip package may include polishing the exposed surface of the sealing layer. By polishing, the smoothness of the surface of the sealing layer can be improved. As the polishing method, the same method as that described in the method for manufacturing a circuit board can be used.

(step (E))

The step (E) is a step of forming a rewiring formation layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip are peeled. In general, the rewiring formation layer is formed on the semiconductor chip and the sealing layer.

Any insulating material can be used as the material of the rewiring formation layer. When a sealing layer is formed from a cured product of the resin composition of the present invention, a rewiring formation layer formed on the sealing layer can also be formed from a photosensitive resin composition.

After the rewiring formation layer is formed, a through hole is usually formed in the rewiring formation layer in order to connect the semiconductor chip and the rewiring layer between layers. When the rewiring layer is formed using the photosensitive resin composition, a method for forming the through hole generally includes exposing the surface of the rewiring layer through a mask. Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. Examples of the exposure method include a contact exposure method in which a mask is brought into close contact with the rewiring formation layer and exposure is performed, and a non-contact exposure method in which exposure is performed using parallel light rays without bringing the mask into close contact with the rewiring formation layer.

Since a latent image can be formed on the rewiring formation layer by the exposure, a part of the rewiring formation layer is removed by development thereafter, and a through hole can be formed as an opening portion penetrating the rewiring formation layer. The development may be either wet development or dry development. Examples of the developing method include a dipping method, a spin immersion (paddle) method, a spraying method, a brush coating method, and a doctor blade (squeegee) method, and the spin immersion method is preferable from the viewpoint of resolution.

The shape of the through-hole is not particularly limited, and a circular shape (substantially circular shape) can be usually employed. The diameter of the top of the through-hole is, for example, 50 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less. Here, the top diameter of the via hole refers to the opening diameter of the via hole at the surface of the rewiring formation layer.

(Process (F))

The step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring formation layer. The method of forming the rewiring layer on the rewiring-forming layer may be the same as the method of forming the conductor layer on the cured layer in the manufacturing method of the circuit substrate. Further, the step (E) and the step (F) may be repeated to alternately deposit (stack) the rewiring layer and the rewiring-forming layer.

(Process (G))

The step (G) is a step of forming a solder resist layer on the rewiring layer. As the material of the solder resist layer, any material having insulating properties can be used. Among them, a photosensitive resin and a thermosetting resin are preferred from the viewpoint of easiness of manufacturing the semiconductor chip package. Further, as the thermosetting resin, the resin composition of the present invention can be used.

In the step (G), a bump processing for forming a bump may be performed as necessary. The bumping process may be performed by solder ball, solder plating (solder plating), and the like. The formation of the through hole in the bump processing can be performed in the same manner as in the step (E).

(Process (H))

The method for manufacturing a semiconductor chip package may include the step (H) in addition to the steps (a) to (G). The step (H) is a step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages and singulating the individual semiconductor chip packages. The method of cutting the semiconductor chip packages into the semiconductor chip packages one by one is not particularly limited.

As the semiconductor chip package according to the third example, there is a semiconductor chip package in which the rewiring formation layer 130 or the solder resist layer 150 is formed from a cured product of the resin composition of the present invention in the semiconductor chip package 100 as an example shown in fig. 1.

[ semiconductor device ]

A semiconductor device includes a semiconductor chip package. Examples of the semiconductor device include various semiconductor devices provided in electric products (for example, computers, mobile phones, smartphones, tablet-type devices, wearable devices, digital cameras, medical devices, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, airplanes, and the like).

Examples

The present invention will be specifically described below with reference to examples. The present invention is not limited by these examples. In the following description, "part" and "%" representing amounts refer to "part by mass" and "% by mass", respectively, unless otherwise explicitly stated. The temperature and pressure conditions when not specified are room temperature (25 ℃) and atmospheric pressure (1 atm).

[ example 1]

(1) Preparation of resin paste A

8 parts of a curing agent ba (acid anhydride curing agent "MH-700" manufactured by Nippon chemical Co., Ltd., acid anhydride group equivalent: 164g/eq.) as the component (B), 8 parts of an epoxy resin aa (liquid epoxy resin "ZX 1059" manufactured by Nippon chemical Co., Ltd., bisphenol A-type epoxy resin and bisphenol F-type epoxy resin (mass ratio), and epoxy equivalent: 169g/eq.) as the component (A), 2 parts of an epoxy resin ab (alicyclic epoxy resin "CELLOXIDE 2021P" manufactured by Dacellosolve Co., epoxy equivalent: 136g/eq.) as the component (A), 2 parts of an epoxy resin ac (naphthalene-type epoxy resin "2 4032D" manufactured by DIC Co., Ltd., epoxy equivalent: 143g/eq.) as the component (A), 2 parts of a curing accelerator da (imidazole curing accelerator "2 MA-OK-4030.4.PW") manufactured by Nippon chemical Co., Ltd., the component (D), 0.4 parts of a curing accelerator da (imidazole curing accelerator "2 MA-4.4.PW") as the component (D), An epoxy resin ad (glycidyl amine type epoxy resin manufactured by ADEKA Co., Ltd.) as the component (A)Lipid "EP 3950L", epoxy equivalent: 95g/eq.)2 parts of an epoxy resin ae (dicyclopentadiene dimethanol type epoxy resin "EP-4088S" manufactured by ADEKA Co., Ltd., epoxy equivalent: 170G/eq.)2 parts, a reactive component E2a (a compound having a methacryloyl group and a polyoxyethylene structure "M-130G" manufactured by shinkamura chemical industries, ltd.) 3 parts as a component (E-2), a radical polymerization initiator (perrexyl (registered trademark) O ", manufactured by nippon oil corporation), a 10-hour half-life temperature T10: 0.1 part at 69.9 ℃ C., silica surface-treated with an inorganic filler ca (surface treating agent "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd.) as component (C), true density: 2.6g/cm³Average particle diameter: 1.5 μm, specific surface area: 2.78m²(iv) g; also referred to as "silica A") and 0.2 part of a silane coupling agent E1a (KBM 403 (3-glycidoxypropyltrimethoxysilane) manufactured by shin-Etsu chemical Co., Ltd.) as a component (E-1) were uniformly dispersed to prepare a resin composition. The resin composition is prepared in the form of a paste. Hereinafter, the resin composition containing at least the component (a), the component (B) and the component (C) thus prepared is also referred to as "resin paste a".

The amount of the solvent contained in the resin paste a of example 1 was 0 mass% (that is, not contained) with respect to 100 mass% of the nonvolatile components of the resin composition. The viscosity of resin paste a of example 1 was measured at 25 ℃ using an E-type viscometer and found to be 80Pa · s. The viscosities thus measured are shown in table 1.

(2) Measurement and evaluation of cured product

Then, using the resin paste a, the measurement and evaluation described below were performed on the cured product thereof.

[ example 2]

In example 1,2 parts each of the epoxy resin aa ("ZX 1059"), the epoxy resin ab ("CELLOXIDE 2021P"), the epoxy resin ac ("HP 4032D"), the epoxy resin ad ("EP 3950L") and the epoxy resin ae ("EP-4088S") was added as the component (A), 2 parts of epoxy resin aa ("ZX 1059") ("CELLOXIDE 2021P"), 2 parts of epoxy resin ac ("HP 4032D"), 2 parts of epoxy resin af (polyether-containing epoxy resin "EX-992L" manufactured by Nagase ChemteX, Inc., epoxy equivalent: 680g/eq.)2 parts of epoxy resin ag (epoxy resin "EG-280" containing a fluorene structure manufactured by Osaka gas chemical Co., Ltd., epoxy equivalent: 460g/eq.)2 parts of epoxy resin ah (glycidyl amine type epoxy resin "EP-3980S" manufactured by ADEKA, epoxy equivalent: 115g/eq.)2 parts of epoxy resin are compounded. In example 1, the amount of the curing accelerator da ("2 MA-OK-PW") as the component (D) was changed from 0.4 parts to 0.5 parts. Further, in example 1,3 parts of a reactive component E2b (2-functional methacrylate "BPE-1300N" manufactured by Ninghamu chemical industries, Ltd.) was added as the (E-2) component in place of 3 parts of the reactive component E2a ("M-130G").

Except for the above matters, resin paste a was prepared in the same manner as in example 1. The amount of the solvent contained in the resin paste a of example 2 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile components of the resin composition. Then, using the resin paste a, the measurement and evaluation of the cured product thereof were performed in the same manner as in example 1.

[ example 3]

In example 1, as the component (a), the compounding amounts of epoxy resin aa ("ZX 1059"), epoxy resin ab ("CELLOXIDE 2021P"), epoxy resin ac ("HP 4032D"), epoxy resin ad ("EP 3950L") and epoxy resin ae ("EP-4088S") were changed from 2 parts to 3 parts, respectively. In example 1, instead of 0.4 part of the curing agent ba ("MH-700"), 3 parts of a curing agent bb (an amine-based curing agent "KAYAHARD A-A" (4,4 '-diamino-3, 3' -diethyldiphenylmethane, manufactured by Nippon Chemicals) was added as component (B). Further, in example 1, 0.4 part of a curing accelerator da ("2 MA-OK-PW") and 0.4 part of a curing accelerator db (imidazole-based curing accelerator "2E 4 MZ" manufactured by Sikkiso Co., Ltd.) were added as the component (D).

Except for the above matters, resin paste a was prepared in the same manner as in example 1. The amount of the solvent contained in the resin paste a of example 3 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile components of the resin composition. Then, using the resin paste a, the cured product thereof was measured and evaluated in the same manner as in example 1.

[ example 4]

In example 1,3 parts of epoxy resin aa ("ZX 1059"), 2 parts of epoxy resin ac ("HP 4032D"), 2 parts of epoxy resin ad ("EP 3950L") and 1 part of epoxy resin ai (epoxidized polybutadiene resin "JP-100" manufactured by japan kodada) were blended as component (a) instead of blending 2 parts of each of epoxy resin aa ("ZX 1059"), epoxy resin ab ("CELLOXIDE 2021P"), epoxy resin ac ("HP 4032D"), epoxy resin ad ("EP 3950L") and epoxy resin ae ("EP-4088S"). In addition, in example 1, 90 parts of an inorganic filler ca ("silica A") was added as the component (C), and an inorganic filler cb (silica surface-treated with a surface treating agent "KBM 573" manufactured by shin-Etsu chemical Co., Ltd., true density: 2.6 g/cm) was added³Average particle diameter: 4 μm, specific surface area: 3.01m²(ii)/g; also referred to as "silica B") 130 parts. Further, in example 1, as the (E-1) component, the amount of the silane coupling agent E1a ("KBM 403") was changed from 0.2 parts to 0.1 parts. The components (E-2) and (F) used in example 1 were not blended.

Resin paste a was prepared in the same manner as in example 1, except for the above-mentioned matters. The amount of the solvent contained in the resin paste a of example 4 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile component of the resin composition. Then, using the resin paste a, the measurement and evaluation of the cured product thereof were performed in the same manner as in example 1.

[ example 5]

In example 4, instead of 3 parts of epoxy resin aa ("ZX 1059"), 2 parts of epoxy resin ac ("HP 4032D") and 1 part of epoxy resin ai ("JP-100"), 3 parts of epoxy resin aa ("ZX 1059"), 1 part of epoxy resin ac ("4032D") and 1 part of epoxy resin ag ("EG-280") were blended as component (a). In example 4, 0.1 part of a silane coupling agent E1a ("KBM 403") and 0.1 part of a silane coupling agent E1b ("KBM 803" (3-mercaptopropyltrimethoxysilane)) were added as the (E-1) component in place of 0.1 part of the silane coupling agent E1a ("KBM 403"). That is, in example 5A plurality of types of silane coupling agents are blended. Further, in example 4, a reactive component e2c (polyoxyalkylene modified silicone resin "KF-6012" manufactured by shin-Etsu Silicone Co., Ltd., viscosity (25 ℃ C.): 1500 mm) was further blended²S)1 part as the (E-2) component. In example 4, the amount of the radical polymerization initiator as the component (F) was changed from 0.1 part to 0 part. That is, in example 5, the component (F) was not blended.

Except for the above matters, resin paste a was prepared in the same manner as in example 4. The amount of the solvent contained in the resin paste a of example 5 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile components of the resin composition. Then, using the resin paste a, the measurement and evaluation of the cured product thereof were performed in the same manner as in example 1.

[ example 6]

In example 5, 1 part of a reactive component E2d (polyoxyethylene polyoxypropylene glycol "L-64" manufactured by ADEKA) was added as the (E-2) component in place of 1 part of the reactive component E2c ("KF-6012").

Resin paste a was prepared in the same manner as in example 5, except for the above-mentioned matters. The amount of the solvent contained in the resin paste a of example 6 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile components of the resin composition. Then, using the resin paste a, the cured product thereof was measured and evaluated in the same manner as in example 1.

[ example 7]

In example 5, instead of compounding 3 parts of epoxy resin aa ("ZX 1059"), 1 part of epoxy resin ac ("HP 4032D") and 1 part of epoxy resin ag ("EG-280"), 3 parts of epoxy resin aa ("ZX 1059"), 1 part of epoxy resin ac ("HP 4032D") and 1 part of epoxy resin ad ("EP 3950L") were compounded as the component (a). In example 5, 1 part of the reactive component E2E (also referred to as "polyether polyol a") was added as the (E-2) component in place of 1 part of the reactive component E2c ("KF-6012"). The reactive component e2e is synthesized as described below.

< Synthesis of reactive ingredient e2e ("polyether polyol A") >)

22.6g of epsilon-caprolactone monomer ("PLACCEM" manufactured by Daiiluo corporation), 10g of polypropylene glycol ("3000" polypropylene glycol, manufactured by Fuji film and Wako pure chemical industries, Ltd.), and 1.62g of tin (II) 2-ethylhexanoate ("Fuji film and Wako pure chemical industries, Ltd.) were charged into a reaction vessel, and the mixture was heated to 130 ℃ under a nitrogen atmosphere and stirred for about 16 hours to effect a reaction. The reaction product was dissolved in chloroform, reprecipitated with methanol, and dried. Thus, as the reactive component e2e ("polyether polyol a"), a polyester polyol having an aliphatic skeleton and hydroxyl group terminals was obtained. The reactive component e2e ("polyether polyol a") had an Mn of 9000 according to GPC analysis.

Resin paste a was prepared in the same manner as in example 5, except for the above-mentioned matters. The amount of the solvent contained in the resin paste a of example 7 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile component of the resin composition. Then, using the resin paste a, the measurement and evaluation of the cured product thereof were performed in the same manner as in example 1.

[ example 8]

In example 3, instead of 3 parts each of epoxy resin aa ("ZX 1059"), epoxy resin ab ("CELLOXIDE 2021P"), epoxy resin ac ("HP 4032D"), epoxy resin ad ("EP 3950L") and epoxy resin ae ("EP-4088S"), 3 parts of epoxy resin aa ("ZX 1059"), 3 parts of epoxy resin ab ("CELLOXIDE 2021P"), 3 parts of epoxy resin ac ("HP 4032D"), 2 parts of epoxy resin ad ("EP 3950L") and 1 part of epoxy resin ae ("EP-4088S") were blended as the component (a). In example 3, instead of 90 parts of the inorganic filler ca ("silica a"), 130 parts of the inorganic filler cb ("silica B") was added as the component (C). Further, in example 3, the amount of the silane coupling agent E1a ("KBM 403") as the component (E-1) was changed from 0.2 parts to 0.3 parts. In example 3, 2 parts of the reactive component E2E ("polyether polyol a") was added as the (E-2) component in place of 3 parts of the reactive component E2a ("M-130G"), and the amount of the radical polymerization initiator added was changed from 0.1 part to 0 part as the (F) component. That is, in example 8, the component (F) was not blended.

Except for the above matters, resin paste a was prepared in the same manner as in example 3. The amount of the solvent contained in the resin paste a of example 8 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile component of the resin composition. Then, using the resin paste a, the measurement and evaluation of the cured product thereof were performed in the same manner as in example 1.

[ example 9]

In example 8, 3 parts of epoxy resin aa ("ZX 1059"), 3 parts of epoxy resin ab ("CELLOXIDE 2021P"), 3 parts of epoxy resin ac ("HP 4032D"), 3 parts of epoxy resin ad ("EP 3950L") and 1 part of epoxy resin af ("EX-992L") were blended as component (a) instead of blending 3 parts of each of epoxy resin aa ("zlxide 2021P"), epoxy resin ad ("HP 4032D"), epoxy resin ad ("EP 3950L") and epoxy resin ae ("EP-4088S"). In example 8, 3 parts of curing agent bb ("KAYAHARD A-A") and 3 parts of curing agent bc ("2, 2-diallyl bisphenol A" manufactured by Sigma-Aldrich Co.) were added as component (B). Further, in example 8, as the component (C), the blending amount of the inorganic filler cb ("silica B") was changed from 130 parts to 100 parts. In example 8, 2 parts of the reactive component E2c ("KF-6012") was added in place of 2 parts of the reactive component E2E ("polyether polyol A") as the component (E-2).

Except for the above matters, resin paste a was prepared in the same manner as in example 8. The amount of the solvent contained in the resin paste a of example 9 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile components of the resin composition. Then, using the resin paste a, the cured product thereof was measured and evaluated in the same manner as in example 1.

[ example 10]

In example 4, instead of 3 parts of epoxy resin aa ("ZX 1059"), 2 parts of epoxy resin ac ("HP 4032D"), and 1 part of epoxy resin ai ("JP-100"), 3 parts of epoxy resin aa ("ZX 1059") and 2 parts of epoxy resin ac ("HP 403 4032D") were blended as component (a). In example 4, the amount of the inorganic filler cb ("silica B") blended was changed from 130 parts to 100 parts as the component (C). Further, in example 4, 1 part of a reactive component E2f ("BMI-689" manufactured by Designers molecules Co., Ltd.) was further blended as a component (E-2).

Resin paste a was prepared in the same manner as in example 4, except for the above-mentioned matters. The amount of the solvent contained in the resin paste a of example 10 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile components of the resin composition. Then, using the resin paste a, the cured product thereof was measured and evaluated in the same manner as in example 1.

Comparative example 1

In example 4, instead of 3 parts of epoxy resin aa ("ZX 1059"), 2 parts of epoxy resin ac ("HP 4032D"), and 1 part of epoxy resin ai ("JP-100"), 3 parts of epoxy resin aa ("ZX 1059"), 1 part of epoxy resin ac ("4032D"), and 2 parts of epoxy resin ad ("EP 3950L") were blended as component (a). In example 4, the amount of the silane coupling agent E1a ("KBM 403") as the component (E-1) was changed from 0.1 part to 0 part (i.e., not included). That is, in comparative example 1, the component (E-1) was not used.

Except for the above matters, resin paste a was prepared in the same manner as in example 4. The amount of the solvent contained in the resin paste a of comparative example 1 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile component of the resin composition. Then, using the resin paste a, the cured product thereof was measured and evaluated in the same manner as in example 1.

Comparative example 2

In comparative example 1, a non-reactive additive E3a (butadiene homopolymer "B-2000" manufactured by Nippon Caoda corporation) was further used as the component (E-3).

Resin paste a was prepared in the same manner as in comparative example 1, except for the above-mentioned matters. The amount of the solvent contained in the resin paste a of comparative example 2 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile component of the resin composition. Then, using the resin paste a, the cured product thereof was measured and evaluated in the same manner as in example 1.

Comparative example 3

In comparative example 2, in place of 130 parts of the inorganic filler ca ("silica A"), 120 parts of the inorganic filler ca ("silica A") and 120 parts of the inorganic filler cc (alumina having been surface-treated with a surface treating agent "KBM 573" manufactured by shin-Etsu chemical Co., Ltd., having a maximum particle diameter of 5 μm or less, having a true density of 3.98 g/cm) were added as the component (C)³And the maximum particle size: 5 μm, average particle diameter: 1.0 μm, specific surface area: 3.98m²(iv) g; also referred to as "alumina a") 30 parts. In comparative example 2, the amount of the non-reactive additive E3a ("B-2000") as the component (E-3) was changed from 13 parts to 8 parts.

Resin paste a was prepared in the same manner as in comparative example 2, except for the above-mentioned matters. The amount of the solvent contained in the resin paste a of comparative example 3 prepared was 0 mass% (i.e., not contained) with respect to 100 mass% of the nonvolatile component of the resin composition. Then, using the resin paste a, the measurement and evaluation of the cured product thereof were performed in the same manner as in example 1.

< measurement and evaluation of cured product >

With respect to the resin pastes a obtained in examples 1 to 10 and comparative examples 1 to 3, cured products thereof were obtained as follows, and measured and evaluated.

< determination of void fraction >

(1) Preparation of cured product

The resin pastes a obtained in examples 1 to 10 and comparative examples 1 to 3 were cured by a curing method comprising the following (1-1) compression molding step and (1-2) post-curing step in this order. Thereby, a cured product having a degree of cure of 95% or more was obtained.

(1-1) compression Molding Process

As the compression molding step, the following steps were employed: after the resin composition was disposed so as to bond to the silicon wafer, compression molding was performed under conditions of a pressure of 15 tons, a temperature of 130 ℃ and 10 minutes, to obtain a compression-molded article of the resin composition having a thickness of 300 μm bonded to the silicon wafer.

Specifically, in the compression molding step, the standardized compression molding step described above is employed, and the following steps (c1) to (c4) are sequentially performed:

(c1) disposing a silicon wafer and a resin composition in a mold having a release film mounted thereon

(c2) A step of clamping the mold within 90 seconds after the resin composition is prepared, and bonding the silicon wafer and the resin composition

(c3) A step of reducing the pressure in the metal mold to a reduced pressure within a range of 0 to 0.7torr

(c4) And a step of compression molding under conditions of a pressure of 15 tons, a temperature of 130 ℃ and 10 minutes to obtain a compression molded article of the resin composition having a thickness of 300 μm bonded to the silicon wafer.

In the step (c1), a compression molding machine (compression molding machine "WCM-300" manufactured by APIC YAMADA) including a pair of separable molds was used as the mold. In this step, the inside of the mold was heated to 130 ℃. As a silicon wafer, for thickness: 775 μm, diameter: a12-inch silicon wafer was used after being subjected to a mold release treatment. The silicon wafer is fixed to a surface of a vertically lower one of the pair of metal molds. The release film is attached to the mold facing the silicon wafer out of the pair of molds. As the release film, AFREX (registered trademark) 50N390NT (mirror-polished) manufactured by AGC Co.

In the step (c1), the resin paste a obtained in examples 1 to 10 and comparative examples 1 to 3 was used as the resin composition. When the resin paste a was placed on a silicon wafer, 40g of the resin paste a was weighed and placed at the center of the silicon wafer. The resin paste A used was an amount sufficient to completely cover the surface of the silicon wafer and to form a resin composition layer having a thickness of 300 μm.

In the step (c4), the thickness of the resulting compression molded body was set to 300 μm. As the compression molding machine, a compression molding machine in which the pressure in the mold was increased from 0 ton to 15 ton within 60 seconds was used. 10 minutes is the time elapsed after reaching a pressure of 15 tons. The thus obtained compression molded body (with silicon wafer) is hereinafter also referred to as "compression molded body C".

The degree of cure of the compression-molded article C of example 1 (the compression-molded article before the post-curing step) obtained through the same steps as the above compression-molding step was measured by differential scanning calorimetry (DSC 7020, High-Tech Science) using a differential scanning calorimetry apparatus after the silicon wafer was taken out of the mold, and was 85%. Further, the void ratio (void ratio before post-curing) of the same compression molded body C was measured, and the result was 0.005%. The porosity was measured in the same manner as the method for measuring the porosity of the cured product D described later.

(1-2) post-curing step

As the post-curing step, the following steps were employed: the obtained compression molded body of the resin composition was heated at 150 ℃ for 1 hour in a nitrogen atmosphere to obtain a cured product.

Specifically, in the post-curing step, the standardized post-curing step described above is used, and the following steps (p1) to (p2) are performed in this order;

(p 1): a step of obtaining a cured product by putting a compression-molded body of the resin composition taken out from the metal mold into an oven set to a temperature of 150 ℃ and 1atm in a nitrogen atmosphere and waiting for 1 hour to elapse; and

(p 2): and (d) a step of taking out the cured product from the oven within 120 seconds after the step (p1), and cooling the cured product at normal temperature and pressure.

In the step (p1), as an oven, "DN 6101" manufactured by YAMATO science corporation was used. Before the step (p1), the oven was put in a nitrogen atmosphere, a temperature of 150 ℃ and a pressure of 1atm, which were set in advance. Further, the compression-molded body to be put into the oven before the step (p1) is a substance (compression-molded body C) taken out from the metal mold used in the above step (C4) together with the silicon wafer. The thickness of the resin composition layer of the compression-molded body C of example 1 charged into the oven was 305 μm.

In the step (p2), the cured product taken out of the oven was allowed to cool in the room. The chamber was at atmospheric pressure (about 1 atmosphere), the temperature was room temperature (about 23 ℃), and the humidity was 50%. It was confirmed that the surface temperature of the cured product after 6 hours had reached 23 ℃.

The thickness of the resin composition layer in the cured product obtained from the resin paste A of example 1 after the step (p2) was confirmed to be less than. + -. 5% of the thickness 305. mu.m before post-curing, and within the range of 300. mu.m. + -. 5. mu.m. The degree of curing of the resin composition layer in the same cured product was measured by differential scanning calorimetry using a differential scanning calorimetry apparatus ("DSC 7020" manufactured by Hitachi High-Tech Science), and the result was 100%. It was also confirmed that the resin composition layer in the cured products of the other examples and comparative examples had a curing shrinkage of. + -. 5% less than 300 μm in thickness before post-curing and a degree of curing of 95% or more. Hereinafter, the thus obtained cured product (with silicon wafer) is also referred to as "cured product D".

(2) Measurement of porosity of cured product

(2-1) determination of Observation region

The following procedure was performed to obtain an SEM cross-sectional image of the cured product D. As SEM (Scanning Electron Microscope), an SEM attached to FIB-SEM mixing System "SMI 3050 SE" manufactured by SII NanoTechnologies (now High-Technologies) was used. First, the cured product D was cut into a 1cm square with a silicon wafer. Then, for each slice, the cross section of the longitudinal section was exposed by using FIB attached to the FIB-SEM mixing system. The position of the FIB at which the width is 30 μm and the depth is 30 μm when the cross section is exposed;

then, the cross section obtained was observed at a magnification of 27000 times by using an SEM, and a region separated by 50 μm or more from the interface between the silicon wafer and the resin composition layer was selected in the observed resin composition layer. The area of the observation region at this time is 1000 pixels in the thickness direction × 1000 pixels in the in-plane direction. The thickness direction refers to a direction parallel to the cut surface of the silicon wafer or the cut surface of the resin composition layer, and the in-plane direction refers to a direction parallel to the surface of the silicon wafer or the formation surface of the resin composition layer. An observation region of 1000 pixels × 1000 pixels approximately corresponds to a region of 9 μm × 9 μm;

the observation area defined as described above is acquired as an SEM sectional image.

(2-2) image analysis of void region

Subsequently, the SEM sectional image obtained in (2-1) above is input to software "ImageJ" (hereinafter also referred to as "analysis software") for image analysis, and image analysis is performed as follows. The version of the software "ImageJ" is "1.51 j 8". It should be noted that the latest version of the parsing software "ImageJ" is available from the internet. First, the analysis software is started to display the SEM sectional image. Fig. 2 is a photograph of an SEM cross-sectional image of the cured product D of example 8 (more specifically, an SEM cross-sectional image of the 3 rd time of the cured product D of example 8 as an object of void fraction measurement) displayed by analysis software. Next, in the displayed image, the outline of each void region is enclosed by a command (command) "free selection" of analysis software. Next, the outline enclosed and the inner region drawn by the outline are cut out using "cut" included in the command "Edit" to specify the void region. The same operation is performed for all void regions identified in the SEM sectional image. Then, the contrast of a specific void region (black region) is adjusted using the "Threshold" of the "Adjust" contained in the instruction "Image" so that only the void region becomes black. Next, the instruction "Red" is used to color the inside of the specific void region in Red. Fig. 3 shows a photograph showing a state in which the void region is colored red in the SEM cross-sectional image of fig. 2. Then, the total area (number of pixels) of the red-colored region (void region) is acquired using "Measure" included in the command "Analyze".

(2-3) calculation of void fraction

Then, the void fraction (%) was calculated by dividing the total area (number of pixels) of the void region acquired in (2-2) above by the number of pixels (1000 pixels × 1000 pixels) of the observation region and multiplying the divided value by 100 times.

(2-4) calculation of average value

The operations (2-1) to (2-3) were repeated 50 times. That is, the observation area was changed by the cross-sectional exposure 50 times (the observation number N was 50), and the porosity was calculated. Then, the sum of the obtained void ratios was divided by 50 to calculate an average value thereof. By increasing the number of observations in this manner, it is expected that the accidental (unevenness of components on the observation surface) and the random (omission of counting) will be eliminated. The average values of the calculated void ratios are shown in table 1.

However, SEM cross-sectional images for which the porosity should be calculated are selected as described below, and the porosity is not calculated for SEM cross-sectional images that do not satisfy the following conditions. First, in each of examples and comparative examples, the volume ratio (%) of the inorganic filler contained in the prepared resin paste a was calculated based on the blending amount and the true density thereof. On the other hand, in the same manner as in (2-2), the number of pixels in the inorganic filler region in the SEM cross-sectional image obtained in (2-1) was divided by the number of pixels in the observation region (1000 pixels × 1000 pixels), and the area ratio (%) which was a value obtained by multiplying the obtained value by 100 times was calculated. Then, the volume ratio (%) and the area ratio (%) of the obtained inorganic filler were compared, and an SEM cross-sectional image satisfying the condition that the value of the area ratio (%) was within ± 3 of the value of the volume ratio (%) was selected as the calculation target of the porosity.

< evaluation of warpage >

The resin compositions prepared in examples and comparative examples were compression-molded on a 12-inch silicon wafer using a compression molding apparatus (mold temperature: 130 ℃, pressure: 6MPa, curing time: 10 minutes) to form a resin composition layer having a thickness of 300. mu.m. Then, the resin composition layer was heated at 180 ℃ for 90 minutes to thermally cure the resin composition layer. Thus, a sample substrate comprising a silicon wafer and a cured product layer of the resin composition was obtained. The warpage amount at 25 ℃ was measured with respect to the sample substrate using a shadow moire (shadow moir) measuring apparatus ("thermoureaxp" manufactured by Akorometrix corporation). The measurement was carried out according to JEITA EDX-7311-24, a standard of the Japan electronic information technology industry Association. Specifically, a fitting plane calculated by the least square method for all data on the substrate surface of the measurement area is used as a reference plane, the difference between the minimum value and the maximum value in the vertical direction from the reference plane is obtained as a warping amount, and the following criteria are used for evaluation;

good component: warpage amount of less than 2000 μm (2mm)

X: the warping amount is more than 2mm

The results of the evaluation of the measured warpage amount and low warpage property are shown in table 1.

< evaluation of Long-term reliability >

1. Production of cured product for evaluation

On a 12-inch silicon wafer subjected to mold release treatment, the resin compositions prepared in examples and comparative examples were compression-molded using a compression molding apparatus (mold temperature: 130 ℃, pressure: 6MPa, curing time: 10 minutes) to form a resin composition layer having a thickness of 300 μm. The resin composition layer was peeled from the silicon wafer, and heated at 180 ℃ for 90 minutes to thermally cure the resin composition layer, thereby obtaining a cured product A for evaluation.

2. Evaluation of Long term reliability

The evaluation of the long-term reliability was performed by: the evaluation of the cured article A was carried out in an HTS test, and the breaking point strength was measured before and after the HTS (High Thermal Storage) test to calculate the rate of change (%) in the breaking point strength.

(1) HTS assay

The cured product A for evaluation was subjected to HTS test. In the HTS test, the cured product A for evaluation was held at 150 ℃ for 1000 hours. Thus, a cured product for evaluation after HTS test was obtained.

(2) Determination of Break Point Strength before and after HTS testing

The cured product for evaluation before the HTS test was cut into a dumbbell shape No. 1 in a plan view, to obtain 5 test pieces. Similarly, the cured product for evaluation after the HTS test was cut into a dumbbell shape No. 1 in a plan view, to obtain 5 test pieces. For each test piece, a tensile test was performed using a tensile tester "RTC-1250A" manufactured by Orientec under the measurement conditions of 23 ℃ and a test speed of 5mm/min, and the tensile breaking point strength (also simply referred to as "breaking point strength") was determined from the stress-strain curve. According to JIS K7127: 1999 the assay was performed. The average of the breaking point strengths of 5 specimens was defined as tensile breaking point strength σ 0 before HTS test. The average of the breaking point strengths of 5 specimens was defined as the tensile breaking point strength σ 1 after the HTS test. Furthermore, the change rate (%) of the tensile breaking point strength before and after the HTS test was calculated based on the following formula;

change rate (%) { (σ 1- σ 0)/σ 0} × 100

Based on the calculated change rate (%), the long-term reliability was evaluated according to the following criteria.

Evaluation criteria for long-term reliability:

o: the absolute value of the change rate (%) is less than 10% (the change rate is small and the long-term reliability is excellent)

X: the absolute value of the change rate (%) is 10% or more (large change rate, poor long-term reliability)

The measured breaking point strengths and the change rates are shown in Table 1.

< evaluation of dielectric characteristics >

The resin compositions prepared in examples and comparative examples were compression-molded on a 12-inch silicon wafer subjected to mold release treatment using a compression molding apparatus (mold temperature: 130 ℃, pressure: 6MPa, curing time: 10 minutes) to form a resin composition layer having a thickness of 300. mu.m. Then, the resin composition was peeled from the silicon wafer subjected to the mold release treatment, and heated at 150 ℃ for 90 minutes to thermally cure the resin composition, thereby preparing a sample. The dielectric constant and the dielectric loss tangent at 60GHz were measured by the Fabry-Perot method. The measurement was performed for 3 test pieces, and the average value was calculated. The average values of the measured dielectric constant and dielectric loss tangent are shown in Table 1.

The results of examples 1 to 10 and comparative examples 1 to 3 are shown in Table 1.

[ Table 1]

^<1>Content of nonvolatile component of 100 mass%

^<2>Measured with an E-type viscometer at 25 ℃

^<3>Relative to each otherArea ratio in all observation regions

^<4>Break Point Strength before HTS testing

^<5>Rate of change of breaking point Strength before and after HTS testing

Description of the symbols

100 semiconductor chip package

110 semiconductor chip

120 sealing layer

130 rewiring forming layer

140 redistribution layer

150 solder mask

160 bumps.

Claims

1. A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,

< compression Molding Process >

< post-curing Process >

2. The resin composition according to claim 1, wherein the void ratio is obtained by: in the SEM sectional image magnified 27000 times, the observation region having a thickness direction dimension of 1000 pixels × an in-plane direction dimension of 1000 pixels is subjected to image analysis, and the area ratio (%) of the void region obtained as the void image to the observation region is calculated.

3. The resin composition according to claim 1, wherein the porosity is an arithmetic average of area ratios (%) of void regions obtained with respect to an SEM cross-sectional image of a cured product at 50 points.

4. The resin composition according to claim 1, wherein the compression molding step includes the following steps (c1) to (c4) in this order:

5. The resin composition according to claim 1, wherein the post-curing step comprises the following steps (p1) to (p2) in this order:

(p2) the step of taking out the cured product from the oven within 120 seconds after the step (p1) and cooling the cured product by cooling the cured product at normal temperature and pressure.

6. The resin composition according to claim 1, wherein a resin void ratio representing an area ratio of a void region in a resin component region to the observation region is in a range of 0.002% to 2%,

the void region in the resin component region is obtained by excluding a void region in a region described by an outer shape region of (C) the inorganic filler, out of void regions that are obtained as void images by image analysis.

7. The resin composition according to claim 1, wherein the component (C) is 30% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass.

8. The resin composition according to claim 1, wherein the component (A) comprises (A-1) a liquid epoxy resin.

9. The resin composition according to claim 1, wherein (E-1) a silane coupling agent is contained, the silane coupling agent being a single species.

10. The resin composition according to claim 1, wherein (E-1) a silane coupling agent is contained, and the silane coupling agent is of a plurality of kinds.

11. The resin composition according to claim 1, wherein the content of the solvent is 3% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

12. The resin composition according to claim 1, wherein the viscosity at 25 ℃ measured with an E-type viscometer is within the range of 1Pa seeds to 1000Pa seeds.

13. The resin composition according to claim 1, wherein the cured product has a dielectric constant (Dk) value of less than 3.6.

14. The resin composition according to claim 1, wherein the dielectric loss tangent (Df) of the cured product is less than 0.03.

15. The resin composition according to claim 1, wherein the cured product has a breaking point strength of more than 45 MPa.

16. The resin composition according to claim 1, wherein the cured product has a degree of cure of 95% or more.

17. The resin composition according to claim 1, which is used for forming an insulating layer of a semiconductor chip package.

18. The resin composition according to claim 1, which is used for a rewiring-forming layer.

19. A resin paste comprising the resin composition according to any one of claims 1 to 18.

20. A cured product of the resin composition according to any one of claims 1 to 18.

21. A cured product of a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the cured product has a porosity in the range of 0.002% to 2%, and the porosity is the area ratio (%) of void regions in an SEM cross-sectional image of the cured product.

22. A semiconductor chip package comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 18.

23. The semiconductor chip package according to claim 22, wherein the insulating layer is a rewiring-forming layer.

24. The semiconductor chip package of claim 22, which is a fan-out package.

25. A semiconductor device comprising the semiconductor chip package of claim 22.