WO2019138919A1

WO2019138919A1 - Liquid sealing resin composition, electronic component device, and method for manufacturing electronic component device

Info

Publication number: WO2019138919A1
Application number: PCT/JP2018/048354
Authority: WO
Inventors: 皓平関
Original assignee: 日立化成株式会社
Priority date: 2018-01-15
Filing date: 2018-12-27
Publication date: 2019-07-18
Also published as: JPWO2019138919A1; JP7358988B2; TW201934652A

Abstract

This liquid sealing resin composition contains an epoxy resin, an amine-based curing agent, and a cyclic carbodiimide.

Description

Liquid sealing resin composition, electronic component device and method of manufacturing electronic component device

The present invention relates to a liquid sealing resin composition, an electronic component device, and a method of manufacturing the electronic component device.

With various semiconductor elements (hereinafter, also referred to as chips) used in electronic component devices such as transistors and integrated circuits (ICs), resin sealing is mainly used in terms of productivity, manufacturing cost, and the like. Epoxy resin is widely used as the resin. This is because the epoxy resin is excellent in balance in various properties required for a sealing material such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, adhesion to an insert, and the like.

As the surface mounting method of the semiconductor element, so-called bare chip mounting in which a bare chip is directly mounted on a wiring substrate has become mainstream along with the miniaturization and thinning of the electronic component device. Examples of semiconductor devices based on bare chip mounting include COB (Chip on Board), COG (Chip on Glass), TCP (Tape Carrier Package), etc. In these semiconductor devices, a liquid sealing resin composition is used. Is widely used.
Further, in a flip chip type semiconductor device in which a semiconductor element is directly bump-connected on a wiring substrate (hereinafter, also simply referred to as a “substrate”), the gap between the bump-connected semiconductor element and the wiring substrate is filled. A liquid sealing resin composition is used as an underfill material. The liquid sealing resin composition plays an important role in protecting electronic parts from temperature, humidity and mechanical external force.

In recent years, with the development of information technology, further miniaturization, higher integration and multifunctionalization of electronic devices have progressed, and the amount of heat generation from electronic components has increased. For this reason, the heat resistance requirement for the sealing material is becoming higher and higher. In addition, when mounted in a car, higher heat resistance is required of the sealing material, and from the viewpoint of reliability improvement, generation of cracks in the sealed portion even when placed under a high temperature environment It is required to reduce it.

One method of improving the heat resistance of the liquid sealing resin composition is to increase the glass transition temperature. As a specific method of raising the glass transition temperature, there is a method of increasing the crosslink density by adding a large amount of polyfunctional resin (see, for example, Patent Document 1).

JP 2014-080455 A

In the method of improving the heat resistance by increasing the crosslink density using a polyfunctional resin as in Patent Document 1 etc., the elastic modulus is increased and the followability to the chip is inferior, so the heat resistance is improved by another method. Technology is needed. Moreover, even if it is exposed to heat, it is required to have excellent reliability by suppressing the occurrence of cracks and the like.

The present invention is a liquid sealing resin composition capable of suppressing weight loss due to heat and raising the glass transition temperature when it is made a cured product, and an electronic component device obtained using this liquid sealing resin composition And providing an electronic component device.

Means for solving the above problems include the following embodiments.
The liquid sealing resin composition containing <1> epoxy resin, an amine-type hardening | curing agent, and cyclic carbodiimide.
<2> The liquid encapsulating resin composition according to <1>, wherein the content of the cyclic carbodiimide is 0.05% by mass to 20% by mass.
The liquid sealing resin composition as described in <1> or <2> whose average particle diameter of <3> said cyclic carbodiimide is 200 micrometers or less.
<4> The liquid encapsulating resin composition according to any one of <1> to <3>, wherein the maximum particle diameter of the cyclic carbodiimide is 2 mm or less.
<5> The liquid sealing resin composition according to any one of <1> to <4>, further comprising an inorganic filler.
<6> The liquid sealing resin composition according to <5>, wherein the content of the inorganic filler is 20% by mass to 90% by mass.
<7> The liquid sealing resin according to any one of <1> to <6>, wherein the epoxy resin contains at least one selected from the group consisting of bisphenol type epoxy resin and glycidyl amine type epoxy resin. Composition.
<8> When the epoxy resin does not contain a trifunctional or higher polyfunctional epoxy resin or contains a polyfunctional epoxy resin, the content of the polyfunctional epoxy resin is 48 mass with respect to the total amount of the epoxy resin The liquid sealing resin composition according to any one of <1> to <7>, which is at most%.
<9> The liquid sealing resin composition according to any one of <1> to <8>, wherein the content of the solvent is 5% by mass or less when the composition does not contain a solvent or contains a solvent.
<10> a supporting member,
An electronic component disposed on the support member;
A cured product of the liquid sealing resin composition according to any one of <1> to <9>, wherein at least a part of a gap between the support member and the electronic component is sealed.
Electronic component device comprising
<11> The electronic component device according to <10>, wherein the distance between the support member and the electronic component is 200 μm or less.
The liquid sealing resin composition as described in any one of <1>-<9> at least one part of the space | gap between a <12> support member and the electronic component arrange | positioned on the said support member And manufacturing the electronic component device.
The manufacturing method of the electronic component apparatus as described in <12> whose distance between the <13> said supporting member and the said electronic component is 200 micrometers or less.

According to the present invention, a liquid sealing resin composition capable of suppressing weight loss due to heat and raising the glass transition temperature when it is made a cured product, an electron obtained using this liquid sealing resin composition A component device and a method of manufacturing an electronic component device are provided.

Hereinafter, modes for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.
In the present disclosure, the term “step” includes, in addition to steps independent of other steps, such steps as long as the purpose of the step is achieved even if it can not be clearly distinguished from other steps. .
In the present disclosure, numerical values described before and after “to” are included in the numerical range indicated using “to” as the minimum value and the maximum value, respectively.
The upper limit value or the lower limit value described in one numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure. . In addition, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the example.

In the present disclosure, each component may contain a plurality of corresponding substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, particles corresponding to each component may contain a plurality of types. When there are a plurality of particles corresponding to each component in the composition, the particle diameter of each component means the value for the mixture of the plurality of particles present in the composition unless otherwise specified.

In the present disclosure, “normal temperature” means 25 ° C., and “liquid” means a substance that exhibits fluidity and viscosity and is a scale indicating viscosity and having a viscosity of 0.0001 Pa · s to 100 Pa · s. . Moreover, "liquid" means being in the state of the liquid.

In the present disclosure, “viscosity” is defined as a value obtained by multiplying a predetermined conversion factor by a measured value obtained by rotating an EHD-type rotational viscometer at 25 ° C. for one minute every predetermined number of minutes. The measured values are obtained for a liquid kept at 25 ± 1 ° C. using an EHD rotary viscometer fitted with a cone rotor of 3 ° cone angle and 14 mm cone radius. The number of revolutions per minute and the conversion factor depend on the viscosity of the liquid to be measured. Specifically, the viscosity of the liquid to be measured is roughly estimated in advance, and the number of revolutions per minute (rpm) and the conversion factor are determined according to the estimated value.

In the present disclosure, when the estimated value of the viscosity of the liquid to be measured is 0 Pa · s or more and less than 1.25 Pa · s, the rotation speed is 10 rpm, the conversion coefficient is 0.5, and the estimated value of viscosity is 1.25 Pa · s. In the case of 2.5 Pa · s or more, the rotation speed is 5 rpm and the conversion factor is 1. The estimated viscosity is 2.5 Pa · s or more and less than 6.25 Pa · s, the rotation speed is 2.5 rpm, the conversion factor When the estimated value of viscosity is 6.25 Pa · s or more and less than 12.5 Pa · s, the rotational speed is 1 rpm, and the conversion factor is 5.

<Liquid sealing resin composition>
The liquid encapsulating resin composition of the present disclosure comprises an epoxy resin, an amine-based curing agent, and a cyclic carbodiimide. The liquid sealing resin composition may contain other components as needed.

In the liquid sealing resin composition of the present disclosure, weight reduction due to heat is suppressed, and it is possible to increase the glass transition temperature (Tg) when it is a cured product. Although the reason is not clear, it can be considered as follows.

The curing reaction between the epoxy resin and the amine curing agent produces a C—N bond. When the crosslinking density is increased by using a polyfunctional resin to increase Tg as in the prior art, more CN bonds are generated. The C—N bond is susceptible to heat and may be thermally decomposed to cause weight loss.
On the other hand, since the liquid sealing resin composition of this indication uses cyclic carbodiimide, high Tg-ization is achieved. The reason is considered to be that the cyclic carbodiimide has a rigid cyclic skeleton and this skeleton fills the interstices of the crosslinks to suppress the movement of the crosslink chains. Therefore, by using cyclic carbodiimide, it is possible to increase Tg without increasing the crosslinking density. Therefore, the use of cyclic carbodiimide makes it possible to increase the Tg without increasing C—N bonds and to suppress the thermal decomposition. By suppressing the weight reduction due to the thermal decomposition, the occurrence of a crack or the like in the sealed portion tends to be suppressed.

(Cyclic carbodiimide)
The cyclic carbodiimide is a compound having a cyclic structure in which one or more carbodiimide groups (—N = C = N—) are contained in the molecule, and two nitrogens constituting the carbodiimide group are linked by a linking group. The cyclic carbodiimide may be used alone or in combination of two or more.

From the viewpoint of improving the heat resistance when the liquid sealing resin composition is a cured product, the cyclic carbodiimide preferably contains two or more carbodiimide groups in the molecule.

The cyclic structure in cyclic carbodiimide may be one or two or more. When it has two or more cyclic structures, two rings may share two or more atoms as in a bicyclo structure, a tricyclo structure, etc., and as in the spiro structure, one atom in two rings is common It may be done. Furthermore, the atoms constituting the cyclic structure may have a cyclic group as a substituent, thereby providing a structure having two or more cyclic structures.

As cyclic carbodiimide, the compound represented by following General formula (1) is mentioned.

In the general formula (1), X is a divalent or higher linking group. When X is a trivalent or higher linking group, it may be bonded to a polymer or to another cyclic structure.
The linking group represented by X contains a carbon atom and a hydrogen atom, and may further contain a hetero atom. As a hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom etc. are mentioned.

The number of atoms (number of members) of the cyclic structure configured to contain a carbodiimide group and X is not particularly limited, and is, for example, preferably 8 to 50, more preferably 10 to 30, and 10 to 20. It is further preferred that The number of members referred to here does not include the number of atoms of substituents.

Specific examples of the linking group represented by X include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a combination thereof, or a combination thereof with a hetero atom.

Examples of the aliphatic hydrocarbon group represented by X include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, an alkanetetrayl group having 1 to 20 carbon atoms, and the like. The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like.

As an alicyclic hydrocarbon group represented by X, a C3-C20 cycloalkylene group, a C3-C20 cycloalkanetriyl group, a C3-C20 cycloalkanetetrayl group can be mentioned. . The alicyclic hydrocarbon group may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like.

Examples of the aromatic hydrocarbon group include arylene groups having 5 to 15 carbon atoms, arenetriyl groups having 5 to 15 carbon atoms, and arenetetrayl groups having 5 to 15 carbon atoms. The aromatic hydrocarbon group may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like.

The molecular weight of the cyclic carbodiimide is preferably 100 to 1,000, more preferably 100 to 750, and still more preferably 250 to 750.

The cyclic carbodiimide may be solid or liquid at room temperature (25 ° C.). When the cyclic carbodiimide is solid, it may be in any form or in the form of particles.
When the cyclic carbodiimide is in the form of particles, the average particle diameter of the particles is preferably 200 μm or less, more preferably 100 μm or less, still more preferably 20 μm or less, particularly 10 μm or less Preferably, it is very preferably 8 μm or less.
The average particle diameter of the cyclic carbodiimide is preferably 0.1 μm or more, more preferably 0.5 μm or more, and still more preferably 0.8 μm or more.

In the present disclosure, the average particle size of cyclic carbodiimide means a volume average particle size. Specifically, it means the particle diameter (D50) at which the accumulation from the small diameter side is 50% in the volume-based particle size distribution curve obtained by the laser diffraction scattering method.

When the cyclic carbodiimide is in the form of particles, the maximum particle size (Dmax) of the particles is preferably 2 mm or less, more preferably 800 μm or less, still more preferably 100 μm or less, and 50 μm or less Is particularly preferred.
The maximum particle size (Dmax) of the cyclic carbodiimide is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more.

In the present disclosure, the maximum particle size (Dmax) of the cyclic carbodiimide is a volume-based particle size distribution curve determined by a laser diffraction scattering method, and means the maximum particle size in this particle size distribution curve.

When cyclic carbodiimide has a spiro structure, as cyclic carbodiimide, the compound represented by following General formula (2) is mentioned.

In the formula, X is a tetravalent group represented by the following formula (3). In the formula, Ar ¹ to Ar ⁴ are each independently an orthophenylene group or a 1,2-naphthalene-diyl group which may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like. Ar ¹ to Ar ⁴ may contain a hetero atom and may have a heterocyclic structure. As a hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom etc. are mentioned.

The following compounds are illustrated as a specific example compound of a compound represented by General formula (2).

These cyclic carbodiimide compounds can be produced by methods known in various documents, patent publications and the like.

Examples of commercially available cyclic carbodiimides include TCC-FP10M (Teijin Limited, trade name) and the like.

The content of the cyclic carbodiimide in the liquid sealing resin composition is not particularly limited, and is, for example, preferably 0.05% by mass to 20% by mass of the entire liquid sealing resin composition, and 0.1% by mass to 20% by mass. The content is more preferably mass%, further preferably 0.2 mass% to 15 mass%, and particularly preferably 0.5 mass% to 10 mass%.

(Epoxy resin)
The epoxy resin is not particularly limited, and, for example, an epoxy resin generally used as a component of a sealing material of an electronic component device can be used. From the viewpoint of obtaining sufficient curability, it is preferable to use an epoxy resin having two or more epoxy groups in one molecule.

Specific examples of the epoxy resin include novolac epoxy resins such as phenol novolac epoxy resin and cresol novolac epoxy resin; bisphenol epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin; Glycidyl amine type epoxy resins such as aromatic glycidyl amine type epoxy resins such as diglycidyl aniline, N, N-diglycidyl toluidine, diaminodiphenylmethane type glycidyl amine, aminophenol type glycidyl amine; hydroquinone type epoxy resins; biphenyl type epoxy resins; Stilbene type epoxy resin; triphenol methane type epoxy resin; triphenol propane type epoxy resin; alkyl-modified triphenol methane type epoxy resin; Nucleated epoxy resin; dicyclopentadiene modified phenol type epoxy resin; naphthol type epoxy resin; naphthalene type epoxy resin; phenol aralkyl type epoxy resin having at least one of phenylene skeleton and biphenylene skeleton, at least one of phenylene skeleton and biphenylene skeleton And an aliphatic epoxy resin such as a cycloaliphatic epoxy resin such as vinylcyclohexene dioxide, dicyclopentadiene oxide, or acyclic diepoxy-adipate. The epoxy resin may be used alone or in combination of two or more.

The epoxy resin preferably includes an epoxy resin having a structure in which a glycidyl structure or a glycidyl amine structure is bonded to an aromatic ring, from the viewpoint of improving the heat resistance, mechanical properties and moisture resistance of a cured product.
Moreover, when an epoxy resin contains an aliphatic epoxy resin, it is preferable to limit the amount to be used from a viewpoint of securing reliability of hardened | cured material, especially adhesiveness.

From the viewpoint of making the sealing resin composition liquid, it is preferable to use a liquid epoxy resin as the epoxy resin, and from the viewpoint of making the liquid sealing resin composition liquid at normal temperature, the epoxy resin liquid epoxy at normal temperature It is more preferable to use a resin.

When the liquid sealing resin composition contains a liquid epoxy resin, all epoxy resins may be liquid, or a combination of liquid epoxy resin and solid epoxy resin.
The combination of a liquid epoxy resin and a solid epoxy resin is preferably a combination in which a mixture of these epoxy resins is liquid as a whole, and more preferably a combination in which it is liquid at normal temperature.
When the liquid sealing resin composition contains a solid epoxy resin, the content is preferably 20% by mass or less of the entire epoxy resin from the viewpoint of maintaining good fluidity.

When the liquid sealing resin composition contains two or more types of epoxy resins, all the epoxy resins used may be mixed and then mixed with other components to prepare a liquid sealing resin composition, The epoxy resin used may be separately mixed to prepare a liquid sealing resin composition.

The content of the epoxy resin in the liquid sealing resin composition is not particularly limited, and is preferably 5% by mass to 60% by mass, and 5% by mass to 50% by mass, based on the total amount of the liquid sealing resin composition. Is more preferred. When the content of the epoxy resin is in this range, the reactivity is excellent, and the heat resistance and mechanical strength when formed into a cured product tend to be excellent as well as the flow characteristics at the time of sealing.

From the viewpoint of balance of various properties of the liquid encapsulating resin composition, the epoxy resin preferably contains at least one selected from the group consisting of bisphenol type epoxy resin and glycidyl amine type epoxy resin, and bisphenol type epoxy resin It is more preferable to contain both and glycidyl amine type epoxy resin. In this case, the total content of the bisphenol type epoxy resin and the glycidyl amine type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more of the whole epoxy resin. Is more preferable, and 80% by mass or more is particularly preferable.

When a liquid sealing resin composition contains both a bisphenol type epoxy resin and a glycidyl amine type epoxy resin as an epoxy resin, the mass ratio (bisphenol type epoxy resin: glycidyl amine type epoxy) is not specifically limited. From the viewpoint of heat resistance, adhesion and flowability, for example, the mass ratio is preferably 20:80 to 95: 5, more preferably 40:60 to 90:10, and 60:40 to 80. More preferably, it is 20.

From the viewpoint of further suppressing weight loss due to heat, in the case where a trifunctional or higher polyfunctional epoxy resin is not contained or a polyfunctional epoxy resin is contained, the content of the polyfunctional epoxy resin is 48 with respect to the total amount of epoxy resin. The content is preferably at most mass%, more preferably at most 45 mass%, further preferably at most 40 mass%, particularly preferably at most 38 mass%, at most 35 mass% Very preferred.
From the viewpoint of further raising the glass transition temperature, the content of the trifunctional or higher polyfunctional epoxy resin is preferably 2% by mass or more of the entire epoxy resin, and more preferably 3% by mass or more. More preferably, it is 4% by mass or more.

The purity of the epoxy resin is preferably as high as possible. In particular, the amount of hydrolyzable chlorine in the epoxy resin is preferably as small as it relates to the corrosion of aluminum wiring on an element such as an IC. From the viewpoint of obtaining a liquid sealing resin composition excellent in moisture resistance, for example, it is preferable to use an epoxy resin having a hydrolyzable chlorine amount of 500 mass ppm or less.

In the present disclosure, the hydrolyzable chlorine content of the epoxy resin is obtained by dissolving 1 g of the epoxy resin as a sample in 30 ml of dioxane, adding 5 ml of 1N KOH (potassium hydroxide) methanol solution and refluxing for 30 minutes. The value obtained by

(Amine curing agent)
The amine-based curing agent is not particularly limited, and, for example, those generally used as components of sealing materials for electronic component devices can be used.

The amine curing agent is a compound containing two or more one or more kinds selected from the group consisting of a primary amino group and a secondary amino group in one molecule (hereinafter, also simply referred to as "amino group") More preferably, it is a compound having 2 to 4 amino groups in one molecule, and more preferably a compound having two amino groups in one molecule (diamine compound). The amine curing agent may be used alone or in combination of two or more.

The amine curing agent is preferably a compound having an aromatic ring (aromatic amine compound), more preferably a liquid aromatic amine compound (liquid aromatic amine compound), and an aromatic amine liquid at normal temperature More preferably, they are compounds.

Specific examples of the liquid aromatic amine compound include diethyltoluenediamine such as 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine, and 1-methyl-3,5- Diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4, 4'-diaminodiphenylmethane, 3,5,3 ', 5'-tetramethyl-4,4'-diaminodiphenylmethane and the like. Among these, from the viewpoint of storage stability, for example, 3,3'-diethyl-4,4'-diaminodiphenylmethane and diethyltoluenediamine are preferable.

The active hydrogen equivalent of the amine curing agent is not particularly limited, and is, for example, preferably 10 g / mol to 200 g / mol, and more preferably 20 g / mol to 100 g / mol from the viewpoint of high heat resistance. And more preferably 30 g / mol to 70 g / mol.

Liquid aromatic amine compounds are also available as commercial products. As commercially available liquid aromatic amine compounds, jER Cure (registered trademark) -W, jER Cure (registered trademark) -Z (Mitsubishi Chemical Corporation, trade name), Kayahard (registered trademark) AA, Kayahard (registered trademark) Trademarks AB, Kayahard (registered trademark) AS (Nippon Kayaku Co., Ltd., trade name), Toutaamine HM-205 (Nippon Steel Sumikin Chemical Co., Ltd., trade name), Adeka Hardener (registered trademark) EH-101 (ADEKA, trade name), Epomic (registered trademark) Q-640, Epomic (registered trademark) Q-643 (Mitsui Chemical Co., Ltd., trade name), DETDA 80 (Lonza, trade name), and the like.

As the curing agent, other curing agents other than the amine curing agent may be used in combination. Examples of other curing agents include phenolic curing agents and acid anhydride curing agents. As another hardening agent, what is generally used as a component of the sealing material of an electronic component apparatus can be used.

The content of the amine curing agent relative to the total amount of curing agent is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more.

From the viewpoint of making the liquid sealing resin composition liquid, it is preferable to use a liquid curing agent, and from the viewpoint of making the liquid sealing resin composition liquid at normal temperature, to use a liquid curing agent at normal temperature More preferable.

When the liquid sealing resin composition contains a liquid curing agent, all the curing agents may be liquid, or a combination of a liquid curing agent and a solid curing agent. The combination of a liquid curing agent and a solid curing agent is preferably a combination in which the mixture of these curing agents is liquid as a whole, and more preferably a combination in which the mixture is liquid at normal temperature.
When the liquid sealing resin composition contains a solid curing agent, the content is preferably 20% by mass or less of the entire curing agent, from the viewpoint of maintaining good fluidity.

The content ratio of the epoxy resin and the curing agent contained in the liquid sealing resin composition is not particularly limited. From the viewpoint of reducing each unreacted content, for example, the ratio of the number of epoxy groups of the epoxy resin to the number of active hydrogens of the curing agent (number of epoxy groups of epoxy resin / number of active hydrogens of curing agent) is 0.7 to 1.6. Is preferably, 0.8 to 1.4 is more preferable, and 0.9 to 1.2 is more preferable.

(Inorganic filler)
The liquid sealing resin composition of the present disclosure may contain an inorganic filler. The inorganic filler is not particularly limited, and, for example, an inorganic filler generally used as a component of a sealing material of an electronic component device can be used.

Specific examples of the inorganic filler include silica such as fused silica and crystalline silica, calcium carbonate, clay, alumina, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, Powders such as forsterite, steatite, spinel, mullite and titania, beads obtained by spheroidizing the powder, glass fibers and the like can be mentioned. As the inorganic filler, one having a flame retardant effect may be used. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate and zinc molybdate. The inorganic filler may be used alone or in combination of two or more.

The particle shape of the inorganic filler is not particularly limited, and may be indeterminate or spherical. From the viewpoint of the fluidity and permeability of the liquid sealing resin composition into fine gaps, it is spherical. Is preferred. Specifically, for example, spherical silica is preferable, and spherical fused silica is more preferable.

The average particle size of the inorganic filler is not particularly limited, and is preferably 0.1 μm to 10 μm, and more preferably 0.3 μm to 5 μm. When the average particle diameter of the inorganic filler is 0.1 μm or more, the dispersibility in the resin component (epoxy resin, curing agent, etc.) is improved, and the flow characteristics of the liquid sealing resin composition tend to be further improved. If the thickness is 10 μm or less, the sedimentation of the inorganic filler can be more easily suppressed, and the permeability to the fine gaps and the flowability tend to be improved, and the generation of voids or unfilled portions tends to be further suppressed.

In the present disclosure, the average particle size of the inorganic filler means the volume average particle size. Specifically, it means the particle diameter (d50) at which the accumulation from the small diameter side is 50% in the volume-based particle size distribution curve obtained by the laser diffraction scattering method.

There is no restriction | limiting in particular in the content rate of the inorganic filler in a liquid sealing resin composition, For example, it is preferable that it is 20 mass%-90 mass% of the liquid sealing resin composition whole, and 30 mass%-80 mass% Is more preferably 40 to 75% by mass, particularly preferably 50 to 75% by mass, and most preferably 60 to 75% by mass.

When the content of the inorganic filler is 20% by mass or more of the whole liquid encapsulating resin composition, the thermal expansion coefficient of the cured product tends to decrease, and when it is 90% by mass or less, the liquid encapsulating resin composition It tends to maintain low viscosity and maintain good flowability, permeability and dispenseability.

(Coupling agent)
The liquid encapsulating resin composition of the present disclosure may contain a coupling agent. The coupling agent is not particularly limited, and, for example, a coupling agent generally used as a component of a sealing material of an electronic component device can be used. When the liquid sealing resin composition contains a coupling agent, effects such as the improvement of the adhesiveness at the interface between the resin component and the inorganic filler or the constituent member of the electronic component, and the improvement of the filling property can be expected.

Specifically as the coupling agent, aminosilane having at least one amino group selected from the group consisting of primary amino group, secondary amino group and tertiary amino group, epoxysilane, mercaptosilane, alkylsilane, ureidosilane And compounds having a silicon atom in the molecular structure such as vinylsilane (silane compounds), titanium compounds, aluminum chelates, aluminum compounds, zirconium compounds, and the like. The coupling agent may be used alone or in combination of two or more.

From the viewpoint of the filling property of the liquid sealing resin composition, a silane compound is preferable as the coupling agent, and epoxysilane is more preferable. Specifically as the epoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-) Epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. Among these, 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferable.

The content of the coupling agent is not particularly limited, and from the viewpoint of strengthening the adhesion at the interface between the resin component and the inorganic filler or the component of the electronic component, and from the viewpoint of improving the filling property, for example, liquid sealing The content is preferably 0.05% by mass to 10% by mass, more preferably 0.2% by mass to 5% by mass, and still more preferably 0.4% by mass to 1% by mass of the entire resin composition. preferable.

(Other ingredients)
The liquid sealing resin composition may contain other components in addition to the components described above. Other components include dyes, colorants such as carbon black, diluents, leveling agents, antifoaming agents and the like.

In addition, since a liquid sealing resin composition is generally used as an underfill material, the content thereof is small even if it does not contain a solvent or contains a solvent from the application, for example, a liquid sealing resin composition It is 5 mass% or less of the whole thing. On the other hand, since cyclic carbodiimide is normally solid at normal temperature, it is not actively used as a component of the liquid encapsulating resin composition. However, even if the liquid encapsulating resin composition containing no solvent or containing a solvent, the liquid sealing resin composition having a solvent content of 5% by mass or less, the cyclic carbodiimide which is solid at normal temperature is excellent in heat resistance. A cured product is obtained.

<Method of Preparing Liquid Sealing Resin Composition>
The preparation method of the liquid sealing resin composition is not particularly limited, as long as the above-mentioned various components can be dispersed and mixed. The liquid sealing resin composition measures, for example, each component of a predetermined compounding amount, mixes and kneads it using a mixer such as a grinder, a mixing roll, a planetary mixer, etc., and defoams if necessary. Can be obtained by The conditions for mixing and kneading may be appropriately determined according to the type of the raw material and the like, and it is preferable to select conditions for uniformly mixing and dispersing the respective components.

<Physical Properties of Liquid Sealing Resin Composition>
The liquid sealing resin composition preferably has a viscosity at 25 ° C. measured using an EHD rotational viscometer of, for example, 1000 Pa · s or less, more preferably 500 Pa · s or less, and 100 Pa · s. It is more preferably s or less, and particularly preferably 30 Pa · s or less.
If the viscosity is 1000 Pa · s or less, the flowability and the permeability tend to be secured, which can cope with the miniaturization of electronic parts, the fine pitch of connection terminals of semiconductor elements, and the fine wiring of wiring boards.
The lower limit of the viscosity of the liquid sealing resin composition is not particularly limited, and from the viewpoint of mountability, for example, it is preferably 1.0 Pa · s or more, and more preferably 5 Pa · s or more.

The viscosity of the liquid sealing resin composition may be appropriately adjusted, for example, according to the types of electronic components and electronic component devices to be sealed. The viscosity of the liquid sealing resin composition can be adjusted, for example, by setting the types, contents, and the like of the components exemplified above.

The liquid sealing resin composition preferably has a weight loss due to heat of, for example, 1.0% by mass or less, more preferably 0.75% by mass or less, and 0.5% by mass or less Is more preferred.

The weight loss due to heat is determined by, for example, heating a sample of 60 mm × 10 mm × 3 mm in a constant temperature bath set at 150 ° C. for 2000 hours and calculating from the mass of the sample before and after heating.
That is, weight reduction due to heat of the liquid sealing resin composition (% by mass) = {(sample mass before heating−sample mass after heating) / sample mass before heating} × 100.

The glass transition temperature of the liquid sealing resin composition can be appropriately set according to the package structure to be sealed, and is preferably 60 ° C. or more, and more preferably 80 ° C. or more. More preferably, the temperature is 100 ° C. or higher.

The glass transition temperature is the change in sample length when the temperature is raised from 0 ° C. to 300 ° C. at 5 ° C./min by a compression method using a thermomechanical analyzer (eg, TMA 2940, manufactured by TA instruments). Measure and determine as the temperature corresponding to the intersection of tangents at 50 ° C and 150 ° C.

The coefficient of thermal expansion is the change in sample length when the temperature is raised from 0 ° C. to 300 ° C. at 5 ° C./min by the compression method using a thermomechanical analyzer (eg, TMA 2940, manufactured by TA instruments). Measure the tangent slope at 10 ° C. to 30 ° C. as the thermal expansion coefficient (ppm / ° C.).

<Application of Liquid Sealing Resin Composition>
The liquid sealing resin composition of the present disclosure includes a lead frame, a tape carrier with wiring, a wiring board (rigid or flexible), a support member such as glass or silicone wafer, an active element such as a semiconductor chip, a transistor, a diode or a thyristor. The present invention can be applied to the manufacture of electronic component devices equipped with electronic components such as passive elements such as capacitors, resistors, resistor arrays, coils, switches and the like.

In particular, the liquid sealing resin composition of the present disclosure can be suitably used as an underfill material having excellent reliability. Specifically, for example, it is suitable as an underfill material used for manufacturing a flip chip type semiconductor device obtained by flip chip bonding an electronic component on a support member by bump connection. Examples of flip chip type semiconductor devices include BGA (Ball Grid Array), LGA (Land Grid Array), COF (Chip On Film), and the like.

The liquid sealing resin composition of the present disclosure is suitable for the production of an electronic component device using a conventional lead-containing solder as a material of bumps connecting the support member and the electronic component, but the lead-containing solder As compared with the above, it is possible to maintain good reliability even in the manufacture of electronic component devices using lead-free solder such as Sn-Ag-Cu-based which is physically fragile, and can be suitably used.

In recent years, with the speeding up of semiconductor devices, an interlayer insulating film with a low dielectric constant is formed on a semiconductor device, but this interlayer insulating film is weak in mechanical strength and easily broken by external stress. Is easy to occur. This tendency becomes more remarkable as the size of the semiconductor element becomes larger, and therefore, it is required to reduce the stress caused by the liquid sealing resin composition.

The liquid encapsulating resin composition of the present disclosure has, for example, a flip that mounts a semiconductor element having an interlayer insulating film having a length of 2 mm or more of the longer side of the semiconductor element and a dielectric constant of 3.0 or less. Excellent reliability can also be provided to chip-type electronic component devices.
In addition, the liquid sealing resin composition of the present disclosure exhibits good flowability and fillability even when the distance between the support member and the bump connection surface of the electronic component is small, and has reliability such as moisture resistance and thermal shock resistance. An excellent electronic component device can be manufactured. Specifically, the distance between the bump connection surfaces may be 200 μm or less, 100 μm or less, or 50 μm or less.

<Electronic component device>
An electronic component device according to the present disclosure includes a support member, an electronic component disposed on the support member, and the liquid according to the present disclosure sealing at least a part of a gap between the support member and the electronic component. And a cured product of the sealing resin composition.

The suitable aspect of the electronic component apparatus provided with the supporting member which comprises the electronic component apparatus of this indication, electronic component, etc. is the same as what was mentioned by the term of the application of the liquid sealing resin composition mentioned above.

In the electronic component device of the present disclosure, it is preferable that at least a part of the gap between the support member and the electronic component is sealed by the cured product of the liquid seal, and it is preferable that the entire gap is sealed. . Moreover, parts other than the space | gap between a supporting member and electronic parts may be sealed by the hardened | cured material of a liquid sealing resin composition.

<Method of manufacturing electronic component device>
A method of manufacturing an electronic component device of the present disclosure seals at least a part of a gap between a support member and an electronic component disposed on the support member using the liquid sealing resin composition of the present disclosure. It has a process.

Preferred embodiments of the electronic component device provided with the support member, the electronic component and the like used in the method of manufacturing the electronic component device of the present disclosure are the same as those mentioned in the application of the liquid sealing resin composition described above. .

In the method of manufacturing an electronic component device of the present disclosure, at least a part of the gap between the support member and the electronic component may be sealed by the liquid sealing resin composition, and it is preferable to seal the entire gap. In addition, the portion other than the gap between the support member and the electronic component may be sealed with the liquid sealing resin composition.

The method for sealing the gap between the support member and the electronic component using the liquid sealing resin composition is not particularly limited, and a conventionally known method such as a dispensing method, a casting method, or a printing method may be applied. it can.

Examples Hereinafter, the liquid sealing resin composition of the present disclosure will be more specifically described by examples, but the present disclosure is not limited to these examples.

(Preparation of liquid sealing resin composition)
The following components are compounded in parts by mass as shown in Table 1 (however, the numerical value of the inorganic filler indicates "% by mass"), and are kneaded and dispersed by a triple roll and a vacuum grinder, and Examples 1 to 6 and The liquid sealing resin compositions of Comparative Examples 1 to 3 were prepared. "-" In the table represents no blending.

Epoxy resin 1: Liquid diepoxy resin having an epoxy equivalent of 160 g / mol obtained by epoxidizing bisphenol F (Nippon Steel & Sumitomo Metal Chemical Co., Ltd., trade name "YDF-8170C")
-Epoxy resin 2: A trifunctional liquid epoxy resin having an epoxy equivalent of 95 g / mol obtained by epoxidizing aminophenol (Mitsubishi Chemical Corporation, trade name "jER630")
-Epoxy resin 3: Liquid epoxy resin of dihydroxy naphthalene type and epoxy equivalent 143 g / mol (DIC Corporation, trade name "HP-4032D")

Hardener 1: Diethyltoluenediamine having an active hydrogen equivalent of 45 g / mol (Mitsubishi Chemical Corporation, trade name "jER Cure (registered trademark)-W")
Hardening agent 2: Active hydrogen equivalent of 63 g / mol of diethyldiaminodiphenylmethane (Nippon Kayaku Co., Ltd., trade name "Kayahard A-A")

-Carbodiimide 1: Cyclic carbodiimide, Teijin Limited, trade name "TCC-FP10M"
Carbodiimide 2: linear carbodiimide, Nisshinbo Chemical Co., Ltd., trade name "Carbodilite (registered trademark) LA-1"

・ Coupling agent: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name "KBM-403")
・ Colorant: carbon black (Mitsubishi Chemical Corporation, trade name "MA-100")
Inorganic filler: Spherical fused silica with an average particle size of 0.5 μm (Admatex Co., Ltd., trade name "SO-24H / 25C")

(Measurement of weight loss due to heat)
A sample of 60 mm × 10 mm × 3 mm in size is prepared from the prepared liquid sealing resin composition, and this sample is heated for 2000 hours in a thermostatic bath set at 150 ° C. I asked for it.
Weight loss due to heat of liquid sealing resin composition (% by mass) = {(sample mass before heating−sample mass after heating) / sample mass before heating} × 100

(Measurement of glass transition temperature)
The prepared liquid sealing resin composition was cured at 150 ° C. for 2 hours to obtain a cured product. The cured product was cut into a size of 8 mm in diameter and 20 mm in length to prepare a measurement sample.
Using a thermomechanical analyzer (TMA 2940, manufactured by TA instruments), measure the change in the length of the measurement sample when the temperature is raised from 0 ° C to 300 ° C at 5 ° C / min by the compression method. The temperature corresponding to the intersection of tangents at 200 ° C. was determined as the glass transition temperature. The results are shown in Table 1.

As shown in Table 1, Examples 1 to 6 containing cyclic carbodiimide have glass transition temperatures compared to Comparative Example 1 containing no cyclic carbodiimide and Comparative Examples 2 to 3 containing a chain carbodiimide instead of cyclic carbodiimide. Is high and the heat resistance is excellent. In particular, it is understood that Example 6 in which the content of cyclic carbodiimide is 7.0% by mass of the whole liquid encapsulating resin composition has a high glass transition temperature and is particularly excellent in heat resistance.

In addition, in consideration of the height of the glass transition temperature of the example, even if the crosslink density is designed to be lower than that of the liquid sealing resin composition of the example and the CN bond in the cured product is reduced, It can be seen that it is possible to make the glass transition temperature higher than the liquid sealing resin composition of the example. As described above, when the crosslink density is lower than that of the example, it is possible to suppress the weight loss (% by mass) due to heat while maintaining the glass transition temperature high. This point is also understood from the fact that the weight loss due to heat is reduced to 0.36% by mass in Comparative Example 4 in which the multifunctional epoxy resin is not used. However, in Comparative Example 4, since the polyfunctional epoxy resin is not used and the cyclic carbodiimide is not contained, the glass transition temperature is considerably low.

The disclosure of Japanese Patent Application No. 2018-004052 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are as specific and individually as individual documents, patent applications, and technical standards are incorporated by reference. Incorporated herein by reference.

Claims

Liquid sealing resin composition containing an epoxy resin, an amine-based curing agent, and cyclic carbodiimide.
The liquid encapsulating resin composition according to claim 1, wherein the content of the cyclic carbodiimide is 0.05% by mass to 20% by mass.
The liquid sealing resin composition of Claim 1 or Claim 2 whose average particle diameter of the said cyclic carbodiimide is 200 micrometers or less.
The liquid encapsulating resin composition according to any one of claims 1 to 3, wherein the maximum particle size of the cyclic carbodiimide is 2 mm or less.
The liquid sealing resin composition according to any one of claims 1 to 4, further comprising an inorganic filler.
The liquid sealing resin composition according to claim 5, wherein the content of the inorganic filler is 20% by mass to 90% by mass.
The liquid encapsulating resin composition according to any one of claims 1 to 6, wherein the epoxy resin contains at least one selected from the group consisting of a bisphenol epoxy resin and a glycidyl amine epoxy resin.
If the epoxy resin does not contain a trifunctional or higher polyfunctional epoxy resin, or if it contains a polyfunctional epoxy resin, the content of the polyfunctional epoxy resin is 48% by mass or less based on the total amount of the epoxy resin The liquid sealing resin composition according to any one of claims 1 to 7.
The liquid sealing resin composition according to any one of claims 1 to 8, wherein the solvent is not contained, or when the solvent is contained, the content of the solvent is 5% by mass or less.
A support member,
An electronic component disposed on the support member;
The cured product of the liquid sealing resin composition according to any one of claims 1 to 9, which seals at least a part of a space between the support member and the electronic component.
Electronic component device comprising
The electronic component device according to claim 10, wherein a distance between the support member and the electronic component is 200 μm or less.
A liquid sealing resin composition according to any one of claims 1 to 9 is used to seal at least a part of a gap between a support member and an electronic component disposed on the support member. A method of manufacturing an electronic component device, comprising:
The method of manufacturing an electronic component device according to claim 12, wherein a distance between the support member and the electronic component is 200 μm or less.