KR102072259B1 - Liquid epoxy resin composition - Google Patents

Abstract

Even if it contains an inorganic filler, the fluidity | liquidity of an epoxy resin composition is good and it aims at providing the liquid epoxy resin composition with a long pot life by suppressing the thickening in storage. Liquid epoxy resin composition containing (A) liquid epoxy resin, the epoxy adduct hardening | curing agent of (B) amine compound, (C) inorganic filler, (D) triisopropyl borate, and (E) phenol resin, 100 mass parts (C) component is 20-65 mass parts, (D) component is 0.02-0.15 mass part, and (E) component is 0.3-15.0, It is a liquid epoxy resin composition.

Description

Liquid epoxy resin composition {LIQUID EPOXY RESIN COMPOSITION}

The present invention relates to a liquid epoxy resin composition, and more particularly, to a liquid epoxy resin composition which can be used as an underfill material or an adhesive for electronic parts, which is excellent in fluidity and has a low coefficient of linear expansion.

In recent years, flip chip bonding is used as a mounting method of a semiconductor chip which can cope with the higher density and higher frequency of wiring of electronic devices. In flip chip mounting, since a semiconductor chip and a board | substrate are directly connected, a crack may generate | occur | produce in a connection part by the stress resulting from the difference of the linear expansion coefficient of a silicon chip and a board | substrate, and it becomes a cause of poor connection reliability. As a countermeasure, the technique of filling the liquid sealing material called an underfill material between a semiconductor chip and a wiring board is used. By using an underfill material, it becomes possible to improve the connection reliability with respect to thermal stress, such as a heat cycle, and the connection reliability with respect to physical stress, such as an impact and a bending.

Here, the linear expansion coefficient of the silicon chip is 4 ppm / 占 폚, and the linear expansion coefficient of the substrate, for example, the glass epoxy substrate, is 20 ppm / 占 폚. In general, the underfill material is mixed with an inorganic filler in order to absorb the difference in the linear expansion coefficient, and a silica filler is usually used as the inorganic filler.

As the underfill material, an epoxy-imidazole curing system is used as a resin that can be cured at low temperature, but when the silica filler is added to the resin system for the purpose of lowering the linear expansion coefficient of the underfill material described above, the fluidity of the underfill material deteriorates. There is a problem. As a cause of this fluid deterioration, it can be considered that the dispersion state of the resin component and the silica filler in the underfill material is nonuniform.

The epoxy resin composition for sealing containing phosphate ester is reported for the purpose of the improvement of the fluidity | liquidity deterioration of the underfill material at the time of adding this silica filler (patent document 1, patent document 2).

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-289123 Patent Document 2: Japanese Patent Application Laid-Open No. 2011-246545

However, when phosphate ester is contained in an epoxy resin composition, there exists a problem that a viscosity rise in storage of an epoxy resin composition becomes large, and pot life becomes short. The problem regarding the pot life to the epoxy resin composition which added this silica filler becomes a problem also when using it as an adhesive agent for electronic components, such as optical semiconductors other than an underfill material use.

An object of this invention is to provide the liquid epoxy resin composition with a long port life by the fluidity | liquidity of an epoxy resin composition being good, and suppressing the thickening in storage, even if it contains an inorganic filler.

This invention relates to the liquid epoxy resin composition which solved the said problem by providing the following structures.

[1] (A) liquid epoxy resin, (B) epoxy adduct curing agent or microencapsulated imidazole compound curing agent of amine compound, (C) inorganic filler, (D) triisopropyl borate and (E) phenol resin , Liquid epoxy resin composition: (C) component is 20-65 mass parts with respect to 100 mass parts, (D) component is 0.02-0.30 mass part, (E) component is 0.3-15.0, It is characterized by the above-mentioned, Liquid epoxy resin composition.

[2] An underfill material comprising the liquid epoxy resin composition according to the above [1].

[3] An adhesive comprising the liquid epoxy resin composition according to the above [1].

[4] A semiconductor device comprising a cured product of the underfill material described in the above [2].

[5] A semiconductor device comprising the cured product of the adhesive according to the above [3].

According to this invention [1], even if it contains an inorganic filler, fluidity | liquidity is good and it can provide the liquid epoxy resin composition with a long pot life by suppressing the thickening in storage.

According to the present invention [4] and [5], a highly reliable semiconductor device can be obtained by appropriate thermal expansion coefficient of the cured epoxy resin composition containing an inorganic filler.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram explaining the evaluation method of the injection property of a liquid epoxy resin composition.

The liquid epoxy resin composition (henceforth a resin composition) of this invention is (A) liquid epoxy resin, the epoxy adduct hardening agent or microencapsulated imidazole compound hardening | curing agent of (B) amine compound, (C) inorganic filler, (D ) Boric acid triisopropyl and (E) phenolic resin,

Liquid epoxy resin composition: It is 20-65 mass parts of (C) component with respect to 100 mass parts, (D) component is 0.02-0.15 mass part, and (E) component is 0.3-15.0, It is characterized by the above-mentioned.

(A) component provides adhesiveness and curability to a resin composition, and provides durability and heat resistance to the resin composition after hardening. As (A) component, a liquid bisphenol-A epoxy resin, a liquid bisphenol F-type epoxy resin, a liquid naphthalene type epoxy resin, a liquid aminophenol type epoxy resin, a liquid hydrogenated bisphenol-type epoxy resin, a liquid alicyclic epoxy resin, Liquid alcohol ether type epoxy resin, liquid cycloaliphatic type epoxy resin, liquid fluorene type epoxy resin, liquid siloxane type epoxy resin, etc. are mentioned, A liquid bisphenol A type epoxy resin, a liquid bisphenol F type epoxy resin, a liquid naphthalene type epoxy Resin is preferable from a viewpoint of adhesiveness, curability, durability, and heat resistance. In addition, as for epoxy equivalent, 80-250 g / eq is preferable from a viscosity adjustment viewpoint. Commercially available products include bisphenol F type epoxy resin (product name: YDF8170) made by Shin-Nitetsu Chemical, bisphenol A type epoxy resin (product name: EXA-850CRP) made by DIC, bisphenol F type epoxy resin (product name: YDF870GS) made by Shinnitetsu Chemical, naphthalene type Epoxy resin (product name: HP4032D), aminophenol type epoxy resin (grade: JER630, JER630LSD) made by Mitsubishi Chemical, siloxane type epoxy resin (article name: TSL9906) made by Momentibu, performances, 1, 4-cyclone made by Shinnitetsu Chemical Co., Ltd. Hexane dimethanol diglycidyl ether (trade name: ZX1658GS) etc. are mentioned. (A) A component may be used individually or in combination of 2 or more types.

(B) component enables hardening at the low temperature of about 80-100 degreeC. The epoxy adduct of the amine compound of (B) component is a compound which has the amino group synthesize | combined by reaction of an amine compound and an epoxy resin.

As an amine compound, what is necessary is just to have one or more active hydrogens in a molecule which can react with an epoxy group, and it is not specifically limited. Examples of the amine compound include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; Aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; Imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, and 2-isopropylimidazole; And imidazoline compounds such as imidazoline, 2-methylimidazoline, and 2-ethylimidazoline.

As an epoxy compound, 1, 2- epoxy butane, 1, 2- epoxy hexane, 1, 2- epoxy octane, styrene oxide, n-butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, copper copper Vaginal acetate and the like.

As a microencapsulated imidazole compound hardener of (B) component, the imidazole compound hardening accelerator microencapsulated with a urethane resin etc. is preferable from a viewpoint of storage stability, and is disperse | distributed in liquid epoxy resins, such as liquid bisphenol-A type, and a masterbatch A microencapsulated imidazole compound hardening accelerator that has been oxidized is more preferable in view of workability, curing speed, and storage stability. Examples of the imidazole curing agent include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-. 4-methylimidazole, 2, 4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2-phenyl-4, 5-dihydroxymethyl Midazole, 2-phenyl-4-methyl-5-hydroxy methylimidazole, 2, 3-dihydro-1H-pyrrolo [1, 2-a] benzimidazole, and the like. -Diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1)- Cure rate, workability, such as ethyl-s-triazine, 2, 4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, etc. It is preferable from a viewpoint of moisture resistance.

As a commercial item of (B) component, the amine adduct type latent hardener made by Ajinomoto Fine Techno (brand name: Amcure PN-23, Amcure PN-40), the latent hardener made by T & K TOKA (brand name: Fujicure FX-1000) And the microencapsulated imidazole compound latent curing agent (product name: Novacure HX3941HP, Novacure HX3088, Novacure HX3722) made by Asahi Kasei Materials. (B) A component may be used individually or in combination of 2 or more types.

By (C) component, the linear expansion coefficient of a resin composition can be controlled. Examples of the component (C) include silica fillers such as colloidal silica, hydrophobic silica, fine silica, and nano silica, acrylic beads, glass beads, urethane beads, bentnight, acetylene black, and ketjen black. In addition, the average particle diameter (the average maximum diameter in the case of not granularity) of the component (C) is not particularly limited, but is preferably 0.01 to 50 µm in order to uniformly disperse the filler in the resin composition, and It is preferable for the reason of being excellent in the injection | pouring property at the time of using a resin composition as an underfill material. If it is less than 0.01 micrometer, the viscosity of a resin composition rises and there exists a possibility that an injection property may deteriorate when using as an underfill material. When it exceeds 50 micrometers, there exists a possibility that it may become difficult to disperse | distribute a filler uniformly in a resin composition. Moreover, it is more preferable that the average particle diameter of (C) component is 0.6-10 micrometers from a viewpoint which protected the copper wire from the thermal stress of the resin composition after hardening. As a commercial item, high purity synthetic spherical silica made from adomatex (article name: SO-E5, average particle diameter: 2 µm; product name: SE-2300, average particle diameter: 0.6 µm), Tatsumori silica (article name: FB7SDX, An average particle diameter: 10 micrometers, the silica made from Mycuron (a brand name: TS-10-034P, an average particle diameter: 20 micrometers), etc. are mentioned. Here, the average particle diameter of a filler is measured with a dynamic light scattering nano track particle size analyzer. (C) component may be individual or may use 2 or more types together.

(D) component is chemical formula (1):

It is triisopropyl borate represented by, and it improves the wettability of the resin component and a silica filler in a resin composition, improves the dispersion state of a resin component and a silica filler, and also suppresses the thickening in the storage of a liquid epoxy resin composition, You can lengthen port life. As the component (D), for example, a reagent commercially available from Wako Pure Chemical Industries, Ltd. may be used.

(E) component suppresses the thickening in the storage of an epoxy resin composition. The phenol resin used as (E) component acts as a hardening retarder by containing a specific amount in a resin composition. As a phenol resin, a phenol novolak, a cresol novolak, an allyl phenol, etc. are mentioned. Phenol novolak is preferable because it is a liquid at 20 ° C. As a commercial item, the phenol novolak (brand name: MEH8005) made from Maywa Chemical Co., Ltd. is mentioned.

From the viewpoint of good reactivity and reliability, the component (B) is preferably 5 to 35 parts by mass, and more preferably 7 to 30 parts by mass with respect to 100 parts by mass of the resin composition.

(C) component is 20-65 mass parts with respect to resin composition: 100 mass parts, Preferably it is 30-60 mass parts, More preferably, 30-40 mass parts is contained. If it is 30-40 parts by mass, the coefficient of linear expansion can be lowered, and the injectability can be deteriorated.

Moreover, (C) component is 20-65 mass parts with respect to 100 mass parts of hardened | cured material of a resin composition, Preferably it is 30-60 mass parts, More preferably, 30-40 mass parts is contained. Here, since the resin composition has little mass reduction at the time of hardening at about 1-2 mass%, content of preferable (C) component in hardened | cured material is the same as content in a resin composition. Here, quantitative analysis of (C) component is performed by mass spectrometry.

(D) component is 0.02-0.30 mass part with respect to 100 mass parts of resin compositions, It is preferable that it is 0.02-0.15 mass part, and it is more preferable if it is 0.02-0.06 mass part. If it is 0.02 mass part or more, injectability will be favorable, and if it is 0.30 mass part or less, the intensity | strength of the resin composition after hardening will be enough.

In addition, (D) component is 0.02-0.30 mass part with respect to 100 mass parts of hardened | cured material of a resin composition, 0.02-0.15 mass part is preferable, and its 0.02-0.06 mass part is more preferable. Here, quantitative analysis of (D) component is performed by mass spectrometry.

It is preferable that (E) component is 0.3-15.0 mass parts with respect to resin composition: 100 mass parts. When (E) component is less than 0.3 mass part, the external appearance defects, such as a color unevenness, generate | occur | produce in the resin composition after hardening, and when it exceeds 15 mass parts, since sclerosis | hardenability will fall and hardening is inadequate in time required, the resin composition after hardening The strength of will fall.

Moreover, it is preferable that (E) component is 0.3-15.0 mass parts with respect to the hardened | cured material of a resin composition: 100 mass parts. Here, quantitative analysis of (E) component is performed by mass spectrometry.

If a resin composition contains the coupling agent which is (F) component, it is preferable from an adhesive viewpoint, and as (F) component, 3-glycidoxy propyl trimethoxysilane, 3-aminopropyl trimethoxysilane, Vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mer Captopropyl trimethoxysilane, bis (triethoxy silylpropyl) tetrasulfide, 3-isocyanate propyl triethoxysilane, etc. are mentioned, 3-glycidoxy propyl trimethoxysilane, 3-aminopropyl trimeth A oxysilane is preferable from a viewpoint of adhesiveness. As a commercial item, KBM403, KBE903, KBE9103, etc. by Shin-Etsu Chemical Co., Ltd. are mentioned. (F) A component may be independent or may use 2 or more types together.

(F) component, Preferably it is 0.05-15 mass parts, More preferably, 0.1-10 mass parts is contained with respect to 100 mass parts of resin compositions. Adhesiveness improves that it is 0.05 mass part or more, and foaming of a resin composition is suppressed when it is 15 mass parts or less.

The resin composition of this invention can be mix | blended with a leveling agent, a coloring agent, an ion trap agent, an antifoamer, a flame retardant, other additives, etc. as needed and the range which does not impair the objective of this invention.

The resin composition of the present invention is obtained by, for example, stirring, melting, mixing, and dispersing the components (A) to (E) and the addition of other components at the same time or separately while applying heat treatment as necessary. Can be. Although it does not specifically limit as such apparatuses, such as mixing, agitation, and dispersion | distribution, Leicai, a three roll mill, a ball mill, a planetary mixer, a bead mill etc. provided with stirring and a heating apparatus can be used. Moreover, you may use combining these apparatus suitably.

If the resin composition of this invention is 1000-80000 mPa * s in the viscosity in temperature: 25 degreeC, it is preferable from a viewpoint of injectability. Here, a viscosity is measured with the E-type viscosity meter (model number: TVE-22H) by Toki Industries.

The resin composition of this invention is formed and apply | coated to a desired position of electronic components, such as a board | substrate and an optical semiconductor, by dispenser, printing, etc. Here, when a resin composition is used as an underfill material, it forms so that at least one part may contact on the wiring of a board | substrate between board | substrates, such as a flexible wiring board, and a semiconductor element.

80-300 degreeC is preferable and hardening of the resin composition of this invention is preferable from a viewpoint of productivity improvement, when it hardens within 200 second.

The resin composition of this invention is suitable as an adhesive agent for electronic components, such as an underfill material and an optical semiconductor. Moreover, since an inorganic filler is disperse | distributed uniformly, the semiconductor device containing the hardened | cured material of an underfill material or the hardened | cured material of an adhesive agent is high reliability.

Example

Although an Example demonstrates this invention, this invention is not limited to these. In addition, in a following example, a part and% represent a mass part and mass% unless there is a clue.

Examples 1 to 17 and Comparative Examples 1 to 20

The resin composition was produced by the compounding shown in Tables 1-4. The produced resin composition was all liquid.

[Evaluation of viscosity]

The viscosity (henceforth an initial viscosity. Unit: mPa * s) of the resin composition immediately after preparation was measured on condition of 10 rotations per minute using the E-type viscosity meter (model number: TVE-22H) by Toki Industries. . The initial viscosity is preferably 1000 to 80000 mPa · s, more preferably 1000 to 8000 mPa · s. In addition, the viscosity after maintaining a resin composition at 25 degreeC for 48 hours was also measured similarly, and the viscosity increase rate (unit:%) was computed. Here, the viscosity increase rate is the following formula:

Viscosity growth rate = [(viscosity after 48 hours)-(initial viscosity)] / (initial viscosity) × 100

Calculated as In Tables 1-4, the measurement result is shown.

[Evaluation of thixotropy index]

The thixotropic index of the resin composition was measured using an E-type viscometer (model number: TVE-22H) manufactured by Toki Industries. The thixotropy index was obtained from a ratio obtained by dividing the measured value obtained under the condition of one rotation per minute by the measured value determined under the condition of 10 revolutions per minute, that is, (viscosity at 1 revolution per minute) / (viscosity at 10 revolutions per minute). . The appropriate range of the thixotropic index is 0.8 to 1.0. In Tables 1-4, the measurement result is shown.

[Evaluation of Injectability of Resin Composition]

The schematic diagram explaining the evaluation method of the injection property of a resin composition is shown in FIG. First, as shown to FIG. 1 (A), the 50 micrometers gap 40 was provided on the board | substrate 20, and the test piece which fixed the glass plate 30 instead of the semiconductor element was produced. However, as the substrate 20, a FR4 substrate was used. Next, the test piece was placed on a hot plate set at 50 ° C., and the produced resin composition 10 was applied to one end side of the glass plate 30, as shown in FIG. 1B, and FIG. 1. As shown to (C), the time until the gap 40 was filled with the resin composition 11 was measured. The suitability range of the injection time is within 1000 seconds. In Table 1-Table 4, the evaluation result of injection property is shown.

[Hardened appearance]

The test piece which evaluated the injection property of the resin composition was put into oven, and it heated at 120 degreeC for 3 minutes, and hardened the epoxy resin composition. The external appearance of the hardened | cured material after heating was observed. The case where appearance defects, such as a wrinkle and a yuzu shell, and color unevenness were not recognized by hardened | cured material was made into (circle), and the case where appearance defects, such as a wrinkle and a yuzu shell shape, and color unevenness were recognized by hardened | cured material was made into x. In Table 1-Table 4, the evaluation result of hardened | cured material external appearance is shown.

[Evaluation of Strength of Cured Resin Composition]

A sample for evaluation was printed on a glass epoxy substrate, and a silicon chip of 2 mm × 2 mm was placed on the sample. This was heat-cured for 90 minutes in a hot air dryer at 80 ± 2 ° C. or 90 minutes in a hot air dryer at 100 ± 2 ° C. Using this as a test piece, the load was applied to a silicon chip using a universal bond tester (model number: DAGE4000) manufactured by dage, and the strength (peel strength) at the time the chip was peeled off was measured. n = 10 and the average value were made into intensity | strength. In addition, in less than 100N, it was set as uncured. In Table 1-Table 4, the evaluation result of intensity | strength is shown.

As can be seen from Tables 1 to 3, in all of Examples 1 to 17, the initial viscosity was within the usable range, and the viscosity increase rate after 48 hours was also 4.3% or less. The thixotropy index was also within the desired range, and the injection time was also within the desired range. Moreover, it hardened | cured at 100 degreeC and the intensity | strength of the resin composition after hardening was also favorable. In particular, Examples 1-4, 7-17 of 0.02-0.12 mass parts of (D) component hardened even at low temperature of 80 degreeC. On the other hand, in the comparative example 1 which does not contain (D) component, the thixotropy index was high and the injection test ended in the middle. In Comparative Example 2 in which the component (D) was too small, the thixotropic index was high. In addition, Comparative Example 3 in which too much (D) component was not cured even at 100 ° C for 90 minutes. In Comparative Example 4 in which too much (C) component was present, the viscosity was too high and could not be measured. The comparative example 5 which does not contain (B) component solidified during the thickening test. In Comparative Example 6 in which the component (E) was too small, appearance defects due to color unevenness occurred. Comparative Example 7 in which too many (E) components had high initial viscosity, high viscosity increase rate, and was uncured at 80 ° C. for 90 minutes. In Comparative Examples 8 to 12 using boric acid tri-n-hexadecyl having a carbon number different from that of the component (D), the thixotropic index was all high, and the injection test ended in the middle. As can be seen from Table 4, all of Comparative Examples 13 to 17 using tetra-n-butylphosphonium benzotriazolate in place of the component (D) had too high a viscosity increase rate. In addition, in Comparative Example 13, the thixotropic index was high, and the injection test ended in the middle. The comparative examples 18 and 20 which used the hardening | curing agent substitute of (B) component were too high in the viscosity increase rate, and did not harden even at 100 degreeC x 90 minutes. The comparative example 19 with too many (E) components was too high in the viscosity increase rate, and also hardened even in 100 degreeC x 90 minutes.

[Industrial availability]

Even if it contains the inorganic filler, the resin composition of this invention can fluidity | liquidity, can suppress the thickening at the time of storage of a resin composition, and can lengthen a pot life. The resin composition of this invention is especially useful as an underfill material and an adhesive agent for electronic components.

10: resin composition
20: substrate
30: glass plate
40: gap

Claims (5)

(A) Liquid epoxy resin, (B) Epoxy adduct hardener or microencapsulated imidazole compound hardener of amine compound, (C) Colloidal silica, hydrophobic silica, fine silica, nano silica, glass beads or bentite Filler, (D) triisopropyl borate and (E) phenol resin,
Liquid epoxy resin composition: The liquid epoxy resin composition whose (C) component is 20-65 mass parts, (D) component is 0.02-0.30 mass part, and (E) component is 0.3-15.0 mass part with respect to 100 mass parts. Underfill material characterized in that it comprises. (A) Liquid epoxy resin, (B) Epoxy adduct hardener or microencapsulated imidazole compound hardener of amine compound, (C) Colloidal silica, hydrophobic silica, fine silica, nano silica, glass beads or bentite Filler, (D) triisopropyl borate and (E) phenol resin, and do not contain solder particles,
Liquid epoxy resin composition: It is 20-65 mass parts of colloidal silica, hydrophobic silica, fine silica, nano silica, glass beads, or bentite contained in (C) component with respect to 100 mass parts, (D) component is 0.02 It is 0.30 mass part and (E) component contains the liquid epoxy resin composition which is 0.3-15.0 mass parts, The adhesive agent characterized by the above-mentioned. The hardened | cured material of the underfill material of Claim 1 is included, The semiconductor device characterized by the above-mentioned. The hardened | cured material of the adhesive agent of Claim 2 is included, The semiconductor device characterized by the above-mentioned. delete

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