JP2013105960A - Lead frame fixing member, lead frame and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lead frame fixing member and the like in a semiconductor device using the lead frame fixed by the lead frame fixing member, which has high adhesiveness as a fixing member without causing internal peeling in a solder reflow process though an inorganic filler is not filled in the lead frame fixing member at a high filling rate.SOLUTION: A lead frame fixing member of an embodiment contains an epoxy resin (A) having more than two epoxy groups in one molecule and a naphthalene type epoxy resin (B). A hardened material of the lead frame fixing member has a glass-transition temperature of 178°C and over.

Description

  The present invention relates to a lead frame fixing material, a lead frame, and a semiconductor device.

  A lead frame is a frame formed with a large number of pins (leads) by photoetching or pressing a thin metal plate, and is a frame in which individual terminals of a semiconductor element are connected to each lead. It is.

  Conventionally, in order to prevent the pins of the lead frame from being deformed or uneven in assembling and manufacturing processes of electronic parts such as ICs and LSIs, pin holding parts and the like have been formed in the lead frame.

  For example, Patent Document 1 describes a method in which a pin holding tape obtained by cutting a polyimide film coated with a heat-resistant adhesive into an appropriate size is adhered to each block of a lead frame on a predetermined portion near each pin tip. Has been.

  However, in the method of bonding using an adhesive tape having a two-layer structure in which an adhesive layer is provided on one side of the support film, a large amount of waste is generated due to die cutting, or depending on the type of lead frame, There are problems from the viewpoint of material, disposal, and management costs, such as the need for molds.

  In order to solve these problems, for example, in Patent Document 2, for the purpose of easily holding a pin regardless of the shape and type of the lead frame, A method is described in which a photocurable resin material is applied between pins, pressed between pressing plates, the resin material enters between the pins, and a holding portion is formed between the pins.

  However, there is a possibility that air bubbles or the like may be interposed between the pins in this method, and there is room for improvement from the possibility that the pins cannot be securely fixed or the contamination of the adhesive resin due to the use of the pressing plate. .

  Regarding the method and material for the improvement, for example, Patent Document 3 uses a lead frame fixing material in which the viscosity of the material is appropriately reduced in the process of heating for the purpose of curing and the lead gap is quickly embedded. For example, a method is described in which a lead frame can be simply fixed without using a pressing plate. In addition, the use of capsule-type amine adducts as a lead frame fixing material as a curing agent has good storage stability of a mixture of an epoxy resin and a curing agent, and quick curing in a relatively low-temperature heating environment. It is described that it is preferable from the viewpoint of realizing the above.

  However, when a lead frame using the lead frame fixing material is used and a mold package is applied, peeling is observed inside the semiconductor device when a solder reflow test is performed after moisture absorption. Here, the main peeling site is the interface between the lead pins and the cured resin sandwiched between the lead pins. If peeling occurs inside the semiconductor device in the solder reflow heating, the reliability is lowered due to migration or the like, which is not preferable.

  In order to prevent such cracks at the time of solder mounting and peeling at each material interface, resin-encapsulated semiconductor devices such as conventional Quad Flat Package and Small Outline Package are represented by biphenyl type epoxy resin. By using a combination of a crystalline epoxy resin and a phenolic resin curing agent with a flexible skeleton, and increasing the amount of inorganic filler, low stress at low temperatures and low moisture absorption at low glass transition temperatures are achieved. Measures are taken (see, for example, Patent Document 4). Further, in order to suppress cracking and peeling at the time of solder mounting, it is necessary to fill the inorganic filler to at least 50% by volume (see, for example, Patent Document 5).

JP 55-021118 A Japanese Examined Patent Publication No. 04-064468 International Publication No. WO2008 / 077565 Japanese Patent Laid-Open No. 11-60687 JP-A-6-322073

  However, when the inorganic filler is filled at a high filling rate of 50% by volume or more with respect to the compound of the epoxy resin and the capsule type epoxy resin curing agent, the storage stability of the compound is lost, and the viscosity of the compound is reduced. It rises with time, resulting in gelation of the compound and a decrease in adhesive strength to the substrate. This is because the inorganic filler filled at a high filling rate breaks the capsule membrane of the capsule-type amine adduct, so that the curing agent oozes out into the epoxy resin and slowly initiates the curing reaction. Therefore, it is difficult to fill a compound using a capsule amine adduct with an inorganic filler at a high filling rate and use it as a lead frame fixing material.

  In a semiconductor device using a lead frame fixed with a lead frame fixing material, the present invention does not cause internal peeling during the solder reflow process even if the lead frame fixing material is not filled with an inorganic filler at a high filling rate. It is an object of the present invention to provide a lead frame fixing material having high adhesion as a fixing material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have created a lead frame fixing material having high adhesion without causing internal peeling in the solder reflow process in the semiconductor device. A suitable glass transition temperature and a combination of epoxy resins to be used were found, and in particular, a blending ratio of these epoxy resins was found to complete the present invention.

  That is, the present invention relates to the following.

[1]
Containing an epoxy resin (A) having three or more epoxy groups in one molecule and a naphthalene type epoxy resin (B);
A lead frame fixing material having a glass transition temperature of 178 ° C. or higher when cured.

[2]
The lead frame fixing material according to [1], wherein the content of the epoxy resin (A) is 8% by mass to 15% by mass with respect to 100% by mass of the resin component of the fixing material.

[3]
The lead frame fixing material according to [1] or [2], wherein the naphthalene type epoxy resin (B) is in a liquid state when slowly cooled from a molten state to 25 ° C.

[4]
The blending ratio (mass) of the epoxy resin (A) and the naphthalene type epoxy resin (B) (epoxy resin (A) / epoxy resin (B)) is 10/90 to 25/75, [1] The lead frame fixing material according to any one of to [3].

[5]
The lead frame fixing material according to any one of [1] to [4], wherein the epoxy resin (A) has a structure represented by the following general formula (1).

(In the formula (1), R ₁ is each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.)
[6]
The epoxy resin (A) according to any one of [1] to [5], wherein the epoxy resin (A) has a structure represented by any one of the groups represented by the following general formulas (2) to (5). Lead frame fixing material.

(In the formula (2), R ₂ are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, m1 is an integer of 2 or more.)

(In formula (4), m2 is a positive integer.)

[7]
The lead frame fixing material according to any one of [1] to [6], further containing an epoxy resin curing agent.

[8]
The lead frame fixing material according to [7], wherein the epoxy resin curing agent is a latent microcapsule type curing agent.

[9]
A lead frame fixed by the lead frame fixing material according to any one of [1] to [8].

[10]
A semiconductor device using the lead frame according to [9].

  The lead frame fixing material of the present invention can realize high adhesion as a fixing material in a semiconductor device using a lead frame fixed with the lead frame fixing material without causing internal peeling during a solder reflow process. .

  Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

≪Lead frame fixing material≫
The lead frame fixing material of this embodiment includes an epoxy resin (A) having three or more epoxy groups in one molecule (hereinafter also simply referred to as “epoxy resin (A)”) and a naphthalene type epoxy resin (B (Hereinafter, also simply referred to as “epoxy resin (B)”), the glass transition temperature when cured is 178 ° C. or higher. With this configuration, the lead frame fixing material of the present embodiment is high without causing peeling or cracking in the semiconductor device during the solder reflow process in the semiconductor device using the lead frame fixed by the lead frame fixing material. Adhesion can be achieved.

  The present inventors have found that if the lead frame fixing material has a glass transition temperature of 178 ° C. or higher when cured, it is possible to suppress peeling in the semiconductor device during solder reflow heating. Generally, in a lead frame fixing material, it is known that when the glass transition temperature of the cured product is increased, the adhesiveness tends to decrease, but in the present application, while maintaining the adhesiveness, It is characterized by finding a glass transition temperature region in which peeling can be suppressed. Therefore, the glass transition temperature of the cured product of the lead frame fixing material is more preferably 178 ° C. or higher and 185 ° C. or lower from the viewpoint of achieving two effects of adhesion and suppression of internal peeling in the semiconductor device. More preferably, it is 179 degreeC or more and 183 degrees C or less. In the present embodiment, the glass transition temperature of the cured product of the lead frame fixing material can be measured by the method described in Examples described later.

  In the lead frame fixing material of the present embodiment, the mechanism for achieving both adhesion and suppression of delamination in the semiconductor device is not clear, but a polyfunctional epoxy resin (naphthalene type epoxy resin (B)) in a polyfunctional epoxy resin ( By compounding the epoxy resin (A)), it is considered that the number of hydroxyl groups in the cured product increased, the interaction between the cured product and the metal of the base material was increased, and the adhesion was improved. Also, the combined use of naphthalene resin and polyfunctional epoxy resin increases the glass transition temperature of the cured product, reduces the linear expansion of the cured product during the solder reflow process, and adds to the adhesive interface between the lead frame fixing material and the lead frame. It is thought that stress decreased and it became difficult to peel.

  As a method for obtaining a lead frame fixing material having a glass transition temperature of 178 ° C. or higher when cured, for example, a naphthalene type epoxy resin (B) and an epoxy resin (A) are used in combination as a raw material for the lead frame fixing material. And the method of adjusting content of an epoxy resin (A) to the below-mentioned range is mentioned.

  In addition, the lead frame fixing material according to the present embodiment achieves two effects of adhesion and suppression of internal peeling in the semiconductor device, and thus an epoxy resin having three or more epoxy groups in one molecule. (A) and a naphthalene type epoxy resin (B) are used together. It has been found that this configuration can sufficiently raise the glass transition temperature without lowering the adhesiveness.

  As described above, the combined use of naphthalene type epoxy resin (B) and polyfunctional epoxy resin (epoxy resin (A)) raises the glass transition temperature, but the adhesive strength between the metal and the resin depends on the blending ratio. It turns out that it improves more. That is, the adhesive strength does not decrease in proportion to the increase in the glass transition temperature, and the higher adhesive strength is expressed even at a high glass transition temperature depending on the composition of the resin composition. . From the above, the content of the epoxy resin (A) in the lead frame fixing material according to the present embodiment is 8% by mass to 15% by mass with respect to 100% by mass of the resin component in the fixing material. Preferably, by adjusting the content of the epoxy resin (A) within this range, the lead frame fixing material can obtain high adhesiveness without causing further internal peeling. Moreover, content of an epoxy resin (A) becomes like this. More preferably, it is 9 mass% or more and 14 mass% or less, More preferably, it is 10 mass% or more and 12 mass% or less.

  In addition, the resin component in a fixing material contains an epoxy resin (A), an epoxy resin (B), and the below-mentioned hardening | curing agent for epoxy resins.

  In the lead frame fixing material of the present embodiment, the blending ratio (mass) of the epoxy resin (A) and the epoxy resin (B) (epoxy resin (A) / epoxy resin (B)) is 10/90 to It is preferably 25/75, more preferably 11/90 to 22/78, and still more preferably 14/86 to 17/83. When the blending ratio (mass) of the epoxy resin (A) and the epoxy resin (B) is within the above range, the lead frame fixing material is soldered in a semiconductor device using a lead frame fixed with the lead frame fixing material. Internal releasability can be further suppressed during the reflow process, and adhesiveness is further improved as a fixing material.

  Conventionally, when the naphthalene type epoxy resin (B), which is a crystalline epoxy resin, occupies most of the composition, there is a tendency for the viscosity at around 25 ° C., which is a temperature normally used as a lead frame fixing material, to increase. When the viscosity is increased, the applicability to the lead frame is lowered, resulting in internal peeling. This is because the crystallization of the naphthalene type epoxy resin (B) proceeds rapidly at around 25 ° C. and crystallizes until it becomes almost solid in 2 to 3 days, and the viscosity increases dramatically. This crystallization tends to become more prominent as the purity of the naphthalene type epoxy resin (B) is higher. However, in the present embodiment, since the lead frame fixing material contains a relatively high molecular weight resin called epoxy resin (A) having three or more epoxy groups in one molecule, as described above. Crystallization at 25 ° C. can be suppressed. As for this, the high molecular weight component (epoxy resin (A)) is dissolved in the naphthalene type epoxy resin (B), thereby inhibiting the crystallization of the naphthalene type epoxy resin (B) from being inhibited. It is thought.

  From the above viewpoint, the molecular weight of the epoxy resin (A) is preferably 460 to 1770, and more preferably 460 to 790.

  The naphthalene type epoxy resin (B) used for the lead frame fixing material according to the present embodiment is preferably in a liquid state when slowly cooled from a molten state to 25 ° C. By using such a liquid naphthalene type epoxy resin (B), the viscosity of the entire lead frame fixing material can be lowered, and it can be suitably used as a lead frame fixing material.

  It is generally known that when a polyfunctional epoxy resin such as the epoxy resin (A) is mixed with a liquid Bis-A type epoxy resin and cured, the glass transition temperature of the cured product rises. However, the polyfunctional epoxy resin is often a solid resin. When the naphthalene type epoxy resin (B) is liquid, the solid resin epoxy resin (A) is dissolved in the liquid naphthalene epoxy resin (B). Causes the viscosity to increase significantly. When the viscosity of the lead frame fixing material is remarkably increased, the coating property is lowered, and the adhesive strength between the lead frame and the lead frame fixing material is reduced. Also from such a viewpoint, the content of the epoxy resin (A) is adjusted to the above range, and the naphthalene type epoxy resin (B) is in a liquid state while maintaining the adhesiveness of the lead frame fixing material. This is preferable in terms of developing viscosity. More preferably, the viscosity of the naphthalene type epoxy resin (B) at 25 ° C. is preferably 1 Pa · s to 100 Pa · s, and more preferably 1 Pa · s to 50 Pa · s.

  It is preferable that the epoxy resin (A) used for the lead frame fixing material according to the present embodiment includes an aromatic ring in its structure. In general, the epoxy resin (A) is often a solid resin, and when the proportion of the resin compound is large, the viscosity of the resin compound increases greatly. If the viscosity of the lead frame fixing material is too high, the coating property is lowered, the adhesive strength is lowered, and internal peeling tends to occur, which is not preferable. By including an aromatic ring in the epoxy resin (A), the glass transition temperature when the lead frame fixing material is a cured product becomes higher with a small amount of the epoxy resin (A). Viscosity can be lowered, applicability is improved, and internal peeling tends to be suppressed.

  The epoxy resin (A) preferably has a structure represented by the following general formula (1).

(In the formula (1), R ₁ is each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.)
When the epoxy resin (A) has the structure represented by the above general formula (1), the glass transition temperature when the lead frame fixing material is a cured product becomes higher with a small amount of the epoxy resin (A). Therefore, the viscosity of the lead frame fixing material can be further lowered, the applicability is further improved, and the internal peeling tends to be further suppressed.

  The epoxy resin (A) more preferably has a structure represented by any one of the groups represented by the following general formulas (2) to (5). By having these structures, high adhesiveness can be obtained while further suppressing internal peeling. Among these, it is particularly preferable to have a structure represented by the formula (3).

(In the formula (2), R ₂ are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, m1 is an integer of 2 or more.)

(In formula (4), m2 is a positive integer.)

In formula (2), R ₂ is each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. Moreover, in Formula (2), it is preferable that m1 is an integer of 2-9, and it is more preferable that it is an integer of 2-6.

  In Formula (4), m2 is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

  An epoxy resin (A) may be used individually by 1 type, and may be used together 2 or more types.

  The naphthalene type epoxy resin (B) can be obtained by glycidylation of the hydroxyl group of naphthalene diol. For example, naphthalene-1,5-diol, naphthalene-1,6-diol, naphthalene-1,7-diol, Examples thereof include resins obtained by glycidylating naphthalene-1,8-diol. Among these, glycidylated naphthalene-1,6-diol which is difficult to crystallize at room temperature is particularly preferable. A naphthalene type epoxy resin (B) may be used individually by 1 type, and may be used together 2 or more types. In the present embodiment, the naphthalene type epoxy resin (B) is a naphthalene type epoxy resin other than the epoxy resin (A).

  It is preferable that the lead frame fixing material according to the present embodiment further contains a curing agent for epoxy resin. Examples of the curing agent for epoxy resin that can be used in the present embodiment include novolak resin curing agents, acid anhydride curing agents, amine curing agents, and amine adduct curing agents. Two or more of these may be used in combination. Among these, an amine adduct type curing agent having a large molecular weight, low volatility, and hardly contaminating the lead frame surface during curing is preferable. Due to the low volatility, the volatile components can be prevented from adhering to the surface of the lead frame, and the wire bondability can be improved.

  Examples of the novolak resin-based curing agent include phenol novolak resin, cresol novolak resin, bisphenol novolak resin, poly p-vinylphenol, and the like. These can be used alone or in combination of two or more.

  Examples of acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, -3-chlorophthalic anhydride, -4-chlorophthalic anhydride, Benzophenone tetracarboxylic anhydride, succinic anhydride, methyl succinic anhydride, dimethyl succinic anhydride, dichlor succinic anhydride, methyl nadic acid, dodecyl succinic acid, chlorendec succinic anhydride, maleic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride , Hexachloroendomethylenetetrahydrophthalic anhydride, methyl-3,6-endomethylenetetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2 -Dicarboxylic anhydride, ethylene glycol Bis anhydrotrimellitate, glycerin bis (anhydrotrimellitate) monoacetate, and the like. These can be used alone or in combination of two or more.

  Examples of amine-based curing agents include compounds having primary, secondary and / or tertiary amino groups. Two or more of these may be used in combination.

  Examples of the compound having a primary amino group include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, Toluidine, diaminodiphenylmethane, diaminodiphenylsulfone and the like can be mentioned. These can be used alone or in combination of two or more.

  Examples of the compound having a secondary amino group include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, phenyl Examples include methylamine and phenylethylamine. These can be used alone or in combination of two or more.

Examples of the compound having a tertiary amino group include trimethylamine, triethylamine, benzyldimethylamine, N, N′-dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo (5,4,0) -undecene-7, Tertiary amines such as 1,5-diazabicyclo (4,3,0) -nonene-5;
2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, Amino alcohols such as N-β-hydroxyethylmorpholine;
Aminophenols such as 2- (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol;
Imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxy- 3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole Imidazoles such as 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole;
1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2- Ethyl imidazoline, 2-ethyl-4-methyl imidazoline, 2-benzyl imidazoline, 2-phenyl imidazoline, 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4 -Tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, , 3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazo Emissions, 1,2-phenylene - bis - imidazoline, 1,3-phenylene - bis - imidazoline, 1,4-phenylene - bis - imidazoline, 1,4-phenylene - bis-4-imidazoline such as methyl imidazoline;
Dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, diethylaminoethylpiperazine Tertiary aminoamines such as
Aminomercaptans such as 2-dimethylaminoethanethiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine;
Aminocarboxylic acids such as N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid and picolinic acid;
And aminohydrazides such as N, N-dimethylglycine hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide. These can be used alone or in combination of two or more.

As an amine adduct type | system | group hardening | curing agent, the amine adduct obtained as a reaction material of the following (b-1) component and (b-2) component can be mentioned, for example.
(B-1) One or more compounds selected from carboxylic acid compounds, sulfonic acid compounds, urea compounds, isocyanate compounds, and epoxy resins usable as lead frame fixing materials.
(B-2) An amine compound.

  As said (b-1) component, as said carboxylic acid compound, a succinic acid, adipic acid, a sebacic acid, a phthalic acid, a dimer acid, etc. are mentioned, for example.

  As said (b-1) component, as said sulfonic acid compound, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid etc. are mentioned, for example.

  Examples of the urea compound as the component (b-1) include urea, methylurea, dimethylurea, ethylurea, t-butylurea, and the like.

  As said (b-1) component, as said isocyanate compound, aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, polyisocyanate etc. can be mentioned, for example.

  Here, examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

  Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4-4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,3-bis. And (2-isocyanatopropyl-2-yl) -cyclohexane.

  Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like.

  Examples of the aliphatic triisocyanate include 1,3,6-triisocyanate methylhexane, 2,6-diisocyanatohexanoic acid-2-isocyanatoethyl, and the like.

  Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the various diisocyanate compounds described above. Examples of such polyisocyanates include isocyanurate type polyisocyanates, burette type polyisocyanates, urethane type polyisocyanates, allophanate type polyisocyanates, carbodiimide type polyisocyanates, and the like.

On the other hand, examples of the component (b-2) include the following components (b-2-1) and components (b-2-2).
(B-2-1) A compound having at least one primary amino group and / or secondary amino group but no tertiary amino group.
(B-2-2) A compound having at least one tertiary amino group and at least one active hydrogen group.

Examples of the component (b-2-1) include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, and isophoronediamine. Primary amines having no tertiary amino group such as aniline, toluidine, diaminodiphenylmethane, diaminodiphenylsulfone, etc .;
Tertiary amino groups such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, phenylmethylamine, phenylethylamine, etc. Secondary amines having no
Etc. These can be used alone or in combination of two or more.
In the component (b-2-2), examples of the active hydrogen group include a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, a carboxylic acid, and a hydrazide group. More specifically, as the component (b-2-2), for example, 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, Amino alcohols such as 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-β-hydroxyethylmorpholine;
Aminophenols such as 2- (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol;
Imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxy- 3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole Imidazoles such as 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole;
1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2- Ethyl imidazoline, 2-ethyl-4-methyl imidazoline, 2-benzyl imidazoline, 2-phenyl imidazoline, 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4 -Tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, , 3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazo Emissions, 1,2-phenylene - bis - imidazoline, 1,3-phenylene - bis - imidazoline, 1,4-phenylene - bis - imidazoline, 1,4-phenylene - bis-4-imidazoline such as methyl imidazoline;
Dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, diethylaminoethylpiperazine Tertiary aminoamines such as
Aminomercaptans such as 2-dimethylaminoethanethiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine;
Aminocarboxylic acids such as N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid and picolinic acid;
And aminohydrazides such as N, N-dimethylglycine hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide. These can be used alone or in combination of two or more.

  The epoxy resin curing agent is preferably a latent curing agent. The curing agent having the potential has a suppressed activity as a curing agent until the time of use, and is the first time when an external stimulus, for example, radiation such as heat, UV light, or the like is given at the time of use. It means a curing agent that exhibits good activity as.

  As one aspect of such a curing agent (latent epoxy resin curing agent) having a potential, it is a capsule type (in the case where the particle size is on the order of μm, it may be referred to as a “microcapsule type”). A curing agent can be mentioned. The capsule-type curing agent means, for example, a curing agent having a structure in which the surface of a core made of an epoxy resin curing agent is covered with a shell made of an inorganic oxide or a synthetic resin. By using such a capsule type curing agent, it is possible to improve the storage stability of the blend of the epoxy resin and the curing agent.

  As the material for the core, the same components as the curing agent can be used. Especially, it is preferable that it is an amine adduct type | system | group hardening | curing agent modified | denatured with imidazole, 2-methylimidazole, or 2-phenylimidazole from a viewpoint that activity is high and it can harden | cure in a short time. Moreover, as a core, it is suitable that it is a core formed using the material which is solid at normal temperature (25 degreeC).

  On the other hand, examples of the material of the shell include inorganic compounds such as boron compounds such as boron oxide and boric acid ester, silicon dioxide, and calcium oxide. Among these, boron oxide is preferably used from the viewpoint of the stability of the shell and the ease of destruction during heating.

  Examples of synthetic resins include epoxy resins, polyester resins, polyethylene resins, nylon resins, polystyrene resins, urethane resins, and the like. Among them, from the viewpoint that the shell is destroyed by heating at a relatively low temperature, a urethane resin, an amine curing agent, or an amine adduct system that is a reaction product of monoalcohol or polyhydric alcohol and monoisocyanate or polyisocyanate. An epoxy resin or a phenol resin, which is a reaction product of a curing agent and an epoxy resin, is desirable.

  In addition, it is preferable that the material of the shell is a synthetic resin from the viewpoints of stability of the shell, ease of destruction during heating, and uniformity of the cured product. In addition, it is possible to form a capsule-type curing agent by coating an amine adduct curing agent with a synthetic resin shell, so that the storage stability of the blend of the main agent (epoxy resin) and the curing agent is good, and relatively This is suitable from the viewpoint of realizing a latent curing agent that can be rapidly cured in a low-temperature heating environment.

  In the lead frame fixing material according to the present embodiment, the content of the epoxy resin curing agent is preferably 30 to 50% by mass, and 30 to 40% by mass with respect to 100% by mass of the resin component of the fixing material. It is more preferable that it is 30-35 mass%. When the epoxy resin curing agent is contained in the above range, it is preferable in that the lead frame fixing material can be sufficiently cured and the degree of freedom in blending other epoxy resins is high.

  The lead frame according to the present embodiment is a lead frame fixed by the lead frame fixing material. The lead frame can be obtained by applying the lead frame fixing material. In general, it is preferable to apply the lead frame fixing material at a position about 600 μm away from the tip of the lead.

  As a method for applying the lead frame fixing material, an air dispensing method, a screw dispensing method, a jet dispensing method, and the like are assumed, and the screw dispensing method seems to be more preferable. With these methods, when the lead frame fixing material is applied in accordance with a different design for each lead frame, it can be applied to an appropriate position by changing the movement program of the dispenser head. By applying it at an appropriate position, the lead frame fixing material develops an appropriate adhesive strength.

  In order to apply the lead frame fixing material to the lead frame by these methods, the viscosity of the lead frame fixing material is an important factor. If the viscosity of the lead frame fixing material is too high, the coating performance of the lead frame fixing material is significantly reduced due to poor resin embedding in the lead gap and the resin followability to the dispenser discharge device, This leads to a decrease in the adhesive strength of the lead frame fixing material. Specifically, the viscosity of the lead frame fixing material at 25 ° C. is preferably 150 Pa · s or less.

  The lead frame fixing material of the present embodiment is not limited to using other epoxy resins (for example, a monoepoxy compound or a bivalent epoxy compound) as long as the object of the invention is not impaired. Examples of the monoepoxy compound include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxyl glycidyl ether, glycidyl acetate, glycidyl butyrate. Glycidyl hexoate, glycidyl benzoate, and the like. These can be used alone or in combination of two or more.

Examples of the divalent epoxy compound include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, and tetrachloro. Bisphenol type epoxy resin obtained by glycidylating bisphenols such as bisphenol A and tetrafluorobisphenol A;
And epoxy resins obtained by glycidylation of other dihydric phenols such as dihydroxybenzene, biphenol, and 9,9-bis (4-hydroxyphenyl) fluorene. These can be used alone or in combination of two or more.

  The lead frame fixing material of the present embodiment is a particularly useful fixing material for fixing a lead frame including an adhesive for forming a dam bar. The semiconductor device of the present embodiment is a semiconductor device using the lead frame. Specifically, the semiconductor device is sealed using a lead frame supported and fixed by the lead frame fixing material. Further, the lead frame fixing material of the present embodiment is not prevented from being used for other purposes. In addition to being used as an adhesive and / or bonding paste and bonding film, it is also effective as a conductive material, anisotropic conductive material, insulating material, sealing material, coating material, coating composition, prepreg, heat conductive material, etc. Can be used for

  Note that as various epoxy resins and curing agents used in this embodiment have fewer chlorine and ionic impurities contained as impurities, the reliability of the semiconductor device is improved and the more preferable as a material.

  EXAMPLES Next, although an Example demonstrates this invention more concretely, the scope of the present invention is not limited to these Examples. In addition, adhesive strength measurement, glass transition temperature measurement of the cured product of lead frame fixing material, creation of lead frame fixed with lead frame fixing material, semiconductor device creation method, internal peeling evaluation (solder reflow test after moisture absorption) and viscosity measurement The following method and conditions were used.

(1) Measurement of adhesive strength A spacer was formed with a 100 μm thick Teflon (registered trademark) heat-resistant tape so that the adhesion area between the standard test piece CP1100P and the lead frame fixing material was 25 mm × 5 mm. A lead frame fixing material was applied to the space formed by the spacer, and another standard test piece was attached. A lead frame fixing material sandwiched between two standard test pieces was heated on a hot plate at 225 ° C. for 20 seconds to cure the lead frame fixing material and prepare a test piece for measuring adhesive strength. The test piece was measured for the adhesive strength of the lead frame fixing material using an AGS-X manufactured by Shimadzu Corporation at a test speed of 10 mm / min. Those adhesive strength during the measurement is 10.0 N / mm ² or more ◎, 9.0N / mm ² or more 10.0 N / mm ² less than that of ○, 9.0N / mm ² less than that of △ It was. Tables 2 and 3 show the adhesion strength measurement results of the lead frame fixing materials obtained in the examples and comparative examples.

(2) Measurement of Glass Transition Temperature of Cured Product of Lead Frame Fixing Material Using a cured product obtained from the test piece after the measurement of the adhesive strength described in (1) above, using EXSTAR6000 manufactured by Seiko Instruments Inc., a temperature increase rate of 10 ° C. The measurement of the cured product is continuously performed twice at / min, and the measurement result obtained by the second measurement is analyzed using the company's muse analysis software, so that the glass of the cured product of the lead frame fixing material is obtained. A transition temperature was obtained.

(3) Creation of Lead Frame Fixed with Lead Frame Fixing Material A copper alloy 194 QFP208 type open lead frame having a lead width of 100 μm at the inner lead tip and a lead gap of 50 μm was used as the lead frame. The lead frame is applied to the lead frame with a screw dispenser at a position 600 μm away from the tip of the lead so that the coating width of the lead frame fixing material is 300 μm to 500 μm and the resin amount is 1.5 mg to 2.0 mg. Fixing material was applied. Next, the lead frame surface reaches 220 ° C. in about 5 seconds, and then the lead frame coated with the fixing material is placed in a reflow oven adjusted to a constant temperature of 220 ° C. for about 20 seconds to heat the fixing material. A lead frame fixed with a lead frame fixing material was prepared by curing and fixing the inner lead.

(4) Semiconductor device preparation method The lead frame fixed with the lead frame fixing material prepared in the above (3) is fixed to an open lead frame sealing mold, and a molding temperature is used by using a commercially available epoxy resin sealing material for semiconductors. A resin-encapsulated semiconductor device was produced at 175 ° C. and a mold pressure of 35 kgf / cm ² .

(5) Internal peeling evaluation (solder reflow test after moisture absorption)
The semiconductor device prepared in (4) above is absorbed for 198 hours at a temperature of 30 ° C. and a relative humidity of 70%, and is passed through a far-infrared heating type reflow oven (250 ° C. or higher for 20 seconds) three times. The inside was observed with an ultrasonic imaging apparatus (HSAM220 manufactured by Hitachi Construction Machinery Co., Ltd.) and the cross section was observed with a scanning electron microscope. As a result of observation, the lead frame fixing material having no peeling or cracking was indicated as “◯”, and the lead frame fixing material having peeling or cracking was indicated as “x”. Tables 2 and 3 show the internal peeling evaluation results of the lead frame fixing materials obtained in the examples and comparative examples.

(6) Viscosity measurement The viscosity of the lead frame fixing material is measured using a TVE-20HT manufactured by Toki Sangyo Co., Ltd. connected to an F25 constant temperature water circulating device manufactured by Julabo Labortechnik GMBH with the circulating water temperature set to 25 ° C. went. The rotor number and range were measured using the proper one for the viscosity of each lead frame fixing material. Those having a viscosity lower than 110 Pa · s are marked with ◎, those with a viscosity of 110 Pa · s to less than 150 Pa · s are marked with ◯, and those with a viscosity of 150 Pa · s or more are marked with △.

[Manufacture of curing agent for epoxy resin]
The curing agent for epoxy resin (microcapsule type amine adduct curing agent) used in Examples and Comparative Examples was produced by the following method.

  In a solvent in which 2-propanol and xylene are mixed at a weight ratio of 50:50, the raw materials (epoxy resin and amine compound) are reacted at the mixing ratio (epoxy group / amino group equivalent ratio) shown in Table 1. The reaction was performed at a temperature of 80 ° C.

  After the reaction, the solvent and the low-molecular amine component were distilled off under reduced pressure to obtain amine adducts b-1 to b-4. All of the obtained amine adducts were solid at 25 ° C.

Epoxy resin 1: bisphenol A type epoxy resin (epoxy equivalent: 185 g / equivalent, total chlorine amount: 1400 ppm).
Epoxy resin 2: bisphenol A type epoxy resin (epoxy equivalent: 470 g / equivalent, total chlorine amount: 1300 ppm).
Epoxy resin 3: Cresol novolac type epoxy resin (epoxy equivalent: 215 g / equivalent, total chlorine content: 1500 ppm).

  Various capsule type curing agents (capsule type amine adduct type curing agents) listed in Tables 2 and 3 were obtained by the following methods.

[Production Example 1: Capsule-type amine adduct b-1-2]
The amine adduct b-1 was pulverized to obtain a pulverized product having an average particle size of 2.4 μm (solid at 25 ° C.). 100 parts by mass of this pulverized product, 1.5 parts by mass of water, and 7 parts by mass of tolylene diisocyanate were added to 200 parts by mass of epoxy resin 1, and the reaction was continued for 3 hours while stirring at 40 ° C. Then, shell formation reaction was performed at 50 degreeC for 8 hours, and the capsule type amine adduct b-1-2 which is a microcapsule type hardening | curing agent was obtained.

[Production Example 2: Capsule-type amine adduct b-2-2]
The amine adduct b-2 was pulverized to obtain a pulverized product having an average particle size of 2.4 μm (solid at 25 ° C.). 100 parts by mass of this pulverized product, 1.5 parts by mass of water, and 7 parts by mass of tolylene diisocyanate were added to 200 parts by mass of epoxy resin 1, and the reaction was continued for 3 hours while stirring at 40 ° C. Then, shell formation reaction was performed at 50 degreeC for 8 hours, and the capsule type amine adduct b-2-2 which is a microcapsule type hardening | curing agent was obtained.

[Production Example 3: Capsule-type amine adduct b-3-2]
Capsule-type amine adduct b-3-2 was obtained in the same manner as capsule-type amine adduct b-1-2 except that amine adduct b-3 was used instead of amine adduct b-1.

[Production Example 4: Capsule-type amine adduct b-3-2F]
A capsule type amine adduct was used except that 50 parts by mass of epoxy resin 1 and 150 parts by mass of bisphenol F type epoxy resin (hereinafter also referred to as “epoxy resin 4”) were used in place of 200 parts by mass of epoxy resin 1. Capsule-type amine adduct b-3-2F was obtained in the same manner as b-3-2.

[Production Example 5: Capsule-type amine adduct b-3-2N]
Instead of 200 parts by mass of epoxy resin 1, 160 parts by mass of epoxy resin 4 (bisphenol F type epoxy resin (epoxy equivalent: 169 g / equivalent, total chlorine amount: 330 ppm)) and 20 parts by mass of naphthalene type epoxy resin (B ) (1,6-bis (2,3-epoxypropoxy) naphthalene (epoxy equivalent: 143 g / equivalent, total chlorine content: 920 ppm)) was used in the same manner as in the capsule amine adduct b-3-2. Capsule type amine adduct b-3-2N was obtained.

[Production Example 6: Capsule-type amine adduct b-4-2]
The amine adduct b-4 was pulverized to obtain a pulverized product having an average particle size of 2.4 μm (solid at 25 ° C.). 100 parts by mass of this pulverized product, 1.5 parts by mass of water, and 7 parts by mass of tolylene diisocyanate were added to 200 parts by mass of epoxy resin 1, and the reaction was continued for 3 hours while stirring at 40 ° C. Then, shell formation reaction was performed at 50 degreeC for 8 hours, and the capsule type amine adduct b-4-2 which is a microcapsule type hardening | curing agent was obtained.

[Examples 1 to 11]
Each of the raw materials weighed at the blending ratio shown in Table 2 was mixed for about 5 minutes using a vacuum mixer to obtain 11 types of target lead frame fixing materials (Examples 1 to 11). The prepared lead frame fixing material was evaluated as described above, and the results of evaluation of internal peeling evaluation, glass transition temperature, adhesive strength and viscosity of the obtained lead frame fixing material are summarized in Table 2.

Naphthalene type epoxy resin (B): 1,6-bis (2,3-epoxypropoxy) naphthalene (epoxy equivalent: 143 g / equivalent, total chlorine content: 920 ppm).
Epoxy resin (A) 1: Corresponding to one having a structure of formula (2), wherein R ₂ is all hydrogen atoms, and having an average value of m1 = 2-9 (specific product name: DIC Corporation N -770, epoxy equivalent: 180-200 g / eq, softening point: 65-75 ° C).
Epoxy resin (A) 2: equivalent to one having the structure of formula (3) (specific product name: jER1032H60 manufactured by Mitsubishi Chemical Corporation).
Epoxy resin (A) 3: equivalent to one having a structure of formula (4) and having an average value of m2 = 1 to 3 (specific product name: EPPN-501H manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 164 g / Eq, softening point: 53 ° C.).
Epoxy resin (A) 4: equivalent to one having the structure of formula (5) (specific product name: jER1031S manufactured by Mitsubishi Chemical Corporation).
Epoxy resin (A) 5: having a structure of the formula (2), and among the plurality of R ₂ in each aromatic ring unit, one is a methyl group, the rest is a hydrogen atom, and the average value of m1 = 2. 6 (specific product name: N-660 manufactured by DIC Corporation, epoxy equivalent: 176 to 180 g / eq, softening point: 61 to 69 ° C.).

[Comparative Examples 1 to 9]
Each of the raw materials weighed at the blending ratio shown in Table 3 was mixed for about 5 minutes using a vacuum mixer to obtain 9 types of target lead frame fixing materials. The prepared lead frame fixing material was evaluated as described above, and the results of evaluation of internal peeling evaluation, glass transition temperature, adhesive strength and viscosity of the obtained lead frame fixing material are summarized in Table 3.

Epoxy resin 4: bisphenol F type epoxy resin (epoxy equivalent: 169 g / equivalent, total chlorine content: 330 ppm).
Naphthalene type epoxy resin (B): 1,6-bis (2,3-epoxypropoxy) naphthalene (epoxy equivalent: 143 g / equivalent, total chlorine content: 920 ppm).
Epoxy resin (A) 2: equivalent to one having the structure of formula (3) (specific product name: jER1032H60 manufactured by Mitsubishi Chemical Corporation).
Phenoxy resin: weight average molecular weight 45000-55000. Epoxy equivalent 8000 g / equivalent. Specific product name: jER1256 manufactured by Mitsubishi Chemical Corporation.

  The lead frame fixing material of the present invention is useful, for example, as a material for fixing an inner lead of a lead frame used in a semiconductor assembly or a material for forming a dam bar of a lead frame.

Claims (10)

Containing an epoxy resin (A) having three or more epoxy groups in one molecule and a naphthalene type epoxy resin (B);
A lead frame fixing material having a glass transition temperature of 178 ° C. or higher when cured.   The lead frame fixing material according to claim 1, wherein the content of the epoxy resin (A) is 8% by mass or more and 15% by mass or less with respect to 100% by mass of the resin component of the fixing material.   The lead frame fixing material according to claim 1 or 2, wherein the naphthalene type epoxy resin (B) is in a liquid state when slowly cooled from a molten state to 25 ° C.   The blending ratio (mass) of the epoxy resin (A) and the naphthalene type epoxy resin (B) (epoxy resin (A) / epoxy resin (B)) is 10/90 to 25/75. The lead frame fixing material according to claim 1. The lead frame fixing material according to any one of claims 1 to 4, wherein the epoxy resin (A) has a structure represented by the following general formula (1).
(In the formula (1), R ₁ is each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.) The said epoxy resin (A) has a structure represented by any one among the groups represented by the following general formula (2)-(5), It is as described in any one of Claims 1-5. Lead frame fixing material.
(In the formula (2), R ₂ are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, m1 is an integer of 2 or more.)
(In formula (4), m2 is a positive integer.)
  The lead frame fixing material according to any one of claims 1 to 6, further comprising an epoxy resin curing agent.   The lead frame fixing material according to claim 7, wherein the epoxy resin curing agent is a latent microcapsule type curing agent.   A lead frame fixed by the lead frame fixing material according to claim 1.   A semiconductor device using the lead frame according to claim 9.