TWI443164B - Adhesive liquid resin composition - Google Patents

Description

Liquid resin composition for adhesive

The present invention relates to a liquid resin composition for an adhesive, a semiconductor device produced using the same, and a method of manufacturing a semiconductor device.

In recent years, the development of high-performance, miniaturization, and weight reduction of mobile phones, mobile information terminals, and DVCs (digital video cameras) has been remarkable, and the high performance and miniaturization of semiconductor packages are strongly demanded. Lightweight. Therefore, in order to increase the functionality of the semiconductor package, and to reduce the size and size of a plurality of semiconductor elements having different functions or a plurality of semiconductor elements having the same function, it is attempting to make the size of the semiconductor element The package size is as close as possible. Therefore, the thinning of the semiconductor element is further advanced, and the distance between the semiconductor element and the bonding pad of the support such as a metal or an organic substrate is getting closer.

In the conventional semiconductor assembly step, the die bonding step is performed by applying a liquid crystalline material to a support and mounting the semiconductor element at room temperature, followed by heat hardening, thereby bonding the semiconductor element to the support, but not Neglecting the problem that the die-bonding material adheres to the surface of the semiconductor element or the wire bond pad, and the contamination caused by the oozing of the die-bonding material (only the liquid component of the die-bonding material is transferred by capillary phenomenon).

Therefore, a method in which a liquid crystal material is used instead of a liquid crystal material, a film-shaped adhesive material is attached to a support, and a semiconductor element is mounted while being heated is used; In the state in which the film-shaped die-bonding material is attached to the back surface of the wafer, it is attached to a dicing sheet, and then diced, and the semiconductor element with the obtained die-bonding material is heated and mounted on the support. a method of attaching a semiconductor wafer to a die-bonding film having a function of a dicing sheet and dicing it, and heating the semiconductor element of the bonded crystal material thus obtained on the support; Refer to Patent Documents 1 and 2).

On the other hand, the film-shaped die-bonding material must be assembled according to the size of the semiconductor component used and the thickness of the die-bonding material, and the variety management is complicated. Therefore, the die-bonding material layer is also started to be printed. A method of forming a support substrate to perform semi-hardening instead of a film material. The adhesive for this purpose usually causes the reaction to proceed to a certain semi-hardened state, so that the reaction must be stopped. Therefore, the hardening system until the semi-hardened state and the hardening system until the next hardening are designed to be used (for example, refer patent document 3).

Among such two-stage hardening adhesives, a mixture of an acrylic resin and an epoxy resin is generally considered. The thickness of the adhesive layer when the semiconductor element is mounted on the support substrate tends to be about 30 μm or less, and it is difficult to control the curing reaction of the acrylic resin at such a thickness, and the adhesive remains in the vicinity of normal temperature. The adhesive near the room temperature causes the support substrates on which the adhesive is printed to adhere to each other, and in the step of mounting the semiconductor element, the automatic transfer of the support substrate causes a problem.

However, if a one-stage hardening adhesive is carried out, the problem caused by the reaction temperature will occur. In other words, when a high-boiling solvent which takes a long time for drying is used, the curing of the adhesive is performed before the semiconductor element is mounted, and the semiconductor element mountability is lowered. On the other hand, if the solvent is changed to a low boiling point, it will dry out during printing, and the continuous printability will be inferior. In addition, in order to give priority to the mounting of the semiconductor element, it is not preferable to introduce a polymer rubber or the like in a large amount in the continuous printing (see, for example, Patent Document 4). In this way, it is difficult to achieve an adhesive which eliminates the adhesiveness at the normal temperature in the case of semi-hardening and which has both continuous printing property and semiconductor element mountability.

(Patent Document 1) Japanese Patent Laid-Open Publication No. 2002-294177

(Patent Document 2) Japanese Patent Laid-Open Publication No. 2003-347321

(Patent Document 3) Japanese Patent Laid-Open Publication No. 2005-513192

(Patent Document 4) Japanese Patent Laid-Open Publication No. 2001-220556

Accordingly, an object of the present invention is to provide a liquid resin composition for an adhesive which is excellent in continuous printing property during printing, has good semiconductor element mountability after solvent evaporation, and has no stickiness at room temperature.

Such an object can be achieved by the present invention described in the following (1) to (11). (1) A liquid resin composition for an adhesive which contains at least a solvent (A), an epoxy resin (B) having two or more epoxy groups in one molecule, and two or more phenolic compounds in one molecule. a hydroxyl group epoxy resin hardener (C) and a hardening accelerator (D), characterized in that the epoxy resin (B) and the epoxy resin hardener (C) are dissolved in the solvent (A); The curing accelerator (D) dissolves the epoxy resin (B) and the epoxy resin curing agent (C) in the solvent at a temperature ranging from normal temperature to a temperature at which the solvent (A) is volatilized ( In the varnish (W) of A), and in the adhesive layer obtained by volatilizing the solvent (A) from the varnish (W), it is present in a visually observable size, and the solvent (A) is volatilized from the solvent In the temperature range from the temperature at which the temperature is high to the curing temperature, it is a size that cannot be visually observed or dissolved in the adhesive layer.

(2) A liquid resin composition for an adhesive which contains at least a solvent (A), an epoxy resin (B) having two or more epoxy groups in one molecule, and two or more phenolic compounds in one molecule. a hydroxyl group epoxy resin hardener (C) and a hardening accelerator (E), characterized in that the epoxy resin (B) and the epoxy resin hardener (C) are dissolved in the solvent (A), The hardening accelerator (E) is a hardening accelerator having a cationic portion and an anionic portion.

(3) The liquid resin composition for an adhesive according to (1) or (2), wherein the curing accelerator having a cationic portion and an anionic portion is a curing accelerator represented by the following general formula (1).

(wherein R ¹ , R ² and R ³ each represent one selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other. n is 0 to 2. A represents naphthalene. a ring or an aromatic group represented by the following general formula (2).)

(wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent one selected from a hydrogen atom, a halogen atom and an organic group having 1 to 6 carbon atoms, and may be the same or different from each other. V represents a single bond, An ether group, a sulfonic group, a sulfide group, a carbonyl group or an organic group having 1 to 13 carbon atoms.

(4) The liquid resin composition for an adhesive according to (1) or (2), wherein the curing accelerator having a cationic portion and an anionic portion is a curing accelerator represented by the following general formula (4).

(wherein R ¹ , R ² and R ³ each represent one selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other. Y ¹ and Y ² are an oxygen atom, Any of a nitrogen atom and a sulfur atom may be the same or different from each other. X represents an organic group and may be the same or different. Z represents a substituted or unsubstituted aromatic cyclic organic group or a heterocyclic organic group. )

(5) The liquid resin composition for an adhesive according to (1) or (2), wherein the curing accelerator having a cationic portion and an anionic portion is a curing accelerator represented by the following general formula (6).

(wherein R ¹ , R ² and R ³ each represent one selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other. Y ³ , Y ⁴ , Y ⁵ and At least one of Y ⁶ is a group in which one proton is released from a proton donor having at least one proton released to the outside of the molecule, and the two may be the same or different from each other.

(6) The liquid resin composition for an adhesive according to any one of (1) to (5), wherein the epoxy resin (B) is an epoxy resin which is solid at normal temperature.

(7) The liquid resin composition for an adhesive according to any one of (1) to (6), wherein the epoxy resin curing agent (C) is an epoxy resin curing agent which is solid at normal temperature.

(8) The liquid resin composition for an adhesive according to any one of (1) to (7) wherein the solvent (A) has a boiling point of 200 ° C or higher.

(9) The liquid resin composition for an adhesive according to any one of (1) to (8) wherein the curing accelerator has a curing reaction initiation temperature of 130 ° C or higher.

(10) A method of producing a semiconductor device comprising: printing a liquid resin composition for an adhesive according to any one of (1) to (9) on a support substrate; and a liquid resin for self-adhesive The step of volatilizing the solvent to form a layer of the adhesive, the step of mounting the semiconductor element, and the step of hardening the layer of the adhesive.

(11) A semiconductor device produced by using the liquid resin composition for an adhesive according to any one of (1) to (9).

According to the present invention, it is possible to provide a liquid resin composition for an adhesive which is excellent in continuous printing property at the time of printing, has good semiconductor element mountability after solvent evaporation, and has no adhesive at room temperature.

The liquid resin composition for an adhesive according to the first aspect of the present invention (hereinafter referred to as the liquid resin composition (1) for an adhesive of the present invention) has at least a solvent (A) and has one molecule. Two or more epoxy group epoxy resins (B), an epoxy resin hardener (C) having two or more phenolic hydroxyl groups in one molecule, and a hardening accelerator (D), the epoxy resin (B) And the epoxy resin curing agent (C) is dissolved in the solvent (A); the curing accelerator (D) is in a temperature range from a normal temperature to a temperature at which the solvent (A) is volatilized, The epoxy resin (B) and the epoxy resin hardener (C) are dissolved in the varnish (W) of the solvent (A), and the adhesive layer obtained by volatilizing the solvent (A) from the varnish (W) In the temperature range from the temperature at which the temperature at which the solvent (A) is volatilized to the curing temperature, the size is not visually observed or dissolved in the adhesive layer.

In the present invention, the temperature at which the solvent (A) is volatilized may be equal to or lower than the boiling point of the solvent (A) if the temperature at which the solvent (A) is volatilized. In addition, the curing temperature refers to a temperature at which the adhesive layer obtained by volatilizing the solvent (A) from the liquid resin composition of the adhesive of the present invention is cured.

The liquid resin composition (1) for an adhesive of the present invention is a liquid resin composition for an adhesive for bonding a semiconductor element to a support substrate. Further, the liquid resin composition (1) for an adhesive of the present invention is used in a method for producing a semiconductor device which has a layer of a liquid resin composition for printing an adhesive to a support by continuous printing. a printing step on the substrate; then, a liquid resin composition layer for the adhesive printed on the support substrate, the solvent (A) is volatilized, thereby forming a volatilization step of the adhesive layer on the support substrate; and then, forming A step of mounting a semiconductor element on a support substrate having an adhesive layer; and thereafter, a step of adhering the semiconductor element to the support substrate by performing a hardening step of curing the adhesive layer.

At this time, in the volatilization step, the volatilization temperature at which the solvent (A) is volatilized is 25 to 150 ° C, preferably 80 to 120 ° C. Further, in the hardening step, the curing temperature at which the adhesive layer is cured is 90 to 170 ° C, preferably 140 to 160 ° C. Further, in the mounting step, the temperature at which the semiconductor element is mounted is the same as the temperature at which the volatilization temperature is the same. Also, the hardening temperature is higher than the volatilization temperature.

The solvent (A) of the liquid resin composition (1) for an adhesive of the present invention is a solvent in which the epoxy resin (B) and the epoxy resin curing agent (C) are dissolved. Further, since the liquid resin composition for an adhesive of the present invention is printed on the semiconductor element mounting surface side of the support substrate by screen printing or stencil printing, the boiling point of the solvent (A) is preferably 200 ° C or higher. Excellent 200~260°C, better 210~250°C. When the epoxy resin (B) and the epoxy resin curing agent (C) are not dissolved in the solvent (A), the surface after printing is not smooth, and when a semiconductor element is mounted, there is a problem (for example, the semiconductor element is not present). After the level, etc.), there is a flaw in the air remaining when mounted on the support substrate. Further, when the boiling point of the solvent (A) is less than 200 ° C, the viscosity change due to the volatilization of the solvent during printing becomes excessive, and the thickness is not uniform, or there is a cause of roughness, and in the solvent. When the boiling point of (A) is higher than 260 ° C, there is a possibility that the solvent is excessively elapsed, the residual volatile amount is excessive, and the residual viscosity remains.

The solvent (A) is not particularly limited as long as it is soluble in the epoxy resin (B) and the epoxy resin curing agent (C). However, since it is used for semiconductor purposes, the solvent having a halogen atom is less. good. Further, a solvent which deteriorates the preservability of the liquid resin composition for an adhesive such as a solvent containing a primary amine or a secondary amine is also poor. The solvent (A) may be one type or a plurality of types may be used in combination.

The solvent (A) may, for example, be ethyl benzoate, propyl benzoate, butyl benzoate, γ-butyrolactone, dibutyl oxalate, dimethyl maleate or maleic acid. Diethyl ester, ethylene glycol monobutyrate, propyl carbonate, N-methylpyrrolidone, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethyl Glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol monomethyl ether, methyl salicylate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acetate and the like. Among them, preferred are ethyl benzoate having a boiling point of 210 to 250 ° C, propyl benzoate, butyl benzoate, γ-butyrolactone, dibutyl oxalate, diethyl maleate, and ethylene glycol. Butyrate, propyl carbonate, diethylene glycol, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol monomethyl ether, methyl salicylate, diethylene glycol Alcohol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

In the liquid resin composition (1) for an adhesive of the present invention, the epoxy resin (B) having two or more epoxy groups in one molecule (hereinafter sometimes referred to as epoxy resin (B)) may be used. For example, phenol novolak type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, Other epoxy resins having a triphenylmethine skeleton, an epoxy resin having a naphthalene skeleton, an epoxy resin having an anthracene skeleton, and the like. Among these, an epoxy resin which is solid at room temperature is preferred. The epoxy resin (B) may be used alone or in combination of plural kinds. In the epoxy resin (B), as the epoxy resin which is solid at normal temperature, for example, an epoxy resin having a softening point of 55 ° C or higher, such as a cresol novolac type epoxy resin or a phenol aralkyl type epoxy resin, A biphenyl aralkyl type epoxy resin, a dicyclopentadiene type epoxy resin, etc., preferably a cresol novolak type epoxy resin, a phenol aralkyl type epoxy resin, a dicyclopentadiene type ring Oxygen resin.

An epoxy resin curing agent (C) having two or more phenolic hydroxyl groups in one molecule in the liquid resin composition (1) for an adhesive of the present invention (hereinafter sometimes referred to as an epoxy resin curing agent (C) )), for example, bisphenols such as bisphenol A, bisphenol F, and bisphenol S; compounds obtained by reacting phenol such as phenol novolak or cresol novolak or a derivative thereof with formaldehyde; phenol or its derivative a compound obtained by reacting a substance with benzaldehyde; a phenol aralkyl type phenol resin, a biphenyl aralkyl type phenol resin, another having a naphthalene skeleton, having an anthracene skeleton, and having two or more phenolic hydroxyl groups in one molecule Compounds and the like. Among the epoxy resin hardeners (C), an epoxy resin hardener which is solid at normal temperature is preferred. The epoxy resin hardener (C) may be one type or a plurality of types may be used in combination. In the epoxy resin curing agent (C), as an epoxy resin curing agent which is solid at normal temperature, for example, an epoxy resin curing agent having a softening point of 55 ° C or higher, for example, a phenol novolak or a phenol aralkyl phenol resin, The biphenyl aralkyl type phenol resin, bisphenol F or the like is preferably a phenol novolak or a phenol aralkyl type phenol resin.

Even if the softening point of the epoxy resin hardener (C) is high, when the epoxy resin (B) is mixed, the softening point of the mixture is lowered, so as the epoxy resin hardener (C), for example, the softening point is 150 ° C. The left and right. Further, any one of the epoxy resin (B) and the epoxy resin curing agent (C) may be partially liquid when it is volatilized at room temperature after volatilization of the solvent (A). Epoxy resin (B) or liquid epoxy resin hardener (C). The liquid epoxy resin (B) or the liquid epoxy resin hardener (C) means a semi-solid resin containing a softening point of less than 55 ° C, and examples thereof include a cresol novolac type epoxy resin and bisphenol. A type epoxy resin, allyl phenol type epoxy resin hardener, and the like.

The ratio of the epoxy resin (B) to the epoxy resin hardener (C) is preferably from 0.7 to 1.3 with respect to the epoxy group. A more preferred ratio is from 0.9 to 1.2 with respect to the epoxy group.

The hardening accelerator (D) in the liquid resin composition (1) for an adhesive of the present invention promotes the reaction of the epoxy group of the epoxy resin (B) with the phenolic hydroxyl group of the epoxy resin hardener (C) Hardening accelerator.

The curing accelerator (D) is a varnish in which the epoxy resin (B) and the epoxy resin curing agent (C) are dissolved in the solvent (A) at a temperature ranging from normal temperature to a temperature at which the solvent (A) is volatilized. In (W), and in the adhesive layer obtained by volatilizing the solvent (A) from the varnish (W), it is present in a visually observable size, and is hardened from a temperature at which the solvent (A) is volatilized at a high temperature. In the temperature range up to the temperature, it is a size that cannot be visually observed or dissolved in the adhesive layer. For example, when the temperature at which the solvent (A) is volatilized is 100 ° C and the curing temperature is 175 ° C, the hardening accelerator (D) is at a temperature ranging from normal temperature to 100 ° C, that is, the solvent is made at 100 ° C ( A) The varnish (W) at the time of volatilization, and the adhesive layer obtained by volatilizing the solvent (A) from the varnish (W) exist in visually observable size. Further, at any temperature at the time of heating at 100 ° C to 175 ° C in order to cure the adhesive layer, it is a size that cannot be visually observed or dissolved in the adhesive layer.

In the liquid resin composition (1) for an adhesive of the present invention, by using a curing accelerator (D) having such a property, hardening reaction hardly occurs in the printing step and the volatilization step, after the mounting step In the hardening step, when the temperature is raised to the hardening temperature, a hardening reaction occurs. When the curing accelerator (D) is in a temperature range from normal temperature to a temperature at which the solvent (A) is volatilized, it is a size that cannot be visually observed, or is dissolved in the varnish (W) or the adhesive layer, even before printing. Since the reaction proceeds slowly at normal temperature, the storage property at normal temperature is deteriorated, or the curing reaction is carried out in the volatilization step, and in the subsequent mounting step of the semiconductor element, sufficient adhesion cannot be obtained, or for example, even The volatilization step is completed in the state of the adhesive force, and the storage property at the time of leaving the normal temperature in the state after the volatilization step is extremely short.

In the present invention, the curing accelerator (D) which is present in a size which can be visually observed is a size which cannot be visually observed or a temperature which is dissolved in the adhesive layer, and is described as a state change temperature of the curing accelerator (D). Since the state change temperature of the hardening accelerator (D) varies depending on the type of the hardening accelerator (D), the curing accelerator (D) having a state change temperature higher than the volatilization temperature and the hardening accelerator (D) can be appropriately selected. The state change temperature is preferably from 100 to 160 ° C, particularly preferably from 120 to 150 ° C. Further, in the present invention, the state change temperature of the curing accelerator (D) means that the curing accelerator (D) is mixed with 5% by weight of the varnish (W) in an amount of 5% by weight, and is heated by visual observation. The temperature at which the hardening accelerator (D) is in a size that cannot be visually observed; or, in 90% by weight of the varnish (W), 10% by weight of the hardening accelerator (D) is mixed by DSC (differential sweep) The calorimeter, manufactured by Seiko Instruments Co., Ltd., DSC220) was measured at a temperature increase rate of 5 ° C / min, and the curing accelerator (D) was subjected to a temperature at which the endothermic peak was dissolved.

The curing reaction initiation temperature of the hardening accelerator (D) is preferably 130 ° C or higher, more preferably 140 ° C or higher. In addition, the curing reaction initiation temperature means that the liquid resin composition for the adhesive is measured by a DSC (differential scanning calorimeter, manufactured by Seiko Instruments, DSC220) at a temperature elevation rate of 7 ° C /min. The starting temperature of the line connecting the lower edges.

The liquid resin composition for an adhesive according to the second aspect of the present invention (hereinafter referred to as the liquid resin composition (2) for an adhesive of the present invention) contains at least a solvent (A) in one molecule. An epoxy resin (B) having two or more epoxy groups, an epoxy resin hardener (C) having two or more phenolic hydroxyl groups in one molecule, and a hardening accelerator (E), the epoxy resin (B) And the epoxy resin hardener (C) is dissolved in the solvent (A); the hardening accelerator (E) is a hardening accelerator having a cationic portion and an anionic portion.

The liquid resin composition (2) for an adhesive of the present invention is a liquid resin composition for adhering a semiconductor element to an adhesive on a support substrate.

The solvent (A), the epoxy resin (B) and the epoxy resin hardener (C) in the liquid resin composition (2) for an adhesive of the present invention are the liquid resin composition for the adhesive of the present invention. The solvent (A), the epoxy resin (B) and the epoxy resin hardener (C) in (1) are the same.

The curing accelerator (E) in the liquid resin composition (2) for an adhesive of the present invention has a curing accelerator for a cationic portion and an anionic portion, and the curing accelerator (E) is, for example, the following general formula (1) ) a hardening accelerator as shown.

(In the formula (1), R ¹ , R ² and R ³ each represent one selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other. n is 0 to 2. A represents a naphthalene ring or an aromatic group represented by the following general formula (2).)

(In the formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent one selected from a hydrogen atom, a halogen atom and an organic group having 1 to 6 carbon atoms, and may be the same or different from each other. A single bond, an ether group, a sulfonic acid group, a sulfur ion group, a carbonyl group or an organic group having 1 to 13 carbon atoms.)

Further, in the curing accelerator represented by the above general formula (1), when n is 0, the anion moiety is a conjugate base having a compound having one or more phenolic hydroxyl groups and a phenoxy group in one molecule, and When n is more than 0, the anion moiety is a molecular complex of a compound having two or more phenolic hydroxyl groups in one molecule and a conjugate base having a compound having one or more phenolic hydroxyl groups and a phenoxy group in one molecule.

The hardening accelerator represented by the above general formula (1) may, for example, be the following general formula (3).

(In the formula (3), R ¹ , R ² and R ³ each represent one selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other. n is 0 to 2. )

In addition, the curing accelerator (E) having a cationic portion and an anionic portion in the liquid resin composition (2) for an adhesive of the present invention may, for example, be a curing accelerator represented by the following general formula (4).

(In the formula (4), R ¹ , R ² and R ³ each represent one selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other. Y ¹ and Y ² are Any of an oxygen atom, a nitrogen atom, and a sulfur atom may be the same or different from each other. X represents an organic group. Z represents a substituted or unsubstituted aromatic cyclic organic group or a heterocyclic organic group.

In the above general formula (4), X, Y ¹ and Y ² form a fitting structure with a ruthenium atom.

The hardening accelerator represented by the above general formula (4) is, for example, the following general formula (5).

(wherein R ¹ , R ² and R ³ each represent one selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other. Ph represents a phenyl group.)

In addition, the hardening accelerator (E) having a cationic portion and an anionic portion in the liquid resin composition (2) for an adhesive of the present invention may, for example, be a curing accelerator represented by the following general formula (6).

(In the formula (6), R ¹ , R ² and R ³ each represent one selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other. Y ³ , Y ⁴ , At least one of Y ⁵ and Y ⁶ is a group in which one proton is released from a proton donor having at least one proton released to the outside of the molecule, and the two may be the same or different from each other.

Y ³ , Y ⁴ , Y ⁵ and Y ⁶ of the above general formula (6) are an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and at least one of Y ³ , Y ⁴ , Y ⁵ and Y ⁶ a phenol compound having one or more aromatic carboxylic acids having at least one acid anhydride group and/or a carboxyl group in one molecule, and one or more hydroxyl groups in one molecule, and an aromatic carboxylic acid having one or more carboxyl groups; A proton donor having a group selection of at least one aromatic compound having at least one carboxyl group and a phenolic hydroxyl group in the molecule, and a base of one proton is released, and the two may be the same or different from each other.

The hardening accelerator represented by the above general formula (6) is, for example, the following general formula (7).

(In the formula (7), R ¹ , R ² and R ³ each represent one selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other. B represents a boron atom.)

The liquid resin composition (2) for an adhesive of the present invention is used in a method for producing a semiconductor device which has a layer of a liquid resin composition for an adhesive printed on a support substrate by continuous printing. a printing step; then, a liquid resin composition layer for the adhesive printed on the support substrate is used to volatilize the solvent (A), thereby forming a volatilization step of the adhesive layer on the support substrate; and then, forming an adhesive layer The semiconductor substrate is mounted on the support substrate of the agent layer, and then the semiconductor element is bonded to the support substrate by a hardening step of curing the adhesive layer.

At this time, in the volatilization step, the volatilization temperature at which the solvent (A) is volatilized is 25 to 150 ° C, preferably 80 to 120 ° C. Further, in the hardening step, the curing temperature at which the adhesive layer is cured is 90 to 170 ° C, preferably 140 to 160 ° C. Further, in the mounting step, the temperature at which the semiconductor element is mounted is the same as the temperature at which the volatilization temperature is the same. Also, the hardening temperature is higher than the volatilization temperature.

The hardening accelerator (E) is in the volatilization step, at a volatilization temperature, in the varnish (W) and in the adhesive layer obtained by volatilizing the solvent (A) from the varnish (W), according to the degree of visual observation. The size exists. In this state, the hardening accelerator (E) hardly promotes the hardening reaction. Further, the curing accelerator (E) is heated to a curing temperature in order to perform the curing step, that is, at any temperature within a temperature range from a temperature at which the volatilization temperature is high to a curing temperature, and the degree of visual observation is not observed. The size, or dissolved in the adhesive layer. Therefore, the hardening accelerator (E) promotes the hardening reaction.

In the liquid resin composition (2) for an adhesive of the present invention, by the action of the hardening accelerator (E), hardening reaction hardly occurs in the volatilization step, and hardening occurs in the hardening reaction itself. The reaction is easy to control the hardening reaction.

In the present invention, the curing accelerator (E) which is present in a size which can be visually observed is a size which cannot be visually observed or a temperature which is dissolved in the adhesive layer, and is described as a state change temperature of the curing accelerator (E). The state change temperature of the hardening accelerator (E) varies depending on the type of the hardening accelerator (E), so the state of the hardening accelerator (E) and the hardening accelerator (E) having a state change temperature higher than the volatilization temperature can be selected. The temperature of change is preferably from 100 to 160 ° C, particularly preferably from 120 to 150 ° C. In addition, the state change temperature of the hardening accelerator (E) means that the curing accelerator (D) of 5% by weight is mixed with 95% by weight of the varnish (W), and is heated to a visually observable size. The curing accelerator (D) is a temperature at which the size is not visually observed; or, in 90% by weight of the varnish (W), 10% by weight of the hardening accelerator (E) is mixed by DSC (differential scanning calorimeter, Seiko Instruments, Inc., DSC 220) was measured at a temperature increase rate of 5 ° C / min, and the temperature indicated by the endothermic peak at the time of dissolution was measured.

The curing reaction initiation temperature of the hardening accelerator (E) is preferably 130 ° C or higher, more preferably 140 ° C or higher. In addition, the curing reaction initiation temperature means that the liquid resin composition for the adhesive is measured by a DSC (differential scanning calorimeter, manufactured by Seiko Instruments, DSC220) at a temperature elevation rate of 7 ° C /min. The starting temperature of the line connecting the lower edges.

The viscosity of the liquid resin compositions (1) and (2) for the adhesive of the present invention is 10 to 600 Pa‧s, preferably 20 to 300 Pa‧s, more preferably 30 to 200 Pa‧s. Further, in the present invention, the viscosity of the liquid resin composition is a value measured at 25 ° C and 2.5 rpm using an E-type viscometer (manufactured by Toyo Kogyo Co., Ltd., 3 degree rotor).

The liquid resin compositions (1) and (2) for an adhesive of the present invention may further contain a filler. The filler is an organic filler such as a siloxane or a urethane particle, or an inorganic filler such as cerium oxide or calcium carbonate, which is used for improving printability. In other words, any one can be used as a function of volatilizing the viscosity adjusting material for holding the shape of the printed matter or suppressing movement to the outside of the opening portion of the mask.

The liquid resin compositions (1) and (2) for an adhesive of the present invention may further contain a coupling agent, a leveling agent, an antifoaming agent, a surfactant, and the like, as needed.

The liquid resin compositions (1) and (2) for an adhesive of the present invention are excellent in continuous printing property at the time of printing, and have good semiconductor element mountability after solvent evaporation, and have no adhesive adhesion at room temperature. A liquid resin composition for the agent.

Hereinafter, a method of manufacturing a semiconductor device using the liquid resin compositions (1) and (2) for an adhesive of the present invention will be described.

First, the liquid resin compositions (1) and (2) for the adhesive of the present invention are printed on a support substrate on which a semiconductor element is mounted. Here, as the support substrate, there is a printed circuit board such as a lead frame, an organic substrate, or a flexible substrate, and a semiconductor element is mounted on the support substrate, and is electrically connected by a gold wire. However, the semiconductor element itself or the like may be used. As a printing method of the liquid resin composition for an adhesive, screen printing, stencil printing, or the like can be used, and from the viewpoint of surface smoothness, it is preferably applied by a stencil printing method using a template mask. The stencil printing method can be carried out in accordance with a known method.

Next, the support substrate on which the liquid resin composition for an adhesive is printed is heated on an oven or a hot plate to carry out a volatilization step of volatilizing the solvent (A). When the adhesive layer in which the solvent is volatilized in the volatilization step contains a large amount of volatile matter, it may cause adhesion of the adhesive layer and voids in the mounting step of the semiconductor element, so the adhesive after the volatilization step is preferred. The volatile matter of the layer is 1% by weight or less. The temperature of the volatilization step may be a range in which the solvent is evaporated and the state of the hardening accelerator is not changed. However, from the viewpoint of productivity, it is preferably 80 ° C or higher in order to complete in 120 minutes. Further, in order to prevent occurrence of warpage by exposing the support substrate before sealing to a high temperature, it is preferably 150 ° C or lower, more preferably 120 ° C or lower.

The volatile component of the adhesive layer after the volatilization step refers to a urethane scraper having a thickness of 50 μm and a length of 27 cm, which is printed on the support substrate according to the load of the squeegee 2 kg and the squeegee speed of 20 mm/s. After heat treatment in a volatilization step, that is, in a dryer at 100 ° C ± 5 ° C for 80 ± 3 minutes, the adhesive layer sampled by the spatula is 5 to 30 mg before the taken-out support substrate is cooled, and the heat balance method is used. (TGA) The weight reduction rate at 200 ° C in the weight reduction curve measured from room temperature to 10 ° C / min to 300 ° C. A preferred weight reduction rate is 0.5% by weight or less, particularly preferably 0.1% by weight or less.

In addition, the adhesive layer is preferably non-tacky (sticky) at room temperature. When there is adhesion, when the support substrates are placed one on another, they are bonded to each other, and a defect occurs in the supporting substrate selection step of the semiconductor element mounting device. Therefore, the liquid resin composition for the adhesive is printed on the support substrate at a weight of 2 kg and a squeegee speed of 20 mm/s using a 50 μm-thick template mask and a 27 cm long urethane scraper. The adhesive layer after heat treatment for 80 ± 3 minutes in a dryer of ° C ± 5 ° C preferably has a viscosity of 0.05 N or less at 25 ° C which is a viscosity index. The viscose force was measured by a viscometer (manufactured by RHESCA), with an Immersion Speed of 30 mm/min, a test speed of 600 mm/min, a preload of 0.2 N, and a press time. 1.0 second, the value measured by the probe 5.1 mmΦ (SUS304).

The support substrate for mounting the semiconductor element with the adhesive layer thus obtained is usually superposed on the die bonder and selected (the step of taking one support substrate from above), and transported to the heater to mount the semiconductor device in a heated state. . When the support substrate is selected, it is necessary to peel off the adhesive layer printed on the selected support substrate and the back surface (back side) of the unprinted adhesive of the other support substrate. When the adhesive force at 25 ° C of the adhesive layer is greater than 0.05 N, the support substrate for mounting the semiconductor element with the overlapping adhesive layer is bonded, and the support substrate cannot be selected. When the support substrate is selected, two pieces are overlapped. The support substrate, a part of the adhesive layer remains on the back surface of the support substrate, and the like.

The support substrate for mounting a semiconductor element with an adhesive layer is a liquid resin composition for printing an adhesive such as a lead frame or an organic substrate, and the solvent is volatilized. When the semiconductor element is laminated, it is mounted on the wire. A liquid resin composition for an adhesive is printed on a second semiconductor element such as a frame or an organic substrate, and is volatilized. The semiconductor element mounting temperature is preferably 150 ° C or lower, more preferably 130 ° C or lower. The semiconductor component mounting at high temperatures often causes a warp. Further, a load is applied in the semiconductor element mounting step, and the load is controlled by the type of the die bonder. Although it is a part of a LOC (Lead On Chip) die-bonding machine that applies a load of about 20 N per semiconductor element, it is usually carried out with a load of 3 to 5 N. In consideration of a thin semiconductor device and a semiconductor element having a low mechanical strength, it is preferably mounted at 5 N or less, more preferably 1 to 4 N. The mounting time (the time for pressurizing the semiconductor element to the support) is preferably 10 seconds or shorter, more preferably 3 seconds or shorter, and particularly preferably 1 second or shorter from the viewpoint of productivity.

In order to mount the semiconductor element at a low temperature in this manner, it is preferable to use a liquid resin composition for the adhesive, a template mask having a thickness of 50 μm, and a urethane scraper having a length of 27 cm, and a load of 2 kg according to the squeegee and a squeegee speed of 20 mm. /s is printed on a support substrate, and heat-treated in a dryer at 100 ° C ± 5 ° C for 80 ± 3 minutes, and then mounted on the adhesive layer (also including dummy elements) at 100 ° C at 100 ° C. The cutting strength is 1 N or more. This is because the semiconductor element is mounted on the support substrate of various adhesive layers having different cutting strengths at 100 ° C in the adhesive layer after the heat treatment, and as a result, the cutting strength at 100 ° C is 1 N. As described above, the mounted semiconductor element has no offset, whereas in the case of less than 1N, the semiconductor element is often shifted.

Here, the measurement of the cutting strength is carried out by selecting a semiconductor element of 6×6 mm on a die bonder, and the weight of the bonded crystal is 1.0 N, the heating temperature of the supporting substrate is 100° C., and the mounting time is 8 seconds (including The PBGA (Plastic Ball Grid Array) substrate was mounted on a PBGA (Plastic Ball Grid Array) substrate (package size: 35 × 35 mm, nuclear material: BT (bis-m-butenylene diimine) - the condition of the time required to support the temperature of the substrate surface to rise to 100 ° C for 7 seconds) three Resin, solder resist: Shear strength at 100 ° C of a sample on PSR4000AUS308 (made by Sun Ink Co., Ltd., thickness 0.56 mm). The cutting strength was measured by a wafer shearing machine (manufactured by Dage Co., Ltd., Series 4000).

After the semiconductor element is mounted, the adhesive layer is cured, and the metal layer is electrically connected, and the curing of the adhesive layer is performed at a temperature higher than or equal to the state of the hardening accelerator. This temperature is preferably 200 ° C or less, more preferably 180 ° C or less, and particularly preferably 160 ° C or less, in consideration of the decomposition temperature of the warp or the adhesive layer of the support substrate.

After the electrical connection is performed in this manner, the resin is sealed. When the lead frame is used as the supporting substrate, the semiconductor device is obtained by performing wire processing, exterior plating, or the like as needed. Moreover, when an organic substrate is used as a support substrate, a solder device is attached as needed, and a semiconductor device is obtained.

(Example) [Liquid resin composition for adhesive] ‧Liquid resin composition A for adhesives

Diethylene glycol monobutyl ether acetate (boiling point 247 ° C) 22.5 parts by weight

O-cresol novolac type epoxy resin (softening point 70 ° C, epoxy equivalent 210) 33.4 parts by weight

Phenolic novolac resin (softening point 110 ° C, hydroxyl equivalent 104) 16.6 parts by weight

The above raw materials were placed in a separation flask, and stirred at 80 ° C for 2 hours to obtain a brown transparent varnish. After cooling to room temperature, the following raw materials were added, and the mixture was kneaded by three rolls at room temperature to obtain a liquid resin composition A for an adhesive.

3-glycidoxypropyltrimethoxydecane 0.2 parts by weight

a curing accelerator of the following formula (8) (state change temperature 140 ° C, hardening reaction initiation temperature 160 ° C) 0.2 parts by weight

Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight

23.0 parts by weight of an organic filler (C-800, manufactured by Kokusai Industrial Co., Ltd.) having an average particle diameter of 6 μm

The viscosity of the obtained liquid resin composition A was 45 Pa‧s. Further, the viscosity was measured by using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., 3 degree rotor) at 25 ° C and 2.5 rpm (the viscosity shown below was also measured in the same manner).

‧Liquid resin composition B for adhesive

Diethylene glycol monobutyl ether acetate (boiling point 247 ° C) 22.5 parts by weight

O-cresol novolac type epoxy resin (softening point 70 ° C, epoxy equivalent 210) 33.4 parts by weight

Phenolic novolac resin (softening point 110 ° C, hydroxyl equivalent 104) 16.6 parts by weight

The above raw materials were placed in a separation flask, and stirred at 80 ° C for 2 hours to obtain a brown transparent varnish. After cooling to room temperature, the following raw materials were added, and the mixture was kneaded by three rolls at room temperature to obtain a liquid resin composition B for an adhesive.

3-glycidoxypropyltrimethoxydecane 0.2 parts by weight

a curing accelerator of the following formula (9) (state change temperature 120 ° C, hardening reaction initiation temperature 140 ° C) 0.2 parts by weight

Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight

23.0 parts by weight of an organic filler (C-800, manufactured by Kokusai Industrial Co., Ltd.) having an average particle diameter of 6 μm

The viscosity of the obtained liquid resin composition B was 45 Pa‧S.

‧Liquid resin composition for adhesive C

Γ-butyrolactone (boiling point 206 ° C) 22.5 parts by weight

O-cresol novolac type epoxy resin (softening point 70 ° C, epoxy equivalent 210) 33.4 parts by weight

Phenolic novolac resin (softening point 110 ° C, hydroxyl equivalent 104) 16.6 parts by weight

The above raw materials were placed in a separation flask, and stirred at 80 ° C for 2 hours to obtain a brown transparent varnish. After cooling to room temperature, the following raw materials were added, and the mixture was kneaded by three rolls at room temperature to obtain a liquid resin composition C for an adhesive.

3-glycidoxypropyltrimethoxydecane 0.2 parts by weight

The curing accelerator of the above formula (8) (state change temperature 140 ° C, hardening reaction initiation temperature 160 ° C) 0.2 parts by weight

Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight

23.0 parts by weight of an organic filler (C-800, manufactured by Kokusai Industrial Co., Ltd.) having an average particle diameter of 6 μm

The viscosity of the obtained liquid resin composition C was 40 Pa‧s.

‧Liquid resin composition D for adhesives

Diethylene glycol monoethyl ether acetate (boiling point 217 ° C) 22.5 parts by weight

O-cresol novolac type epoxy resin (softening point 70 ° C, epoxy equivalent 210) 33.4 parts by weight

Phenolic novolac resin (softening point 110 ° C, hydroxyl equivalent 104) 16.6 parts by weight

The above raw materials were placed in a separation flask, and stirred at 80 ° C for 2 hours to obtain a brown transparent varnish. After cooling to room temperature, the following raw materials were added, and the mixture was kneaded by three rolls at room temperature to obtain a liquid resin composition D for an adhesive.

3-glycidoxypropyltrimethoxydecane 0.2 parts by weight

The curing accelerator of the above formula (8) (state change temperature 140 ° C, hardening reaction initiation temperature 160 ° C) 0.2 parts by weight

Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight

23.0 parts by weight of an organic filler (C-800, manufactured by Kokusai Industrial Co., Ltd.) having an average particle diameter of 6 μm

The viscosity of the obtained liquid resin composition D was 45 Pa‧s.

‧Liquid resin composition E for adhesives

Diethylene glycol monobutyl ether acetate (boiling point 247 ° C) 22.5 parts by weight

O-cresol novolac type epoxy resin (softening point 70 ° C, epoxy equivalent 210) 33.4 parts by weight

Phenolic novolac resin (softening point 110 ° C, hydroxyl equivalent 104) 16.6 parts by weight

The above raw materials were placed in a separation flask, and stirred at 80 ° C for 2 hours to obtain a brown transparent varnish. After cooling to room temperature, the following raw materials were added, and the mixture was kneaded by three rolls at room temperature to obtain a liquid resin composition E for an adhesive.

3-glycidoxypropyltrimethoxydecane 0.2 parts by weight

a curing accelerator of the following formula (10) (state change temperature 140 ° C, hardening reaction initiation temperature 160 ° C, n = 0.5) 0.2 parts by weight

Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight

23.0 parts by weight of an organic filler (C-800, manufactured by Kokusai Industrial Co., Ltd.) having an average particle diameter of 6 μm

The viscosity of the obtained liquid resin composition E for the adhesive was 47 Pa‧s.

(in the formula (10), n = 0.5.)

‧Liquid resin composition for adhesive F

Cyclohexanone (boiling point 156 ° C) 22.5 parts by weight

O-cresol novolac type epoxy resin (softening point 70 ° C, epoxy equivalent 210) 33.4 parts by weight

Phenolic novolac resin (softening point 110 ° C, hydroxyl equivalent 104) 16.6 parts by weight

The above raw materials were placed in a separation flask, and stirred at 80 ° C for 2 hours to obtain a brown transparent varnish. After cooling to room temperature, the following raw materials were added, and the mixture was kneaded by three rolls at room temperature to obtain a liquid resin composition F for an adhesive.

3-glycidoxypropyltrimethoxydecane 0.2 parts by weight

The curing accelerator of the above formula (8) (state change temperature 140 ° C, hardening reaction initiation temperature 160 ° C) 0.2 parts by weight

Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight

23.0 parts by weight of an organic filler (C-800, manufactured by Kokusai Industrial Co., Ltd.) having an average particle diameter of 6 μm

The viscosity of the obtained liquid resin composition F was 10 Pa‧S.

‧Liquid resin composition for adhesive G

Cyclohexanone (boiling point 156 ° C) 22.5 parts by weight

O-cresol novolac type epoxy resin (softening point 70 ° C, epoxy equivalent 210) 33.4 parts by weight

Phenolic novolac resin (softening point 110 ° C, hydroxyl equivalent 104) 16.6 parts by weight

The above raw materials were placed in a separation flask, and stirred at 80 ° C for 2 hours to obtain a brown transparent varnish. After cooling to room temperature, the following raw materials were added, and the mixture was kneaded by three rolls at room temperature to obtain a liquid resin composition G for an adhesive.

3-glycidoxypropyltrimethoxydecane 0.2 parts by weight

2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-three (State change temperature: 80 ° C or lower, hardening reaction initiation temperature: 100 ° C) 0.2 parts by weight

Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight

23.0 parts by weight of an organic filler (C-800, manufactured by Kokusai Industrial Co., Ltd.) having an average particle diameter of 6 μm

The viscosity of the obtained liquid resin composition G for the adhesive was 11 Pa‧s.

‧Liquid resin composition for adhesive H

Diethylene glycol monobutyl ether acetate (boiling point 247 ° C) 22.5 parts by weight

O-cresol novolac type epoxy resin (softening point 70 ° C, epoxy equivalent 210) 33.4 parts by weight

Phenolic novolac resin (softening point 110 ° C, hydroxyl equivalent 104) 16.6 parts by weight

The above raw materials were placed in a separation flask, and stirred at 80 ° C for 2 hours to obtain a brown transparent varnish. After cooling to room temperature, the following raw materials were added, and the mixture was kneaded by three rolls at room temperature to obtain a liquid resin composition H for an adhesive.

3-glycidoxypropyltrimethoxydecane 0.2 parts by weight

2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-three (State change temperature: 80 ° C or lower, hardening reaction initiation temperature: 100 ° C) 0.2 parts by weight

Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight

23.0 parts by weight of an organic filler (C-800, manufactured by Kokusai Industrial Co., Ltd.) having an average particle diameter of 6 μm

The viscosity of the obtained liquid resin composition H was 45 Pa‧s.

‧Liquid resin composition for adhesive I

Diethylene glycol monobutyl ether acetate (boiling point 247 ° C) 22.5 parts by weight

O-cresol novolac type epoxy resin (softening point 70 ° C, epoxy equivalent 210) 33.4 parts by weight

Phenolic novolac resin (softening point 110 ° C, hydroxyl equivalent 104) 16.6 parts by weight

The above raw materials were placed in a separation flask, and stirred at 80 ° C for 2 hours to obtain a brown transparent varnish. After cooling to room temperature, the following raw materials were added, and the mixture was kneaded by three rolls at room temperature to obtain a liquid resin composition I for an adhesive.

3-glycidoxypropyltrimethoxydecane 0.2 parts by weight

Triphenylphosphine (state change temperature 80 ° C or lower, hardening reaction initiation temperature 120 ° C) 0.2 parts by weight

Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight

23.0 parts by weight of an organic filler (C-800, manufactured by Kokusai Industrial Co., Ltd.) having an average particle diameter of 6 μm

The viscosity of the obtained liquid resin composition I was 45 Pa‧s.

‧Liquid resin composition for adhesive J

Γ-butyrolactone (boiling point 206 ° C) 22.5 parts by weight

O-cresol novolac type epoxy resin (softening point 70 ° C, epoxy equivalent 210) 33.4 parts by weight

Phenolic novolac resin (softening point 110 ° C, hydroxyl equivalent 104) 16.6 parts by weight

The above raw materials were placed in a separation flask, and stirred at 80 ° C for 2 hours to obtain a brown transparent varnish. After cooling to room temperature, the following raw materials were added, and the mixture was kneaded by three rolls at room temperature to obtain a liquid resin composition J for an adhesive.

3-glycidoxypropyltrimethoxydecane 0.2 parts by weight

2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-three (State change temperature: 80 ° C or lower, hardening reaction initiation temperature: 100 ° C) 0.2 parts by weight

Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight

23.0 parts by weight of an organic filler (C-800, manufactured by Kokusai Industrial Co., Ltd.) having an average particle diameter of 6 μm

The viscosity of the obtained liquid resin composition J was 40 Pa‧s.

The adhesive resin composition A to J is printed on a substrate for a BOC (Board On Chip) type semiconductor device, that is, BT (bis-m-butylene diimide-three) Resin substrate (photoresist: PSR4000AUS308 (made by Sun Ink Manufacturing Co., Ltd.), thickness 0.56 mm). The stencil mask used had a thickness of 50 μm, and the printing thickness adjusted the squeegee moving speed and the squeegee load to make the solvent volatilized to a thickness of 35 μm ± 5. This was subjected to heat treatment at 100 ° C for 80 minutes to volatilize the solvent from the liquid resin composition for the adhesive to obtain a semiconductor support substrate with an adhesive layer. The printing was carried out using a metal squeegee (stainless steel type, length 27 cm) manufactured by Toray Engineering (VE500), and was carried out by a load of about 20 N and a squeegee moving speed of 25 mm/s.

Further, using the liquid resin compositions A to J for the above-mentioned adhesive, the liquid resin composition for an adhesive was printed on a glass slide to a thickness of 50 μm, and heat-treated at 100 ° C for 80 minutes to prepare a solvent for the adhesive. The liquid resin composition was volatilized to obtain a glass slide with an adhesive layer.

[State change temperature and evaluation of hardening accelerator]

The varnish at the time of preparation of the liquid resin compositions A to J for the above-mentioned adhesive was mixed with 5% by weight of a varnish, and a 5% by weight of a hardening accelerator was heated on a heating plate to be visually observed. The hardening accelerator that exists is a temperature that cannot be visually observed, and is a state change temperature. In the following test, since the solvent volatilization temperature is set to 100 ° C, the state change temperature is less than 100 ° C, and the state change temperature is 100 ° C or more is set to ○ (normal temperature to volatilization temperature). . In the following test, since the curing temperature was 175 ° C, the state change temperature was higher than 100 ° C and 175 ° C or lower, and the state change temperature was over 175 ° C. ).

The curing reaction initiation temperature was measured by DSC (differential scanning calorimeter, manufactured by Seiko Instruments, DSC220) at a heating rate of 7 ° C / min, using a liquid resin composition A to J. The initial temperature of the line connecting the lower edges was measured.

The measurement results are shown in the first table. The blending amount is parts by weight.

[Example 1]

The following test was carried out using the semiconductor supporting substrate with the adhesive layer prepared by using the liquid resin composition A for the above adhesive and the glass slide with the adhesive layer.

[volatiles]

The volatiles were determined by the volatiles of the adhesive layer after the volatilization step. Using a 50 μm thick template mask and a 27 cm long urethane scraper, printed on the support substrate according to the weight of the squeegee 2 kg and the squeegee speed of 20 mm/s, in the volatilization step, that is, at 100 ° C ± 5 ° C After heat treatment in the dryer for 80±3 minutes, 5~30mg of the adhesive layer sampled by the spatula before cooling the taken-out support substrate is heated to 300°C from room temperature at 10°C/min by the heat balance method (TGA). The weight reduction rate at 200 ° C in the weight reduction curve measured at ° C.

[Semiconductor component mountability and adhesion test]

Heated by a heater under the glass slide with the adhesive layer to confirm whether the 6×6mm square semiconductor component can be weighted by the die bonder, and the heating temperature is 100°C for 20 seconds (including the slide). Mounting (semiconductor element mounting property) under the condition that the temperature of the surface is raised to 100 ° C for 15 seconds.

At this time, when the semiconductor element of the 6 × 6 mm square is in contact with the adhesive layer, the area is 90% or more, and it is regarded as 0K. Eight semiconductor components are mounted, and if one of the semiconductor components is less than 90%, it is regarded as NG. Further, the contact area is obtained from the back surface of the slide glass, and the contact surface of the semiconductor element is photographed, and the area of the contact portion is calculated. In the semiconductor element mountability test, it was not NG, and the viscosity test at room temperature was performed.

Using a test piece equipped with the above-described semiconductor element, a viscose measuring machine (manufactured by RHESCA Co., Ltd.) was used, and the probe descending speed (intrusion speed) was 30 mm/min, the test speed was 600 mm/min, and the dense load (preceding load) was 0.2 N. The adhesion retention time (pressure-bonding time) was 1.0 second, and the probe was 5.1 mmΦ (SUS304).

[Continuous printability]

Approximately 20 g of the adhesive liquid composition was placed in a template mask for printing, and after two consecutive printings, the period of one hour was directly stopped in this state as one cycle, and ten cycles were performed, and the evaluation was continuous. Printability. In the cycle, the adhesive is dried with the liquid resin composition, and if the printed matter is rough, it is regarded as NG, or dried on the stencil mask, although there is no roughness, if the thickness of the solvent is volatilized, the thickness is deviated by 35 μm ± 5 μm. It is considered as NG.

[Normal temperature placement test]

When the glass slide with the above adhesive layer is placed at normal temperature, the time during which the semiconductor element can be mounted is used as the life of the adhesive layer. Whether or not the semiconductor element is mounted is the same as the semiconductor element mounting test, and the glass slide with the adhesive layer is used, and n=8 is performed.

[Dress resistance test]

The analog semiconductor wafer (Phase8, manufactured by Hitachi U.S.) was protected by a polyimide resin (CRC-8800, manufactured by Sumitomo Bakelite Co., Ltd.) using an automatic die bonder, and cut to 10.5 × 5 mm. The prepared semiconductor element was placed on a semiconductor support substrate (BOC (Board On Chip) type package) belonging to the above-mentioned adhesive layer on the side of the polyimide resin at 100 ° C for 8 seconds and a load of 300 g. The adhesive layer of the BT resin substrate is mounted and electrically connected by a metal wire. This was molded into a semiconductor sealing material (EME-G700, manufactured by Sumitomo Bakelite Co., Ltd.) at 175 ° C for 90 seconds, and then cured for 4 hours to form a semiconductor device having a size of 12.3 × 8.3 mm. Using this semiconductor device, drying (125 ° C, 20 hours), moisture absorption treatment (85 ° C, relative humidity 85%, 168 hours), reflow processing (maximum temperature 255 ~ 260 ° C, 20 seconds, equivalent to JEDEC level 1 The wet solder resistance test of 3 consecutive treatments. The test was carried out with n=10, and the penetration observation was performed for the internal poor use of the ultrasonic probe device 5 MHz probe. The number of semiconductor devices having internal peeling or cracking was calculated as poor.

The results are as shown in Table 1.

[Embodiment 2]

The semiconductor support substrate with the adhesive layer and the glass slide with the adhesive layer were prepared using the above-mentioned adhesive resin composition B, and the test was carried out in the same manner as in Example 1.

[Example 3]

Using the liquid resin composition C for the above adhesive, a semiconductor supporting substrate with an adhesive layer and a glass slide with an adhesive layer were prepared, and the test was carried out in the same manner as in Example 1.

[Example 4]

The semiconductor support substrate with the adhesive layer and the glass slide with the adhesive layer were prepared using the above-mentioned adhesive resin composition D, and the test was carried out in the same manner as in Example 1.

[Example 5]

The semiconductor supporting substrate with the adhesive layer and the glass slide with the adhesive layer were prepared using the above-mentioned liquid resin composition E for an adhesive, and the test was carried out in the same manner as in Example 1.

[Comparative Examples 1 to 5]

The semiconductor supporting substrate with the adhesive layer and the glass slide with the adhesive layer were prepared using the above-mentioned adhesive resin compositions F to J, and the test was carried out in the same manner as in Example 1.

Further, in Comparative Examples 1 and 2, since the solvent was dried during the continuous printing and was rough, the continuous printing property NG was obtained. In Comparative Examples 3 to 5, when the solvent was volatilized, excessive hardening occurred, and semiconductor element mounting was not possible. Therefore, the semiconductor element mountability NG was obtained.

(industrial availability)

By using the liquid resin composition for an adhesive used in the present invention, it is possible to provide a semiconductor support substrate with an adhesive layer which is excellent in continuous printing and has an excellent adhesiveness after the solvent is volatilized, and the adhesive layer is excellent in continuous printing. By providing a semiconductor device using a semiconductor supporting substrate with an adhesive layer, productivity can be improved.

Claims (5)

A liquid resin composition for an adhesive, comprising at least a solvent (A), an epoxy resin (B) having two or more epoxy groups in one molecule, and a ring having two or more phenolic hydroxyl groups in one molecule. The oxygen resin hardener (C) and the hardening accelerator (D) are characterized in that the solvent (A) has a boiling point of 200 to 260 ° C; and the hardening accelerator (D) is represented by the following general formula (1). a curing accelerator, a curing accelerator represented by the following general formula (4) or a curing accelerator represented by the following general formula (6); the epoxy resin (B) and the epoxy resin curing agent (C) Is dissolved in the solvent (A); the state of the hardening accelerator (D) varies from 100 to 160 ° C; general formula (1): (wherein R ¹ , R ² and R ³ each represent one selected from a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other; n is 0.5 to 2; A represents naphthalene Ring or an aromatic group represented by the following general formula (2); general formula (2): (wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent one selected from a hydrogen atom, a halogen atom and an organic group having 1 to 6 carbon atoms, and may be the same or different from each other; and V represents a single bond, An ether group, a sulfonic group, a sulfide group, a carbonyl group or an organic group having 1 to 13 carbon atoms; general formula (4): (wherein R ¹ , R ² and R ³ each represent one selected from a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other; Y ¹ and Y ² are an oxygen atom, Any of a nitrogen atom and a sulfur atom may be the same or different from each other; X represents an organic group, which may be the same or different; and Z represents a substituted or unsubstituted aromatic cyclic organic group or a heterocyclic organic group) ; general formula (6): (wherein R ¹ , R ² and R ³ each represent one selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other; Y ³ , Y ⁴ , Y ⁵ and At least one of Y ⁶ is a group in which one proton is released from a proton donor having at least one proton released to the outside of the molecule, and the two may be the same or different from each other. The liquid resin composition for an adhesive according to the first aspect of the invention, wherein the epoxy resin (B) is an epoxy resin which is solid at normal temperature. The liquid resin composition for an adhesive according to claim 1 or 2, wherein the epoxy resin curing agent (C) is an epoxy resin curing agent which is solid at normal temperature. The liquid resin composition for an adhesive according to the first or second aspect of the invention, wherein the curing accelerator has a curing reaction initiation temperature of 130 ° C or higher. The liquid resin composition for an adhesive according to the third aspect of the invention, wherein the hardening accelerator has a curing reaction initiation temperature of 130 ° C or higher.