JP5901349B2 - Adhesive film, tape for wafer processing, and method for producing adhesive film - Google Patents

Description

  The present invention relates to an adhesive film, a wafer processing tape, and an adhesive film manufacturing method.

  Conventionally, silver paste is used for fixing a semiconductor chip to a lead frame or an electrode member in a manufacturing process of a semiconductor device. The fixing process is performed by applying a paste adhesive on a die pad or the like of the lead frame, mounting a semiconductor chip on the lead adhesive, and curing the paste adhesive layer.

  However, paste adhesives have large variations in coating amount, coating shape, etc. due to their viscosity behavior and deterioration. As a result, the thickness of the paste-like adhesive formed is not uniform, and the reliability of the fixing strength related to the semiconductor chip is poor. That is, when the application amount of the paste adhesive is insufficient, the bonding strength between the semiconductor chip and the electrode member is lowered, and the semiconductor chip may be peeled off in the subsequent wire bonding process. On the other hand, when the application amount of the paste adhesive is too large, the paste adhesive is cast onto the semiconductor chip, resulting in poor characteristics, and the yield and reliability in the resin sealing process are lowered. Such a problem in the adhering process becomes particularly prominent with an increase in the size of the semiconductor chip. Therefore, it is necessary to frequently control the amount of paste adhesive applied, which hinders workability and productivity.

  In this paste adhesive application step, there is a method in which the paste adhesive is separately applied to a lead frame or a formed chip. However, in this method, it is difficult to make the paste adhesive layer uniform, and a special apparatus and a long time are required for applying the paste adhesive. For this reason, there has been proposed a wafer processing tape that can adhere and hold a semiconductor wafer in a dicing process and can provide an adhesive layer for chip fixation necessary for a mounting process (see, for example, Patent Document 1).

  This tape for wafer processing is provided with a peelable adhesive film on a support substrate having an adhesive layer. After bonding the adhesive film to the back of the semiconductor wafer, the semiconductor wafer is bonded to the adhesive film. Dicing is performed, the supporting substrate is stretched, the chip with the adhesive film is peeled off, and the chips are individually picked up and fixed to an adherend such as a lead frame through the adhesive film.

Semiconductor wafers tend to be thinned, and there is a risk of damaging the semiconductor chip if thermocompression is applied with a strong load when the chip with the adhesive film is fixed to the adherend. For this reason, it is required to perform thermocompression bonding with a relatively low load (3 × 9.8 N or less per semiconductor chip), and in the concave and convex recesses formed on the surface of the adherend only by the thermocompression bonding process. It is difficult to completely fill (follow) the adhesive film. Therefore, in fixing the semiconductor chip to which the adhesive film is applied, the adhesive film is not completely cured before the resin sealing step, and the adhesive film is placed in the recess of the support member by the temperature and pressure of the resin sealing step. A sealing filling method is adopted in which the liquid is filled. Furthermore, in recent years, semiconductor devices in which a plurality of semiconductor chips are stacked in multiple stages have been manufactured, and the time spent for the wire bonding process for wire bonding to the semiconductor chips tends to be longer. Therefore, the heat history given to the adhesive film increases, the curing of the adhesive film proceeds excessively, the elastic modulus increases, and it becomes impossible to completely fill the adhesive film in the recesses in the resin sealing process, (Void) sometimes remained. This void causes a problem that the semiconductor chip is peeled off from the adherend and the adhesion reliability is impaired.
On the other hand, it has been proposed to use a clathrate having a specific structure as a curing agent or a curing accelerator (see Patent Documents 2 and 3), but the above problems are not necessarily satisfactory. There wasn't.

JP-A-60-57642 JP 2007-39449 A JP 2011-225840 A

  The present invention has been made in view of the above-described problems, and is applicable to a semiconductor device stacked in multiple stages, and provides a highly reliable adhesive film, a wafer processing tape using the same, and a method for manufacturing the adhesive film. With the goal.

（一般式（Ｉ）中、ｍは２〜４の整数を表し、ｎは２〜４の整数を表し、ｍ≦ｎかつｍ＋ｎ≦６である。Ｒ ^１ は置換基を表す。ただし、２つのＲ ^１ は互いに結合して環を形成する。）
（２）前記複合化合物以外に含有する芳香族カルボン酸化合物またはイミダゾール化合物が、前記複合化合物を形成する芳香族カルボン酸化合物もしくはイミダゾール化合物と同一構造の化合物であることを特徴とする（１）に記載の接着フィルム。
（３）前記複合化合物以外に含有する芳香族カルボン酸化合物またはイミダゾール化合物を、前記複合化合物１００モルに対して、０．１〜８０モルの割合で含有することを特徴とする（１）または（２）に記載の接着フィルム。
（４）前記複合化合物以外に含有する芳香族カルボン酸化合物またはイミダゾール化合物が、イミダゾール化合物であることを特徴とする（１）〜（３）のいずれか１項に記載の接着フィルム。
（５）前記複合化合物を形成する、前記一般式（Ｉ）で表される芳香族カルボン酸化合物が、１，４−ナフタレンジカルボン酸であることを特徴とする（１）〜（４）のいずれか１項に記載の接着フィルム。
As a result of diligent research to solve the above problems, the present inventors have studied various compounds as a curing agent. Among them, a composite compound composed of a specific aromatic carboxylic acid compound and an imidazole compound has a curability. In the case of increasing the aromatic carboxylic acid inhibits, in the case of increasing the adhesion with the adherend, the effect promoting action by imidazole promotes the curing shrinkage and inhibits the adhesion. Further examination was made because it was not always sufficient, and it was found that the above problems could be solved by combining an aromatic carboxylic acid and an imidazole compound as a curing agent for an epoxy resin, thereby completing the present invention. .
That is, the means for solving the above-described problems of the present invention are as follows.
(1) It contains at least one thermoplastic resin having an glass transition temperature of -20 to 120 ° C., an epoxy resin, and a curing agent, and the curing agent has the following general formula (I) having at least two carboxyl groups. A composite compound formed from an aromatic carboxylic acid compound and an imidazole compound , wherein the imidazole compound is 0.1 to 1 mole relative to 1 mole of the aromatic carboxylic acid compound, The adhesive film further contains an aromatic carboxylic acid compound or an imidazole compound.

(In general formula (I), m represents an integer of 2 to 4, n represents an integer of 2 to 4, and m ≦ n and m + n ≦ 6. R ¹ represents a substituent. R ¹ is bonded to each other to form a ring.)
(2) The aromatic carboxylic acid compound or imidazole compound contained in addition to the composite compound is a compound having the same structure as the aromatic carboxylic acid compound or imidazole compound forming the composite compound. The adhesive film as described.
(3) The aromatic carboxylic acid compound or imidazole compound contained in addition to the composite compound is contained at a ratio of 0.1 to 80 moles with respect to 100 moles of the composite compound (1) or (1) The adhesive film as described in 2).
(4) The adhesive film according to any one of (1) to (3), wherein the aromatic carboxylic acid compound or imidazole compound contained in addition to the composite compound is an imidazole compound.
(5) The aromatic carboxylic acid compound represented by the general formula (I) that forms the composite compound is 1,4-naphthalenedicarboxylic acid, any of (1) to (4) 2. The adhesive film according to claim 1.

（一般式（Ｉ）中、ｍは２〜４の整数を表し、ｎは２〜４の整数を表し、ｍ≦ｎかつｍ＋ｎ≦６である。Ｒ ^１ は置換基を表す。ただし、２つのＲ ^１ は互いに結合して環を形成する。）
(6 ) The adhesive film according to any one of (1) to ( 5 ), wherein the at least one thermoplastic resin is a phenoxy resin, an imide resin, or a (meth) acrylic resin.
( 7 ) The thermoplastic resin is contained at a ratio of 10 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin and all the curing agents contained therein. (1) to ( 6 ) The adhesive film according to any one of the above.
(8) Content of the said imidazole compound which comprises the said composite compound is 0.3-5.0 mol with respect to 1 mol of epoxy groups of the said epoxy resin, (1)-(7) The adhesive film according to any one of the above.
(9) In addition to the complex and the aromatic carboxylic acid compound or the imidazole compound, the composition further contains a curing agent selected from a phenol resin, an acid anhydride, and a polyamine as the curing agent (1) The adhesive film of any one of-(8).
(10) The adhesive film according to any one of (1) to (9), further comprising an inorganic filler.
(11) The inorganic filler is further contained in a proportion of 100 parts by mass or less with respect to 100 parts by mass of the total amount of the thermoplastic resin and the epoxy resin, and any one of (1) to (10) The adhesive film as described in 2.
(12) The adhesive film according to any one of (1) to (11), wherein the adhesive film is a wafer processing tape.
(13) A tape for wafer processing, wherein the adhesive film according to any one of (1) to (12) above and a supporting substrate having at least one pressure-sensitive adhesive layer are laminated.
(14) An aromatic carboxylic acid represented by the following general formula (I) having at least two kinds of carboxyl groups which are at least one thermoplastic resin, epoxy resin and curing agent having a glass transition temperature of −50 to 120 ° C. A compound formed of a compound and an imidazole compound , wherein the imidazole compound is 0.1 to 1 mol relative to 1 mol of the aromatic carboxylic acid compound, and in addition to the complex compound, an aromatic carboxylic acid compound or A method for producing an adhesive film comprising a step of preparing a dispersion by mixing an imidazole compound with a solvent, a step of applying the dispersion on a carrier film, and a drying step.

(In general formula (I), m represents an integer of 2 to 4, n represents an integer of 2 to 4, and m ≦ n and m + n ≦ 6. R ¹ represents a substituent. R ¹ is bonded to each other to form a ring.)

  The present invention can provide an adhesive film that can be satisfactorily filled in the concave and convex portions formed on the surface of the adherend such as a lead frame after a long wire bonding step, and a method for manufacturing the same. It is possible to provide a tape for wafer processing that improves the reliability of the fixing of the semiconductor chip to the lead frame or electrode member in the manufacturing process of the semiconductor device using the same.

The adhesive film of the present invention contains at least one thermoplastic resin, an epoxy resin, and a curing agent, and a composite compound formed from at least one specific aromatic carboxylic acid compound and an imidazole compound as the curing agent. And an aromatic carboxylic acid and / or an imidazole compound in addition to the composite compound.
<Thermoplastic resin>
The adhesive film of the present invention contains at least one thermoplastic resin. Examples of the thermoplastic resin used in the present invention include polyimide resins such as phenoxy resin, polyimide resin and polyetherimide resin, polyamide resins such as polyamide resin and polyamideimide resin, and (meth) acrylic resins. Among these, in this invention, a phenoxy resin, a polyimide resin, and a (meth) acrylic resin are preferable, a phenoxy resin and a polyimide resin are more preferable, and a phenoxy resin is especially preferable. Here, “(meth) acryl” includes both “acryl” and “methacryl”.

  In the present invention, the glass transition temperature (Tg) of the thermoplastic resin is -20 to 120 ° C. The glass transition temperature of the thermoplastic resin is preferably -10 to 110 ° C, more preferably 0 to 110 ° C. If the glass transition temperature is less than the lower limit, there is no problem in the filling property after a long wire bonding process, but the tack in the state before curing of the adhesive film for a semiconductor is too large, and the chip with the adhesive film is an adhesive. In some cases, the layer cannot be peeled off. When the upper limit is exceeded, flexibility is lost, and even if the progress of curing of the adhesive film is suppressed, the elasticity may be high and the filling property may be lowered.

(Phenoxy resin)
The phenoxy resin is preferably a resin obtained by reacting various bisphenols with epichlorohydrin. Examples of the bisphenol include bisphenol A, bisphenol bisphenol AF, bisphenol AD, bisphenol F, and bisphenol S.
A resin preferable as the phenoxy resin used in the present invention is a resin having a repeating unit represented by the following general formula (P).

In general formula (P), X represents a single bond or a divalent linking group.
Examples of the divalent linking group include an alkylene group, a phenylene group, —O—, —S—, —SO—, and —SO ₂ —.
Here, the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably —C (R ^a ) (R ^b ) —. R ^a and R ^b each independently represents a hydrogen atom or an alkyl group, and the alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl , Isooctyl, 2-ethylhexyl, 1,3,3-trimethylbutyl and the like. The alkyl group may be substituted with a halogen atom, and examples thereof include a trifluoromethyl group.
X is preferably an alkylene group, —O—, —S— or —SO ₂ —, more preferably an alkylene group, —SO ₂ —. Of _{these, -C (CH 3) 2 -} , - CH (CH 3) -, - CH 2 -, - SO 2 - are _{preferred, -C (CH 3) 2 -} , - CH (CH 3) -, - CH ₂ — is more preferable, and —C (CH ₃ ) ₂ — is particularly preferable.

As long as the phenoxy resin used in the present invention has a repeating unit represented by the general formula (P), even if any X is a resin having a plurality of different repeating units, X is the same. You may be comprised only from the repeating unit.
In the present invention, a resin in which X is composed of only the same repeating unit is preferable.

  The mass average molecular weight of the phenoxy resin used in the present invention is preferably 5,000 to 150,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 100,000. The glass transition temperature (Tg) is preferably -40 to 110 ° C, more preferably -20 to 110 ° C, more than 50 ° C, more preferably 110 ° C or less, and still more preferably 55 to 110 ° C.

  Examples of the phenoxy resin include PKHB, PKHC, PKHH, PKHJ, PKFEPHHP-200 manufactured by InChem, and YP-50, YP-50S, and YP-55U manufactured by Nippon Steel Chemical Co., Ltd.

(Polyimide resin)
The polyimide resin may have any structure as long as the glass transition temperature (Tg) satisfies −20 to 120 ° C. The glass transition temperature (Tg) of the polyimide resin is preferably 0 to 120 ° C.
Examples of the polyimide resin include those condensed with an anhydride of a divalent or higher carboxylic acid compound and a diamine compound, and the dianhydride of a tetracarboxylic acid compound is preferable as the anhydride of the divalent or higher carboxylic acid compound. Examples of dianhydrides of tetracarboxylic acid compounds include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2 -Bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4, 5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9, 10-perylenetetra Aromatic tetracarboxylic acid compounds such as carboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 4,4'-hexafluoroisopropylidenediphthalic anhydride These dianhydrides can be used, and these can be used alone or in combination of two or more.

  On the other hand, the diamine compound may be an aromatic diamine compound or an aliphatic diamine compound, such as m-phenylene diamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis (3-aminophenyl) sulfide. , (3-aminophenyl) (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3 -Aminophenyl) sulfone, bis (4-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'- Diaminodiphenylmethane, 3,4'-di Minodiphenylmethane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4- Aminophenoxy) benzene, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4 -(4-aminophenoxy) phenyl] ketone,

Bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (4-amino Phenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, 1, 4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl Diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether 3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino-5,5′-diphenoxybenzophenone, 3,4′-diamino-4,5′-diphenoxybenzophenone, 3, , 3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3, 3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3 ' -Diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-dia Mino-4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4 -Bipheno) oxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,3-bis ( 3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, bis (trifluoromethyl) -1,1′-biphenyl-4,4′-diamine These may be used alone or in combination of two or more.

As the polyimide resin, various modified polyimide resins are also preferable, and examples thereof include allyl-modified polyimide resins.
The average mass molecular weight of the polyimide resin is preferably 5,000 to 200,000, more preferably 5,000 to 150,000, and still more preferably 10,000 to 120,000.

  In the polyimide resin, the molar ratio of the carboxylic acid compound anhydride to the diamine compound (carboxylic acid compound anhydride / diamine compound) is preferably 1.0 / 1.2 to 1.2 / 1.0, 1.0 /1.1 to 1.1 / 1.0 is more preferred, and substantially equimolar (1.0 / 1.0) is still more preferred.

((Meth) acrylic resin)
(Meth) acrylic resin means a resin [(meth) acrylic resin] having at least a repeating unit obtained from (meth) acrylic acid and derivatives thereof, specifically acrylic acid, methacrylic acid, methyl acrylate, Examples thereof include acrylic acid esters such as ethyl acrylate, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, polymers such as acrylonitrile and acrylamide, and copolymers with other monomers.
The epoxy group, a hydroxyl group, a carboxyl group, having a functional group such as nitrile group (meth) acrylic resin [particularly, (meth) acrylic acid copolymer] is preferred.
By having a functional group, the adhesion to an adherend such as a semiconductor element can be further improved and the filling property can be improved. As the functional group compound having include glycidyl methacrylate having a glycidyl ether group, hydroxy methacrylate having a hydroxyl group, carboxy methacrylate having a carboxyl group, acrylonitrile having a nitrile group.
In the present invention, the functional group is preferably a nitrile group from the viewpoint of heat resistance history.
Furthermore, in this invention, it is more preferable to have an epoxy group (preferably glycidyl group) with a nitrile group, and more specifically, it has a repeating unit obtained from (meth) acrylonitrile and glycidyl (meth) acrylate (meta) ) Acrylic resin is preferred.

  The content of the compound having a functional group is not particularly limited, but is preferably 0.5 to 50% by mass, and particularly preferably 5 to 30% by mass, based on the entire (meth) acrylic resin. If the content is less than the lower limit, the heat resistance history may be insufficient, and if the content exceeds the upper limit, the flexibility is lost, and even if the progress of curing of the adhesive film is suppressed, the elasticity is high and the filling property is lowered. There is a case.

The mass average molecular weight of the thermoplastic resin used in the present invention, preferably the (meth) acrylic resin, is not particularly limited, but is preferably 50,000 or more, particularly preferably 50,000 to 1,200,000. When the mass average molecular weight is within the above range, it is possible to achieve both releasability and filling property particularly from the pressure-sensitive adhesive layer of the adhesive film for semiconductor.
Moreover, although the glass transition temperature (Tg) of (meth) acrylic-type resin used by this invention is -20-120 degreeC, -20-110 degreeC is preferable and -20-100 degreeC is more preferable.

  Although content of a thermoplastic resin is not specifically limited, The ratio of 10-1000 mass parts is preferable with respect to 100 mass parts of hardening components which totaled all the hardening | curing agents to contain the said epoxy resin, and especially 30-300 mass parts. Is preferred. When the content of the thermoplastic resin is less than the lower limit, it may be difficult to form a film shape, and when the content exceeds the upper limit, the fillability may be reduced.

<Epoxy resin>
As the epoxy resin used in the present invention, various conventionally known polyepoxy compounds can be used. For example, bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4-hydroxy-3,5-dibromophenyl) propanedi Glycidyl ether, bis (4-hydroxyphenyl) ethane diglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, resorcinol diglycidyl ether, phloroglicinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, tetraglycidyl benzophenone, Bisresorcinol tetraglycidyl ether, tetramethylbisphenol A diglycidyl ether, bisphenol C diglycidyl ether, bisphenol hexafluoropro Diglycidyl ether, 1,3-bis [1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl] benzene, 1,4-bis [1- (2 , 3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl] benzene, 4,4′-bis (2,3-epoxypropoxy) octafluorobiphenyl, phenol novolac bisepoxy compound Arocyclic polyepoxy compounds such as aromatic glycidyl ether compounds, alicyclic diepoxy acetals, alicyclic diepoxy adipates, alicyclic diepoxy carboxylates, vinylcyclohexene dioxide, diglycidyl phthalate, diglycidyl Tetrahydrophthalate, diglycidyl hexahydride Glycidyl ester compounds such as phthalate, dimethyl glycidyl phthalate, dimethyl glycidyl hexahydrophthalate, diglycidyl-p-oxybenzoate, diglycidyl cyclopentane-1,3-dicarboxylate, dimer acid glycidyl ester, diglycidyl aniline, diglycidyl toluidine, Examples thereof include glycidylamine compounds such as triglycidylaminophenol, tetraglycidyldiaminodiphenylmethane, diglycidyltribromoaniline, and heterocyclic epoxy compounds such as diglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and triglycidylisocyanurate.

<Curing agent>
In the present invention, the curing agent contains a complex compound formed from an aromatic carboxylic acid compound having at least two carboxyl groups and an imidazole compound, and in addition to the complex compound, an aromatic carboxylic acid compound or an imidazole compound. Containing.

(Composite compound)
The complex compound is a complex of the aromatic carboxylic acid compound and the imidazole compound, and the complex is preferably an clathrate or a salt, more preferably an clathrate. The clathrate is prepared by using an aromatic carboxylic acid compound and an imidazole compound as raw materials in a solvent (for example, methanol, ethanol, acetone, ethyl acetate, etc.) as described in, for example, the re-published patent WO2009 / 037862. It can be dissolved, heated to reflux for several hours, cooled, and the resulting crystals are filtered off and dried. Moreover, formation of the clathrate can be confirmed by ¹ H-NMR, TG-DTA (differential thermal-thermogravimetric measurement) and XRD (X-ray diffraction). Moreover, it can be confirmed by infrared absorption spectrum (IR), solid NMR spectrum, etc., and the composition of the complex (particularly the inclusion body) is thermal analysis, ¹ H-NMR spectrum, high performance liquid chromatography (HPLC), elemental analysis, etc Can be confirmed.

The aromatic carboxylic acid compound having at least two carboxyl groups forming the composite compound may be any aromatic carboxylic acid as long as it has at least two carboxyl groups. Here, the aromatic carboxylic acid compound has an aromatic ring, and examples of the aromatic ring include a benzene ring and a naphthalene ring, and a benzene ring is preferable.
The aromatic ring may have a substituent other than a carboxyl group. Such substituents include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, acyl groups, alkylsulfonyl groups, arylsulfonyl groups, amino groups. Group (including alkylamino group, arylamino group and heterocyclic amino group), acylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, halogen atom, hydroxyl group, cyano group , A nitro group, a sulfo group and the like.
In addition, these aromatic rings may be condensed with an alicyclic ring, an aromatic ring or a heterocyclic ring.
In the present invention, the aromatic carboxylic acid compound preferably has 2 to 4 carboxyl groups, more preferably 2 or 3, and particularly preferably 2 compounds.

  As an aromatic carboxylic acid compound having at least two carboxyl groups, a preferred compound is a compound represented by the following general formula (I).

In general formula (I), m represents an integer of 0 to 4, n represents an integer of 2 to 4, and m ≦ n and m + n ≦ 6. R ¹ represents a substituent. When m is 2 or more, the plurality of R ¹ may be the same or different from each other, and these may be bonded to each other to form a ring.
The substituent is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a nitro group or a hydroxyl group. The above preferred substituents will be further described below.

The alkyl group is a linear or branched alkyl group, which may have a substituent, and preferably has 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms.
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, cyclopropylmethyl, pentyl, isopentyl, 2-methylbutyl, neopentyl, hexyl, isohexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl and the like can be mentioned.

The cycloalkyl group may have a substituent, and the number of carbon atoms is preferably 3 to 12, and more preferably 5 to 12.
Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, 1-ethylpropyl, cyclopentyl, cyclohexyl and the like.

The alkoxy group may have a substituent, and the number of carbon atoms is preferably 1 to 12, and more preferably 1 to 4.
Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentoxy, isopentoxy, 2-methylbutoxy, 1-ethylpropoxy, 2-ethylpropoxy, neopentoxy, hexyl. Oxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 3,3-dimethylbutoxy, 2,2-dimethylbutoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1, Examples include 3-dimethylbutoxy and 2,3-dimethylbutoxy.

Examples of the substituent that the alkyl group, cycloalkyl group, and alkoxy group may have include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, and an alkylsulfonyl group. Group, arylsulfonyl group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), acylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, Examples include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a sulfo group, and a carboxyl group.
In the present invention, an unsubstituted alkyl group, an unsubstituted cycloalkyl group, and an unsubstituted alkoxy group are preferred.

R ¹ is preferably an alkyl group, an alkoxy group, a nitro group or a hydroxyl group.
m represents an integer of 0 to 4, preferably 0 to 2, and more preferably 0 to 1.
n represents an integer of 2 to 4, preferably 2 and 3, and more preferably 2.

  Among the aromatic carboxylic acid compounds represented by the general formula (I), a preferable compound can be represented by the following general formula (II).

In general formula (II), R ¹ represents a substituent.
R ¹ has the same meaning as R ¹ in formula (I), and the preferred range is also the same.

Examples of the aromatic carboxylic acid compound represented by the general formula (II) include isophthalic acid, terephthalic acid, 5-t-butylisophthalic acid, 5-nitroisophthalic acid, 5-hydroxyisophthalic acid, trimellitic acid, and trimesin. Preferred examples include acid and pyromellitic acid.
In the present invention, in the aromatic carboxylic acid compound represented by the general formula (I), m is an integer of 2 to 4, n is an integer of 2 to 4, and m ≦ n and m + n ≦ 6. It is. R ¹ is a substituent, but the two R ¹ are bonded to each other to form a ring.

The imidazole compound forming the composite compound may have any structure and any substituent as long as it has an imidazole skeleton.
The imidazole compound used in the present invention is preferably an imidazole compound represented by the following general formula (III).

In general formula (III), R ² represents a hydrogen atom, an alkyl group or an aryl group, and R ^{3 to} R ⁵ each independently represents a hydrogen atom or a substituent. Here, R ³ and R ⁴ may be bonded to each other to form a ring. Examples of such a ring include a benzene ring and a heterocycle.
As a substituent in R < ³ > -R < ⁵ >, the substituent which the alkyl group, cycloalkyl group, and alkoxy group in general formula (I) may have is mentioned.

The alkyl group in R ² is a linear or branched alkyl group which may have a substituent, the carbon number is preferably from 1 to 20, more preferably 1 to 12, 1 to 4 is more preferable.
The aryl group in R ² may have a substituent, and the carbon number is preferably 6 to 20, more preferably 6 to 12. Examples of the aryl group include phenyl and naphthyl, and a phenyl group which may have a substituent is preferable.
Examples of the substituent that the alkyl group or aryl group in R ² may have include a substituent that the alkyl group, cycloalkyl group, or alkoxy group in general formula (I) may have.
In the present invention, the alkyl group in R ² is preferably an unsubstituted or substituted alkyl group, and more preferably an unsubstituted alkyl group. The aryl group for R ² is preferably an unsubstituted aryl group.
In the present invention, R ² is most preferably a hydrogen atom.
R ^{3 to} R ⁵ are preferably a hydrogen atom, an alkyl group, an aryl group, or a hydroxyl group.

Among the imidazole compounds represented by the general formula (III), R ² is preferably a hydrogen atom, and R ^{3 to} R ⁵ are preferably a hydrogen atom, an aryl group, or a hydroxyl group. Among these, R ³ is a hydrogen atom or an alkyl group. Alternatively, an aryl group is preferable, R ⁴ is preferably a hydrogen atom or an alkyl group, and R ⁵ is preferably a hydrogen atom or a hydroxyl group.
The imidazole compound represented by the general formula (III) is more preferably R ² is a hydrogen atom, R ³ and R ⁴ are substituents, and R ⁵ is a hydrogen atom. ^It is preferable that ² is a hydrogen atom, R ³ is an alkyl group or an aryl group, and R ⁴ is a hydrogen atom or an alkyl group.

  Examples of the imidazole compound include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4 -Ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutyl Imidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-di Tyrimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-phenylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, etc. It is done.

  Among these, an imidazole compound selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole is more preferable. .

The composite compound of the aromatic carboxylic acid compound and the imidazole compound is not particularly limited as long as it is in the above range, but among them, isophthalic acid, terephthalic acid, 5-t-butylisophthalic acid, 5 -An aromatic compound which is at least one selected from the group consisting of nitroisophthalic acid, 5-hydroxyisophthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, 2-methylimidazole, 2-ethyl-4-methyl It is more preferably a combination or complex with at least one imidazole compound selected from the group consisting of imidazole, 2-undecylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.
Here, in the present invention, the complex exhibits an action of controlling the reaction start temperature, and shifts the curing action to a high temperature side.

The ratio of the aromatic carboxylic acid compound and the imidazole compound in the composite compound is not particularly limited as long as a complex (preferably an inclusion compound) can be formed, but with respect to 1 mol of the aromatic carboxylic acid compound. The imidazole compound is preferably 0.1 to 5.0 mol, and more preferably 0.5 to 4.0 mol.
However, in this invention, an imidazole compound is 0.1-1 mol with respect to 1 mol of said aromatic carboxylic acid compounds.

The 50% particle size of the composite compound (particularly the inclusion body) is not particularly limited, but is usually about 0.01 to 30 μm, preferably about 0.01 to 20 μm, more preferably about 0.1 to 10 μm. . When the average particle diameter exceeds about 30 μm, the composite (particularly inclusion body) particles protrude as foreign substances from the film surface during film production, which is not preferable.
The 50% particle diameter represents the particle diameter μm at which the cumulative curve is 50% when the cumulative curve is obtained with the powder population as 100%.

  The content of the composite compound may be the same amount used as a normal curing agent or curing accelerator, and depends on the curing method. In the case of an addition-type curing agent in which a curing agent molecule is always incorporated into a cured resin by reacting with an epoxy group, a composite compound is usually added to 1 mol of an epoxy group, depending on the properties of the required resin. The constituting imidazole compound (curing agent and / or curing accelerator) is preferably 0.3 to 5.0 mol. In addition, in the case of a polymerization type curing agent or a photoinitiated type curing agent that induces a polymerization addition reaction between oligomers without causing the curing agent molecule to be incorporated into the resin, it is also a curing accelerator. In the case of using as a complex compound, 1.0 mol or less of the composite compound is sufficient for 1 mol of the epoxy group. If the content is less than the lower limit, the curability may be insufficient, and if the content exceeds the upper limit, the heat resistance of the cured product may be reduced. These composite compounds can be used alone or in combination of two or more.

(Aromatic carboxylic acid compounds or imidazole compounds other than complex compounds)
In the present invention, an aromatic carboxylic acid compound or an imidazole compound is contained in addition to the composite compound.

As the aromatic carboxylic acid compound, any aromatic carboxylic acid having one or more carboxyl groups may be used. For example, the benzoic acid which may have a substituent, and the aromatic carboxylic acid compound which has two or more carboxyl groups which comprise a composite compound are mentioned.
The aromatic carboxylic acid compound is preferably an aromatic carboxylic acid compound having two or more carboxyl groups, and in particular, an aromatic carboxylic acid compound having the same structure as the aromatic carboxylic acid compound constituting the composite compound is preferable.

An imidazole compound is synonymous with the imidazole compound which comprises a composite compound, and its preferable range is also the same.
In the present invention, an imidazole compound having the same structure as the imidazole compound constituting the composite compound is particularly preferable.
Moreover, an imidazole compound is preferable among the said compounds used together with the said composite compound.

  These aromatic carboxylic acid compounds or imidazole compounds are preferably contained in an amount of 100 moles or less, particularly preferably 0.1 to 80 moles, more preferably 10 moles per 100 moles of the composite compound. It is preferable to contain in the ratio of -50 mol.

(Other curing agents)
In this invention, although it contains the said composite compound and an aromatic carboxylic acid compound or an imidazole compound, you may further contain the hardening | curing agent of another structure other than this. The curing agent is not particularly limited as long as it is a compound that reacts with an epoxy group in the epoxy resin to cure the epoxy resin. As such a hardening | curing agent, arbitrary things can be selected and used from what is conventionally used as a hardening | curing agent of the conventional epoxy resin. For example, amine compounds or polyamine compounds (compounds having two or more amino groups) such as aliphatic amines, alicyclic and heterocyclic amines, aromatic amines, modified amines, imidazoline compounds, amides Compound, ester compound, phenol compound, alcohol compound, thiol compound, ether compound, thioether compound, urea compound, thiourea compound, Lewis acid compound, phosphorus compound, acid anhydride compound, Examples thereof include onium salt compounds and active silicon compounds-aluminum complexes.

Specific examples of such a curing agent include the following compounds.
Examples of aliphatic amines include ethylenediamine, trimethylenediamine, triethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, dimethylaminopropylamine, diethylaminopropylamine, Trimethylhexamethylenediamine, pentanediamine, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, alkyl-t-monoamine, 1,4-diazabicyclo (2,2,2) octane (triethylenediamine), N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylethylenediamine , N, N-dimethylcyclohexylamine, dibutylaminopropylamine, dimethylaminoethoxyethoxy, triethanolamine, dimethylaminohexanol, and the like.

  Examples of alicyclic and heterocyclic amines include piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-s-triazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis (4-aminocyclohexyl) methane N, N′-dimethylpiperazine, 1,8-diazabicyclo (4,5,0) undecene-7, and the like.

Examples of aromatic amines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine, picoline, α- And methylbenzylmethylamine.
Examples of the modified amines include epoxy compound-added polyamine, Michael addition polyamine, Mannich addition polyamine, thiourea addition polyamine, ketone-capped polyamine, dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amine imide, boron trifluoride-piperidine. Complex, boron trifluoride-monoethylamine complex, etc. are mentioned.

Examples of the imidazoline-based compound include 2-methylimidazoline, 2-phenylimidazoline, and the like.
Examples of the amide compound include polyamide obtained by condensation of dimer acid and polyamine.
Examples of the ester compounds include active carbonyl compounds such as aryl and thioaryl esters of carboxylic acids.

Examples of phenol compounds, alcohol compounds, thiol compounds, ether compounds, and thioether compounds include phenol resin curing agents, aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins, and phenol novolac resins. , Novolac type phenol resins such as cresol novolac resin, these modified resins, for example, epoxidized or butylated novolac type phenol resin, dicyclopentadiene modified phenol resin, paraxylene modified phenol resin, triphenol alkane type phenol resin, Examples thereof include functional phenol resins. In addition, polyol, polymercaptan, polysulfide, 2- (dimethylaminomethylphenol), 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol tri-2- And ethyl hexyl hydrochloride.
Examples of the urea compound, thiourea compound, and Lewis acid compound include butylated urea, butylated melamine, butylated thiourea, boron trifluoride, and the like.

  Examples of the phosphorus compound include organic phosphine compounds, for example, alkylphosphine such as ethylphosphine and butylphosphine, first phosphine such as phenylphosphine, dialkylphosphine such as dimethylphosphine and dipropylphosphine, diphenylphosphine such as diphenylphosphine, and methylethylphosphine. 2 phosphine; tertiary phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine, and the like.

  Examples of the acid anhydride compound include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride. Acid, maleic anhydride, tetramethylene maleic anhydride, trimellitic anhydride, chlorendic anhydride, pyromellitic anhydride, dodecenyl succinic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (Anhydro trimellitate), methylcyclohexene tetracarboxylic acid anhydride, polyazeline acid anhydride and the like.

  Examples of onium salt compounds and active silicon compounds-aluminum complexes include aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, triphenylsilanol-aluminum complexes, triphenylmethoxysilane-aluminum complexes, and silyl peroxides. An aluminum complex, a triphenylsilanol-tris (salicylide aldehyde) aluminum complex, etc. are mentioned.

  As the curing agent, it is particularly preferable to use an amine compound, an acid anhydride compound, or a phenol compound. Among amine compounds, polyamine compounds having two or more amino groups are preferable, and among phenol compounds, it is more preferable to use a phenol resin curing agent.

The adhesive film of the present invention preferably contains an inorganic filler.
The inorganic filler is not particularly limited. For example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker , Boron nitride, crystalline silica, amorphous silica and the like. These may be used alone or in combination of two or more. In order to improve thermal conductivity, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, amorphous silica and the like are preferable. Silica is preferable from the viewpoint of balance of properties.

The average particle size of the inorganic filler is preferably 0.005 to 10 μm, more preferably 0.01 to 5 μm, and still more preferably 0.04 to 2 μm. In addition, in this invention, an average particle diameter means the average value calculated | required from the particle size of 100 inorganic fillers measured with the transmission electron microscope (TEM), the scanning electron microscope (SEM), etc.
In the present invention, the content of the inorganic filler is preferably 150 parts by mass or less (preferably 0.1 to 150 parts by mass), preferably 100 parts by mass or less, with respect to 100 parts by mass of the total amount of the thermoplastic resin and the epoxy resin. (Preferably 0.1 to 100 parts by mass) is more preferable, 50 parts by mass or less (preferably 0.1 to 50 parts by mass) is further preferable, and 20 parts by mass or less (preferably 0.1 to 20 parts by mass) is preferable. Particularly preferred.
Inorganic fillers are commercially available, for example, from Toa Gosei Co., Ltd., Nippon Aerosil Co., Ltd., CI Kasei Co., Ltd., Nippon Seiko Co., Ltd., and the like.

The adhesive film preferably further contains a coupling agent. Thereby, the adhesiveness between the resin and the adherend and between the resin and the silica interface can be improved.
Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, among which silane-based coupling agents are preferable.

  Examples of the coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxy. Propylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N- β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl -Γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and the like.

Although content of the said coupling agent is not specifically limited, 0.01-10 mass parts is preferable with respect to 100 mass parts of said epoxy resins, and 0.5-10 mass parts is especially preferable.
If the content is less than the lower limit, the effect of adhesion after filling may be insufficient, and if it exceeds the upper limit, it causes outgassing, and voids occur even if the adhesive film has sufficient fillability. There is a case.

The adhesive film of the present invention is, for example, a carrier film using a comma coater, a die coater, a gravure coater, etc. after dissolving the resin composition in a solvent such as methyl ethyl ketone, acetone, toluene, dimethylformaldehyde, etc. It is obtained by coating and drying.
Although the thickness of the said adhesive film for semiconductors is not specifically limited, 3-100 micrometers is preferable and 5-70 micrometers is especially preferable. When the thickness is within the above range, it is particularly easy to achieve both fillability and thinning.

<Adhesive film and manufacturing method thereof>
The adhesive film of the present invention comprises at least one thermoplastic resin having an glass transition temperature of -20 to 120 ° C, an epoxy resin, an aromatic carboxylic acid compound having at least two carboxyl groups as a curing agent, and an imidazole compound. Produced by the step of preparing a dispersion by mixing an aromatic carboxylic acid compound or an imidazole compound with a solvent in addition to the composite compound formed, a step of applying the dispersion on a carrier film, and a drying step can do.
Examples of the solvent include solvents such as methyl ethyl ketone, acetone, toluene, dimethylformaldehyde and the like, and a dispersion in a varnish state obtained by mixing and dispersing these is used as a carrier using a comma coater, a die coater, a gravure coater, or the like. It is obtained by coating on a film and drying.

In addition, although what is used with the adhesive film for semiconductors is used as a carrier film, polyester like a polyethylene terephthalate is preferable and polyester which has mold release property is preferable.
Although the thickness of an adhesive film is not specifically limited, 2-150 micrometers is preferable, 3-100 micrometers is preferable, and 5-70 micrometers is especially preferable. When the thickness is within the above range, it is particularly easy to achieve both fillability and thinning.

<Wafer processing tape>
The adhesive film of the present invention is preferably used as a wafer processing tape in which this adhesive film and a supporting substrate having at least one pressure-sensitive adhesive layer are laminated.
A commercially available dicing tape can be used for the support base material which has such an adhesive layer.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

(Synthesis of complex compounds)
[Composite Compound 1]
To a 3 L three-necked flask were added 180.0 g of 5-tert-butylisophthalic acid, 107.1 g of 2-ethyl-4-methylimidazole, and 810 ml of methanol, and the mixture was stirred and heated to reflux for 3 hours. After cooling, filtration and vacuum drying were performed to obtain 201.3 g of 5-tert-butylisophthalic acid / 2-ethyl-4-methylimidazole (1: 1) composite compound 1.

[Composite Compound 2]
To a 3 L three-necked flask were added 43.2 g of 1,4-naphthalenedicarboxylic acid, 44.5 g of 2-undecylimidazole, and 1000 ml of ethyl acetate, and the mixture was stirred and heated to reflux for 3 hours. After cooling, 85.9 g of 1,4-naphthalenedicarboxylic acid / 2-undecylimidazole (1: 1) composite compound 2 was obtained by filtration and vacuum drying.

[Preparation of curing agent]
[Curing agent group A-1]
A combination of 0.1 mol of 2-ethyl-4-methylimidazole with respect to 100 mol of composite compound 1 was designated as curing agent A-1.

[Curing agent group A-2 to A-6]
Curing agents A-2 to A-6 were further prepared in combinations as shown in Table 1.

  In the table, “2E4MZ” means 2-ethyl-4-methylimidazole, and “C11Z” means 2-undecylimidazole.

[Synthesis of polyimide resin]
<Synthesis Example 1>
In a 500 ml flask equipped with a thermometer, stirrer and calcium chloride tube was added 41.05 g (0.1 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 150 g of N-methyl-2-pyrrolidone. Were stirred. After dissolution of the diamine, 52.2 g (0.1 mol) of 1,10- (decamethylene) bis (trimellitate anhydride) was added in small portions while the flask was cooled in an ice bath. After reacting at room temperature for 3 hours, 30 g of xylene was added, and heated at 150 ° C. while blowing nitrogen gas to azeotropically remove xylene together with water. The reaction solution was poured into water, and the precipitated polymer was filtered off and dried to obtain polyimide resin PI-1. PI-1 had a glass transition temperature (Tg) of 120 ° C. and a mass average molecular weight of 120,000.

[Measurement of Tg]
Measurement was carried out using a suggestion scanning calorimeter (hereinafter abbreviated as DSC) (Perkin Elmer, DSC-7 type) at a temperature elevation rate of 10 ° C./min.
(Mass average molecular weight)
It was measured by gel permeation chromatography (hereinafter abbreviated as GPC) and converted to standard polystyrene.

<Synthesis Example 2>
Into a 1 liter four-necked flask equipped with a stirrer, a nitrogen introducing tube, and a drying tube was placed 41.0 g (0.10 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane. In a nitrogen stream, 250 g of N-methyl-2-pyrrolidone was added to make a solution. The flask was transferred to a water bath, and 41.0 g (0.10 mol) of 1,2- (ethylene) bis (trimellitate dianhydride) was added little by little with vigorous stirring. When the acid dianhydride was almost dissolved, the reaction was performed for 6 hours with slow stirring to obtain a polyamic acid solution. Next, a distillation apparatus was attached to the four-necked flask containing the polyamic acid solution, and 220 g of xylene was added. Condensed water produced by imidization was distilled off azeotropically with xylene while stirring vigorously in an oil bath at 180 ° C. under a nitrogen stream. The reaction solution was poured into water, and the precipitated polymer was separated by filtration and dried to obtain polyimide resin PI-2. PI-2 had a glass transition temperature (Tg) of 180 ° C. and a mass average molecular weight of 150,000.

(Examples 1-13, Comparative Examples 1-5)
<Preparation of adhesive film>
Methyl ethyl ketone was added to each adhesive composition having the formulation shown in Table 2 below, followed by stirring and mixing to prepare each adhesive varnish. This adhesive varnish was coated on a release film so that the thickness after drying was 10 μm, and dried at 110 ° C. for 3 minutes to prepare each adhesive film. Next, the release film was peeled from the adhesive film to produce adhesive films of Examples 1 and 2, Reference Examples 1 to 11 and Comparative Examples 1 to 5.

  In Table 2, the unit of the blending ratio of each component is part by mass. Moreover, the following were used for each component. Here, “epoxy” described in Table 2 is an epoxy resin.

Phenoxy resin: PKHH (trade name, INCHEM, weight average molecular weight 52000, glass transition temperature 90 ° C.)
Polyimide resin 1: PI-1 (mass average molecular weight 120,000, glass transition temperature 120 ° C.)
Polyimide resin 2: PI-2 (mass average molecular weight 150,000, glass transition temperature 180 ° C.)
Acrylic resin 1: SG-70L (trade name, manufactured by Nagase ChemteX Corporation, mass average molecular weight 900000, glass transition temperature -13 ° C)
Acrylic resin 2: W-166.3 (trade name, manufactured by Negami Kogyo Co., Ltd., mass average molecular weight 900000, glass transition temperature −22 ° C.)

Epoxy resin: 828 (trade name, manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 187 g / eq)
Inorganic filler: SO-C2 (trade name, manufactured by Admafine Co., Ltd., average particle size 0.5 μm)

  In Table 2, “C-10” is an amine compound diaminodiphenylsulfone (manufactured by Konishi Chemical Co., Ltd.), and “MT-500” is an anhydrous oxide compound methyltetrahydrophthalic anhydride ( New Nippon Rika Co., Ltd.) and MEH-7800-S are xylylene novolacs (Maywa Kasei Co., Ltd.) which are phenolic compounds.

(Reliability test)
(Manufacture of semiconductor devices)
Examples 1, 2, Reference Examples 1 to 11 and each adhesive film of Comparative Example 1-5, manufactured by a commercially available dicing tape as a supporting substrate having a pressure-sensitive adhesive layer (Furukawa Electric Co., Ltd., trade name: UC-334EP-110) was pre-cut to produce wafer processing tapes, and each adhesive film portion was bonded to a semiconductor wafer. Subsequently, after dicing the semiconductor wafer and the adhesive film using a dicer, the substrate is irradiated with ultraviolet rays (300 mJ / cm ² ) to separate the adhesive film and the adhesive layer from each other. A semiconductor chip with an adhesive film was obtained.

Each obtained semiconductor chip with an adhesive film was thermocompression bonded to the 42-alloy alloy lead frame through the adhesive film at 130 ° C. while applying a force of 0.1 MPa for 0.5 seconds. Then, it heated for 1 and 3 hours on a 160 degreeC hotplate, and gave the thermal history equivalent to wire bonding.
Next, resin sealing was performed using epoxy sealing resin (trade name: CEL-9700HF, manufactured by Hitachi Chemical Co., Ltd.) under the conditions of 180 ° C., 6.75 MPa, 90 seconds, and a semiconductor device sample was 100 Individually manufactured. Thus, Example 1, 2, using the adhesive film of Reference Examples 1 to 11 and Comparative Examples 1 to 5, respectively, in Example 1, 2, Reference Examples 1 to 11 and Comparative Examples 1 to 5 Semiconductor A sample of the device was obtained.

Next, for each sample, using an ultrasonic exploration imaging device, the presence or absence of voids between the lead frame after resin sealing and the adhesive film, and solder reflow treatment for each sample, the adhesive film It was evaluated whether or not peeled off from the lead frame.
The evaluation was performed under two conditions: when heated at 160 ° C. for 1 hour (in Table 3, “1 hour”) and when heated at 160 ° C. for 3 hours (in Table 3, “3 hours”).
The obtained results are shown in Table 3 below. In Table 3, ○ indicates that no voids or peeling was confirmed in all 100 pieces, and × indicates that one or more voids or peeling was confirmed.

(Shearing adhesive strength)
By the method similar to the said reliability test, the semiconductor chip with an adhesive film of Example 1 , 2, Reference Examples 1-11, and Comparative Examples 1-5 was obtained. The semiconductor chip was 5 mm long × 5 mm wide × 0.5 mm thick. The obtained semiconductor chip with an adhesive film was thermocompression bonded at a pressure of 0.1 MPa at 130 ° C. for 0.5 seconds to a 42-alloy alloy lead frame through the adhesive film, and then at 180 ° C. for 1 hour. Under the heat treatment, the adhesive film was thermally cured.

After heat curing, a shear strength at a stage temperature of 260 ° C., a head height of 25 μm, and a speed of 0.5 mm / sec was measured using a bond tester (DAGE, # 4000).
The obtained results are shown in Table 3 below. In Table 3, ◯ indicates that the shear adhesive strength is 3.0 MPa or more, and X indicates that the shear adhesive strength is less than 3.0 MPa.

(Pre-cut processing)
Each of the produced adhesive films was subjected to circular precut processing with a diameter of 220 mm by adjusting the cut depth into the polyester film to 10 μm or less. Thereafter, an unnecessary part of the adhesive film is removed, and a commercially available ultraviolet curable dicing tape (manufactured by Furukawa Electric Co., Ltd., trade name: UC-334EP-110) is used as a supporting base material having an adhesive layer. Lamination was performed at room temperature so as to contact the adhesive film. And the tape for wafer processing was produced by adjusting so that the cutting depth to a polyester film might be 10 micrometers or less with respect to a support base material, and performing the circular precut process of diameter 290mm concentrically with an adhesive film.

In Comparative Example 1, both the shear adhesive strength and the adhesive strength during reflow were insufficient, and reliability was not obtained. In Comparative Examples 2, 3, and 5, the shear adhesive strength was not sufficiently obtained due to insufficient curing power, and thus peeling occurred after reflow. In Comparative Example 4, the curing proceeded excessively, and the adhesive force was insufficient for the curing shrinkage force, so that peeling occurred after reflow.
On the other hand, both Examples 1 and 2 of the present invention were excellent in shearing adhesive strength, were free of voids after resin sealing, and were not observed after reflow.

Claims (14)

It contains at least one thermoplastic resin having an glass transition temperature of -20 to 120 ° C., an epoxy resin and a curing agent, and the curing agent is represented by the following general formula (I) having at least two carboxyl groups. A composite compound formed from an aromatic carboxylic acid compound and an imidazole compound , wherein the imidazole compound is 0.1 to 1 mole relative to 1 mole of the aromatic carboxylic acid compound, and in addition to the composite compound, An adhesive film comprising an aromatic carboxylic acid compound or an imidazole compound.

(In general formula (I), m represents an integer of 2 to 4, n represents an integer of 2 to 4, and m ≦ n and m + n ≦ 6. R ¹ represents a substituent. R ¹ is bonded to each other to form a ring.)   The adhesive according to claim 1, wherein the aromatic carboxylic acid compound or imidazole compound contained other than the composite compound is a compound having the same structure as the aromatic carboxylic acid compound or imidazole compound forming the composite compound. the film.   The aromatic carboxylic acid compound or imidazole compound contained in addition to the composite compound is contained at a ratio of 0.1 to 80 moles with respect to 100 moles of the composite compound. Adhesive film.   The adhesive film according to any one of claims 1 to 3, wherein the aromatic carboxylic acid compound or imidazole compound contained other than the composite compound is an imidazole compound. The aromatic carboxylic acid compound represented by the general formula (I) that forms the composite compound is 1,4-naphthalenedicarboxylic acid, according to any one of claims 1 to 4. Adhesive film. The adhesive film of the at least one thermoplastic resin, phenoxy resin, according to any one of claims 1 to 5, wherein the imide resin or (meth) acrylic resin. For all of the total amount 100 parts by weight of the curing agent containing said epoxy resin, any one of claim 1 to 6, characterized in that it contains the thermoplastic resin at a ratio of 10 to 1000 parts by weight The adhesive film as described. 8. The content of the imidazole compound constituting the composite compound is 0.3 to 5.0 mol with respect to 1 mol of the epoxy group of the epoxy resin. The adhesive film as described in 2.   In addition to the complex and the aromatic carboxylic acid compound or the imidazole compound, a curing agent selected from a phenol resin, an acid anhydride, and a polyamine is further contained as a curing agent. The adhesive film according to any one of the above.   Furthermore, an inorganic filler is contained, The adhesive film of any one of Claims 1-9 characterized by the above-mentioned.   Furthermore, an inorganic filler is contained in the ratio of 100 mass parts or less with respect to 100 mass parts of total amounts of a thermoplastic resin and an epoxy resin, The adhesive film of any one of Claims 1-10 characterized by the above-mentioned. .   The adhesive film according to claim 1, wherein the adhesive film is a wafer processing tape.   A tape for wafer processing, wherein the adhesive film according to any one of claims 1 to 12 and a supporting substrate having at least one pressure-sensitive adhesive layer are laminated. An aromatic carboxylic acid compound represented by the following general formula (I) having at least two carboxyl groups that are at least one kind of thermoplastic resin, epoxy resin, and curing agent having a glass transition temperature of -20 to 120 ° C. and imidazole A compound compound in which the imidazole compound is 0.1 to 1 mol per 1 mol of the aromatic carboxylic acid compound, and in addition to the compound compound, an aromatic carboxylic acid compound or an imidazole compound A method for producing an adhesive film comprising a step of preparing a dispersion by mixing with a solvent, a step of applying the dispersion on a carrier film, and a drying step.

(In general formula (I), m represents an integer of 2 to 4, n represents an integer of 2 to 4, and m ≦ n and m + n ≦ 6. R ¹ represents a substituent. R ¹ is bonded to each other to form a ring.)