JP5344880B2 - Adhesive resin composition and laminate comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve heat conductivity as well as both adhesivity and flexibility in a resin composition containing a polyimide resin and an inorganic filler. <P>SOLUTION: There is provided an adhesive resin composition containing an inorganic filler and a polyimide resin. The inorganic filler content in the resin composition is not greater than 58% by a volume ratio; the resin composition contains secondary particles produced by agglomerating 15-1,000 of primary particles each other of the inorganic filler; and the volume ratio of a tertiary aggregation of a region of the secondary particles disposed with an each distance of not greater than 0.05 &mu;m to the entire resin composition is not less than 20 vol.%. Further, the polyimide resin is a polyimide obtained by reacting (a) moles of a tetracarboxylic acid dianhydride constituent and (b) moles of a diamine constituent within the range of a/b=0.8-1.2; and the diamine constituent contains (c) moles of an amine constituent of the chemical formula (1) within the range of c/b=0.01-1.0 (wherein n is an integer of 1-50; and Xs are each independently a 1-10C alkylene group). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an adhesive resin composition and a resin film having excellent thermal conductivity, and a laminate having the adhesive resin composition layer.

  As means for imparting thermal conductivity to a resin composition, it is generally known to add an inorganic filler having high heat dissipation (see Patent Documents 1 and 2). For example, Patent Document 1 describes an insulating adhesive sheet containing an epoxy resin and an inorganic filler, and Patent Document 2 describes a heat-resistant adhesive containing siloxane-modified polyamideimide and spherical alumina.

  On the other hand, a polyimide resin is known as an adhesive resin composition having excellent heat resistance. There has been reported an adhesive in which an inorganic filler is added to this polyimide resin to enhance thermal conductivity (see Patent Document 3).

Moreover, the technique which tries to make low temperature adhesiveness and the low stress property of a resin cured material compatible by adding an inorganic filler to the polyimide resin containing a siloxane structure is reported (patent documents 4 and 5). . Furthermore, a technique for improving the mechanical strength of a cured resin or suppressing thermal expansion by adding a scaly inorganic filler to a heat-resistant resin such as polyimide has been reported (Patent Document 6). See).
JP-A-6-162855 JP 2004-217861 A Japanese Patent Laid-Open No. 5-117596 JP 2006-131914 A JP 2006-117949 A JP 2002-69309 A

  An object of this invention is to make the improvement of the heat conductivity of resin cured | curing material, and the improvement of adhesiveness compatible in the resin composition containing a polyimide resin and an inorganic filler. Another object of the present invention is to achieve both improvement in thermal conductivity of a cured resin and improvement in flexibility in a resin composition containing a polyimide resin and an inorganic filler.

  As described above, in order to improve the thermal conductivity of the cured resin, it is desirable to increase the content of the inorganic filler. On the other hand, if the content of the inorganic filler is too high, the adhesiveness is likely to decrease, and the Flexibility is also likely to decrease. Therefore, the present inventor studied to achieve both thermal conductivity, adhesiveness, and flexibility by controlling the dispersion state of the inorganic filler while suppressing the content of the inorganic filler below a certain level. Furthermore, it was studied to impart low temperature adhesiveness to the adhesive resin composition.

That is, the first of the present invention relates to the adhesive resin composition shown below.
[1] An adhesive resin composition comprising an inorganic filler (A) and a polyimide resin (B),
Content of the said inorganic filler (A) in the said resin composition is 58 vol% or less by volume ratio; The secondary particle which the primary particles of 15-1000 said inorganic filler (A) aggregated; The volume ratio of the tertiary aggregate, which is a region in which the secondary particles are arranged at an interval of 0.05 μm or less to each other, is 20 vol% or more, and
The polyimide resin (B) is a polyimide obtained by reacting a mole of a tetracarboxylic dianhydride component with a mole of a diamine component in a range of a / b = 0.8 to 1.2; The said diamine component is an adhesive resin composition which contains the diamine component cmol of Chemical formula (1) description in the range of c / b = 0.01-1.0.

(N represents an integer of 1 to 50, and each X independently represents an alkylene group having 1 to 10 carbon atoms)

[2] The inorganic filler (A) is at least one selected from the group consisting of boron nitride, aluminum nitride, alumina, alumina hydrate, silicon oxide, silicon nitride, silicon carbide, diamond, hydroxyapatite, and barium titanate. The adhesive resin composition according to [1], comprising an inorganic compound.
[3] The adhesive resin composition according to [1] or [2], further including a silane coupling agent (C).
[4] The adhesive resin composition according to [3], wherein the inorganic filler (A) is coupled with the silane coupling agent (C).
[5] The adhesive resin composition according to any one of [1] to [4], wherein the glass transition temperature is in the range of 0 to 150 ° C. and the storage elastic modulus at 150 ° C. is 300 MPa or less.
[6] A film comprising the adhesive resin composition according to any one of [1] to [5] and having a thickness of 10 to 200 μm.

2nd of this invention is related with the laminated body shown below.
[7] A layered product in which a thermoplastic polyimide resin layer having a thickness of 5 μm or less is formed on one side or both sides of the layer made of the adhesive resin composition according to any one of [1] to [5],
The thermoplastic polyimide resin layer is prepared by reacting the polyimide resin (B); or a mole of a tetracarboxylic dianhydride component and a mole of a diamine component in a range of a / b = 0.8 to 1.2. The diamine component is a thermoplastic polyimide resin containing the diamine component d mol described in the chemical formula (1) in the range of b / d = 0.01 to 1.0. Laminate containing.

(N represents an integer of 1 to 50, and each X independently represents an alkylene group having 1 to 10 carbon atoms)
[8] A laminate in which a conductor layer is formed on one side or both sides of a layer made of the adhesive resin composition according to any one of [1] to [5].
[9] A laminate comprising the laminate according to [7] and a conductor layer disposed on the thermoplastic polyimide resin layer.

3rd of this invention is related with the manufacturing method of the resin composition shown below.
[10] A method for producing the resin composition according to [1], comprising: preparing a varnish of the polyimide resin (B); adding the inorganic filler (A) to the varnish and stirring A step, wherein the stirring shear strength is 10 Pa to 1000 Pa.

1. Adhesive resin composition The adhesive resin composition of this invention contains an inorganic filler (A) and a polyimide resin (B), and can contain another arbitrary component, Preferably a silane coupling agent (C).

  The inorganic filler (A) is not particularly limited as long as it is an inorganic substance having electrical insulation and high heat dissipation. Examples of the material include boron nitride, aluminum nitride, alumina, alumina hydrate, silicon oxide, silicon nitride, silicon carbide, diamond, hydroxyapatite, and barium titanate. A more preferable material for the inorganic filler (A) is boron nitride or the like.

  The content of the inorganic filler (A) in the resin composition can be 58 vol% or less, and more preferably 49 vol% or less. The greater the content of the inorganic filler (A), the more heat conductivity can be imparted to the adhesive resin composition. On the other hand, if the content is too large, the adhesiveness may decrease, Flexibility may be reduced. The adhesive resin composition of the present invention has sufficient thermal conductivity despite having a low content of the inorganic filler (A), and of course can also have high adhesion and flexibility.

  The average particle size of the primary particles of the inorganic filler (A) is preferably 0.1 to 30 μm. This is because the particles of the inorganic filler (A) are aggregated to form secondary particles.

  The primary particles of the inorganic filler (A) are preferably aggregated to form secondary particles. The number of primary particles contained in one secondary particle is preferably 15 to 1000, and more preferably 15 to 100. Moreover, it is preferable that the average particle diameter of a secondary particle is 2-30 micrometers.

  The secondary particles of the inorganic filler (A) are dispersed in the resin composition, but are not uniformly dispersed and are dotted with regions having high secondary particle density (referred to as “tertiary aggregates”). It is preferable. The tertiary aggregate means a region where secondary particles are arranged at intervals of 0.05 μm or less in the resin composition.

  The volume ratio of the tertiary aggregate to the resin composition is preferably 20 vol% or more, and more preferably 21 vol% or more. The higher the volume ratio of the tertiary aggregate, the higher the thermal conductivity of the resin composition.

  The volume ratio of the tertiary aggregate to the entire resin composition can be obtained from image analysis of the SIM image. Specifically, the analysis may be performed according to the procedure described in the examples.

  The aggregation state or dispersion state of the inorganic filler (A) is the kind of the inorganic filler (A) and its treatment (for example, coupling treatment) state; the resin solid content concentration of the polyimide varnish in which the inorganic filler (A) is dispersed; It can be controlled by the stirring conditions when A) is dispersed in the polyimide varnish. These will be described in detail later.

  The inorganic filler (A) may be subjected to a coupling treatment. The coupling treatment may be performed by surface treatment with a silane coupling agent (C) described later, whereby secondary particles can be easily formed, and the proportion of tertiary aggregates in the composition can be increased.

  The polyimide resin (B) is a polyimide obtained by reacting a mole of a tetracarboxylic dianhydride component with a mole of a diamine component, or a precursor thereof. The molar ratio of the tetracarboxylic dianhydride component to be reacted and the diamine component is preferably in the range of a / b = 0.8 to 1.2. This is to obtain a polymer having a certain degree of polymerization.

  The tetracarboxylic dianhydride component to be reacted is not particularly limited. Tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride bonded to an organic group containing 4 or more carbons. An aromatic tetracarboxylic dianhydride is preferably used from the viewpoint of heat resistance, and an aliphatic tetracarboxylic dianhydride is preferably used from the viewpoint of flexibility.

  Examples of tetracarboxylic dianhydrides include oxydiphthalic acid, pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3,6-bis (tri Fluoromethyl) pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4 , 4'-biphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -terphenyltetracarboxylic dianhydride, 3,3 '", 4,4'"-quaterphenyl Tetracarboxylic dianhydride, 3,3 ″ ″, 4,4 ″ ″-kinkphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, Methylene-4,4′-diphthalic dianhydride, 1,1-ethynylidene-4,4′-diphthalic dianhydride, 2,2-propylidene-4,4′- Phthalic dianhydride, 1,2-ethylene-4,4′-diphthalic dianhydride, 1,3-trimethylene-4,4′-diphthalic dianhydride, 1,4-tetramethylene-4,4 '-Diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3 , 3-Hexafluoropropane dianhydride, difluoromethylene-4,4′-diphthalic dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene-4,4′-diphthalic acid Anhydride, 1,1,2,2,3,3-hexafluoro-1,3-trimethylene-4,4′-diphthalic dianhydride, 1,1,2,2,3,3,4,4 -Octafluoro-1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4,5,5-decafluoro-1,5-penta Methylene-4,4'-diphthalic dianhydride, oxy-4,4'-diphthalic dianhydride Thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetra Methylsiloxane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,3-bis ( 3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2- (3,4-dicarboxyphenyl)- 2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl Methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2 -Bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [3- (3,4-Dicarboxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) ) Phenyl] propane dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) -1,1,3,3-tetramethyldi Siloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride Anhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-F Nanthrenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, Cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride Anhydride, carbonyl-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2 -Ethylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethynylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 2 , 2-Propylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) Anhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4 ′ -Bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis (cyclohexane-1) , 2-dicarboxylic acid) dianhydride, 2,2′-difluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′-difluoro-3,3 ′, 4,4 '-Biphenyltetracarboxylic dianhydride, 6,6'-difluoro-3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 5,5', 6,6'- Hexafluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2′-bis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 5,5'-bi (Trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 6,6′-bis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydride, 2,2 ', 5,5'-tetrakis (trifluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 6,6'-tetrakis (Trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5 ′, 6,6′-tetrakis (trifluoromethyl) -3,3 ′, 4,4 ′ -Biphenyltetracarboxylic dianhydride, 2,2 ', 5,5', 6,6'-hexakis (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3 , 3'-Difluorooxy-4,4'-diphthalic dianhydride, 5,5'-difluorooxy-4,4'-diphthalic dianhydride, 6,6'-difluorooxy-4,4'- Diphthalic acid Anhydride, 3,3 ′, 5,5 ′, 6,6′-Hexafluorooxy-4,4′-diphthalic dianhydride, 3,3′-bis (trifluoromethyl) oxy-4,4 ′ -Diphthalic dianhydride, 5,5'-bis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 6,6'-bis (trifluoromethyl) oxy-4,4'-diphthal Acid dianhydride, 3,3 ′, 5,5′-tetrakis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 3,3 ′, 6,6′-tetrakis (trifluoromethyl) Oxy-4,4′-diphthalic dianhydride, 5,5 ′, 6,6′-tetrakis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ', 6,6'-Hexakis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 3,3'-difluorosulfonyl-4,4'-diphthalic dianhydride, 5,5'- Difluorosulfonyl-4,4'- Phthalic dianhydride, 6,6'-difluorosulfonyl-4,4'-diphthalic dianhydride, 3,3 ', 5,5', 6,6'-hexafluorosulfonyl-4,4'-diphthalate Acid dianhydride, 3,3′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic acid dianhydride, 5,5′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic acid Anhydride, 6,6′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5,5′-tetrakis (trifluoromethyl) sulfonyl-4,4′- Diphthalic dianhydride, 3,3 ′, 6,6′-tetrakis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 5,5 ′, 6,6′-tetrakis (trifluoromethyl) ) Sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) sulfonyl-4,4′-diphthalic acid Anhydride, 3,3'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5'-difluoro-2,2-perfluoropropylidene-4,4 ' -Diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3 ', 5,5', 6,6'-hexa Fluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3'-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4'-diphthalic acid Dianhydride, 5,5′-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 6,6′-difluoro-2,2-perfluoropropi Riden-4,4′-diphthalic dianhydride, 3,3 ′, 5,5′-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, , 3 ′, 6,6′-Tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 5,5 ′, 6,6′-tetrakis (trifluoro Methyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) -2,2-par Fluoropropylidene-4,4′-diphthalic dianhydride, 9-phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis (tri Fluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 9 , 9-bis [4- (3,4-dicarboxy) phenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxy) phenyl] fluorene dianhydride , And the like, ethylene glycol bistrimellitate dianhydride.

  Although the diamine component (b mol) to be reacted is not particularly limited, it preferably contains a diamine (c mol) represented by the following formula (1) and contains c / b in the range of 0.01 to 1. It is more preferable to contain in the range of c / b = 0.05-1.0.

  In Formula (1), n represents an integer of 1 to 50, preferably an integer of 10 to 20. On the other hand, X represents an alkylene group having 1 to 10 carbon atoms, and preferably represents an alkylene group having 1 to 5 carbon atoms.

  By making at least one part of a diamine component into the diamine shown by Formula (1), the glass transition temperature of the polyimide resin (B) obtained falls. Therefore, the low temperature adhesiveness of the adhesive resin composition is enhanced. The glass transition temperature of the polyimide resin (B) is preferably 0 to 150 ° C.

  On the other hand, when c / b is less than 1, the diamine component to be reacted contains any diamine other than the diamine represented by the formula (1). Among the diamine components to be reacted, examples of diamines other than the diamine represented by the formula (1) include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-amino) Phenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3′-diaminobenzophenone, 3,4′-diamino Benzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-di Aminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3 -A Minophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3 -Hexafluoropropane, 1,3-bis (3-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- (aminophenoxy) ) Feni ] Sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- ( 4-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, 4,4′-bis [4- (4-amino-α, α -Dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminopheno) P) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α -Dimethylbenzyl] benzene, 1,3-bis (3- (4-aminophenoxy) phenoxy) benzene, 1,3-bis (3- (2-aminophenoxy) phenoxy) benzene, 1,3-bis (4- (2-Aminophenoxy) phenoxy) benzene, 1,3-bis (2- (2-aminophenoxy) phenoxy) benzene, 1,3-bis (2- (3-aminophenoxy) phenoxy) benzene, 1,3- Bis (2- (4-aminophenoxy) phenoxy) benzene, 1,4-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,4-bis (3- (4-aminophenoxy) phenoxy) benzene, 1,4-bis (3- (2-a Nophenoxy) phenoxy) benzene, 1,4-bis (4- (2-aminophenoxy) phenoxy) benzene, 1,4-bis (2- (2-aminophenoxy) phenoxy) benzene, 1,4-bis (2 -(3-aminophenoxy) phenoxy) benzene, 1,4-bis (2- (4-aminophenoxy) phenoxy) benzene, 1,2-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,2 -Bis (3- (4-aminophenoxy) phenoxy) benzene, 1,2-bis (3- (2-aminophenoxy) phenoxy) benzene, 1,2-bis (4- (4-aminophenoxy) phenoxy) benzene 1,2-bis (4- (3-aminophenoxy) phenoxy) benzene, 1,2-bis (4- (2-aminophenoxy) phenoxy) benzene, 1,2-bis (2- (2-aminophenoxy) ) Feno Ii) benzene, 1,2-bis (2- (3-aminophenoxy) phenoxy) benzene, 1,2-bis (2- (4-aminophenoxy) phenoxy) benzene, 1,3-bis (3- (3 -Aminophenoxy) phenoxy) -2-methylbenzene, 1,3-bis (3- (4-aminophenoxy) phenoxy) -4-methylbenzene, 1,3-bis (4- (3-aminophenoxy) phenoxy) -2-ethylbenzene, 1,3-bis (3- (2-aminophenoxy) phenoxy) -5-sec-butylbenzene, 1,3-bis (4- (3-aminophenoxy) phenoxy) -2,5- Dimethylbenzene, 1,3-bis (4- (2-amino-6-methylphenoxy) phenoxy) benzene, 1,3-bis (2- (2-amino-6-ethylphenoxy) phenoxy) benzene, 1,3 -Bis (2- (3-aminophenoxy) -4-methylphen Xyl) benzene, 1,3-bis (2- (4-aminophenoxy) -4-tert-butylphenoxy) benzene, 1,4-bis (3- (3-aminophenoxy) phenoxy) -2,5-di -tert-butylbenzene, 1,4-bis (3- (4-aminophenoxy) phenoxy) -2,3-dimethylbenzene, 1,4-bis (3- (2-amino-3-propylphenoxy) phenoxy) Benzene, 1,2-bis (3- (3-aminophenoxy) phenoxy) -4-methylbenzene, 1,2-bis (3- (4-aminophenoxy) phenoxy) -3-n-butylbenzene, 1, 2-bis (3- (2-amino-3-propylphenoxy) phenoxy) benzene, bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane, bis (10-aminodecamethylene) teto Lamethyldisiloxane, bis (3-aminophenoxymethyl) tetramethyldisiloxane, 1,12-dodecanediamine, norbornanediamine and the like.

  The diamine other than the diamine represented by the formula (1) is preferably an aromatic diamine from the viewpoint of heat resistance, and is preferably an aliphatic diamine or a silicone diamine from the viewpoint of flexibility.

  The adhesive resin composition of this invention may contain arbitrary components other than an inorganic filler (A) and a polyimide resin (B). Examples of the optional component may contain a surface modifier, and examples of the surface modifier include a silane coupling agent (C). A surface modifier may be used to treat the surface of the filler.

  Examples of the silane coupling agent (C) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, 3-glycidoxypropylmethyldiethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldi Ethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1- Propanamine, N, N'-bis (3- (trimethoxysilyl) propyl) ethylenediamine, polyoxyethylenepropyltrialkoxysilane, polyethoxydimethylsiloxane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane Etc. are included.

  The filler surface may be modified by a coupling reaction of the silane coupling agent (C) with the surface of the inorganic filler (A) contained in the resin composition. Thereby, the aggregation and dispersion state of the filler can be controlled as described above.

  Moreover, when the inorganic filler (A) is coupled with the silane coupling agent (C) in the resin composition of the present invention, the amount of the silane coupling agent (C) relative to the inorganic filler (A) The following formula may be used. This is to prevent the unreacted silane coupling agent (C) from remaining in the resin composition. The following equation is a theoretical equation calculated from “Stuart-briegleb molecular model”.

Minimum covered area with silane coupling agent (m ² / g) =
6.02 × 10 ²³ × 13 × 10 ⁻²⁰ ÷ molecular weight of silane coupling agent silane addition amount =
Filler weight x Filler specific surface area ÷ Minimum coating area with silane coupling agent

  After performing the adsorption treatment of the silane coupling agent on the filler, if the treated filler is added to the resin composition, the amount of the silane coupling agent added to the resin composition is adjusted to the amount of the silane cup adsorbed on the filler surface. It can be the amount of the ring agent.

  The storage elastic modulus at 150 ° C. of the resin composition of the present invention is preferably 300 MPa or less. If the storage elastic modulus is too high, the adhesiveness may be lowered, or the electronic component may be difficult to be embedded when applied to a component-embedded substrate. The storage elastic modulus of the resin composition mainly increases as the filler content increases. However, since the content of the inorganic filler (A) in the resin composition of the present invention is 58 vol% or less, the above storage elasticity Easy to realize rate.

  The adhesive resin composition of the present invention is characterized in that the volume fraction of the tertiary aggregate of the inorganic filler (A) is high although the content of the inorganic filler (A) contained therein is relatively low. Therefore, the resin composition is excellent in adhesiveness, flexibility, and flexibility and has sufficient thermal conductivity.

2. Method for Producing Adhesive Resin Composition The adhesive resin composition of the present invention comprises, for example, a step of preparing a polyimide varnish containing a polyimide resin (B); an inorganic filler (A) is blended in the polyimide varnish, and the varnish is stirred A step of solidifying the polyimide varnish.

  The polyimide varnish contains a polyimide resin (B) and preferably a solvent. The resin solid content concentration in the polyimide varnish is preferably 5 to 50 wt%, and more preferably 10 to 30 wt%. This is for appropriately controlling the conditions of stirring described later.

  The type of the solvent is not particularly limited, and N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexamethyl In addition to phosphoramide, N-methyl-2-pyrrolidone, dimethylsulfone, 1,3,5-trimethylbenzene, etc., these two or more mixed solvents, or these solvents and benzene, toluene, xylene, benzonitrile, What is necessary is just a mixed solvent with a dioxane, cyclohexane, etc.

  The polyimide varnish may be prepared by mixing an acid dianhydride component and a diamine component in a solvent, synthesizing amic acid by a dehydration reaction, and further imidizing. What is necessary is just to let the acid dianhydride component and diamine component to mix | blend with each component mentioned above.

  An inorganic filler (A) is added to the obtained polyimide varnish. The inorganic filler (A) to be added may be the inorganic filler described above. Moreover, the inorganic filler (A) to be added may be treated with a silane coupling agent (C). The inorganic filler (A) may be treated by any method, but the inorganic filler (A) is added to the aqueous solution of the silane coupling agent (C) and mixed to obtain a slurry; water is removed from the slurry. To obtain solids; the solids may be ground into particles.

  By stirring the polyimide varnish to which the inorganic filler (A) is added, the inorganic filler (A) is dispersed in the polyimide varnish. Stirring may be performed with a normal stirrer or a disperser such as a roughing machine, a three-roller, or a ball mill. The shear strength of stirring is preferably 10 Pa to 1000 Pa. If the shear strength when stirring is too high, secondary particles are not formed, or the volume ratio of the tertiary structure is reduced. On the other hand, if the shear strength when stirring is too small, huge aggregates are formed, and the film forming ability may be lost.

  Moreover, the temperature of the polyimide varnish stirred is not specifically limited, What is necessary is just to be 10-50 degreeC.

  In any case, it is preferable to control the aggregation state or dispersion state of the inorganic filler (A) in the polyimide varnish by stirring the polyimide varnish to increase the ratio of the tertiary aggregate in the resin composition.

  The polyimide varnish itself in which the inorganic filler (A) is dispersed may be used as an adhesive. For example, the polyimide varnish may be applied to the adherend. On the other hand, the polyimide varnish may be formed into a film and used as an adhesive film. For example, the polyimide varnish can be applied to a release-treated film and solidified, and then peeled to obtain an adhesive film. The thickness of the film is usually 10 to 200 μm.

A laminate can be obtained by forming a thermoplastic polyimide resin layer having a thickness of 5 μm or less on a film made of the resin composition of the present invention.
The thermoplastic polyimide resin layer may contain a polyimide resin (B). The thermoplastic polyimide resin layer is a thermoplastic polyimide obtained by reacting a mole of a tetracarboxylic dianhydride component with a mole of a diamine component in a range of a / b = 0.8 to 1.2. It is resin, Comprising: The said diamine component may contain the thermoplastic polyimide resin which contains the diamine component dmol of Chemical formula (1) description in the range of b / d = 0.01-1.0.
If these thermoplastic polyimide resin layers are thinly formed as described above on a film made of the resin composition of the present invention, the adhesiveness with copper foil or substrate is improved without lowering the thermal conductivity. This is because it becomes possible.

The symbols in general formula (1) are defined in the same manner as in general formula (1).

  The adhesive resin composition of the present invention is preferably used for bonding a conductor layer, preferably a metal foil. For example, it can be used for adhesion between a base resin film and a metal foil in a circuit board, a heat dissipation board, and a component-embedded board that are a laminate of a base resin film and a metal foil (preferably a copper foil). Moreover, it is good also considering the base material of a circuit board as a film which consists of an adhesive resin composition of this invention.

  Although the thickness of the said laminated body should just be set suitably according to a use and it does not restrict | limit especially, it is preferable that the thickness of an adhesive resin composition layer is 10-200 micrometers. The laminate may be a flexible body or a rigid body, and is appropriately set by selecting a thickness and a material according to the purpose.

Since the adhesive resin composition of the present invention has high adhesiveness and high flexibility and flexibility, it is preferably used for a flexible circuit board. Moreover, since the resin resin has high fluidity, the adhesive resin composition of the present invention is preferably used for a semiconductor encapsulated package in which an electronic component is embedded in the resin, or a component-embedded substrate.
Furthermore, since the adhesive resin composition of the present invention has high thermal conductivity, when an element (such as an LSI chip) is mounted on a circuit board obtained using the adhesive resin composition of the present invention, heat generated by the element is generated. It is easy to disperse. Even if a semiconductor chip having a large calorific value such as for power device is mounted on a heat dissipation substrate obtained by using the adhesive resin composition of the present invention, heat can be sufficiently dissipated.

[Example 1]
Preparation of polyimide varnish
In a solvent prepared by adjusting NMP and mesitylene at a ratio of 7/3, three kinds of diamines (1Si, 14EL, HAB) shown below and one kind of acid dianhydride (ODPA) are mixed with 1Si: 14EL: It was blended at a molar ratio of HAB: ODPA = 0.87: 0.1: 0.03: 1.0. The obtained mixture was stirred for 4 hours or more in a flask into which dry nitrogen gas could be introduced to obtain a polyamic acid solution having a resin solid content weight of 20 to 25 wt%. After sufficiently stirring, the reaction system was heated to about 180 ° C. while stirring in a flask equipped with a Dean-Stark tube, and water generated by the dehydration reaction was taken out of the system to obtain a polyimide varnish.

1Si; 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane (PAM-E) (manufactured by Shin-Etsu Silicone)
14EL; polytetramethylene oxide di-p-aminobenzoate (Elastomer 1000) (manufactured by Ihara Chemical)
HAB; 4,4'-diamino-3,3'-biphenyldiol (Wakayama Seika)
ODPA; 4,4'-oxydiphthalic dianhydride (manufactured by Tokyo Chemical Industry)

Preparation of filler A silane coupling agent (N-2 (aminoethyl) 3-aminopropyl trimethoxysilane, KBM-603, manufactured by Shin-Etsu Silicone) was blended in a 1% aqueous acetic acid solution to a concentration of 1 wt%. Boron nitride filler (brand: MBN-010T, manufactured by Mitsui Chemicals) was blended with the obtained solution to obtain a slurry-like liquid. The amount of the silane coupling agent relative to the boron nitride filler was set so as to correspond to the minimum coating surface area calculated from the following two formulas.

Minimum coverage area of silane coupling agent (m ² / g) =
6.02 × 10 ²³ × 13 × 10 ⁻²⁰ / molecular weight of silane coupling agent silane addition amount =
Filler weight x Filler specific surface area ÷ Minimum coating area of silane coupling agent

  Water was removed from the obtained slurry and dried at 150 ° C. for 4 hours or longer to obtain a cake-like lump of boron nitride filler treated with a silane coupling agent. The obtained mass was sufficiently ground with a mortar or the like, and classified to a size equivalent to primary particles (30 μm or less) using a metal mesh or the like.

The obtained filler was blended in the polyimide varnish so that the amount was 38 vol% with respect to the resin solid content. The polyimide varnish blended with the filler was stirred to disperse the filler. Stirring "Awatori Rentaro (ARE310, THINKY Corporation)" After initial stirring using was performed by stirring kneaded at a shear strength 1 2P a corresponding by means of a three-roll mill. As a result, a polyimide varnish solution containing a filler was obtained.

  The polyimide varnish solution blended with the filler was applied at a rate of 10 mm / sec onto the PET film that had been subjected to the mold release treatment. The obtained coating film was dried at 130 ° C. for 30 minutes to remove the solvent. After drying, the film portion was peeled off from the PET film using tweezers or the like to prepare a polyimide film (film thickness: 90 μm) in which the boron nitride filler was dispersed.

The state of the filler in the produced polyimide film (the presence of secondary particles and the volume ratio of the tertiary aggregate of the filler) was measured. Specifically, the SIM image obtained by observing the cross section of the polyimide film by SIM (Scanning Ion Microscope) was subjected to image analysis according to the following procedure, and the volume ratio of the tertiary aggregate was measured.
(1) The SIM image is divided into two gradations. The white area is the filler part and the black area is the resin part.
(2) From the white region, a portion where 15 or more primary particles are aggregated is extracted as secondary particles.
(3) The secondary particles close to each other within 0.05 μm are formed as a tertiary aggregate in a separate frame.
(4) The proportion of the tertiary aggregate portion is estimated from the image.

The thermal conductivity of the produced polyimide film was evaluated. Specifically, the thermal conductivity was calculated by measuring “thermal diffusivity α”, “specific heat Cp”, and “density ρ” of the sample, and applying these measured values to the following equation.
Thermal conductivity λ = thermal diffusivity α × specific heat Cp × density ρ

  The thermal diffusivity was measured by a laser flash method. The measuring apparatus was a laser flash method thermal constant measuring apparatus (TC-9000) manufactured by ULVAC-RIKO. Specific heat was measured by DSC method. The measuring apparatus was a Diamond DSC apparatus manufactured by PerkinElmer. The weight was measured with an electronic balance, the volume was calculated from the sample area and the sample thickness, and the density was calculated.

The adhesive strength of the produced polyimide film was evaluated. Specifically, the produced polyimide film was cut into a predetermined size. An electrolytic copper foil (brand: F1-WS, manufactured by Furukawa Circuit Foil) having a thickness of 12 μm was stacked on both surfaces of the cut out film. Furthermore, it was pressed and laminated under temperature, time, and pressure conditions of 100 ° C. × 60 minutes × 25 kg / cm ² .

  An IC tape corresponding to a width of 3.2 mm × 30 mm was pasted on the copper foil surface of the laminated sample after pressing, and several mask portions were produced. Copper around the mask part was removed by etching using an aqueous ferric chloride solution to form a copper pattern for measuring the adhesive strength. The edge of the formed copper pattern was turned up and the copper pattern was pulled perpendicularly to the film surface to measure the adhesive strength between copper and the film sample.

  The flexibility of the produced polyimide film was evaluated. Specifically, the produced polyimide film was cut into a size of 50 mm in length and 10 mm in width. The cut out film 1 was fixed to a plate 2 having a thickness of 1 mm, and a load (0.98 N) of 100 g was applied (see FIG. 1A). The plate 2 to which the film 1 was fixed was set in a testing machine, rotated 180 degrees with the end 2-1 of the plate 2 as a base point, and the film 1 adhered to the plate 2 was bent 180 degrees (see FIG. 1B). . The bending part 1-2 of the film 1 was observed with the microscope 3 to confirm the presence or absence of cracks.

  One folding operation includes an operation of “folding completely 180 ° (FIG. 1B) and folding the sample back to the original state (FIG. 1A)”. The folding operation was repeated, and the number of foldings until a crack occurred in the film was measured.

  The viscoelasticity of the produced polyimide film was evaluated in “tensile mode” using RSA-II (manufactured by TA). The measurement temperature was 30 to 300 ° C., the temperature increase rate was 3 ° C./min, and the measurement frequency was 1 Hz. The storage elastic modulus (E ′) at 150 ° C. of the polyimide film was measured.

[Comparative Example 1]
A polyimide film was prepared in the same manner as in Example 1 except that the blending amount of the filler was set to 0, and each evaluation was performed.

[Comparative Example 2]
In place of the boron nitride filler treated with the silane coupling agent, an untreated boron nitride filler was used; and in the stirring of the polyimide varnish to which the filler was added, the shear strength in the stirring using the three rolls was 0.1 Pa. Except for the above, a polyimide film was prepared in the same manner as in Example 1, and each evaluation was performed.

[Comparative Example 3]
The untreated boron nitride filler was used instead of the boron nitride filler treated with the silane coupling agent; and the shear strength in the stirring using the three rolls in the stirring of the polyimide varnish to which the filler was added was 5 Pa. A polyimide film was produced in the same manner as in Example 1 except that it was evaluated, and each evaluation was performed.

[Comparative Example 4]
An untreated boron nitride filler was used in place of the boron nitride filler treated with the silane coupling agent; the amount of filler added to the polyimide varnish was 59 vol% with respect to the resin solid content; and the filler was added in stirring polyimide varnish, except that the shear strength and 5 2P a in stirred using a three-roll, a polyimide film was prepared in the same manner as in example 1 were each evaluated.

  The production conditions of the polyimide resin composition and the evaluation results of the polyimide film in Example 1 and Comparative Example are shown below.

  As shown in the above table, in the polyimide film of Example 1, the volume ratio of the tertiary aggregate is 22.2%, and the thermal conductivity is extremely high as compared with each comparative example (3.11 W). / M · K). And the content of the filler of Example 1 was suppressed to 38 vol%, the adhesive strength was as high as that of Comparative Example 1 (without filler) (0.7 kN / m), and the flexibility was sufficient. .

[Example 2]
The polyimide varnish used in Example 1 was applied to the polyimide film produced in Example 1 and dried to form a thermoplastic resin layer of 5 μm or less. The thermal conductivity was evaluated in the same manner as described above, and the adhesive strength (with the thermoplastic resin layer as the adhesive surface) was determined.

  A laminate can be obtained by using the adhesive resin composition of the present invention as an adhesive between a conductor layer and a film. The laminate can be applied to, for example, a circuit board, a heat dissipation board, a component built-in board, and the like. In particular, the laminate can be a flexible circuit board in which a conductor layer is firmly bonded to a base material or a circuit board having high thermal conductivity. In addition, when the element (such as an LSI chip) is mounted on the circuit board, heat from the element can be efficiently dissipated. In addition, the mounting process can be improved by enabling attachment at a low temperature.

It is a figure explaining the test for evaluating the flexibility of a polyimide film.

Claims (10)

An adhesive resin composition comprising an inorganic filler (A) and a polyimide resin (B),
Content of the said inorganic filler (A) in the said resin composition is 58 vol% or less by volume ratio,
Including secondary particles in which primary particles of 15 to 1000 inorganic fillers (A) are aggregated,
The volume ratio of the tertiary aggregate, which is a region in which the secondary particles are arranged at an interval of 0.05 μm or less to each other, is 20 vol% or more, and
The polyimide resin (B) is a polyimide obtained by reacting a mole of a tetracarboxylic dianhydride component and a mole of a diamine component in a range of a / b = 0.8 to 1.2,
The said diamine component is an adhesive resin composition which contains the diamine component cmol of Chemical formula (1) description in the range of c / b = 0.01-1.0.
(N represents an integer of 1 to 50, and each X independently represents an alkylene group having 1 to 10 carbon atoms)   The inorganic filler (A) is at least one inorganic compound selected from the group consisting of boron nitride, aluminum nitride, alumina, alumina hydrate, silicon oxide, silicon nitride, silicon carbide, diamond, hydroxyapatite, and barium titanate. The adhesive resin composition according to claim 1, comprising:   The adhesive resin composition according to claim 1 or 2, further comprising a silane coupling agent (C).   The adhesive resin composition according to claim 3, wherein the inorganic filler (A) is subjected to a coupling treatment with the silane coupling agent (C).   The adhesive resin composition according to any one of claims 1 to 4, wherein the glass transition temperature is in the range of 0 to 150 ° C and the storage elastic modulus at 150 ° C is 300 MPa or less.   A film comprising the adhesive resin composition according to any one of claims 1 to 5 and having a thickness of 10 to 200 µm. A layered product in which a thermoplastic polyimide resin layer having a thickness of 5 μm or less is formed on one or both sides of a layer made of the adhesive resin composition according to claim 1,
The thermoplastic polyimide resin layer is
A thermoplastic polyimide resin obtained by reacting the polyimide resin (B) or the tetracarboxylic dianhydride component a mole and the diamine component b mole in the range of a / b = 0.8 to 1.2. And the said diamine component is a laminated body containing the thermoplastic polyimide resin which contains the diamine component dmol of Chemical formula (1) description in the range of b / d = 0.01-1.0.
(N represents an integer of 1 to 50, and each X independently represents an alkylene group having 1 to 10 carbon atoms)   The laminated body in which the conductor layer was formed in the single side | surface or both surfaces of the layer which consists of an adhesive resin composition as described in any one of Claims 1-5.   The laminated body containing the laminated body of Claim 7, and the conductor layer arrange | positioned on the said thermoplastic polyimide resin layer. A method for producing the resin composition according to claim 1, comprising:
Preparing a varnish of the polyimide resin (B), adding the inorganic filler (A) to the varnish, and stirring.
The manufacturing method whose shear strength of the said stirring is 10 Pa-1000 Pa.