WO2010053186A1 - シロキサン含有ポリイミド樹脂 - Google Patents
シロキサン含有ポリイミド樹脂 Download PDFInfo
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- WO2010053186A1 WO2010053186A1 PCT/JP2009/069071 JP2009069071W WO2010053186A1 WO 2010053186 A1 WO2010053186 A1 WO 2010053186A1 JP 2009069071 W JP2009069071 W JP 2009069071W WO 2010053186 A1 WO2010053186 A1 WO 2010053186A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
Definitions
- the present invention relates to a polyimide resin having a hexafluoroisopropanol group and a siloxane structure.
- Polyimide resins with excellent heat resistance are widely used in the electronics and aerospace fields.
- a material having both heat resistance and low elasticity has been developed by introducing a siloxane structure into the polyimide resin.
- a polyimide resin having a siloxane structure in which a phenolic hydroxyl group is introduced to impart reactivity with an epoxy resin is known (Patent Document 1).
- the siloxane structure-containing polyimide resin into which the phenolic hydroxyl group was introduced had a large change in elastic modulus with a change in temperature, resulting in a decrease in heat resistance.
- the reactivity with other thermosetting resins such as epoxy resins decreases.
- a siloxane structure-containing polyimide resin into which a hexafluoroisopropanol group is introduced has a small change in elastic modulus with a change in temperature and is excellent in heat resistance and other heat resistance.
- the inventors have found that the reactivity with the curable resin is also good and completed the present invention.
- R1 represents a tetravalent organic group
- R2 represents a divalent diamine residue having a hexafluoroisopropanol group
- R3 represents a divalent siloxane diamine residue, and is represented by the formula (1)
- the repeating number M in one molecule of the unit is an integer of 1 to 100
- the repeating number N in one molecule of the repeating unit represented by the formula (2) is an integer of 1 to 100.
- the polyimide resin as described in said (1) which has a repeating unit represented by these.
- (3) The above (1) or (2) produced by reacting a tetrabasic dianhydride represented by the formula (3) with a diamine compound represented by the formulas (4) and (5)
- R1 represents a tetravalent organic group
- R2 represents a divalent diamine residue having a hexafluoroisopropanol group
- R3 represents a divalent siloxane diamine residue.
- A represents an oxygen atom, a sulfur atom, CO, SO, SO 2 , CH 2 , CH (CH 3 ), C (CH 3 ) 2 , C (CF 3 ) 2 , or C (CCl 3 ) 2.
- the hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms.
- a divalent diamine residue having a hexafluoroisopropanol group represented by R2 is represented by the following formula:
- the hydrogen atom on the aromatic ring may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms.
- the divalent siloxane diamine residue represented by R3 is represented by the following formula:
- the hydrogen atom may be substituted with a halogen atom or an alkyl group having 1 to 8 carbon atoms.
- polyimide resin having a structure represented by the formula: (7)
- X represents the functional group equivalent number of the acid anhydride group of the tetrabasic acid dianhydride represented by the formula (3)
- Y represents the functional group equivalent number of the amino group of all diamine compounds present in the reaction system.
- the polyimide resin according to the above (3) which is reacted so as to satisfy the relationship of 0 ⁇ (XY) /X ⁇ 0.3.
- a resin composition comprising the polyimide resin according to any one of (1) to (10) and a thermosetting resin.
- a polyimide resin having both heat resistance and low elasticity a polyimide resin having a small change in elastic modulus with temperature and excellent heat resistance and good reactivity with other thermosetting resins and the resin.
- a composition is provided.
- the polyimide resin of the present invention has a hexafluoroisopropanol group and a siloxane structure.
- the polyimide resin preferably has a repeating unit represented by the following formulas (1) and (2).
- R1 represents a tetravalent organic group
- R2 represents a divalent diamine residue having a hexafluoroisopropanol group
- R3 represents a divalent siloxane diamine residue.
- the number M of repeating units in one molecule of the repeating unit represented by the formula (1) is preferably an integer of 1 to 100 (1 ⁇ M ⁇ 100).
- the repeating number N in 1 molecule of the repeating unit represented by Formula (2) is an integer of 1 or more and 100 or less (1 ⁇ N ⁇ 100).
- Examples of the tetravalent organic group represented by R1 include those having the following structure.
- A represents an oxygen atom, a sulfur atom, CO, SO, SO 2 , CH 2 , CH (CH 3 ), C (CH 3 ) 2 , C (CF 3 ) 2 , or C (CCl 3 ) 2 .
- a hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.
- Examples of the divalent diamine residue having a hexafluoroisopropanol group represented by R2 include those having the following structure.
- A represents the same meaning as described above.
- J represents an integer of 1 to 4.
- K represents an integer of 1 to 6.
- P and Q each independently represent an integer of 0 to 2, and 1 ⁇ (P + Q) ⁇ 4.
- a hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.
- R4 and R5 each independently represent an alkylene group having 1 to 5 carbon atoms, a phenylene group or an oxyalkylene group
- R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms or a carbon number.
- An alkoxy group of 1 to 5 or a phenoxy group; a, b and c each independently represents 0 or an integer of 1 or more, and b + c ⁇ 1 and a + b + c ⁇ 60.
- a hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.
- the tetravalent organic group represented by R1 of the tetrabasic acid dianhydride represented by the formula (3) is as described above.
- Specific examples of the tetravalent organic group represented by R1 include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid.
- Examples of the diamine compound having a hexafluoroisopropanol group represented by the formula (4) include those represented by the following formula.
- A represents an oxygen atom, a sulfur atom, CO, SO, SO 2 , CH 2 , CH (CH 3 ), C (CH 3 ) 2 , C (CF 3 ) 2 , or C (CCl 3 ) 2 .
- J represents an integer of 1 to 4.
- K represents an integer of 1 to 6.
- P and Q each independently represent an integer of 0 to 2, where 1 ⁇ (P + Q) ⁇ 4.
- a hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.
- the amino groups on the naphthalene ring may be bonded to the same benzene ring or may be bonded to different benzene rings.
- each may be bonded to the same benzene ring, or may be bonded to different benzene rings.
- the diamine compound represented by the formula (4-a) can be produced according to a known method described in International Publication No. 2006/043501.
- the diamine compound represented by the formula (4-c) can be produced according to a known method described in International Publication No. 2006/041115.
- the diamine compound represented by the formula (4-b) can be prepared by reacting the corresponding naphthalenediamine compound with hexahexadiene according to a known method described in International Publication No. 2006/043501 and International Publication No. 2006/041115. It can be produced by reacting fluoroacetone or hexafluoroacetone trihydrate and introducing a hexafluoroisopropanol group onto the naphthalene ring. These diamine compounds having a hexafluoroisopropanol group can be used in combination of two or more.
- Examples of the diaminosiloxane represented by the formula (5) include those represented by the following formula.
- R4 and R5 each independently represent an alkylene group having 1 to 5 carbon atoms, a phenylene group or an oxyalkylene group
- R6 to R10 each independently represent an alkyl group having 1 to 5 carbon atoms or a carbon number.
- An alkoxy group of 1 to 5 or a phenoxy group; a, b and c each independently represents 0 or an integer of 1 or more, and b + c ⁇ 1 and a + b + c ⁇ 60.
- a hydrogen atom on the aromatic ring may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, or the like.
- the siloxane structure in the present invention is preferably a structure represented by the following formula (5b).
- Re and Rf each independently represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a phenyl group, or a phenoxy group, m is an integer of 60 or more, and a repeating unit For each, Re or Rf may be different.
- Examples of the diaminosiloxane represented by the formula (5a) include 1,3-bis (3-aminopropyl) -1,1,2,2-tetramethyldisiloxane, 1,3-bis (3-aminobutyl) ) -1,1,2,2-tetramethyldisiloxane, bis (4-aminophenoxy) dimethylsilane, 1,3-bis (4-aminophenoxy) tetramethyldisiloxane, 1,1,3,3-tetra Methyl-1,3-bis (4-aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetra Phenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetra
- Diamine compounds other than the diamine compounds represented by formulas (4) and (5) may be used alone or in combination of two or more.
- the diamine compound can be represented by the following formula (6).
- R11 represents a divalent organic group other than a divalent diamine residue having a hexafluoroisopropanol group and a divalent siloxane diamine residue.
- the diamine compound is not particularly limited.
- Diamine compounds containing two benzene rings 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4 Such as bis (3-aminophenyl) benzene, ⁇ , ⁇ '-bis (4-aminophenyl) -1,4-diisopropylbenzene, ⁇ , ⁇ '-bis (4-aminophenyl) -1,3-diisopropylbenzene, etc.
- Diamine compounds containing three benzene rings 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4 ′-(4-aminophenoxy) biphenyl, 4,4 '-(3-aminophenoxy) biphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl)
- the diaminosiloxane represented by the formula (5) preferably has an NH 2 equivalent in the range of 400 to 6000 g / mol, more preferably in the range of 400 to 2500 g / mol, and further in the range of 400 to 1000 g / mol. Are more preferred.
- the NH 2 equivalent is larger than this range, the hydrophobicity of the resin becomes too strong due to the large molecular weight of the siloxane structure and the compatibility with the thermosetting resin deteriorates. The difference in polarity of the siloxane part becomes too large, making it difficult to stably synthesize the resin.
- the number of functional group equivalents of the acid anhydride group of the tetrabasic acid dianhydride used is X and the number of functional group equivalents of the amino group of all amine compounds used is Y, 0 ⁇
- the reaction is preferably performed under the condition of
- the functional group equivalent represents the molecular weight of the compound per functional group
- the functional group equivalent number represents the number of functional groups per compound weight (charge amount).
- Functional group equivalent A3 (g / mol) of amino group of diaminosiloxane, charge amount B3, functional group equivalent A4 (g / mol) of amino group of diamine compound represented by formula (6), charge amount B4 ( g), Y (B2 / A2) + (B3 / A3) + (B4 / A4).
- the charging ratio of the diamine compounds of the formulas (4) and (5) is reflected in the content of the siloxane structure and the content of hexafluoroisopropanol groups (hereinafter referred to as HFA groups) in the obtained resin. Therefore, by arbitrarily setting these two values, the range of the charging ratio of the diamine compounds of formulas (4) and (5) is inevitably determined.
- the amount of the siloxane structure contained in the obtained resin is preferably 40 to 90% by weight, and more preferably 50 to 80% by weight. When the proportion of the siloxane structure is larger than 90% by weight, the resulting resin has high adhesiveness and is difficult to handle, and conversely when it is smaller than 40% by weight, the flexibility of the resin becomes poor.
- the end of the polyamide resin is considered to be a dicarboxyl group in which an amino group, an acid anhydride group or an acid anhydride group is ring-opened, although it varies depending on the reaction ratio of the tetrabasic acid dianhydride and the diamine compound.
- the reaction operation is not particularly limited, for example, it is more preferable to carry out heat dehydration imidization in a polymerization solution in view of simplicity of work.
- a solvent azeotropic with water such as toluene or xylene is added to a solvent in which a diamine compound having a hexafluoroisopropanol group and a siloxane diamine are dissolved.
- tetrabasic dianhydride is added and reacted at 80 ° C. or less, preferably 0 to 50 ° C. for about 1 to 24 hours to obtain a polyamic acid solution.
- the resulting polyamic acid solution is heated at 100 to 200 ° C., preferably 150 to 200 ° C., and the polyimide solution can be obtained by ring-closing while removing water azeotropically with toluene. At this time, the reaction was completed when it was confirmed that almost the theoretical amount of water was distilled off and that no outflow of water was observed. On the other hand, apart from this method, the polyamic acid dehydration ring closure reaction can also be carried out at a low temperature using an acetic anhydride / pyridine mixed solution.
- thermosetting resin composition having a small curing shrinkage, high flexibility, high heat resistance, and adhesiveness is obtained. Obtainable. At this time, it is preferable to select a thermosetting resin having a functional group capable of reacting with the HFA group contained in the resin (A) structure, and an epoxy resin having two or more glycidyl groups is more preferable. Furthermore, you may add the hardening
- the epoxy resin used in the embodiment of the present invention is not particularly limited as long as it contains two or more glycidyl groups.
- glycidyl ethers of phenols such as bisphenol A, bisphenol F, bisphenol S, resorcinol, phenol novolak, cresol novolak, etc.
- glycidyl ethers of alcohols such as butanediol, polyethylene glycol, polypropylene glycol, phthalic acid, isophthalic acid, tetrahydrophthal Glycidyl type (including methyl glycidyl type) epoxy resins such as glycidyl groups substituted with active hydrogen bonded to nitrogen atoms such as glycidyl ethers of carboxylic acids such as acids, aniline and isocyanuric acid, epoxy olefin bonds in the molecule Vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohex
- the epoxy resin curing agent used in the embodiment of the present invention is not particularly limited as long as it cures an epoxy resin.
- a phenol compound, a carboxylic acid compound, an acid anhydride compound, an amine compound examples include benzoxazine resins, amine imide resins, and cyanate ester compounds.
- phenolic curing agents are particularly preferable.
- phenolic compound those having two or more phenol groups are preferable.
- carboxylic acid compound those having two or more carboxyl groups are preferable.
- examples include organic acids such as terephthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, pyromellitic acid, trimellitic acid, methyl nadic acid, dodecyl succinic acid, chlorendic acid, maleic acid, and adipic acid. It can be used alone or in combination of two or more.
- acid anhydride compound those having one or more acid anhydride groups are preferable.
- examples include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, maleic anhydride, etc. These can be used alone or in admixture of two or more.
- Aromatic amine compounds such as 3,3′-aminodiphenylmethane and 3,4′-diaminodiphenylmethane, aliphatic amine compounds such as m-xylylenediamine, diethylenetriamine
- benzoxazine-based compound those having two or more benzoxazine moieties are preferable, and examples thereof include Ba type benzoxazine and Bb type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd.).
- cyanate ester compound those having two or more cyanate groups are preferable, and examples thereof include Primate BADDY, Primeset BA230S, and Primate SET LECY manufactured by Lonza Japan.
- a filler can be further added as necessary.
- the filler may be either an organic filler or an inorganic filler. Any two or more kinds of fillers can be mixed and used.
- the compounding quantity of an inorganic filler is not specifically limited, Preferably, it can add in 60 weight% or less in a thermosetting resin composition. If it exceeds 60% by weight, the flexibility of the cured product of the resin composition tends to be impaired and fragile.
- Inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, titanate Examples include strontium, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Silica is particularly preferable.
- the inorganic filler preferably has an average particle size of 5 ⁇ m or less, and more preferably has an average particle size of 1 ⁇ m or less.
- Examples of the organic filler include acrylic rubber particles and silicone particles.
- the organic filler preferably has an average particle size of 5 ⁇ m or less, and more preferably has an average particle size of 1 ⁇ m or less.
- the average particle size can be measured with a laser diffraction / scattering particle size distribution analyzer LA-500 (manufactured by Horiba, Ltd.).
- resin additives and resin components other than the components (A) and (B) can be blended within a range in which the effects of the present invention are exhibited.
- resin additives include thickeners such as Orben (manufactured by Shiraishi Kogyo Co., Ltd.) and Benton (manufactured by Leox), silicone-based, fluorine-based or acrylic antifoaming agents, leveling agents, imidazole-based, thiazole.
- triazole-based adhesion promoters silane coupling agents and other surface treatment agents, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black and other colorants, phosphorus-containing compounds, bromine-containing compounds, hydroxylation Examples thereof include flame retardants such as aluminum and magnesium hydroxide, and antioxidants such as phosphorus antioxidants and phenolic antioxidants.
- HFA-NAP 2,6-bis (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -1,5-naphthalenediamine
- the obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried.
- absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁇ 1 and 1720 cm ⁇ 1.
- absorption of a hydroxyl group derived from an HFA group was confirmed at 3300 to 3500 cm ⁇ 1 .
- reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C.
- the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (A2) having an HFA group was produced.
- A2 polyimide resin
- ipzol is an aromatic high-boiling solvent manufactured by Idemitsu Kosan Co., Ltd.
- the content of the siloxane structure in the resin is 58.4% by weight
- the HFA group equivalent is 3316 g / mol.
- the obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried.
- absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁇ 1 and 1720 cm ⁇ 1.
- absorption of a hydroxyl group derived from an HFA group was confirmed at 3300 to 3500 cm ⁇ 1 .
- HFA-MDA 3,3′-bis (1-hydroxy-1-trifluoromethyl-2,2,2 -Trifluoroethyl) -4,4'-methylenedianiline
- reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C.
- the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (A4) having an HFA group was produced.
- the content of the siloxane structure in the resin is 70.9% by weight, and the HFA group equivalent is 2881 g / mol.
- the obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried.
- absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁇ 1 and 1720 cm ⁇ 1.
- absorption of a hydroxyl group derived from an HFA group was confirmed at 3300 to 3500 cm ⁇ 1 .
- the obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried.
- absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁇ 1 and 1720 cm ⁇ 1.
- absorption of a hydroxyl group derived from an HFA group was confirmed at 3300 to 3500 cm ⁇ 1 .
- reaction solution was heated and condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C.
- the temperature was further raised, and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, cooling was terminated, and a varnish containing 55% by weight of a polyimide resin (B1) having no phenol group and HFA group was produced.
- the content of the siloxane structure in the resin is 70.2% by weight.
- the obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried.
- absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁇ 1 and 1720 cm ⁇ 1. confirmed.
- 36 mg of the obtained polyimide resin varnish was weighed out and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the whole was adjusted to 5 g.
- the obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried.
- absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁇ 1 and 1720 cm ⁇ 1. confirmed.
- 36 mg of the obtained polyimide resin varnish was weighed out and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the whole was adjusted to 5 g.
- the obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried.
- absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁇ 1 and 1720 cm ⁇ 1. confirmed.
- 36 mg of the obtained polyimide resin varnish was weighed out and mixed with N-methylpyrrolidone in which 0.4% by weight of lithium bromide was dissolved, and the whole was adjusted to 5 g.
- AHPB 3-bis (4-amino-3-hydroxyphenoxy) benzene
- a varnish containing 55% by weight of a polyimide resin (B4) having a phenol group but not having an HFA group was prepared.
- the content of the siloxane structure in the resin is 65.3% by weight, and the OH equivalent is 1744 g / mol.
- DABS 3′-diamino-4,4′-dihydroxydiphenylsulfone
- the obtained polyimide resin varnish was applied on a copper plate, heated from 75 ° C. to 120 ° C. over 12 minutes, and further heated at 180 ° C. for 90 minutes to be dried.
- absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was observed at 1780 cm ⁇ 1 and 1720 cm ⁇ 1.
- absorption derived from a phenolic hydroxyl group was confirmed at 3300 to 3500 cm ⁇ 1 .
- dicyclopentadiene modified phenolic resin DPP6115L (manufactured by Nippon Oil Co., Ltd.) was used as a curing agent
- imidazole P200 (manufactured by Japan Epoxy Resin Co., Ltd.) was used as a curing accelerator.
- a solvent was mixed and used as necessary.
- the polyimide resin obtained in Synthesis Examples 1 to 10 and the resin composition prepared from the polyimide resin in the same manner as described above were applied to the glossy surface of the copper foil so that the thickness when dried was in the range of 40 to 100 ⁇ m. After heating at ⁇ 120 ° C. for 12 minutes, it was further heated at 180 ° C. for 90 minutes to produce a cured film on the copper foil. The copper foil on which the cured film was formed was immersed in a ferric chloride solution and etched away, and then dried at 100 ° C. for 10 minutes to produce a cured film from which the copper foil was removed.
- the cured film from which the copper foil has been removed is subjected to a tensile test using a Tensilon universal testing machine (manufactured by A & D Co., Ltd.) in accordance with Japanese Industrial Standard (JIS K7127), and the elastic modulus before heat treatment is measured. did.
- the cured film with copper foil obtained by the above method was (1) 220 ° C in air for 30 minutes, (2) 250 ° C in air for 30 minutes, (3) 270 ° C in air for 30 minutes, respectively.
- Heat treatment was performed.
- the cured film with copper foil after the heat treatment was immersed in a ferric chloride solution, the copper foil was removed by etching, and then dried at 100 ° C. for 10 minutes to prepare a cured film from which the copper foil was removed.
- the cured film from which the copper foil has been removed is subjected to a tensile test with a Tensilon universal testing machine (manufactured by A & D Co., Ltd.) in accordance with Japanese Industrial Standard (JIS K7127) and cured after heat treatment under each condition.
- JIS K7127 Japanese Industrial Standard
- Table 1 shows the results of the heat resistance test of the polyimide resins described in the table.
- Table 2 shows the results of the heat resistance test and solvent resistance test of the composition of the polyimide resin and the thermosetting resin described in the table.
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Abstract
Description
(1)ヘキサフルオロイソプロパノール基及びシロキサン構造を有するポリイミド樹脂。
(2)下式(1)及び(2);
で表される繰り返し単位を有する上記(1)記載のポリイミド樹脂。
(3)式(3)で表される四塩基酸二無水物と式(4)及び(5)であらわされるジアミン化合物とを反応させることにより製造されたものである上記(1)又は(2)記載のポリイミド樹脂。
(4)R1で示される4価の有機基が以下の式;
で表されるいずれかの構造を有する上記(2)又は(3)のポリイミド樹脂。
(5)R2で示されるヘキサフルオロイソプロパノール基を有する2価のジアミン残基が以下の式;
で表されるいずれかの構造を有する上記(2)~(4)のいずれかに記載のポリイミド樹脂。
(6)R3で示される2価のシロキサンジアミン残基が、以下の式;
で表される構造を有する上記(2)~(5)のポリイミド樹脂。
(7)式(3)で表される四塩基酸二無水物の酸無水物基の官能基当量数をX、反応系中に存在させる全てのジアミン化合物のアミノ基の官能基当量数をYとした場合に、0≦(X-Y)/X≦0.3の関係を満たすように反応させる上記(3)記載のポリイミド樹脂。
(8)ポリアミド樹脂中に含まれるシロキサン構造の割合が40~90重量%である上記(1)~(7)のいずれかに記載のポリイミド樹脂。
(9)ポリイミド樹脂中に含まれるヘキサフルオロイソプロパノール基の官能基当量が1000~5000g/molである上記(1)~(8)のいずれかに記載のポリイミド樹脂。
(10)数平均分子量が9000~50000である上記(1)~(9)のいずれかに記載のポリイミド樹脂。
(11)上記(1)~(10)のいずれかに記載のポリイミド樹脂及び熱硬化性樹脂を含有する樹脂組成物。
式中、芳香族環上の水素原子は、ハロゲン原子、炭素数1~8のアルキル基等で置換されていてもよい。
式中、芳香族環上の水素原子は、ハロゲン原子、炭素数1~8のアルキル基等で置換されていてもよい。
なお式(4-b)において、ナフタレン環上のアミノ基はそれぞれ同じベンゼン環に結合していてもよく、異なるベンゼン環に結合していてもよい。同様に、ヘキサフルオロイソプロパノール基が複数ある場合、それぞれ同じベンゼン環に結合していてもよく、異なるベンゼン環に結合していてもよい。
式(4-a)で表されるジアミン化合物は、国際公開第2006/043501号パンフレットに記載されている公知の方法に従って製造することができる。式(4-c)で表されるジアミン化合物は、国際公開第2006/041115号パンフレットに記載されている公知の方法に従って製造することができる。式(4-b)で表されるジアミン化合物は、国際公開第2006/043501号パンフレット、国際公開第2006/041115号パンフレットに記載されている公知の方法に準じて、対応するナフタレンジアミン化合物にヘキサフルオロアセトン又はヘキサフルオロアセトン・3水和物を反応させ、ヘキサフルオロイソプロパノール基をナフタレン環上に導入することにより製造することができる。これらヘキサフルオロイソプロパノール基を有するジアミン化合物は2種類以上を組み合わせて用いることができる。
なお酸無水物基の官能基当量数X(mol)は、酸無水物基の官能基当量をA1(g/mol)、仕込み量をB1(g)とすると、X=B1/A1の式で求めることができる。
すなわち、官能基当量とは、官能基1個当たりの化合物の分子量を表し、官能基当量数とは、化合物重量(仕込量)あたりの官能基の個数を表す。
[合成例1]
環流冷却器を連結した水分定量受器、窒素導入管、攪拌器を備えた500mLのセパラブルフラスコに、4,4’-(ヘキサフルオロイソプロピリデン)-ビス-(フタル酸二無水物)(以下、6FDAという)を25質量部、γ-ブチロラクトンを69.9質量部、トルエンを7質量部、ジアミノシロキサンX-22-9409(信越化学工業(株)製)を55.7質量部(アミン当量665)、2,6-ビス(1-ヒドロキシ-1-トリフルオロメチル-2,2,2-トリフルオロエチル)-1,5-ナフタレンジアミン(以下、HFA-NAPという)を6.7質量部加え、窒素気流下で45℃にて2時間攪拌して反応を行った。次いでこの反応溶液を昇温し、約160℃に保持しながら窒素気流下で縮合水をトルエンとともに共沸除去した。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認したところでさらに昇温し、200℃で1時間攪拌した。その後冷却して終了とし、HFA基(ヘキサフルオロイソプロパノール基)を有するポリイミド樹脂(A1)を55重量%含むワニスを作製した。この場合の、樹脂中のシロキサン構造の含有量は65.2重量%で、HFA基当量は3313g/molである。
環流冷却器を連結した水分定量受器、窒素導入管、攪拌器を備えた500mLのセパラブルフラスコに、6FDAを32質量部、γ-ブチロラクトンを28.6質量部、イプゾール150を28.6質量部、トルエンを7質量部、ジアミノシロキサンKF-8010(信越化学工業(株)製)を50.1質量部(アミン当量430)、HFA-NAPを6.3質量部加え、窒素気流下で45℃にて2時間攪拌して反応を行った。次いでこの反応溶液を昇温し、約160℃に保持しながら窒素気流下で縮合水をトルエンとともに共沸除去した。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認したところでさらに昇温し、200℃で1時間攪拌した。その後冷却して終了とし、HFA基を有するポリイミド樹脂(A2)を55重量%含むワニスを作製した。なお、イプゾールは出光興産(株)製の芳香族系高沸点溶剤である。この場合の、樹脂中のシロキサン構造の含有量は58.4重量%で、HFA基当量は3316g/molである。
環流冷却器を連結した水分定量受器、窒素導入管、攪拌器を備えた500mLのセパラブルフラスコに、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物(以下、BTDAという)を23質量部、γ-ブチロラクトンを30.9質量部、イプゾール150を30.9質量部、トルエンを7質量部、ジアミノシロキサンKF-8010(信越化学工業(株)製)を49.0質量部(アミン当量430)仕込み、窒素気流下で45℃にて1時間攪拌して反応を行い、さらに続いて、3,3’-ビス(1-ヒドロキシ-1-トリフルオロメチル-2,2,2-トリフルオロエチル)-4,4’-メチレンジアニリン(以下、HFA-MDAという)を6.1質量部加えて45℃にて2時間攪拌して反応を行った。次いでこの反応溶液を昇温し、約160℃に保持しながら窒素気流下で縮合水をトルエンとともに共沸除去した。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認したところでさらに昇温し、200℃で1時間攪拌した。その後冷却して終了とし、HFA基を有するポリイミド樹脂(A3)を55重量%含むワニスを作製した。この場合の、樹脂中のシロキサン構造の含有量は64.9重量%で、HFA基当量は3271g/molである。
環流冷却器を連結した水分定量受器、窒素導入管、攪拌器を備えた500mLのセパラブルフラスコに、BTDAを20質量部、γ-ブチロラクトンを70.9質量部、トルエンを7質量部、ジアミノシロキサンX-22-9409(信越化学工業(株)製)を61.5質量部(アミン当量665)、HFA-NAPを7.4質量部加えて窒素気流下で45℃にて2時間攪拌して反応を行った。次いでこの反応溶液を昇温し、約160℃に保持しながら窒素気流下で縮合水をトルエンとともに共沸除去した。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認したところでさらに昇温し、200℃で1時間攪拌した。その後冷却して終了とし、HFA基を有するポリイミド樹脂(A4)を55重量%含むワニスを作製した。この場合の、樹脂中のシロキサン構造の含有量は70.9重量%で、HFA基当量は2881g/molである。
環流冷却器を連結した水分定量受器、窒素導入管、攪拌器を備えた500mLのセパラブルフラスコに、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物(以下、DSDAという)を19質量部、γ-ブチロラクトンを22.7質量部、イプゾール150を22.7質量部、トルエンを7質量部、ジアミノシロキサンKF-8010(信越化学工業(株)製)を30.9質量部(アミン当量430)仕込み、窒素気流下で45℃にて1時間攪拌して反応を行い、さらに続いて、HFA-NAPを7.5質量部加えて45℃にて2時間攪拌して反応を行った。次いでこの反応溶液を昇温し、約160℃に保持しながら窒素気流下で縮合水をトルエンとともに共沸除去した。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認したところでさらに昇温し、200℃で1時間攪拌した。その後冷却して終了とし、HFA基を有するポリイミド樹脂(A5)を55重量%含むワニスを作製した。この場合の、樹脂中のシロキサン構造の含有量は55.7重量%で、HFA基当量は1810g/molである。
環流冷却器を連結した水分定量受器、窒素導入管、攪拌器を備えた500mLのセパラブルフラスコに、6FDAを25質量部、γ-ブチロラクトンを68.1質量部、トルエンを7質量部、ジアミノシロキサンX-22-9409(信越化学工業(株)製)を58.4質量部(アミン当量665)、1,5-ジアミノナフタレン(以下、NDAという)を1.8質量部加え、窒素気流下で45℃にて2時間攪拌して反応を行った。次いでこの反応溶液を昇温し、約160℃に保持しながら窒素気流下で縮合水をトルエンとともに共沸除去した。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認したところでさらに昇温し、200℃で1時間攪拌した。その後冷却して終了とし、フェノール基およびHFA基を有していないポリイミド樹脂(B1)を55重量%含むワニスを作製した。この場合、樹脂中のシロキサン構造の含有量は70.2重量%である。
環流冷却器を連結した水分定量受器、窒素導入管、攪拌器を備えた500mLのセパラブルフラスコに、6FDAを36質量部、γ-ブチロラクトンを19.6質量部、イプゾール150を29.3質量部、トルエンを7質量部、ジアミノシロキサンKF-8010(信越化学工業(株)製)を51.5質量部(アミン当量430)仕込み、窒素気流下で45℃にて1時間攪拌して反応を行い、さらに続いて、NDAを3.2質量部、γ-ブチロラクトンを16.4質量部、さらに6.7質量部のイプゾール150を加えて45℃、2時間攪拌して反応を行った。次いでこの反応溶液を昇温し、約160℃に保持しながら窒素気流下で縮合水をトルエンとともに共沸除去した。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認したところでさらに昇温し、200℃で1時間攪拌した。その後冷却して終了とし、フェノール基およびHFA基を有していないポリイミド樹脂(B2)を55重量%含むワニスを作製した。この場合、樹脂中のシロキサン構造の含有量は58.6重量%である。
環流冷却器を連結した水分定量受器、窒素導入管、攪拌器を備えた500mLのセパラブルフラスコに、BTDAを23質量部、γ-ブチロラクトンを29.5質量部、イプゾール150を29.5質量部、トルエンを7質量部、ジアミノシロキサンKF-8010(信越化学工業(株)製)を49.1質量部(アミン当量430)仕込み、窒素気流下で45℃にて1時間攪拌して反応を行い、さらに続いて、4,4’-ジアミノ-3,3’-ジメチルジフェニルメタン(以下、C-100という)を2.6質量部加えて45℃にて2時間攪拌して反応を行った。次いでこの反応溶液を昇温し、約160℃に保持しながら窒素気流下で縮合水をトルエンとともに共沸除去した。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認したところでさらに昇温し、200℃で1時間攪拌した。その後冷却して終了とし、フェノール基およびHFA基を有していないポリイミド樹脂(B3)を50重量%含むワニスを作製した。この場合、樹脂中のシロキサン構造の含有量は68.0重量%である。
環流冷却器を連結した水分定量受器、窒素導入管、攪拌器を備えた500mLのセパラブルフラスコに、DSDAを19質量部、γ-ブチロラクトンを55.2質量部、トルエンを7質量部、ジアミノシロキサンX-22-9409(信越化学工業(株)製)を44.1質量部(アミン当量665)仕込み、窒素気流下で45℃にて1時間攪拌して反応を行い、さらに続いて、1,3-ビス(4-アミノ-3-ヒドロキシフェノキシ)ベンゼン(以下、AHPBという)を6.3質量部加えて45℃にて2時間攪拌して反応を行った。次いでこの反応溶液を昇温し、約160℃に保持しながら窒素気流下で縮合水をトルエンとともに共沸除去した。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認したところでさらに昇温し、200℃で1時間攪拌した。その後冷却して終了とし、フェノール基を有するがHFA基を有していないポリイミド樹脂(B4)を55重量%含むワニスを作製した。この場合、樹脂中のシロキサン構造の含有量は65.3重量%で、OH当量は1744g/molである。
環流冷却器を連結した水分定量受器、窒素導入管、攪拌器を備えた500mLのセパラブルフラスコに、DSDAを19質量部、γ-ブチロラクトンを54.5質量部、トルエンを7質量部、ジアミノシロキサンX-22-9409(信越化学工業(株)製)を44.1質量部(アミン当量665)仕込み、窒素気流下で45℃にて1時間攪拌して反応を行い、さらに続いて、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルスルホン(以下、DABSという)を5.4質量部加えて45℃にて2時間攪拌して反応を行った。次いでこの反応溶液を昇温し、約160℃に保持しながら窒素気流下で縮合水をトルエンとともに共沸除去した。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認したところでさらに昇温し、200℃で1時間攪拌した。その後冷却して終了とし、フェノール基を有するがHFA基を有していないポリイミド樹脂(B5)を55重量%含むワニスを作製した。この場合、樹脂中のシロキサン構造の含有量は66.2重量%で;OH当量は1722g/molである。
エポキシ樹脂、硬化促進剤、硬化剤および、上記合成例1~10に従って合成したシロキサン含有ポリイミド樹脂を、表2に示す配合量(固形分の重量部で表示)で混合し、遠心脱泡混合機(商品名「泡取り練太郎」、(株)シンキー製)を用いて攪拌混合を行って樹脂組成物を得た。なお、エポキシ樹脂として、フェノールノボラック型エポキシ樹脂EP157(ジャパンエポキシレジン(株)製)を用いた。また、硬化剤として、ジシクロペンタジエン変性フェノール樹脂DPP6115L(新日本石油(株)製)を用い、硬化促進剤としてイミダゾール系P200(ジャパンエポキシレジン(株)製)を用いた。なお、必要に応じて溶剤を混合使用した。
次に得られた樹脂組成物を、離型処理を施したPETフィルム上に塗布し、75~120℃で12分加熱した後、さらに、180℃、90分加熱して40μm厚の硬化フィルムを得た。
硬化フィルムの表面を、アセトンを含ませた綿棒を用いて10gの加重で5回往復ラビングさせ、表面変化の有無について確認した。
(結果)実施例6~10および比較例9,10は、表面変化が観察されなかった(表2中、○で表示)。比較例6~8は色落ちが発生した(表2中、×で表示)。
合成例1~10で得られたポリイミド樹脂および上記と同様に該ポリイミド樹脂から調整した樹脂組成物を、乾燥時の厚みが40~100μmの範囲になるよう、銅箔光沢面に塗布し、75~120℃で12分加熱した後、さらに、180℃、90分加熱して銅箔上に硬化フィルムを作製した。硬化フィルムが形成された銅箔を、塩化第2鉄溶液に浸漬させてエッチング除去し、その後、100℃、10分間乾燥することで銅箔が除去された硬化フィルムを作製した。銅箔が除去された硬化フィルムを、日本工業規格(JIS K7127)に準拠し、テンシロン万能試験機((株)エー・アンド・デイ製)を用いて引っ張り試験し、熱処理前の弾性率を測定した。
Claims (11)
- ヘキサフルオロイソプロパノール基及びシロキサン構造を有するポリイミド樹脂。
- 式(3)で表される四塩基酸二無水物の酸無水物基の官能基当量数をX、反応系中に存在させる全てのジアミン化合物のアミノ基の官能基当量数をYとした場合に、0≦(X-Y)/X≦0.3の関係を満たすように反応させる請求項3記載のポリイミド樹脂。
- ポリアミド樹脂中に含まれるシロキサン構造の割合が40~90重量%である請求項1~7のいずれか1項に記載のポリイミド樹脂。
- ポリイミド樹脂中に含まれるヘキサフルオロイソプロパノール基の官能基当量が1000~5000g/molである請求項1~8のいずれか1項に記載のポリイミド樹脂。
- 数平均分子量が9000~50000である請求項1~9のいずれか1項に記載のポリイミド樹脂。
- 請求項1~10のいずれか1項に記載のポリイミド樹脂及び熱硬化性樹脂を含有する樹脂組成物。
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