JP4918057B2 - Phosphorus-containing ester group-containing tetracarboxylic acid or dianhydride thereof and phosphorus-containing polyesterimide - Google Patents

Description

  The present invention relates to a novel phosphorus-containing ester group-containing tetracarboxylic acid or a dianhydride thereof, a phosphorus-containing polyesterimide precursor produced using the same, and a phosphorus-containing polyesterimide.

  Polyimide is widely used as a material for electrical and electronic parts. For example, it has been adopted and studied for various applications such as base films for flexible printed boards, adhesive layers, protective films / insulating films for semiconductor elements, and display elements such as liquid crystal displays. As the application expands, the required characteristics have to change. In particular, as the flexible printed circuit board is made thinner, the base polyimide film is also made thinner. At the same time, the thin film of polyimide may reduce the inherent flame retardancy of the polyimide. For this reason, even a thin-film polyimide is required to have flame retardance equal to or higher than that of the conventional one.

  A technique for introducing a phosphazene compound, which is a phosphorus compound, as a highly flame-retardant polyimide has been disclosed (see, for example, Patent Documents 1 and 2). However, the flame retardant properties of membranes thinner than 25 μm are not described. Moreover, the synthesis method of the phosphazene compound to be introduced is complicated and includes a plurality of steps, and is not practical.

  Moreover, the phosphorus-containing diamine compound which contains phosphorus in a diamine component has been reported (for example, refer nonpatent literature 1 and 2). These are mainly used as epoxy resin curing agents to improve flame retardancy and heat resistance. However, there are few known techniques in which these phosphorus-containing diamine compounds are used for polyimide.

  There is a report of a heat-resistant material obtained by polymerizing phosphorus-containing diamine and bismaleimide to form polyamideimide (for example, Non-Patent Document 3). In addition, there is a report of using polyimide obtained by polymerizing phosphorus-containing diamine and aromatic dianhydride not containing phosphorus as a biomaterial (for example, Patent Document 3). However, these documents do not describe examples of flame retardant thin films.

Furthermore, with the recent high density integration of electronic materials, it is strongly desired that polyimide has good thermal diffusivity, but no polyimide thin film having good thermal diffusibility has been found so far.
JP 2006-77064 A JP 2006-124525 A International Publication No. 2006/127763 Pamphlet Journal of Adhesion Society, vol. 40, no. 2, 15-20 (2004) Polymer digest, 55 (6), 27-33 (2003) Polymer, vol. 43 (6), 1773-1779, (2002)

  The present invention provides a novel phosphorus-containing ester group-containing tetracarboxylic acid or its dianhydride that contributes to flame retardancy and high thermal diffusibility, a phosphorus-containing polyesterimide precursor and a phosphorus-containing polyesterimide produced using the same. It is to provide.

The present inventors have conducted various studies in order to solve the above-mentioned problems, and have found a phosphorus-containing ester group-containing tetracarboxylic acid having a specific structure or a dianhydride thereof, and further produced it using the same. The present invention was completed by finding that the phosphorus-containing polyesterimide precursor and phosphorus-containing polyesterimide produced have excellent flame retardancy and thermal diffusivity.
That is, the present invention is as follows.

〔式（１）及び（２）中、
Ａｒは、式（３）：

より選択される三価の芳香族基を表し、
式（１）〜（３）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、及びＲ_５は、同一または異なって、水素原子或いは炭素数１〜４のアルキル基を表す〕。 1. Phosphorus-containing ester group-containing tetracarboxylic acid represented by formula (1) or its dianhydride represented by formula (2):

[In Formula (1) and (2),
Ar represents the formula (3):

Represents a trivalent aromatic group selected from
In formulas (1) to (3), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

（式（５）中、Ａｒは式（１）及び（２）におけるのと同義であり、Ｒ_１及びＲ_２は式（１）〜（３）におけるのと同義であり、Ｘは、二価の芳香族基、脂環式基または脂肪族基を表し、Ｒは水素原子、或いは炭素数１〜４のアルキル基を表す。）で表される反復単位を有する含リンポリエステルイミド前駆体。 2. Formula (5):

(In the formula (5), Ar is as defined in the formulas (1) and (2), R ₁ and R ₂ are as defined in the formulas (1) to (3), and X is divalent. An aromatic group, an alicyclic group, or an aliphatic group, and R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

（式（４）中、Ａｒは式（１）及び（２）におけるのと同義であり、Ｒ_１及びＲ_２は式（１）〜（３）におけるのと同義であり、Ｘは式（５）におけるのと同義である）で表される反復単位を有する含リンポリエステルイミド。 3. Formula (4):

(In the formula (4), Ar has the same meaning as in the formulas (1) and (2), R ₁ and R ₂ have the same meaning as in the formulas (1) to (3), and X represents the formula (5 And a phosphorus-containing polyesterimide having a repeating unit represented by the following formula.

  The phosphorus-containing ester group-containing tetracarboxylic acid or its dianhydride according to the present invention is a raw material for a polyesterimide film having excellent flame retardancy and / or thermal diffusibility, a curing agent or resin modification for a heat-resistant flame-retardant epoxy resin. Useful as an agent.

  Although embodiments of the present invention will be described in detail below, these are examples of the embodiments of the present invention, and the present invention is not limited to these.

<Phosphorus-containing ester group-containing tetracarboxylic acid or dianhydride thereof and production method thereof>
The phosphorus-containing ester group-containing tetracarboxylic acid or dianhydride thereof of the present invention is represented by the formula (1) or (2). Here, hydrogen, methyl and ethyl are preferable as R ₁ , R ₂ and R ₃ .

  The manufacturing method of the phosphorus-containing ester group containing tetracarboxylic acid or its dianhydride of this invention is not specifically limited, It can manufacture by a conventionally well-known method. For example, it can be manufactured based on the technique disclosed in JP-A-2006-206486.

（式（６）中、Ａｒは式（１）及び（２）におけるのと同義であり、Ｒ_１及びＲ_２は式（１）〜（３）におけるのと同義であり、Ｒ_ａは、同一または異なって、炭素数１〜４のアルキル基を表す）で表される含リン芳香族アルカンエステルと、式（７）：

で示されるトリメリット酸無水物とを、相間移動触媒の存在下、溶媒中でエステル交換反応させて製造することができる。 That is, the phosphorus-containing ester group-containing tetracarboxylic acid or dianhydride thereof of the present invention has the formula (6):

(In the formula (6), Ar is as defined in the formulas (1) and (2), R ₁ and R ₂ are as defined in the formulas (1) to (3), and R _a is the same. Or a phosphorus-containing aromatic alkane ester represented by the formula (7):

The trimellitic anhydride represented by the formula (1) can be produced by a transesterification reaction in a solvent in the presence of a phase transfer catalyst.

（式（８）中、Ａｒは式（１）及び（２）におけるのと同義であり、Ｒ_１及びＲ_２は式（１）〜（３）におけるのと同義である。）
で表される化合物を塩化アセチル等のハロゲン化アセチルによりアセトキシ化することで容易に製造することができる。 The phosphorus-containing aromatic alkane ester according to the formula (6) in the present invention has the formula (8):

(In the formula (8), Ar has the same meaning as in the formulas (1) and (2), and R ₁ and R ₂ have the same meaning as in the formulas (1) to (3).)
Can be easily produced by acetoxylation with an acetyl halide such as acetyl chloride.

  Examples of the phosphorus-containing aromatic alkane ester according to the formula (6) in the present invention include acetic acid ester, propionic acid ester, butyric acid or isobutyric acid ester, preferably acetic acid ester.

  The transesterification reaction between the phosphorus-containing aromatic alkane ester represented by the formula (6) and trimellitic anhydride is carried out in a solvent in the presence of a phase transfer catalyst, and the phosphorus-containing ester represented by the formula (2) A group-containing tetracarboxylic dianhydride is obtained. Here, it is preferable to react 0.95 to 1.50 mol of phosphorus-containing aromatic alkane ester with respect to 2 mol of trimellitic anhydride. The phosphorus-containing ester group-containing tetracarboxylic acid represented by the formula (1) can be easily obtained by reacting the phosphorus-containing ester group-containing tetracarboxylic dianhydride represented by the formula (2) with water.

  The phase transfer catalyst according to the present invention may be any catalyst that can withstand the reaction temperature set in the above method, and known ones such as ammonium salts, phosphonium salts, sulfonium salts, crown ethers and the like can be used. Preferably, a phosphonium salt or a sulfonium salt can be used. Examples of the phosphonium salt include triphenylphosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, and tetrabutylphosphonium chloride. Examples of the sulfonium salt include sulfonium iodide and triphenylsulfonium bromide.

  The amount of the phase transfer catalyst is 0.1 to 10% by weight, preferably 0.3 to 5.0% by weight, based on the phosphorus-containing aromatic alkane ester represented by the formula (6).

  A solvent is used for the transesterification reaction. The solvent to be used has a boiling point in the vicinity of the reaction temperature (170 to 250 ° C.) or exceeding the reaction temperature, and is appropriately selected according to the set reaction temperature, but does not participate in the reaction, that is, a phosphorus-containing aromatic alkane ester, Must be inert to trimellitic anhydride and phase transfer catalyst. For example, polychlorinated benzenes such as 1,2-dichlorobenzene and 1,2,4-trichlorobenzene, and polychlorinated toluenes such as 2,3-dichlorotoluene can be used. Dehydrated aprotic polar solvents such as sulfolane and N-methylpyrrolidone can also be used. The usage-amount of a solvent is 50 to 800 weight% with respect to the phosphorus-containing aromatic alkane ester shown by Formula (6), Preferably it is 100 to 500 weight%.

  The transesterification reaction temperature is 170 to 250 ° C, preferably 200 to 240 ° C.

  After completion of the reaction, the reaction mother liquor is filtered off as it is to obtain a crude product. The crude product is purified by reflux washing with an aromatic solvent such as toluene, xylene, or chlorinated benzene such as monochlorobenzene. At this time, an amide solvent such as dimethylformamide or dimethylacetamide may coexist. The purified product washed under reflux is filtered off and dried at 160 to 250 ° C., preferably 180 to 220 ° C., to obtain the desired product.

<Phosphorus-containing polyesterimide precursor and method for producing the same>
The phosphorus-containing polyesterimide precursor of the present invention has a repeating unit represented by the formula (5). X in Formula (5) is an arbitrary divalent aromatic group, alicyclic group or aliphatic group, and is derived from a diamine as a synthesis raw material. Particularly preferred as X is 4,4′-oxydianiline as the divalent aromatic group, cyclohexanediamine as the divalent alicyclic group, and divalent aliphatic group as the divalent aliphatic group. Hexamethylenediamine.

  The phosphorus-containing polyesterimide precursor preferably contains 5% or more, more preferably 50% or more, and most preferably 100% of the repeating unit represented by the formula (5) with respect to all repeating units.

  The phosphorus-containing polyesterimide precursor may have a viscosity of preferably 2000 mPa · s or more, more preferably 2000 to 200000 mPa · s, and most preferably 2000 to 100000 mPa · s. The phosphorus-containing polyesterimide precursor contributes to the flame retardancy and high thermal diffusibility of the phosphorus-containing polyesterimide.

  The phosphorus-containing polyesterimide precursor can be produced by a known method using the phosphorus-containing ester group-containing tetracarboxylic dianhydride obtained above. That is, a method for producing a phosphorus-containing polyesterimide precursor (polyamic acid) includes an acid dianhydride containing a phosphorus-containing ester group-containing tetracarboxylic dianhydride represented by the formula (1) as an essential component, and a formula (4 ) And one or more diamine components corresponding to X are reacted with the acid dianhydride at an arbitrary ratio within the range of 0.5 to 2.0 equivalents. When the molecular weight of the phosphorus-containing polyesterimide, which will be described later, obtained from the phosphorus-containing polyesterimide precursor is reduced and the end of the phosphorus-containing polyesterimide is obtained as an acid anhydride, the amount of the diamine component relative to the acid anhydride is brought close to 0.5 equivalents. In addition, when the molecular weight of the phosphorus-containing polyesterimide is reduced and the terminal is obtained as an amine, the amount of the diamine component relative to the acid anhydride may be close to 2.0 equivalents. Furthermore, when it is desired to increase the molecular weight of the resulting phosphorus-containing polyesterimide, the amount of the diamine component relative to the acid anhydride may be close to 1.0 equivalent.

  The reaction temperature is generally in the range of 0 ° C to 100 ° C. Preferably it is 0 degreeC-60 degreeC, More preferably, it is 0 degreeC-40 degreeC. Depending on the reactivity of the diamine component to be used, if the reaction temperature is too low, the reaction takes time. On the other hand, if the reaction temperature is too high, the molecular weight tends not to increase when a polyamic acid is used. The reaction time is approximately 30 minutes to 48 hours.

  When producing a phosphorus-containing polyesterimide precursor using a phosphorus-containing ester group-containing tetracarboxylic dianhydride, in order to exert the flame-retardant effect of the phosphorus-containing polyesterimide, the total of the acid dianhydrides to be used, The phosphorus-containing ester group-containing tetracarboxylic dianhydride needs to be 1 mol% to 100 mol%, preferably 5 mol% to 100 mol%, more preferably 7 to 100 mol%. If the ratio of the phosphorus-containing ester group-containing tetracarboxylic dianhydride is 1 mol% or less, the flame retardant effect becomes insufficient, and even if the ratio is 20 mol% or more, a significant improvement in the flame retardant effect cannot be expected. The ratio can be 1 to 20 mol%, preferably 5 to 15 mol%, more preferably 7 to 13 mol%.

  When producing a phosphorus-containing polyesterimide precursor using a phosphorus-containing ester group-containing tetracarboxylic dianhydride, in order to exert the thermal diffusion effect of the phosphorus-containing polyesterimide, the total of the acid dianhydrides to be used, The phosphorus-containing ester group-containing tetracarboxylic dianhydride is required to be 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more. When it is less than 50 mol%, the thermal diffusion effect is not remarkable.

  As the reaction solvent, an aprotic polar solvent is usually used, but other solvents may be used. Usable solvents include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, sulfolane, hexamethyl phosphor Amide, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- Examples include xylenol, ethylene glycol, diethylene glycol, triethylene glycol, glyme, diglyme, triglyme, toluene, xylene and the like. These solvents can be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount of a solvent, It is desirable for the content of the polyamic acid to produce | generate to be 5 to 20 weight% or less.

  In addition to the phosphorus-containing ester group-containing tetracarboxylic dianhydride which is an essential component, other acid dianhydrides can be used, but there is no particular limitation on the other acid dianhydrides. For example, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, Pyromellitic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ) Methane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2 , 3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, , 2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis ( 3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′ 3,3′-benzophenone tetracarboxylic dianhydride and the like.

  There is no restriction | limiting in particular as 1 or more types of diamine component used for reaction. For example, aromatic diamines include p-phenylene diamine, m-phenylene diamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether. 3,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Sulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 4,4 '-Diam Benzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 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-aminophenoxy) phenyl] 1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, , 3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4′-bis (4-aminophenoxy) benzene, 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] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bi [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] Examples of aliphatic or cycloaliphatic diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9 Diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 4,4-dimethylheptamethylenediamine, di (aminomethyl) cyclohexane, Diaminodicyclohexylmethane, diaminodicyclohexyl ether, diaminocyclohexane, diaminohexahydrodiphenyl, isophoronediamine, m-xylylenediamine, p-xylylenediamine, 1,3-bis (aminopropyl) tetramethylsiloxane, α, ω-bis ( 3-aminopropyl) polydimethylsiloxane. Moreover, phosphorus-containing diamine as described in a nonpatent literature 1-3 and the patent document 3 can also be used as a diamine component.

  Furthermore, the following monoamines and dicarboxylic acid anhydrides can be added for the purpose of adjusting the molecular weight or for other purposes. The monoamine used is aniline, 4-phenylaniline, 4-phenoxyaniline, cyclohexylamine, m-aminophenylacetylene, etc., and the dicarboxylic acid anhydride is maleic acid anhydride, phthalic acid anhydride, nadic acid anhydride. Products, phenylethynylphthalic anhydride, trimellitic anhydride, acetylinylphthalic anhydride, and the like.

<Phosphorus-containing polyesterimide and production method thereof>
The phosphorus-containing polyesterimide of the present invention has a repeating unit represented by the formula (4). X in formula (4) is the same as in formula (5). The phosphorus-containing polyesterimide preferably contains 5% or more, more preferably 50% or more, and most preferably 100% of the repeating unit represented by the formula (4) with respect to all repeating units. The phosphorus-containing polyesterimide is insoluble in an organic solvent, and the viscosity may not be measured. However, when the solvent is soluble, it is preferably 1000 mPa · s or more, more preferably 1000 to 50000 mPa · s, and most preferably 1000 to 30000 mPa. Has a viscosity of s. The phosphorus-containing polyesterimide has flame retardancy and high thermal diffusivity.

  The method for producing the phosphorus-containing polyesterimide of the present invention is a method in which the polyamic acid solution, which is the above-mentioned phosphorus-containing polyesterimide precursor, is heated and dehydrated, or chemically ring-closed in a solution in the presence of a condensation catalyst. A known method such as a method for imidization can be used.

  The method of heating and dehydrating a polyamic acid solution to imidize is to apply a polyamic acid solution to the surface of a substrate such as stainless steel foil, aluminum foil, copper foil, glass, silicon, etc., and heat dehydrate in the range of 100 ° C to 500 ° C. To make polyimide. In this method, the phosphorus-containing polyesterimide is usually obtained in a film state by peeling from the substrate. Moreover, when apply | coating to copper foil etc. and imidating, it may be used for materials, such as a laminated board, as it is. Alternatively, imidization by heat dehydration is performed by adding a solvent that azeotropes with water in advance to the polyamic acid solution, performing thermal imidization in the solvent, and discharging water generated along with the imidization to the outside of the system. It can carry out also by the method of obtaining a polyimide inside. In this case, the polyimide is obtained in a state where it is dissolved or precipitated in the solvent. When the obtained polyimide is dissolved in a solvent, as described above, the solution is applied to the surface of a substrate such as stainless steel foil, aluminum foil, copper foil, glass, silicon, etc. The mixture is heated to the boiling point of the solvent to remove the solvent and peeled from the substrate to obtain a polyimide film, or used as a material for a laminated board or the like as it is. Moreover, what is necessary is just to fractionate the depositing polyimide by methods, such as filtration, when depositing in a solvent. The separated polyimide can be dried and dissolved in another solvent and used for applications such as a film, or can be pulverized after drying and used for injection molding or compression molding.

  The method of imidization by chemical ring closure in a solution in the presence of a condensation catalyst is the addition of acetic anhydride and pyridine, picoline, imidazole, quinoline, triethylamine, etc. to the polyamic acid solution that is the resulting phosphorus-containing polyesterimide precursor. Then, imidization is performed by heating in the range of 40 ° C. to 160 ° C. for 1 to 24 hours. After completion of the reaction, the phosphorus-containing polyesterimide is usually obtained in the form of a solution. Therefore, the solution is put into a poor solvent such as water, methanol, ethanol, toluene, xylene, acetone, or a mixture thereof, and the polyimide is added. The target product is obtained in a solid state by precipitation and filtration. The obtained polyimide can be dissolved in another solvent and used for applications such as a film, or can be pulverized after drying and used for injection molding or compression molding.

  Hereinafter, the present invention will be illustrated by specific examples, but the present invention is not limited to the contents of the examples.

^１Ｈ−ＮＭＲスペクトル：日本電子社製 核磁気共鳴装置 ＪＮＭ−ＡＬ４００ （ＤＭＳＯ−ｄ_６）
燃焼試験：ＵＬ規格に準じて判定した。
熱拡散率：（株）アイフェイズ社製 アイフェイズモバイル
ガラス転位温度：（株）島津製作所製 ＤＳＣ−６０ （昇温速度：１０℃／分、窒素ガス中）
粘度：東機産業（株）製 Ｂ形粘度計 （測定温度２５℃） (Description of abbreviations and test methods)

¹ H-NMR spectrum: JEOL nuclear magnetic resonance apparatus JNM-AL400 (DMSO-d ₆ )
Combustion test: Determined according to UL standards.
Thermal diffusivity: manufactured by Eye Phase Co., Ltd. Eye phase mobile glass transition temperature: manufactured by Shimadzu Corporation DSC-60 (heating rate: 10 ° C./min, in nitrogen gas)
Viscosity: Toki Sangyo Co., Ltd. B-type viscometer

で示され、Ｒ_ａがＣＨ_３である式（６）で表される化合物：マナック社製）３２.４３ｇ（０.１０モル）、トリメリット酸無水物３８．４３ｇ（０．２０モル）、１，２，４−トリクロロベンゼン１２０ｇ及び臭化テトラフェニルホスホニウム０．４２ｇを仕込み、窒素雰囲気下２１０℃で８時間反応させた。反応生成物を濾別し、粗製物を得た。粗製物をジメチルホルムアミド１０％を含むトルエン溶液で１時間還流洗浄し、冷却後、濾別した。得られたウエット品を１８０℃で乾燥し、目的物５７.０ｇを得た。本化合物の構造はＮＭＲにて確認した（図１）。融点：３０８.０℃。 (Example 1) Method for producing phosphorus-containing ester group-containing acid dianhydride (* 1: TAHCHQ) Phosphorus-containing aromatic alkane ester in a four-necked flask equipped with a stirrer, thermometer, condenser for distillation, and nitrogen gas inlet tube (Ar is the following formula:

A compound represented by formula (6) wherein R _a is CH ₃ : Manac Co., Ltd.) 32.43 g (0.10 mol), trimellitic anhydride 38.43 g (0.20 mol), 120 g of 1,2,4-trichlorobenzene and 0.42 g of tetraphenylphosphonium bromide were charged and reacted at 210 ° C. for 8 hours in a nitrogen atmosphere. The reaction product was filtered off to obtain a crude product. The crude product was refluxed and washed with a toluene solution containing 10% of dimethylformamide for 1 hour, cooled and filtered. The obtained wet product was dried at 180 ° C. to obtain 57.0 g of the desired product. The structure of this compound was confirmed by NMR (FIG. 1). Melting point: 308.0 ° C.

で示され、Ｒ_ａがＣＨ_３である式（６）で表される化合物４５.８４ｇ（０.１０モル）を用いた以外、実施例１に記載した方法に従って、本発明の式（２）で表される含リンエステル基含有酸二無水物（＊５：ＴＡＨＣＮＱ）を合成し、目的物６２．１ｇを得た。本化合物の構造はＮＭＲにて確認した（図２）。融点：３１１．２℃。 (Example 2) Method for producing phosphorus-containing ester group-containing acid dianhydride (* 5: TAHCNQ) As a phosphorus-containing aromatic alkane ester, Ar is represented by the following formula:

In accordance with the method described in Example 1, except that 45.84 g (0.10 mol) of the compound represented by formula (6) wherein R _a is CH ₃ is used, the formula (2) of the present invention is used. A phosphorus-containing ester group-containing acid dianhydride represented by the formula (* 5: TAHCNQ) was synthesized to obtain 62.1 g of the desired product. The structure of this compound was confirmed by NMR (FIG. 2). Melting point: 311.2 ° C.

(Example 3)
In a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction tube, * 2: ODA (manufactured by Wakayama Seika Kogyo Co., Ltd.) 920.02 g (0.1 mol), N-methyl-2 -350 g of pyrrolidone was charged and dissolved. Next, 67.25 g (0.1 mol) of the phosphorus-containing ester group-containing acid dianhydride (* 1: TAHCHQ) obtained in Example 1 was charged into the flask. At this time, the temperature in the flask was kept at 20 ° C. to 45 ° C., and stirring was continued for 8 hours to complete the reaction. The viscosity (by a B-type viscometer) of the obtained reaction liquid containing polyamic acid was 100,000 mPa · s. Subsequently, this polyamic acid is applied to a glass plate and heated in a hot air dryer in order of 80 ° C. for 5 minutes, 130 ° C. for 5 minutes, 180 ° C. for 5 minutes, 210 ° C. for 5 minutes, 260 ° C. for 10 minutes, and 310 ° C. for 10 minutes. Then, thermal imidization was performed. After thermal imidization, the film was peeled off from the glass plate, and the thickness was measured and found to be 20 μm. It was 220 degreeC when the glass transition temperature (Tg) of this film was measured by DSC. When the flammability of this film was determined according to the UL standard, it was 94 VTM-0. Moreover, it was 1.23E-7 when the thermal diffusivity of this film was measured.

Example 4
In a four-necked flask equipped with a stirrer, a thermometer, a distillation condenser, and a nitrogen gas inlet tube, 13.5 g (0.02 mol) of TAHCHQ obtained in Example 1, * 3: ODPA (manac Co., Ltd.) ) 55.84 g (0.18 mol), mixed xylene 125 g, and N-methyl-2-pyrrolidone 140 g, and α, ω-bis (3-aminopropyl) polydimethylsiloxane (Shin-Etsu Chemical Co., Ltd.) ) 49.8 g (0.06 mol) of KF-8010 amine equivalent 415) was added and stirred at 40 ° C. or lower for 4 hours. Next, * 4: BAPP (manufactured by Wakayama Seika Kogyo Co., Ltd.) 57.47 g (0.14 mol) was added, and stirring was continued at 40 ° C. or lower for 4 hours. The viscosity (by a B-type viscometer) of the obtained reaction liquid containing polyamic acid was 10000 mPa · s. Further, the system was heated and stirred to 200 ° C. over 1 hour, and stirring was continued at 200 ° C. for 6 hours. The solvent and water distilled off in the middle were discharged out of the system through a distillation condenser. After the heating, the solution was diluted with N-methyl-2-pyrrolidone to obtain a polyimide solution having a concentration of about 30%. The viscosity of the obtained phosphorus-containing polyesterimide solution was 3000 mPa · s. This solution was applied to a glass plate, and the solvent was removed by drying in a hot air dryer in the order of 80 ° C. for 5 minutes, 130 ° C. for 3 minutes, 180 ° C. for 3 minutes, 210 ° C. for 3 minutes, and 260 ° C. for 10 minutes. After drying, the film was peeled off from the glass plate and the thickness was measured and found to be 20 μm. It was 130 degreeC when the glass transition temperature (Tg) of this film was measured by DSC. It was 94 VTM-1 when the combustibility of this film was measured according to UL specification.

(Comparative Example 1)
A film was prepared in the same manner as in Example 4 except that TAHCHQ was not used and the amount of ODPA used was changed to 0.2 mol. It was 130 degreeC when the glass transition temperature (Tg) of this film was measured by DSC. When the flammability of this film was determined according to the UL standard, it was not flame retardant because it burned.

(Reference Example 1)
It was 8.18E-8 when the thermal diffusivity of Kapton (trademark) H by Toray DuPont Co., Ltd. which is a general purpose polyesterimide which does not contain phosphorus was measured.

  The polyesterimide obtained by using the phosphorus-containing ester group-containing tetracarboxylic dianhydride of the present invention can maintain the same heat and flame resistance as before even when the electronic parts are made lighter and shorter. it can. And since it has a favorable thermal diffusivity, the thermal storage of an electronic device can be thermally radiated effectively. In addition, it can be used as a curing agent for epoxy resins and a heat and flame retardant modifier for other resins.

1 is a diagram showing a ¹ H-NMR spectrum of TAHCHQ described in Example 1. FIG. 1 is a diagram showing a ¹ H-NMR spectrum of TAHCNQ described in Example 1. FIG.

Claims (3)

Phosphorus-containing ester group-containing tetracarboxylic acid represented by formula (1) or its dianhydride represented by formula (2):

[In Formula (1) and (2),
Ar represents the formula (3):

Represents a trivalent aromatic group selected from
In formulas (1) to (3), R ₁ , R ₂ , R _3, R ₄ and R ₅ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Formula (5):

(In formula (5), Ar has the same meaning as in formulas (1) and (2) of claim _1, and R ₁ and R ₂ have the same meaning as in formulas (1) to (3) of claim 1. X represents a divalent aromatic group, alicyclic group or aliphatic group, and R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Phosphor polyesterimide precursor. Formula (4):

(In the formula (4), Ar has the same meaning as in the formula of claim 1 (1) and (2), _{R 1} and _{R 2} are same as in the formula of claim 1 (1) - (3) Wherein X is as defined in formula (5) of claim 2).

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