JP3931387B2 - Polyamideimide resin and non-aqueous electrolyte secondary battery and circuit board using the same - Google Patents

Description

【００３７】
実施例 ６
反応容器に、トリメリット酸無水物９１ｇ、シクロヘキサンジカルボン酸８２ｇ、イソホロンジイソシアネート２２９ｇ、フッ化カリウム１．１６ｇ、ＨＹＣＡＲ−ＣＴＢＮ１３００×１３を１７５ｇをγ−ブチロラクトン４８９ｇとともに仕込み、１２０℃で１．５時間反応させた後、１８０℃に昇温して約３時間反応させた。冷却しながら６５２ｇのエタノールを加えて固形分濃度３０％のポリマー溶液を得た。
【００３８】
このポリマー溶液を大量の水中に投入して凝固させ、十分洗浄した後乾燥させた白色のポリマー粉をエタノール／トルエン（５０／５０重量％）の混合溶剤に固形分濃度が２５％となるように溶解した。このポリマーの物性を表２に示す。このポリマー溶液を２５μｍのポリイミド（東レ製カプトン）フイルムに乾燥膜厚が２０μｍとなるように塗布、乾燥後、塗布面に１２μｍの圧延銅箔を２００℃のプレス機で圧着させ銅張り積層板を得た。この銅張り積層板の１００℃、１５０℃における銅箔との密着力を表２に示す。
【００３９】
比較例 ３
反応容器に、トリメリット酸無水物９６ｇ、シクロヘキサンジカルボン酸を８６ｇ、イソホロンジイソシアネートを２２９ｇ、フッ化カリウム１．１６ｇとγ−ブチロラクトン３２３ｇを仕込み、実施例７と同じ条件でポリアミドイミド樹脂を合成、水中で凝固、洗浄、乾燥し、エタノール／トルエン（５０／５０重量％）に２５％となるように溶解した。このポリマーの物性を表２に示す。このポリマー溶液を用いて実施例７と同様の条件で、銅張り積層板の作製を試みたが、銅箔およびポリイミドフイルムに全く密着しなかった。
【００４０】
比較例 ４
市販のアクリロニトリル−ブタジエンゴム（日本合成ゴム製ニポール１００１ｊ）をトルエン／メチルエチルケトン（５０／５０重量％）に２５％となるように溶解した溶液を用いて、実施例７と同じ方法で銅張り積層板を作製した。表２に示すように高温での密着力が不十分であった。
【００４１】
【表２】

【００４２】
【発明の効果】
以上詳述したように、本発明のポリアミドイミド樹脂は、本来の耐熱性や耐薬品性を損なうことなく、柔軟性、着色性、溶剤溶解性を向上させているので、コーティング、回路基板などの接着剤、塗料、非水電解質二次電池電極用バインダーおよび液晶表示体や感熱記録用部材、繊維、フイルムなどに有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel polyamideimide resin. More specifically, coating agents and adhesives with excellent solvent solubility, flexibility, and heat resistance, optical members such as liquid crystal displays utilizing colorless transparency, paints utilizing chemical resistance, other injection molding materials, The present invention relates to a polyamide-imide resin useful for fibers, films and the like. In particular, the present invention provides a polyamide-imide resin useful for an electrode binder of a nonaqueous electrolyte secondary battery utilizing chemical resistance and a circuit board adhesive utilizing high-temperature adhesive force.
[0002]
[Prior art]
Originally, the polyamide-imide resin is excellent in heat resistance, chemical resistance, abrasion resistance, etc., can be injection-molded, and is dissolved in a solvent although special, such as N-methyl-2-pyrrolidone. Solution processing is possible, and it is applied to molding materials and heat-resistant insulating paints.
However, conventional aromatic polyamide-imide resins are colored and have limited properties because they are hard, brittle, and do not dissolve in solvents other than high-boiling amides.
[0003]
[Problems to be solved by the invention]
The present invention was devised in view of the current state of the prior art, and the object thereof is a novel polyamide-imide resin excellent in solvent solubility, flexibility, and heat resistance, and a non-aqueous electrolyte secondary battery using the same. And providing a circuit board.
[0004]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the present inventors have found that a polyamideimide copolymerized with a butadiene rubber is useful, and have completed the present invention.
That is, the present invention is a polyamide-imide characterized by comprising a copolymer of acrylonitrile-butadiene rubber containing a carboxyl group and trimellitic anhydride as an acid component, and having a logarithmic viscosity of 0.1 dl / g or more. Resin.
In a preferred embodiment of the present invention, acrylonitrile-butadiene rubber containing a carboxyl group is copolymerized in the polyamide-imide resin by 1% by weight or more.
In a preferred embodiment of the present invention, cyclohexanedicarboxylic acid is used as an acid component in the polyamideimide resin, and it contains a dicyclohexylmethane residue and / or an isophorone residue as an amine residue.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The polyamideimide resin of the present invention can be easily produced by dissolving trimellitic anhydride (acid chloride) and diamine or diisocyanate and butadiene rubber in a polymerization solvent and stirring with heating.
[0006]
In the present invention, the polymerization temperature of polyamideimide is usually 50 ° C to 220 ° C, more preferably 80 ° C to 200 ° C.
[0007]
When synthesizing a polyamideimide resin by the diisocyanate method, amines such as triethylamine, lutidine, picoline, triethylenediamine, lithium methoxide, sodium methoxide, The reaction may be carried out in the presence of a catalyst of an alkali metal such as potassium butoxide, potassium fluoride, or sodium fluoride, an alkaline earth metal compound, a metal such as cobalt, titanium, tin, or zinc, or a metalloid compound.
[0008]
As the acid component used for the synthesis of the polyamide-imide resin of the present invention, trimellitic anhydride is used, but a part thereof is other polycarboxylic acid anhydride, aliphatic and alicyclic dicarboxylic acid, aromatic Dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid can be substituted.
[0009]
Examples of the polyvalent carboxylic acid anhydride include pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid anhydride, 3,3 ′, 4,4 ′. -Diphenyltetracarboxylic acid anhydride, 4,4'-oxydiphthalic acid anhydride, ethylene glycol bisanhydro trimellitate, propylene glycol bis anhydro trimellitate, 1,4-butanediol bis anhydro trimellitate, hexa Examples include methylene glycol bisanhydro trimellitate, polyethylene glycol bis anhydro trimellitate, polypropylene glycol bis anhydro trimellitate, etc. Among them, ethylene glycol bis anhydro trimellitate is flexible and adherent. , Polymerizability and cost From the viewpoint of.
[0010]
Examples of the aliphatic and alicyclic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, vimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and tridecanedioic acid. , Cyclohexanedicarboxylic acid and acid chlorides thereof. Among these, cyclohexanedicarboxylic acid is preferable from the viewpoint of polymerizability, transparency, heat resistance, and chemical resistance.
[0011]
Examples of the aromatic dicarboxylic acid include isophthalic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, terephthalic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylmethane-2,4-dicarboxylic acid, and diphenylmethane-3. , 4-dicarboxylic acid, diphenylmethane-3,3'-dicarboxylic acid, 1,2-diphenylethane-4,4'-dicarboxylic acid, diphenylethane-2,4-dicarboxylic acid, diphenylethane-3,4-dicarboxylic acid Diphenylethane-3,3′-dicarboxylic acid, 2,2′-bis- (4-carboxyphenyl) propane, 2- (2-carboxyphenyl) -2- (4-carboxyphenyl) propane, 2- (3 -Carboxyphenyl) -2- (4-carboxyphenyl) propane, diphenyl ether- , 4'-dicarboxylic acid, diphenyl ether-2,4-dicarboxylic acid, diphenyl ether-3,4-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylsulfone-2 , 4-dicarboxylic acid, diphenylsulfone-3,4-dicarboxylic acid, diphenylsulfone-3,3'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, benzophenone-3,3'-dicarboxylic acid, pyridine-2 , 6-dicarboxylic acid, naphthalenedicarboxylic acid, bis-[(4-carboxy) phthalimide] -4,4′-diphenyl ether, bis-[(4-carboxy) phthalimide] -α, α′-metaxylene, and the like Examples include acid chlorides. Of these, isophthalic acid and terephthalic acid are preferred.
[0012]
Examples of the tricarboxylic acid include butane-1,2,4-tricarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, trimellitic acid, and the like. Moreover, these acid chlorides are mentioned.
[0013]
Examples of the tetracarboxylic acid include butane-1,2,3,4-tetracarboxylic acid, pyromellitic acid, benzophenone-3,3 ', 4,4'-tetracarboxylic acid, diphenyl ether-3,3', 4, 4'-tetracarboxylic acid, biphenyl-3,3 ', 4,4'-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid And naphthalene-1,4,5,8-tetracarboxylic acid.
[0014]
These acid components can be used as one kind or a mixture of two or more kinds or with trimellitic anhydride.
[0015]
On the other hand, diamine and diisocyanate are mentioned as an amine component used for the synthesis | combination of the polyamide-imide resin of this invention. Specifically, for example, m-phenylenediamine, p-phenylenediamine, oxydianiline, methylenediamine, hexafluoroisopropylidenediamine, diamino-m-xylylene, diamino-p-xylylene, 1,4-naphthalenediamine, 1, 5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, 2,2'-bis- (4-aminophenyl) propane, 2,2'-bis- (4-aminophenyl) hexafluoropropane 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ether, 3,4-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4-diaminodiphenyl ether, Sopropylidenedianiline, 3,3'-diaminobenzophenone, o-tolidine, 2,4-tolylenediamine, 1,3-bis- (3-aminophenoxy) benzene, 1,4-bis- (4-amino) Phenoxy) benzene, 1,3-bis- (4-aminophenoxy) benzene, 2,2'-bis- [4- (4-aminophenoxy) phenyl] propane, bis- [4- (4-aminophenoxy) phenyl ] Sulfone, bis- [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-bis- (4-aminophenoxy) biphenyl, 2,2'-bis- [4- (4-aminophenoxy) phenyl ] Aromatic diamines such as hexafluoropropane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, ethylenedia , Propylene diamine, tetramethylene diamine, hexamethylene diamine and other aliphatic diamines, isophorone diamine, 4,4'-diaminodicyclohexyl methane and other alicyclic diamines, etc., but are not particularly limited thereto. .
[0016]
Moreover, the isocyanate which substituted the amino group of the said diamine with -N = C = O group is mentioned. Among these, 4,4'-diaminodiphenylmethane (4,4'-diphenylmethane diisocyanate) and 4,4'-diaminodicyclohexylmethane (4,4'-dicyclohexylmethane diisocyanate) and / or isophorone diamine (isophorone diisocyanate). A mixture is preferable from the viewpoints of reactivity, cost, solubility, and flexibility. The said amine component may be used independently and may be used in mixture of 2 or more types.
[0017]
The acid component and amine component are usually synthesized by equimolar mixing, but one component can be slightly increased or decreased as necessary.
[0018]
The present invention is characterized in that a part of the acid component is replaced with a butadiene rubber for the purpose of further improving the flexibility and adhesiveness of the polyamideimide resin. As such a butadiene-based rubber, butadiene, acrylonitrile-butadiene and styrene-butadiene are preferable, and those containing a carboxyl group are particularly preferable. The carboxyl group may exist in the skeleton molecule of the butadiene rubber, or may exist at the terminal. Alternatively, hydrogenated butadiene rubber in which unsaturated groups in butadiene are substituted with hydrogen may be used. In addition, only 1 type of this butadiene-type rubber may be copolymerized, and 2 or more types may be copolymerized.
[0019]
In the polyamideimide resin of the present invention, the copolymerization amount of the butadiene rubber is preferably 1% by weight or more, and more preferably 5% by weight or more. When the copolymerization amount is less than 1% by weight, the flexibility and adhesiveness which are the objects of the present invention are not sufficiently improved. The average molecular weight of the butadiene-based rubber is preferably 1000 or more, and more preferably 3000 or more.
[0020]
Examples of the solvent used for the polymerization of the polyamideimide resin of the present invention include amide solvents such as N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, and dimethylimidazolidinone, and sulfur solvents such as dimethyl sulfoxide and sulfolane. Nitro solvents such as nitromethane and nitroethane, ether solvents such as diglyme and tetrahydrofuran, ketone solvents such as cyclohexanone and methyl ethyl ketone, nitrile solvents such as acetonitrile and propionitrile, γ-butyrolactone and tetramethyl urea A solvent having a relatively high dielectric constant may be used. Among these, N-methyl-2-pyrrolidone, dimethylimidazolidinone, and γ-butyrolactone are preferable from the viewpoint of polymerizability. These can be used alone or as a mixed solvent. Further, a solvent having a relatively low dielectric constant such as xylene or toluene may be mixed and used.
[0021]
The logarithmic viscosity of the polyamideimide resin in the present invention is 0.1 dl / g or more, preferably 0.2 dl / g or more, from the viewpoint of toughness, flexibility and the like. A logarithmic viscosity of less than 0.1 dl / g is not preferable because the resin becomes brittle even though it has flexibility. In the present invention, the logarithmic viscosity is measured by dissolving 0.5 g of a polymer in 100 ml of N-methyl-2-pyrrolidone and using an Ubbelohde viscosity tube.
[0022]
The polyamide-imide resin of the present invention can be used as it is as a polymer solution, for example, as an insulating paint, a chemical can paint, a binder for electrodes of secondary batteries such as lithium ion secondary batteries, etc. As a comparatively general-purpose, low-boiling solvent solution, it can be used as an adhesive for circuit boards, optical members such as plastic and film coating agents, liquid crystal display bodies and heat-sensitive recording bodies utilizing transparency and heat resistance. it can.
[0023]
The method for performing the solvent replacement is not particularly limited, and a known technique such as dry spinning or wet spinning may be applied. For example, in the case of a wet method, a polyamideimide resin solution is extruded from a nozzle into a coagulation bath made of a non-solvent of polyamideimide resin and mixed with the above polymerization solvent (preferably water), coagulated and desolvated, and then dried. Then, it may be redissolved in a low boiling point general-purpose solvent.
[0024]
The low-boiling general-purpose solvent is appropriately selected depending on the polymer composition. For example, ketones such as cyclohexanone, cyclopentanone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, methyl alcohol, ethyl alcohol and isopropyl alcohol And one or more mixed solvents of alcohols such as butyl alcohol and hydrocarbons such as benzene, toluene and xylene. Of these, the alcohol can be appropriately selected according to the purpose, but the most preferred are alcohols and hydrocarbon-based mixed solvents from the viewpoints of price, solubility, safety and the like.
[0025]
The polyamide-imide resin of the present invention exhibits excellent heat resistance, adhesiveness, chemical resistance, transparency, etc. even if used as it is, but depending on the application, acrylic resin, polyester resin, epoxy resin, melamine resin, Inorganic fillers such as functional isocyanate compounds, carbon particles, titanium oxide, silicon oxide, calcium carbonate, antistatic agents such as dyes, pigments, surfactants, etc. can be blended as long as the original performance of the polyamide-imide resin is not impaired. It is.
[0026]
【Example】
Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not particularly limited by these examples. Moreover, the characteristic of the polymer in an Example was measured with the following method.
[0027]
(1) 0.5 g of a logarithmic viscosity polymer was dissolved in 100 ml of N-methyl-2-pyrrolidone and measured with an Ubbelohde viscosity tube.
[0028]
(2) Glass transition temperature (Tg)
A rheology dynamic viscoelasticity measuring device was used. In an air atmosphere, the heating rate was 2 ° C./min and the frequency was 110 Hz.
[0029]
(3) Elongation at break Measured using Tensilon manufactured by Toyo Baldwin. The test was carried out at 25 ° C. and 65% RH at a pulling speed of 20 mm / min.
[0030]
Examples 1-4
In a reaction vessel, trimellitic anhydride (TMA), diphenylmethane diisocyanate (MDI), carboxyl-terminated acrylonitrile-butadiene rubber (HYCAR-CTBN 1300 × 13: acrylonitrile 27%, molecular weight 3500, manufactured by Ube Industries) (rubber component) and N- Methyl-2-pyrrolidone (NMP) was charged according to the formulation shown in Table 1, reacted at 120 ° C. for about 1 hour, then heated to 170 ° C. and reacted for 5 hours. While cooling, N-methyl-2-pyrrolidone was further added to obtain each polymer solution having a solid content concentration of 20%. Table 1 shows the physical properties of these polymers.
[0031]
A solution obtained by mixing 90 g of a carbon material having an average particle size of 25 μm and 60 g of N-methyl-2-pyrrolidone obtained by reacting and firing furfuryl alcohol with 50 g of these polymer solutions is dried on a copper foil having a thickness of 12 μm. A lithium ion secondary battery having a negative electrode formed by applying the film so as to have a thickness of 100 μm and pressing it at a pressure of 1 ton / cm ² after drying was produced. In all cases, the initial charge / discharge capacity exceeded 300 mAh / g, and the charge / discharge efficiency after 100 cycles was also good at 85% or more.
[0032]
Example 5
Polymerization was carried out with the same raw material composition as in Example 3 except that the amount of trimellitic anhydride in Example 3 was 1.1 times and the amount of NMP was changed as shown in Table 1. Table 1 shows the physical properties of this polymer. Moreover, as a result of producing and testing the negative electrode of a lithium ion secondary battery using this polymer in the same manner as in Example 1, the initial charge / discharge capacity was 300 mAh / g or more, and the charge / discharge efficiency after 100 cycles was 85%. It was good with the above.
[0033]
Comparative Example 1
A reaction vessel was charged with 192 g of trimellitic anhydride, 250 g of diphenylmethane diisocyanate, and 531 g of N-methyl-2-pyrrolidone, reacted under the same conditions as in Example 1, and 885 g of N-methyl-2-pyrrolidone was added. A polymer solution having a solid content concentration of 20% was obtained. Table 1 shows the physical properties of this polymer. Using this polymer solution, a negative electrode of a lithium ion secondary battery was produced in the same manner as in Example 1, and a charge / discharge test was performed. As a result, the initial charge / discharge capacity was as low as 225 mAh / g, and lacked practicality. .
[0034]
Comparative Example 2
The reaction vessel was charged with the raw material having the same formulation as in Example 3 and reacted at 80 ° C. for about 1 hour, after which 970 g of a mixed solution of n-butanol / N-methyl-2-pyrrolidone (10/90 wt%) was added. The reaction was stopped to obtain a polymer solution having a solid concentration of 20%. Table 1 shows the physical properties of this polymer. Using this polymer solution, an attempt was made to produce a negative electrode for a lithium ion secondary battery in the same manner as in Example 1. However, adhesion and flexibility were poor, and the negative electrode was easily peeled off from the copper foil.
[0035]
Reference Example The reaction was carried out under the same conditions as in Example 3, except that the carboxyl group-terminated acrylonitrile-butadiene rubber in Example 3 was replaced with butadiene rubber (HYCAR-CTB2000 × 162, molecular weight 3500, manufactured by Ube Industries). Table 1 shows the physical properties of this polymer. As a result of producing and testing a negative electrode of a lithium ion secondary battery using this polymer solution in the same manner as in Example 1, the initial charge / discharge capacity exceeded 300 mAh / g, and the charge / discharge efficiency after 100 cycles was also 85%. Exceeded value.
[0036]
[Table 1]

[0037]
Example 6
A reaction vessel was charged with 91 g of trimellitic anhydride, 82 g of cyclohexanedicarboxylic acid, 229 g of isophorone diisocyanate, 1.16 g of potassium fluoride, 175 g of HYCAR-CTBN1300 × 13 together with 489 g of γ-butyrolactone, and reacted at 120 ° C. for 1.5 hours. Then, the temperature was raised to 180 ° C. and reacted for about 3 hours. While cooling, 652 g of ethanol was added to obtain a polymer solution having a solid content of 30%.
[0038]
This polymer solution is poured into a large amount of water to coagulate, thoroughly washed, and dried white polymer powder in a mixed solvent of ethanol / toluene (50/50% by weight) so that the solid content concentration becomes 25%. Dissolved. Table 2 shows the physical properties of this polymer. This polymer solution was applied to a 25 μm polyimide (Toray Kapton) film so that the dry film thickness was 20 μm, dried, and then a 12 μm rolled copper foil was pressed onto the coated surface with a 200 ° C. press to form a copper-clad laminate. Obtained. Table 2 shows the adhesion of the copper-clad laminate to the copper foil at 100 ° C and 150 ° C.
[0039]
Comparative Example 3
A reaction vessel was charged with 96 g of trimellitic anhydride, 86 g of cyclohexanedicarboxylic acid, 229 g of isophorone diisocyanate, 1.16 g of potassium fluoride and 323 g of γ-butyrolactone, and a polyamideimide resin was synthesized under the same conditions as in Example 7, The solution was coagulated, washed, dried, and dissolved in ethanol / toluene (50/50% by weight) to 25%. Table 2 shows the physical properties of this polymer. An attempt was made to produce a copper-clad laminate under the same conditions as in Example 7 using this polymer solution, but it did not adhere to the copper foil and polyimide film at all.
[0040]
Comparative Example 4
A copper-clad laminate in the same manner as in Example 7 using a solution of commercially available acrylonitrile-butadiene rubber (Nipol 1001j made by Nippon Synthetic Rubber) dissolved in toluene / methyl ethyl ketone (50/50 wt%) to 25% Was made. As shown in Table 2, the adhesion at high temperature was insufficient.
[0041]
[Table 2]

[0042]
【The invention's effect】
As described above in detail, the polyamideimide resin of the present invention has improved flexibility, colorability, and solvent solubility without impairing the original heat resistance and chemical resistance. It is useful for adhesives, paints, binders for non-aqueous electrolyte secondary battery electrodes, liquid crystal displays, thermal recording members, fibers, films and the like.

Claims (9)

  A polyamide-imide resin comprising a copolymer of acrylonitrile-butadiene rubber containing a carboxyl group and trimellitic anhydride as an acid component, and having a logarithmic viscosity of 0.1 dl / g or more.   2. The polyamide-imide resin according to claim 1, wherein the acrylonitrile-butadiene rubber containing a carboxyl group is copolymerized in an amount of 1% by weight or more.   The polyamideimide resin according to claim 1 or 2, wherein cyclohexanedicarboxylic acid is used as a part of the acid component.   The polyamidoimide resin according to any one of claims 1 to 3, which contains a dicyclohexylmethane residue and / or an isophorone residue as an amine residue.   A non-aqueous electrolyte secondary battery comprising the polyamideimide resin according to claim 1 as a binder for a positive electrode and / or a negative electrode.   A circuit board using the polyamideimide resin according to claim 1 as an adhesive.   A polyamide-imide resin comprising at least one butadiene rubber copolymerized and having a logarithmic viscosity of 0.1 dl / g or more, wherein the butadiene rubber contains a carboxyl group, and a part of the acid component Polyamideimide resin characterized by using cyclohexanedicarboxylic acid for   A non-aqueous electrolyte secondary battery comprising the polyamideimide resin according to claim 7 as a binder for a positive electrode and / or a negative electrode.   A circuit board comprising the polyamideimide resin according to claim 7 as an adhesive.