JP6465724B2 - Polyamide resin and polyimide resin - Google Patents

Description

  The present invention is obtained by reacting a polyfunctional acid anhydride (A) obtained by introducing an acid anhydride group having a specific structure with a polyhydric alcohol compound, with a compound (B-1) further having an amino group. Polyamide resin (E) obtained by reacting a compound (B-2) having an isocyanate group with a polyamide resin (C), a polyimide resin (D) derived from (C), and a polyfunctional acid anhydride (A) ), A polyamide resin (C), a polyimide resin (D), or a composition containing a polyimide resin (E), and applications.

  Polyamide resins and polyimide resins are resins derived from carboxylic acid anhydride compounds and amino group-containing compounds or isocyanate group-containing compounds, and are widely used as compounds having high heat resistance. In general, it is widely used for applications such as electrical and electronic materials and high heat resistant materials. However, generally used polyamide resins and polyimide resins have high colorability and have been difficult to use in applications with high transparency (Patent Document 1).

  For this reason, in order to obtain a polyamide resin and a polyimide resin imparted with transparency, various acid anhydride-containing compounds, amino group-containing compounds, and isocyanate group-containing compounds are reacted to obtain a resin (Patent Document 2). Patent Document 3).

  However, heat resistance, transparency, and toughness of resin are contradictory properties. Transparency and toughness deteriorate when trying to improve heat resistance. It became difficult to obtain a material having these characteristics at a high level.

JP 2000-038662 A JP 2010-1000067 A JP 2013-010917 A

  An object of this invention is to obtain the polyamide resin and polyimide resin which have transparency, heat resistance, and toughness.

  The present inventors have obtained a polyamide resin obtained by reacting a polyfunctional acid anhydride (A) having a specific structure with a compound (B-1) having an amino group or a compound (B-2) having an isocyanate group. Or it discovered that the polyimide resin had the characteristics which have transparency, heat resistance, and toughness.

That is, the present invention relates to (1) a polyhydric alcohol (a) having three or more hydroxyl groups in one molecule and a nuclear hydrogenated trimellitic anhydride halide (b-1) or a nuclear hydrogenated trimellitic anhydride halide (b -1) and a trimellitic anhydride (b-2) mixture obtained by reacting a polyfunctional acid anhydride (A) with an amino group-containing compound (B-1) to obtain a polyamide resin Regarding (C).
(2) The polyhydric alcohol (a) is represented by the following general formula (1)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６はそれぞれ独立して、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は水素原子、水酸基、炭素数１〜１１の炭化水素基、もしくは炭素数１〜４のヒドロキシアルキル基を表し、Ｒ^２は水酸基、もしくは炭素数１〜４のヒドロキシアルキル基を表す。ｌは０〜１１、ｍとｎはそれぞれ１〜１１の整数を表す。）で表される多価アルコール（ａ−１）である前記ポリアミド樹脂（Ｃ）に関する。

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are a hydrogen atom, hydroxyl group, carbon number 1 Represents a hydrocarbon group having ˜11 or a hydroxyalkyl group having 1 to 4 carbon atoms, R ² represents a hydroxyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, l is 0 to 11, m and n are each 1; To the polyamide resin (C), which is a polyhydric alcohol (a-1) represented by.

(3) The polyhydric alcohol (a) obtained by reacting the polyfunctional acid anhydride (A) with the polyhydric alcohol (a) at least one selected from the group consisting of alkylene oxide, cyclic ether, and cyclic ester. 2) obtained by reacting a mixture of nuclear hydrogenated trimellitic anhydride halide (b-1) or a mixture of nuclear hydrogenated trimellitic anhydride halide (b-1) and trimellitic anhydride halide (b-2). The present invention relates to a polyamide resin (C) which is a functional acid anhydride (A).
(4) It relates to a polyimide resin (D) derived from the polyamide resin (C).
(5) A polyimide resin (E) obtained by reacting the polyfunctional acid anhydride (A) with a compound (B-2) having an isocyanate group.
(6) It is related with the resin composition containing the said polyamide resin (C), a polyimide resin (D), or a polyimide resin (E).
(7) It is related with the said resin composition which is a film forming material.

  The polyamide resin and polyimide resin of the present invention give a resin composition having high transparency, heat resistance and toughness. The resin composition of the present invention is suitable for applications such as film forming materials, preferably insulating materials, resist materials, paints, printing inks, adhesives, etc., taking advantage of this characteristic.

  The polyamide resin and polyimide resin of the present invention are prepared by adding a nuclear hydrogenated trimellitic anhydride halide (b-1) or a nuclear hydrogenated anhydrous trihydrate to a polyhydric alcohol (a) having three or more hydroxyl groups in one molecule. It is derived from a polyfunctional acid anhydride (A) obtained by reacting a mixture of merit acid halide (b-1) and trimellitic anhydride halide (b-2).

  When the polyhydric alcohol (a) has two or less hydroxyl groups in one molecule, heat resistance, transparency and toughness cannot be obtained.

  As the polyhydric alcohol (a), for example, triols such as tris (2-hydroxyethyl) isocyanurate, cyclohexanetriol and cyclohexanetrimethanol, and sugar-derived polyols such as inositol are preferable.

  Among these, polyhydric alcohol (a) having a structure represented by the following general formula (1) is particularly preferable.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６はそれぞれ独立して、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は水素原子、水酸基、炭素数１〜１１の炭化水素基、もしくは炭素数１〜４のヒドロキシアルキル基を表し、Ｒ^２は水酸基、もしくは炭素数１〜４のヒドロキシアルキル基を表す。ｌは０〜１１、ｍとｎはそれぞれ１〜１１の整数を表す。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are a hydrogen atom, hydroxyl group, carbon number 1 Represents a hydrocarbon group having ˜11 or a hydroxyalkyl group having 1 to 4 carbon atoms, R ² represents a hydroxyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, l is 0 to 11, m and n are each 1; Represents an integer of ˜11.)

In the above general formula (1), when l or m is 2 or more, a plurality of R ¹ , R ³ , R ⁴ , and R ⁶ are the same as R ¹ , R ³ , R ⁴ , and R ⁶ , respectively. Different substituents may be taken. For example, when 1 = 4, four R ^{1 s} may be the same or different from each other. R ³ , R ⁴ and R ⁶ are the same as R ¹ .

  Specific examples of the polyhydric alcohol (a) include glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxyalkylmethyl-1,4-butanediol, and tris (2-hydroxyethyl) isocyanurate. And tetraols such as triols, ditrimethylolpropane and pentaerythritol, and polyols such as dipentaerythritol and polyglycerin.

  Among these, when the polyhydric alcohol (a) having 4 to 6 hydroxyl groups in the molecule represented by the general formula (1) is used, the properties of the obtained cured product are excellent. In particular, pentaerythritol, ditrimethylolpropane, and dipentaerythritol are preferable from the viewpoint of good properties of the cured product and easy availability of the material.

  In the present invention, the polyhydric alcohol (a-2) has a structure in which any one or more selected from the group consisting of alkylene oxides, cyclic ethers, and cyclic esters are added to the polyhydric alcohol (a). Refers to a compound. Moreover, polyhydric alcohol (a-2) can also optimize the characteristic of reactivity and hardened | cured material according to a use.

In general formula (1), the hydrocarbon group represented by R ¹ refers to an atomic group composed of only carbon atoms and hydrogen atoms.

  As for carbon number of a hydrocarbon group, 1-11 are preferable. Specific examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, linear or branched pentyl group, linear or branched Aliphatic hydrocarbon groups such as hexyl group, straight chain or branched heptyl group, straight chain or branched octyl group, alicyclic hydrocarbon groups such as cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, Examples thereof include aromatic groups such as phenyl group, tolyl group, naphthyl group, and methylnaphthyl group, and aromatic substituted alkyl groups such as benzyl group and naphthylmethyl group. Among these, in the present invention, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group is preferable in terms of good transparency of the cured product of the present invention, and a methyl group and an ethyl group have good toughness and heat resistance. It is more preferable from the point which gives the hardened | cured material of invention.

The hydroxyalkyl group represented by R ¹ or R ² refers to an atomic group in which one or more hydrogen atoms of a linear or branched alkyl group are substituted with a hydroxyl group.

  As for carbon number of a hydroxyalkyl group, 1-4 are preferable. Specific examples include those in which one or more hydrogen atoms of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group are substituted with a hydroxyl group. Of these, in the present invention, one in which one hydroxyl group is substituted on the terminal carbon is preferable in terms of easy reaction. Hydroxymethyl groups and hydroxyethyl groups are more preferred from the viewpoint of good toughness and heat resistance of the cured product of the present invention.

  The alkylene oxide used in the present invention refers to a compound having a three-membered cyclic ether.

  As for carbon number of alkylene oxide, 2-8 are preferable. Examples thereof include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. These alkylene oxides may be one kind or a mixture of two or more kinds as required. Among these, at least one selected from ethylene oxide and propylene oxide is preferable in the present invention because it is easily available and inexpensive.

  The amount of alkylene oxide used is usually 0.1 to 6.0 equivalents of a 3-membered cyclic ether, preferably 0.2 to 2.0 equivalents, per equivalent of hydroxyl group of the polyhydric alcohol (a). . Within this range, the resulting cured product has good heat resistance and toughness.

  The cyclic ether used in the present invention is not particularly limited as long as it is a compound having a structure in which one or more carbons of a cyclic hydrocarbon having 4 or more members are substituted with oxygen.

  The cyclic ether is preferably a 4- to 6-membered ring, and specific examples include oxetane, tetrahydrofuran, and tetrahydropyran. These cyclic ethers may be one kind or a mixture of two or more kinds as necessary. Of these, tetrahydrofuran is preferred in the present invention because it is readily available and inexpensive.

  The usage-amount of cyclic ether is 0.1-6.0 equivalent of cyclic ether with respect to 1 equivalent of hydroxyl groups of a polyhydric alcohol (a), Preferably, it is 0.2-2.0 equivalent. Within this range, the resulting cured product has good heat resistance and toughness.

  The cyclic ester used in the present invention is not particularly limited as long as it is a compound having a structure containing an ester bond in a cyclic hydrocarbon.

  It is preferable that carbon number of cyclic ester is 2-6. Specific examples of the cyclic ester include acetolactone, propiolactone, butyrolactone, valerolactone, caprolactone and the like. These cyclic esters may be one kind or a mixture of two or more kinds as required. Of these, caprolactone is preferred in the present invention because it is readily available and inexpensive.

  The usage-amount of cyclic ester is 0.1-6.0 equivalent of cyclic ester with respect to 1 equivalent of hydroxyl groups of a polyhydric alcohol (a), Preferably, it is 0.2-2.0 equivalent. Within this range, the resulting cured product has good heat resistance and toughness.

  Specific examples of the polyhydric alcohol (a-2) include trimethylolpropane ethylene oxide adduct, trimethylolpropane propylene oxide adduct, trimethylolpropane tetrahydrofuran adduct, trimethylolpropane caprolactone adduct, pentaerythritol ethylene. Oxide adduct, pentaerythritol propylene oxide adduct, pentaerythritol tetrahydrofuran adduct, pentaerythritol caprolactone adduct, dipentaerythritol ethylene oxide adduct, dipentaerythritol propylene oxide adduct, dipentaerythritol tetrahydrofuran adduct, dipentaerythritol caprolactone Adduct, tris (2-hydroxyethyl) isocyanurate ethylene oxide Id adduct, tris (2-hydroxyethyl) isocyanurate propylene oxide adduct, tris (2-hydroxyethyl) isocyanurate tetrahydrofuran oxide adduct, tris (2-hydroxyethyl) isocyanurate caprolactone oxide adduct, etc. .

  The anhydrous nuclear hydrogenated trimellitic acid halide (b-1) used in the present invention is used to introduce an acid anhydride group into a polyhydric alcohol to obtain a polyfunctional acid anhydride compound. Thereby, an acid anhydride group can be introduced without ring-opening esterification of the acid anhydride group. Moreover, since it is nuclear hydrogenated, there is little coloring under heat and light resistance, and the cured product is excellent in heat resistance and toughness while maintaining high optical properties. Therefore, it can be suitably used for a resin material or the like that requires high transparency as a resin.

  The trimellitic anhydride halide (b-2) used in the present invention is also used for the same purpose as (b-1). By using this together, high heat resistance can be exhibited.

  Examples of the anhydrous hydrogenated trimellitic acid halide (b-1) or trimellitic anhydride halide (b-2) include fluorinated compounds, chlorinated compounds, brominated compounds, and iodinated compounds. To chlorinated products are preferred.

  The synthesis of the polyfunctional acid anhydride (A) can be performed by a known method. The method of adding a reagent in the reaction between the polyhydric alcohol (a) and the anhydrous nuclear hydrogenated trimellitic acid halide (b-1) or the trimellitic anhydride halide (b-2) (hereinafter, halides) is particularly limited. Any addition method can be employed. For example, a method in which a polyhydric alcohol (a) and a basic substance are dissolved in a solvent, and the above-mentioned halides dissolved in the solvent are slowly added dropwise thereto, or conversely, the above-mentioned halide dissolved in a solvent if necessary A method of dropping a mixed solution of a polyhydric alcohol (a) and a basic substance into a compound, a method of dropping a basic substance into a mixed solution of a halide (a compound and a polyhydric alcohol (a), For example, a solution of a nuclear hydrogenated trimellitic anhydride halide and a solution of a basic substance may be simultaneously dropped into the alcohol (a) solution.

  In the reaction of the polyhydric alcohol (a) and halides in the presence of a basic substance, a hydrochloride formed by neutralization of the basic substance is generated as the reaction proceeds. After removing this by filtration, the filtrate is concentrated to obtain a crude product of polyfunctional acid anhydride (A) in high yield. This is dissolved in a suitable solvent, washed with water, concentrated and dried under reduced pressure to obtain a polyfunctional acid anhydride (A) having a high purity. Furthermore, a polyfunctional acid anhydride (A) with higher purity can be obtained by performing recrystallization with an appropriate solvent as required.

  The use amount of the polyhydric alcohol (a) is usually a hydroxyl group equivalent, and is 0.6 to 1.0, preferably 0.8 to 1.0 with respect to the halides 1. Within this range, all the hydroxyl groups of the polyhydric alcohol (a) are esterified, and unreacted halides do not remain in the system.

  The solvent that can be used in the reaction between the halide and the polyhydric alcohol (a) is not particularly limited as long as it is inert to the raw material, but tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane-bis (2- Ether solvents such as methoxyethyl) ether, aromatic amine solvents such as picoline and pyridine, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbon solvents such as toluene and xylene, dichloromethane and chloroform Halogen-containing solvents such as 1,2-dichloroethane, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, Phosphorus-containing solvents such as hexamethylphosphoramide, dimethylsulfur Sulfur-containing solvents such as oxide, ester solvents such as γ-butyrolactone, ethyl acetate, butyl acetate, nitrogen-containing solvents such as 1,3-dimethyl-2-imidazolidinone, phenol, o-cresol , M-cresol, p-cresol, o-chlorophenol, m-chlorophenol, aromatic solvents having a hydroxyl group such as p-chlorophenol, and the like. These solvents may be used alone or in combination of two or more.

  The solvents mentioned here contain cyclic ethers and cyclic esters used in the production of polyhydric alcohol (a-2) from polyhydric alcohol (a). Halides are included in polyhydric alcohol (a). When the is reacted, the reaction temperature is -10 ° C to 80 ° C, preferably 0 ° C to 70 ° C, more preferably 10 ° C to 60 ° C. When the reaction temperature is higher than 80 ° C., the polyhydric alcohol (a) reacts with the cyclic ether or cyclic ester to obtain the polyhydric alcohol (a-2), and the reaction rate between the polyhydric alcohol (a) and halides. Decreases. The reaction time is not particularly limited, but is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours. The reaction is usually carried out at normal pressure, but can be carried out under pressure or under reduced pressure as necessary.

  When the polyhydric alcohol (a) is reacted with a cyclic ether or cyclic ester to produce the polyhydric alcohol (a-2), the reaction temperature is 80 ° C to 250 ° C, preferably 90 ° C to 220 ° C, more preferably. 100 to 200 ° C. The reaction time is not particularly limited, but is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours. The reaction is usually carried out at normal pressure, but can be carried out under pressure or under reduced pressure as necessary.

  The concentration of the solute in the reaction for obtaining the polyfunctional acid anhydride (A) is usually 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass in consideration of side reaction control and precipitation filtration step. . More preferably, it is carried out in the range of 10 mass% or more and 40 mass% or less.

  The reaction atmosphere is usually carried out under nitrogen. The reaction vessel may be a closed type reaction vessel or an open type reaction vessel, but in order to keep the reaction system in an inert atmosphere, an open type vessel that can be sealed with an inert gas is used.

  The basic substance is used to neutralize hydrogen chloride generated as the reaction proceeds. The type of basic substance used at this time is not particularly limited, but organic basic amines such as pyridine, triethylamine and N, N-dimethylaniline, and inorganic basic substances such as potassium carbonate and sodium hydroxide are used. be able to. Pyridine and triethylamine are preferable in that they can be obtained at low cost and are easy to operate because they are liquid and highly soluble. Moreover, an inorganic basic substance is preferable in that it can be obtained at low cost.

  The amount of the basic substance to be used is not particularly limited, but if it is used excessively, it will be mixed into the product or the purification load will be increased. The mole times, preferably 1.2 mole times to 20 mole times, more preferably 1.5 mole times to 10 mole times are employed.

  During the water washing operation, the polyfunctional acid anhydride (A) undergoes partial hydrolysis and changes to a polycarboxylic acid, which is produced by partial hydrolysis by heat treatment under reduced pressure. The polyvalent carboxylic acid thus obtained can be easily returned to the polyfunctional acid anhydride (A). The temperature employed in the heat treatment step under reduced pressure is 80 ° C. to 200 ° C., preferably 100 ° C. to 180 ° C., the degree of reduced pressure is 10 MPa or less, preferably 1 MPa or less, and the upper limit of the heating time is particularly limited. However, it is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours.

  It is also possible to further purify the polyfunctional acid anhydride thus obtained. As a purification method in that case, recrystallization, sublimation, washing, activated carbon treatment, column chromatography and the like can be arbitrarily performed. These purification methods can be repeated or combined. The purity of the polyfunctional acid anhydride thus obtained is usually 90% or more, preferably 95% or more, and more preferably as an area ratio of peaks obtained by analysis such as gel permeation chromatography (hereinafter referred to as “GPC”). Is over 98%

  The acid anhydride group of the polyfunctional acid anhydride (A) and the amino group of the compound (B-1) having an amino group used in the present invention become an amic acid by an addition reaction, and the polyamide resin (C) of the present invention becomes can get. Furthermore, if necessary, the polyamide resin (C) of the present invention can be condensed and derived into the polyimide (D) of the present invention.

  Specific examples of the compound having one amino group in one molecule include ethylamine, propylamine, butylamine, hexaneamine, octaneamine, decanamine, stearylamine, cyclohexaneamine, cyclohexanemethylamine, norborneneamine, norbornenemethylamine, adamantyl Linear and cyclic aliphatic monoamines such as amines, aniline, toluidine, ethylaniline, butylaniline, dimethylaniline, anisidine, benzylamine, naphthylamine, aminoanthracene, N, N-dimethylphenylenediamine, Aromatic molecules such as N, N-diphenylphenylenediamine, N-phenylparaphenylenediamine, aminodiphenylmethane, chloroaniline, bromoaniline, iodoaniline, etc. Amines, and the like.

  Specific examples of the compound having two amino groups in one molecule include linear and cyclic such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, octamethylenediamine, cyclohexanediamine and norbornanediamine. , Bicycloaliphatic aliphatic diamines, phenylenediamine, dimethylbiphenyldiamine, diaminonaphthalene, diaminodiphenyl ether, diaminodiphenylmethane, diaminodimethyldiphenylmethane, diaminobenzophenone, methylenebisdiethylaniline, bis (aminophenyl) cyclohexane, bis (aminophenyl) fluorene Bis (aminophenyl) sulfone, bis (hydroxyaminophenyl) ether, bis (hydroxyaminophenoxy) ) Benzene.

The number of the amino groups contained in the compound (B-1) is preferably 1 to 2 in one molecule, so that the molecular weight of the polyamide resin (C) is in a desirable range. One molecule per molecule does not increase the molecular weight, and three or more molecules may gel.
The control of the molecular weight of the polyamide resin (C) of the present invention is carried out using a mixture of one containing one amino group and one containing two amino groups in one molecule.

  The acid anhydride group of the polyfunctional acid anhydride (A) and the isocyanate group of the compound (B-2) having an isocyanate group used in the present invention are added and decarboxylated to obtain the polyimide resin of the present invention.

  Specific examples of the compound having one isocyanate group in one molecule include aliphatic mono- acrylates such as ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclopentyl isocyanate, cyclohexyl isocyanate, butyl isocyanate. Isocyanates, phenyl isocyanate, methyl phenyl isocyanate, ethyl phenyl isocyanate, butyl phenyl isocyanate, dimethyl phenyl isocyanate, dipropyl phenyl isocyanate benzyl isocyanate, methyl benzyl isocyanate, phenyl ethyl isocyanate, naphthyl isocyanate, naphthyl ethyl isocyanate, methoxyphenyl isocyanate Sulfonates, ethoxy phenyl isocyanate, aromatic monoisocyanates such as chloromethyl phenyl isocyanate.

  Specific examples of the compound having two isocyanate groups in one molecule include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, hexahydroxy diisocyanate, cyclohexane diisocyanate, dicyclohexylmethylene diisocyanate, norbornene diisocyanate, Aromatic diisocyanates such as phenylene diisocyanate, toluene diisocyanate, xylene diisocyanate, bis (isocyanatopropyl) benzene, methylenebis (phenylisocyanate), diisocyanate dimethyldiphenylmethane, and the like.

  Examples of the compound having three or more isocyanate groups in one molecule include lysine triisonate or the above-mentioned bifunctional isocyanates, isocyanurate-modified products, burette-modified products, adduct-modified products, and the like.

For example, when taking out polyimide resin, without giving shape, such as film formation, it is preferable that the compound (B-2) has 1-2 isocyanate groups in one molecule. By doing in this way, the molecular weight of a polyimide resin (D) is made into a desirable range. If one molecule is used, the molecular weight is not increased, and if two or more molecules are used, gelation may occur if used in a large amount. The solubility is lowered by imidization, and particularly those having a high molecular weight are difficult to be coated or filmed.
The molecular weight of the polyimide resin (D) is controlled by mixing one having one isocyanate group and one having two or more isocyanate groups in one molecule.

  On the other hand, when the polybasic acid anhydride (A) and the compound (B-2) having an isocyanate group are mixed and given a shape before the reaction and reacted to obtain a polyimide resin (E), polyfunctional It is preferable to use the compound (B-2) which has the following isocyanate group.

  A known method can be applied to the reaction between the polyfunctional acid anhydride (A) and the compound (B-1) having an amino group or the compound (B-2) having an isocyanate group.

  In this case, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is a reaction product, that is, a polyfunctional acid anhydride (A), a compound (B-1) or a compound (B-2). In some cases, the content is 0.1 to 10% by mass based on the total amount of the reaction product with the addition of a solvent or the like. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include inorganic acids such as sulfuric acid, organic acids such as toluenesulfonic acid and methanesulfonic acid, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide. , Organic bases such as triphenylphosphine, triphenylstibine, and methyltriphenylstibine, and metal salts such as chromium octoate and zirconium octoate.

  The acid addition reaction can be performed without a solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it has solubility and is inert to the reaction.

  A preferable amount of the solvent to be used should be appropriately adjusted depending on the viscosity and use of the resin to be obtained, and is preferably 90 to 30% by mass, more preferably 80 to 50% by mass as a solid content.

Specific examples include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and petroleum ether and white gasoline which are mixtures thereof. And solvent naphtha.
Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipine Polyesters of polycarboxylic acids such as dialkyl acids Kind, and the like.
Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Glycol ethers, and cyclic ethers such as tetrahydrofuran.
Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.
In addition, highly polar solvents such as dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone are also preferably used.

  In the polyfunctional acid anhydride (A) and the compound (B-1) having an amino group, an amino group is first added to the acid anhydride group to obtain a polyamide resin (C) called amic acid or amic acid. It is done. At this stage, since it is still highly soluble in a solvent or the like and has high thermoplasticity, it is also suitable for applying a shape to a target shape, for example, a sheet shape at this stage and for coating.

  By further heating the polyamide resin (C), the amic acid undergoes a condensation reaction to induce the polyimide resin (D). When the shape imparting property required for the polyimide resin (D) can be maintained, the shape can be imparted after the polyimide resin (D) is formed.

  In the reaction of the polyfunctional acid anhydride (A) and the compound (B-2) having an isocyanate group, first, an isocyanate group is added to the acid anhydride group, and then removed via a relatively unstable cyclic intermediate. It reaches a polyimide resin (E) through a carbonic acid reaction. Although it is difficult to process the intermediate as it passes through a relatively unstable intermediate, it can be guided to the polyimide resin (E) in a lump.

  In the production of the polyimide resin of the present invention, the compound (B-1) having an amino group or the compound (B-2) having an isocyanate group is selected according to the required properties.

The present invention also includes a resin composition containing the polyamide resin (C), polyimide resin (D) or polyimide resin (E) of the present invention. The resin composition of this invention can also add another component to 70 mass% in an upper limit according to each objective in a composition.
Other materials used in the composition include, for example, other reactive resins, non-reactive so-called inert resins, colored pigments, extender pigments, curing agents, stabilizers, plasticizers, volatile solvents. Etc. Reactive carboxyl groups remain in the polyamide resin (C). The resin composition of the present invention may contain a curing agent capable of reacting with a carboxyl group.

  Other reactive resins in the present invention are resins that can be cured and reacted independently, whether or not they react with polyamide resin (C), polyimide resin (D), or polyimide resin (E). Refers to reactive diluents. Examples include (meth) acrylic esters, epoxy (meth) acrylates, urethane (meth) acrylates, epoxy resins having ester (meth) acrylates, and the like. These are preferably used in the range up to 70% by mass.

As the epoxy resin that can be used here, a known general epoxy resin can be used. Among these, it is preferable that two or more epoxy groups are contained in one molecule, and the so-called epoxy equivalent (molecular weight per equivalent of epoxy group) is in the range of 180 to 400. If the value is smaller than this range, it becomes a fragile cured product, and if it is large, it does not exhibit sufficient curability.
Specifically, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, isocyanurate type An epoxy resin, a tricyclodecane type epoxy resin, etc. are mentioned.

  Other non-reactive resins (so-called inert polymers) such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins Natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in a range of up to 40% by mass.

  In the present invention, the color pigment is used for using the resin composition of the present invention as a coloring material. These are classified into organic pigments and inorganic pigments depending on the configuration, and these are appropriately selected according to the intended color and application.

Organic pigments are classified according to their basic skeleton. For example, polycyclic rings such as isoindolinone, isoindoline, azomethine, anthraquinone , anthrone, xanthene, diketopyrrolopyrrole, perylene, perinone, quinacridone, indigoid, dioxazine, phthalocyanine Examples thereof include pigments, azo pigments such as monoazo, disazo, and condensed disazo, lake pigments, and fluorescent pigments.

  Examples of inorganic pigments include titanium dioxide, calcium carbonate, barium sulfate, zinc oxide, mica, carbon black, bengara, and aluminum flakes.

  The extender pigment shown in the present invention is a pigment not intended for coloring, and is used for the purpose of obtaining the viscosity and fluidity of the composition and the mechanical properties of the cured product.

  For example, barium sulfate, calcium carbonate, talc, clay, glass flakes, glass beads, graphite, aluminum oxide, aluminum hydroxide, polystyrene beads, polyethylene beads, polypropylene beads, polytetrafluoroethane beads and the like can be mentioned.

  Moreover, the hardening | curing agent shown by this invention is used in order to raise the crosslinking degree of hardened | cured material further. For example, the compound etc. which have a functional group which can react with the carboxyl group etc. of a polyamide resin (C) are illustrated. Specifically, polyfunctional epoxy resins such as bisphenol type epoxy resin, cresol novolak type epoxy resin, phenol novolac type epoxy resin, polyfunctional phenol resins such as diallyl phthalate resin, phenol novolak resin, cresol novolak resin, melamine, methylol Polyfunctional amines such as melamine fluoride and benzoguanamine can also be used.

  Other additives include, for example, thermosetting catalysts such as melamine, other initiators for curing reactive resins, thixotropic agents such as aerosil, silicone-based, fluorine-based leveling agents and antifoaming agents, hydroquinone, Polymerization inhibitors such as hydroquinone monomethyl ether, stabilizers, antioxidants and the like can be used.

  Depending on the purpose of use, for the purpose of adjusting the viscosity, a volatile solvent may be added in a range of 50% by mass, more preferably up to 35% by mass.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, metal and other various adhesives. This applies to adhesive materials such as adhesives and adhesives, and resist materials. Furthermore, after the film-forming material is temporarily applied to a peelable substrate and formed into a film, it is pasted on the originally intended substrate to form a film. To do.

  There are no particular restrictions on the method for forming the film, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater, Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

Synthesis Example 1: Synthesis 1 of polyfunctional acid anhydride (A)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, and the anhydride chloride (b) described in the table was added in an amount equivalent to the amount described in the table (1.1 equivalents relative to the hydroxyl group of (a)). ), 45 g of tetrahydrofuran was added to make a uniform solution. The solution was cooled to 5 ° C. with stirring, and (a) described in the table was added in the amount shown in the table, and pyridine (1.2 equivalents relative to the hydroxyl group of (a)) and 54 g of tetrahydrofuran were added to make uniform. The solution was gradually added dropwise while maintaining the liquid temperature at 10 ° C. or lower. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, then heated to 50 ° C., and the reaction was continued for 8 hours. Subsequently, the reaction solution was cooled to 20 ° C., and pyridine hydrochloride as an insoluble component was removed by filtration, and then the filtrate was concentrated. The concentrate was dissolved in 120 ml of ethyl acetate, washed 3 times with 30 ml of water, and then dried over anhydrous magnesium sulfate. After anhydrous magnesium sulfate was removed by filtration, the filtrate was concentrated, and the resulting concentrate was dissolved in 15 ml of ethyl acetate and recrystallized from toluene to obtain a product.

Comparative Synthesis Example 1: Synthesis of Bifunctional Acid Anhydride A polyfunctional acid anhydride was synthesized according to Synthesis Example 1. The results are shown in the following table together with Synthesis Example 1.

Abbreviations in Table TMP: Trimethylolpropane PE: Pentaerythritol PE4EO: Pentaerythritol 4 mol ethylene oxide adduct BPA2EO: Bisphenol A 2 mol ethylene oxide adduct BG: 1,3-butylene glycol THI: Tris (2-hydroxyethyl) isocyanurate HTAC: Nuclear hydrogenated trimellitic anhydride chloride TMAC: Trimellitic anhydride chloride

Example 1 Preparation of Polyamide Resin (C) 20 mmol of polyfunctional acid anhydride (A) prepared in Synthesis Example 1 in a flask equipped with a stirrer, reflux condenser, and stirrer (mass is listed in the table) As an example, γ-butyrolactone was added in an amount of 20% by mass with respect to the total amount of (A) and (B) and dissolved by stirring.
Furthermore, the compound of the table | surface was added as a compound (B-1) which has an amino group, and reaction was performed at 80 degreeC for 5 hours.

Comparative Example 1: Preparation of bifunctional polyamide resin In the same manner as in Example 1, the reaction was carried out using 20 mmol (mass is described in the table) of other bifunctional acid anhydrides described in the table.

Abbreviations in Table MW: Weight average molecular weight in terms of polystyrene by gel permeation chromatograph (GPC) An: Aniline ODA: Diaminodiphenyl ether DADPS: Bis (aminophenyl) sulfone
NBDA: Norbornenediamine ADAM: Adamantylamine

Example 2 Preparation of Polyimide Resin (D) The polyamide resin (C) solution prepared in Example 1 in a nitrogen stream was placed in a flask equipped with a stirrer, a Dean-Stark reflux condenser, and a stirrer as a solid content equivalent. 15 g (actual charge amount divided by 20 mass% solid content), 10 g of toluene for the purpose of taking out water generated by dehydration reaction from the outside of the reaction system, 0.1 mass% of pyridine as a catalyst, 170 ° C. The reaction was carried out for 5 hours while removing the condensed water using a Dean-Stark tube under reflux.
It was confirmed that the distillation of water was completed, and it was confirmed that absorption (1780 cm ⁻¹ , 1720 cm ⁻¹ ) specific to the imide compound occurred in the infrared absorption spectrum.
The molecular weight of the polyimide resin (D) was measured using GPC using N-methylpyrrolidone as an eluent.

Example 3 Preparation of Polyimide Resin (E) 20 mmol of polyfunctional acid anhydride (A) prepared in Synthesis Example 1 in a flask equipped with a stirrer, reflux condenser, and stirrer (mass is listed in the table) As an example, γ-butyrolactone was added in an amount of 20% by mass with respect to the total amount of (A) and (B), and dissolved by stirring.
Furthermore, the compound of the table | surface was added as a compound (B-2) which has an isocyanate group, and reaction was performed at 180 degreeC in nitrogen stream for 5 hours.

Comparative Example 3 Preparation of Bifunctional Polyimide Resin Similarly to Example 3, the reaction was carried out using 20 mmol (mass is described in the table) of other bifunctional acid anhydrides described in the table.

Abbreviations in the table DPPI: Diisopropylphenyl isocyanate MBPI: Methylene bis (phenyl isocyanate)
CHI: cyclohexyl isocyanate NBDI: norbornene diisocyanate

Example 4: Evaluation of polyamide resin (C) The polyamide resin (C) solution synthesized in Example 1 and Comparative Example 1 was 6 g in terms of solid content (the actual charge was divided by 20 mass% solid content), Bisphenol-type epoxy resin (4 (4 (1,1-bis (p-hydroxyphenyl) -ethyl) α, α-dimethylbenzyl) phenol)): NC-6300, Nippon Kayaku, epoxy equivalent 230 g / eq as a curing agent 2 g), 0.1 g of melamine as a curing catalyst was further added, and the mixture was dissolved and stirred until uniform. The obtained resin composition was poured into a mold having been subjected to a peeling process, and cured at 150 ° C. for 5 hours while volatilizing the solvent under reduced pressure. The cured product was evaluated as follows.

(1) Evaluation of heat resistance The glass transition point of the obtained cured product was measured using a dynamic mechanical property evaluation apparatus (DMA).
Evaluation criteria ○: 180 ° C. or higher; Δ: 140 ° C. or higher; X: Less than 140 ° C. (2) Colorability evaluation evaluation criteria ○: Almost colorless and transparent; Δ: Slightly yellow; X: Colored from yellow to brown (3) Light resistance evaluation The obtained coating film was irradiated with ultraviolet light for 8 hours with a super UV tester (Iwasaki Electric Co., Ltd.). And evaluated. The evaluation criteria are as follows.
◎: No discoloration = Coloration at almost the same level as before irradiation ○: Slightly discolored to yellowish △: Yellow discoloration is observed ×: Discolored to brown

  From the above results, it was shown that the polyamide resin (C) of the present invention is a film-forming material having excellent heat resistance, colorability, and light resistance.

Example 5: Evaluation of polyimide resin (D) and polyimide resin (E), evaluation as a coating material for metal The polyimide resin (D) and polyimide resin (E) solutions obtained in Examples 2 and 3 were used as solids. A white coating composition obtained by kneading 6 g in terms of conversion (actual charge is divided by 20% by mass of solid content) and 3 g of titanium oxide pigment Typek CR-90 (Ishihara Sangyo Co., Ltd.) as a coloring pigment using a small bead mill. Got.

  The obtained coating composition was coated on a TFS substrate (tin-free steel plate) with a wire bar coater # 8, and the solvent was evaporated in an inert oven in a nitrogen gas stream at 180 ° C. for 1 hour to obtain a coating film. It was. Evaluation of the obtained coating film was performed as follows.

Evaluation of coating material for metal (1) Evaluation of curability The hardness of the cured coating film was evaluated according to a pencil hardness test (JIS-K5600-5-4: 1999).
(2) Adhesion evaluation Adhesion to a metal substrate was evaluated according to a cross-cut peel test (JIS-K5600-5-6: 1999).
Evaluation criteria were also based on JIS-K5600 and evaluated according to the following classification.
Category 0: No peeling, good Classification 1: Slight peeling at the corners Category 2: Peeling at the corners Category 3: Peeling less than half of the squares Category 4: Peeling more than half of the squares Category 5: There was almost complete peeling and poor (3) Impact resistance evaluation The impact resistance of the coating film was evaluated according to the DuPont impact test (JIS-K5600-5-6: 1999). The weight was 500 g, the impact type was 6.35 mm, and the drop height was 250 mm.
○: No cracking; Δ: Cracking but no peeling; x: Peeling (4) Light resistance evaluation The obtained coating film was irradiated with ultraviolet light for 8 hours with a super UV tester (Iwasaki Electric) and after the irradiation was completed The colorability of the white coating film was visually evaluated. The evaluation criteria are as follows.
◎: No discoloration ○: Slightly discolored to yellowish △: Yellow discoloration is observed ×: Discolored to brown

  The above results show that the polyimide resin (D) and the polyimide resin (E) of the present invention give a coating composition excellent in adhesion, curability and impact resistance.

Example 6: Evaluation of polyimide resin (E), evaluation as a copper foil coating material The acid anhydride (A) obtained in Synthesis Example 1 is described in the table, and the isocyanate compound (B-2) is described in the table. As a solvent, propylene glycol monomethyl ether acetate was added and dissolved so as to have a solid content of 80% by mass with respect to the total of (A) and (B). After that, pyridine as a catalyst is dissolved to 0.5% by mass with respect to the total of (A) and (B), and wire mat coater # 8 is used to form a copper foil mat surface (rough surface). Coated.
After coating, heat up at 180 ° C for 5 hours using an inert oven in a nitrogen atmosphere while raising the temperature step by step, solvent evaporation and imidization on copper foil to obtain polyimide resin (E) It was. Evaluation of the obtained polyimide resin (E) was performed as follows.

(1) Curability evaluation It carried out according to Example 5.
(2) Adhesion evaluation (3) Bendability evaluation performed in accordance with Example 5 The coating film was folded 180 ° into the coating film surface together with the copper foil, and then the state of the coating film was returned again. The state was observed with an optical microscope.
Evaluation criteria ○: Cracks and cracks are not observed; Δ: Slight cracks are observed; ×: Cracks are generated (4) Curl property evaluation The obtained coated material is cut into a 10 cm square and is on a glass plate The four sides were attached with adhesive tape with the coating surface facing up. After that, a cut was made with a cutter knife on a diagonal of a 7 cm square, and after being allowed to fit in a constant temperature and humidity chamber at 25 ° C. and 50% RH for 24 hours, the degree of curl of the cut was warped upward. Evaluated by height.
Evaluation criteria A: Almost no warping observed ○: Less than 1 cm in height Δ: Less than 3 cm in height ×: More than 3 cm in height

Abbreviations in the table
IPDI: Isophorone diisocyanate THMDI: Trimethylhexamethylene diisocyanate

  The above results show that the polyimide resin (E) of the present invention is an excellent copper foil coating material.

  As the uses of the polyamide resin (C), the polyimide resin (D) and the polyimide resin (E) of the present invention, this time, characteristics were evaluated by taking a metal coating material and a copper foil coating material as examples. This resin has little discoloration, is excellent in adhesion, toughness and heat resistance, and is suitable for coating materials and printing inks having excellent colorability.

Claims (5)

Polyhydric alcohol (a) having three or more hydroxyl groups in one molecule and nuclear hydrogenated trimellitic anhydride halide (b-1) or nuclear hydrogenated trimellitic anhydride halide (b-1) and trimellitic anhydride The polyfunctional acid anhydride (A) obtained by reacting a mixture of halides (b-2) with at least one compound having one amino group in one molecule and one compound as the compound (B-1) having an amino group A polyamide resin (C) obtained by reacting a compound containing two amino groups in the molecule . The polyhydric alcohol (a) is represented by the following general formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are a hydrogen atom, hydroxyl group, carbon number 1 Represents a hydrocarbon group having ˜11 or a hydroxyalkyl group having 1 to 4 carbon atoms, R ² represents a hydroxyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, l is 0 to 11, m and n are each 1; The polyamide resin (C) according to claim 1, which is a polyhydric alcohol (a-1) containing at least three hydroxyl groups in one molecule represented by ˜11. The polyfunctional acid anhydride (A) according to claim 1 is obtained by reacting the polyhydric alcohol (a) with one or more selected from the group consisting of alkylene oxide, cyclic ether, and cyclic ester ( a-2) and nuclear hydrogenated trimellitic anhydride halide (b-1) or a mixture of nuclear hydrogenated trimellitic anhydride halide (b-1) and trimellitic anhydride halide (b-2) Polyamide resin (C) which is a polyfunctional acid anhydride (a). A polyimide resin (D) derived from the polyamide resin (C) according to any one of claims 1 to 3. Polyhydric alcohol (a) having three or more hydroxyl groups in one molecule and nuclear hydrogenated trimellitic anhydride halide (b-1) or nuclear hydrogenated trimellitic anhydride halide (b-1) and trimellitic anhydride Polyimide resin (E) obtained by making the compound (B-2) which has an isocyanate group react with the polyfunctional acid anhydride (A) obtained by making the mixture of halide (b-2) react .