KR20110027586A - Non-aqueous ink for ink jet and method for applying ink - Google Patents

Abstract

PURPOSE: Ink for non-aqueous inkjet is provided to obtain desired pattern layers since little crawling or moisture diffusion on a flat substrate without surface treatment after jetting. CONSTITUTION: Ink for non-aqueous inkjet contains surfactants(B). The concentration of the surfactant(B) is 0.00001 weight% or more and a critical micelle concentration or less. A method for applying the ink comprises a step for applying the ink for non-aqueous inkjet through an ink jet application method. A method for forming a polyimide film comprises the steps of: applying the non-aqueous inkjet ink on a substrate according to an ink-jet application method to form a film; and heating the film to form a polyimide film.

Description

Non-aqueous inkjet ink, ink coating method {NON-AQUEOUS INK FOR INK JET AND METHOD FOR APPLYING INK}

In the production of electronic components, an inkjet ink which can be used when forming an insulating film layer, a polyimide film formed using a non-aqueous inkjet ink, a film substrate having the polyimide film, a semiconductor wafer, a substrate for an electronic material, It relates to an electronic component, an ink coating method, and a method for forming a polyimide film.

Polyimide, which is one kind of compound (imide compound) having an imide bond, is a material widely used in the field of electronic communication because of its excellent heat resistance and electrical insulation (see Patent Document 1, for example).

When using a polyimide as a desired pattern film, the method of forming a pattern using the etching or the photosensitive polyimide was conventionally used conventionally. However, this method requires a large amount of various chemical liquids such as photoresist, developer, etching solution, and stripping solution, and requires a complicated process. Therefore, in recent years, the method of forming a desired pattern film simply by the inkjet coating method is examined.

Various types of inks (hereinafter also referred to as "ink jet inks") used in the inkjet coating method have been proposed (see Patent Document 2, for example). However, in order to discharge and print as inkjet ink, various parameters such as viscosity, surface tension, and boiling point of a solvent must be optimized. For example, the viscosity is generally required to have a low viscosity of about 1 to 50 mPa · s, preferably about 5 to 30 mPa · s. In particular, in the case of piezoelectric inkjet printing, since the discharge pressure of the piezoelectric element is small, the discharge may be impossible in some cases when the viscosity increases. The surface tension should be adjusted in the range of 20 to 70 mN / m, preferably in the range of 20 to 45 mN / m. If the surface tension is small, the ink diffuses onto the substrate immediately after exiting the nozzle of the print head, making it impossible to form good droplets. On the contrary, if the surface tension is too large, the meniscus cannot be formed, and thus the discharge may be impossible. Moreover, the boiling point of a solvent needs the range of 100-300 degreeC, Preferably it is the range of 150-250 degreeC. If the boiling point is too low, the solvent in the ink in the nozzle portion of the print head is evaporated. As a result, the viscosity of the ink may change, so that the ink may not be ejected or the components of the ink may solidify. On the contrary, when a boiling point is too high, drying after printing may be delayed too much and a printing pattern may deteriorate.

The polyimide inkjet ink has a relatively high molecular weight of polyamic acid, and in order to prepare an ink having an optimum viscosity as the inkjet ink, it is necessary to increase the proportion of the solvent to reduce the polyamic acid content in the ink. However, when the polyamic acid content in the ink is reduced, there is a problem that the thickness of the film obtained by one ink jetting becomes thin.

In order to solve this problem, for example, a method of reducing the ink viscosity and increasing the content of the polyamic acid by controlling the weight average molecular weight of the polyamic acid to 10,000 to 50,000 has been proposed (for example, , Patent document 3). However, even with the above method, the polyamic acid content in the ink is still not enough at about 15 to 20% by weight, and the ink has a problem that ink jet ejection defects are likely to occur since the viscosity is relatively high at 18 to 23 mPa · s. .

Moreover, the thermosetting resin composition for inkjets containing the weight average molecular weight 300-9,000 polyimide or polybenzoxazole which has a heat crosslinking agent and the group which can react with the said thermal crosslinking agent as a thermosetting resin composition for inkjets with small viscosity even at high concentration is proposed. (See, for example, Patent Document 4). The said composition is a composition containing the polyimide or polybenzoxazole which has groups, such as a phenolic hydroxyl group, carboxyl, and sulfonamide, which can react with a heat crosslinking agent. Therefore, since the composition requires a thermal crosslinking agent such as a cyclic ether, a methylol compound, an alkoxymethylol compound, a bismaleimide, a bisimide compound having an unsaturated bond, an acetylene compound, the storage stability is poor, and There is a problem such that an unreacted substance remains.

On the other hand, the amic acid oligomer or imide oligomer obtained by making tetracarboxylic dianhydride, diamine, and a terminal crosslinking agent react at the molecular terminal is proposed (for example, refer patent document 5). However, these oligomers provide a prepreg that produces an imide resin having good heat resistance, and in particular, as a matrix resin of a fiber-reinforced composite material made of glass fibers, aramid fibers, carbon fibers, alumina fibers, silicon carbide fibers, and the like as reinforcing materials. To use. The prepreg is usually used by impregnating fiber for reinforcement in a solution of 20% by weight or more, and its design concept and use are completely different from those for inkjet inks.

Moreover, although the imide compound which has a thermosetting functional group at the terminal is disclosed (for example, refer patent document 6), the said imide compound also does not assume use as an inkjet ink.

Therefore, since these oligomers and imide compounds are not considered at all about the optimization of the viscosity and surface tension which are required as inkjet ink, there exists a problem that it is difficult to form a desired pattern film.

In order to solve said various problems, the molecular crosslinking group is made to react at the terminal of polyamic acid, molecular weight is controlled, and the ink for ink and thermosetting inkjet of high density | concentration at low viscosity is proposed (for example, refer patent document 7). ). This inkjet ink contains polyester amic acid, an epoxy resin, a pigment, etc., and shows favorable jetting property, electrical property, and chemical resistance. However, even if the jetting property is good, since the ink is low in viscosity, after the droplets of the ink reach the substrate, it is wet and diffused on the flat substrate. Therefore, there is a problem that it is difficult to obtain a desired pattern with the ink.

Further, in order to suppress the wet diffusion of the liquid, a high viscosity non-aqueous inkjet ink is also proposed as the inkjet ink (see Patent Document 8, for example), but since the inkjet head needs to be heated, the inkjet head capable of heating There is a problem that the use is limited.

Moreover, in order to suppress the wet diffusion of a liquid, the method of apply | coating resin which has liquid repellency beforehand, and then printing a desired pattern with inkjet ink is also proposed (for example, refer patent document 9). However, this method has a problem that the process becomes complicated to obtain a desired pattern.

[Patent Document 1] Japanese Patent Application Publication No. 2004-094118 [Patent Document 2] Japanese Patent Application Publication No. 2003-213165 [Patent Document 3] Japanese Patent Application Publication No. 2005-187596 [Patent Document 4] Japanese Patent Application Publication No. 2007-314647 [Patent Document 5] Japanese Patent Application Publication No. 2004-331801 [Patent Document 6] Japanese Patent Application Publication No. 62-29584 [Patent Document 7] Japanese Patent Application Publication No. 2009-052023 [Patent Document 8] Japanese Patent Application Publication No. 2008-133335 [Patent Document 9] Japanese Patent Application Publication No. 2008-106165

The present invention provides a non-aqueous system which does not require heating of the inkjet head because, under the above-described circumstances, after jetting, there is little crawling or wet diffusion on a flat substrate without surface treatment, thereby obtaining a desired pattern film and low viscosity. It is a subject to provide ink for inkjets.

MEANS TO SOLVE THE PROBLEM This inventor carried out research and examination in order to solve the said subject. As a result, in the non-aqueous inkjet ink containing the surfactant (B), by setting the concentration of the surfactant (B) in a specific range, various parameters such as viscosity, surface tension, and boiling point of the solvent are used for the inkjet. It was found that the above problems can be solved as appropriate and the present invention has been completed.

This invention has the following structures.

[1] An ink for non-aqueous inkjet containing a surfactant (B),

A non-aqueous inkjet ink, wherein the concentration of the surfactant (B) is 0.00001% by weight or more and less than or equal to the critical micelle concentration.

[2] The surfactant (B) is one selected from the group consisting of silicone surfactants, fluorine surfactants, silicone fluorine surfactants, acrylic surfactants, cationic surfactants, anionic surfactants and betaine surfactants. It is an above-mentioned surfactant, The ink for non-aqueous inkjet of the said [1] description.

[3] The non-aqueous inkjet for the above-mentioned [1], wherein the surfactant (B) is at least one surfactant selected from the group consisting of silicone surfactants, fluorine surfactants and acrylic surfactants. ink.

[4] The compound according to any one of the above [1] to [3], which comprises at least one compound (A) selected from the group consisting of a compound capable of forming a polyimide and a polyimide. Non-aqueous inkjet ink.

[5] The non-aqueous inkjet according to the above [4], wherein the compound (A) is at least one compound selected from the group consisting of compounds represented by the following general formulas (1) to (6). Dragon ink.

(In Formulas (1) to (6), each R independently represents a hydrogen atom or a group represented by the following Formula (a), and each R ′ independently represents an amino group (NH ₂ ) or the following Formula (b). R ¹ , R ² , R ^3, and R ⁴ are each independently an organic group having 2 to 500 carbon atoms, and n is an integer of 0 to 1000. However, when n is 0, R is R 'is a group represented by the following formula (b), and R ^{1 having} a silicon structure represented by the following formula (z) is less than 10 mol% in R ¹ 100 mol%. , R ² of the silicon structure represented by the following formula (z) is less than 10 mol% in R ² 100 mol%).

(In formula (z), R <^5> and R <^6> is respectively independently a hydrogen atom, a C1-C12 alkyl, a C3-C6 alkenyl, a C5-C8 cycloalkyl, a C6-C12 aryl, or Benzyl, R ⁷ is each independently methylene, phenylene or alkyl substituted phenylene, each x is an integer of 1 to 6 independently and y is an integer of 1 to 200).

[6] The nonaqueous inkjet ink according to any one of [1] to [5], wherein the solvent (C) is contained.

[7] The solvent (C) may be ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol methyl isopropyl ether. , Diethylene glycol methylbutyl ether, diethylene glycol dibutyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxypropionate methyl, Group consisting of ethyl 3-ethoxypropionate, cyclohexanone, tetraglyme, triglyme, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone It is at least 1 type of solvent chosen from the non-aqueous inkjet ink of the said [6] description.

[8] The nonaqueous inkjet ink according to any one of [1] to [7], wherein the cyclic ether (D) is contained.

[9] The cyclic ether (D) is N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane , N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-glycidoxypropyltrimethoxysilane and represented by the following formulas (7) to (16): The non-aqueous inkjet ink according to the above [8], which is at least one compound selected from the group consisting of compounds.

(N is an integer of 0 to 10 in formula (10).)

(In Formula (15), R <^c> is a C2-C100 tetravalent organic group, R <^d> is respectively independently a C1-C30 divalent organic group, R <^e> is respectively independently the following formula ( c) to monovalent organic groups selected from the group consisting of compounds represented by (e))

(In formula (c), ^Rf is a hydrogen atom or C1-C3 alkyl.)

(N is an integer of 2-4 in Formula (16).)

[10] The non-aqueous inkjet ink according to any one of [1] to [9], wherein the ink is thermosetting.

[11] The nonaqueous inkjet ink according to any one of [1] to [9], wherein the ink is photocurable.

[12] An ink coating method comprising the step of applying the ink for non-aqueous ink jet according to any one of [1] to [11] according to the ink jet coating method.

[13] a step of coating the nonaqueous inkjet ink according to the above [4] or [5] on a substrate by an inkjet coating method to form a coating film, and

Process of forming a polyimide film by heating the said coating film

Method of forming a polyimide film comprising a.

[14] a step of forming a coating film by applying the ink for non-aqueous inkjet according to the above [4] or [5] in a pattern form on a substrate according to an inkjet coating method;

A step of forming a patterned polyimide film by heating the coating film

Method of forming a polyimide film comprising a.

[15] A polyimide film obtained by the method for forming a polyimide film according to the above [13].

[16] A patterned polyimide membrane, obtained by the method for forming a polyimide membrane according to the above [14].

[17] A film substrate comprising the polyimide film according to the above [15] or the patterned polyimide film according to the above [16].

[18] A semiconductor wafer comprising the polyimide film according to the above [15] or the patterned polyimide film according to the above [16].

[19] A substrate for an electronic material, comprising the polyimide film according to the above [15] or the patterned polyimide film according to the above [16].

[20] An electronic component comprising the polyimide film according to the above [15] or the patterned polyimide film according to the above [16].

[21] An electronic component comprising the film substrate according to the above [17], the semiconductor wafer according to the above [18] or the substrate for an electronic material according to the above [19].

By using the ink for non-aqueous ink jet of the present invention, a good insulating film layer can be formed in electronic component fabrication. For example, by the inkjet coating method, a good patterned polyimide film can be easily and efficiently formed on a flat substrate.

In addition, when the nonaqueous inkjet ink of the present invention is used, in the formation of a patterned polyimide film, it is possible to draw only on a necessary portion by inkjet coating, and the amount of material used can be overwhelmingly reduced. In addition, since there is no need to use a photomask, mass production of various types is possible, and the number of processes required for manufacturing is small.

Since the polyimide film formed from the ink for nonaqueous inkjets of this invention has high heat resistance and electrical insulation, for example, the electronic component which has the said polyimide film is highly reliable, and can improve a yield.

Fig. 1 shows the relationship between surface tension and surfactant concentration and the relationship between the total point and the surfactant concentration in the nonaqueous inkjet inks obtained in Examples 1 to 5 and Comparative Examples 1 to 3 and 5 to 7; A graph representing.
2 is a graph showing a method for calculating the critical micelle concentration.
3 is a photomicrograph of each pattern of the polyimide film 1 formed in Example 1. FIG.
4 is a micrograph of each pattern of the polyimide film (C1) formed in Comparative Example 1. FIG.

[Non-aqueous inkjet ink]

The ink for nonaqueous inkjet of this invention contains surfactant (B) in 0.00001 weight% or more and the range of critical micelle concentration or less, It is characterized by the above-mentioned. The content of the surfactant (B) is preferably 0.001% by weight or more and critical micelle concentration or less, more preferably 0.01% by weight or more and critical micelle concentration or less. The upper limit of the concentration of the surfactant (B) is particularly preferably less than the critical micelle concentration. In such a concentration range, the ink for non-aqueous ink jet containing the surfactant (B) can be stably discharged by the ink jet, and can form a coating film having a good pattern with little crawling and wet diffusion.

In the present invention, the critical micelle concentration is a concentration at which the surfactant (B) begins to form micelles in the ink for non-aqueous ink jet. Therefore, below the critical micelle concentration, the surfactant (B) does not form micelles in the non-aqueous inkjet ink, and when it exceeds the critical micelle concentration, the surfactant (B) forms micelles in the non-aqueous inkjet ink.

When the concentration of the surfactant (B) in the non-aqueous inkjet ink reaches the critical micelle concentration, as shown in Fig. 2, even if the concentration of the surfactant (B) is increased, the decrease in the surface tension of the non-aqueous inkjet ink is reduced. It rarely happens. Using this phenomenon, the critical micelle concentration can be determined from the relationship between the concentration of the surfactant (B) and the surface tension. In addition, confirmation that surfactant (B) in non-aqueous inkjet ink is less than a critical micelle concentration is possible by adding the same kind of surfactant (B) further in the said ink. That is, by adding the same type of surfactant (B) in the ink, if the surface tension decreases as compared with before addition, it can be determined that the concentration of the surfactant (B) in the ink before the addition is less than the critical micelle concentration. . On the other hand, the critical micelle concentration is selected from the group consisting of polyimide and a compound capable of forming other components in the nonaqueous inkjet ink, for example, the polyimide described later, even when the same surfactant (B) is added. It changes with the kind and quantity of 1 or more types of compound (A), a solvent (C) which become.

The critical micelle concentration is not only measured using the surface tension of the ink as described above, but also there is a method of measuring by the electric conduction method, the viscosity method, the dye method, the light scattering method and the like. Although it may be measured using any method, a method using surface tension is preferable because it is the most common and simple.

In addition, the presence or absence of micelle formation in a non-aqueous inkjet ink adds surfactant similar to surfactant (B) contained in the said ink to a non-aqueous inkjet ink, and is a surfactant ( It can confirm by measuring the surface tension before and after addition of B). When the same type of surfactant (B) is added and the content concentration of the surfactant (B) in the non-aqueous ink jet ink is increased, when the surface tension of the non-aqueous ink jet ink is lowered, the same type of surfactant (B) It can be judged that the ink for non-aqueous inkjet before addition of this does not form the micelle by surfactant (B). In addition to the above methods, micelle formation in non-aqueous inkjet inks is also determined by dynamic light scattering method, zeta potential measurement method, small angle neutron scattering method, wide angle X-ray scattering method, small angle X-ray scattering method, and transmission electron microscope. You can check it.

On the other hand, in the present invention, the ink for non-aqueous ink jet may be either colored or colorless.

1. Surfactant (B)

The surfactant (B) contained in the nonaqueous inkjet ink of the present invention has the ability to change the surface tension of the nonaqueous inkjet ink. In addition, although the said micelle (B) does not form a micelle in the nonaqueous inkjet ink of this invention, when the quantity of the said surfactant (B) is increased, it is surfactant which can form a micelle.

The surfactant (B) is at least one surfactant selected from the group consisting of silicone surfactants, fluorine surfactants, silicone fluorine surfactants, acrylic surfactants, cationic surfactants, anionic surfactants and betaine surfactants. It is preferable that it is and it is more preferable that it is 1 or more types of surfactant chosen from the group which consists of a silicone type surfactant, a fluorine type surfactant, and an acrylic type surfactant. As said silicone type surfactant, the compound which has a silicone structure represented by following formula (B-1)-(B-6) is mentioned as a especially preferable example.

Compounds having a silicone structure represented by the following formulas (B-1) to (B-6) use at least a siloxane diamine and / or a siloxane acid dianhydride as raw materials, and as an arbitrary raw material, diamine, monoamine, The compound which has two or more acid anhydride groups, and the compound which has one acid anhydride group can be combined suitably, and can be obtained by making it react.

Non-aqueous inkjet inks containing such a surfactant are preferable since they are less likely to be splashed or wet-diffused after coating on a substrate, and thus to form a cured film having a good pattern.

In formulas (B-1) to (B-6), each E independently represents a hydrogen atom or a group represented by the following formula (Ba), and each E ′ independently represents an amino group (NH ₂ ) or the following formula ( B 1), and E ¹ , E ² , E ³ and E ⁴ are each independently an organic group having 2 to 500 carbon atoms, preferably an organic group having 2 to 300 carbon atoms, and more preferably carbon atoms. It is an organic group of 2-50, More preferably, it is an organic group of 2-20 carbon atoms, m1 is an integer of 1-1000, Preferably it is an integer of 1-500, More preferably, it is an integer of 1-100 and n1 is an integer of 0-1000, Preferably it is an integer of 0-500, More preferably, it is an integer of 0-10O. However, at least E ² of the group represented by the following general formula (Bz) derived from siloxane-based diamine is 10 mol% or more in E ² 100 mol%, or the following derived from siloxane tetracarboxylic dianhydride in E ¹ 100 mol% E ¹ having a structure represented by General Formula (Bz) is 10 mol% or more.

In formula (Bz), E <^5> and E <^6> are respectively independently a hydrogen atom, C1-C12 alkyl, C3-C6 alkenyl, C5-C8 cycloalkyl, C6-C12 aryl, or benzyl Is preferably alkyl having 1 to 12 carbons, aryl or benzyl having 6 to 12 carbon atoms, more preferably alkyl having 1 to 6 carbon atoms, aryl or benzyl having 6 to 12 carbon atoms, and E ⁷ is each independently Methylene, phenylene or alkyl substituted phenylene, preferably methylene or alkyl substituted phenylene, more preferably methylene, and x1 are each independently an integer of 1 to 6, preferably 1 to 5 It is an integer, More preferably, it is an integer of 2-3, y1 is an integer of 1-200, Preferably it is an integer of 2-150, More preferably, it is an integer of 3-140.

In the present specification, "organic" is not particularly limited, but examples thereof include hydrocarbon groups, alkoxy, aryloxy, alkylamino, alkylsilyl, alkylthio, arylthio, alkylsulfonyl, and aryl sulfonyl. . Moreover, 2-100, 1-30 etc. are mentioned as carbon number of the said organic group.

The hydrocarbon of the "hydrocarbon group" may be a saturated or unsaturated acyclic ring or a saturated or unsaturated cyclic ring. In the case where the hydrocarbon is acyclic, it may be linear or branched. "Hydrocarbon group" includes alkyl, alkenyl, alkynyl, alkyldienyl, aryl, alkylaryl, arylalkyl, cycloalkyl, cycloalkenyl and the like.

Examples of the alkylthio include alkylthio (-SY ¹ , wherein Y ¹ represents alkyl having 2 to 20 carbon atoms, which may have a substituent), and may have a substituent as the arylthio. Arylthio (-SY ² , in which Y ² represents aryl having 6 to 18 carbon atoms which may have a substituent) may be mentioned as the alkylsulfonyl. Alkylsulfonyl which may have a substituent may be mentioned (-SO ₂ Y ^3, formula, Y ³ represents an alkyl having a carbon number of 2~2O which may have a substituent).

In the present specification, when not particularly limited, "alkyl" is preferably alkyl having 1 to 20 carbon atoms, more preferably alkyl having 1 to 10 carbon atoms, still more preferably alkyl having 2 to 6 carbon atoms. Do. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, when not particularly limited, "alkenyl" is preferably alkenyl having 2 to 20 carbon atoms, more preferably alkenyl having 2 to 10 carbon atoms, and alkenyl having 2 to 6 carbon atoms. More preferably. Examples of alkenyl include, but are not limited to, vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylaryl, 2-butenyl, and the like.

In the present specification, when not particularly limited, "alkynyl" is preferably alkynyl having 2 to 20 carbon atoms, more preferably alkynyl having 2 to 10 carbon atoms, and alkynyl having 2 to 6 carbon atoms. Is also preferred. Examples of alkynyl include, but are not limited to, ethynyl, propynyl, butynyl and the like.

In the present specification, when not particularly limited, "alkyldienyl" is preferably an alkyldienyl having 4 to 20 carbon atoms, preferably an alkyldienyl having 4 to 10 carbon atoms, and preferably an alkyldienyl having 4 to 6 carbon atoms. It is more preferable that it is alkyldienyl. Examples of alkyldienyl include, but are not limited to, 1,3-butadienyl and the like.

In this specification, when it is not specifically limited, it is preferable that "aryl" is C6-C18 aryl, and it is more preferable that it is C6-C10 aryl. Examples of the aryl include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

In this specification, when it is not specifically limited, "alkylaryl" is preferably C7-20 alkylaryl, and more preferably C7-12 alkylaryl. Examples of alkylaryl include, but are not limited to, o-tril, m-tril, p-tril, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, o-cumenyl, m- Cumenyl, p-cumenyl, mesityl and the like.

In this specification, when it is not specifically limited, it is preferable that "aryl alkyl" is C7-20 aryl alkyl, and it is more preferable that it is C7-12 aryl alkyl. Examples of aryl alkyls include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4- Phenyl butyl, 5-phenylpentyl, etc. are mentioned.

In the present specification, when not particularly limited, "cycloalkyl" is preferably a cycloalkyl having 4 to 20 carbon atoms, and more preferably a cycloalkyl having 4 to 10 carbon atoms. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

In the present specification, when not particularly limited, "cycloalkenyl" is preferably cycloalkenyl having 4 to 20 carbon atoms, and more preferably cycloalkenyl having 4 to 10 carbon atoms. Examples of cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.

In the present specification, when not particularly limited, "alkoxy" is preferably an alkoxy having 1 to 20 carbon atoms, more preferably an alkoxy having 1 to 10 carbon atoms, further preferably an alkoxy having 2 to 6 carbon atoms, desirable. Examples of alkoxy include, but are not limited to, ethoxy, propoxy, butoxy, pentyloxy and the like.

In this specification, when it is not specifically limited, it is preferable that "aryloxy" is C6-C20 aryloxy, and it is more preferable that it is C6-C10 aryloxy. Examples of the aryloxy include, but are not limited to, phenyloxy, naphthyloxy, biphenyloxy and the like.

In the present specification, when not particularly limited, "alkylthio (-SY ¹ , wherein Y ¹ represents alkyl having 2 to 20 carbon atoms which may have substitution)" and "alkylsulfonyl (-SO ₂ Y) ³ , wherein, Y ³ represents alkyl having 1 to 20 carbon atoms which may have a substituent. &Quot; Y ¹ and Y ³ are preferably alkyl having 2 to 10 carbon atoms, and alkyl having 2 to 6 carbon atoms. It is also preferred. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, when not particularly limited, "arylthio (-SY ² , wherein Y ² represents aryl having 6 to 18 carbon atoms which may have substitution)" and "arylsulfonyl (-SO ₂ Y ⁴ , wherein, Y ⁴ represents aryl having 6 to 18 carbon atoms which may have a substituent &quot;, and preferably Y ² and Y ⁴ are aryl having 6 to 10 carbon atoms. Examples of the aryl include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

In the present specification, when not particularly limited, "hydrocarbon group", "alkoxy", "aryloxy", "alkylamino", "alkylsilyl", "alkylthio", "arylthio", "alkylsulfonyl The substituent may be introduced into "" arylsulfonyl ". As this substituent, ester, carboxyl, amide, alkyn, trimethylsilyl, amino, phosphonyl, thio, carbonyl, nitro, sulfo, imino, halogeno, alkoxy, etc. are mentioned, for example. In this case, 1 or more substituents may be introduce | transduced into the position which can be substituted, and the maximum number which can be substituted may be introduce | transduced, Preferably 1-4 may be introduce | transduced. When the number of substituents is two or more, each substituent may be the same and may differ.

In the present specification, examples of the "alkylamino which may have a substituent" include, but are not limited to, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

In the present specification, examples of the "alkylsilyl which may have a substituent" include, but are not limited to, dimethylsilyl, diethylsilyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenylmethylsilyl , Triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl and the like.

As mentioned above, although the specific example of monovalent organic group was given, in this specification, the group which further increased one valence in the monovalent organic group described in this specification is mentioned. . Similarly, in this specification, as a specific example of a tetravalent organic group, the group which added three valences further in the monovalent organic group described in this specification is mentioned.

The compounds represented by the formulas (B-1), (B-2) and (B-3) (hereinafter also referred to as "amic acid (Ba)") are monomers having an amic acid structure and a silicone structure, Or oligomers or polymers having repeating units of an amic acid structure and a silicone structure.

Compounds represented by the formulas (B-4), (B-5) and (B-6) (hereinafter also referred to as "imide (Bi)") are monomers having an imide structure and a silicone structure, or It is an oligomer or polymer which has a repeating unit of an imide structure and a silicone structure.

Hereinafter, amic acid (Ba) and imide (Bi) are demonstrated in detail.

1.1 amic acid ( Ba )

As a raw material for synthesizing amic acid (Ba), for example, compound (a1) having two or more acid anhydride groups, compound (a3) having one acid anhydride group, diamine (Ba2) and monoamine (a4) Can be mentioned. As a synthesis | combining method of amic acid (Ba), the method of making compound (a3) and diamine (Ba2) which have one acid anhydride group react, for example, the compound (a1) and diamine (Ba2) which have two or more acid anhydride groups A method of reacting a compound, a method of reacting a monoamine (a4) and a diamine (Ba2) with a compound (a1) having two or more acid anhydride groups, a compound (a1) and a monoamine (a4) having two or more acid anhydride groups A method of reacting, a compound (a3) having one acid anhydride group and a compound (a1) having two or more acid anhydride groups and a diamine (Ba2), a compound (a3) having an acid anhydride group and an acid anhydride group A method of reacting a compound (a1) having two or more with a monoamine (a4), a compound (a3) having one acid anhydride group and a compound (a1) having two or more acid anhydride groups, a monoamine (a4) and a diamine ( Method of reacting a2), having one acid anhydride group Although the method of making compound (a3), monoamine (a4), and diamine (a2) react, etc. are mentioned, The method of making compound (a3) and diamine (Ba2) which have one acid anhydride group react, and two acid anhydride groups Method to react compound (a1) and diamine (Ba2) which have the above-mentioned, Method to react compound (a1) which has monoamine (a4) and diamine (Ba2) and two or more acid anhydride groups, Having two or more acid anhydride groups A method of reacting a compound (a1) with a monoamine (a4), a method of reacting a compound (a3) having one acid anhydride group and a compound (a1) having two or more acid anhydride groups and a diamine (Ba2), an acid anhydride group More preferably, a compound (a1) having one or more compounds (a3) and two or more acid anhydride groups, a monoamine (a4) and a diamine (a2) are reacted, and a compound (a3) having one acid anhydride group; Method of reacting diamine (Ba2), monoamine (a4) and dia A method of reacting a compound (a1) having two or more acid anhydride groups, a method of reacting a compound (a1) having a two or more acid anhydride groups and a monoamine (a4), a compound having one acid anhydride group The method of making compound (a1) and diamine (Ba2) which have (a3) and two or more acid anhydride groups react is more preferable.

Hereinafter, the compound (a1) which has two or more acid anhydride groups, the diamine (Ba2), the compound (a3) which has one acid anhydride group, and a monoamine (a4) are demonstrated.

1.1.1 Compounds having two or more acid anhydride groups ( a1 )

Specific examples of the compound (a1) having two or more acid anhydride groups include a radical polymerizable monomer having an anhydride group such as a styrene-maleic anhydride copolymer and a methyl methacrylate-maleic anhydride copolymer with another radically polymerizable monomer. A copolymer, tetracarboxylic dianhydride, etc. are mentioned. As tetracarboxylic acid dianhydride, For example, 2,2 ', 3,3'- benzophenone tetracarboxylic acid dianhydride, 2,3,3', 4'- benzophenone tetracarboxylic dianhydride, 2,2 ', 3 , 3'-diphenylsulfontetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylsulfontetracarboxylic dianhydride, 2,2', 3,3'-diphenylethertetracarboxylic dianhydride, 2, 3,3 ', 4'- diphenyl ether tetracarboxylic acid dianhydride, ethylene glycol bis (anhydro trimellitate), ethane tetracarboxylic dianhydride, ethylenediamine tetraacetic acid dianhydride, the following formula a1-1 to formula a1-80 Tetracarboxylic dianhydrides, such as a compound represented by these, are mentioned.

Among the specific examples of compound (a1) having two or more acid anhydrides, formula a1-1, formula a1-2, formula a1-3, formula a1-4, formula a1-6, formula a1-7, formula a1- 8, Expression a1-9, Expression a1-14, Expression a1-18, Expression a1-20, Expression a1-22, Expression a1-39, Expression a1-74, Expression a1-75, Expression a1-76, Expression a1- 77, The compound represented by formula a1-79 is more preferable. When the compound (a1) which has two or more such acid anhydrides is used, since the solubility to the solvent of amic acid (Ba) improves, there exists a tendency for the mechanical characteristic of the cured film finally obtained to improve. Moreover, although high transparency is required according to the use of a non-aqueous inkjet ink, in this case, a styrene maleic anhydride copolymer, Formula a1-6, Formula a1-7, Formula a1-8, Formula a1-9, It is especially preferable to use the compound represented by Formula a1-14 and Formula a1-18.

In the present invention, as another example of the compound (a1) having two or more acid anhydrides used for the synthesis of the amic acid (Ba), a siloxane-based acid dianhydride having a siloxane bond alone or a siloxane-based acid 2 having a siloxane bond And mixtures of anhydrides with other acid dianhydrides listed above. As the siloxane acid dianhydride having a siloxane bond, it is preferable to use a siloxane acid dianhydride represented by at least the following formula (B1-y). When the obtained amic acid (Ba) does not have a repeating structure, it is preferable to use the said siloxane-based dianhydride alone, and when the obtained amic acid (Ba) has a repeating structure, a siloxane-based acid having a siloxane bond When the total amount of the dianhydride and the other acid dianhydride is 10 mol%, it is preferable to use a siloxane-based acid dianhydride having a siloxane bond in a ratio of 10 mol% or more. The larger the ratio, the stronger the resulting amic acid (Ba) can express the surfactant activity. When the siloxane-based acid dianhydride is used alone as the compound (a1) having two or more acid anhydrides, the resulting amic acid (Ba) can express the surfactant activity more strongly.

In formula (B1-y), E <^5> and E <^6> respectively independently represent a hydrogen atom, C1-C12 alkyl, C3-C6 alkenyl, C5-C8 cycloalkyl, and C6-C12 aryl Or benzyl, preferably alkyl having 1 to 12 carbons, aryl or benzyl having 6 to 12 carbon atoms, more preferably alkyl having 1 to 6 carbon atoms, aryl or benzyl having 6 to 12 carbon atoms, and E ⁷ is each Independently methylene, phenylene or alkyl-substituted phenylene, preferably methylene, alkyl-substituted phenylene, more preferably methylene, and x1 is each independently an integer of 1 to 6, preferably 1 to It is an integer of 5, More preferably, it is an integer of 2-3, y1 is an integer of 1-200, Preferably it is an integer of 2-150, More preferably, it is an integer of 3-140.

When the compound (a1) which has two or more such acid anhydrides is used, there exists a tendency for the pattern property of the film finally obtained to improve.

In addition, the said compound (a1) may be used individually by 1 type, and may use 2 or more types together.

1.1.2 diamines ( Ba2 )

In this invention, as diamine (Ba2) used for the synthesis | combination of amic acid (Ba), the siloxane type diamine which has a siloxane bond alone, or the mixture of the siloxane type diamine which has a siloxane bond, and another diamine is mentioned, for example. Can be. As the diamine (Ba2), it is preferable to use a siloxane diamine represented by at least the following formula (B1-z). When the obtained amic acid (Ba) does not have a repeating structure, it is preferable to use the said siloxane diamine independently, and when the obtained amic acid (Ba) has a repeating structure, it differs from the siloxane diamine which has a siloxane bond. When total sum with diamine is 100 mol%, it is preferable to use the siloxane type diamine which has a siloxane bond in the ratio of 10 mol% or more. The larger the ratio, the stronger the resulting amic acid (Ba) can express the surfactant activity. When the siloxane-based diamine is used alone as the diamine (Ba2), the resulting amic acid (Ba) can express the surfactant activity more strongly.

In formula (B1-z), E <^5> and E <^6> respectively independently represent a hydrogen atom, C1-C12 alkyl, C3-C6 alkenyl, C5-C8 cycloalkyl, and C6-C12 aryl Or benzyl, preferably alkyl having 1 to 12 carbons, aryl or benzyl having 6 to 12 carbon atoms, more preferably alkyl having 1 to 6 carbon atoms, aryl or benzyl having 6 to 12 carbon atoms, and E ⁷ is each Independently methylene, phenylene or alkyl-substituted phenylene, preferably methylene, alkyl-substituted phenylene, more preferably methylene, and x1 is each independently an integer of 1 to 6, preferably 1 to It is an integer of 5, More preferably, it is an integer of 2-3, y1 is an integer of 1-200, Preferably it is an integer of 2-150, More preferably, it is an integer of 3-140.

When such diamine (Ba2) is used, there exists a tendency for the pattern property of the film finally obtained to improve.

1.1.3 Acid Anhydride Group With one  compound( a3 )

In this invention, if the compound (a3) which has one acid anhydride group used for the synthesis | combination of an amic acid (Ba) is a compound represented by following formula (1-1), it will not specifically limit.

In formula (1-1), E <^1> is a C2-C500 organic group, Preferably it is a C2-C300 organic group, More preferably, it is a C2-C50 organic group, More preferably, it is C2 It is the organic group of -30, Especially preferably, it is a C2-C20 organic group.

Specific examples of the compound (a3) having one acid anhydride group include maleic anhydride, citraconic anhydride, allylnadic acid anhydride, allylsuccinic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydro Phthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, cyclohexene-1,2-dicarboxylic anhydride, cis-1,2- Cyclohexanedicarboxylic anhydride, 1,3-cyclohexanedicarboxylic anhydride, itaconic anhydride, p- (trimethoxysilyl) phenylsuccinic anhydride, p- (triethoxysilyl) phenylsuccinic anhydride, m- (trimethoxy Silyl) phenylsuccinic anhydride, m- (triethoxysilyl) phenylsuccinic anhydride, trimethoxysilylpropylsuccinic anhydride, 2- [3- (triethoxysilyl) propyl] succinic anhydride, represented by the following formula (α) The compound and the compound represented by following formula ((beta)) are preferable. The compound represented by the following formula (α) can be obtained by, for example, reacting 5-norbornene-2,3-dicarboxylic anhydride with trimethoxysilane. Moreover, the compound represented by following formula ((beta)) can be obtained by making allylnadic acid anhydride and trimethoxysilane react, for example.

Among these, maleic anhydride, citraconic anhydride, allylnadic acid anhydride, trimethoxysilylpropyl succinic anhydride and 2- [3- (triethoxysilyl) propyl] succinic anhydride are preferable.

When the compound (a3) which has such an acid anhydride group is used, there exists a tendency for the ejectability of the inkjet of the ink obtained to improve.

The compound (a3) which has one such acid anhydride group may be used individually by 1 type, and may use 2 or more types together.

In formulas (α) and (β), TO is CH ₃ O (methoxy) or C ₂ H ₅ O (ethoxy).

1.1.4 Monoamines ( a4 )

In this invention, although monoamine (a4) used for the synthesis | combination of amic acid (Ba) is not specifically limited unless the objective of this invention is impaired, As a specific example, 3-aminopropyl trimethoxysilane, 3- Aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyl triethoxysilane, 4-aminobutylmethyldiethoxy Silane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, m-amino Phenylmethyldiethoxysilane, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-furfurylamine, tyramine, 2- (4-aminophenyl) ethylamine, trans-4-aminocyclohexanol, mono Ethanolamine, 2-aminoethanol, 3-amino-1-propanol, 1-amino-2- Propanol, 2- (2-aminoethoxy) ethanol, 5-amino-1-pentanol, n-butylamine, aniline, 3-ethylaniline, 4-ethylaniline, pentafluoroaniline, tryptophan, lysine, methionine , Phenylalanine, threonine, valine, isoleucine, leucine, histidine, alanine, arginine, asparagine, serine, asparagine acid, cysteine, glutamine, glutamic acid, glycine, proline, tyrosine, 12-aminolauric acid, o-phosphorylethanol Amine, hydrogen sulfide 2-aminoethyl, 2-aminoethanesulfonic acid and the like.

Among these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and p-aminophenyltrimethoxysilane are preferable, and 3-aminopropyltriethoxysilane is especially preferable.

When such a monoamine (a4) is used, there exists a tendency for the ejectability of the inkjet of the obtained ink to improve.

Such monoamine (a4) may be used individually by 1 type, and may use 2 or more types together.

1.1.5 Amic acid (Ba)  Reaction Conditions for Synthesis

The amic acid (Ba) is reacted by appropriately combining a compound (a1) having two or more acid anhydride groups and a compound (a3) having one acid anhydride group with a diamine (Ba2) and a monoamine (a4), for example. Can be synthesized.

It is preferable that the reaction temperature of the said reaction is 0-100 degreeC, It is more preferable that it is 0-80 degreeC, It is especially preferable that it is 0-50 degreeC.

It is preferable that the reaction pressure of the said reaction is 90-120 kPa, It is more preferable that it is 95-110 kPa, It is especially preferable that it is 97-105 kPa.

It is preferable that the reaction time of the said reaction is 0.2 to 20 hours, It is more preferable that it is 0.5 to 15 hours, It is especially preferable that it is 1 to 12 hours.

The proportion of each raw material is n1 for the number of moles of the compound (a1) having two or more acid anhydride groups, n2 for the number of moles of the diamine (Ba2), n3 for the number of moles of the compound (a3) having one acid anhydride group, and monoamine (a4). When the number of moles of N is set to n4, it is preferable to set n1 + (1/2) × n3 = n2 + (1/2) × n4. In addition, the compound, diamine, amine, and acid anhydride which have two or more acid anhydrides which do not contribute to reaction may exist. In addition, when the obtained amic acid (Ba) is an oligomer or a polymer, the terminal of the amic acid (Ba) may be an amino group terminal or an acid anhydride terminal.

1.1.6 Reaction Solvent

The reaction solvent used for synthesizing amic acid (Ba) is not particularly limited as long as the amic acid (Ba) can be synthesized. As said reaction solvent, For example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxolane, propylene glycol dimethyl ether, propylene Glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropylmethyl ether, dipropylene glycol monomethyl Ether, diethylene glycol diethyl Ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene Glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy-2- Propanol), methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2 -Pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-diethylacetoamide, N, N-dimethylpropionamide, N- Methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone.

Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methylethyl ether, and diethylene glycol dimethyl ether are more preferable.

These reaction solvents may be used individually by 1 type, and may use 2 or more types together. In addition, other solvents may be used in addition to the reaction solvent.

100 weight part or more of reaction solvent is used with respect to a total of 100 weight part of compound (a1) which has two or more acid anhydride groups, diamine (Ba2), the compound (a3) which has one acid anhydride group, and monoamine (a4). This is preferable because the reaction proceeds smoothly.

1.1.7 To the reaction system  Order of addition

In addition, the order of addition of the reaction raw materials to the reaction system is not particularly limited. Namely, a method of simultaneously adding a compound (a1) having two or more acid anhydride groups, a diamine (Ba2), a compound having a single acid anhydride group (a3) and a monoamine (a4) to the reaction solvent, a diamine (Ba2) and an acid anhydride After dissolving compound (a3) having one group in a reaction solvent, a method of adding compound (a1) and monoamine (a4) having two or more acid anhydride groups, compound (a1) having two or more acid anhydride groups, and After dissolving monoamine (a4) in a reaction solvent and further reacting the compound (a3) which has one acid anhydride group previously, the method of adding diamine (Ba2) and the compound (a1) which has two or more acid anhydride groups And a method of adding a compound (a3) having a single acid anhydride group and a monoamine (a4) after reacting the diamine (Ba2) in advance to synthesize a polymer, and the like.

1.1.8 Of amic acid (Ba)  Weight average molecular weight

In the present invention, when the amic acid (Ba) is an oligomer or a polymer, the weight average molecular weight of the amic acid (Ba) is preferably 1, OOO to 10O, OOO, more preferably 1,000 to 50,000, and 1,000 It is more preferable that it is -20,000. When the weight average molecular weight of amic acid (Ba) is in the said range, the inkjet discharge property of ink improves and the film excellent in pattern property can be obtained.

In this invention, the weight average molecular weight of amic acid (Ba) can be measured by a gel permeation chromatography (GPC) method. For example, specifically, the obtained amic acid (Ba) is diluted with dimethylformamide (DMF) so that the concentration of the amic acid (Ba) is about 1% by weight, and Shodex Asahipak GF-510 HQ and Shodex Asahipak as columns. Using GF-310 HQ, DMF can be used as a developing agent, measured by gel permeation chromatography (GPC), and can be obtained by polystyrene conversion.

1.2 Imide (Bi)

Imide (Bi) can be synthesize | combined, for example by dehydrating and ring-closing the amic acid (Ba) synthesize | combined as mentioned above.

In the synthesis of amic acid (Ba), the reaction raw material of the compound (a1) having two or more acid anhydride groups, the compound (a3) having one acid anhydride group, the diamine (Ba2) and the monoamine (a4), the reaction conditions, In the addition procedure to a reaction solvent and a reaction system, it is the same as that of the above-mentioned amic acid (Ba).

Imide (Bi) can be synthesize | combined by dehydrating and ring-closing the amic acid (Ba) mentioned above.

The method of dehydration and ring closure may be by heating or chemical method. For example, the amic acid (Ba) may be heated to 100 to 200 ° C. in a solvent to dehydrate and close the ring. Furthermore, pyridine and acetic anhydride may be added to amic acid (Ba), for example, and it may dehydrate and ring-close. A more preferable method of dehydration and ring closure is a method of heating amic acid (Ba) so that impurities are not contained. It is preferable that the temperature in the said heating is 140-180 degreeC.

When imide (Bi) obtained in this way is used, there exists a tendency for the storage stability of the film finally formed to improve.

1.2.1 Weight average molecular weight of imide (Bi)

In the present invention, when the imide (Bi) is an oligomer or a polymer, the weight average molecular weight of the imide (Bi) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and more preferably 1,000 to 20,000. More preferred. When the weight average molecular weight of imide (Bi) exists in the said range, there exists a tendency which the inkjet discharge property of ink improves and the film excellent in pattern property can be obtained.

In this invention, the weight average molecular weight of imide (Bi) can be measured by a gel permeation chromatography (GPC) method. For example, specifically, the obtained imide (Bi) is diluted with dimethylformamide (DMF) so that the concentration of the imide (Bi) is about 1% by weight, and Shodex Asahipak GF-510 HQ and Shodex Asahipak GF as columns. It can be calculated | required by measuring by gel permeation chromatography (GPC) method using -310 HQ, using DMF as a developing agent, and polystyrene conversion.

1.3  That  Other Silicone Surfactants

In the present invention, the silicone-based surfactants other than the amic acid (Ba) and the imide (Bi) described above are not particularly limited. For example, Japanese Patent Application Laid-open No. 2009-035702 and Japanese Patent Application Publication No. 2009-032023, Japanese Patent Application Publication No. 2009-051931, Japanese Patent Application Publication No. 2008-133336, Japanese Patent Application Publication No. 2008-133335, Japanese Patent Application Publication No. 2008-106165 You can use the ones listed in.

Preferably, the silicone type surfactant shown below is mentioned.

For example, the brand names "FM-3306", "FM-3311", "FM-3321", "FM-3325", "FM-4411", "FM-4421", "FM-4425", "FM- 7711 "," FM-7721 "," FM-7725 "," FM-0411 "," FM-0421 "," FM-0425 "," FM-DA11 "," FM-DA21 "," FM-DA26 " , "FM-0711", "FM-0721", "FM-0725", "TM-O7O1", "TM-O7O1T" (manufactured by Chisso Corp.), and the like, trade names "Byk-3OO" and "Byk-306" "," Byk-335 "," Byk-310 "," Byk-341 "," Byk-344 "," Byk-370 "(Bikkemi Corporation make), etc. are mentioned.

Especially preferred of these are, for example, trade names "FM-3306", "FM-3311", "FM-3321", "FM-3325", "FM-4411", "FM-7711" and "FM-0411". "," FM-DA11 "," FM-0711 "(Tosoh Co., Ltd. product), etc. are mentioned.

When the ink containing such a silicone type surfactant is used, there exists a tendency which can obtain the film excellent in patternability.

1.4 Fluorinated Surfactants

In the present invention, the fluorine-based surfactant is not particularly limited. For example, Japanese Patent Application Publication No. 2009-035702, Japanese Patent Application Publication No. 2009-032023, and Japanese Patent Application Publication No. 2009-051931 Unexamined-Japanese-Patent No. 2008-133336, Unexamined-Japanese-Patent No. 2008-133335, Unexamined-Japanese-Patent No. 2008-106165 (our prior document) can be used.

Preferably, the fluorine-type surfactant shown below is mentioned.

For example, the product names "R-08", "F-472SF", "R-30", "BL-20", "R-61", "R-90", "F-114", and "F- 410 "," F-493 "," F-494 "," F-443 "," F-444 "," F-445 "," F-446 "," F-470 "," F-471 " , "F-474", "F-475", "F-477", "F-478", "F-479", "F-480 SF", "F-482", "F-483", "F-484", "F-486", "F-487", "F-489", "F-1720", "F-178 K", "ESM-1", "MCF-350 SF", "TF-2066", "F-472 SF", "TF-1366", "TF-1367", "F-552", "F-553", "F-554", "TF-1425", " TF-1437 "," TF-1507 "," F-1535 "(manufactured by DIC Corporation, MegaPac series), etc., trade names" DFX-18 "," Pentent 250 "," Pentent 251 "," FTX -208G "," FTX-218G "," FTX-240G "," FTX-212P "," FTX-220P "," FTX-228P "," FTX-218GL "," FTX-206D "," FTX-218 "," FTX-220D "," FTX-230D "," FTX-24OD "," FTX-75OLL "," FTX-73OLS "," FTX-73OLM "," FTX-73OLL "," FTX-71OLL ", "FTX-75OFM", "FTX-73OFS", "FTX-73OFM", "FTX-73OFL", "Pentent 212D", "Pentent 71OFL", "Pentent 730FM", "FTX-209F", "FTX -213F "," FTX-233F "," Phentent 222F "," Phentent 245F " Can.

Especially preferred of these are, for example, trade names "R-08", "F-472 SF", "R-30", "F-477", "F-479", "TF-1366", "TF -1367 "," TF-1425 "(manufactured by DIC Corporation, MegaPac series), etc.," DFX-18 "," FTX-208G "," FTX-218G "," FTX-240G "," FTX- 212P "," FTX-220P "," FTX-228P "," FTX-218GL "" Pentent 71OFL "," Pentent 730FM "," FTX-209F "," Pentent 222F "," Pentent 245F "( Neos Co., Ltd., Pentgent series) etc. are mentioned.

When the ink containing such a fluorine type surfactant is used, there exists a tendency which can obtain the film excellent in patternability.

1.5 Acrylic Surfactants

In this invention, although it does not specifically limit as an acrylic surfactant, For example, Unexamined-Japanese-Patent No. 2009-035702, Unexamined-Japanese-Patent No. 2009-032023, Japan Patent Application Publication No. 2009-051931 Unexamined-Japanese-Patent No. 2008-133336, Unexamined-Japanese-Patent No. 2008-133335, Unexamined-Japanese-Patent No. 2008-106165 (our prior document) can be used.

Preferably, the acrylic surfactant shown below is mentioned.

For example, acrylic surfactant, such as brand names "Byk-354", "ByK-358", and "Byk-361N" (Bikkemi Co., Ltd. product) etc. are mentioned.

Among these, acrylic surfactants, such as a brand name "Byk-361N" (Bikkemi Co., Ltd. product) etc. are mentioned.

When the ink containing such an acrylic surfactant is used, there exists a tendency which can obtain the film excellent in patternability.

1.6 Particulate Dispersion Containing Surfactant (B)

In the present invention, in order to contain the surfactant (B) as a component of the nonaqueous inkjet ink, the surfactant (B) may be mixed with other components contained in the nonaqueous inkjet ink, but the surfactant (B The solution containing a) may be mixed with other components contained in the nonaqueous inkjet ink, or the fine particle dispersion containing the surfactant (B) may be mixed with other components contained in the nonaqueous inkjet ink. Although the said fine particle dispersion is not specifically limited, Preferably, the fine particle dispersion shown below is mentioned.

For example, trade names "IPA-ST", "MIBK-ST", "IPA-ST-L", "IPA-ST-ZL", "PGM-ST" (manufactured by Nippon Chemical Co., Ltd.), "Oscal 101 "," Oscal 105 "," Oscal 106 "," Cataloid-S "(manufactured by Chemical Engineering Co., Ltd.)," PL-2L-PGME "," PL-2L-lPA "," PL-2L -T0L "," PL-2L-MEK "," PL-2L-BL "," PL-2L-DAA "," PL-2L "," GP-2L "(manufactured by Chemical Engineering Co., Ltd.)," And fine particle dispersions such as "Leolosyl" (manufactured by Tokuyama Co., Ltd.).

Particularly preferred among these is a fine particle dispersion of a trade name "2L-PL-PGME" (manufactured by Chemical Industries, Ltd.).

When using the ink containing such surfactant containing fine particle dispersion, there exists a tendency which can obtain the film excellent in patternability.

The inkjet ink of the present invention is not particularly limited as long as it contains the surfactant (B) in the concentration range and can be discharged by inkjet. The inkjet ink of the present invention is a component other than the surfactant (B), and for example, at least one compound (A) selected from the group consisting of a compound capable of forming a polyimide and a polyimide, and a solvent ( It is preferable to contain C) and the like. Hereinafter, each component is explained in full detail.

2. Compound (A)

It is preferable that the ink for nonaqueous inkjets of this invention contains 1 or more types of compound (A) chosen from the group which consists of a compound which can form polyimide, and a polyimide.

It is preferable to make content of the said compound (A) into 20 to 80 weight% with respect to the inkjet ink total weight, It is more preferable to set it as 25 to 70 weight%, It is more preferable to set it as 25 to 60 weight% Do. When content of the said compound (A) exists in the said range, there exists a tendency for the ejectability of the inkjet of ink to improve.

Examples of the compound (A) include amic acid and imide.

Moreover, it is more preferable that the said compound (A) is 1 or more types of compounds chosen from the group which consists of a compound represented by following General formula (1)-(6).

In formulas (1) to (6), each R independently represents a hydrogen atom or a group represented by the following formula (a), and each R ′ independently represents an amino group (NH ₂ ) or the following formula (b). R ¹ , R ² , R ^3, and R ⁴ are each independently an organic group having 2 to 500 carbon atoms, preferably an organic group having 2 to 30 carbon atoms, and R ¹ and R ² are more preferable. Preferably they are each independently an organic group having 2 to 80 carbon atoms, more preferably each independently an organic group having 2 to 50 carbon atoms, and R ³ and R ⁴ are more preferably each independently an oil having 2 to 20 carbon atoms. It is an apparatus, More preferably, they are each independently a C2-C15 organic group, n is an integer of 0-1,000, Preferably it is an integer of 0-800, More preferably, it is an integer of 0-500. Provided that when n is 0, R is a group represented by the following formula (a), R 'is a group represented by the following formula (b), and silicon represented by the following formula (z) in R ¹ 100 mol%. R ¹ having the structure is less than 10 mol%, R ² R ² of the silicon structure represented by the following formula (z) of the 1OOmol% is less than 10 mol%.

In formula (z), R <^5> and R <^6> are respectively independently a hydrogen atom, C1-C12 alkyl, C3-C6 alkenyl, C5-C8 cycloalkyl, C6-C12 aryl, or benzyl And R ⁷ are each independently methylene, phenylene or alkyl-substituted phenylene, each independently represents an integer of 1 to 6, and y is an integer of 1 to 200.

By using the nonaqueous inkjet ink containing such a compound (A), the polyimide film excellent in heat resistance, chemical-resistance, mechanical characteristics, and an electrical characteristic can be formed as mentioned later.

The compound represented by the above formulas (1) to (3) (hereinafter also referred to as "amic acid (a)") is a monomer having an amic acid structure or an oligomer or polymer having a repeating unit having an amic acid structure and a silicone structure. to be.

Compounds represented by the formulas (4) to (6) (hereinafter also referred to as "imide (a ')") are oligomers or polymers having a monomer having an imide structure or a repeating unit having an imide structure and a silicone structure. to be.

Hereinafter, amic acid (a) and imide (a ') are demonstrated in detail.

2.1 Amic acid (a)

As a raw material in synthesizing amic acid (a), for example, compound (a1) having two or more acid anhydride groups, compound (a3) having one acid anhydride group, diamine (a2) and monoamine (a4) Can be mentioned. As a synthesis | combining method of an amic acid (a), the method of making compound (a3) and diamine (a2) which have one acid anhydride group react, for example, the compound (a1) and diamine (a2) which have two or more acid anhydride groups A method of reacting a compound, a method of reacting a monoamine (a4) and a diamine (a2) with a compound (a1) having two or more acid anhydride groups, a compound (a1) and a monoamine (a4) having two or more acid anhydride groups A method of reacting, a compound (a3) having one acid anhydride group and a compound (a1) having two or more acid anhydride groups and a diamine (a2), a compound (a3) having one acid anhydride group and an acid anhydride group A method of reacting a compound (a1) having two or more with a monoamine (a4), a compound (a3) having one acid anhydride group and a compound (a1) having two or more acid anhydride groups, a monoamine (a4) and a diamine ( Method of reacting a2), the oxidation having one acid anhydride group The method of reacting water (a3), a monoamine (a4), and a diamine (a2), the method of reacting the compound (a3) and monoamine (a4) which have one acid anhydride group, etc. are mentioned. A method of reacting a compound (a3) and a diamine (a2), a method of reacting a compound (a1) and a diamine (a2) having two or more acid anhydride groups, a monoamine (a4) and a diamine (a2) and an acid anhydride A method of reacting a compound (a1) having two or more groups, a method of reacting a compound (a1) having a two or more acid anhydride groups and a monoamine (a4), a compound (a3) having one acid anhydride group and an acid anhydride group A method of reacting a compound (a1) having two or more with a diamine (a2), a compound (a3) having one acid anhydride group and a compound (a1) having two or more acid anhydride groups, a monoamine (a4) and a diamine (a2) ) Is more preferable, and has one acid anhydride group Method of reacting compound (a3) with diamine (a2), Method of reacting compound (a1) having monoamine (a4) and diamine (a2) with two or more acid anhydride groups, Compound having two or more acid anhydride groups ( The method of making a1) react with a monoamine (a4), the compound (a3) which has one acid anhydride group, and the method of making compound (a1) and diamine (a2) which have two or more acid anhydride groups react are more preferable.

Hereinafter, the compound (a1) which has two or more acid anhydride groups, the diamine (a2), the compound (a3) which has one acid anhydride group, and a monoamine (a4) are demonstrated.

2.1.1 Compounds having two or more acid anhydride groups ( a1 )

For example, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyl Sulfontetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylsulfontetracarboxylic dianhydride, 2,2', 3,3'-diphenylethertetracarboxylic dianhydride, 2,3,3 ', 4 '-Diphenyl ether tetracarboxylic dianhydride, ethylene glycol bis (anhydro trimellitate), ethane tetracarboxylic dianhydride, ethylenediamine tetraacetic acid dianhydride, compounds represented by the following formulas a1-1 to the following formula a1-80 Tetracarboxylic dianhydride is mentioned.

Also in the said specific example of compound (a1) which has two or more acid anhydrides, Formula a1-1, Formula a1-5, Formula a1-6, Formula a1-7, Formula a1-8, Formula a1-9, Formula mentioned above When the compounds represented by a1-14, formula a1-18, and formula a1-20 are used, the solubility of the resulting amic acid (a) in the solvent (C) to be described later is high and a high concentration of non-aqueous inkjet ink can be prepared. Therefore, it is preferable. In addition, although high transparency is required depending on the use of a non-aqueous inkjet ink, in this case, a styrene-maleic anhydride copolymer as the compound (a1) having two or more acid anhydride groups, the above formula a1-6, formula It is preferable to use the compound represented by a1-7, a1-8, a1-9, a1-14, a1-18, and the like.

In the present invention, as the compound (a1) having two or more acid anhydrides used in the synthesis of the amic acid (a), the siloxane-based acid dianhydride alone represented by the following formula (B1-y) is excluded. The following formula in the case of a combination of siloxane-based acid-anhydride and other acid anhydride represented by (B1-y), the general formula (1) to (3), wherein the following formula (z) of the R ¹ 100mol% in It is necessary to control the compounding ratio of the siloxane-based dianhydride represented by the following formula (B1-y) so that R ¹ having a silicon structure represented by the formula is less than 10 mol%.

In formula (B1-y), E <^5> and E <^6> respectively independently represent a hydrogen atom, C1-C12 alkyl, C3-C6 alkenyl, C5-C8 cycloalkyl, and C6-C12 aryl Or benzyl, preferably alkyl having 1 to 12 carbons, aryl or benzyl having 6 to 12 carbon atoms, more preferably alkyl having 1 to 6 carbon atoms, aryl or benzyl having 6 to 12 carbon atoms, and E ⁷ is each Independently methylene, phenylene or alkyl-substituted phenylene, preferably methylene, alkyl-substituted phenylene, more preferably methylene, and x1 is each independently an integer of 1 to 6, preferably 1 to It is an integer of 5, More preferably, it is an integer of 2-3, y1 is an integer of 1-200, Preferably it is an integer of 2-150, More preferably, it is an integer of 3-140.

When compound (a1) which has two or more such acid anhydrides is used, there exists a tendency which can obtain the film excellent in patternability.

In addition, the said compound (a1) may be used individually by 1 type, and may use 2 or more types together.

2.1.2 diamines ( a2 )

In the present invention, as the diamine (a2) used for the synthesis of the amic acid (a), the siloxane diamine alone having a structure represented by the following general formula (z) is excluded. When using together the siloxane-based diamine and other diamine which have a structure represented by following General formula (z), it is represented by following formula (z) in R <^2> OOmol% in said General formula (1)-(3). It is necessary to control the compounding ratio of the siloxane-based diamine having a structure represented by the following general formula (z) so that R ² of the silicon structure to be less than 10 mol%.

In formula (z), R <^5> and R <^6> are respectively independently a hydrogen atom, C1-C12 alkyl, C3-C6 alkenyl, C5-C8 cycloalkyl, C6-C12 aryl, or benzyl And R ⁷ are each independently methylene, phenylene or alkyl-substituted phenylene, each independently represents an integer of 1 to 6, and y is an integer of 1 to 200.

As siloxane-based diamine which has a structure represented by the said general formula (z), what is represented by following formula (4-1) is mentioned.

Wherein R ⁵ and R ⁶ are independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁷ is independently methylene, phenylene or phenylene with at least one hydrogen substituted by alkyl, and x is independently 1 to It is an integer of 6 and y is an integer of 1-200.

As a specific example of another diamine (a2), 3, 3'- diamino diphenyl sulfone, 4,4'- diamino diphenyl ether, 4,4'- diamino diphenylmethane, 3,3'- diaminodi Phenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4 -Aminophenoxy) phenyl] hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylenediamine, p-xylenediamine, 2- (4-aminophenyl) ethylamine, 2,2'- Diaminodiphenylpropane, benzidine, 1,1-bis [4- (4-aminobenzyl) phenyl] methane, 1,4-bis (3-aminopropyl) piperazine, N, N'-bis (3-amino Propyl) ethylenediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, represented by the following formula (4-1-1), and the following formula (II) to (VIII) The compound which becomes.

In formula (ll), A <^1> is a C1-C20 alkyl group, a cycloalkyl group, and an oxyalkyl group.

In formulas (lV), (Vl) and (Vlll), A ¹ is a single bond, -O-, -S-, -SS-, -SO2-, -CO-, -CONH-, -NHCO-,- C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _{m 2-} , -O- (CH ₂ ) _{m 2} -O-, -S- (CH ₂ ) _{m 2} -S-, M2 is an integer of 1-6 here.

In formulas (Vll) and (Vlll), A ² is a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , or carbon number 1 Alkylene of -3.

In formulas (ll) to (Vlll), hydrogen bonded to a cyclohexane ring or a benzene ring may be substituted with -F or -CH ₃ .

As diamine represented by a formula (ll), the diamine represented by formula (ll-1)-(ll-11) is mentioned, for example.

As diamine represented by a formula (lll), the diamine represented by formula (lll-1)-(lll-3) is mentioned, for example.

As diamine represented by Formula (lV), the diamine represented by Formula (lV-1)-(lV-4) is mentioned, for example.

As diamine represented by Formula (V), the diamine represented by Formula (V-1) (V-7)-is mentioned, for example.

As diamine represented by Formula (Vl), the diamine represented by Formula (Vl-1) (Vl-35) is mentioned, for example.

As diamine represented by a formula (Vll), the diamine represented by Formula (VII-1)-(VII-6) is mentioned, for example.

As diamine represented by a formula (Vlll), the diamine represented by formula (Vlll-1) (Vlll-12)-is mentioned, for example.

Among the above specific examples of the diamine (a2) represented by formulas (ll) to (Vlll), more preferably, formulas (V-1) to (V-5) and formulas (Vl-1) to (Vl-12) ), Formula (Vl-26), formula (Vl-27), formula (Vll-1), formula (Vll-2), formula (Vll-6), formulas (Vlll-1) to (Vlll-5) The diamine shown can be mentioned, More preferably, the diamine represented by Formula (V-6), Formula (V-7), and Formula (Vl-1)-(Vl-12) is mentioned.

Among these, 3,3'- diamino diphenyl sulfone, 4,4'- diamino diphenyl ether, 4,4'- diamino diphenylmethane, 3,3'- diamino diphenylmethane, 3,3 '-Dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylenediamine, p-xylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis [4- ( 4-aminobenzyl) phenyl] methane and the like can be preferably used.

In this invention, as diamine (a2) used for the synthesis | combination of an amic acid (a), the diamine represented by a formula (lX) is mentioned further.

Formula (lX) of, A3 is a single bond, -O-, -COO-, -OCO-, -CO- , -CONH- or - (CH _{2) m3} -, wherein, m3 is an integer from 1 to 6 to be.

In formula (lX), R ⁶ is a group having a steroid skeleton, a group having one or more selected from the group consisting of a cyclohexane ring and a benzene ring, or the positional relationship between two amino groups bonded to the benzene ring is para-positioned. Is alkyl having 1 to 30 carbon atoms or alkyl having 1 to 10 carbon atoms or phenyl when the positional relationship is meta, and in the alkyl, any CH ₂ -is CF _2- , -CHF-, -O-,- CH = CH-, or is optionally substituted by -C≡C-, and may have been substituted with -CH ₃ CH ₂ F, -CHF ₂ or -CF _3, hydrogen which is bonded to a ring forming carbon of the phenyl is , -F, -CH ₃ , -OCH ₃ , -CH ₂ F, -OCHF _2, or -OCF ₃ may be substituted.

In formula (lX), although two amino groups are couple | bonded with the phenyl ring carbon, Preferably, it is preferable that the bond position relationship of two amino groups is a meta position or a para position. Moreover, it is preferable that two amino groups are respectively couple | bonded in the 3rd position and 5th position, or 2nd position and the 5th position, when the coupling | positioning position of "R <^6> -A <^3->" is set to 1 position.

As a diamine represented by Formula (lX), the diamine represented by Formula (lX-1)-(lX-11) is mentioned, for example.

In formulas (lX-1), (lX-2), (lX-7) and (lX-8), R ¹⁸ is an organic group having 1 to 30 carbon atoms, but among these, alkyl having 3 to 12 carbon atoms or 3 to 3 carbon atoms. 12 alkoxy is preferable, and C5-C12 alkyl or C5-C12 alkoxy is more preferable. In addition, in said formula (lX-3)-(lX-6) and (lX-9)-(lX-11), R <^19> is a C1-C30 organic group, Among these, C1-C10 alkyl or Alkoxy having 1 to 10 carbon atoms is preferable, and alkyl having 3 to 10 carbon atoms or alkoxy having 3 to 10 carbon atoms is more preferable.

As diamine represented by a formula (lX), the diamine represented by the following formula (lX-12) (lX-17) is mentioned further, for example.

In Formulas (IX-12) to (IX-15), R ²⁰ is an organic group having 1 to 30 carbon atoms, alkyl having 4 to 16 carbon atoms is preferable, and alkyl having 6 to 16 carbon atoms is more preferable. In formula (IX-16) and formula (IX-17), R <^21> is a C1-C30 organic group, C6-C20 alkyl is preferable and C8-C20 alkyl is more preferable.

As a diamine represented by a formula (lX), the diamine represented by the following formula (lX-18) (lX-38) is mentioned further, for example.

Formula (lX-18), (lX-19), (lX-22), (lX-24), (lX-25), (lX-28), (lX-3O), (lX-31) , (lX-36) and (lX-37), R ²² is an organic group having 1 to 30 carbon atoms, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms is preferable, and alkyl having 3 to 12 carbon atoms. Or alkoxy having 3 to 12 carbon atoms is more preferable. Further, the formulas (lX-20), (lX-21), (lX-23), (lX-26), (lX-27), (lX-29), and (lX-32) to (lX-35). ) and (according to lX-38), R ²³ is a hydrogen atom _3, -F, having 1 to 12 carbon atoms in the alkyl group having 1 to 12 carbon atoms in the _{alkoxy, -CN, -OCH 2 F, -OCHF} 2 or -OCF, More preferable are C3-C12 alkyl or C3-C12 alkoxy. In said Formula (lX-33) and (lX-34), A <^9> is C1-C12 alkylene.

As a diamine represented by a formula (lX), the diamine represented by the following formula (lX-39)-(lX-48) is mentioned further, for example.

Among the diamines (a2) represented by the formula (lX), the diamines represented by the formulas (lX-1) to (lX-11) are preferable, and formulas (lX-2), (lX-4), and formula ( x-5) and the diamine represented by a formula (lX-6) are more preferable.

In this invention, the compound represented by following formula (Xl)-(Xll) is mentioned further as diamine (a2) used for the synthesis | combination of an amic acid (a).

In formulas (Xl) and (Xll), R ¹⁰ is hydrogen or —CH ₃ , R ¹¹ is each independently hydrogen or alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms, and A ⁶ is each independently As a single bond, -C (= O)-or -CH _2- .

In formula (Xll), R <^13> and R <^14> is respectively independently hydrogen, C1-C20 alkyl, or phenyl.

In the formula (Xl), one of the two "NH ₂ -Ph-A ⁶ -O-" (-Ph- represents phenylene) is bonded to the 3 position of the steroid nucleus, and the other is located at the 6 position It is preferable that they are combined. Moreover, it is preferable that two amino groups couple | bond with the phenyl ring carbon, respectively, and are couple | bonded with the meta position or the para position with respect to the bonding position of A <^6> .

As diamine represented by Formula (Xl), the diamine represented by Formula (Xl-1) (Xl-4)-is mentioned, for example.

In formula (Xll), two "NH _2- (R ^14- ) Ph-A ⁶ -O-" (-Ph- represents phenylene) are each bonded to a phenyl ring carbon, but preferably a steroid It is bonded to the carbon of meta position or para position with respect to the carbon which the nucleus is bonded. Moreover, although two amino groups are each couple | bonded with the phenyl ring carbon, it is preferable that they are couple | bonded with the meta position or para position with respect to A <^6> .

As a diamine represented by Formula (Xll), the diamine represented by Formula (Xll-1) (Xll-8)-is mentioned, for example.

In this invention, the compound represented by a formula (Xlll) and (XlV) is mentioned further as diamine (a2) used for the synthesis | combination of an amic acid (a).

In formula (XIII), R ¹⁵ is hydrogen or alkyl having 1 to 20 carbon atoms, and optionally -CH ₂ -of alkyl having 2 to 20 carbon atoms in the alkyl is -O-,-CH = CH- or -C≡. May be substituted with C-, A ⁷ is each independently -O- or alkylene having 1 to 6 carbon atoms, A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms, and ring T is 1,4-phenyl; Ylene or 1,4-cyclohexylene, and h is 0 or 1.

In formula (XlV), R <^16> is C2-C30 alkyl, Among these, C6-C20 alkyl is preferable. R <^17> is hydrogen or C1-C30 alkyl, Among these, C1-C10 alkyl is preferable. A ⁷ is each independently -O- or alkylene having 1 to 6 carbon atoms.

In said Formula (Xlll), although two amino groups are each couple | bonded with the phenyl ring carbon, it is preferable that they are couple | bonded with the meta position or para with respect to A <^7> .

As the diamine represented by the formula (XIII), for example, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl ] -4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] 4-methylcyclohexane, formula The diamine represented by (XIII-1)-(XIII-9) is mentioned.

Among these, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane, 1,1 -Bis [4- (4-aminobenzyl) phenyl] cyclohexane and 1,1-bis [4- (4-aminobenzyl) phenyl] -4-methylcyclohexane are preferred. In the formulas (XIII-1) to (XIII-3), R ²⁴ is preferably hydrogen or alkyl having 1 to 20 carbon atoms, and in formulas (XIII-4) to (XIII-9), R is ²⁵ is preferably hydrogen or alkyl having 1 to 10 carbon atoms.

In said Formula (XlV), although two amino groups are each couple | bonded with the phenyl ring carbon, it is preferable that they are couple | bonded with the meta position or para position with respect to A <^7> .

As a diamine represented by a formula (XlV), the diamine represented by (XlV-1) (XlV-3)-is mentioned, for example.

In formulas (XlV-1) to (XlV-3), R ²⁶ is alkyl having 2 to 30 carbon atoms, and among these, alkyl having 6 to 20 carbon atoms is preferable, R ²⁷ is hydrogen or alkyl having 1 to 30 carbon atoms, and these Among them, hydrogen or alkyl having 1 to 10 carbon atoms is preferable.

In this invention, the compound represented by Formula (XV-1)-(XV-16) is mentioned further as diamine (a2) used for the synthesis | combination of an amic acid (a).

N is an integer of 2-15 in a formula (XV-15). Specific examples of the product include elastomer P 1000n (n (average) = 13.62), elastomer 650P (n (average) = 8.76), and elastomer 250P (n (average) = 3.21) manufactured by Ihara Chemical Co., Ltd.).

In formula (XV-16), m and n are positive integers and molecular weights are 1200-1300. As a specific product, Porare SL-100A by Ihara Chemical Co., Ltd. can be mentioned.

As described above, in the present invention, the diamine (a2) used in the synthesis of the amic acid (a) may be, for example, diamines represented by formulas (l) to (XV-16). Diamines other than diamine can also be used. For example, a naphthalene-based diamine having a naphthalene structure, a fluorene-based diamine having a fluorene structure, a siloxane-based diamine having a siloxane bond, a triazine-based diamine containing a triazine skeleton, and the like can be used alone or in combination with other diamines. Can be used.

In this invention, the diamine (a2) used for the synthesis | combination of an amic acid (a) can preferably mention the fluorene-type diamine represented by following formula (4-2).

In the present invention, the diamine (a2) used for the synthesis of the amic acid (a) is further represented by the following formulas (4-3-1), (4-3-2) and (4-3-3). Triazine diamine is mentioned preferably.

Moreover, Preferably, in this invention, the diamine represented by following formula (21)-(28) is mentioned as diamine (a2) used for the synthesis | combination of an amic acid (a). In the formula, R ^{3 0} and R ^{3 1} are independently alkyl having ³ to 20 carbon atoms.

In addition, the diamine (a2) which can be used for synthesize | combining amic acid (a) is not limited to the diamine of this specification, A various form of diamine can be used within the range by which the objective of this invention is achieved. .

In addition, the diamine (a2) which can be used in order to synthesize | combine amic acid (a) may be used individually by 1 type, and may use 2 or more types together. That is, as a 2 or more types of combination, the said diamine, the diamine and other diamine, or diamines other than the said diamine can be used.

Moreover, although high transparency is required according to the use of inkjet ink, in that case, using 3,3'- diamino diphenyl sulfone and the diamine which is an integer of y = 1-15 in Formula (4-1) is used. Particularly preferred.

2.1.3 Compound having one acid anhydride group ( a3 )

In this invention, if the compound (a3) which has one acid anhydride group used for the synthesis | combination of an amic acid (a) is a compound represented by following formula (1-1), it will not specifically limit.

In formula (1-1), R <^1> is a C2-C500 organic group, Preferably it is a C2-C300 organic group, More preferably, it is a C2-C50 organic group, More preferably, It is a C2-C30 organic group, Especially preferably, it is a C2-C20 organic group.

Specific examples of the compound (a3) having one acid anhydride group include maleic anhydride, citraconic anhydride, allylnadic acid anhydride, allyl succinic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydro Phthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, cyclohexene-1,2-dicarboxylic anhydride, cis-1,2-cyclo Hexanedicarboxylic anhydride, 1,3-cyclohexanedicarboxylic anhydride, itaconic anhydride, p- (trimethoxysilyl) phenylsuccinic anhydride, p- (triethoxysilyl) phenylsuccinic anhydride, m- (trimethoxysilyl ) Phenyl succinic anhydride, m- (triethoxysilyl) phenyl succinic anhydride, trimethoxysilyl propyl succinic anhydride, 2- [3- (triethoxy silyl) propyl] succinic anhydride, the compound represented by following formula ((alpha)) And the compound represented by following formula ((beta)) are preferable. The compound represented by the following formula (α) can be obtained by, for example, reacting 5-norbornene-2,3-dicarboxylic anhydride with trimethoxysilane.

Moreover, the compound represented by following formula ((beta)) can be obtained by making allylnadic acid anhydride and trimethoxysilane react, for example.

When the compound (a3) which has such an acid anhydride group is used, there exists a tendency for the inkjet discharge property of ink to improve.

Among the above specific examples, as the compound (a3) having one acid anhydride group, maleic anhydride, citraconic anhydride, allylnadic acid anhydride, trimethoxysilylpropylsuccinic anhydride and 2- [3- (triethoxysilyl) propyl ] When succinic anhydride is used, there exists a tendency for the durability of the polyimide membrane finally formed to become excellent.

The compound (a3) which has one such acid anhydride group may be used individually by 1 type, and may use 2 or more types together.

In formulas (α) and (β), TO is CH ₃ O (methoxy) or C ₂ H ₅ O (ethoxy).

2.1.4 Monoamines ( a4 )

In this invention, although monoamine (a4) used for the synthesis | combination of an amic acid (a) is not specifically limited unless the objective of this invention is impaired, As a specific example, 3-aminopropyl trimethoxysilane, 3- Aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxy Silane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, m-amino Phenylmethyldiethoxysilane, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-furfurylamine, tyramine, 2- (4-aminophenyl) ethylamine, trans-4-aminocyclohexanol, mono Ethanolamine, 2-aminoethanol, 3-amino-1-propanol, 1-amino-2- Ropanol, 2- (2-aminoethoxy) ethanol, 5-amino-1-pentanol, n-butylamine, aniline, 3-ethynylaniline, 4-ethynylaniline, pentafluoroaniline, tryptophan, lysine , Methionine, phenylalanine, threonine, valine, isoleucine, leucine, histidine, alanine, arginine, asparagine, serine, asparagine acid, cysteine, glutamine, glutamic acid, glycine, proline, tyrosine, 12-aminolauryl acid, O-force Poly ethanolamine, 2-aminoethyl hydrogen sulfide, 2-aminoethanesulfonic acid, etc. are mentioned.

When such a monoamine (a4) is used, there exists a tendency for the ejectability of the inkjet of ink to improve.

Among these, when 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and p-aminophenyltrimethoxysilane are used as monoamine (a4), the durability of the polyimide film finally formed will become excellent. There is a tendency. Particular preference is given to using 3-aminopropyltriethoxysilane.

Such monoamine (a4) may be used individually by 1 type, and may use 2 or more types together.

2.1.5 Amic acid (a)  Reaction Conditions for Synthesis

The amic acid (a) is reacted by appropriately combining a compound (a1) having two or more acid anhydride groups and a compound (a3) having one acid anhydride group with a diamine (a2) and a monoamine (a4), for example. Can be synthesized.

It is preferable that the reaction temperature of the said reaction is 0-100 degreeC, It is more preferable that it is 0-80 degreeC, It is especially preferable that it is 0-50 degreeC.

It is preferable that the reaction pressure of the said reaction is 90-120 kPa, It is more preferable that it is 95-110 kPa, It is especially preferable that it is 97-105 kPa.

It is preferable that the reaction time of the said reaction is 0.2 to 20 hours, It is more preferable that it is 0.5 to 15 hours, It is especially preferable that it is 1 to 12 hours.

The proportion of each raw material is n1 for the number of moles of the compound (a1) having two or more acid anhydride groups, n2 for the number of moles of the diamine (a2), n3 for the number of moles of the compound (a3) having one acid anhydride group, and monoamine (a4). N1 + (1/2) x n3 = n2 + (1/2) x n4 is preferable. In addition, the compound, diamine, amine, and acid anhydride which have two or more acid anhydrides which do not contribute to reaction may exist. In addition, when the obtained amic acid (Ba) is an oligomer or a polymer, the terminal of the amic acid (a) may be an amino group terminal or an acid anhydride terminal.

2.1.6 Reaction Solvent

The reaction solvent used for synthesizing the amic acid (a) is not particularly limited as long as the amic acid (a) can be synthesized. As said reaction solvent, For example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxolane, propylene glycol dimethyl ether, propylene Glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl Ether, diethylene glycol die Ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene Glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy-2- Propanol), methyl benzoate, ethyl benzoate, 1-vinylpyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrroli Don, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε -Caprolactam, 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone.

Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methylethyl ether, and diethylene glycol dimethyl ether are more preferable.

These reaction solvents may be used individually by 1 type, and may use 2 or more types together. In addition, other solvents may be used in addition to the reaction solvent.

100 weight part or more of reaction solvent is used with respect to a total of 100 weight part of a compound (a1) which has two or more acid anhydride groups, a diamine (a2), the compound (a3) which has one acid anhydride group, and a monoamine (a4). This is preferable because the reaction proceeds smoothly.

2.1.7 To the reaction system  Order of addition

The order of addition of the reaction raw materials to the reaction system is not particularly limited. That is, the compound (a1) which has 2 or more acid anhydride groups, the diamine (a2), the compound (a3) which has one acid anhydride group, and a monoamine (a4) are simultaneously added to a reaction solvent, a diamine (a2) and an acid anhydride After dissolving compound (a3) having one group in a reaction solvent, a method of adding compound (a1) and monoamine (a4) having two or more acid anhydride groups, compound (a1) having two or more acid anhydride groups, and After dissolving monoamine (a4) in a reaction solvent and previously reacting the compound (a3) which has one acid anhydride group, the method of adding diamine (a2), the compound (a1) which has two or more acid anhydride groups, and After reacting a diamine (a2) previously and synthesize | combining a polymer, the method of adding the compound (a3) and monoamine (a4) which have one acid anhydride group, etc. can be used.

Amic acid (a) has a molecular terminal group according to the molar ratio of the compound (a1) which has 2 or more acid anhydride groups, the diamine (a2), the compound (a3) which has one acid anhydride group, and a monoamine (a4). In some cases, amic acid (a) to be mixed with amic acid (a) that is not retained may be mixed.

In addition, the synthesis | combining method of amic acid (a) is not limited to the said method.

2.1.8 Of amic acid (a)  Weight average molecular weight

In the present invention, when the amic acid (a) is an oligomer or a polymer, the weight average molecular weight of the amic acid (a) is preferably 900 to 7,500. If the weight average molecular weight of the amic acid (a) is 900 or more, the amic acid (a) is chemically and mechanically stable in the step of forming a polyimide film by heat treatment. When the weight average molecular weight of the amic acid (a) is 7,500 or less, the solubility of the amic acid (a) in the solvent (C) described later can be improved and the viscosity can be lowered, so that the thickness of the resulting film can be increased. In addition, in amic acid (a), in order to further improve the solubility to the solvent (C) mentioned later and to make it low viscosity, it is preferable that the weight average molecular weight of amic acid (a) is 900-3,500, and 900- It is more preferable that it is 2,500.

In the present invention, the weight average molecular weight of the amic acid (a) can be measured by gel permeation chromatography (GPC) method. For example, specifically, the obtained amic acid (a) is diluted with dimethylformamide (DMF) so that the concentration of the amic acid (a) is about 1% by weight, and Shodex Asahipak GF-510 HQ and Shodex Asahipak as columns. It can obtain | require by measuring by poly permeation chromatography (GPC) method using GF-310 HQ using DMF as a developing agent, and polystyrene conversion.

2.1.9 Of amic acid (a)  content

It is preferable to make content of the said amic acid (a) into 20 to 80 weight% with respect to the inkjet ink total weight, It is more preferable to set it as 25 to 70 weight%, It is more preferable to set it as 25 to 60 weight% desirable. When content of the said amic acid (a) exists in the said range, there exists a tendency for the ejectability of the inkjet of ink to improve.

2.2 imide ( a ' )

The imide (a ') can be synthesized by, for example, dehydrating and ring closing the amic acid (a). Imide (a ') which has a molecular terminal group according to the molar ratio of the compound (a1) which has 2 or more acid anhydride groups, the diamine (a2), the compound (a3) which has one acid anhydride group, and a monoamine (a4) And imide (a ') which does not have a molecular terminal group may be mixed. In addition, the manufacturing method of imide (a ') is not limited to the said method.

In the synthesis of the amic acid (a) for obtaining the imide (a '), a compound (a1) having two or more acid anhydride groups, a compound (a3) having one acid anhydride group, a diamine (a2) and a monoamine ( The order of addition to the reaction raw material, reaction conditions, reaction solvent and reaction system of a4) is the same as in the case of the amic acid (a) described above.

Imide (a ') can be synthesize | combined by dehydrating and ring-closing the amic acid (a) mentioned above.

The method of dehydration and ring closure may be a method by heating or a chemical method. For example, the amic acid (a) may be heated to 100 to 200 ° C in a solvent to dehydrate and close the ring. Further, pyridine and acetic anhydride may be added to the amic acid (a), for example, to dehydrate and close the ring. A more preferable method of dehydration and ring closure is to heat the amic acid (a) so that impurities are not contained. It is preferable that the temperature in the said heating is 140-180 degreeC.

When the imide (a ') obtained in this way is used, the ink finally obtained tends to become low viscosity from high concentration. As said imide, the compound represented by said Formula (4)-(6), an imide compound (a'-1), an alkenyl substituted naziimide (a'-2), etc. are mentioned.

2.2.1 Of imide (a ')  Weight average molecular weight

In the present invention, when the imide (a ') is an oligomer or a polymer, the weight average molecular weight of the imide (a') is preferably 900 to 7,500. If the weight average molecular weight of imide (a ') is 900 or more, in the process of forming a polyimide film by heat processing, imide (a') is chemically and mechanically stable without evaporating. If the weight average molecular weight of imide (a ') is 7,500 or less, since it is possible to improve the solubility of imide (a') with respect to the solvent (C) mentioned later, and to make it low viscosity, it is possible to enlarge the thickness of the film | membrane obtained. Become. In addition, in the imide (a '), in order to further improve the solubility in the solvent (C) described later and lower the viscosity, the weight average molecular weight of the imide (a') is preferably 900 to 3,500, and 900 It is more preferable that it is -2,500.

In this invention, the weight average molecular weight of imide (a ') can be measured by a gel permeation chromatography (GPC) method. For example, specifically, the obtained imide (a ') is diluted with dimethylformamide (DMF) so that the concentration of the imide (a') is about 1% by weight, and Shodex Asahipak GF-510 HQ and Shodex as columns. It can be calculated | required by using Asahipak GF-31O HQ, measuring by gel permeation chromatography (GPC) method using DMF as a developing agent, and polystyrene conversion.

2.2.2 Of imide (a ')  content

It is preferable to make content of the said imide (a ') into 20 to 80 weight% with respect to the total weight of the inkjet ink, It is more preferable to set it as 25 to 70 weight%, It is set as 25 to 60 weight% It is more preferable. When content of the said imide (a ') exists in the said range, there exists a tendency for the ejectability of the inkjet of ink to improve.

2.3 Other Imide

As other imides other than the compound represented by said Formula (4)-(6), the imide compound (a'-1) mentioned later, maleimide, etc. are mentioned, for example. Alkenyl-substituted naziimides (a'-2) can also be used. It is preferable to use the imide compound (a'-1) and alkenyl substituted naziimide (a'-2) which are excellent in solubility in a solvent (C).

Hereinafter, an imide compound (a'-1) and an alkenyl substituted naziimide (a'-2) are demonstrated.

2.3.1 Imide  compound( a ' -One)

The imide compound (a'-1) is at least one of the monomers of the imide (a ') obtained by using the compound (a3) having at least one monoamine (a4) and an acid anhydride group.

Although the imide compound (a'-1) contained in the inkjet ink of this invention can be obtained using the process of reacting at least a monoamine (a4) and the compound (a3) which has one acid anhydride group, the said method It is not limited to the imide compound obtained by these.

As an imide compound (a'-1), the compound represented by a following formula ((gamma)) is mentioned. R ^a in formula (γ) is a reaction residue of compound (a3) having one acid anhydride group, and R ^b is a reaction residue of monoamine (a4). Reaction residue means group other than the site which comprises the imide bond contained in Formula ((gamma)) in the compound (a3) which has one monoamine (a4) or an acid anhydride group.

R ^a and R ^b in the formula (γ) are not particularly limited as long as they are each independently an organic group having 1 to 100 carbon atoms, but are preferably an organic group having 2 to 70 carbon atoms, and more preferably 4 to 50 carbon atoms. It is an organic group.

The compound (a3) which has one monoamine (a4) and one acid anhydride group which can be used for obtaining an imide compound (a'-1) is as having mentioned above.

2.3.1.1 Imide  compound( a ' Reaction conditions for synthesizing -1)

An imide compound (a'-1) can be obtained by the manufacturing method including the process of making at least the compound (a3) which has a monoamine (a4) and one acid anhydride group react.

2.3.1.2 Dose of Reaction Raw Material

As for the input amount of the compound (a3) which has one monoamine (a4) and an acid anhydride group, it is preferable to use 0.5-2.0 mol of compound (a3) which has one acid anhydride group with respect to 1 mol of monoamine (a4). It is more preferable to use 0.7-1.5 mol, and it is still more preferable to use 1.0-12 mol.

2.3.1.3 Reaction Solvent

The reaction solvent used for synthesizing the imide compound (a'-1) is not particularly limited as long as the imide compound can be synthesized. For example, diethylene glycol dimethyl ether and diethylene glycol diethyl ether can be used. , Diethylene glycol methylethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, γ- Butyrolactone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, Methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, or diphenyldiethoxysilane can be mentioned.

Among these reaction solvents, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, cyclohexanone, butyrolactone, tetraethoxysilane, tetrapropoxysilane or tetrabu When oxysilane is used, even if the said solvent is used as an inkjet solvent as it is after reaction, since it can be set as ink with little damage to an inkjet head, it is preferable.

These reaction solvents can be used alone or as a mixed solvent of two or more kinds. In addition, other solvents may be used in addition to the reaction solvent.

The reaction solvent is preferably 100 parts by weight or more based on 100 parts by weight of the total of the monoamine (a4) and the compound (a3) having one acid anhydride group, so that the reaction proceeds smoothly. It is preferable that reaction temperature is 0 degreeC-200 degreeC, and it is preferable that reaction time is 0.2 to 20 hours.

2.3.1.4 To the reaction system  Order of addition

The order of addition of the reaction raw materials to the reaction system is not particularly limited. That is, the method of simultaneously adding the compound (a3) which has a monoamine (a4) and one acid anhydride group to a reaction solvent, and after dissolving a monoamine (a4) in a reaction solvent, the compound (a3) which has one acid anhydride group is added. Any method, such as the method of making it, the method of adding a monoamine (a4) after dissolving the compound (a3) which has one acid anhydride group in a reaction solvent, can be used.

2.3.1.5 Imidization

The imide compound (a'-1) can be obtained by reacting a monoamine (a4) with a compound (a3) having one acid anhydride group in a reaction solvent to obtain an amic acid compound and imidating the amic acid compound. .

As a method of imidating an amic acid compound, the chemical method using a dehydration catalyst and a dehydrating agent, or the method of imidating by a thermal method is mentioned, but it imidates by the thermal method which can be used as a component of an ink, without performing a purification process. The method of doing is preferable. Moreover, the method of refluxing and imidating is preferable. Although the conditions of the said reflux vary with reaction solvent to be used, it is preferable that reflux temperature is 140-230 degreeC, and it is preferable that reflux time is 1.5-10 hours. If reflux temperature is 140 degreeC or more, imidation fully advances and a firm film | membrane can be finally obtained. If reflux temperature is 230 degrees C or less, even if it uses a comparatively high boiling point solvent, it can reflux.

 In particular, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimeth as monoamine (a4) Methoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p- When using a silane compound having an amino group and an alkoxy group, such as aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane or m-aminophenylmethyldiethoxysilane, the water produced by imidization in the course of reflux is It is preferable because it is consumed for hydrolysis of part of the alkoxysilane and imidization and hydrolysis proceed simultaneously.

2.3.1.6 Imide  compound( a ' -1) content

The content of the imide compound (a'-1) is preferably 5 to 95% by weight, more preferably 25 to 70% by weight, more preferably 30 to 50% by weight, based on the total weight of the inkjet ink. More preferably. When content of an imide compound (a'-1) is 5 weight% or more, when inkjet apply | coating using a non-aqueous inkjet ink, the film formed from an imide compound will not become too thin by one jetting. Moreover, when content of an imide compound (a'-1) is 95 weight% or less, the viscosity of a non-aqueous inkjet ink will not become large too much, and there exists a tendency for the jetting characteristic at the time of inkjet coating to become favorable.

2.3.2 Alkenyl  substitution Naziimide ( a ' -2)

Alkenyl substituted naziimide (a'-2) is an imide (a ') which has at least 1 alkenyl substituted naziimide structure in a molecule | numerator, Preferably it is alkenyl substituted represented by following formula (F-1) Although a naziimide compound is mentioned, It is not limited to this. Moreover, the hardening | curing agent mentioned later can be used as needed.

It is preferable that alkenyl substituted naziimide (a'-2) is a low molecular weight imide monomer which has a bulky structure. Such alkenyl-substituted naziimides (a'-2) are soluble in most organic solvents and can be used stably without precipitation or gelation of crystals even when stored for a long time in a solution state. Moreover, alkenyl substituted naziimide (a'-2) forms the polyimide of a three-dimensional crosslinked structure by heating, and the said polyimide hardened | cured material tends to show favorable heat resistance, mechanical property, electrical property, and chemical resistance. .

In formula (F-1), R <^1> and R <^2> respectively independently represents a hydrogen atom, C1-C12 alkyl, C3-C6 alkenyl, C5-C8 cycloalkyl, and C6-C12 aryl Or benzyl and n is an integer of 1 to 4;

In formula (F-1), when n = 1, R <^3> is a hydrogen atom, C1-C12 alkyl, C1-C12 hydroxyalkyl, C5-C8 cycloalkyl, C6-C12 Aryl, benzyl,-{(C _q H _2q ) O _t (C _r H _2r O) _u C _s H _2s X} (where q, r and s are each independently an integer of 2 to 6, and t is Polyoxyalkylenealkyl represented by an integer of 0 or 1, u is an integer of 1 to 30, X is a hydrogen atom or a hydroxyl group,-(R) _a -C ₆ H ₄ -R ⁴ , wherein a Is O or an integer of 1, R is an alkylene of 1 to 4 carbon atoms, R ⁴ is a hydrogen atom or an alkyl of 1 to 4 carbon atoms, -C ₆ H ₄ -TC ₆ H ₅ , wherein , T is -CH _2- , -C (CH ₃ ) _2- , -CO-, -S-, or -SO _2- ), or 1 to 3 groups directly connected to the aromatic ring of these groups A hydrogen atom is a group substituted with a hydroxyl group.

In formula (F-1), when n = 2, R ³ is alkylene having 2 to 20 carbon atoms (any methylene not adjacent to each other in alkylene is substituted with —O— or —CH═CH— Optionally, an arbitrary hydrogen atom may be substituted with a fluorine atom), cycloalkylene having 5 to 8 carbon atoms, allylene having 6 to 12 carbon atoms, and-(R) _a -C ₆ H ₄ -R ^5- (wherein a is an integer of 0 or 1, and R and R ⁵ are each independently an alkylene having 1 to 4 carbon atoms, -C ₆ H ₄ -TC ₆ H _4- , -C ₆ H ₄ -TC ₆ H ₄ -TC ₆ H ₄ - or _{-C 6 H 4 -T'-C 6} H 4 -TC 6 H 4 -T'-C 6 H 4 - ( However, T is a single bond, a group having 1 to 6 carbon atoms Alkylene, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -CO-, -O-, -S- or -SO _2- , and T 'is -CH ₂ -or -O- Or 1 to 3 hydrogen atoms directly connected to the aromatic ring of these groups, or a group represented by the formula (F-8).

In addition, in formula (F-1), when n = 3, R <_3> is group represented by following formula (F-5) or (F-5 ') normally.

In formula (F-5), R is a hydrogen atom, a fluorine atom, a chlorine atom, -OH, -OCF ₃ , -OCF ₂ H, -CF ₃ , -CF ₂ H, -CFH ₂ , -OCF ₂ CF ₂ H, -OCF ₂ CFHCF ₃ , or alkyl having 1 to 10 carbon atoms, R ⁴ , R ⁵ and R ⁶ each independently represent a single bond, in the formula (F-5) and the formula (F-5 '). Trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom, or 1 to 10 carbon atoms Arbitrary methylene which is not adjacent to each other in alkylene may be substituted by -O- or -CH = CH-, and arbitrary hydrogen atoms may be substituted by the fluorine atom.

In addition, in formula (F-1), when n = 4, R <^3> is group represented by a following formula (F-6) normally.

In formula (F-6), R <^4> , R <^5> , R <^6> , R <^7> is respectively independently a single bond, trans-1, 4- cyclohexylene, and 1, 3- dioxane-2, 5- diyl , 1,4-phenylene, 1,4-phenylene in which the hydrogen atom may be substituted with a fluorine atom, or alkylene having 1 to 10 carbon atoms, and any methylene not adjacent to each other in the alkylene is -O- or -CH It may be substituted by = CH- and the arbitrary hydrogen atom may be substituted by the fluorine atom.

In the formula (F-1), when n = 3, R ³ is represented by the following formula (F-5-1), formula (F-5'-1) or formula (F-5'-2). It may be a group.

In formula (F-5-1), R is C1-C10 alkyl or -OH, and in formula (F-5'-2), R <^4> , R <^5> and R <^6> are respectively independently 1, 2-ethylene, 1,4-butylene.

In addition, in formula (F-1), when n = 4, R <^3> is good also as group represented by following formula (F-6-1).

The alkenyl substituted naziimide (a'-2) includes an alkenyl substituted naziimide compound in which n is 1 (hereinafter, only referred to as "alkenyl substituted naziimide (a'-2-1)"), and Alkenyl substituted naziimide compounds in which n is 2 (hereinafter sometimes referred to as only "bisalkenyl substituted naziimides (a'-2-2)"), and alkenyl substituted naziimides compounds in which n is 3 (hereinafter , Sometimes only referred to as "trisalkenyl substituted naziimide (a'-2-3)", and an alkenyl substituted naziimide compound in which n is 4 (hereinafter, only "tetrakisalkenyl substituted naziimide (a May be referred to as "-2-4)".

The ink for nonaqueous inkjet of this invention is an alkenyl substituted naziimide (a'-2-1), a bisalkenyl substituted naziimide (a'-2-2), and a trisalkenyl substituted naziimide (a'-2) It may contain at least 2 types of alkenyl substituted naziimides (a'-2) selected from -3) and tetrakis alkenyl substituted naziimides (a'-2-4).

On the other hand, the alkenyl substituted naziimide (a'-2) is an alkenyl obtained by reacting a monoamine, diamine, triamine or tetraamine with an alkenyl substituted nadic acid anhydride represented by the following formula (F-1 '). A substituted naziimide compound may be sufficient.

In formula (F-1 '), R <^1> and R <^2> is respectively independently a hydrogen atom, C1-C12 alkyl, C3-C6 alkenyl, C5-C8 cycloalkyl, C6-C12 Aryl or benzyl.

In formula (F-1), R ¹ and R ² are each independently a hydrogen atom or alkyl having 1 to 6 carbon atoms, R ³ is alkyl having 1 to 12 carbon atoms (n = 1) and having 6 to 12 carbon atoms. Aryl (n = 1),-(CH ₂ ) _p- (n = 2, p is an integer of 6 to 12), a group represented by the formula (F-2-1), represented by the formula (F-3) Group, group represented by formula (F-4-1), group represented by formula (F-7-1), group represented by formula (F-8), represented by formula (F-5-2) Group, group represented by formula (F-5-3), group represented by formula (F-5'-1), group represented by formula (F-5'-3), formula (F-6-1 Alkenyl substituted naziimide (a'-2) which is group represented by The ink for non-aqueous inkjet of this invention may contain at least 2 sorts of such alkenyl substituted naziimides (a'-2).

2.3.2.1 Alkenyl Substituted Naziimides (a'-2-1)

As a specific example of the alkenyl substituted naziimide compound (a'-2-1) used by this invention, the following are mentioned, for example.

Allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

Metalylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

Metalylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-hydroxyallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-hydroxyallylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-hydroxymetallbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-hydroxymetallmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methylallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methylallylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methylmetallbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methylmetallmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2-ethylhexyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

And these oligomers etc. are mentioned.

Also,

N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-cyclohexyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-cyclohexyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-cyclohexyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-phenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

And these oligomers etc. are mentioned.

Also,

N-phenyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-benzyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-benzyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-benzyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2'-hydroxyethyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2'-hydroxyethyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2'-hydroxyethyl) -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

And these oligomers etc. are mentioned.

Also,

N- (2 ', 2'-dimethyl-3'-hydroxypropyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2 ', 2'-dimethyl-3'-hydroxypropyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2 ', 3'-dihydroxypropyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2 ', 3'-dihydroxypropyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (3'-hydroxy-1'-propenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4'-hydroxy-cyclohexyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

And these oligomers etc. are mentioned.

Also,

N- (4'-hydroxyphenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4'-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4'-hydroxyphenyl) -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4'-hydroxyphenyl) -metallylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (3'-hydroxyphenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (3'-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (p-hydroxy benzyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {2 '-(2'-hydroxyethoxy) ethyl} -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

And these oligomers etc. are mentioned.

Also,

N- {2 '-(2'-hydroxyethoxy) ethyl} -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {2 '-(2'-hydroxyethoxy) ethyl} -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {2 '-(2'-hydroxyethoxy) ethyl} -metallmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- [2 '-{2'-(2 "-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- [2 '-{2'-(2 "-hydroxyethoxy) ethoxy} ethyl] -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- [2 '-{2'-(2 "-hydroxyethoxy) ethoxy} ethyl] -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {4 '-(4'-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {4 '-(4'-hydroxyphenylisopropylidene) phenyl} -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {4 '-(4'-hydroxyphenylisopropylidene) phenyl} -metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

And these oligomers etc. are mentioned.

In addition, these alkenyl substituted naziimides (a'-2-1) may be used independently and may be used together 2 or more types.

 As said alkenyl substituted naziimide (a'-2-1), what is preferable is

N-methyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methyl-metallmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2-ethylhexyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, etc. are mentioned.

Also,

N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-cyclohexyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-cyclohexyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-cyclohexyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-phenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, etc. are mentioned.

Also,

N-phenyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-benzyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-benzyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-benzyl-metall bicyclo [2.2.1] hepto-5-ene-2, 3- dicarboxyimide, etc. are mentioned.

Further preferred as alkenyl substituted naziimide (a'-2-1) is

N-methyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-methyl-metallmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2-ethylhexyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, etc. are mentioned.

Also,

N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-allyl-metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N-isopropenyl-metall bicyclo [2.2.1] hepto-5-ene-2,3- dicarboxyimide, etc. are mentioned.

2.3.2.2 Bisalkenyl  substitution Naziimide ( a ' -2-2)

As a specific example of bisalkenyl substituted naziimide (a'-2-2) used by this invention, the following are mentioned, for example.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

And these oligomers etc. are mentioned.

Also,

1,2-bis {3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethane,

1,2-bis {3 '-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethane,

1,2-bis {3 '-(metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethane,

Bis [2 '-{3'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethyl] ether,

Bis [2 '-{3'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethyl] ether,

1,4-bis {3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} butane,

1,4-bis {3 '-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} butane,

And these oligomers etc. are mentioned.

Also,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N '-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

And these oligomers etc. are mentioned.

Also,

2,2-bis [4 '-{4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

And these oligomers etc. are mentioned.

Also,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metallylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone,

And these oligomers etc. are mentioned.

Also,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone,

1,6-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -3-hydroxy-hexane,

1,12-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -3,6-dihydroxydecane,

1,3-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -5-hydroxycyclohexane,

1,5-bis {3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} -3-hydroxy-pentane,

1,4-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-benzene,

And these oligomers etc. are mentioned.

Also,

1,4-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2,5-dihydroxybenzene,

N, N'-p- (2-hydroxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p- (2-hydroxy) xylene-bis (allylmethylcyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m- (2-hydroxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m- (2-hydroxy) xylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p- (2,3-dihydroxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

And these oligomers etc. are mentioned.

Also,

2,2-bis [4 '-{4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2'-hydroxy-phenoxy} phenyl] propane,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-phenyl} methane,

Bis {3- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -4-hydroxy-phenyl} ether,

Bis {3- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -5-hydroxy-phenyl} sulphone,

1,1,1-tri {4 '-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)} phenoxymethylpropane,

N, N ', N "-tri (ethylenemetallylcyclocyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) isocyanurate,

And these oligomers etc. are mentioned.

In addition, bisalkenyl substituted naziimide (a'-2-2) may be the following containing asymmetric alkylene phenylene group.

In addition, these bisalkenyl substituted naziimides (a'-2-2) may be used independently and may use 2 or more types together.

As said bisalkenyl substituted naziimide (a'-2-2), what is preferable is

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), etc. are mentioned.

Also,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N '-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4 '-{4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane and the like.

Also,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metallylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone and the like.

Also,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone and the like.

As bisalkenyl substituted naziimide (a'-2-2), what is preferable is

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-ethylene-bis (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), etc. are mentioned.

Also,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N '-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-m-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) etc. are mentioned.

Also,

2,2-bis [4 '-{4'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

2,2-bis [4 '-{4'-(metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane,

Bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane and the like.

Also,

Bis {4- (metallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metallylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane and the like.

2.3.2.3 Tris alkenyl  substitution Naziimide ( a ' -2-3)

Examples of the synthesis of the trisalkenyl substituted naziimide (a'-2-3) used in the present invention include the following methods. First, 3.0-5.0 mol of alkenyl substituted nadic acid anhydrides are mixed with respect to 1.0 mol of triamines. Next, at room temperature (25 ° C.), for example, benzene, toluene, xylene, mesitylene, methylnaphthalene, tetralin, chloroform, trilene, tetrachloroethylene, chlorobenzene, dioxane, tetrahydrofuran, hexa The mixture is dissolved in an arbitrary solvent such as methylene ether, anisole, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, N, N-dimethylformamide, dimethyl sulfoxide or a mixture of two or more thereof. To obtain a solution. The solution is allowed to react with stirring for 0.5-30 hours. After the reaction, the solvent is dried under reduced pressure at 20 to 80 ° C. to obtain amic acid. The amic acid is refluxed in the solvent at a temperature of 0.5 to 30 hours in the vicinity of the boiling point of the solvent to dehydrate and close the ring. Thereafter, the solvent is dried under a reduced pressure to obtain a target trisalkenyl substituted naziimide (a'-2-3). Alternatively, the target trisalkenyl-substituted naziimide (a'-2-3) can be obtained by heating the amic acid itself at 160 to 200 ° C and dehydrating the ring. The target trisalkenyl substituted naziimide (a'-2-3) can be confirmed by NMR and IR.

The following are mentioned as a specific example of the tris alkenyl substituted naziimide (a'-2-3) used by this invention.

Tris {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) triethyl} amine,

Tris {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) triphenyl} methane,

Tris {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} hydroxymethane.

2.3.2.4 Tetrakis Alkenyl  substitution Naziimide ( a ' -2-4)

Examples of the synthesis of the tetrakis alkenyl substituted nazimidide (a'-2-4) used in the present invention include the following methods. First, 4.0-6.0 mol of alkenyl substituted nadic acid anhydrides are mixed with respect to 1.0 mol of tetraamines. Next, at room temperature (25 ° C.), for example, benzene, toluene, xylene, mesitylene, methylnaphthalene, tetralin, chloroform, trilene, tetrachloroethylene, chlorobenzene, dioxane, tetrahydrofuran, hexa The mixture is dissolved in an arbitrary solvent such as methylene ether, anisole, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, N, N-dimethylformamide, dimethyl sulfoxide or a mixture of two or more thereof. To obtain a solution. The solution is allowed to react with stirring for 0.5-30 hours. After the reaction, the solvent is dried under reduced pressure at 20 to 80 ° C. to obtain amic acid. The amic acid is refluxed in the solvent at a temperature of 0.5 to 30 hours in the vicinity of the boiling point of the solvent to dehydrate and close the ring. Thereafter, the solvent is dried under a reduced pressure to obtain the desired tetrakis alkenyl substituted naziimide (a'-2-4). Alternatively, the desired tetrakis alkenyl-substituted naziimide (a'-2-4) can be obtained by heating the amic acid itself to 160 to 200 ° C and dehydrating and closing the ring. It can be confirmed by NMR and IR that it is a tetrakis alkenyl substituted naziimide (a'-2-4) made into the objective.

The following are mentioned as a specific example of the tetrakis alkenyl substituted naziimide (a'-2-4) used by this invention.

Tetrakis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) tetraphenyl} methane.

The amic acid (a), imide (a '), and alkenyl substituted naziimide (a'-2) mentioned above may be used individually by 1 type, and may use 2 or more types together.

2.3.2.5 Hardener

The ink for non-aqueous inkjet of this invention can contain the azobis type compound and the compound which generate | occur | produces an acid as a hardening | curing agent of the above-mentioned alkenyl substituted naziimide (a'-2). These hardeners may be used individually by 1 type, and may use 2 or more types.

2.3.2.5.1 Azobis  compound

Although it does not specifically limit as an azobis type compound which is a hardening | curing agent, For example, 2,2'- azobis (4-methoxy-2, 4- dimethylvaleronitrile), 2,2'- azobis ( 2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azo Bis (cyclohexane-1-carbonitrile), 2,2'-azobis (N- (2-propenyl) -2-methylpropionamide, 2,2'-azobis (N-butyl-2-methylpropion) Amide), α, α'-azobisisobutyronitrile, and the like, and 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2-methylbuty). Ronitrile), and 1,1'- azobis (cyclohexane-1-carbonitrile) are preferable, and these azobis type compounds may be used individually by 1 type, and may use 2 or more types.

When the said azobis type compound is contained as a hardening | curing agent with an alkenyl substituted naziimide (a'-2), since it is not adhesiveness at the time of film drying mentioned later, and it is excellent in handleability, it is preferable.

3 solvent (C)

The ink for nonaqueous inkjet of this invention may contain the solvent (C).

The nonaqueous inkjet ink of the present invention can be obtained by mixing components such as the compound (A) and the surfactant (B) with a solvent (C), for example. Therefore, the solvent contained in the inkjet ink of the present invention is not particularly limited as long as it is a solvent that can dissolve components such as the compound (A) and the surfactant (B).

As a specific example of the solvent (C) contained in the ink for non-aqueous inkjet of this invention, ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl Ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1, 3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, diethylene Glycol dimethyl ether, dipropylene glycol dimethyl ether, di Ethylene glycol methyl isopropyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol methylbutyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol Monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy -2-propanol), propylene glycol monomethyl ether (1-methoxy-2-propanol), triglyme, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrroli Don, 1-ethyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, 1-acetyl-2-methyl-ε-cap Rolactam and γ-butyrolactone.

The solvent (C) is ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol methyl isopropyl ether, diethylene Glycol methylbutyl ether, diethylene glycol dibutyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxypropionate methyl, 3-e Selected from the group consisting of ethyl oxypropionate, cyclohexanone, tetraglyme, triglyme, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone It is preferable that it is 1 or more types.

Among these solvents (C), for example, from the viewpoint of improving the durability of the inkjet head, ethyl lactate, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, Propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, butyrolactone are particularly preferred.

These solvent (C) may be used individually by 1 type, and may use 2 or more types together. Components, such as the said compound (A) and said surfactant (B), may melt | dissolve in 2 or more types of mixed solvent, even if it does not melt | dissolve in a single solvent. The solvent (C) is preferably used in a range such that the solid content concentration in the inkjet ink is 25 to 80% by weight.

Tetracyclic ether (D)

The ink for nonaqueous inkjet of this invention may contain cyclic ether (D). The cyclic ether (D) is not particularly limited as long as it has oxirane or oxetane, but a compound having two or more oxiranes is preferable.

As the cyclic ether (D), for example, a bisphenol A cyclic ether, a glycidyl ester cyclic ether, an alicyclic cyclic ether, a polymer of a monomer having an oxysilane, and a copolymer of a monomer having an oxysilane and another monomer may be used. Can be mentioned.

Specific examples of the monomer having an oxysilane include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methylglycidyl (meth) acrylate.

Moreover, as a specific example with the other monomer which copolymerizes with the monomer which has an oxysilane, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) Acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Oxypropyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, and the like. Can be.

As a preferable specific example of the polymer of the monomer which has an oxysilane, and the copolymer of the monomer which has an oxysilane, and another monomer, a polyglycidyl methacrylate, a methyl methacrylate- glycidyl methacrylate copolymer, and a benzyl methacrylate- Glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3- Oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, a styrene-glycidyl methacrylate copolymer, etc. are mentioned.

The cyclic ether (D) is N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N- diglycidylaminomethyl) cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'- diaminodiphenylmethane, 3-glycidoxy propyl trimethoxysilane, and the compound represented by following formula (7)-(16) It is more preferable that it is 1 or more types of compounds chosen from the group. Among these, the compound represented by Formula (11) and (16) is preferable because the flatness of the polyimide film obtained becomes especially favorable.

(In formula (10), n is an integer of 0 to 10.)

(In Formula (15), R <^c> is a C2-C100 tetravalent organic group, R <^d> is respectively independently a C1-C30 divalent organic group, R <^e> is each independently following formula (c)- (e) monovalent organic group selected from the group consisting of

(In Formula (c), R ^f is a hydrogen atom or alkyl having 1 to 3 carbon atoms.)

(In formula (16), n is an integer of 2-4.).

The compound represented by Formula (15) is obtained by reaction of the compound which has the tetracarboxylic acid dianhydride represented by following formula (f), and the hydroxyl represented by formula (g), for example.

In formula (f), R ^c is a tetravalent organic group having 2 to 100 carbon atoms.

In formula (g), R ^d is a divalent organic group having 1 to 30 carbon atoms, and R ^e is a monovalent organic group selected from the group consisting of the formulas (c) to (e).

In formula (g), although R <^d> is a C1-C30 divalent organic group, it is a C1-C30 linear or branched bivalent organic group, for example, may contain ring structure or oxygen, Examples of the ring structure include phenyl, cyclohexyl, naphthyl, cyclohexenyl, tricyclo [5.2.1.O ^2,6 ] decanyl, and the like.

As a compound represented by Formula (15), Especially preferably, the compound of following formula (15-1) is mentioned.

The compound represented by the formula (15) can be produced, for example, by reacting a compound having a tetracarboxylic acid represented by the formula (f) with an anhydride and a hydroxyl represented by the formula (g) in a solvent.

On the other hand, it is preferable that the tetracarboxylic dianhydride represented by Formula (f) is tetracarboxylic dianhydride used for the synthesis | combination of the amic acid (a) mentioned above.

It is preferable to use 1.9-2.1 mol of compounds which have a hydroxyl represented by Formula (g) with respect to 1 mol of tetracarboxylic dianhydride represented by Formula (f), It is more preferable to use 1.95-2.05 mol, Particular preference is given to using 2 moles. Although the compound which has a hydroxyl represented by a formula (g) may use 2 or more types of compounds together, it is preferable to use 1 type independently.

In addition, the compound represented by Formula (15) reacts, for example, the tetracarboxylic dianhydride represented by Formula (f) with the compound which has hydroxyl and a double bond, and then oxidizes the double bond part of the obtained compound. By making it into an epoxy group, it can manufacture.

Although the solvent used in order to synthesize | combine the compound represented by Formula (15) is not specifically limited, For example, the solvent for synthesize | combining the amic acid (a) mentioned above is mentioned.

The solvent is preferable because the reaction proceeds smoothly when 50 parts by weight or more is used with respect to 100 parts by weight of the total of the raw materials for producing the compound represented by the formula (15). It is preferable that reaction temperature is 80 degreeC-130 degreeC, and it is preferable that reaction time is 2 to 8 hours. In addition, the order of addition of the reaction raw materials to the reaction system is not particularly limited.

Specific examples of the cyclic ether (D) include the brand names "Epicoat 807", "Epicoat 815", "Epicoat 825", "Epicoat 827", "Epicoat 828", "Epicoat 190P", "Epicoat 191P" "(Above, manufactured by Shell Chemical Co., Ltd.), brand name" Epicoat 1004 "," Epicoat 1256 "(above, manufactured by Japan Epoxy Resin Co., Ltd.), brand name" Araldite CY177 ", brand name" Araldai " CY184 "(manufactured by Nihon Chiba Co., Ltd.), trade names" Celoxide 2021P "," Celoxide 3000 "," EHPE-3150 "(manufactured by Daicel Chemical Co., Ltd.), trade name" Techmore VG31O1L "( Mitsui Chemical Co., Ltd. product, EPICLON HP-72OO series, brand name "HP-72OOHH" (made by DIC Corporation) is mentioned. Among these, the brand names "Araldite CY184", the brand names "Celoxide 2021P", the brand names "Techmore VG3101L", and the brand name "Epicoat 828" are preferable because the flatness of the polyimide film obtained becomes especially favorable.

A cyclic ether (D) may be used individually by 1 type, and may use 2 or more types together. Although the amount which adds cyclic ether (D) to an inkjet ink is not specifically limited, It is preferable that it is 0.1-50 weight%, It is more preferable that it is 5-40 weight%, It is further more preferable that it is 10-30 weight%. . If it is this concentration range, there exists a tendency for the heat resistance, chemical-resistance, and flatness of the film | membrane formed with inkjet ink to become favorable.

5 acrylic resin (a-3)

The inkjet ink of the present invention may contain an acrylic resin (a-3). Such acrylic resin (a-3) is not particularly limited as long as it has an acrylic group or a methacryl group.

Although the content density | concentration of the acrylic resin (a-3) in an inkjet ink is not specifically limited, It is preferable that it is 0.1-20 weight%, It is more preferable that it is 0.5-15 weight%, It is more preferable that it is 1-10 weight% Do. When it exists in this density | concentration range, there exists a tendency for the heat resistance, chemical-resistance, and flatness of the film | membrane formed with inkjet ink to become favorable.

As the acrylic resin (a-3), for example, a monofunctional polymerizable monomer having a hydroxyl, a monofunctional polymerizable monomer not having a hydroxyl, a bifunctional (meth) acrylate, or a trifunctional or higher polyfunctional ( Meth) acrylate.

As a specific example of the monofunctional polymerizable monomer which has a hydroxyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, 4- Cyclohexane dimethanol mono (meth) acrylate is mentioned. Especially, 4-hydroxybutyl acrylate and 1, 4- cyclohexane dimethanol monoacrylate are preferable at the point which can make the film | membrane formed soft.

Specific examples of the monofunctional polymerizable monomer having no hydroxyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methylglycidyl (meth) acrylate, and 3-methyl 3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meta ) Acryloxyethyl oxetane, p-vinylphenyl-3-ethyloxeta-3-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meta ) Acryloxymethyl oxetane, 4-trifluoromethyl-2- (meth) acryloxymethyl oxetane, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acryl Rate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate , Styrene, Methylstyrene, Glomethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, vinyltoluene, (meth) acrylic Amide, tricyclo [5.2.1.O ^2,6 ] decanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, glycerol Ethylene oxide addition of mono (meth) acrylate, polystyrene macromonomer, polymethylmethacrylate macromonomer, N-acryloyl morpholine, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, and lauryl alcohol Mono (meth) acrylate, (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate , Succinic acid mono [2- (Meth) acryloyloxyethyl], maleic acid mono [2- (meth) acryloyloxyethyl], or cyclohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl] Can be mentioned.

Specific examples of the bifunctional (meth) acrylate include bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified diacrylate, polyethylene glycol diacrylate, and polypropylene glycol diacrylate. Acrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,4 -Cyclohexane dimethanol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, trimethylolpropane diacrylate, or dipentaerythritol diacrylate is mentioned.

Specific examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, Epichlorohydrin modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, diglycerine tetra (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, alkyl modified dipenta Erythritol tetra (meth) acrylate, alkyl modified dipenta Listhritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate, tris [(meth) acryloxy Ethyl] isocyanurate, caprolactone modified tris [(meth) acryloxyethyl] isocyanurate, or urethane (meth) acrylate is mentioned. These acrylic resins may be used individually by 1 type, and may use 2 or more types together.

6 Non-aqueous Of ink for inkjet  How to prepare

The ink for non-aqueous inkjet of this invention can be prepared by mixing the solution which melt | dissolved surfactant (B) in the solvent (C), and the solution which melt | dissolved the compound (A) in the solvent (C), for example. Moreover, it can prepare by mixing the solution which melt | dissolved the compound (A) in the solvent (C), and surfactant (B).

It is preferable that it is 0-50 degreeC, and, as for the temperature at the time of the said mixing, it is more preferable that it is 10-30 degreeC.

7 concentration of each ingredient

Although the content concentration of said each component other than surfactant (B) in the nonaqueous inkjet ink of this invention is not specifically limited, Compound (A) and cyclic ether (D) with respect to 100 weight part of inkjet inks It is preferable to contain 20-85 weight part of acrylic resin (a-3) in total, It is more preferable to contain 25-80 weight part, It is especially preferable to contain 25-70 weight part. If it is such a density range, when the inkjet coating | coating using the said non-aqueous inkjet ink, the thickness of the film | membrane obtained by one inkjetting becomes optimal, and the jetting precision becomes preferable, it is preferable.

8 Other additives

In the ink for non-aqueous inkjet of the present invention, an antistatic agent, a coupling agent, an epoxy curing agent, a diester dicarboxylic acid, a curing agent, a pH adjuster, a rust preventive agent, a preservative, a deflecting agent, an antioxidant, an anti-reducing agent, and evaporation depending on the desired properties. You may select and add additives, such as an accelerator, a chelating agent, a water-soluble polymer, a pigment, and dye as needed.

8.1 Antistatic Agent

The antistatic agent that may be added to the ink for nonaqueous inkjet of the present invention is not particularly limited, and a known antistatic agent can be used. Specific examples thereof include metal oxides and quaternary ammonium salts such as tin oxide, tin oxide-antimony oxide composite oxide, and tin oxide-indium oxide composite oxide. These antistatic agents may be used individually by 1 type, and may use 2 or more types together.

An antistatic agent is what is used in order to prevent an electric charge. It is preferable that the content concentration of an antistatic agent is 0.01-1 weight part with respect to 100 weight part of non-aqueous inkjet inks.

8.2 Coupling agent

As a coupling agent which may be added to the ink for non-aqueous inkjet of this invention, although it does not specifically limit but a well-known coupling agent can be used, A silane coupling agent is preferable. Specifically, a trialkoxysilane compound, a dialkoxysilane compound, etc. are mentioned. As a more preferable specific example, (gamma) -vinyl propyl trimethoxysilane, (gamma) -vinyl propyl triethoxysilane, (gamma) -acryloyl propylmethyl dimethoxysilane, (gamma) -acryloylpropyl trimethoxysilane, (gamma) -acryloyl Propylmethyldiethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldie Oxysilane, γ-methacryloylpropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl- γ-iminopropylmethyldimethoxysilane, N -Aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropyl diethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxy Silane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mer Captopropylmethyl diethoxysilane, gamma -mercaptopropyltriethoxysilane, gamma -isocyanatopropylmethyldiethoxysilane, and gamma -isocyanatopropyltriethoxysilane. Among these, (gamma) -vinyl propyl trimethoxysilane, (gamma) -acryloyl propyl trimethoxysilane, (gamma) -methacryloyl propyl trimethoxysilane, (gamma)-isocyanatopropyl triethoxysilane, etc. are mentioned. have.

These coupling agents may be used individually by 1 type, and may use 2 or more types together. It is preferable that the content density | concentration of a coupling agent is 0.01-3 weight part with respect to 100 weight part of inkjet ink.

8.3 Epoxy Curing Agent

The epoxy curing agent that may be added to the ink for non-aqueous inkjet of the present invention is not particularly limited, and a known epoxy curing agent can be used. Specific examples thereof include organic acid dihydrazide compounds, imidazoles and derivatives thereof, dicyandiamides, aromatic amines, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, and the like. More specifically, organic acids dihydrazide, such as dicyandiamide, such as a dicyandiamide, adipic dihydrazide, and 1, 3-bis (hydrazino carboethyl) -5-isopropyl hydantoin, 2, 4-diamino-6- [2'-ethylimidazolyl- (1 ')]-ethyltriazine, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4- Imideazole derivatives such as methyl-5-hydroxymethylimidazole, acid anhydrides such as phthalic anhydride, trimellitic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, or trimellitic acid Can be mentioned.

Among them, trimellitic anhydride having good transparency and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride are preferable.

These epoxy curing agents may be used individually by 1 type, and may use 2 or more types together. It is preferable to add 0.2-10 weight part of epoxy curing agents to 100 weight part of non-aqueous inkjet inks, and it is more preferable to add 0.2-5 weight part.

8.4 Diester Dicarboxylic acid

The diester dicarboxylic acid that may be added to the ink for non-aqueous inkjet of the present invention is not particularly limited, and a known diester dicarboxylic acid can be used. Specifically, the compound represented by the following general formula (E) is mentioned as a reaction material of the compound (a1) which has two or more acid anhydride groups mentioned above with alcohol.

(Wherein R _E is a tetravalent organic group having 1 to 30 carbon atoms, and R _E2 and R _E2 ′ are each independently alkyl or phenyl having 1 to 10 carbon atoms).

Especially, the reactants of oxydiphthalic anhydride and methanol which are good in solubility, and the reactant of oxydiphthalic anhydride and ethanol which are illustrated by the following general formula (E-1) and (E-2) are preferable.

These diester dicarboxylic acids may be used individually by 1 type, and may use 2 or more types together. It is preferable that it is 1-50 weight part with respect to 100 weight part of ink for non-aqueous inkjets, and, as for the content density | concentration of diester dicarboxylic acid, it is also preferable that it is 10-30 weight part.

9 Non-aqueous Ink  characteristic

The ink for non-aqueous inkjet of this invention can be made thermosetting or photocurable by selecting each component mentioned above suitably.

Although the viscosity of the ink for non-aqueous inkjet of this invention is not specifically limited, When performing jetting at normal temperature (25 degreeC), it is 1-50 mPa * s, It is preferable at the point which the jetting precision by an inkjet coating method improves. Do. The viscosity of the nonaqueous inkjet ink at 25 ° C is more preferably 5 to 30 mPa · s, and more preferably 8 to 15 mPa · s. If the viscosity of the ink for non-aqueous ink jet at 25 ° C. is 15 mPa · s or less, inkjet ejection failure is unlikely to occur.

When the ink head is heated and jetted, the viscosity of the ink for non-aqueous inkjet at the heating temperature (preferably 40 to 120 ° C) is preferably 1 to 50 mPa · s, and is 5 to 30 mPa · s. It is more preferable, and it is especially preferable that it is 8-15 mPa * s. When the viscosity at the heating temperature is 15 mPa · s or less, inkjet ejection failure is unlikely to occur.

[Ink coating method]

The ink coating method of this invention is characterized by including the process of apply | coating the ink for non-aqueous inkjet mentioned above according to the inkjet coating method.

As the inkjet coating method, there are various types depending on the method of discharging ink, and examples thereof include piezoelectric element type, bubble jet (registered trademark) type, continuous jet type, or electrostatic induction type. The above-mentioned nonaqueous inkjet ink can be discharged by various methods by appropriately selecting each component contained in the ink, and the nonaqueous inkjet ink can be applied in a predetermined pattern form.

The preferable discharge method at the time of apply | coating the above-mentioned non-aqueous inkjet ink by the inkjet coating method is a piezoelectric element type. This piezoelectric element type head is provided with a nozzle forming substrate having a plurality of nozzles, a pressure generating element made of a piezoelectric material and a conductive material disposed to face the nozzle, and an ink filling the periphery of the pressure generating element. It is an on-demand inkjet application head. In the piezoelectric element type discharging method, the pressure generating element is displaced by an applied voltage, and a small droplet of ink is discharged from the nozzle.

Examples of the inkjet coating apparatus include those in which the coating head and the ink containing portion are separately formed. However, the inkjet coating apparatus is not limited to this. In the case of the integrated configuration, the ink containing portion may or may not be detachable with respect to the application head. In addition, the inkjet coating apparatus is provided with an ink receiving portion integrated with the application head and mounted on the carriage, and the ink receiving portion is provided at a fixed portion of the apparatus, and is provided to the application head via an ink supply member, for example, a tube. It may be in the form of supplying ink.

In the case where the ink tank is provided with a configuration for applying a desired negative pressure to the application head, an absorbent body is disposed in the ink containing portion of the ink tank, or a flexible ink containing bag and its contents. The form etc. which have a spring part which acts the pressing force of the direction which expands an enemy can be employ | adopted. In addition to employing the serial coating method, the inkjet coating apparatus may take the form of a line printer formed by aligning the coating elements over a range corresponding to the entire width of the coating medium.

After the non-aqueous inkjet ink described above is applied to a substrate to form a coating film according to an inkjet coating method, the coating film may be heated and dried (removing the solvent) with a hot plate or an oven to form a cured film.

Although heating conditions change with kinds and compounding ratio of each component, it is 5 to 15 minutes normally when using an oven at 70-120 degreeC normally, and 1 to 5 minutes normally when using a hotplate.

In addition, you may form the said coating film in predetermined pattern form (for example, line shape).

In addition, the formation method of the said cured film is not limited to heat processing, Processes, such as UV processing, an ion beam, an electron beam, gamma ray, and infrared rays, may be sufficient.

[Formation Method of Polyimide Film]

The method for forming a polyimide film of the present invention is a step of applying a non-aqueous inkjet ink containing the compound (A) described above to a substrate by an inkjet coating method to form a coating film, and heating the coating film to form a polyimide. And forming a film. Moreover, the formation method of the patterned polyimide film of this invention is the process of apply | coating the nonaqueous inkjet ink containing the compound (A) mentioned above in a pattern form on a board | substrate according to the inkjet coating method, and forming a coating film, It is characterized by including the process of forming a patterned polyimide film | membrane by heating the said coating film.

The formation process of a coating film is as above-mentioned.

After forming a coating film, it heat-processes to 180-350 degreeC normally, Preferably it is 200-300 degreeC. At this time, when an oven is used, a polyimide membrane can be obtained by heat-processing normally for 30 to 90 minutes, and when using a hot plate for 5 to 30 minutes normally. When the coating film is formed in a pattern form, a patterned polyimide film is formed. In the present specification, unless otherwise specified, the polyimide film includes a patterned polyimide film.

[Polyimide Membrane]

The polyimide membrane of this invention is obtained by the formation method of the polyimide membrane mentioned above. It is characterized by the above-mentioned. The polyimide membrane obtained by the formation method of the polyimide membrane mentioned above is excellent in heat resistance and electrical insulation, and can be used as an insulating film, for example.

[Film substrate]

The film substrate of this invention has the above-mentioned polyimide membrane or patterned polyimide membrane, It is characterized by the above-mentioned.

In the film substrate of the present invention, for example, a non-aqueous ink jet ink containing the compound (A) described above on a substrate such as a resin film on which wiring is formed, the entire surface or a predetermined pattern type according to an ink jet coating method. It applies to (line shape), forms a coating film, and after that, the board | substrate with the said coating film was dried, and a polyimide film is formed by heating again, and is obtained.

The polyimide film is preferably formed on a substrate such as the resin film described above, but is not particularly limited thereto, and can be formed on a known substrate.

In the present invention, as an applicable substrate, for example, a glass epoxy substrate, a glass composite substrate, which conforms to various standards such as FR-1, FR-3, FR-4, CEM-3, or E668, Paper phenol substrates, paper epoxy substrates, green epoxy substrates, or BT resin substrates.

In addition, in this invention, as another applicable board | substrate, the board | substrate which consists of metals, such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium, or stainless, for example, May be a substrate having a surface); Aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), silicate (zircon) of zirconium, magnesium oxide (magnesia), aluminum titanate, barium titanate, lead titanate (PT), lead zirconate titanate (PZT), zirconate titanate PLNT, lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllia), silicon oxide (silica), silicon carbide (silicon carbide), silicon nitride (silicon nitride), boron nitride ( Boron nitride), zinc oxide, mullite, ferrite, steatite, forsterite, spinel or spodumene (substrates having a surface of these ceramics); PET (polyethylene terephthalate) resin, PBT (polybutylene terephthalate) resin, PCT (polycyclohexylenedimethylene terephthalate) resin, PPS (polyphenylene sulfide) resin, polycarbonate resin, polyacetal resin, polyphenyl Leneether resins, polyamide resins, polyallylate resins, polysulfone resins, polyethersulfone resins, polyetherimide resins, polyamidoimide resins, epoxy resins, acrylic resins, Teflon®, thermoplastic elastomers, or liquid crystal polymers Board | substrates which consist of resin, such as these (it may be a board | substrate which has the surface of these resin); Semiconductor substrates such as silicon, germanium, or gallium arsenide; Glass substrates; Or a substrate having an electrode material such as tin oxide, zinc oxide, ITO, or ATO formed on its surface; and gel sheets such as? GEL (alpha gel),? GEL (beta gel),? GEL (theta gel), or? GEL (gamma gel) (above, registered trademark of Daika Corporation).

[Semiconductor Wafer]

The semiconductor wafer of this invention has a polyimide film | membrane or a patterned polyimide film | membrane mentioned above, It is characterized by the above-mentioned.

The semiconductor wafer of the present invention is made of, for example, an insulator made of silicon dioxide, fluorinated silicon oxide, amorphous carbon, polycrystalline silicon, single crystal silicon, germanium, gallium arsenide, tantalum oxide, silicon nitride, titanium silicide, and aluminum gallium arsenide. On a substrate such as a wafer made of a semiconductor and a wiring made of aluminum, copper, titanium, or the like, a non-aqueous inkjet ink containing the compound (A) described above may be formed on the entire surface or in a predetermined pattern shape according to the inkjet coating method. To form a coating film, and then, the substrate on which the coating film is formed is dried and then heated again to form a polyimide film.

[Substrate for Electronic Materials]

The board | substrate for electronic materials of this invention has the above-mentioned polyimide film or patterned polyimide film, It is characterized by the above-mentioned.

The board | substrate for electronic materials of this invention is a non-aqueous inkjet ink containing the compound (A) mentioned above on the board | substrate, such as a piezoelectric element, a crystal oscillator, and a ceramic oscillator, according to the inkjet coating method, for the whole surface. Or a coating pattern is formed by apply | coating in a predetermined pattern form (line shape etc.), Then, the board | substrate with the said coating film is dried, and it heats again, and a polyimide film is formed and obtained.

[Electronic parts]

The electronic component of this invention has the above-mentioned polyimide membrane or patterned polyimide membrane, It is characterized by the above-mentioned. It is preferable that the said electronic component has the above-mentioned film substrate, the above-mentioned semiconductor wafer, or the above-mentioned substrate for electronic materials.

Such an electronic component is a non-aqueous inkjet ink as described above, for example, on a film substrate such as a polyimide film having a wiring formed in advance, on a substrate such as a silicon wafer on which a wiring is formed in advance, or on a ceramic substrate for an electronic component. The polyimide film can be obtained by applying the inkjet coating method to form a coating film, and then drying and heating the film substrate on which the coating film is formed. The electronic component obtained in this way is coated with the polyimide film which has insulation, and is excellent in electrical characteristics.

[Example]

Hereinafter, although this invention is demonstrated concretely by a synthesis example, an Example, and a comparative example, this invention is not limited to these examples.

In addition, the names of the compound (a3), diamine (a2), monoamine (a4), cyclic ether (D), and solvent (C) which have one or more acid anhydride groups used by the synthesis example, the Example, and the comparative example are as follows. It may be represented by an abbreviation.

Compounds having at least one acid anhydride group ( a3 )

Abbreviation of 2- [3- (triethoxysilyl) propyl] succinic anhydride: TESA

Abbreviation for Maleic Anhydride: MA

Abbreviation of trimellitic anhydride: TMDA

Diamine ( a2 )

Abbreviation for 2,2-bis [4- (4-aminophenoxy) phenyl] propane: BAPP

In the formula (B1-z), E ⁵ and E ⁶ are all methyl, E ⁷ is methylene, x1 is 3, and y1 is 3-8, the abbreviation of the mixture of compounds: FM-3306 Manufacture Co.Ltd.

In the formula (B1-z), E ⁵ and E ⁶ are all methyl, E ⁷ is methylene, x1 is 3 and y1 is 10-15. The abbreviation of the mixture of compounds: FM-3311 Manufacture Co.Ltd.

In the formula (B1-z), E ⁵ and E ⁶ are all methyl, E ⁷ is methylene, x1 is 3, and y1 is 60 to 70. The abbreviation of a mixture of compounds: FM-3321 Manufacture Co.Ltd.

In the formula (B1-z), E ⁵ and E ⁶ are all methyl, E ⁷ is methylene, x1 is 3, and y1 is 120 to 140. The abbreviation for a mixture of compounds: FM-3325 Manufacture).

Monoamines ( a4 )

Abbreviation for 2- (2-aminoethoxy) ethanol: AEE

Cyclic ether (D)

Tekmore VG3101L (trade name, Mitsui Chemical Co., Ltd.) abbreviation: VG3101L

In addition, "techmore VG3101L" is a compound represented by following formula (9).

Abbreviation for S510 (brand name, Tosso Co., Ltd.): S510

Meanwhile, "S510" is 3-glycidoxypropyltrimethoxysilane.

Solvent (C)

Abbreviation for diethylene glycol methylethyl ether: EDM

Each measuring method performed in this example is shown below.

[Measurement of Viscosity of Solution]

The viscosity of the solution was measured with an E-type viscometer (manufactured by TOKYOKEIKI, VISCONIC ELD), and the surface tension by DM500 (manufactured by Wako Chemical Co., Ltd.).

[Measurement of Surface Tension]

The surface tension of the ink was measured by DM500 (manufactured by Japan Chemical Industries, Ltd.). The thermostat set to 25 degreeC was prepared, and the surface tension of the ink was measured by the pendant drop type in 25 degreeC atmosphere. It measured five times or more and computed the average value as surface tension.

[Measurement of Weight Average Molecular Weight]

The weight average molecular weight of amic acid and surfactant was measured by the gel permeation chromatography (GPC) method. The sample was diluted with dimethylformamide (DMF) so that the sample concentration was about 1% by weight, and the dilution liquid was prepared using JASCO GULLIVER 1500 (Intelligent Differential Refractometer RI-1530) manufactured by Nippon Kogyo Co., Ltd. as a GPC apparatus. It measured by GPC method as a developing agent and calculated | required by polystyrene conversion. The column was connected using two Shodex Asahipak GF-510 HQ and Shodex Asahipak GF-310 HQ in this order, and the column was measured on the conditions of a column temperature of 40 degreeC and a flow rate of 1.0 ml / min.

Synthesis Example 1 Synthesis of Solution (1) Containing Amic Acid (1)

A raw material was added to a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet as shown in Table 1, and stirred for 5 hours at 25 ° C. under a dry nitrogen stream. ), A light yellow transparent solution (1) containing 35% by weight) was obtained. The viscosity of the solution (1) containing this amic acid (1) was 15.6 mPa * s (25 degreeC). It was 28.1 (mN / m) when the surface tension of the solution (1) containing amic acid (1) was measured.

Synthesis Examples 2 to 5, 7 to 9 Synthesis of solutions (2) to (5) and (7) to (9) containing amic acid (2) to (5), (7) to (9)

Except having added the raw material as shown in Table 1, the solution (2)-(5) which contains amic acid (2)-(5), (7)-(9) on the conditions similar to the synthesis example 1, (( 7) to (9) were prepared.

Synthesis Example 6 Synthesis of Solution (6) Containing Ester Amic Acid (6)

Into a 300 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 60 g of EDM, 10.6 g of AEE, and 9.9 g of MA were added and stirred at 25 ° C. under a dry nitrogen stream for 1 hour. After the MA was dissolved, 19.5 g of TMDA was added, stirred at 110 ° C. for 3 hours under a dry nitrogen stream, and a brown transparent solution containing 40% by weight of ester amide acid was obtained. The viscosity of the solution containing this ester amic acid was 29.6 mPa * s (25 degreeC).

Synthesis Example 10 Synthesis of Solution 10 Containing Ester Amic Acid (10)

Into a 300 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 70 g of EDM, 12.6 g of BAPP, and 3.0 g of MA were added and stirred at 25 ° C. under a dry nitrogen stream for 1 hour. After the MA was dissolved, 14.5 g of S510 was added thereto, stirred at 110 ° C. for 1 hour under a dry nitrogen stream, and a brown transparent solution containing 30% by weight of amic acid was obtained. The viscosity of the solution containing this amic acid was 5.10 mPa * s (25 degreeC).

Synthesis Example 11 Synthesis of Solution 11 Containing Ester Amic Acid (11)

Into a 300 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 60 g of EDM, 14.0 g of AEE, and 13.0 g of MA were added and stirred at 25 ° C. under a dry nitrogen stream for 1 hour. After MA was dissolved, 13.0 g of MA was further added, stirred for 3 hours at 110 ° C. under a dry nitrogen stream, and a yellow transparent solution containing 40% by weight of ester amide acid was obtained. The viscosity of the solution containing this ester amic acid was 14.2 mPa * s (25 degreeC).

Synthesis Example 12 A solution containing 3.46 g of a solution 10 containing an amic acid (10), 10.4 g of a solution (6) containing an ester amic acid (6) and an ester amic acid (11) (11) ) To 10.4 g, 26.6 g of VG3101L, 4.05 g of TMDA, and 45.1 g of EDM were added to prepare a solution 12 containing epoxy ester amic acid (12). The viscosity of the solution 12 containing the epoxy ester amic acid (12) was 11.9 mPa * s (25 degreeC). It was 29.5 (mN / m) when the surface tension of the solution 12 containing the epoxy ester amic acid (12) was measured.

Synthesis Example 13 Synthesis of Solution (13) Containing Epoxyester Amic Acid (13)

20.6 g of VG3101L and 31 g of EDM were added to 48.3 g of the solution (6) containing the ester amic acid to obtain a solution (13) containing the epoxy ester amic acid (13). The viscosity of the solution 13 containing the epoxy ester amic acid (13) was 17.2 mPa * s (25 degreeC). It was 29.8 (mN / m) when the surface tension of the solution 13 containing the epoxy ester amic acid (13) was measured.

Dosing amount and surface tension of raw material of solution containing each amic acid solution
number Mixing solution
number mountain
anhydride
(a3) Diamine
(a2) Monoamine
(a4) Annular
ether
(D) menstruum
(C) Solution
Surface tension
(mN / m) Synthesis Example 1 (One) TESA
20.9 g BAPP
14.1 g EDM
65 g 28.1 Synthesis Example 2 (2) TESA
15.1 g FM-3306
14.9 g EDM
70 g Synthesis Example 3 (3) TESA
11.4 g FM-3311
18.6 g EDM
70 g 23.5 Synthesis Example 4 (4) TESA
3.2 g FM-3321
26.8 g EDM
70 g Synthesis Example 5 (5) TESA
1.8g FM-3325
28.2 g EDM
70 g Synthesis Example 6 (6) MA
9.9 g
TMDA
19.5 g AEE
10.6 g EDM
60 g Synthesis Example 13 (13) (6)
48.3 g VG3101L
20.6 g EDM
31 g 29.8 Synthesis Example 7 (7) TESA
15.1 g FM-3311
24.9 g EDM
60 g 23.7 Synthesis Example 8 (8) TESA
18.9 g FM-3311
31.1 g EDM
50 g 23.4 Synthesis Example 9 (9) TESA
7.6 g FM-3311
12.4 g EDM
80 g 23.4 Synthesis Example 10 10 MA
3.0 g BAPP
12.6 g S510
14.5g EDM
70 g Synthesis Example 11 (11) MA
26.0 g AEE
14.0 g EDM
60 g Synthesis Example 12 (12) (6)
10.4 g
10
3.46 g
(11)
10.4 g TMDA
4.05g VG3101L
26.6 g EDM
45.1 g 29.5

Example 1

1. Preparation of Non-aqueous Inkjet Ink (1)

99.9 g of solution (1) containing amic acid (1) synthesized in Synthesis Example 1 and 0.1 g of solution (3) containing amic acid (3) synthesized in Synthesis Example 3 which is a surfactant (B) are mixed. To prepare a non-aqueous inkjet ink 1.

It was 26.2 mN / m (25 degreeC) when the surface tension of the obtained non-aqueous inkjet ink 1 was measured. The content concentration of surfactant (B) in the nonaqueous inkjet ink 1 was 0.03% by weight.

In addition, in the non-aqueous inkjet ink 1, as a result of increasing the content of the same type of surfactant (B), the surface tension of the ink was lowered as compared with before the increase. Therefore, it turned out that surfactant (B) contained in the nonaqueous inkjet ink 1 is less than the critical micelle concentration.

On the other hand, the weight average molecular weight of the amic acid (3) in the solution containing the amic acid (3) was 6900.

2. Formation of Polyimide Film 1

The nonaqueous inkjet ink 1 obtained in the above 1 was applied onto the substrate in a pattern form as shown in Fig. 3 by the inkjet coating method to form a coating film. In addition, the copper foil substrate, the glass substrate, and the Kapton substrate were used as a board | substrate. In addition, the inkjet coating used the inkjet coating apparatus DMP-2831 made from FUJIFILM Dimatix. As inkjet coating conditions, dot pitch was set to 20 micrometers by 1 dot width, pattern application was performed at normal temperature (25 degreeC), the heater of the inkjet head was set to 30 degreeC, the piezo voltage was 20V, and the drive frequency was 10kHz. .

Next, the coating film formed on each board | substrate was dried for 5 minutes with the 80 degreeC hotplate, and it heated for 30 minutes in 230 degreeC oven, and obtained the insulating polyimide film 1 formed in pattern shape.

3. Evaluation of Polyimide Membrane (1)

On each board | substrate, the polyimide film 1 formed in the pattern form was observed with the optical microscope, and it evaluated as follows. The evaluation results are shown in Table 8.

(Evaluation standard)

When I could apply it according to a pattern: ○ (two points)

When the angle is rounded and the pattern collapses slightly: △ (1 point)

If the pattern collapses badly and there is a wet spread, or crawl: × (zero).

On the other hand, the application | coating pattern was judged to be favorable, when the printing evaluation total point was four points (two (○), one (circle), two (DELTA), or four (triangle | delta)) or more.

The polyimide film 1 was wet-diffused on the Kapton substrate, but a good pattern was formed on the copper foil substrate and the glass substrate (see FIG. 3), and the print evaluation total point was 9 points. Therefore, it can be said that the favorable coating pattern (4 points or more of printing evaluation total points) was formed in the polyimide film 1.

Comparative Example 1

1. Preparation of non-aqueous inkjet ink (C1)

As shown in Table 2, 100 g of the solution (1) containing the amic acid (1) synthesized in Synthesis Example 1 was used as a non-aqueous inkjet ink (C1) without using a surfactant (B). . Table 3 shows the surface tension of the non-aqueous inkjet ink C1.

2. Formation of Polyimide Film (C1)

A polyimide film (C1) was obtained in the same manner as in Example 1 except that a nonaqueous inkjet ink (C1) was used.

3. Evaluation of Polyimide Membrane (C1)

On each board | substrate, the polyimide film (C1) formed in the pattern form was observed with the optical microscope, and it evaluated by the method similar to Example 1. The evaluation results are shown in Table 8. In the copper foil substrate, the coating pattern collapsed, and in the glass substrate and the Kapton substrate, the wet pattern was severely wet-diffused, and the target coating pattern could not be obtained (see FIG. 4).

[Examples 2 to 5]

1. Preparation of Non-aqueous Inkjet Inks (2) to (5)

As shown in Table 2, a non-aqueous ink jet ink was prepared by combining a solution 1 containing an amic acid (1) and a solution 3 containing an amic acid (3), each of which was used for a non-aqueous ink jet ink. Inks 2 to 5 were used. Table 2 shows the surface tensions of the obtained nonaqueous inkjet inks 2 to 5. In addition, the surfactant concentration in the non-aqueous inkjet inks 2 to 5 is shown in Table 2.

In addition, in the non-aqueous inkjet inks 2 to 5, the content of the surfactant (B) of the same kind was increased, and as a result, the surface tension of the ink was lowered compared to before the increase. Therefore, it was found that the surfactant (B) contained in the nonaqueous inkjet inks 2 to 5 was less than the critical micelle concentration.

2. Formation of Polyimide Membrane

Except having used the non-aqueous inkjet ink (2)-(5), the polyimide membrane (2)-(5) was obtained in the same manner as Example 1 in order.

3. Evaluation of Polyimide Membrane

On each board | substrate, the polyimide film | membrane (2)-(5) formed in the pattern form was observed with the optical microscope, and it evaluated by the method similar to Example 1. The evaluation results are shown in Table 8. In every polyimide film, the favorable application | coating pattern (4 or more points of printing evaluation total points) was formed.

Comparative Example 2

1. Preparation of non-aqueous inkjet ink (C2)

As shown in Table 2, a non-aqueous inkjet ink is prepared by combining a solution (1) containing amic acid (1) and a solution (3) containing amic acid (3), and a nonaqueous inkjet ink (C2 ). Table 2 shows the surface tension of the obtained nonaqueous inkjet ink (C2).

In the non-aqueous inkjet ink (C2), the content of the surfactant (B) of the same kind was increased, and as a result, the surface tension of the ink was hardly changed compared with before the increase.

Separately, in the non-aqueous inkjet ink (C2), the content of the surfactant (B) of the same kind was decreased, and as a result, the surface tension of the ink was hardly changed compared with before the reduction.

Therefore, it was found that the surfactant (B) contained in the non-aqueous inkjet ink (C2) exceeds the critical micelle concentration.

2. Formation of Polyimide Membrane

A polyimide film (C2) was obtained in the same manner as in Example 1 except that a nonaqueous inkjet ink (C2) was used.

3. Evaluation of Polyimide Membrane

On each board | substrate, the polyimide film (C2) formed in the pattern form was observed with the optical microscope, and it evaluated by the method similar to Example 1. The evaluation results are shown in Table 8. Remarkable crawling generate | occur | produced in the copper foil board | substrate, a glass substrate, and a Kapton board | substrate, and the target coating pattern was not able to be obtained.

Comparative Example 3

1. Preparation of non-aqueous inkjet ink (C3)

As shown in Table 2, 100 g of the solution (3) containing the amic acid (3) synthesized in Synthesis Example 3 was used as a non-aqueous ink jet ink (C3). Table 2 shows the surface tension of the non-aqueous inkjet ink (C3).

In the non-aqueous inkjet ink (C3), the content of the surfactant (B) of the same kind was increased, and as a result, the surface tension of the ink was hardly changed compared with before the increase.

Separately, in the non-aqueous inkjet ink (C3), the content of the surfactant (B) of the same kind was decreased, and as a result, the surface tension of the ink was hardly changed compared with before the reduction.

Therefore, it was found that the surfactant (B) contained in the non-aqueous inkjet ink (C3) exceeds the critical micelle concentration.

2. Formation of Polyimide Membrane

A polyimide film (C3) was obtained in the same manner as in Example 1 except that a nonaqueous inkjet ink (C3) was used.

3. Evaluation of Polyimide Membrane

On each board | substrate, the polyimide film (C3) formed in the pattern form was observed with the optical microscope, and it evaluated by the method similar to Example 1. The evaluation results are shown in Table 8. Remarkable crawling generate | occur | produced in the copper foil board | substrate, a glass substrate, and a Kapton board | substrate, and the target coating pattern was not able to be obtained.

[Comparative Example 5]

1. Preparation of non-aqueous inkjet ink (C5)

As shown in Table 2, 100 g of the solution (7) containing the amic acid (7) synthesized in Synthesis Example 7 was used as a non-aqueous inkjet ink (C5). Table 2 shows the surface tension of the non-aqueous inkjet ink (C5).

In the non-aqueous inkjet ink (C5), the content of the surfactant (B) of the same kind was increased, and as a result, the surface tension of the ink was hardly changed as compared with before the increase.

Separately, in the non-aqueous inkjet ink (C5), the content of the surfactant (B) of the same kind was decreased, and as a result, the surface tension of the ink was almost unchanged as compared with before the reduction.

Therefore, it was found that the surfactant (B) contained in the non-aqueous inkjet ink (C5) exceeds the critical micelle concentration.

2. Formation of Polyimide Membrane

A polyimide film (C5) was obtained in the same manner as in Example 1 except that a nonaqueous inkjet ink (C5) was used.

3. Evaluation of Polyimide Membrane

On each board | substrate, the polyimide film (C5) formed in the pattern form was observed with the optical microscope, and it evaluated by the method similar to Example 1. The evaluation results are shown in Table 8. Remarkable crawling generate | occur | produced in the copper foil board | substrate, a glass substrate, and a Kapton board | substrate, and the target application | coating pattern was not able to be obtained (print evaluation total point 0 points).

[Comparative Example 6]

1. Preparation of non-aqueous inkjet ink (C6)

As shown in Table 2, 100 g of the solution (8) containing the amic acid (8) synthesized in Synthesis Example 3 was used as a non-aqueous inkjet ink (C6). Table 2 shows the surface tension of the non-aqueous inkjet ink C6.

In the non-aqueous inkjet ink (C6), the content of the surfactant (B) of the same kind was increased, and as a result, the surface tension of the ink was hardly changed compared with before the increase.

Separately, in the non-aqueous inkjet ink (C6), the content of the surfactant (B) of the same kind was decreased, and as a result, the surface tension of the ink was hardly changed compared with before the reduction.

Therefore, it was found that the surfactant (B) contained in the non-aqueous inkjet ink (C6) exceeds the critical micelle concentration.

2. Formation of Polyimide Membrane

A polyimide film (C6) was obtained in the same manner as in Example 1 except that a nonaqueous inkjet ink (C6) was used.

3. Evaluation of Polyimide Membrane

On each board | substrate, the polyimide film (C6) formed in the pattern form was observed with the optical microscope, and it evaluated by the method similar to Example 1. The evaluation results are shown in Table 8. Remarkable crawling generate | occur | produced in the copper foil board | substrate, a glass substrate, and a Kapton board | substrate, and the target application | coating pattern was not able to be obtained (print evaluation total point 0 points).

Comparative Example 7

1. Preparation of non-aqueous inkjet ink (C7)

As shown in Table 2, 100 g of the solution (9) containing the amic acid (9) synthesized in Synthesis Example 3 was used as a non-aqueous ink jet ink (C7) as it is. Table 2 shows the surface tension of the non-aqueous inkjet ink C7.

In the non-aqueous inkjet ink (C7), the content of the surfactant (B) of the same kind was increased, and as a result, the surface tension of the ink was hardly changed compared with before the increase.

Separately, in the non-aqueous inkjet ink (C7), the content of the surfactant (B) of the same kind was decreased, and as a result, the surface tension of the ink was hardly changed compared with before the reduction.

Therefore, it was found that the surfactant (B) contained in the non-aqueous inkjet ink (C7) exceeds the critical micelle concentration.

2. Formation of Polyimide Membrane

A polyimide film (C7) was obtained in the same manner as in Example 1 except that a nonaqueous inkjet ink (C7) was used.

3. Evaluation of Polyimide Membrane

On each board | substrate, the polyimide film (C7) formed in the pattern form was observed with the optical microscope, and it evaluated by the method similar to Example 1. The evaluation results are shown in Table 8. Remarkable crawling generate | occur | produced in the copper foil board | substrate, a glass substrate, and a Kapton board | substrate, and the target application | coating pattern was not able to be obtained (print evaluation total point 0 points).

Non-aqueous
For inkjet
ink
number
Formed
Poly
Imide
Membrane number For non-aqueous inkjet
Composition of ink Non-aqueous
For inkjet
Ink
Surface tension
(mN / m) Interface
Active agent
density
(weight%) Interface
Active agent
weight
Average
Molecular Weight Amic acid
Contains 1
doing
Solution (1) Amic acid (3)
(Surfactants)
Containing
Solution (3) Comparative Example 1 (C1) (C1) 100 g - 27.8 0 - Example 1 (One) (One) 99.9 g 0.1g 26.2 0.03 6900 Example 2 (2) (2) 99.99 g 0.01 g 27.0 0.003 6900 Example 3 (3) (3) 99.5 g 0.5 g 24.7 0.15 6900 Example 4 (4) (4) 99 g 1 g 24.6 0.3 6900 Example 5 (5) (5) 98 g 2 g 24.2 0.6 6900 Comparative Example 2 (C2) (C2) 80 g 20g 23.6 6 6900 Comparative Example 3 (C3) (C3) - 100 g 23.5 30 6900 Comparative Example 5 (C5) (C5) - 100g (* 1) 23.7 40 7200 Comparative Example 6 (C6) (C6) - 100g (* 2) 23.4 50 7100 Comparative Example 7 (C7) (C7) - 100 g (* 3) 23.4 20 6950

* 1: using a solution (7) containing amic acid (7)

* 2: using a solution (8) containing amic acid (8)

* 3: using a solution (9) containing amic acid (9)

FIG. 1 graphically shows the surface tension, the surfactant concentration, the print evaluation result total point and the surfactant concentration from the results of Examples 1 to 5 and Comparative Examples 1 to 3 and 5 to 7. FIG. According to FIG. 1, it turns out that the favorable pattern film | membrane was formed, when the content concentration of surfactant is 0.00001 weight% or more and below critical micelle concentration.

[Examples 6 to 35]

1. Preparation of Non-aqueous Inkjet Inks 6 to 36

As shown in Tables 3-6, the solution containing amic acid and surfactant were mix | blended and the ink for non-aqueous inkjet was prepared, and each was set as the non-aqueous inkjet ink (6)-(36). Tables 3 to 6 show surface tensions of the obtained nonaqueous inkjet inks 6 to 36.

In addition, in the non-aqueous inkjet inks 6 to 36, when the content of the same kind of surfactant (B) was increased, the surface tension of the ink was lowered as compared with before the increase. Therefore, it was found that the surfactant (B) contained in the non-aqueous inkjet inks 6 to 36 was less than the critical micelle concentration.

2. Formation of Polyimide Membrane

The polyimide films 6 to 36 were obtained in the same manner as in Example 1 except that the nonaqueous inkjet inks 6 to 36 were used.

3. Evaluation of Polyimide Membrane

On each board | substrate, the polyimide film 6-36 formed in the pattern form was observed with the optical microscope, and it evaluated by the method similar to Example 1. The evaluation results are shown in Table 8.

About the obtained polyimide membrane, it evaluated on the conditions similar to the printing example 1. The results are shown in Table 8. In every polyimide film, the favorable application | coating pattern (4 or more points of printing evaluation total points) was formed.

Comparative Example 4 Formation of Polyimide Film (C4)

1. Preparation of non-aqueous inkjet ink (C4)

As shown in Table 7, 100 g of the solution 13 synthesized in Synthesis Example 13 was used as a non-aqueous ink jet ink (C4) as it is. Table 7 shows the surface tension of the obtained nonaqueous inkjet ink (C4).

2. Formation of Polyimide Membrane

A polyimide film (C4) was obtained in the same manner as in Example 1 except that a nonaqueous inkjet ink (C4) was used.

3. Evaluation of Polyimide Membrane

On each board | substrate, the polyimide film (C4) formed in the pattern form was observed with the optical microscope, and it evaluated by the method similar to Example 1. The evaluation results are shown in Table 8. With respect to the polyimide film (C4), the coating pattern collapsed on the copper foil substrate, severely wet-diffused on the glass substrate and the Kapton substrate, and the target coating pattern was not formed (the print evaluation total point was one point).

Comparative Example 8

1. Preparation of non-aqueous inkjet ink (C8)

As shown in Table 7, 100 g of the solution 12 synthesized in Synthesis Example 12 was used as a non-aqueous ink jet ink (C8) as it is. Table 7 shows the surface tension of the obtained nonaqueous inkjet ink (C8).

2. Formation of Polyimide Membrane

A polyimide film (C8) was obtained in the same manner as in Example 1 except that a nonaqueous inkjet ink (C8) was used.

3. Evaluation of Polyimide Membrane

On each board | substrate, the polyimide film (C8) formed in the pattern form was observed with the optical microscope, and it evaluated by the method similar to Example 1. The evaluation results are shown in Table 8. With respect to the polyimide film (C8), the coating pattern collapsed on the copper foil substrate, severely wet-diffused on the glass substrate and the Kapton substrate, and the target coating pattern was not formed (one point of total printing evaluation).

Non-aqueous
Inkjet ink
number
Formed
Poly
Imide
Membrane number For non-aqueous inkjet
Composition of ink Non-aqueous
For inkjet
Ink
Surface tension
(mN / m) Interface
Active agent
density
(weight%) Interface
Active agent
weight
Average
Molecular Weight Amic acid
Contains 1
doing
Solution (1) Surfactants
Containing
Solution (3) Example 6 (6) (6) 99.9 g Solution (2)
0.1g 27.1 0.03 7600 Example 7 (7) (7) 99.9 g Solution (4)
0.1g 26.5 0.03 8000 Example 8 (8) (8) 99.9 g Solution (5)
0.1g 26.3 0.03 12000 Example 9 (9) (9) 99.9 g FM-3306
0.1g 27.1 0.1 8800 Example 10 10 10 99.95 g FM-3311
0.05g 27 0.05 15000 Example 11 (11) (11) 99.9 g FM-3321
0.1g 26 0.1 21000 Example 12 (12) (12) 99.9 g FM-3325
0.1g 26.6 0.1 25000 Example 13 (13) (13) 99.95 g FM-4411
0.05g 27.5 0.05 1800 Example 14 (14) (14) 99.99 g FM-7711
0.01 g 28.4 0.01 1200 Example 15 (15) (15) 99.9925 g FM-0411
0.0075g 27.8 0.0075 1250 Example 16 (16) (16) 99.995 g FM-DA11
0.005g 27.7 0.005 1300 Example 17 (17) (17) 99.99 g FM-0711
0.01 g 26.2 0.01 1400 Example 18 (18) (18) 99.9 g (* 4) Solution (3)
0.1g 27.8 0.03 6900 Example 36 (19) (19) 99.9 g (* 5) Solution (3)
0.1g 27.6 0.03 6900

* 4: The solution (13) containing the epoxy ester amic acid (13) was used.

* 5: The solution (12) containing the epoxy ester amic acid (12) was used.

In addition, in Table 3, it shows below about FM-4411, FM-7711, FM-0411, FM-DA11, and FM-0711.

In the formula (B1-x), E ⁵ and E ⁶ are all methyl, E ⁷ is methylene, x1 is 3, and y1 is 10-15. The abbreviation of the mixture of compounds: FM-4411 Manufacture Co.Ltd.

In the formula (B1-w), E ⁵ , E ⁶ are all methyl, E ⁷ is methylene, x1 is 3, and y1 is 8 to 13, the abbreviation of a mixture of compounds: FM-7711 Manufacture Co.Ltd.

In the formula (B1-v), E ⁵ and E ⁶ are all methyl, E ⁷ is methylene, x1 is 3, and y1 is 10-15. The abbreviation of the mixture of compounds: FM-0411 Manufacture Co.Ltd.

In the formula (B1-u), E ⁵ and E ⁶ are all methyl, E ⁷ is methylene, x1 is 3, and y1 is 10-15. The abbreviation of a mixture of compounds: FM-DA11 (trade name, Chisoso) Manufacture Co.Ltd.

In the formula (B1-t), E ⁵ and E ⁶ are all methyl, E ⁷ is methylene, x1 is 3, and y1 is 10-15. The abbreviation of the mixture of compounds: FM-0711 Manufacture Co.Ltd.

Non-aqueous
For inkjet
ink
number
Formed
Poly
Imide
Membrane number For non-aqueous inkjet
Composition of ink Non-aqueous
For inkjet
Ink
Surface tension
(mN / m) Amic acid (1)
Containing
Solution (1) Surfactants
Containing
Silica fine particles
Dispersion Example 19 (19) (19) 50 g PL-2L-PGME
50 g 26.7

"2L-PL-PGME" (trade name, manufactured by Chemical Engineering Co., Ltd., high purity organocolloidal solution, particle diameter (specific surface area) 15-20 nm, silica concentration 25.0%, dispersion medium propylene glycol monomethyl ether, moisture 1%) Specific gravity 1.08 (20/4 ° C) or less

Non-aqueous
For inkjet
ink
number Formed
Poly
Imide
Membrane number Amic acid
(1)
Containing
Solution (1) Interface
Active agent Non-aqueous
For inkjet
Ink
Surface tension
(mN / m) Interface
Active agent
density
(weight%) Interface
Active agent
weight
Average
Molecular Weight Example 20 (20) (20) 99.9 g Byk-361N
0.1g 27.0 0.1 9500

"Byk-361 N" (Brand name, BIC Chemie Co., Ltd. product, polyacrylate type, acrylic surfactant, specific gravity 1.03 g / ml (20 degreeC), nonvolatile component> 98%, flash point 246 degreeC)

Non-aqueous
Inkjet ink
number
Formed
Poly
Imide
Membrane number For non-aqueous inkjet
Composition of ink Non-aqueous
For inkjet
Ink
Surface tension
(mN / m) Interface
Active agent
density
(weight%) Interface
Active agent
weight
Average
Molecular Weight Amic acid
Contains 1
doing
Solution (1) Surfactants
Example 21 (21) (21) 99.9 g R-08
0.1g 27.5 0.1 6900 Example 22 (22) (22) 99.9 g F-477
0.1g 27.3 0.1 11600 Example 23 (23) (23) 99.99 g F-479
0.01 g 27.7 0.01 13000 Example 24 (24) (24) 99.9 g TF-1366
0.1g 27.3 0.1 11400 Example 25 (25) (25) 99.9 g TF-1367
0.1g 26.9 0.1 12600 Example 26 (26) (26) 99.99 g TF-1425
0.01 g 27.1 0.01 9300 Example 27 (27) (27) 99.99 g FTX-208G
0.01 g 27.3 0.01 1040 Example 28 (28) (28) 99.99 g FTX-212P
0.01 g 27.3 0.01 1400 Example 29 (29) (29) 99.99 g FTX-218G
0.01 g 27.8 0.01 2100 Example 30 (30) (30) 99.9 g FTX-220P
0.1g 26.4 0.1 1900 Example 31 (31) (31) 99.99 g FTX-228P
0.01 g 27.8 0.01 2500 Example 32 (32) (32) 99.5 g FTX-240G
0.5g 25.9 0.5 4500 Example 33 (33) (33) 99.9 g Pgentant 710FL
0.1g 25 0.05 13000 Example 34 (34) (34) 99.9 g Pgentant730FM
0.1g 27.2 0.05 12500 Example 35 (35) (35) 99.99 g DFX-18
0.01 g 27.5 0.01 8000

"R-08" (trade name, manufactured by DIC Corporation, megapack series, perfluoroalkyl group, hydrophilic group, lipophilic group-containing oligomer, fluorine-based surfactant)

"F-477" (trade name, DIC Corporation make, megapack series, perfluoroalkyl group, hydrophilic group, lipophilic group-containing oligomer, fluorine-based surfactant)

"F-479" (trade name, DIC Corporation make, megapack series, perfluoroalkyl group, hydrophilic group, lipophilic group-containing oligomer, fluorine-based surfactant)

"TF-1366" (trade name, DIC Corporation make, megapack series, perfluoroalkyl group (C6). Hydrophilic group, lipophilic group-containing oligomer, fluorine-based surfactant)

"TF-1367" (trade name, DIC Corporation make, megapack series, perfluoroalkyl group (C6). Hydrophilic group, lipophilic group-containing oligomer, fluorine-based surfactant)

"TF-1425" (trade name, DIC Corporation make, megapack series, perfluoroalkyl group (C6). Hydrophilic group, lipophilic group-containing oligomer type, fluorine-based surfactant)

"FTX-208G" (trade name, manufactured by Neos, Pentgent Series, 3-terminal perfluoroalkyl group type, fluorine-based surfactant)

"FTX-212P" (brand name, Neos Co., Ltd., Pentgent series, fluorine-based surfactant)

"FTX-218G" (trade name, product made by Neos, Pentgent series, polyoxyethylene ether 3-terminal perfluoroalkyl group type, fluorine-based surfactant)

"FTX-220P" (brand name, Neos Co., Ltd., Pentgent series, fluorine-based surfactant)

"FTX-228P" (brand name, neos Co., Ltd., Pentgent series, fluorine-based surfactant)

"FTX-240G" (trade name, manufactured by Neos, Pentgent Series, 3-terminal perfluoroalkyl group type, fluorine-based surfactant)

"Phentgent 71OFL" (trade name, product made by NEOS, Ltd., Pentgent series, fluorine-containing monomer, hydrophilic group-containing monomer, fluorine-based surfactant, solid content 50% by weight)

"Phentgent 730FM" (trade name, manufactured by Neos, Pentgent series, fluorine-containing monomer, hydrophilic group-containing monomer, fluorine-based surfactant solid content 50% by weight)

"DFX-18" (brand name, neos Co., Ltd., Pentgent series, fluorine-based surfactant)

Non-aqueous
For inkjet
ink Poly
Imide membrane Epoxy ester
Amide membrane
Containing
solution Surfactants
density
(weight%) For non-aqueous inkjet
Ink
Surface tension
(mN / m) Comparative Example 4 (C4) (C4) (13)
100 g 0 29.8 Comparative Example 8 (C8) (C8) (12)
100 g 0 29.5

Claims (21)

Non-aqueous inkjet ink containing a surfactant (B),
A non-aqueous inkjet ink, wherein the concentration of the surfactant (B) is 0.00001% by weight or more and less than or equal to the critical micelle concentration. The method of claim 1,
The surfactant (B) is at least one surfactant selected from the group consisting of silicone surfactants, fluorine surfactants, silicone fluorine surfactants, acrylic surfactants, cationic surfactants, anionic surfactants and betaine surfactants. Ink for non-aqueous inkjet which is characterized by the above-mentioned. The method of claim 1,
The said surfactant (B) is 1 or more types of surfactant chosen from the group which consists of a silicone type surfactant, a fluorine type surfactant, and an acrylic type surfactant, The ink for non-aqueous inkjets. 4. The method according to any one of claims 1 to 3,
A non-aqueous inkjet ink, comprising at least one compound (A) selected from the group consisting of a compound capable of forming a polyimide and a polyimide. The method of claim 4, wherein
The ink for a non-aqueous ink jet, wherein the compound (A) is at least one compound selected from the group consisting of compounds represented by the following general formulas (1) to (6):

(In Formulas (1) to (6), each R independently represents a hydrogen atom or a group represented by the following Formula (a), and each R ′ independently represents an amino group (NH ₂ ) or the following Formula (b). Group represented by R ¹ , R ² , R ³ And R ⁴ are each independently an organic group having 2 to 500 carbon atoms, n is an integer of 0 to 1000, provided that when n is 0, R is a group represented by the following formula (a), and R 'is by the following formula (b) group and, R ¹ is of 100mol%, R ¹ having the silicon structure represented by the following formula (z) is less than ^{10 mol%, R 2 1OOmol%} , the following formula (z) of the represented by the R ² of the silicon structure represented is less than 10 mol%)

(In formula (z), R <^5> and R <^6> is respectively independently a hydrogen atom, a C1-C12 alkyl, a C3-C6 alkenyl, a C5-C8 cycloalkyl, a C6-C12 aryl, or Benzyl, R ⁷ is each independently methylene, phenylene or alkyl substituted phenylene, each x is an integer of 1 to 6 independently and y is an integer of 1 to 200). The method according to any one of claims 1 to 5,
A non-aqueous ink jet ink, comprising a solvent (C). The method of claim 6,
The solvent (C) is ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol methyl isopropyl ether, diethylene Glycol Methyl Butyl Ether, Diethylene Glycol Dibutyl Ether, Diethylene Glycol Monoethyl Ether Acetate, Ethylene Glycol Monobutyl Ether, Ethylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monomethyl Ether Acetate, 3-Methoxypropionate Methyl, 3-E Selected from the group consisting of ethyl oxypropionate, cyclohexanone, tetraglyme, triglyme, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone Non-aqueous inkjet ink, characterized in that at least one solvent. The method according to any one of claims 1 to 7,
A non-aqueous inkjet ink, further comprising a cyclic ether (D). The method of claim 8,
The cyclic ether (D) is N, N, N ', N-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N From, N ', N- tetraglycidyl-4,4'-diaminodiphenylmethane, 3-glycidoxypropyltrimethoxysilane, and the group consisting of a compound represented by following formula (7)-(16) Non-aqueous inkjet ink, characterized in that at least one compound selected:

(N is an integer of 0-10 in formula (10).)

(In Formula (15), R <^c> is a C2-C100 tetravalent organic group, R <^d> is respectively independently, a C1-C30 divalent organic group, R <^e> is each independently, and following formula (c ) Is a monovalent organic group selected from the group consisting of compounds represented by (e))

(In formula (c), R ^f is a hydrogen atom or alkyl having 1 to 3 carbons.)

(N is an integer of 2-4 in Formula (16).). The method according to any one of claims 1 to 9,
Non-aqueous inkjet ink, characterized by being thermosetting. The method according to any one of claims 1 to 9,
Non-aqueous inkjet ink, characterized in that it is photocurable. An ink coating method comprising the step of applying the ink for non-aqueous ink jet according to any one of claims 1 to 11 according to an ink jet coating method. The process of apply | coating the nonaqueous inkjet ink of Claim 4 or 5 on a board | substrate according to the inkjet coating method, and forming a coating film, and
Process of forming a polyimide film by heating the said coating film
Method of forming a polyimide film comprising a. A process of forming a coating film by apply | coating the ink for non-aqueous inkjet of Claim 4 or 5 in a pattern form on a board | substrate according to the inkjet coating method, And
A step of forming a patterned polyimide film by heating the coating film
Method of forming a polyimide film comprising a. It is obtained by the formation method of the polyimide membrane of Claim 13. The polyimide membrane characterized by the above-mentioned. It is obtained by the formation method of the polyimide membrane of Claim 14, The patterned polyimide membrane characterized by the above-mentioned. The polyimide membrane of Claim 15, or the patterned polyimide membrane of Claim 16 was provided, The film substrate characterized by the above-mentioned. The semiconductor wafer provided with the polyimide film of Claim 15, or the patterned polyimide film of Claim 16. The polyimide film of Claim 15, or the patterned polyimide film of Claim 16 was provided, The board | substrate for electronic materials characterized by the above-mentioned. The polyimide membrane of Claim 15 or the patterned polyimide membrane of Claim 16 was provided, The electronic component characterized by the above-mentioned. The film board | substrate of Claim 17, the semiconductor wafer of Claim 18, or the board | substrate for electronic materials of Claim 19 was provided. The electronic component characterized by the above-mentioned.

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