PHOTOSENSITIVE AMPHIPHILIC HIGH POLYMERS AND PROCESS FOR THEIR PRODUCTION

Abstract: A photosensitive amphiphilic high polymer comprises a linear recurring unit containing an at least divalent 1st organic group (R¹) having at least two carbon atoms and an at least divalent 2nd organic group (R²) having at least two carbon atoms, said organic groups R¹ and R² being connected to each other by a divalent linkage group formed by a reaction of an acid group (A) containing a hetero atom and a basic group (B) containing a hetero group; at least one hydrocarbon-containing group having 10 to 30 carbon atoms, which may have a substituent, being bonded to said recurring unit by a covalent bond or an ionic bond; and a dimerizable or polymerizable unsaturated bond or an orthonitrobenzyl group which may have a substituent, being contained in a part or the whole of said recurring units.

Description: This invention relates to a photosensitive amphiphilic high polymer and a process for producing the polymer. More particularly, the invention relates to a photosensitive amphiphilic high polymer which is modifed to enable the formation of a film by Langmuir-Blodgett technique (hereinafter referred to as LB method) and which contains structural units capable of being decomposed by the irradiation of ultraviolet rays, X-rays, electron beams, etc., and a process for producing such a polymer. In the 1930's, it was found by Langmuir and Blodgett that fatty acids having 16 to 22 carbon atoms can form a mono-molecular film on the surface of water and that the film can be built up on a base material. The investigation of the application of the built-up films however has started only recently. The investigations made heretofore are summaried in Kotai Butsuri (Solid Phisics) , (12), 45(1982), Thin Solid Films , 68 , No. 1 (180), ibid , 99 , Nos. 1, 2, and 3 (1983), G.L. Gains, Insoluble Monolayers at Liquid-Gas Interfaces (Interscience Publishers, New York, 1966), etc.. A Langmuir-Blodgett film (hereinafter referred to as LB film) obtained from a conventional straight chain saturated fatty acid has the disadvantage that it is inferior in heat resistance and mechanical strength and hence it cannot be used for practical purposes as it is. For overcoming the above problems, polymerizable polymer films formed by using unsaturated fatty acids such as ω-tricosenoic acid, ω-heptadecenoic acid, α-octadecylacrylic acid, etc., unsaturated esters of fatty acids such as vinyl stearate, octadecyl acrylate, etc., and diacetylene derivatives have been proposed. These films too are still insufficient in heat resistance and are not excellent in electric properties. It is known that some polymers having a hydrophilic group, such as polyacids, polyalcohols, ethyl acrylate, polypeptides, etc., have film-forming properties but these polymers have never been examined for their ability to become modified, in particular, as materials for LB film. Therefore these polymers cannot be used as excellent LB film materials. On the other hand, polyimides are known as heat-resistive films but the thickness of a film formed by spin coating cannot be reduced below 1,000 Å (1 Å = 10 nm) and is usually 1 µm or more. In other words, it is very difficult to form a heat-resistive thin film with a thickness of less than 1,000 Å having no pin holes by using such a polymer. Also, various photosensitive polyimides have been developed but it is also very difficult to obtained a thin film as described above by using such polyimides. Further prior art documents are discussed in the following: US-A-4 551 522 is directed to a process for the synthesis of photosensitive polyamic acid derivatives which are polyimide precursors. Subsequently, said polymer is photopolymerized. The moiety capable of polymerization is an ethylenically unsaturated group. WO-A-81/01855 relates to heat curable compositions comprising polyetherimides having terminal aliphatically unsaturated groups. JP-A-58-43449 describes polyamic acid derivatives having photopolymerizable or photodimerizable groups. US-A-4 239 880 provides polymers which are readily soluble and can also be processed from the melt, without this resulting in a deterioration in the properties of the polymers; i.e. by using new diamines corresponding to the following formula as polycondensation components for the manufacture of polyamide, polyamide-imide and polyimide polymers. US-A-4 022 732 provides a novel class of release agents for pressure-sensitive adhesive tapes. This object has been achieved by the finding of a novel class of polymeric release agents of pressure-sensitive adhesive tapes, the poly(amide acids) of which may be described by the following general recurring repeating unit: An object of this invention is, therefore, to enable the formation of a thin film by the LB method by modifying a high polymer which cannot be formed into a thin film by the LB method as it is. Another object of this invention is to provide a photosensitive amphiphilic high polymer capable of forming a thin polymer film having a thickness which is generally difficult to achieve, having improved mechanical properties such as heat resistance, chemical resistance, adhesive strength, etc., said thin polymer film being able to very easily form patterns. This object is achieved by incorporating therein a structure causing decomposition by the irradiation with light such as ultraviolet rays, etc., or X-rays, electron beams, etc. Still another object of this invention is to provide a process for producing the above-described photosensitive amphiphilic high polymer. That is, according to one embodiment of this invention, there is provided a photosensitive amphiphilic high polymer comprising a linear recurring unit containing a) an at least divalent 1st organic group (R¹) having at least two carbon atoms and an at least divalent 2nd organic group (R²) having at least two carbon atoms, said organic groups R¹ and R² being connected to each other by a divalent linkage group formed by the reaction of an acid group (A) containing a hetero atom and a basic group (B) containing a hetero atom; b) least one hydrocarbon-containing group having 10 to 30 carbon atoms, which may have a substituent, being bonded to said recurring unit by a covalent bond or an ionic bond ; and c) an orthonitrobenzyl group which may have a substituent, being contained in a part or the whole of said recurring units. According to another embodiment of this invention, there is provided a process for producing a photosensitive amphiphilic high polymer, which comprises polymerizing a monomer containing an at least divalent 1st organic group (R¹) having at least two carbon atoms and a monomer containing an at least divalent 2nd organic group (R²) having at least two carbon atoms in a combination of any one of those shown below ; A ( R¹ ) A + B ( R² ) B A ( R¹ ) B + A ( R² ) B B ( R¹ ) B + A ( R² ) A (wherein, A represents an acid group containing a hetero atom, B represents a basic group containing a hetero atom, and when R¹ and R² are trivalent or more, further groups A and/or B are attached according to the valence number), at least one of the two kinds of monomers in the above combination containing at least one hydrocarbon-containing group having 12 to 30 carbon atoms, which may have a substituent, and a part or the whole of at least one of the monomer containing the 1st organic group R¹ and the monomer containing the 2nd organic group R² having an orthonitrobenzyl group, which may have a substituent. The invention is now explained in detail. The high polymer of this invention is a polymer or copolymer composed of ( A - R¹ - AB - R² - B ) (101) ( A - R¹ - BA - R² - B ) (102) ( B - R¹ - BA - R² - A ) (103) as linear recurring units, which form the basic skeleton. In the above formulae, AB and BA are a divalent linking group formed by the reaction of an acid group A and a basic group B each containing a hetero atom such as O, N, S, P, B. More specifically, AB and BA are a group formed by the reaction of an acid group such as -COOR (wherein, R represents an alkyl group or a hydrogen atom), -COX (wherein, X represents a chlorine atom or a bromine atom ), -NCO, -NCS, -CONHR, -SO NHR, etc., and a basic group such as -NHR, -OR, -SR, -X, etc. Specific examples of AB are and specific examples of BA are In formulae (101) to (103) described above, R¹ is an at least divalent 1st organic group having at least two carbon atoms and R² is an at least divalent 2nd organic group having at least two carbon atoms. When R¹ and R³ are trivalent or more, further groups A and/or B, which do not take part in the formation of the linear recurring unit, are bonded thereto according to the valence number. Now , R¹ and R² are explained in detail. R¹ and R² are at least divalent groups having at least two, and preferably 5 to 20 carbon atoms. They may represent an aliphatic group, an alicyclic group, an aromatic group, a group composed of a combination of the aforesaid groups, or the abovedescribed groups substituted by a monovalent group having 1 to 30 carbon atoms (said monovalent group may further be substituted by a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group, etc.) selected from an aliphatic group, an alicyclic group, or an aromatic group (these groups may be combined with each other) or such groups containing -O-, -COO-, -NHCO-, -CO-, -S-, -CSS-, -NHCS-, -CS-. However, the case that R¹ and R² are a group characterized by a benzenoid structure having at least 6 carbon atoms is preferred in terms of heat resistance, chemical resistance, mechanical properties, etc. The term "benzenoid unsaturated structure" in this invention is used in contrast with a quinoid structure in relation to the structure of a carbocyclic compound and is the structure of the carbon ring contained in an ordinary aromatic compound. There is no particular restriction on the valence number of R¹ and R² but it is particularly preferred that R¹ and R² are divalent, trivalent or tetravalent and also at least one of them is trivalent or tetravalent. Specific examples of such preferred R¹ and R² are as follows. Example of tetravalent residues: [wherein R¹⁰ represents -(CH₂) n - (wherein n is 1 to 3), (wherein R¹¹ represents an alkyl group or an aryl group)], Examples of trivalent residues: wherein R¹⁰ is as defined above. Examples of divalent residues: (wherein R¹⁰ is as defined above), There is no particular restriction on the position of the bonds corresponding to the valence number of R¹ and R², that is the bonds for forming the linear recurring unit and other bonds to the acid group A and/or the basic group B which are not used to form recurring units. The case that two of the four bonds when R¹ and/or R² is tetravalent, and two of the three bonds when R¹ and/or R² is trivalent exist at two adjacent carbon atoms constituting R¹ and/or R² is advantageous for improving the heat resistance, mechanical properties, chemical resistance, etc., by causing cyclization by heating, chemical curing, etc., after forming the film to obtain a 5-membered ring or 6-membered ring. Hence, this case is particularly preferred. Specific examples of such preferred tetravalent or trivalent residues R¹ and R² are illustrated below although the invention is not limited to them. Then, the modification enabling the high polymer having the recurring unit shown by formula (101) to (103) described above to form a thin film by the LB method is explained. Such a modification is attained by introducing at least one, and preferably two hydrocarbon-containing groups R x having 10 to 30, and preferably 16 to 22 carbon atoms, which group may have a substituent, (hereinafter, the group is referred to as hydrophobicity imparting group) into the recurring unit shown by formula (101) to (103) by a covalent bond or an ionic bond to render the high polymer hydrophobic. For realizing the aforesaid modification, there are following 4 methods. [I] A method of bonding R x to an atom contained in the group AB or BA in the linear recurring unit shown by formula (101) to (103) as a substituent. [II] A method of directly bonding R x to R¹ and/or R² as substituent(s). [III] A method of bonding R x to R¹ and/or R² in the linear recurring unit as substituent(s) through other residues A and/or B than the residues A and/or B used for forming the linear recurring unit containing R¹ and R². [IV] A method of bonding R x to R¹ and/or R² in the linear recurring unit as substituent(s) through other residues A and/or B than the residues A and/or B used for forming the linear recurring unit containing R¹ and R² by an ionic bond. As a matter of course, methods [I], [II], [III], and [IV] may be employed in any desired combination thereof. Also when two or more groups R x exist, said R x may be the same or different. Methods [I], [II], [III], and [IV] are practically illustrated below. Method [I] In method [I], the hydrogen atom on the nitrogen atom of AB or BA is substituted for R x as shown in the above table. Method [II] is a process of directly bonding R x to R¹ and/ R² as substituent(s) and specific examples thereof are as follows. In method [III], at least one at least trivalent organic group is used as R¹ and/or R² and R x is bonded to such R¹ and/or R² as substituent(s) through other residues A and/or B than the residues A and/or B used for forming the linear recurring unit containing R¹ and R². For example, in each of the following recurring units R x may be bonded to R¹ and/or R² as substituent(s) through the residues A and/B which are not used for making the linear recurring unit. For example, in the case of bonding through such A, R x is bonded to R¹ or R² as -COOR x , -CONHR x , -NHCOOR x , -NHCSOR x . and in the case of bonding through such B, R x is bonded as -NHR x , -OR x , -SR x . In method [IV], R x is bonded through residues A and/or B which are not used for making the linear recurring unit as in method [III] in such a manner that R x bonded to B is bonded to A and R x bonded to A is bonded to A by an ionic bond. For example, if A is -COOH, R x may be bonded by the following ionic bond wherein, R³¹, R³², and R³³ each represents a hydrocarbon-containing group having 1 to 30 carbon atoms, which may have a substituent, or a hydrogen atom, at least one of said R³¹, R³², and R³³ being R x ). On the other hand, if B is -NH₂, -NHR⁹¹, or R x may be bonded by the following ionic bond wherein, R⁹¹ and R⁹² each represents a hydrocarbon-containing group having 1 to 30 carbon atoms, which may have a substituent, or a hydrogen atom, and is preferably a hydrocarbon-containing group having 1 to 4 carbon atoms or a hydrogen atom. In the case of improving heat resistance, etc., by performing a cyclization reaction by means such as heating, chemical curing, etc., after forming the film, R x bonded by another method than method [II] is removed during the cyclization reaction. On the other hand, R x bonded by method [II], that is, R x directly bonded to R¹ or R² is not released in the cyclization reaction and remains in the LB film. Since the existence of R x is disadvantageous for heat resistance, etc., the employment of method [I], [III], or [IV] is preferred from the view point of heat resistance, etc. Now , the hydrophobicity imparting group R x is practically explained. R x is a hydrocarbon-containing group having 10 to 30, and preferably 16 to 22 carbon atoms and preferred examples thereof are a monovalent group selected from aliphatic groups, alicyclic group, aromatic groups, groups formed by bonding the aforesaid groups to each other, and substituted derivatives of these groups. Specific examples are illustrated as follows; wherein n is 12 to 20, and preferably 16 to 22. A straight chain aliphatic hydrocarbon group is a particularly preferred example. Examples of the substituent for the aforesaid groups are a halogen atom, a nitro group, an amino group, a cyan group, a methoxy group, an acetoxy group, although they are not indispensible. However, it is preferred to use a fluorine atom as the substituent since the fluorine atom improves the hydrophobicity more than a hydrogen atom. In other words, by the incorporation of a fluorine atom, the length of the alkyl chain can be reduced. For example, it is generally necessary that the carbon atom number is at least 12 but in C₈F₁₇(CH₂) k , it is sufficient that k is 2, that is, a carbon number of 10 enables the film forming. Furthermore, for imparting photosensitivity to the high polymer of this invention, at least a part, i.e., at least 5%, and preferably at least 30% of the recurring units contain a structural unit capable of being decomposed by the irradiation of light such as ultraviolet rays, etc., X-rays, electron beams. When the recurring unit contains a structural unit capable of being decomposed, the high polymer becomes a positive type photosensitive compound. Now the positive type photosensitive compound is explained. In the positive type photosensitive compound of this invention, at least 5%, and preferably at least 30% of the recurring units contain at least one group having a structural unit capable of being dosed by the irradiation of light such as ultraviolet rays, etc., X-rays, electron beams, according to the invention an orthonitrobenzyl group, which may have a substituent, (hereinafter, the group is referred to as positive type photosensitive group) in the recurring unit. By using the above-described hydrophobicity imparting group as the substituent for the orthonitrobenzyl group, the positive type photosensitive group can be provided with hydrophobicity and decomposability (hereinafer, the group is referred to as hydrophobic positive type photosensitive group). Such a positive type photosensitive group can be introduced into the recurring unit by selecting a compound having a recurring unit containing at least one carboxy group and substituting the hydrogen atom of the carboxy group for the positive type photosensitive group. There is no particular restriction with respect to the molecular weight of the high polymer of this invention. A thin film can be formed by the LB method even if the molecular weight of the high polymer is low. However, good heat resistance, mechanical strength and chemical resistance cannot be obtained if the molecular weight is low. On the other hand, if the molecular weight is too large, the viscosity becomes too high to form the desired thin film. Accordingly, the number average molecular weight is preferably from about 2,000 to about 300,000, and more preferably from about 10,000 to about 150,000. Specific examples of the preferred photosensitive amphiphilic high polymer of this invention are polyamic acids (and the esters or salts thereof) in which the polymer or copolymer have the recurring units represented by the following formulae (1), (2), (3), or (4) (wherein R¹ represents the aforesaid trivalent or tetravalent group having at least two carbon atoms; R² represents a divalent, trivalent, or tetravalent group having at least two carbon atoms; when R² is trivalent, X is bonded to R² and when R² is tetravalent, X and Y are bonded to R²; X and Y each represents an acid group A containing a hetero atom, which group may have a substituent, or a basic group B containing a hetero atom, which group may have a substituent, and R³, R⁴, R⁵, R⁶, R³¹, R³², R³³, R⁴¹, R⁴², and R⁴³ each represents a hydrocarbon group having 1 to 30 carbon atoms, which group may have a substituent, or a hydrogen atom), wherein at least one, and preferably two of said R³, R⁴, R⁵, R⁶, R³¹, R³², R³³, R⁴¹, R⁴², and R⁴³ are the abovedesribed hydrophobicity imparting group R x having 10 to 30 carbon atoms, and preferably 16 to 22 carbon atoms and at least 5%, and preferably at least 30% of the recurring units contain the positive type photosensitive group in the recurring unit. R¹ and R² in formulae (1), (2), (3), and (4) described above are as described above but it is particularly preferred that at least one of R¹ and R² is a group having a benzenoid structure having at least 6 carbon atoms. Furthermore, it is particularly preferred that when R¹ and/or R² is tetravalent, each two bonds of four bonds bonded to R¹ and/or R² exist in two adjacent carbon atoms constituting R¹ and/or R² to form a precursor of a 5-membered ring or 6-membered ring structure, and when R¹ and/or R² is trivalent, each two bonds of three bonds bonded to R¹ and/or R² exist in two adjacent two carbon atoms to form a precursor of a 5-membered ring or 6-membered ring structure. R³, R⁴, R⁵, R⁶, R³¹, R³², R³³, R⁴¹ , R⁴², and R⁴³ each is a hydrogen atom or a group having 1 to 30, and preferably 1 to 22 carbon atoms, which may be an aliphatic group, an aromatic group, a group formed by the combination of the aforesaid groups, the aforesaid groups being substituted by a monovalent group having 1 to 30 carbon atoms such as an aliphatic group, an alicyclic group, and an aromatic group (they may be combined with each other) (said monovalent group may be substituted by a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group), or a group containing -O-, -COO-, -NHCO-, -CO-, -S-, -CSS-, -NHCS-, -CS-. It is necessary that at least one, and preferably two of R³, R⁴, R⁵, R⁶, R³¹, R³², R³³, R⁴¹, R⁴², and R⁴³ are the above-described hydrophobicity imparting group R x . The amphiphilic photosensitive high polymer of this invention is now explained more practically. Then, the positive type amphiphilic high polymer having the recurring unit shown by formula (1), (2), (3), or (4) described above is explained. Such a positive type photosensitive amphiphilic high polymer is generally obtained by introducing the above-described positive type photosensitive group into a part or the whole of recurring units of the amphiphilic polymer having the recurring unit shown by formula (1), (2), (3) or (4), but it is preferred that a part or the whole of the recurring units of polyamic acid or the ester thereof shown by formula (1) or (2) is a recurring unit shown by following (12), (12'), or (13), wherein R³ and/or R⁴ in formula (1) or (2) is an orthonitrobenzyl group which may have a substituent; wherein R¹, R², R³, R⁴, R⁵, X and Y are as defined in formula (3) described above and R⁷¹ and R⁷² have the same significance as defined on R³, R⁴, R⁵, and R⁶, since in this case the production is easy and the cost is low. Then, the recurring units shown by formula (12), (12'), and (13) are explained more practically. R¹ and R² are as described above and it is preferred that at least one of R¹ and R² is a group having a benzenoid structure and has a precursor structure such that the position of the bond is at the position capable of forming a 5-membered ring or a 6-membered ring. It is preferred that at least one, and preferably two of R⁷¹, R⁷², R³, R⁵, and R⁶ are the above-described hydrophobicity imparting group R x but the hydrophobicity imparting group may be bonded to R² directly or through X or Y bonded to R². Furthermore, the case that said R⁷¹ and R⁷², said R⁷¹ and R³, or said R⁵ and R⁶ are all hydrogen atoms is particularly preferred since in this case, the production is easy and the cost is low. In particular, in the above-described preferred precursors shown by formula (12), the polyimide precursors shown by following formula (12A), wherein R² is divalent; wherein R¹, R², R⁵, R⁶, R⁷¹, and R⁷² are same as those in formula (12) are recurring units giving typical polyamic acid esters of this invention. Specific examples of the recurring units giving such positive type photosensitive polyimide precursors are as follows: wherein R⁷¹ and R⁷² are the above-described hydrophobicity imparting group R x . wherein R⁵ and R⁶ are the above-described hydrophobicity imparting group R x . wherein R⁷¹ and R⁴ are the above-described hydrophobicity imparting group R x . wherein R³ is the above-described hydrophobicity imparting group R x . wherein R⁵ and R⁶ are the above-described hydrophobicity imparting group R x . wherein R⁷¹ and R⁷² are an alkyl group having 1 to 6 carbon atoms, and R⁸¹ and R⁸² are the above-described hydrophobicity imparting group R x . Furthermore, preferred specific examples of the recurring unit shown by formula (13) described above are those shown by the following formula; wherein R⁸¹ and R⁸² are the above-described hydrophobicity imparting group R x . In the formulae (33) to (39) described above, the symbol → shows isomerizm. For example, the following formula This invention includes the case that (a) or (b) exists alone and the case that both (a) and (b) exist together. In the photosensitive amphiphilic polymers described above, when only a part of the recurring units contains the positive type photosensitive group, the polymer becomes a copolymer of recurring units containing the positive type photosensitive group and recurring units containing no such photosensitive group. But, there are various copolymers in addition to the aforesaid copolymer. For example specific examples of the copolymer composed of the recurring units shown by formula (1), wherein R¹ differs in each recurring unit is as follows. Furthermore, specific examples of the copolymer composed of the recurring units shown by formula (1), wherein R² differs in each recurring unit is as follows. In the above formulae (41) to (43), R¹, R², R³, R⁵ and R⁶ are as defined in formula (1) described above and x' and y' represent ratios as 0<x'<1, 0<y'<1, and x' + y' = 1. Also, copolymers of the recurring units shown by formula (1), wherein R³, R⁴, R⁵, or R⁶ differs in each recurring unit can be, as a matter of course, formed. Such copolymers can also be formed from the units shown in the formulae (2), (3) and (4). Also copolymers comprising recurring units of the above formulae (1), (2), (3), and (4) combined with each other and also copolymers comprising recurring units of the above formulae and other recurring units than those shown by the above formulae can be formed. In addition, if the total number of the recurring units containing no hydrophobicity imparting group R x is in the range of 30% or less, the copolymer may contain such a recurring unit. Examples of such a copolymer are as follows. wherein, R x is the above-described hydrophobicity imparting group, R represents an alkyl group having 1 to 11 carbon atoms or a hydrogen atom, and x' and y' are ratios, as 0<y'≦0.3, 0.7≦x'<1, and x' + y' = 1. Now, the production process for the photosensitive amphiphilic high polymer of this invention is explained. The photosensitive amphiphilic high polymer of this invention is produced by polymerizing or copolymerizing a monomer having a 1st organic group R¹ and a 2nd organic group R² in any combination of A ( R₁ ) A + B ( R₂ ) B , A ( R¹ ) B + A ( R² ) B, and B ( R¹ ) B + A ( R² ) A (wherein, A represents an acid group containing a hetero atom, B represents a basic group containing a hetero atom, and when R¹ and R² are trivalent or tetravalent, further group A and/or B are attached thereto according to the valence number thereof, for example, at least one of the two kinds of the monomers in said combination containing at least one, preferably two abovedescribed hydrophobic imparting groups R x s , using a monomer containing the above-described positive type photosensitive group in a part or the whole of the monomer containing R¹ and/or R². In another process, after producing a high polymer by polymerizing or copolymerizing a monomer containing the aforesaid 1st organic group R¹ and a monomer containing the 2nd organic group R² each containing neither the hydrophobicity imparting group R x nor the photosensitive gorup, the hydrophobicity imparting group R x and the photosensitive group can be introduced into the polymer. However, it is not so convenient to introduce these groups into the high polymer by forming a covalent bond in a chemical reaction. In addition, the process of introducing these hydrophobicity imparting groups and photosensitive groups in the form of salts as shown in formula (3) or (4) is preferable. Now, the production process of the photosensitive amphiphilic high polymer of this invention having the recurring units shown by formula (1), (2), (3) or (4) is explained. For producing the photosensitive amphiphilic high polymer of this invention having the recurring units shown by formula (1) described above, first, a tetracarboxylic acid dianhydride shown by formula (5) wherein R¹ is same as defined above is caused to react with R³OH and R⁴OH (wherein, R³ and R⁴ are same as defined above) to provide a compound shown by formula (6) wherein R¹, R³, and R⁴ are same as defined above. Then the compound of formula (6) is caused to react with thionyl chloride, phosphorus pentachloride, benzenesulfonyl chloride, etc., in a substantially anhydrous polar organic solvent at a temperature of from -10°C to 50°C, and preferably from about 0°C to 40°C to provide an acid halide, and further the acid halide is caused to react with a diamine shown by formula (7A) R⁵-NH-R²-NH-R⁶ (7A) wherein, R², R⁵, and R⁶ are same as defined above as a monomer containing the 1st organic group R¹. (In addition, the explanation is on the case that R² is divalent but the case that R² is trivalent or tetravalent is almost the same.) Specific examples of the compound shown by formula (5) described above are as follows. Also, specific examples of R³OH and R⁴OH are as follows: CH₃OH, CH₃CH₂OH, CH₃(CH₂) ₂OH, CH₃(CH₂) ₃OH, CH₃(CH₂) ₅ OH, CH₃(CH₂) ₇ OH, CH₃(CH₂) ₉ OH, CH₃(CH₂) ₁₁ OH, CH₃(CH₂) ₁₃ OH, CH₃(CH₂) ₁₅ OH, CH₃(CH₂) ₁₇ OH, CH₃(CH₂) ₁₉ OH, CH₃(CH₂) ₂₁ OH, CH₃(CH₂) ₂₃ OH, CF₃(CH₂) ₁₅ OH, H(CF₂)₂ (CH₂) ₁₅ OH, H (CF₂) ₄ (CH₂) ₁₃ OH, F(CF₂)₈ (CH₂) ₂OH, F(CF₂)₈ (CH₂)₄ OH. Also, specific examples of R³OH and R⁴OH in cases where R³ and R⁴ form the above-described positive type photosensitive group are as follows. wherein, specific examples of R⁷ are CH₃-, CH₃CH₃-, CH₃(CH₂)₂, CH₃(CH₂)₃, CH₃(CH₂)₅, CH₃(CH₂)₇, CH₃(CH₂)₉, CH₃(CH₂)₁₁, CH₃(CH₂)₁₃, CH₃(CH₂)₁₅, CH₃(CH₂)₁₇, CH₃(CH₂)₁₉, CH₃(CH₂)₂₁, CH₃(CH₂)₂₃, CF₃(CH₂)₁₅, H(CF₂)₂(CH₂)₁₅, H(CF₂)₄(CH₂) ₁₃-, F(CF₂)₈(CH₂)₂-, F(CF₂)₈(CH₂)₄-, There is no particular restriction in the reaction conditions of the production of the compound shown by formula (6) described above from the tetracarboxylic acid dihydride shown by formula (5) and R³OH or R⁴OH. For example, the compound is obtained by stirring the reactants for several hours at about 100°C under a nitrogen gas stream and also the general condition that the system is stirred for about 4 days at room temperature in a solvent such as hexamethylphosphoramide can be used. It is, however, preferred from the point of shortening the reaction time, i.e., the improvement of productivity to perform the aforesaid reaction by heating the reactants to about 100°C with stirring for 3 hours under a nitrogen gas stream, dissolving the reaction product in hexamethylphorphoramide after cooling, and then forming the acid halide. Specific examples of the polar solvent in the case of forming the acid halide are hexamethylphosphoramide, N,N-dimethylacetamide, dimethylformamide, and the reaction for forming the acid halide is performed in a state that the solvent is substantially anhydrous, i. e., in the state that thionyl chloride, phosphoric pentachloride, benzenesulfonyl chloride, used at the formation of the acid halide is not decomposed to provide the acid halide almost quantitatively. If the temperature in the formation of the acid halide is lower than -10°C, the reaction system becomes an unpreferably heterogeneous system caused by freezing to solidification by the influence of the long chain alkyl group. However, it has been clarified that if the temperature is higher than -10°C, any temperature upto about the boiling point of the acid halide can be employed without any particualr restriction. Usually, the temperature of from about 0°C to 40°C is preferred. The acid halide thus produced is further caused to react with a diamine shown by formula (7A) described above to provide the amphiphilic high polymer having the recurring unit shown by formula (1) described above. It is preferred from workability, etc., that the acid halide is used as it is after the production thereof. Specific examples of the compound shown by formula (7A) described above are as follows. (In the above formulae, R¹⁰ is as defined above and R⁵ and R⁶ are same as those described above as the specific examples of R⁷.) In the case of reacting the above-described acid halide and the diamine shown by formula (7A), the diamine shown by formula (7A) may be added to the acid halide or the acid halide may be added to the diamine shown by formula (7A) but since the reactants and the reaction products tend to be frozen to solidification by R³, R⁴, R⁵, R⁶, etc., existing in these compounds, it is generally preferred to use a solvent such as N,N-dimethylacetamide, N,N-dimethylformamide. The reaction temperature is from -10°C to 20°C, and preferably from 0°C to 10°C. If the reaction temperature is lower than -10°C, the reaction system becomes heterogeneous and if the temperature is over 20°C, it is considered that undesirable reactions are liable to occur and such high temperature is undesirable. However, it has been clarified that it is preferred for performing the reaction in a homogeneous system until the completion of the reaction to perform the reaction after addition of the reactant at a temperature of higher than 20°C. Also, as the case may be, it is sometimes preferred to use another reaction temperature than those generally explained above. That is, when R⁵ and R⁶ are the aforesaid group having 12 to 20 carbon atoms, i.e., the above-described hydrophobicity imparting group R x , a process of adding the acid halide to a solution of the diamine shown by formula (7A) kept at 50°C to 60°C is employed for reacting the diamine in a homogeneous system. The ratio of the aforesaid acid halide and the diamine shown by formula (7A) may be properly selected for obtaining a desired molecular weight of the photosensitive amphiphilic high polymer of this invention but in the case of producing the polyamic acid for film forming, stoichiometric amounts of purified monomers and and a purified solvent are usually used for obtaining the product having high molecular weight. However, it has been confirmed that in the case of depositing the thin films of the photosensitive amphiphilic high polymer of this invention by the LB method on a substrate a high molecular weight is not always necessary to obtain sufficient characteristics of the films and hence the ratio employed may deviate from the stoichiometeric ratio. For example, it has been clarified that the monomer ratio of from about 1/0.8 to 1/1.2 can be employed without giving any problems. The case that R⁵ and R⁶ of the compound shown by formula (7A) are all hydrogen atoms is preferred since the reactivity thereof is good and the raw material cost is low. Also, in this case, since the carboxylic acid of the amphiphilic high polymer obtained is in an ester, the polymer is thermally stable, the product can be separated as a solid powder since the reaction does not proceed by the operation of isolation and drying, and also the product can be easily purified by the above procedure. The polyamic acid ester of this invention having the recurring unit shown by formula (1) described above is generally produced by the process as described above but when the recurring unit of formula (1) is shown by by formula (14A), wherein R³ and R⁴ are hydrogen atom, the polyamic acid ester is obtained by directly reacting the tetracarboxylic acid dihydride shown by formula (5) and the diamine shown by formula (7A) containing the above-described hydrophobicity imparting group R x and the photosensitive group without employing the process as described above. The reaction conditions in this case are the same as those in the reaction of the above-described acid halide and the diamine of formula (7), wherein R⁵ and R⁶ are all the hydrophobicity imparting group R x . The photosensitive amphiphilic high polymer of this invention having the recurring unit shown by formula (14A) thus obtained has the features that the polymer can be easily produced as well as a film can be formed by the LB method using the polymer, and the polymer gives a polyimide by heating. Then, the photosensitive amphiphilic high polymer of this invention having the recurring unit shown by formula (2) described above is obtained by using a tricarboxylic acid anhydride shown by formula (10) wherein R¹ is same as defined above in place of the tetracarboxylic acid dianhydride shown by formula (5) in the above-described production of the polyamic acid and the ester thereof having the recurring unit shown by formula (1). That is, by reacting R³OH (wherein, R³ is same as defined above) with the tricarboxylic acid anhydride shown by formula (10), a compound of formula (11) wherein R³ is same as defined above is obtained in place of the compound shown by formula (6). The compound is converted into an acid halide as in the case of the compound shown by formula (6) as described above and the acid halide is caused to react with the diamine shown by formula (7) to provide a polyamic acid ester of this invention having the recurring acid unit shown by formula (2). Also, the polyamic acid of this invention having the recurring unit shown by formula (15A) (i.e., formula (2), wherein R³ is hydrogen atom) is similarly obtained by the direct reaction of the acid halide of tricarboxylic acid anhydride shown by formula (10) and the diamine shown by formula (7A), containing the above-described hydrophobicity imparting group R x and the photosensitive group. The reaction conditions for the production of the polyamic acid or the ester thereof having the recurring unit shown by formula (2) are the same as the above-described case of producing the polyamic acid or the ester thereof having the recurring unit shown by formula (1). Specific examples of the compound shown by formula (10) are as follows: The photosensitive high polymer of this invention thus prepared is easily soluble in an organic polar solvent such as N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, hexamethylphosphoramide, etc., soluble in a mixed solvent of the aforesaid organic polar solvent and an ordinary organic solvent such as chloroform, and sparlingly soluble or insoluble in benzene, ether, chloroform, acetone, methanol. Also, in infrared spectral analysis, there are characteristic absorptions of a divalent linkage group -AB- formed by the reaction of the aforesaid acid group A containing a hetero atom and the basic group B containing a hetero atom, the acid group A and/or the basic group B(e.g., an amide in the aforesaid polyimide precursor shown by (1A), (3A), (12A), or (14A), a carboxylic acid (carboxylic acid ester as the case may be), and long chain alkyl group. There are also characteristic absorptions of a nitro group. Also, in the case of the polyamic acid or the ester thereof having a precursor structure capable of becoming a 5-membered or 6-membered ring having a hetero atom as the above-described polyimide precursor, the thermal analysis result shows a feature, that is, an abrupt reduction of weight begins at about 200°C and it is completed at about 400°C. After the completion of the reduction of weight, in the case of, for example, the polyimide precursor, the absorptions of amide, carboxylic acid ester, nitro group, and long chain alkyl vanish and the absorption of imide ring appear, which shows thermally proceeding of ring closing reaction. On the other hand, in the case that the precursor is a polyamic acid salt, the ring closing reaction does not generally proceed thermally, but the ring closing reaction is completed by immersing in a ring closing reagent such as glacial acetic acid, pyridine. After the completion of the ring closing reaction, in the case of, for example, the polyimide precursor, the absorptions of amide, carboxylate, and long chain alkyl group vanish and the absorption of imide ring appears. Now, the production of an LB film using the high polymer of this invention is explained. As a method for forming an LB film, there is a vertical dipping method wherein a film forming material is spread onto the surface of water, the material spread on the surface of water is compressed at a constant surface pressure to form a monomolecular film, and the film is transferred onto a substrate by moving the substrate upward and downward through the film. Also, there are the horizontal dipping method, the revolving cylindrical method, etc., Shin Jikken Kagaku Koza (New Experimental Chemistry Course ), Vol. 18, "Kaimen to Colloid (Intercirface and Colloid)", pages 498-508). That is, any method ordinarily performed can be used without any restriction. The LB method is a method capable of forming an oriented film and controlling the thickness with an accuracy of some tens Å, that is, an excellent method of forming a thin film of less than 2000 Å, or further less than 1000 Å as well as several hundreds Å or several tens Å. However, also a film having a thickness of 10,000Å or more can be formed by the method. In the case of spreading a LB film forming material on the surface of water, a solvent which is not dissolved in water and evaporates into the gaseous phase, such as benzene, chloroform, is generally used but in the case of the photosensitive amphiphilic high polymer of this invention, it is preferred to use the solvent together with an organic polar solvent for increasing the solubility. Examples of such an organic polar solvent are N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylsulfone, dimethyltetramethylenesulfone. In the case of using the organic polar solvent with benzene, chloroform, it is considered that when the high polymer is spread on the surface of water using the mixed solvent, benzene, chloroform, etc., evaporates into gaseous phase and the organic polar solvent dissolves in a large amount of water. There is no particular restriction with respect to the concentration of the solution used for spreading the precursor of this invention onto the surface of water but the concentration is usually from 2 x 10⁻³M to 5 x 10⁻³M. For obtaining good film-forming property, the addition of metal ions and the pH control are not always necessary, but the exclusion of metal ions is considered to be advantageous in the case of using the films in the field of electronics. There is no particular restriction with respect to the substrate for forming thereon an LB film using the photosensitive amphiphilic high polymer of this invention and the material may be properly selected according to the use of the LB film formed. In the case of using the LB film by cyclizing the LB film into a film of polyimide, etc. by heating or chemical curing, the substrate is required to have good heat resistance and chemical resistance. Specific examples of the substrate are inorganic substrates such as glass, alumina, quarts, etc., metallic or plastic base plates, substrates of semiconductors of groups IV, III-V, II-VI, etc., such as Si, GaAs, ZnS, substrates of ferroelectric materials such as PbTiO₃, BaTiO₃, LiNbO₃, LiTaO₃, etc., and those made of magnetic materials. As a matter of course, a thin metal film formed on a substrate as described above may be patterned suitable for application and also semiconductors or ferroelectric substrate, such as Si, GaAs, ZnS, may be previously processed to form an element. Also, as a matter of course, the substrate may be subjected to a surface treatment as usually applied before use. The photosensitive amphiphilic high polymer of this invention has generally a tendency of showing weak adhesion strength for the surface of glass, quartz, Si, SiO₂. Thus, by treating the surface of such a substrate with a silane coupling agent, in particular a silane coupling agent having an epoxy group and an alkoxy group (e.g., A-1100, A-187, trade name, made by Union Carbide Corporation) or treating the surface thereof with a chelating agent containing aluminum to form an aluminum oxide layer thereon, the film-forming property and the adhesive strength are improved, which is a preferred embodiment of this invention. As a matter of course, the substrate may be treated in several layers with a metal salt of a fatty acid. Also, when a mixture of the photosensitive amphiphilic high polymer of this invention and a known film-forming compound is used in the case of depositing the high polymer of this invention on a base plate, the film-forming property is improved, which is a preferred embodiment of this invention. The aforesaid known LB film-forming compounds are compounds described in the literature cited hereinbefore and known in the field of art. The compounds composed of a hydrocarbon group having from about 16 to 22 carbon atoms and a hydrophilic group shown by the following formula are particularly preferred: CH₂(CH₂) n-1 Z. In the above formula, n represents 16 to 22, and Z represents OH, NH₂, NHR', NR'R', COOH, CONH₂, CONHR', CONR'R', or COOR' (wherein R' represents a lower aliphatic hydrocarbon group). The compound shown by the formula CH₃(CH₂) n-1 Z is excellent in the point of cost. There is no particuar restriction on the mixing ratio of the aforesaid compound described above and the high polymer of this invention. Also, two or more compounds selected from the above-described polyimide precursors and/or copolymers can be used for film-forming. Also, in this invention, it is preferred to use a sensitizer as described below and the long chain hydrocarbon-substututed product thereof. Examples of the preferred sensitizer are anthraquinone, benzoquinone, naphthoquinone, benzoanthraquinone, benzophenone, which are known as sensitizers in the field of art and long chain hydrocarbon-substituted products of such sensitizers so modified as to be suitable for the LB film. By using the photosensitive amphiphilic high polymer of this invention, an LB film having less defects can be formed on a substrate by the LB method and the LB film can be patterned by an ordinary fine patterning technique. That is, a relief pattern can be obtained by irradiating the LB film with ultraviolet rays, visible rays, electron beams, X-rays, through a photomask and dissolving of the exposed portions in the case of a positive type photosensitive polymer with a developer. When the positive type photosensitive amphiphilic high polymer of this invention having an orthonitrobenzyl group as explained practically hereinbefore is irradiated by light such as ultraviolet rays, etc., electron beams, X-rays, etc., the orthonitrobenzyl ester is decomposed to form a polyamic acid. For example; Since the polyamic acid formed by the decomposition of the precursor of this invention by the irradiation of ultraviolet rays, etc., is soluble in an aqueous alkali solution, a solution mainly composed of an aqueous alkali solution can be used as the developer in the case of pattern formation. A solution for washing a relief pattern formed by development and removing a developing solvent is preferably a liquid compatible with a developing solution such as water, methanol, ethanol, isopropanol, benzene, toluene, xylene and the like. Such a patterned thin film of the high polymer may be used as it is but by partially or completely converting the polymer of the thin film into imide or partially or completely ring-closing the polymer of the thin film, the thin layer is provided with an imide ring or other ring structure having high heat resistance. There is no particular restriction with respect to the method of converting the polymer into an imide or ring closing the polymer but in the case of the polyamic acid or the ester thereof, heating to a temperature of from about 300°C to 400°C is general and laser beam may be used. For example, in the case of the polymer having the recurring unit shown by formula (1A), the reaction occurs as follows. Also, in the case of the polymer having the recuring unit shown by formula (14A), the reaction occurs as follows; Furthermore, in the case of the polymer having the recuring unit shown by formula (12A), the reaction occurs as follows to form a polyimide compound; Furthermore, when the photosensitive amphiphilic high polymer of this invention is a polyamic acid salt having the recurring units shown by formula (3) or (4), it is preferred that the treatment of the thin layer is performed by a chemical curing agent, which is used for curing a polyamic acid, such as acetic anhydride, pyridine. In this case, for example, in the case of the polymer having the recurring unit shown by formula (3A), the reaction occurs as follows to form also an imide compound; Also, since the LB film formed by the photosensitive amphiphilic high molecular having the precursor structure of this invention has improved heat resistance and chemical resistance as compared to a conventional LB film, the LB film of this invention can be used as it is for various devices without applying imide-formation or ring closing. As described above, the thin film of polyamide, etc. obtained is excellent in heat resistance, chemical resistance, and mechanical properties. In addition it is very thin, e.g. less than 10,000 Å or, if desired, as 10 to 1,000 Å. Accordingly, the LB film of this convention can be used in the electronic field as an insulating film for IC, LSI, etc., as well as an insulating layer for various electric and electronic elements such as capacitors, MIS, MIM, etc., and further can be used for electric field effect transistors, photoelectric convertors, light-receiving elements, light emitting elements, light-detecting elements, hot electron transistors, etc. Moreover, the LB film can be utilized as clad material for wave guides, optical circuit components, etc., and also suitably used as coating material including for protection. Also, the LB film can be used in the field of energy conversion or material separation. When the particularly important patterned thin film of the photosensitive amphiphilic high polymer of this invention and said photosensitive high polymer has the precursor structure capable of causing a ring-closing reaction, the heat-resisting high polymer thin film formed by ring-closing the thin film of the photosensitive high polymer can be used as resist capable of being dry etched for very fine patterning such as submicron and quater micron by utilzing the features of being a very thin film having high heat resistance and chemical resistance. Now, the production process for the precursors of this invention is explained based on the following examples. Example 1 Synthesis of pyromellitic acid di-o-nitrobenzyl ester After reacting 10.91 g of pyromellitic acid dianhydride and 15.3 g of o-nitrobenzyl alcohol for 3 hours at 120°C, the product thus obtained was recrystallized to provide pyromellitic acid di-o-nitrobenzyl ester. The structure thereof was determined by IR, ¹HNMR, and elemental analysis. Synthesis of N,N'-distearyl-p-phenylenediamine A mixture of 15.6 g of p-phenylenediamine, 15.5 g of stearyl bromide, and 1.96 g of powdered sodium hydroxide was heated to 140 to 150°C for about 3.5 hours with stirring under a nitrogen gas stream. After the reaction was over, 50 ml of water was poured to the reaction mixture and black-purple solids thus formed were recovered by filtration. When the solids were washed with water, ethanol, and methylene chloride and filtered to provide about 5.8 g of a pink powder of N,N'-distearyl-p-phenylenediamine The structure was confirmed by ¹HNMR, IR spectra, and elemental analysis. Synthesis of precursor from pyromellitic aicd di-o-nitrobenzylester and N,N'-distearyl-p-phenylenedaimine In 50 ml of hexamethylphosphoramide was dissolved 1.57 g of pyromellitic acid di-o-nitrobenzyl ester and after adding dropwise 0.714 g of thionyl chloride to the solution, the mixture was stirred for one hour. The solution was added dropwise to a solution of 1.85 g of N,N'-distearyl-p-phenylenediamine in 80 ml of hexamethylphopshoramide at about 50 to 60°C with stirring. After stirring the mixture for one hour at the same temperature, the reaction mixture was poured in 600 ml of re-distilled water and the resultant mixture was allowed to stand for one hour. The precipitates thus deposited were recovered by filtration and washed to provide 3.9 g of a precursor as a gray-green powder. The powder obtained was identified by IR spectral analysis, ¹HNMR analysis, thermal analysis, and molecular measurement by GPC. Example 2 The film-forming characteristics of the precursor obtained in Example 1 as LB film were evaluated. When the surface pressure-area curve on the surface of re-distilled water was measured at 20°C, the surface pressure abruptly raised at about 65 Å/unit and good condensed film was formed. The limiting area was 60 Å²/unit and the collaps pressure was about 50 dyn/cm. Then, the film on re-distilled water was deposited on an Al evaporated glass substrate by LB method at a surface pressure of 25 dynes/cm and accumulation speed of 10 mm/min to provide a Y-type film. The deposited precursor film of 201 layers was irradiated with ultraviolet rays through a mask using a high pressure mercury lamp. Thereafter, the film was developed with an aqueous 2% KOH solution to form a pattern. By heating the pattern to 400°C for one hour inder nitrogen gas stream, it was clarified that the precursor was converted into imide and the pattern of the polyimide was formed. According to this invention, a film can be formed by the LB method. The photosensitive amphiphilic high polymer is modified in such a way that the polymer can be decomposed by the irradiation of light such as ultraviolet rays, etc., electron beams, X-rays, etc., to form a stable film on the surface of water and the film can be well accumulated on a substrate. By forming a relief pattern by light curing or light decomposing the accumulated film and then, if desired, partially or completely converting the film into an imide or cyclizing the film, a patterned very thin film of less than 10,000 Å, if desired, 10 Å to 1,000 Å in thickness and having very good heat resistance and good chemical resistance and mechanical properties can be obtained.

Claims: A photosensitive amphiphilic high polymer comprising a linear recurring unit containing a) an at least divalent 1st organic group (R¹) having at least two carbon atoms and an at least divalent 2nd organic group (R²) having at least two carbon atoms, said organic groups R¹ and R² being connected to each other by a divalent linkage group formed by a reaction of an acid group (A) containing a hetero atom and a basic group (B) containing a hetero group; b) at least one hydrocarbon-containing group having 10 to 30 carbon atoms, which may have a substituent, being bonded to said recurring unit by a covalent bond or an ionic bond; c) and an orthonitrobenzyl group which may have a substituent, being contained in a part or the whole of said recurring units. The photosensitive amphiphilic high polymer as claimed in claim 1, wherein at least one of said 1st organic group R¹ and 2nd organic group R² is a group having a benzenoid structure having at least 6 carbon atoms. The photosensitive amphiphilic high polymer as claimed in claim 1 or 2, wherein the recurring unit has a precursor structure forming a 5-membered or 6-membered ring containing a hetero atom. The photosensitive amphiphilic high polymer as claimed in claim 1, wherein the high polymer comprises the recurring units represented by formula (1), (2),(3) or (4) wherein R¹ represents a tetravalent or trivalent group having at least 2 carbon atoms, R² represents a divalent, trivalent, or tetravalent group having at least 2 carbon atoms, when said R² is trivalent, X is bonded to R², when said R² is tetravalent, X and Y are bonded to R² , at least one of R¹ and R² is a group of a benzenoid structure having at least 6 carbon atoms, X and Y each represents an acid group A containing a hetero atom, which group may have a substituent, and R³, R⁴, R⁵, R⁶, R³¹, R³², R³³, R⁴¹, R⁴² and R⁴³ each represents a monovalent hydrocarbon group having 1 to 30 carbon atoms, or a hydrogen atom, at least one of R³, R⁴, R⁵, R⁶, R³¹, R³², R³³, R⁴¹, R⁴² and R⁴³ being the aforesaid group having 10 to 30 carbon atoms, and a part or the whole of the recurring units contains an orthonitrobenzyl group which may have a substituent. The photosensitive amphiphilic high polymer as claimed in claim 4, wherein the high polymer contains the recurring unit of formula (1) or (3) wherein R³, R⁴, R⁵, R⁶, R³¹, R³², R³³, R⁴¹, R⁴² and R⁴³ each is the aforesaid monovalent group having 1 to 22 carbon atoms or a hydrogen atom and at least one of R³, R⁴, R⁵, R⁶, R³¹, R³², R³³, R⁴¹, R⁴² and R⁴³ is a group having 16 to 22 carbon atoms. The photosensitive amphiphilic high polymer as claimed in claim 4, wherein the high polymer is a polyamic acid or the ester thereof containing the recurring unit shown by formula (2), wherein R³, R⁵, and R⁶ each is the aforesaid monovalent group having 1 to 22 carbon atoms or a hydrogen atom and at least one of R³, R⁵, and R⁶ is a group having 16 to 22 carbon atoms. The photosensitive amphiphilic high polymer as claimed in claim 4, wherein the high polymer has a precursor structure such that in formula (1) or (3), each two of the four groups bonded to R¹ are bonded to adjacent two carbon atoms constituting R¹ so that the can form a 5-membered ring and/or two of the three groups -CONR⁵, -CONR⁶, and X bonded to R² when R² is trivalent, or two of the four groups, -CONR⁵, CONR⁶, X and Y bonded to R² when R² is tetravalent, are bonded to adjacent two carbon atoms constituting R² so that they can form a 5-membered ring or a 6-membered ring. The photosensitive amphiphilic high polymer as claimed in claim 4, wherein the high polymer has a precursor structure containing the recurring unit shown by formula (2), wherein two of the three groups, -R³OCO-, -NR⁵-CO-, and -CO-NR⁶-R²- bonded to R¹ are bonded to adjacent two carbon atoms constituting R¹ so that they can form a 5-membered ring and/or two of the three groups -CONR⁵, -CONR⁶, and X bonded to R² when R² is trivalent, or two of the four groups, -CONR⁵, -CONR⁶, X, and Y bonded to R² when R² is tetravalent are bonded to adjacent two carbon atoms constituting R² so that they can form a 5-membered ring or a 6-membered ring. The photosensitive amphiphilic high polymer as claimed in claim 4, wherein the high polymer is a polyamic acid ester containing the recurring units of formula (1) or (2), wherein in a part or the whole of the recurring units shown by formula (1) or (2), R³ and/or R⁴ is an orthonitrobenzyl group shown by wherein R⁷ represents a hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, or a hydrogen atom. The photosensitive amphiphilic high polymer as claimed in claim 4, wherein in formulae (1) and (2) R⁵ and R⁶ are a hydrogen atom. A process for producing the photosensitive amphiphilic high polymer according to claims 1 to 10, which comprises polymerizing a monomer containing an at least divalent 1st organic group (R¹) having at least two carbon atoms and a monomer containing an at least divalent 2nd organic group (R²) having at least two carbon atoms in a combination of any one of those shown below; A ( R¹ ) A + B ( R² ) B A ( R¹ ) B + A ( R² ) B B ( R¹ ) B + A ( R² ) A (wherein A represents an acid group containing a hetero atom, B represents a basic group containing a hetero atom, and when R¹ and R² are trivalent or more, further groups A and/or B are attached thereto according to the valence number), at least one of the two kinds of monomers in the above combination containing at least one hydrocarbon-containing group having 12 to 30 carbon atom, which may have a substituent, and a part or the whole of at least one of the monomer containing the 1st organic group R¹ and the monomer containing the 2nd organic group R² having an orthonitrobenzyl group which may have a substituent. The process for producing a photosensitive amphiphilic high polymer as claimed in claim 11, wherein for the production of a polyamic acid or the ester thereof having recurring units shown by formula (1) or (2) of claim 4, a tetracarboxylic acid dianhydride or tricarboxylic acid anhydride shown by formula (5) or (8) wherein R¹ represents a tetravalent or trivalent group having at least two carbon atoms, is reacted with an alcohol shown by R³OH or R⁴OH (wherein R³ and R⁴ are as defined in formulae (1) and (2) with the exclusion of a hydrogen atom) to provide a compound shown by formula (6) or (9) the compound thus obtained is converted into an acid halide in a substantially anhydrous polar organic solvent at a temperature of not lower than -10°C, and the product is reacted as a monomer containing the 1st organic group R¹ with a diamine shown by formula (7) wherein, R², R⁵, R⁶, X and Y are same as defined in formula (1) as a monomer containing the 2nd organic group R² at a temperature of not lower than -10°C; wherein at least one of R³ and R⁴ or R⁵ and R⁶ of at least one of the compounds shown by formula (6) or (9) and the diamine shown by formula (7) is a group having 10 to 30 carbon atoms and a part or the whole of at least one of the compound shown by formula (6) and the diamine shown by formula (7) contains an orthonitrobenzyl group which may have a substituent. The process for producing a photosensitive amphiphilic high polymer as claimed in claim 12, wherein for the production of a polyamic acid or the ester thereof having the recurring units shown by formula (1) or (2), the anhydride shown by formula (5) or (8) is caused to react with an orthonitrobenzyl alcohol shown by the following formula wherein R⁷¹ or R⁷² represents a hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent, or a hydrogen atom to form a compound shown by formula (10), (10'), or (11) wherein R¹, R³, R⁷¹, and R⁷² are same as defined above, the compound obtained is converted into an acid halide in a substantially anhydrous polar organic solvent at a temperature of not lower than -10°C., and the acid halide thus obtained is used as a part or the whole of the monomer containing the 1st organic group R¹, to obtain a polymer in which a part or the whole of the recurring units comprises a unit shown by formula (12), (12') or (13); The process for producing a photosensitive amphiphilic high polymer as claimed in claim 12, wherein in the production of the polyamic acid or the ester or salt thereof having the recurring units shown by formula (1), (2), (3), or (4), R⁵ and R⁶ of the diamine shown by formula (7) are a hydrogen atom. A film formed by the Langmuir-Blodgett method from a photosensitive amphiphilic high polymer according to any one of claims 1 to 10. The film as claimed in claim 15 which includes thereof. The film as claimed in claim 15 or 16 which includes a known Langmuir-Blodgett film forming compound. A patterned film obtainable by irradiating a film according to any one of claims 15 to 17 with UV-rays, visible light, electron beam or X-rays and developing the exposed film. The patterned film as claimed in claim 18, wherein the film after developing is treated for partial or complete conversion of the amide groups of the polymer into imide groups or partial or complete ring-closure in the polymer to obtain a film having high heat resistance.

Inventors: AWAJI, HIROSHI, UEKITA, MASAKAZU
Applicants: KANEGAFUCHI KAGAKU KOGYO KABUSHIKI KAISHA
Application year: 1987
Main classification: G03F7
IPC codes: G03F7, C08G73