JPH02153934A - Low-stress polyimide precursor, photosensitive composition containing the same and polyimide composite molded body using the same - Google Patents

Abstract

PURPOSE:To obtain the subject precursor, having specific recurring units and polymerization degree, excellent in preservation stability, good in water-resistant adhesion to substrates after imidation and capable of photolithography in the precursor stage when photosensitivity is imparted thereto. CONSTITUTION:The objective precursor, containing (B) >=20mol% chemical structural units expressed by formulas III and IV [Ar1 is a group expressed by formulas V, VI, etc.; X1 is a group expressed by formula VII or VIII (Ar2 is a group expressed by formula V, IX, etc.; Ar3 is p-phenylene, etc.; Y is -O-, -S-, etc.)] in (A) a polymer consisting of recurring units expressed by formulas I and II [Ar is 6-30C tetrafunctional aromatic group; X is 6-30C bifunctional organic group; A and B are -OR1 or -NHR1 (R1 is 1-20C organic group), -OH, etc.] and having 10-200ml/g viscosity (the value of etasp/C when C is 1.0g/dl; the solvent is N-methylpyrrolidone at 30 deg.C) and capable of providing a low-stress polyimide.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a precursor that provides a low stress polyimide having a specific chemical structure, a novel photosensitive composition comprising the same and a photoinitiator, and a polyimide composite molded article using the same. It is related to. The polyimide obtained by heating and curing the precursor and photosensitive composition according to the present invention has high heat resistance suitable for electrical and electronic materials, good mechanical properties, sufficient adhesion to substrates, and equivalent to inorganic materials. It is a very useful new material that also has the excellent property of generating extremely low thermal stress due to its low coefficient of thermal expansion. Moreover, the photosensitive composition according to the present invention has excellent storage stability and
Since fine patterns can be easily formed using IJ sogerafy, it has the advantage of being able to significantly improve the processes used for conventional materials. [Prior Art] Most organic polymers have a thermal expansion coefficient of 4X10 or more even in the temperature range below the glass transition temperature.
Because it has a much larger value compared to metals and inorganic materials,
Many problems occur. To put it bluntly, this may even be the reason why the development of organic polymer applications has not progressed as expected.For example, they have extremely high heat resistance, and in recent years
No protection! ! Even in the case of polyimide resin, which is beginning to be used as a polyimide resin, if it is applied onto a metal plate or inorganic material whose coefficient of thermal expansion is smaller than that of polyimide, thermal stress caused by the difference in coefficient of expansion will cause deformation, film cranking, peeling, and base formation. Damage to the material may occur. That is, when a coating film is formed on a silicon wafer as a protective film for IC or LSI,
There are problems such as warping of the wafer, making it impossible to perform photolithography for patterning, or the resolution becoming extremely poor.If the thermal stress is large, the passivation film may peel off, and the silicon wafer itself may suffer from inter-fold fracture. There is a problem. In addition, for flexible printed circuit boards (FPC) consisting of a film and a conductor, a film obtained by coating or thermocompression bonding a flexible film material on a metal foil is desired, but after coating, it is hardened and dried at high temperature. Alternatively, since thermocompression bonding is required, there is a problem in that after cooling to room temperature, the material curls due to thermal stress caused by a difference in coefficient of thermal expansion. In addition, in recent years, polymer materials that have two useful functions, heat resistance and photosensitivity, have been actively developed, especially for use in electronic and optical materials.For example, passivation films, α-ray Applications are being considered for surface protection films such as shielding films and junction coat films, insulating films for semiconductor devices such as glabellar insulating films for multilayer wiring, alignment films for liquid crystal display devices, and insulating films for thin-film magnetic heads. For example, "functional materials"
, July issue, pp. 9-19 (1983) and “Photographic Science and Inquiry (P.
photographic 5science and E
) pp. 303-309 (19
1979)], heat-resistant polymer materials for lithography, typified by the so-called photosensitive polyimides, include, for example, those in which active functional groups such as double bonds are introduced into the ester side chains of polyimide acid, which is a polyimide precursor. Po, Rimmer,
A photosensitive composition containing a photoinitiator, etc. (Japanese Patent Publication No. 55-3
0207 Publication, Special Publication No. 55-41422),
A photosensitive composition containing as a main component a mixture of polyamic acid and an amine compound having an active functional group such as a double bond (JP-A-57-168942, JP-A-54-14579)
4, JP-A-59-160140), and the like. However, polyimide obtained by heating and curing these materials also has a large coefficient of thermal expansion, just like general organic materials, so when forming composite molded products with inorganic materials using these materials, thermal expansion may occur due to thermal stress. A problem occurs and becomes a big problem. The large coefficient of linear thermal expansion of organic polymers causes many problems, and the development of a polyimide resin having a low coefficient of thermal expansion that improves this problem has been strongly desired for quite some time. Under these circumstances, several polyimides with low coefficients of thermal expansion have been recently announced.
Publication No. 08358, Japanese Unexamined Patent Publication No. 60-243120,
JP-A-60-250031, JP-A-61-607
25, etc., or by Matsuura et al. in JP-A-60-210629 and JP-A-60-210.
894, JP 60-221426, JP 80-221427, JP 61-69833
There have been reports on the production of polyimide with a low coefficient of thermal expansion using specific raw material components, such as those described in the above publications. Furthermore, in Japanese Patent Application Laid-open No. 175035/1983, Numata, Kinjo et al. have proposed several aromatic heterocyclic polymers having a low coefficient of thermal expansion. On the other hand, organic materials are generally easily affected by moisture, causing deterioration of mechanical properties. Polyimide is no exception, and this is because the imide structure has poor hydrolysis resistance. On the other hand, in addition to the imide structure, imidazole,
Polymers with a heterocyclic structure such as oxazole are
Yoda, Dogoshi et al., Japanese Patent Publication No. 45-24593, Japanese Patent Publication No. 46-120, "Thermal Decomposition and Heat Resistance of Polymers"
(Baifukan) It is proposed in "Synthesis and Application of Alternating Aromatic Heterocyclic Copolymers" starting from page 86. Also, Jack Breston, Billy M. Talbertsson (J
ack Preston, 5illy M, Cu1
berLson et al. in U.S. Patent No. 4.087
, 409, No. 3,661.849,
Polyimide having a heterocycle has been proposed as a material having high strength and high heat resistance. [Problems to be Solved by the Invention] However, the polyimide or aromatic heterocyclic polymer obtained by the techniques of Numata, Kinjo et al., and Matsuura et al. In order to obtain the performance as a low thermal expansion material, some kind of orientation treatment is required. However, when used as a coating material, no special orientation treatment can be performed during heat curing. Therefore, polyimide materials that exhibit performance as a low thermal expansion material even without any special orientation treatment are available. It was wanted. Further, polyimides containing heterocycles by Yoda, Dogoshi et al. and Breston et al. have flexibility in molecular bonds in order to obtain high strength and high heat resistance. Therefore, these materials generally have a high coefficient of thermal expansion, which poses a major problem when combined with inorganic materials having a low coefficient of thermal expansion. Moreover, these materials are obtained by heating and curing the corresponding polyamic acids. However, it is known that polyamic acid undergoes hydrolysis during heat curing, resulting in a decrease in molecular weight and a significant decrease in physical properties (
(Japanese Unexamined Patent Publication No. 18183ff). This phenomenon is particularly noticeable in mechanical strength and thermal expansion characteristics. For this reason, the molecular weight of the precursor polyamic acid must be high. However, when used as a coating material, if it is made into a high molecular weight product, the viscosity becomes too high, making it very difficult to coat. Additionally, in order to lower the viscosity, the concentration of the precursor polyamic acid solution is lowered, but because the precursor has poor solubility, the solution becomes extremely dilute, making it impossible to form a film with the desired thickness. There is a problem. This phenomenon is particularly noticeable in polyimides that have a low coefficient of thermal expansion. Therefore, there has been a desire for a material that is a precursor with high concentration and low viscosity, and which does not cause a decrease in physical properties due to a decrease in molecular weight during heat curing. Furthermore, this polyamic acid is very unstable in a solution state and easily hydrolyzed, causing a decrease in viscosity, resulting in poor storage stability, and improvements in this point have been desired. Further, the polyimide having a low coefficient of thermal expansion that has been proposed so far has a polyamic acid as a precursor, and is a so-called non-photosensitive type. Therefore, in order to carry out photolithography, a separate photoresist must be used, and in addition, harmful hydrazine must be used to etch the obtained polyimide. Furthermore, since the etching conditions are greatly influenced by the heat curing conditions of the polyamic acid, there is also a major problem in the reproducibility of the process. Therefore, for these reasons, a so-called photosensitive type polyimide with a low coefficient of thermal expansion has also been desired. or,
Polyimide generally has a problem in that it has poor adhesion to inorganic materials such as glass and metals. In response, improvements have been made so far by treatment with silane cambling agents, chelating agents such as titanium or aluminum. However, the adhesiveness between polyimide and inorganic materials is greatly affected by pressurized heated water in accelerated moisture resistance tests. This phenomenon is particularly noticeable in low thermal expansion polyimides, and it is thought that this is because the film quality is impaired by the influence of moisture, resulting in a decrease in adhesiveness. Therefore, a polyimide with a low coefficient of thermal expansion and excellent water-resistant adhesive properties has been strongly desired. [Means for Solving the Problems] Based on these backgrounds, the present inventors have developed a precursor that does not have the above problems, that is, has the characteristics of high concentration and low viscosity required for a coating agent. Furthermore, even if this precursor is applied onto an inorganic material with a low coefficient of thermal expansion and then heated and cured, the resulting polyimide will maintain its physical properties. The material has a low coefficient of thermal expansion, does not cause thermal stress on the Go playing surface, and has excellent water-resistant adhesion to the base material after imidization, and if this precursor is made photosensitive. Furthermore, since photolithography is possible at the precursor stage, we have conducted intensive research with the aim of developing a material that has these features, which will be an extremely superior material in terms of processing. As a result, they found that a photosensitive composition consisting of a precursor that provides a low-stress polyimide with a specific structure, a precursor that imparts photosensitivity to it, and a photopolymerization initiator can be suitable for this purpose. The present invention was completed based on the findings. That is, the present invention provides the following: +1) - Formulas (1) and (II) [wherein Ar is a tetravalent aromatic group having 6 to 30 carbon atoms, and X is a group, both ASB and ASB are 10H groups Never. Here, R1 and R2 are organic groups having 1 to 20 carbon atoms] In a polymer consisting of a repeating unit represented by:
Below - Formulas (I [I) and (IV) (wherein Ar is $,
The aromatic group selected from 2 or , y@, Ar3 is a viscosity number [polymer concentration C=
vsp/C value at 1.0 g/dl, however, η3p-(
η−η, )/η, where η is the viscosity of the polymer solution, η. : Viscosity of solvent (N-methylpyrrolidone): Measurement temperature 30
℃] A precursor capable of providing a low stress polyimide of 10 to 200 m/g (2) In claim (1), the general formula [l]
[■] (III) In (IV), R1 and R2 are carbon-
Represented by a group having a carbon double bond, with a viscosity number of 10 to 10
0 m1/g of a photosensitive composition comprising a polymer and a photopolymerization initiator, (3) the low stress polyimide precursor according to claim (1) and the photosensitive composition ζ according to claim (2), a metal,
The present invention provides a low-stress polyimide composite molded body for electronic materials, which is obtained by combining ceramics and other inorganic materials and curing them by heating. The polymer used in the present invention has the general formula ([)
and [■], and Ar in the formula represents a tetravalent aromatic group having 6 to 30 carbon atoms. Examples of such Ar include benzene rings, naphthalene rings, Condensed polycyclic aromatic rings such as anthracene rings, heterocyclic groups such as pyridine and thiophene, and general formula (n
-1) l is 0 or 1, Z is CH3 or CF3. ] and the like. Among these, these are particularly preferred. X in general formulas (1) and [■] is a divalent organic group having 6 to 30 carbon atoms, and in addition to XI in general formulas (III) and (IV), (T) Aromatic group selected from Figure D → Ωpi1 (in the formula & is the same or different, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a fluorinated alkyl group, fluorine -〇-o-=o-
0-kara selection barrel group, R4, R, ha carbonffi number 1 to 14
a divalent organic group, Rs, Rヮ are monovalent organic groups having 1 to 16 carbon atoms, m is O to 4, n is 0 or hp, q is an integer larger than 1) can be mentioned. Ar in the general formula [■], (IV) is (summer, Rφ+
Y is a group represented by 10-1-S-1, and the aromatic group selected from From this point of view, a particularly preferable combination is a group represented by (wherein Ar+ is an aroma selected from (or) (In the formula, Ar2, Ar3, Yt are the same as above.) In the above formula, A and B are each independently e Φ -OR,, -NR,, -OR2 and A group selected from -〇H, and neither A nor B is -OH, where R1 and R2 are organic groups having 1 to 20 carbon atoms, and R1
For example, an alkyl group, an alkoxyalkyl group,
Examples include a phenyl group, a benzyl group, and groups represented by the following formulas. -4,R//-0-)-C-C-C8, (1-13r6
k・ 1, #+ c) [-CH2 (1-3) -CH- magazine-R"-0-8-t-CHz (I -4
)-R"-CH horse mackerel C sushi (I-53-
R"-NH-j-g, -CH2(I-6)c in the formula R"
is a hydrogen atom or a methyl group, R" is an alkylene group having 1 to 3 carbon atoms, and r is 1 or 2. If R1 is a group represented by the above formulas (1-1) to (1-63), the precursor It is preferable because it can impart photosensitivity to the body.Specific examples of R1 include methyl group, ethyl group, n-
Propyl group, 1so-propyl group, n-butyl group, 1s
o-butyl group, phenyl group, benzyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxy-1-
As a specific example of a propyl group, a 2,3-dimethoxy-1-propyl group, and the formula (l-1), "2;3-c"
2-o-:j-c”=°“2-g,”s-C”! −°
A specific example of 1-k0"゛(1-2) is -CH, -C8, -o-g-CH-co-. A specific example of (1-3) is CHz- o-CH"= C)+2, -CHz -CI+
A specific example of H-CH2, (1-4) is -CH2iH-CH2-0-g-絋C1h-C)Iz-
G-CH2-0-g-C= CHz-C)+2-gH-
CHrCH "0-g-C-C)l. A specific example of (1-5) is -C~-CH-CH, -C)I2-C)l, -C1l cloud C8゜(1- Specific examples of 6) include -CH, -N11-g-CI(3G)1., -CH2
-CH2-NHI-C=C)12 and the like,
It is not limited to these. Among these, 2-methoxyethyl, 3-methoxy-1-
Groups having an ether bond, such as propyl and 2,3-dimethoxy-1-propyl, are preferred because they improve the solubility of the precursor in organic solvents and improve the processability of the precursor. In the case of a group having a carbon double bond,
The group represented by the general formula ([7) is preferred because it can impart photosensitivity in terms of photosensitivity, storage stability, etc. [In the formula, R is an alkyl group or an alkoxyalkyl group having 1 to 15 carbon atoms, Ro and R8 are each a hydrogen atom or a methyl group, R is an alkylene group having 1 to 3 carbon atoms, and r' is a methyl group or an ethyl group. ] Among these, preferred specific examples include -CH2-G=Ch-0-8-g, =, CHt, -C
)It-G-CH, -0-(,, -C1(-CH.
Examples include groups represented by the following, and precursors include the following. A and B in the above-mentioned formulas (1) and (II) are each independently 10R0 from the viewpoint of solubility and stability of the precursor.
The groups represented by the following are particularly preferred, and as R1, the groups represented by the above formulas (1-1) and (1-4) are preferred. In a polymer consisting of repeating units represented by formulas (I) and (ff), the chemical structural units represented by formulas (I[I) and (IV) account for 20 mol% or more, preferably 50 mol% or more. If the content is less than this, the resulting low stress heat resistant resin will have low thermal expansion characteristics,
This is undesirable because mechanical properties and water-resistant adhesive properties deteriorate. The viscosity number of the polymer consisting of repeating units represented by formulas (1) and (II) is 10 to 200 m1/g, and the viscosity number of the polymer when used as a photosensitive composition is 1
0 to 100 a+1/g. Viscosity number is 10m1/g
If it is less than
If it exceeds +l/g, the viscosity of the precursor solution becomes too high, making coating on the substrate difficult and reducing workability. In addition, in the case of a photosensitive composition, the viscosity number is 100
If it exceeds m1/g, developability will deteriorate during photolithography, which is not preferable. The polymer used in the present invention has formula (III) and (
rV), if it is a different X, or At
It may also be a copolymer consisting of 1, in which case what is physically insufficient as a homopolymer is thereby improved. Furthermore, among the polymers having the structures represented by formulas (1) and (III), polymers having different structures may be mixed and used. In the case of the photosensitive composition according to the present invention, the photopolymerization initiators used include, for example, anthraquinone derivatives such as anthraquinone, 2-methylanthraquinone, and 2-ethylanthraquinone, benzoin, benzoin methyl ether,
Benzoin derivatives such as benzoin butyl ether, thioxanthone derivatives such as chlorothioxanthone and diisopropylthioxanthone, benzophenone, 4.4'-
Dichlorobensifunone, Michler's ketone [4,4-bis(dimethylamino)benzophenone, 4,4'-bis(
benzophenone derivatives such as benzyl, benzyl dimethyl ketal, benzyl-β-butoxyethyl acetal, p-dimethylaminoacetophenone, p-dobutyl Trichloroacetophenone, 2-
Examples include acetophenone derivatives such as bitroxy-2-methylpropiophenone and 2,2-jethoxyacetophenone, and oximes represented by the following general formula (V). sulfonyl group, or aliphatic sulfonyl group having 1 to 6 carbon atoms,
R1 is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aromatic group having 6 to 10 carbon atoms, or 6 carbon atoms
~10 represents a monoloxy group] Among these, oxime type photopolymerization initiators are preferred from the viewpoint of photosensitivity, for example, [In the formula, R9, R10%, R11 is a hydrogen atom,
-6 alkyl group, alkoxy group having 1 to 6 carbon atoms, or nitro group, and B, aromatic acyl group having 7 to 11 carbon atoms, aliphatic acyl group having 2 to 7 carbon atoms, alkoxy having 2 to 7 carbon atoms These photopolymerization initiators include, but are not limited to, carbonyl groups, aromatic groups having 6 to 10 carbon atoms, and may be used alone or in combination. There is no particular restriction on the amount used, but it is preferably 0.1 to 20% by weight based on the polymer used. If the amount used is small, the photosensitivity will decrease, and if it is too large, the film properties after heat curing will be affected. decreases. A compound having a molecular weight of 80 to 1000 and having a group represented by the following general formula at the molecular end can be added to the photosensitive composition of the present invention, if necessary. [In the formula, R14 is complementary or -NH-1R+5 is a hydrogen atom or a methyl group. ] This compound is a compound that facilitates the photopolymerization reaction by adding it, and as such, 2
-Ethylhexyl acrylate, 2-hydroxyethyl acrylate, N-vinyl-2-pyrrolidone, carpitol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene Glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane I-reacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, tetraethylene glycol diacrylate, nonane ethylene glycol diacrylate Examples include acrylate, methylenebisacrylamide, N-methylol acrylamide, and those obtained by changing the above acrylate or acrylamide to methacrylate or methacrylamide. Among these, preferred ones have two or more carbon-carbon double bonds. It is a compound. The proportion of these compounds added to the present composition is preferably 1 to 20% by weight based on the polymer used. Moreover, a general sensitizer can also be added to the photosensitive composition of the present invention. This sensitizer can improve the photosensitivity of the composition by adding it, and examples thereof include Michler's Katone, 4,4'-bis(diethylamino)-benzophenone, and 2,5-bis(4''-diethylaminobenzal). ) cyclopentanone, 2°6-bis(4°-diethylaminobenzal)cyclohexanone, 2.6-bis(4
゛-dimethylaminobenzal)-4-methylcyclohexanone, 2.6-bis(4゜-diethylaminobenzal)-4-methylcyclohexanone, 414゛-bis(dimethylamino)chalcone, 4.4゛-his(diethylamino) ) Chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1. 3-bis(4'-dimethylaminobenzal)acetone, 1.3-bis(4-diethylaminobenzal)acetone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-
Dimethylaminobenzophenone, 4-morpholinopenbuphenone, N-phenyldiethanolamine, N-p-
) Lyldiethanolamine, N-p-tolyldiethylamine, and a coumarin compound represented by the following general formula. R41 group, R71 is ethoxycarbonyl group, cyano group, 1-
represents a butoxycarbonyl group, carboxyl group, or acetyl group] Among these coumarin compounds represented by the formula (1), those in which R1 is an alkoxy group having 1 to 7 carbon atoms are particularly preferred. [In the formula, R1'l is
Methyl group or ethyl group, - is an aliphatic group having 1 to 4 carbon atoms,
Aromatic hydrocarbon group having 6 to 10 carbon atoms, or 1 to 7 carbon atoms
an alkoxy group, preferably a methyl group, ethyl group, isopropyl group, phenyl group, tolyl group, methoxy group, ethoxy group, n-propoxy group, 1so-propoxy group, n-butoxy group, 1so-butoxy group, ter 't
-butoxy group, benzyloxy group. Examples of R1 include a methyl group, ethyl group, or trifluoromethyl group, and R1° includes a hydrogen atom or methane. Regarding the content ratio, it is 0.01-10% by weight based on the polymer, preferably 0.
．． 05-5% by mass. Furthermore, if necessary, a mercaptan compound can be added to the photosensitive composition of the present invention to further improve photosensitivity. Examples of mercaptan compounds include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-IH-tetrazole, 2-mercaptothiazole, 2-mercapto-4-
Phenylthiazole, 2-amino-5-mercapto-1
, 3,4-thiazole, 2-mercaptoimidazole,
2-mercapto-5-methyl-l, 3.4-thiadiazole, 5-mercapto-1-methyl-1 totitrazole, 2,4.6-drimerkabuto, S-triazine, 2-
Dibutylamino-4,6-dimercabuto s-triazine, 2,5-dimercabuto-1,3,4-thiadiazole, 5-mercapto 4,3,4-thiadiazole, ■-
Ethyl-5-mercapto 1.2,3.4-tetrazole, 2-mercapto 6-nitrothiapur, 2-mercaptobenzoxazole, 4-phenyl-2-mercaptothiazole, mercaptopyridine, 2-mercapto 1-hequinoline, l-methyl -2-mercaptoimidazole,
Examples include 2-mercapto-β-naphthothiazole. The content ratio is preferably 10% by weight based on the polymer, and more preferably 5M% or less. Furthermore, a silane compound can be added to the precursor for providing the low stress polyimide according to the present invention and the photosensitive composition formed therefrom, if necessary. This silane compound is a compound that improves the adhesion of the interface between the heat-resistant polymer film of the composition of the present invention and the Si and inorganic material serving as the base material, and may be used by pre-coating the base material. Examples of these include, for example, γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)
γ-aminopropyldimethoxysilane, γ=glycidoxypropylmethyldimethoxysilane, T-mercaptopropylmethyldimethoxysilane, dimethoxy-3-mercaptobrobylmenalsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxy Propyltrimethoxysilane, dimethoxymethyl-3-piperidinenobrobylsilane, jetoxy-3-glycidoxypropylmethylsilane, N-(3-jethoxymethylsilylpropyl)succinimide, 3-meccryloxybrobyltriethoxy Examples include silane. The content is 0.05 to 10%, preferably 0.05% to the polymer.
It is 1 to 5% by weight. Further, in order to improve the storage stability of the solution of the photosensitive composition according to the present invention, a polymerization inhibitor may be added. Examples of the polymerization inhibitor include hydroquinone, N-
Examples include, but are not limited to, nitrosodiphenylamine, p-tert-butylcatechol, fetch 7 gin, N-phenylnaphthylamine, 2,6-tert-butyl-ρ-methylphenol, and the like. The content ratio is 5% by weight or less based on the polymer, preferably less than O, SI mass commercially available. , the normal polymer used in the present invention: has a polyamic acid ester or polyamide structure synthesized by chemically bonding a tetracarboxylic acid moiety, a diamine moiety, and an alcohol or amine moiety; It also includes those having the structure of a polyamic acid or a polyamic acid salt. There are no particular restrictions on the method for synthesizing this, but after reacting the corresponding tetracarboxylic dianhydride with an alcohol or amine to produce a tetracarboxylic diester or tetracarboxylic diamide, the dicarboxylic acid and diamine are condensed. In many cases, a method is used in which a polyamic acid ester or polyamide is produced by condensing it with a corresponding diamine in a condensation reaction similar to that described above. As a method for carrying out the condensation reaction, Rubner et al.
JP-A-61-72022, JP-A-61-127731, JP-A-62-7
2724, JP-A No. 62-74931, etc., methods using organic dehydration condensation agents, active methods as disclosed by Ueda et al. Various methods can be used, such as a method via an ester intermediate. Among these methods, the method disclosed in JP-A-61-72022 is more preferable because it can synthesize polyamic acid ester or polyamide with a very low content of ionic impurities such as chlorine ions, and The method disclosed in JP-A-61-127731 is more preferred since side reactions are extremely unlikely to occur. In addition, when synthesizing polyamic acid ester, other methods are disclosed in JP-A-60-26033 by Minema et al.
As disclosed in the above publication, a polyamic acid is prepared by reacting a tetracarboxylic dianhydride and a diamine in advance, and then a special activated alcohol is reacted with the polyamic acid to synthesize a polyamic acid ester. Methods can also be used. It is also possible to use a method such as that disclosed by Arne et al. in JP-A-56-35131, in which a polyamic acid is synthesized in advance and an epoxy compound is added thereto to synthesize a polyamic acid ester. In addition, when synthesizing a polyamide having an unsaturated double bond or the like in the form of an amide bond, it is obtained by first synthesizing polyamic acid and then reacting it with an isocyanate compound by the method disclosed in JP-A-60-100143. You can also do that. The terminal ends of the polymer obtained by these methods are residues of the tetracarboxylic acid or diamine component constituting the polymer according to the present invention and derivatives thereof, and specific examples include -X-N)l, -X- N J −R1゜ (A in the formula
r, X: A, B are the same as above, R16 is a hydrogen atom or -
A valent organic group, R1? ,I? , represents a -valent organic group). By introducing a group represented by the following, it is also possible to increase the molecular weight of the polyimide produced after heat curing. The tetracarboxylic acid used to obtain the polymer in the present invention is a derivative thereof, preferably an acid anhydride. In the above-mentioned formulas (I[[), (IV), and lomelift dianhydride, 3,3°, 4,4°-biphenyltetraca/1478 dianhydride and p-terphenyl-3,4
, 3g, 4μ tetracarboxylic dianhydride. Moreover, in the above-mentioned formula (13, (II)), -formula [III]
, it is also possible to use a tetracarboxylic acid other than that used in (IV), and in this case, a fused polycyclic aromatic ring such as a naphthalene ring or anthracene ring, a heterocyclic group such as pyridine or thiophene, and the above formula - ((1-1). Specific examples of these include 2,3.3',4'-tetracarboxydiphenyl, 2.3.3',4'-tetracarboxydiphenyl, Carboxydiphenyl ether, 3,3°, 4,4°-tetracarboxybenzophenone, 2.3.3', 4'-tetracarboxybenzophenone, 2,3,6.7-tetracarboxynaphthalene, 1.4,5.8 -tetracarboxynaphthalene, 2.3゜6.7-tetracarboxynaphthalene,
3.3', 4.4°-tetracarboxydiphenylmethane, 2.2-bis(3°4-dicarboxyphenyl)hexafluoropropane, 3.3', 4.4'-tetracarboxydiphenylsulfone, 3, 4.9.10-Tetracarboxyperylene, 2゜2-bis(4-(3,4-
dicarboxyphenoxy)phenyl]propane, 2.2
-bis(4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane, etc., and derivatives thereof, preferably acid anhydrides, can be used.As the component of the diamine, the above formula (III) is used. , C.N.
3, H is expressed as Hz N-XI-NH2, where X is an aromatic group selected from [l-1) ~ (lll-4
), (IV-1) to (IV-4) are diamines used in )ltN-X, NH,, HIN X3-NH3
, H2N-X4 NH4, where x2 is a group represented by (wherein Ar is an aromatic group selected from aromatic or X, where Ars and Yl are the same as above), and X4 is Examples of +1!N-X, -NH. are groups represented by (in the formula, ^r2, r3, so, are the same as above). Specific examples of these diamines are given below. However, it is not limited to these. Examples of flLN Xl-N)11 include the following. Examples of more than Hi, N -X4-N include and %N Xz NN2, Hl N -N3- N
N2. The diamines mentioned above can be mentioned as examples. In addition, in the above formulas (III) and (IV), N
Specific examples of the diamine represented by 2 N Xl-N112 include H and the like in addition to those listed above. These heterocycle-containing diamines are Makromol. Chen+, 77, P33 (1964), P
lyIIer, ll, P279 (1970),
J, Po1)n++, Sci, 54. P51
10961), J, Po1ya+, Sci.
A-1, 16, P2275. P1831 (1978
), but a method using polyphosphoric acid as both a solvent and a dehydration condensation agent is particularly preferred because the desired diamine can be obtained in one step. A synthesis example is shown in the following formula. (In the formula, Art, ^r3, and Y are the same as above.) Here, the diamine derivative that is the raw material for the above reaction can be obtained by the method described above. Also, - in formulas (1) and (II), )Ix N-X
The diamine represented by -N Hz has the formula (II
In addition to Hl N-XrN) 11 in I) and (IV), for example, p-phenylenediamine, tophenylenediamine, 2.5-diaminotoluene, 2.5-dimethyl-p
-Phenylenediamine, 2.6-dimethyl-p-phenylenediamine, diaminodurene, 2.4-diaminotoluene, 2.6-diaminotoluene, 1.5-diaminonaphthalene, 2.6-diaminonaphthalene, 4,4 “−
Diaminoterphenyl, 4°4'-diaminoquaterphenyl, 4,4°-diaminodiphenylmethane, 4,
4°-diaminodiphenyl ether, diaminodiphenylsulfone, 2,2-bis(p-aminophenyl)propane, 2,2-bis(p-aminophenyl)hexafluoropropane, 3,3°-dimethylbenzidine, 3,3
゛-dimethoxybenzidine, 3.3°-dimethyl-4,
4''-diaminodiphenyl ether, 3.3'-dimethyl-4,4''-diaminodiphenylmethane, 1,4-bis(p-aminophenoxy)benzene, 4.4'-bis(p-aminophenoxy)biphenyl, 2, 2-bis(
4-(p-aminophenoxy)phenyl]propane, diaminoanthraquinone, 4°4'-his(3-aminophenoxyphenyl)diphenylsulfone, 1,3-bis(anilino)hexafluoropropane,! , 4-bis(
anilino) octafluorobutane, ■,5~bis(anilino)decafluorobencune, 2,2-bis(4-(p
-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-(
4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis(4-(4-
aminophenoxy)-3,5-ditrifluoromethylphenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4
．． 4'-bis(4-amino)-2-trifluoromethylphenoxy)biphenyl, 4.4°-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4
, 4°-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4.4°-bis(3-
Amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis(4-(4-amino)3-
Examples include trifluoromethylphenoxy)phenyl]hexafluoropropane. In addition, silicone diamines such as diamine tojishita can also be used. When synthesizing the polymer used in the present invention, the formula (
When A and B in 1) and [■] are ester bonds, the alcohol component that becomes the raw material is - formula! ? , -OH
In formula C, R+ is an organic group having 1 to 20 carbon atoms, and preferred examples thereof include 2-methoxyethanol, 2-ethoxyethanol, 3-methoxy-1-propatol, and 2,3-dimethoxy. Examples include alcohols having an ether bond such as -1-propatol. In addition, in those having a carbon-carbon double bond, especially the above-mentioned -
Alcohols corresponding to formula (1-1) are preferred, and specific examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. Furthermore, in the polymer according to the present invention, an epoxy compound can be used as a raw material for the ester moiety. These substances correspond to formulas [I to 4], and specific examples include glycidyl methacrylate and glycidyl acrylate. In the polymer according to the present invention, the general 2N), CUE
When AXB is an amide bond, - formula (1-13 ~ (
Although it is also possible to use an amine compound corresponding to 1-6), a preferred method is to first synthesize a polyamic acid and then react with a corresponding isocyanate compound. Preferred examples of the isocyanate compound used at this time include methacryloyloxyethyl isocyanate and acryloyloxyethyl isocyanate, which have a carbon-carbon double bond in the molecule, since they can impart photosensitivity to the precursor. . The polymer synthesized from the above components is mainly made into a solution and then processed by coating, molding, film formation, etc. The solvent used in this process is N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide. , γ−
Polar solvents such as butyrolactone, cyclohexanone, cyclopentanone, tetrahydrofuran, dioxane and the like are preferred, and other solvents may be mixed as necessary to improve coating properties. This solvent can also be used as a solvent during synthesis, and the synthesis reaction solution can be used as it is. After filtering the solution obtained in this way, the solution is coated on a substrate using, for example, a spin coater, bar coater, blade coater, roll coater or screen printing method, or the substrate is immersed in the solution. A method of spraying the solution onto a substrate, etc. can be used. Examples of base materials include metals, glass, silicon semiconductors,
Heat-resistant materials such as compound semiconductors, metal oxide insulators, and silicon nitride are preferable, and when heat treatment is not performed, materials such as copper-clad glass epoxy laminates can be used. Next, the coating film thus obtained is dried by an appropriate method such as air drying, heating drying, or vacuum drying. In the case of photosensitive compositions, the next step is photolithography, which is usually carried out through a photomask.The bimonthly active rays include, for example, ultraviolet rays, X-rays, and electron beams. Among them, ultraviolet rays are preferred, and examples of the light source include low-pressure mercury lamps, high-pressure mercury lamps,
Examples include ultra-high pressure mercury lamps and halogen lamps. Among these light sources, an ultra-high pressure mercury lamp is preferred, and furthermore, exposure can also be performed by an exposure method (g-line stepper) using only the g-line of this light source. Further, it is preferable that the exposure is performed under a nitrogen atmosphere. After exposure in this manner, development is performed using a dipping method, a spray method, or the like in order to remove the unirradiated portions. Examples of the developer used at this time include N-methylpyrrolidone, N-
Acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, N-
An aprotic polar solvent such as benzyl-2-pyrrolidone or T-butyrolactone may be used alone, or an alcohol such as ethanol or isopropanol, or an aromatic solvent such as toluene or xylene may be used as a second component. Hydrocarbon compounds, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and methyl propionate, and solvents such as tetrahydrofuran and ethers such as dioxane may be used in combination, and the second component may be added immediately after development. It is preferable to rinse with a solvent such as that shown in . In this way, a desired fine pattern can be obtained in the photosensitive composition. Next, a coating film made of this precursor is coated with a coating film of 150 to 500
By heating in the temperature range of °C, it is converted into a polymer with a heat-resistant structure. By integrating the low-stress heat-resistant resin thus obtained with an inorganic material, it becomes possible to create a composite molded body used for electronic material applications such as those listed below. ■Multilayer wiring LSI that is coated on silicon, gallium arsenide, etc. chips and used as a multilayer wiring interlayer insulating film, ■Semiconductor devices that are coated on LSI chips and used as pansivation films and alpha-ray shielding films, ■Silicon, alumina, etc. , Kamaishi substrate made of silicon carbide, zircon, beryllia, sapphire, etc. substrate laminated with polyimide as an insulating plate between the eyebrows, ■ Liquid crystal display device coated on a glass plate and used as a liquid crystal alignment film, ■ Formed on a metal plate. printed circuit boards, ■Magnetic recording media such as magnetic tapes and magnetic disks, ■Amomorphus solar cell substrates. [Operation] It is known that rigid polyimides having a linear molecular structure have a low coefficient of thermal expansion, a high modulus of elasticity, and thermal properties. However, due to their rigidity, these polyimides have problems such as insufficient elongation and poor water-resistant adhesion. In addition, since the polyimide precursor is polyamic acid, it has poor storage stability (and when heated and cured, hydrolysis occurs and the molecular weight decreases, resulting in the failure of the above-mentioned properties). Synthesizes molecular polyamic acid to prevent extreme deterioration of physical properties, but due to the poor solubility of polyamic acid in organic solvents, the solution becomes extremely dilute, making it impossible to form the necessary coating film and poor moldability. In addition, polyimides containing a heterocyclic structure have been proposed to improve the water-resistant adhesion mentioned above, but these generally have a high coefficient of thermal expansion, and some have structures with a low coefficient of thermal expansion. However, since the precursor is polyamic acid, the molecular weight decreases during heat curing, resulting in a decrease in physical properties.Also, there are problems with storage stability and solubility, so it is difficult to process as well. In addition, since these imide precursors are non-photosensitive, a separate photoresist must be used when performing lithography, making the process very complicated. The film must be etched using harmful hydrazine, etc. Also, depending on the curing temperature of the polyimide film, the etching speed is high (variation) and other process problems are also quite large. By using a precursor that provides a low-stress heat-resistant resin and a photosensitive composition using the same, the drawbacks of the aforementioned rigid polyimide and the drawbacks in physical properties and processes derived from the precursor can be significantly improved. As a result, a new low-stress heat-resistant material with various useful properties was developed.
We were able to develop a precursor and photosensitive composition that provides i4 fat. [Effects of the Invention] The low-stress, heat-resistant coating film obtained by heating and curing the polymer of the present invention has a lower coefficient of thermal expansion than conventional organic materials. Since it has almost no stress and has excellent water-resistant adhesion and mechanical properties, it can be widely applied to the fields of electricity, electronic materials, and semiconductors. Further, in the photosensitive composition according to the present invention, a heat-resistant fine pattern can be easily formed on a substrate by a simple process of coating, patterning, and heat curing. Furthermore, the polymer according to the present invention has high solubility in organic solvents and excellent storage stability in a solution state, so that workability during processing is greatly improved. [Example] Examples of the present invention are shown below, but the present invention is not limited thereto. The sensitizer, mercaptan compound, silane compound, polymerization inhibitor) are shown in Table 1. Here, the viscosity number (hereinafter abbreviated as VN) was used as an index representing the molecular weight of the polymer. Desired. That is, 1 g of polymer is converted into N-methylpyrrolidone (hereinafter abbreviated as NMP).
100+++1 to prepare a solution with a concentration of C-1 (g/di). 10 ml of this solution was taken into an Oswald viscometer and the flow time was measured at 30°C.
), and in the same way, measure NMP only lQ+al with an Oswald viscosity needle, measure the flow time, and calculate this as 7
o (sec), NV is defined as follows and calculated based on this formula. VN=1/C(η-ηo/ηo) (ml/g
) The polymers listed in Table 1 (1-1) used in Examples and Comparative Examples are synthesized as follows. That is, a flask equipped with a thermometer, a stirrer, and a drying tube was
il 2.5 times the volume of N for the amount of tetracarboxylic dianhydride, alcohol component and acid anhydride shown in (1-1).
, Nl-dimethylacetamide was added thereto, and 20.6 g of pyridine was added while stirring at room temperature. After stirring at room temperature for 16 hours, a solution of 54.2 g of dicyclohexyl sulfodiamide in 27 ml of N,N-dimethylaminoacetamide was added under water cooling for 10 minutes, and then diamines listed in Table 1 (1-1) were added. A suspension in 2 volumes of N,N-dimethylacetamide was added over 20 minutes. Next, the temperature was gradually raised to room temperature, and after stirring for 2 hours,
511 Il of ethanol was added and the mixture was further stirred for 1 hour. After filtering the insoluble matter in the reaction solution, the resulting solution was
The resulting precipitate was washed with ethanol and dried under vacuum to obtain a yellow powder. The VN of the polymer thus obtained is also listed. The polymers listed in Table 1 (1-2) are synthesized as follows. That is, the diamine shown in Table 1 (L2) was placed in a flask equipped with a thermometer, a stirring device, and a drying tube, dissolved in 330 g of N,N-dimethylacetamide, and then added to the diamine shown in Table 1 (1-2). The acid anhydride shown in 1 was added in small portions as a powder over a period of 15 minutes. After subsequent stirring for 3 hours at room temperature, 1.5 g of 2-hydroxyethyl methacrylate are added to the reaction mixture in order to bind the terminal anhydride still present. After stirring at room temperature for 2 hours, 65 g of glycidyl methacrylate was added to the reaction solution.
Hensyl methylamine 0.7g and hydroquinone 0.0
Add 5g. The solution was then stirred at 50-60°C for 2 hours.
Heat for 3 hours, then add 4 mL of ethanol while stirring vigorously.
Drip into 1. The precipitate that forms is filtered off with suction and dried under vacuum at room temperature. The VN of the polymer thus obtained is shown in the same table. In the polymer synthesis of Table 1 (1-2), the synthesis was carried out in the same manner except that the amount of glycidyl methacrylate was changed to 18.5 g, and the polymers shown in Table 1 (1-3) were obtained. Table 1 (1 The polymer described in -4> is synthesized as follows.That is, the diamines shown in Table 1 (1-4> are placed in a flask equipped with a temperature needle, a stirring device, and a drying tube, and N,N - It was dissolved in 330 g of dimethylacetamide, and then the acid anhydrides shown in Table 1 (1-4) were added in powder form little by little over 15 minutes.After stirring at room temperature for 3 hours, the remaining acid anhydrides were added. To bind the anhydride at the terminal position, 1.5 g of 2-hydroxyethyl methacrylate was added to the reaction solution.After stirring at room temperature for 2 hours, 12.1 g of 2-isocyanate ethyl methacrylate was added to the reaction solution, and the mixture was stirred at room temperature for 24 hours. The reaction is stirred for a period of time. After the reaction is complete, this reaction solution is added dropwise to ethanol 41 with stirring. The precipitate formed at this time is suction filtered and dried at room temperature in vacuo. The VN of the polymer thus obtained is shown in the same table. The polymer solution (varnish) listed in Table 1 (1-5) is
It is synthesized as follows. That is, diamines in the amounts shown in Table 1 (1-5) were placed in a flask equipped with a temperature needle, a stirring device, and a drying tube, and then polymers P-1(A) and P-
5(A), P-10(A), and P-19(A), the concentration was 30%, and P-1(AM)P
For -42 (AM) and P-47 (AM), NMP was added so that the concentration was 10%, and the mixture was stirred and dissolved.Next, the tetracarboxylic dianhydride listed in the same table was added to this while stirring. . This reaction solution was stirred and reacted at room temperature for about 6 hours to obtain polyamic acid varnish shown in Table 1 (1-5). The same table shows the molecular weight (VN) of the polymer obtained by reprecipitating this polyamic acid varnish in ethanol. In addition, the abbreviations of tetracarboxylic dianhydride, diamine, and alcohol used in Examples and Comparative Examples are shown below. --Carbon diamine 7 diamine-PD H? (tNH2 0DA H2N-o-O+NH2 H3 EA CH2=C)I-8-0-C)12-C)12-0)1
EO C) 13-0-C) I2-CIl 08 Table 1 Compound List (]-I1 Polymer (1-2) Polymer (1-3) Polymer (1-4) Polymer (1-5) Polyamide Acid varnish (2) Photopolymerization initiator (3) Heptanomer (7) Polymerization inhibitor Examples 1 to 44.49, Comparative Examples 1 to 13 For 100 parts by weight of the polymer shown in Table 2, additives were added in the same amount. Add the parts by weight shown in , and dissolve in 150 parts by weight of N and methylpyrrolidone to obtain a photosensitive composition.The resulting solution was spin-coded onto a silicon wafer (2000 rpa+ x 3 Q seconds).
A uniform coating film was obtained by drying in air at 70° C. for 90 minutes. The film thickness of the coating film was about 20 μ-. Next, it was exposed to light through a test pattern photomask under a nitrogen atmosphere. For exposure, Canon FPA 1550
MII (Illuminance on the silicon wafer surface is 520mW
/cd) was used. After this wafer was left at room temperature for 1 hour, it was developed with a mixed solution of N-methylpyrrolidone/isopropyl alcohol-3/1 (volume ratio) using a spray type developer, rinsed with isopropyl alcohol, and dried. The photosensitivity was determined from the exposure amount at which the 20 μ-line and space portions of the test pattern were clearly resolved (the smaller the exposure amount, the higher the photosensitivity). The obtained results are shown in the same table. From this result, the photosensitive composition according to the present invention was able to be patterned in the same manner as the conventional photosensitive composition made of a polyimide precursor, and was also able to form a very sharp pattern. Furthermore, it can be seen that it has sensitivity to a light source (g-line) even without adding a photosensitizer. Examples 45 to 48, Comparative Example 14.15 In the same manner as Examples 1 to 44, a photosensitive composition consisting of the polymer and additives listed in Table 2 was coated on a silicon wafer, and a film thickness of about lθμ was obtained. A coating film was obtained. Next, after exposure in the same manner, 3% choline aqueous solution/isopropyl alcohol/diglyme-70/5/25 (
A pattern was obtained by developing with a solution (volume ratio) and rinsing with water. The results are shown in the same table. From the results, the photosensitive composition according to the present invention can also be developed using phulkari. However, as the polymer molecular weight increases, the developability deteriorates in both solvent development and alkali development. The optimal molecular weight is VN<80 (m17g), VN>1
It can be seen that development cannot be carried out at 00 (ml/g). Example 50.51 The photosensitive compositions prepared in Examples 45 and 47 were further treated with N.
, N'-dimethylaminoethyl methacrylate were added in an amount of 11.0 g and 19.2 g, respectively, and evaluated in the same manner as in Examples 1 to 44. In both cases, the sensitivity was 560 mJ/-
Met. (Margin below)

[Evaluation of film physical properties]

°1 The photosensitive compositions used in Examples 1 to 49 and Comparative Examples 1 to 13 were spin-coated onto an aluminum disk with a thickness of 5a+m and a diameter of 1.5cm to a thickness of about 30μm. . Dry at 70°C for 1 hour, cool, and then use an ultra-high pressure mercury lamp (8II
Width 3III using IW/cIi) and a photomask.
11. A dumbbell-shaped pattern having a straight portion with a length of 20 mm+ and a slightly wider portion for sandwiching was exposed for 120 seconds. Next, this was developed with a solvent or alkali, and the pattern thus obtained was heated under a nitrogen stream at 140°C for 2 hours and at 450°C for 2 hours to obtain an aluminum disk with a polyimide pattern. . This was soaked in 3N hydrochloric acid to melt the aluminum, washed with water, and dried at 70°C for 8 hours to obtain a test piece. From this test piece, a tensile tester (TENSION, manufactured by Toyo Baldwin) was used.
The tensile strength, elongation, and tensile modulus were measured using UTM-If-20 type). U of Table 128 Polyamic acid ester (P-52) to (P-
55) 100 ffi parts were added, 150 parts by weight of NMP was added, and the mixture was stirred and dissolved to obtain a polymer varnish. The mechanical strength of the polymer film of this polymer varnish, the non-photosensitive polyamic acid varnish listed in Table 1 (1-5), and the composition used in Comparative Example 14.15 was measured as follows. . That is, this varnish was applied uniformly to a glass plate using an applicator, dried at 80 to 100°C for 30 to 60 minutes to form a film, peeled off from the glass plate, fixed on an iron frame, and heated for 140 minutes under a nitrogen stream. °C, 400 °C
A polyimide film having a thickness of about 15 μm was obtained by holding the film for 2 hours. This was cut into a 3 mm x 8 (la + s) to obtain a test piece. Using this, the measurement of mechanical strength was carried out in the same manner as in -■ Examples 1 to 49, Comparative Examples 1 to 13 The photosensitive composition used in the above was spin-coated onto a 3-inch silicon wafer and dried at 70°C for 1 hour to obtain a coating film of about 30 μm. A 1.51 square grid pattern was exposed for 120 seconds using a predetermined photomask.Hereafter, development and heat curing were performed in the same manner as in the mechanical strength measurement-■, and a water-resistant pattern was formed on a silicon wafer. A diagonal pattern was obtained for adhesion evaluation. Next, this sample was left in an atmosphere of 133°C, 3 atm, and 100% humidity for 100 hours, and then subjected to a tape peeling test (
Scotch (Mending Tape manufactured by Sumitomo 3M) was used to measure the residual rate of the pattern. -■ A polymer varnish consisting of the non-photosensitive polyamic acid varnish and polymers (P-52) to (P-55) listed in Table 1 (1-5) was spin coated on a *3 inch silicon wafer, and After drying at ℃ for 1 hour, under nitrogen stream, 140℃, 40
A polyimide coating film having a thickness of approximately 15 μm was obtained by holding each sample at 0° C. for 2 hours. Next, a cant of 5 ma+square was placed in this coating film to prepare a sample for evaluation of water-resistant adhesion. Hereinafter, evaluation of water resistant adhesion was carried out in the same manner as in ①. *0.2 of γ-aminopropyldimethoxymethylsilane
% methanol solution was spin-coated at 5000 rpm for 30 seconds and heated on a hot plate at 150° C. for 10 minutes. 3-inch silicon wafer with a shallow depth of 5 dB and a thickness of 370 μm (when applying non-photosensitive polyamic acid and polyamic acid ester varnishes, perform silane treatment as in the evaluation of water-resistant adhesion - ■)
The photosensitive compositions used in Examples 1 to 49 and Comparative Examples 1 to 13, and the polyamic acid varnishes and polymers (P-52) to (P-55) listed in Table "L(1-5)" The varnish was spin-coated to a film thickness of 10-15 μm, dried at 90°C for 1 hour, and then dried at 140°C for 2 hours for 40
It was heated at 0° C. for 2 hours to obtain a polyimide coating. After cooling, the curvature of the central portion 3cn+ of the back of the wafer was measured using a contact type surface roughness needle (manufactured by SLOAN, DEKTA, IIA). The distance from the center of the string of the obtained figure that can be approximated to an almost arch shape to the bow is measured, and if this distance is set as Δ, then the residual stress δ is expressed by the following equation (1). E: Young's modulus of silicon wafer ■: Poisson's ratio of silicon wafer: Veri constant length Ts: Thickness of silicon wafer T: Coating film thickness (after curing) Here, the dotted line in the equation is the value specific to silicon wafer. Therefore, it becomes a constant in this measurement. Therefore,
The residual stress δ is expressed by the following equation (2). Δ δ−K・−(2) Here, the value of K is calculated as K = 3.91 (Kg/a+♂).Next, the paint film was scratched and measured using the same contact type surface roughness meter. The coating film thickness T was measured, and the value of residual stress δ was obtained from T, Δ, and K according to equation (2).
-P-1(AM), P-42(AM), P-47(
When creating a sample using a varnish obtained from AM), multiple layers were required to obtain the desired film thickness. Chamber of the photosensitive composition, polyamic acid ester varnish, and polyamic acid varnish used in the measurement of residual stress! The change in viscosity (value measured with an E-type viscosity needle at 23°C) after standing for 2a was determined. The above evaluation results are summarized in Table 3. In addition, in the table, "brittle" in the elongation column means that it was brittle and could not be measured. In addition, in the storage stability evaluation, + means an increase in viscosity, and - means a decrease in viscosity. From these results, the low-stress, heat-resistant coating film obtained from the polymer varnish and photosensitive composition made of the polymer of the present invention has a low stress and heat-resistant coating film that leaves very little stress on the silicon wafer during heat curing compared to conventional polyimide. It can be seen that it is a material with a high expansion rate. In addition, compared to conventional polyimides with low thermal expansion coefficients, the inclusion of a petrostructure in the skeleton improves brittleness, and although polymers containing imidazole rings are slightly affected by moisture, other heterocycles are The polyimide contained also has excellent water-resistant adhesive properties. or,
Conventionally water-treated betero ring-containing polyimides generally have a large coefficient of thermal expansion, and the residual stress on silicon wafers is greater than that of ordinary polyimide groups. Furthermore, the polymer according to the present invention and the photosensitive composition made from it have extremely high stability against hydrolysis compared to conventionally used polyamic acids, so even if the molecular weight is the same, the physical properties of the final polyimide will be affected. It can also be seen that there is a big difference. To solve this problem, polyamic acid with a high molecular weight was used to improve its physical properties, but due to its poor solubility in solvents,
There are problems in terms of formability, such as the solution concentration being very dilute and a film having the desired thickness not being easily obtained. These problems are solved by using the photosensitive composition of the present invention. (Left below) Example 52.53, Comparative Example 16.11 A 30% NMP solution was prepared using polyamic acid esters (P-52>, (P-53), (P-54), and (P-55)) Coated on rolled copper foil with a thickness of 35 μm and heated at 80°C in air.
Heat for 60 minutes, then -1Ii! The foil was fixed and heat treated in a nitrogen atmosphere at 140° C. for 30 minutes and at 400° C. for 60 minutes to obtain a substrate for a flexible printed wiring board having a film thickness of about 20 μm. The substrates obtained using polyamic acid esters (P-52) and (P-53) did not curl after heat treatment or etching. Further, even when immersed in a solder bath at 350°C, there was almost no swelling or change in shape. On the other hand, the substrates made using polyamic acid esters (P-54) and (P-55>) were curled with the polyimide film surface inward due to heat treatment. Example 54 Photosensitive material used in Example 2 An α-ray shielding film was formed using the photosensitive composition on a large number of memory elements formed on a silicon wafer with a diameter of 5 inches.That is, first, the photosensitive composition was coated on the silicon wafer so that the film thickness after curing would be about 601 zm. After drying it at 80°C for 1 hour, it was exposed to light through a photomask and developed to form a polyimide film only on the memory element, and then heated at 140°C. An α-ray shielding film was formed on the memory element by heat curing at 400°C for 1 hour and 2 hours at 400°C.As a result, when the above photosensitive composition was used, it was formed without any abnormality. I was able to save 133 wafers of
There was no change in the pressure tanker test (hereinafter abbreviated as PCT) for 100 hours at 3 atm at ℃. Comparative Example 1 Translation 19 Polyamic acid varnish P- described in Table 1 (1-5) above
Example 5 using P-42 (AM) and P-47 (8M)
An α-ray shielding film was formed in the same manner as in 1. That is, first, a 0.2% methanol solution of T-aminopropyldimethoxymethylsilane was applied onto a silicon wafer, and the mixture was heated at 200°C for 15 minutes.
Heat treated for minutes. Next, each of the polyamic acid varnishes was applied using a spin coater so that the thickness after curing was 60 μm.
Since it was not possible to form a single layer, multiple layers had to be applied. Furthermore, it was difficult to obtain a uniform coating because of the multilayer coating. Next, dry and half cure at 90"C for 1 hour at 250"C.
'C I went there in 1 hour. Next, in order to leave the resist only on the memory element, patterning was performed using a photoresist and etching was performed using a mixed solution of hydrazine and ethylenediamine. At this time, the etching speed was considerably affected by the half-cure conditions of polyimide, causing problems in process reproducibility. Thereafter, the photoresist was further removed and heat treatment was performed at 400° C. for 2 hours to form an α-ray shielding film on the memory element. As a result, when polyamic acid varnish made of P-42 (AM) was used, it was possible to form the film without any abnormality, but when this wafer was subjected to PCT at 133°C, 3 atm, and 100 hours, the polyimide film peeled off. Then the problem arose,
Unfavorable results were obtained in terms of long-term reliability. or,
P-47 (^ When using the old polyamic acid varnish, there are problems such as the wafer being greatly bent due to thermal stress after the polyimide film etching and final processing steps, and in extreme cases, the memory element may peel off from the wafer. Example 55 Using the photosensitive composition used in Example 6, an LSI having a two-layer wiring structure as shown in FIG. After forming an AI film for wiring by sputtering, a first layer of wiring 22 was formed through patterning using a photoresist, etching, and a resist removal process.The photosensitive composition was coated on top of this. After drying, the polyimide layer 2 having through-holes with a thickness of about 1 μm was formed by patterning and curing by heating at 140° C. for 30 minutes and 400° C. for 1 hour.
After the surface treatment was carried out after forming No. 3, a second layer of AI wiring 24 was formed by sputtering, and polyimide llllI 25 was further formed in the same manner as the first layer. An stN film 26 is formed on the surface of this polyimide film by plasma CVD, and electrodes are formed by etching and heat cycle (
After the test (150°C, -50°C), no abnormality occurred. Further, there was no change after PCT at 133° C. and 3 atm pressure for 100 hours. Comparative Example 20 Polyamic acid varnish P- described in Table 1 (1-5) above
5(A), an LSI having a two-layer wiring structure was similarly created. First, on the LSI created by the predetermined operation,
After forming the first layer of wiring AI film by sputtering, the first layer of AI wiring was formed through patterning using photoresist, etching, and resist removal steps. Next, a 0.2% methanol solution of T-aminopropyldimethoxymethylsilane was applied and heat treated at 200°C for 15 minutes, and then the above polyamic acid varnish was applied so that the film thickness after curing would be about 1 μI, and heated at 90°C. After drying for 20 minutes with
Through-holes were formed in the polyimide film by patterning, etching, and photoresist removal using a 0-order photoresist that had been cured at 50°C for 30 minutes and then at 350"C for 30 minutes. Next, after surface treatment, two layers were formed. A of the wiring
IIQ was formed by sputtering, and 11 wirings were patterned in the same manner as the first layer. After forming a polyimide film in the same manner, a SiN film was formed by plasma CVD, and electrodes were formed by etching.
A crank had occurred in the SiN film. Also, 13 wafers
When left for 24 hours at 3°C and 3 atm, corrosion occurred in the internal AI wiring. Example 56 After cleaning a ceramic substrate of 50 mm square and 1 nua thickness, 1000 Crx and 2
Deposit 500 Å of Cu. Thereafter, a photoresist for the Menki resist was patterned to a thickness of 6 μm. Subsequently, it was placed in a copper sulfate plating bath, and the current density was 50 mA/c.
Copper plating was performed in step d, with a thickness of 5 μm and a line width of 50 μm.
A copper pattern with a land diameter of 100 μm and a land spacing of 500 μm was obtained. After removing the Menki resist with a special remover, remove unnecessary Cu with an ammonium persulfate aqueous solution and a cerium nitrate aqueous solution.
And the Cr layer was quick-notched. The photosensitive composition prepared in Example 49 was spin-coded onto the obtained first-layer wiring board, and then dried for 40 minutes using a hot air dryer at 70°C. Next, 5 black circles with a diameter of 75 μm are added to this.
A photomask with a lattice spacing of 0.08 m was attached with vE, and exposure was performed for 2 minutes using an exposure machine equipped with a 250-m ultra-high pressure mercury lamp. After further developing this, under a nitrogen atmosphere, 140
Polyimide with a thickness of 10 μm was obtained by heating and curing at ℃ for 1 hour and 400℃ for 2 hours. A hard insulating layer was formed. Next, after cleaning and roughening the surface of several layers and the inside of the via hole, this was subjected to pretreatment for electroless copper plating, and then electroless copper plating was performed. Next, a second layer wiring pattern having a thickness of 5 μm was formed by electroplating in the same manner as the first layer wiring pattern. Repeat insulating layer formation and wiring pattern formation in the same way,
A multilayer wiring board consisting of four wiring layers was manufactured. Using a multilayer wiring board with 500 via holes,
After conducting a heat shock test of 60 minutes with dry heat and 60 minutes of leaving at room temperature at 23°C 50 times, via hole connection reliability evaluation was performed, and no abnormality such as disconnection was observed. Further, this multilayer wiring board was subjected to PCT at 133° C. and 3 atm for 100 hours, but no abnormality was observed. Note that FIG. 2 shows a specific example of each step in manufacturing a multilayer wiring board. 4. Brief explanation of the drawings Figure 1 shows an LS with a two-layer wiring structure obtained in the example.
FIGS. 2A-2J are vertical sectional views showing an example of each process in the production of a multilayer wiring board. 21...LSI (upper layer 5iO1, lower layer silicon wafer) 22...aluminum wiring 23...polyimide layer 24...aluminum wiring 25...polyimide layer 26...SiN film 1...support substrate 2 ...First layer wiring pattern 3...Photosensitive composition 4...Photomask 5...Portion hardened by ultraviolet rays 6...Polyimide layer 7...Via hole hole 8...None Plating active layer 9 by electrolytic plating or sputtering method...Photoresist for plating 10...Plating mask 11 cured by ultraviolet rays...Conductor layer by electroplating Patent applicant representative Asahi Kasei Corporation Patent attorney Toru Hoshino

Claims (3)

[Claims] (1) General formulas [I] and [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼…[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼…[II] [In the formula, A_r has 6 to 30 carbon atoms A tetravalent aromatic group, X is a divalent organic group having 6 to 30 carbon atoms, A and B are each independently a group selected from -OR_1, ▲Formula, chemical formula, table, etc.▼ and -OH However, both A and B are not -OH groups. Here, R_1 and R_2 are organic groups having 1 to 20 carbon atoms] In polymers consisting of repeating units represented by the following general formulas [III] and [IV] ▲Mathematical formulas, chemical formulas, tables, etc.▼ …[III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼…[IV] [In the formula, A_r_1 is an aromatic group selected from ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The groups, A, and B are the same as above, and X_1 is ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ has a mathematical formula, chemical formula, table, etc. ▼ (A_r_2 in the formula is ▲ has a mathematical formula, chemical formula, table, etc.) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A_r_3 is an aromatic group selected from ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼The aromatic group selected from Y is ▲ There are mathematical formulas, chemical formulas, tables, etc.▼
Or ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ A group selected from
g/dl, ηsp/C value, however, ηsp=(η-η
_ρ)/η_ρ, η: polymer solution viscosity, η_ρ
: Viscosity of solvent (N-methylpyrrolidone): Measurement temperature 30
℃] A precursor capable of providing a low stress polyimide of 10 to 200 ml/g. (2) In claim (1), the general formula [I], [
II], [III], and [IV], R_1 and R_2 are represented by a group having a carbon-carbon double bond, and the viscosity number is 10 to 100.
ml/g of a polymer and a photoinitiator. (3) An electronic material obtained by combining the low stress polyimide precursor according to claim (1) and the photosensitive composition according to claim (2) with a metal, ceramic, or other inorganic material and curing the mixture by heating. Low stress polyimide composite molded body for materials.