JP4876851B2 - Heat-resistant resin precursor composition and semiconductor device using the same - Google Patents

Description

  The present invention relates to a heat resistant resin precursor composition and a semiconductor device using the same. More specifically, the present invention relates to a heat-resistant resin precursor composition suitably used for an interlayer insulating film, a surface protective film, and the like in the semiconductor field, and a semiconductor device using the same.

  The heat-resistant resin precursor composition is used as an interlayer insulating film, a surface protective film (buffer coat film, alpha ray shielding film) and the like in the semiconductor field. When the heat-resistant resin precursor composition is used for semiconductor applications, the heat-resistant resin after heat-curing remains as a permanent film in the device, and thus the adhesive property of the heat-cured film is very important. In order to ensure reliability in semiconductor packages, not only adhesives with silicon-based materials formed on the surface of semiconductor chips such as silicon, silicon oxide, silicon nitride, and phosphorous silicate glass, but also packages represented by epoxy resin Adhesion with the material is important.

Particularly in recent years, higher reliability is required for package materials, and materials having higher adhesion than conventional polyimide materials are required. In order to solve this problem, a positive photosensitive resin composition containing an organosilicon compound has been proposed (see, for example, Patent Document 1-2). However, even if this method is used, sufficient adhesion improvement effect cannot be obtained, and the chemical composition and surface roughness of the surface are changed by treating the heat-resistant resin surface after heat curing with oxygen plasma etc. The main method was to improve the adhesion by improving the above. However, since the improvement in the process is costly and damages the film itself, it is not necessary to improve the adhesion in the process, and the heat resistant resin precursor composition having high adhesion is not required. Demand was increasing.
Japanese Patent Laid-Open No. 10-22281 JP-A-11-102069

  Materials used in the semiconductor industry are required to have high adhesion at different material interfaces. The present invention relates to a heat-resistant resin precursor composition having high adhesion between a heat-cured film and a packaging material such as an epoxy resin, in particular, low degradation of adhesive properties even under high temperature and high humidity, and a semiconductor device using the same The purpose is to provide.

  The present invention is a heat-resistant resin precursor composition comprising a resin composed mainly of a repeating unit represented by the following general formula (1) or a repeating unit represented by the following general formula (2). is there.

(In General Formula (1), R ¹ represents a divalent to hexavalent organic group having 2 or more carbon atoms. Q represents an integer of 0 to 4. R ² represents a carbon containing an aromatic ring or an aromatic condensed ring. the ^.R 3 to R ⁶ which indicates the number 6-30 organic group may be the same or different, ^.R 7 ^{to R 10} showing an organic group having 6 to 30 carbon atoms containing an aromatic ring or aromatic fused ring It may be the same or different, and consists of —H, —F, —OH, —NHR ¹⁵ , —NHCOR ¹⁶ , —N═CHR ¹⁷ , an alkyl group having 1 to 20 carbon atoms, and a fluoroalkyl group having 1 to 10 carbon atoms. R ¹¹ and R ¹² are each an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring, and R ¹³ and R ¹⁴ are hydrogen or 1 to C carbon atoms. 20 represents an organic group, provided that COOR ¹³ represents —R ¹ —NHCO—R ^11. -Relative to the CO group in the main chain, COOR ¹⁴ is in the ortho position relative to the CO group in the main chain -R ¹² -CONH-R ^1, where a is 1 or 2, and b and c are 0 Or R ¹⁵ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ¹⁶ and R ¹⁷ represent a monovalent organic group having 1 to 20 carbon atoms.

In the general formula (2), R ¹⁸ represents a divalent to octavalent organic group having 2 or more carbon atoms. R ¹⁹ may be the same or different and represents hydrogen or an organic group having 1 to 20 carbon atoms. m represents an integer of 0 to 2, and p represents an integer of 0 to 4. R ²⁰ represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{21 to} R ²⁴ may be the same or different and each represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{25 to} R ²⁸ may be the same or different and are —H, —F, —OH, —NHR ²⁹ , —NHCOR ³⁰ , —N═CHR ³¹ , an alkyl group having 1 to 20 carbon atoms, and 1 to 10 carbon atoms. And a monovalent group selected from the group consisting of fluoroalkyl groups. d and e are 0 or 1, and f is 1 or 2. However, ^{R 25} when d is 0, ^{R 26} are each ^-NHR 29 when e is ^0, -NHCOR 30, a group selected from the group consisting of -N = ^{CHR 31.} R ²⁹ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ³⁰ and R ³¹ represent a monovalent organic group having 1 to 20 carbon atoms. )

  According to the present invention, there is provided a heat resistant resin precursor composition having a small adhesive deterioration under high temperature and high humidity between a heat-cured film and a package material by containing a resin having a specific repeating unit as a main component. Can be provided. A semiconductor device having a cured film obtained by heat-treating the heat-resistant resin precursor composition of the present invention can maintain high reliability over a long period of time.

  Hereinafter, the present invention will be described in detail. The heat resistant resin precursor composition of the present invention is a resin having a repeating unit represented by the following general formula (1) or a repeating unit represented by the following general formula (2) (hereinafter referred to as a heat resistant resin precursor). In some cases). As a result, a heat resistant resin precursor composition with little deterioration in adhesion with the package material under high temperature and high humidity after heat curing is obtained. Here, the main component means that the repeating unit represented by the following general formula (1) or the repeating unit represented by the following general formula (2) contains 70% or more of the total structural units, preferably It is 80 mol% or more, more preferably 90 mol% or more.

In general formula (1), R ¹ represents a divalent to hexavalent organic group having 2 or more carbon atoms. q shows the integer of 0-4. R ² represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{3 to} R ⁶ may be the same or different and each represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{7 to} R ¹⁰ may be the same or different, and are —H, —F, —OH, —NHR ¹⁵ , —NHCOR ¹⁶ , —N═CHR ¹⁷ , an alkyl group having 1 to 20 carbon atoms, and 1 to 10 carbon atoms. And a monovalent group selected from the group consisting of fluoroalkyl groups. R ¹¹ and R ¹² represent an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ¹³ and R ¹⁴ represent hydrogen or an organic group having 1 to 20 carbon atoms. However, COOR ¹³ is in the ortho position with respect to the CO group in the —R ¹ —NHCO—R ¹¹ — main chain, and COOR ¹⁴ is in the ortho position with respect to the CO group in the —R ¹² —CONH—R ¹ — main chain. is there. a is 1 or 2, b and c are 0 or 1. R ¹⁵ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ¹⁶ and R ¹⁷ represent a monovalent organic group having 1 to 20 carbon atoms.

In the general formula (2), R ¹⁸ represents a divalent to octavalent organic group having 2 or more carbon atoms. R ¹⁹ may be the same or different and represents hydrogen or an organic group having 1 to 20 carbon atoms. m represents an integer of 0 to 2, and p represents an integer of 0 to 4. R ²⁰ represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{21 to} R ²⁴ may be the same or different and each represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{25 to} R ²⁸ may be the same or different and are —H, —F, —OH, —NHR ²⁹ , —NHCOR ³⁰ , —N═CHR ³¹ , an alkyl group having 1 to 20 carbon atoms, and 1 to 10 carbon atoms. And a monovalent group selected from the group consisting of fluoroalkyl groups. d and e are 0 or 1, and f is 1 or 2. However, ^{R 25} when d is 0, ^{R 26} are each ^-NHR 29 when e is ^0, -NHCOR 30, a group selected from the group consisting of -N = ^{CHR 31.} R ²⁹ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ³⁰ and R ³¹ represent a monovalent organic group having 1 to 20 carbon atoms.

  The heat-resistant resin precursor used in the present invention has an amide bond in the main chain and is a polyimide precursor, polyamic acid, polyamic acid ester, polyhydroxyamide that can be a polybenzoxazole precursor, polybenzimidazole precursor Examples include polyaminoamides that can form polybenzoamides, polythiohydroxyamides that can form polybenzothiazole precursors, polyamides, polyamideimides, and the like. In addition to these, the repeating unit represented by the above general formula (1) or the above general formula What is necessary is just resin which has the repeating unit represented by (2) as a main component. These resins are remarkably improved in heat resistance and solvent resistance by forming a cyclic structure by heating or an appropriate catalyst.

In the general formula (1), residues constituting the R ¹ represents a structural component of a diamine, a divalent to hexavalent organic group having 2 or more carbon atoms. From the viewpoint of heat resistance, R ¹ is preferably a divalent to hexavalent organic group having 6 to 30 carbon atoms and containing an aromatic ring or an aromatic heterocyclic ring. q shows the integer of 0-4.

Preferable examples of —R ¹ (OH) _q — include those represented by the following general formula (5) or hydrogenated products thereof.

Here, R ³² is a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —,> C═O, —SO ₂ —, —O—, —S—. A group selected from the group consisting of R ³³ and R ³⁴ may be the same or different and each represents a monovalent group selected from the group consisting of —F, —OH, an alkyl group having 1 to 20 carbon atoms, and a fluoroalkyl group having 1 to 10 carbon atoms. Preferably they are a C1-C5 alkyl group or a C1-C5 fluoroalkyl group. o, s, and t represent an integer of 0-4. The range of o and s is preferably 0 to 2, more preferably 0 or 1. Moreover, 0-3 are preferable and, as for the range of t, 0 or 1 is more preferable. Preferable specific examples include the following structures or hydrogenated products thereof.

In the structure X of the general formula (1), R ² represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. The total number of aromatic rings and fused aromatic ring contained in R ² is 1-2 are preferable. Preferable specific examples of R ² include the following structures, but are not limited thereto.

In the structure X of the general formula (1), R ^{3 to} R ⁶ may be the same or different and each represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. It preferably has one aromatic ring or one aromatic condensed ring. R ^{7 to} R ¹⁰ may be the same or different, and are —H, —F, —OH, —NHR ¹⁵ , —NHCOR ¹⁶ , —N═CHR ¹⁷ , an alkyl group having 1 to 20 carbon atoms, and 1 to 10 carbon atoms. And a monovalent group selected from the group consisting of fluoroalkyl groups. Here, R ¹⁵ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ¹⁶ and R ¹⁷ represent a monovalent organic group having 1 to 20 carbon atoms. From the viewpoints of heat resistance and adhesiveness, R ^{7 to} R ¹⁰ are preferably groups selected from the group consisting of —H, —F, —NHR ¹⁵ , —NHCOR ¹⁶ and —N═CHR ¹⁷ . In particular, it is more preferable that R ^{7 to} R ¹⁰ are groups selected from the group consisting of —NHR ¹⁵ , —NHCOR ¹⁶ and —N═CHR ¹⁷ and are ortho to the amide group of the main chain. In this case, there is an advantage that heat resistance is further improved by forming a heterocyclic ring by heat treatment. R ¹¹ and R ¹² represent an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. Among them, particularly preferred structures include trimellitic acid and naphthalene tricarboxylic acid residue. R ¹³ and R ¹⁴ represent hydrogen or an organic group having 1 to 20 carbon atoms. However, COOR ¹³ and COOR ¹⁴ may be the same or different, COOR ¹³ is —R ¹ —NHCO—R ¹¹ —the CO group in the main chain, and COOR ¹⁴ is —R ¹² —CONH—R ¹ —the main. Each is in an ortho position relative to the CO group in the chain. a represents 1 or 2, and is preferably 2. Moreover, it is more preferable that the a-OH group is in an ortho position with respect to the main chain of the resin. In this case, there is an advantage that heat resistance is further improved by forming a heterocyclic ring by heat treatment. b and c are 0 or 1.

  Although the structure shown below is mentioned as a preferable specific example of the structure represented by the structure X of General formula (1), It is not limited to these.

In the structure of the general formula (1), preferably b = c = 0 and R ⁷ and R ⁸ each represents a group selected from the group consisting of —NHR ¹⁵ , —NHCOR ¹⁶ and —N═CHR ¹⁷ ; , B = c = 1, and R ^{7 to} R ¹⁰ each represent a group selected from the group consisting of —NHR ¹⁵ , —NHCOR ¹⁶ and —N═CHR ^17, wherein R ¹ (OH) _q is the above [ This is a case represented by at least one structure selected from Chemical Formula 4]. In this combination, since more heterocycles per structural unit are formed by heat curing, there is an advantage that the deterioration of the adhesive properties to the package material is further reduced, and the heat resistance and mechanical properties are improved.

In the general formula (2), R ¹⁸ represents a divalent to octavalent organic group having 2 or more carbon atoms. R ¹⁹ may be the same or different and represents hydrogen or an organic group having 1 to 20 carbon atoms. m represents an integer of 0 to 2, and p represents an integer of 0 to 4. Preferable specific examples of —R ¹⁸ (OH) _p (COOR ¹⁹ ) _m — include, but are not limited to, those represented by the following general formula (6).

In the general formula (6), R ³⁵ represents a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —,> C═O, —SO ₂ —, —O— and A group selected from the group consisting of -S- is shown. R ³⁶ and R ³⁷ may be the same or different and are a monovalent group selected from the group consisting of —H, —F, —OH, an alkyl group having 1 to 20 carbon atoms, and a fluoroalkyl group having 1 to 10 carbon atoms. Indicates. Preferably, it is a monovalent group selected from the group consisting of -H, an alkyl group having 1 to 5 carbon atoms and a fluoroalkyl group having 1 to 5 carbon atoms. R ³⁸ and R ³⁹ may be the same or different and each represents a monovalent group selected from the group consisting of —H, an alkyl group having 1 to 20 carbon atoms, and a fluoroalkyl group having 1 to 10 carbon atoms. Preferably, it is a monovalent group selected from the group consisting of -H, an alkyl group having 1 to 5 carbon atoms and a fluoroalkyl group having 1 to 5 carbon atoms. u represents an integer of 0 to 2, and v represents 0 or 1. w represents an integer of 0 to 4, and 0 or 1 is preferable. Preferable specific examples include the following.

In the structure Y of the general formula (2), R ²⁰ represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. The total number of aromatic rings and fused aromatic ring contained in R ²⁰ is 1 to 2 is preferred. Preferable specific examples of R ²⁰ include the following structures, but are not limited thereto.

In the structure Y of the general formula (2), R ^{21 to} R ²⁴ may be the same or different and each represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. It preferably has one aromatic ring or one aromatic condensed ring. R ^{25 to} R ²⁸ may be the same or different and are —H, —F, —OH, —NHR ²⁹ , —NHCOR ³⁰ , —N═CHR ³¹ , an alkyl group having 1 to 20 carbon atoms, and 1 to 10 carbon atoms. And a monovalent group selected from the group consisting of fluoroalkyl groups. Here, R ²⁹ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ³⁰ and R ³¹ represent a monovalent organic group having 1 to 20 carbon atoms. From the viewpoints of heat resistance and adhesiveness, R ^{25 to} R ²⁸ are preferably groups selected from the group consisting of —H, —F, —NHR ²⁹ , —NHCOR ³⁰ and —N═CHR ³¹ . d and e represents 0 or 1, ^{R 25} when d is 0, ^{R 26} are each ^-NHR 29 when e is 0, a group selected from the group consisting of -NHCOR ³⁰ and -N = ^{CHR 31} . Preferably, R ^{25 to} R ²⁸ are groups selected from the group consisting of —NHR ²⁹ , —NHCOR ³⁰ and —N═CHR ^31, and are in an ortho position with respect to the main chain of the resin. In this case, there is an advantage that heat resistance is further improved by forming a heterocyclic ring by heat treatment. Similarly, R ^{29 to} R ³¹ are more preferably hydrogen or an aliphatic hydrocarbon having 1 to 5 carbon atoms from the viewpoint of heat resistance. f is 1 or 2, and 2 is preferable. Further, it is more preferable that the f number of —OH groups are in the ortho position with respect to the main chain of the resin. In this case, there is an advantage that heat resistance is further improved by forming a heterocyclic ring by heat treatment.

  Although the structure shown below is mentioned as a preferable specific example of the structure represented by the structure Y of General formula (2), It is not limited to these.

Preferred as the repeating unit represented by the general formula (2) is d = e = 0 in the general formula (2), and R ²⁵ and R ²⁶ are —NHR ²⁹ , —NHCOR ³⁰ and —N═CHR, respectively. If a group selected from the group consisting of ^31, or, d = a e = 1 ^R 25 ~R ²⁸ respectively ^-NHR 29, a group selected from the group consisting of -NHCOR ³⁰ and -N = ^{CHR 31} This is the case. In this combination, since more heterocycles per repeating unit are formed by heat curing, there is an advantage that the deterioration of the adhesive property to the package material becomes smaller. Furthermore, in these combinations, from the viewpoint of improving heat resistance and mechanical properties, it is more preferable that R ¹⁸ (COOR ¹⁹ ) _m (OH) _p is represented by at least one structure selected from the following structures.

  Each of the repeating units represented by the general formula (1) or (2) may be used alone, or a plurality of repeating units may be mixed or copolymerized. Moreover, the other structural unit may be included as needed.

  The weight average molecular weight of the heat-resistant resin precursor used in the present invention is preferably 1,000 or more in terms of polystyrene by gel permeation chromatography from the viewpoint of heat resistance after heat treatment and mechanical properties, and 5,000. The above is more preferable. The upper limit is preferably 100,000 or less, and more preferably 50,000 or less from the viewpoint of solubility in a developer when the photosensitive resin precursor composition is used.

  The heat-resistant resin precursor used in the present invention is synthesized by a known method. For example, in a polyimide precursor, a tetracarboxylic dianhydride and a diamine are selectively combined, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethyl. A method such as reacting in a polar solvent mainly containing phosphorotriamide or a solvent mainly containing γ-butyrolactone, or after reacting tetracarboxylic dianhydride with an alcohol compound, thionyl chloride, etc. Used to synthesize acid chlorides and then selectively combine with a suitable diamine, or with a suitable dehydrating agent such as dicyclohexylcarbodiimide, and selectively combine with a diamine, which are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl A method of reacting in a polar solvent mainly containing sulfoxide, hexamethylphosphorotriamide or the like, or a solvent mainly containing γ-butyrolactone, or tetracarboxylic dianhydride and diamine selectively. In combination, these are polar solvents mainly composed of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide and the like, and γ-butyrolactone as a main component. After the reaction in the solvent, a part of the side chain carboxyl group can be obtained by alkyl esterification using an esterification reagent or the like.

  For example, in the case of polybenzoxazole precursor and polybenzimidazole precursor, condensation of dihydroxydiamine or tetraamine with a halogenated dicarboxylic acid, or condensation of dihydroxydiamine or tetraamine with dicarboxylic acid in the presence of a dehydration condensing agent such as dicyclohexylcarbodiimide. Alternatively, dihydroxydiamine or tetraamine and a dicarboxylic acid ester can be obtained by a method such as an ester-amide exchange reaction.

  The heat resistant resin precursor used in the present invention is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (3) with a diamine compound, or a diamine compound represented by the following general formula (4) And tetracarboxylic dianhydride, dicarboxylic acid or a diesterified product thereof can be obtained. By reacting a tetracarboxylic dianhydride represented by the following general formula (3) with a diamine compound, a resin having a repeating unit represented by the general formula (1) is obtained. Moreover, the resin which has a repeating unit represented by General formula (2) by making the diamine compound represented by following General formula (4), and tetracarboxylic dianhydride, dicarboxylic acid, or its diesterified product react. can get.

In General Formula (3), R ^{3 to} R ⁶ may be the same or different and each represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{7 to} R ¹⁰ may be the same or different, and are —H, —F, —OH, —NHR ¹⁵ , —NHCOR ¹⁶ , —N═CHR ¹⁷ , an alkyl group having 1 to 20 carbon atoms, and 1 to 10 carbon atoms. And a monovalent group selected from the group consisting of fluoroalkyl groups. R ¹¹ and R ¹² represent an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. a is 1 or 2, b and c are 0 or 1. R ¹⁵ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ¹⁶ and R ¹⁷ represent a monovalent organic group having 1 to 20 carbon atoms.

In the general formula (4), R ²⁰ represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{21 to} R ²⁴ may be the same or different and each represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{25 to} R ²⁸ may be the same or different and are —H, —F, —OH, —NHR ²⁹ , —NHCOR ³⁰ , —N═CHR ³¹ , an alkyl group having 1 to 20 carbon atoms, and 1 to 10 carbon atoms. And a monovalent group selected from the group consisting of fluoroalkyl groups. d and e are 0 or 1, and f is 1 or 2. However, ^{R 25} when d is 0, ^{R 26} are each ^-NHR 29 when e is ^0, -NHCOR 30, a group selected from the group consisting of -N = ^{CHR 31.} R ²⁹ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ³⁰ and R ³¹ represent a monovalent organic group having 1 to 20 carbon atoms.

  In particular, when the diamine compound represented by the general formula (4) is used, it is preferably at least one diamine compound selected from the following structures. The use of these diamine compounds has the advantage that the molecular weight of the polymer is improved and the mechanical properties are improved.

  Furthermore, in order to further improve the adhesive properties with a base material such as a silicon substrate or an aluminum substrate, it is preferable that at least one of both ends of the heat-resistant resin precursor contains a phenol group and / or a thiophenol group. Specific examples of the terminal containing these groups include, but are not limited to, the structures shown below.

  The heat-resistant resin precursor having a phenol group and / thiothio group at the terminal is used in the above-described various known synthesis methods when a reaction is performed by selectively combining diamine or tetracarboxylic dianhydride. It can be obtained by adding a compound having a phenol group and / or a thiophenol group (terminal agent) at the same time or slightly later than that.

  Furthermore, it is more preferable that the heat-resistant resin precursor is obtained by precipitating in a poor solvent for the resin such as methanol or water after the completion of polymerization, and then washing and drying. By reprecipitation, by-products from the polymerization agent, condensing agent, and acid chloride used during polymerization, and low molecular weight components of the resin precursor can be removed. There is a significant improvement.

  The heat-resistant resin precursor composition of the present invention contains the heat-resistant resin precursor and a solvent, and if necessary, a photoacid generator, a photoinitiator, a photopolymerizable compound, a surfactant, a silicon-based additive, and the like. .

  The heat-resistant resin precursor composition of the present invention may contain a photoacid generator and can impart positive photosensitivity. Examples of the photoacid generator include a quinonediazide compound and a sulfonic acid onium salt compound, but a quinonediazide compound is preferable, and an o-quinonediazide compound is particularly preferable. The quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, and a sulfonic acid of quinonediazide in an ester bond and / or sulfone. Examples include amide-bonded ones. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. When 50 mol% or more is substituted with quinonediazide, there is an advantage that the solubility in an alkali developer is improved and a fine pattern having a high contrast with the unexposed portion can be obtained. By using such a quinonediazide compound, a positive photosensitive resin precursor composition sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet ray, is obtained. be able to.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR- PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A , Bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Manufactured by Manabu Kogyo Co.) and the like, but not limited to.

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Although sulfide etc. are mentioned, it is not limited to these.

  Examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. In addition, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used together.

  Further, the molecular weight of the quinonediazide compound is preferably 300 or more, and more preferably 350 or more. Moreover, 1500 or less is preferable and 1200 or less is more preferable. When the molecular weight is 300 or more, the exposure sensitivity is high, and when it is 1500 or less, there is an advantage that the mechanical properties of the film after thermosetting are improved.

  As a whole, the content of the photoacid generator is preferably 1 part by weight or more, more preferably 3 parts by weight or more with respect to 100 parts by weight of the heat-resistant resin precursor. Moreover, 50 weight part or less is preferable and 40 weight part or less is more preferable. Moreover, 1 weight part or more is preferable with respect to 100 weight part of heat-resistant resin precursors, and, as for content of a quinonediazide compound, 3 weight part or more is more preferable. Moreover, 50 weight part or less is preferable and 40 weight part or less is more preferable. Within this range, there is an advantage that the mechanical properties of the cured film are good.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

Moreover, in order to provide negative photosensitivity, the heat resistant resin precursor composition of the present invention has an ethyl methacrylate group, an ethyl acrylate group, a propyl methacrylate as R ¹³ or R ¹⁴ in the general formula (1). A group having an ethylenically unsaturated double bond such as a group, a propyl acrylate group, an ethyl methacrylamide group, a propyl methacrylamide group, an ethyl acrylamide group, or a propyl acrylamide group can be used. Moreover, in order to improve the photosensitive performance of a heat resistant resin precursor composition, it is preferable to contain a photopolymerizable compound. As photopolymerizable compounds, 2-hydroxyethyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate ethylene glycol dimethacrylate, diethylene glycol dimethacrylate triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, methylene Examples include, but are not limited to, bismethacrylamide and methylenebisacrylamide. The photopolymerizable compound is preferably contained in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the heat resistant resin precursor. Within this range, the sensitivity is high, and the film has a good mechanical property after thermosetting. These photopolymerizable compounds can be used alone or in combination of two or more.

  As a more preferable example of the photopolymerizable compound, a compound represented by the following general formula (7) containing an ethylenically unsaturated double bond and an amino group can be given.

In the general formula ^{(7), R} 40 ~R ⁴² is an organic group having 1 to 30 carbon atoms. The organic group is preferably an aliphatic organic group, and examples thereof include, but are not limited to, a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group. However, at least one of R ^{40 to} R ⁴² includes an ethylenically unsaturated double bond.

  Preferred specific examples of the compound represented by the general formula (7) include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethyl Examples include aminopropyl acrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, diethylaminopropyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl methacrylamide, dimethylaminoethyl acrylamide, diethylaminoethyl acrylamide, etc. But it is not limited. Moreover, the compound represented by General formula (7) may be single type, and 2 or more types may be sufficient as it.

  The content of the compound represented by the general formula (7) is preferably 20 mol% or more, more preferably 50 mol% or more, and further preferably 70 mol% or more with respect to the carboxyl group of the heat-resistant resin precursor. Moreover, 500 mol% or less is preferable, 300 mol% or less is more preferable, and 250 mol% or less is more preferable. Within this range, the sensitivity is high, and the film has a good mechanical property after thermosetting.

  Furthermore, when giving negative photosensitivity to the heat-resistant resin precursor composition of this invention, you may contain a photoinitiator. Suitable photopolymerization initiators for the present invention include aromatic amines such as N-phenyldiethanolamine and N-phenylglycine, aromatic ketones such as Michler's ketone, and cyclic oximes represented by 3-phenyl-5-isoxazolone. Compounds, chain oxime compounds typified by 1-phenylpropanedione-2- (o-ethoxycarbonyl) oxime, benzophenone, benzophenone derivatives such as methyl o-benzoylbenzoate, dibenzylketone, fluorenone, thioxanthone, 2-methyl Examples include, but are not limited to, thioxanthone derivatives such as thioxanthone and 2-isopropylthioxanthone.

  The content of the photopolymerization initiator is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the heat resistant resin precursor. Moreover, 30 weight part or less is preferable and 20 weight part or less is more preferable. Within this range, the sensitivity is high, and the film has a good mechanical property after thermosetting. These photoinitiators can be used alone or in combination of two or more.

  Furthermore, it is more preferable to contain a photosensitizer in order to improve the negative photosensitive characteristics. Examples of photosensitizers suitable for the present invention include aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone, aminocoumarins such as 7-diethylaminobenzoylcoumarin, 3,3′-carbonylbis (diethylaminocoumarin), and benzanthrone. And aromatic ketones such as phenanthrenequinone, which are generally used for photocurable resins. In addition, it may be preferably used as long as it is used as a charge transfer agent for an electrophotographic photoreceptor.

  The content of the photosensitizer is preferably 0.01 parts by weight and more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the heat resistant resin precursor. Moreover, 30 weight part or less is preferable and 20 weight part or less is more preferable. Within this range, the sensitivity is high, and the film has a good mechanical property after thermosetting. These photosensitizers can be used alone or in combination of two or more.

  When imparting photosensitivity to the heat resistant resin precursor composition of the present invention, the heat resistant resin precursor is desirably as transparent as possible to the actinic radiation to be exposed. Therefore, the absorbance at 365 nm of a pre-baked film prepared using a γ-butyrolactone solution (resin concentration 40%) of a heat resistant resin precursor is preferably 0.1 or less per 1 μm of film thickness. More preferably, it is 0.08 or less. If it is 0.1 or less, the absorption of the composition with respect to 365 nm actinic radiation becomes small, and there is an advantage that the sensitivity when exposed to this actinic radiation is improved. The pre-baked film referred to here is a thickness obtained by applying the solution to a “Pyrex (registered trademark)” glass substrate and baking it on a hot plate at 120 ° C. (SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) for 2 to 4 minutes. It is a film of 3 to 10 μm.

  In order to further suppress deterioration of adhesive properties with the package material, the heat-resistant resin precursor composition of the present invention may further contain a polyhydroxy compound. Preferred polyhydroxy compounds include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F, and the like. Among these, particularly preferred polyhydroxy compounds are, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F It is.

  The content of the polyhydroxy compound is preferably 1 part by weight or more with respect to 100 parts by weight of the heat resistant resin precursor, and more preferably 5 parts by weight or more. When the amount is 1 part by weight or more, there is an advantage that deterioration of adhesive properties with the package material can be reduced by the polar effect of the hydroxy group. Moreover, 100 weight part or less is preferable and 40 weight part or less is more preferable. When it is 100 parts by weight or less, there is an advantage that the heat resistance of the film after thermosetting is improved.

  The heat resistant resin precursor composition of the present invention may contain a thermal crosslinking agent. As the thermal crosslinking agent, any compound such as a methylol compound, a methoxymethylol compound, or a urea compound can be preferably used. In particular, a methoxymethylol compound is preferably used from the standpoint of stability after exposure. Specific examples thereof include, but are not limited to, the following compounds.

  By containing these thermal crosslinking agents, the shrinkage after curing is small and a film with high dimensional reproducibility is obtained. In addition, when the composition is photosensitive, it hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. There are advantages you can do.

  The content of the thermal crosslinking agent is preferably 0.5 parts by weight or more, more preferably 3 parts by weight or more with respect to 100 parts by weight of the heat resistant resin precursor, while preferably 50 parts by weight or less, more preferably 40 parts by weight or less. Within this range, there is an advantage that the chemical resistance of the composition is improved.

  Solvents used in the present invention include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, etc. Ethers, acetone, methyl ethyl ketone, diisobutyl ketone and other ketones, ethyl acetate, propylene glycol monomethyl ether acetate, esters such as ethyl lactate, and aromatic hydrocarbons such as toluene and xylene, alone or in combination It can be used above.

  The heat-resistant resin precursor composition of the present invention uses a silane coupling agent, a titanium chelating agent, or the like in order to further improve the adhesion to silicon-based materials such as silicon, silicon nitride, silicon oxide, and phosphorus silicate glass. You can also. It is preferable to contain 0.5 to 10 parts by weight of a silane coupling agent such as methylmethacryloxydimethoxysilane and 3-aminopropyltrimethoxysilane, a titanium chelating agent, and an aluminum chelating agent with respect to 100 parts by weight of the heat-resistant resin precursor. .

Further, as a method for further improving the adhesiveness with the silicon-based material, it is also preferable to use ¹ to 10 mol% of R ¹ in the general formula (1) as a residue of a diamine compound having a siloxane bond. Specific examples of the diamine compound having a siloxane bond include, but are not limited to, bis (3-aminopropyl) tetramethyldisiloxane.

  In addition, it is possible to further improve the adhesion by pre-treating the surface of the silicon-based material in advance. Examples of the pretreatment method include the following methods. A solution obtained by dissolving 0.5 to 20 parts by weight of the coupling agent described above in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate Is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. In some cases, the reaction between the surface of the silicon-based material and the coupling agent is allowed to proceed by applying a temperature of 50 to 300 ° C. thereafter.

  If necessary, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate are used for the purpose of improving the wettability between the heat-resistant resin precursor composition of the present invention and the substrate to which the composition is applied. The composition may contain alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

  The heat-resistant resin precursor composition of the present invention can be obtained by stirring and mixing the above-mentioned heat-resistant resin precursor and, if necessary, a solvent and other additives. The conditions for stirring and mixing are not particularly limited.

  Next, a method for forming a pattern using the heat resistant resin precursor composition of the present invention will be described.

  The heat resistant resin precursor composition of the present invention is applied on a substrate. As the substrate, a wafer made of silicon, ceramics, gallium arsenide or the like, or a substrate on which an electrode and / or wiring made of a metal material such as copper, gold, or titanium-based metal is used is used. It is not limited to. Examples of the application method include spin coating using a spinner, spray coating, and roll coating. Further, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying becomes 0.1 to 150 μm.

  Next, the substrate coated with the heat resistant resin precursor composition is dried to obtain a heat resistant resin precursor composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at 50 to 150 ° C. for 1 minute to several hours. If necessary, drying can be performed in two or more stages, such as 2 minutes at 80 ° C. and 2 minutes at 120 ° C.

  Next, the film is exposed to actinic radiation through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp. . When photosensitivity is not given to the heat resistant resin precursor composition, it is necessary to form another layer of a photoresist film on the heat resistant resin precursor film. For this photoresist, a general novolak resist such as OFPR-800 (manufactured by Tokyo Ohka Co., Ltd.) is preferably used. The formation of the photoresist film is performed by the same method as the formation of the heat resistant resin precursor film.

  If the resolution of the pattern at the time of development is improved or the allowable range of development conditions is increased, a baking process may be incorporated before development. As this temperature, the range of 50-180 degreeC is preferable, and the range of 60-150 degreeC is especially more preferable. The time is preferably 10 seconds to several hours. Within this range, there are advantages that the reaction proceeds satisfactorily and the development time can be shortened.

  In order to form the pattern of the heat resistant resin precursor composition, development processing is performed. When the heat-resistant resin precursor composition is negative photosensitive, a relief pattern can be obtained by removing the unexposed area with a developer, and when positive photosensitive, removing the exposed area with a developer. .

  A suitable developer can be selected according to the structure of the heat-resistant resin precursor, but ammonia, tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, An aqueous solution of an alkaline compound such as triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine can be preferably used.

  Further, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl, which are good solvents for the heat-resistant resin precursor composition of the present invention, are used as a developer. Methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene, which are poor solvents for heat-resistant resin precursor compositions, such as sulfoxide, hexamethyl phosphortriamide, etc. Glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, ethyl acetate, etc. alone or in combination with several good solvents Preferred use It can be.

  The development can be performed by a method such as irradiating the developer on the coating film as it is or in the form of a mist, immersing in the developer, or applying ultrasonic waves while immersing.

  Then, it is preferable to wash the relief pattern formed by development with a rinse solution. As the rinse solution, water can be preferably used when an alkaline aqueous solution is used as the developer. At this time, rinse treatment may be performed by adding an ester such as ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, an acid such as carbon dioxide, hydrochloric acid, or acetic acid to water.

  When rinsing with an organic solvent, methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxy, which are miscible with the developer Propionate, 2-heptanone, ethyl acetate and the like are preferably used.

  When photosensitivity is not imparted to the heat resistant resin precursor composition, the photoresist film formed on the heat resistant resin precursor film must be removed after development. This removal is often performed by dry etching or wet etching with a stripping solvent. As the peeling solvent, organic solvents such as acetone, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate, An aqueous solution of sodium hydroxide or potassium hydroxide is used, but not limited thereto.

  When a resin that forms a cyclic structure by heating or a catalyst such as a polyimide precursor or a polybenzimidazole precursor is used as the heat resistant resin precursor, a temperature of 200 to 500 ° C. is used for conversion to a heat resistant resin having a cyclic structure. Add The heat treatment of these heat resistant resins is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise or by selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be mentioned.

  The cured film obtained by heat-treating the heat-resistant resin precursor composition of the present invention as described above is a permanent film such as a surface protective film (passivation film, buffer coat film, α-ray shielding film) or an interlayer insulating film, It is preferably used for a semiconductor device.

  Hereinafter, in order to describe the present invention in detail, examples will be described.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound (DA1) In a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) was added to acetone. It was dissolved in 100 ml and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 ml of acetone was added dropwise thereto. After completion of dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The solution was concentrated on a rotary evaporator, and the resulting solid was recrystallized with a solution of tetrahydrofuran and ethanol.

  The solid collected by recrystallization was dissolved in 100 ml of ethanol and 300 ml of tetrahydrofuran, 2 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 4 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound DA1 shown below. The obtained solid was used for the reaction as it was.

Synthesis Example 2 Synthesis of Hydroxyl Group-Containing Diamine Compound (DA2) A hydroxyl group-containing diamine compound DA2 shown below was obtained in the same manner as in Synthesis Example 1 except that 18.3 g of BAHF was changed to 30.2 g (0.05 mol) of DA1. It was. The obtained solid was used for the reaction as it was.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine compound (DA3) Except that 18.3 g of BAHF was changed to 14.0 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) sulfone (APBS). A diamine compound was obtained in the same manner as in Synthesis Example 1. Furthermore, using 25.9 g (0.05 mol) of this diamine compound as a starting material, the reaction of Synthesis Example 1 was repeated once more to obtain a hydroxyl group-containing diamine compound DA3 represented by the following formula. The obtained solid was used for the reaction as it was.

Synthesis Example 4 Synthesis of Hydroxyl Group-Containing Diamine Compound (DA4) Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and the temperature was reduced to −15 ° C. Cooled down. A solution prepared by dissolving 25.4 g (0.11 mol) of 3,4-dinitrobenzoyl chloride in 100 ml of acetone was added dropwise thereto. After completion of dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The solution was concentrated on a rotary evaporator, and the resulting solid was recrystallized with a solution of tetrahydrofuran and ethanol.

  The solid collected by recrystallization was dissolved in 100 ml of ethanol and 300 ml of tetrahydrofuran, 2 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 4 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, filtration was performed to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a tetraamine compound. 31.7 g (0.05 mol) of this tetraamine compound was dissolved in 100 ml of N-methyl-2-pyrrolidone (NMP) and cooled to 0 ° C. To this, 10.21 g (0.1 mol) of acetic anhydride was added dropwise. After completion of dropping, the mixture was stirred at 0 ° C. for 1 hour, and then stirred at room temperature for 3 hours. The precipitate obtained by throwing the solution into 10 l of water was collected by filtration. Then, it was dried with a vacuum dryer at 60 ° C. for 20 hours to obtain a hydroxyl group-containing diamine compound DA4 represented by the following formula. The obtained solid was used for the reaction as it was.

Synthesis Example 5 Synthesis of hydroxyl group-containing diamine compound (DA5) A hydroxyl group-containing diamine compound DA5 represented by the following formula was obtained in the same manner as in Synthesis Example 4 except that 18.3 g of BAHF was changed to 14.0 g (0.05 mol) of APBS. It was. The obtained solid was used for the reaction as it was.

Synthesis Example 6 Synthesis of Hydroxyl Group-Containing Diamine Compound (DA6) The same as Synthesis Example 4 except that 18.3 g of BAHF was changed to 35.9 g (0.05 mol) of hydroxyl group-containing diamine compound DA4 obtained in Synthesis Example 4. Thus, a hydroxyl group-containing diamine compound DA6 represented by the following formula was obtained. The obtained solid was used for the reaction as it was.

Synthesis Example 7 Synthesis of hydroxyl group-containing diamine compound (DA7) In the same manner as in Synthesis Example 4, except that 18.3 g of BAHF was changed to 31.6 g (0.05 mol) of hydroxyl group-containing diamine compound DA5 obtained in Synthesis Example 5. Thus, a hydroxyl group-containing diamine compound DA7 represented by the following formula was obtained. The obtained solid was used for the reaction as it was.

Synthesis Example 8 Synthesis of Hydroxyl Group-Containing Diamine Compound (DA8) Similar to Synthesis Example 4, except that 18.3 g of BAHF was changed to 30.2 g (0.05 mol) of hydroxyl group-containing diamine compound DA1 obtained in Synthesis Example 1. Thus, a diamine compound DA8 represented by the following formula was obtained. The obtained solid was used for the reaction as it was.

Synthesis Example 9 Synthesis of hydroxyl group-containing acid anhydride (DH1) Under dry nitrogen flow, 18.3 g (0.05 mol) of BAHF and 34.2 g (0.3 mol) of allyl glycidyl ether were dissolved in 100 g of ethyl acetate. Cooled to 15 ° C. Thereto was added dropwise 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of ethyl acetate so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the mixture was stirred at 0 ° C. for 4 hours.

  This solution was concentrated with a rotary evaporator and charged into 1 liter of toluene to obtain a hydroxyl group-containing acid anhydride DH1 represented by the following formula. The obtained solid was used for the reaction as it was.

Synthesis Example 10 Synthesis of hydroxyl group-containing acid anhydride (DH2) Same as Synthesis Example 9 except that 18.3 g of BAHF was changed to 30.2 g (0.05 mol) of hydroxyl group-containing diamine compound DA1 obtained in Synthesis Example 1. Thus, a hydroxyl group-containing acid anhydride DH2 represented by the following formula was obtained. The obtained solid was used for the reaction as it was.

Synthesis Example 11 Synthesis of hydroxyl group-containing acid anhydride (DH3) 18.6 g of BAHF was changed to 14.0 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) sulfone (APBS). Produced a hydroxyl group-containing diamine compound in the same manner as in Synthesis Example 1. Furthermore, the hydroxyl group-containing acid anhydride DH3 represented by the following formula was obtained by performing the reaction of Synthesis Example 9 using 25.9 g (0.05 mol) of this hydroxyl group-containing diamine compound instead of BAHF. The obtained solid was used for the reaction as it was.

Synthesis Example 12 Synthesis of Hydroxyl Group-Containing Acid Anhydride (DH4) 35.9 g (0.05 mol) of hydroxyl group-containing diamine compound DA4 obtained in Synthesis Example 4 and 34.2 g (0.3 mol) of allyl glycidyl ether It was dissolved in 100 g of ethyl acetate and cooled to -15 ° C. Thereto was added dropwise 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of ethyl acetate so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the mixture was stirred at 0 ° C. for 4 hours.

  This solution was concentrated with a rotary evaporator and charged into 1 liter of toluene to obtain a hydroxyl group-containing acid anhydride DH4 represented by the following formula. The obtained solid was used for the reaction as it was.

Synthesis Example 13 Synthesis of Hydroxyl Group-Containing Acid Anhydride (DH5) Similar to Synthesis Example 12, except that 35.9 g of hydroxyl group-containing diamine compound DA4 was changed to 31.6 g (0.05 mol) of hydroxyl group-containing diamine compound DA5. Thus, a hydroxyl group-containing acid anhydride DH5 represented by the following formula was obtained.

Synthesis Example 14 Synthesis of Active Diester (ES1) In a dry nitrogen stream, 14.8 g (0.05 mol) of 4,4′-diphenyl ether dicarboxylic acid chloride and 13.5 g (0.1 mol) of 1-hydroxybenzotriazole were added to 100 mL of NMP. And cooled to -15 ° C. A solution prepared by diluting 10.1 g (0.1 mol) of triethylamine with 50 mL of NMP was slowly added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at -15 ° C for 1 hour and then at room temperature for 3 hours, and the amine salt was removed by filtration. The filtrate was poured into 1 L of pure water and washed 3 times with isopropyl alcohol. After washing, it was dried with a vacuum dryer at 40 ° C. for 30 hours to obtain an active diester ES1 represented by the following formula.

Synthesis Examples 15 to 42
Hereinafter, the heat resistant resin precursor was polymerized with a combination of the diamine component, acid component, and terminal agent shown in Table 1 to obtain heat resistant resins 1 to 28. At this time, the reaction was carried out as follows depending on the acid component used.

1) When an acid component is an acid anhydride Under a dry nitrogen stream, a diamine compound was dissolved in 500 mL of NMP, an acid anhydride was added thereto, and the mixture was stirred at 40 ° C. for 2 hours. Thereafter, a terminal agent was added as necessary, and the mixture was further stirred at 40 ° C. for 1 hour. N, N-dimethylformamide diethyl acetal (33.7 g, 0.23 mol) was added thereto, and the mixture was stirred at 40 ° C. for 2 hours and cooled to room temperature. Thereafter, 60 g (1 mol) of acetic acid was added and stirred at room temperature for 1 hour. This was poured into 15 L of water, the precipitate was filtered off, and dried at 50 ° C. for 120 hours to obtain the desired heat-resistant resin.

2) When acid component is active diester Under a dry nitrogen stream, the diamine compound was dissolved in 500 mL of NMP, and the active diester was added thereto and stirred at 75 ° C. for 12 hours. Thereafter, a terminal agent was added as necessary, and the mixture was further stirred at 75 ° C. for 12 hours. This was put into a mixed solution of 15 L of water and 5 L of methanol, and the precipitate was filtered off and dried at 50 ° C. for 120 hours to obtain the desired heat resistant resin.

The symbols used in Table 1 are as follows.
SiDA: bis (3-aminopropyl) tetramethyldisiloxane ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride DAE: 4,4′-diaminodiphenyl ether 3-Aph: 3-aminophenol NA : Norbornene dicarboxylic acid anhydride.

Examples 1-32 and Comparative Examples 1-4
These heat-resistant resin precursors 1 to 28 are dissolved in γ-butyrolactone, and the photoinitiator, photoacid generator, polymerizable compound, phenol compound and the like are each in parts by weight shown in Table 2 with respect to 100 parts by weight of the heat-resistant resin. The heat resistant resin precursor composition 1 to 36 having a heat resistant resin precursor concentration of 28% was added. The following evaluation was performed about the obtained heat-resistant resin precursor composition. The results are shown in Table 3. The symbols used in Table 2 are as follows.
TPPA-280 (Toyo Gosei):

Tekp-4HBPA (Honshu Chemical):

CGI-242 (Ciba Geigy):

PDBE-250 (Nippon Yushi Co., Ltd.):

Z-6851 (made by Toray Dow Corning Silicone):

a) Adhesiveness to package material The heat-resistant resin precursor composition is spin-coated on a 6-inch silicon wafer with a spinner, and then vacuum-adsorbed hot plate (SCW636 type manufactured by Dainippon Screen Co., Ltd.) is used. Drying was performed at 2 ° C. for 2 minutes and at 100 ° C. for 2 minutes. This was cured in an oven at 140 ° C. for 30 minutes and then at 320 ° C. for 1 hour in a nitrogen atmosphere. An epoxy sealing resin TM20-100 manufactured by Toray Industries, Inc. was formed on the post-cure film by transfer molding into a columnar shape having a height of 5 mm and a diameter of 5 mm. Tensilon (Toyo Baldwin Co., Ltd.) was used to determine the strength when the sealing resin was peeled off from the cured film. The cured film with the sealing resin was heated and humidified by a pressure cooker test (PCT) for 100 hours and then subjected to the same peeling test as above, and compared with the strength when the PCT treatment was not performed. The strength reduction rate due to the PCT treatment was less than 30%, and the others were rejected. The PCT treatment was performed under a saturation condition of 121 ° C. and 2 atm.

b) Mechanical properties (elongation of cured film)
The heat-resistant resin precursor composition was spin-coated on a 6-inch silicon wafer with a spinner, and then vacuum suction type hot plate (SCW636 type manufactured by Dainippon Screen Co., Ltd.) for 2 minutes at 100 ° C. Drying was performed for 2 minutes. This was cured in an oven at 140 ° C. for 30 minutes and then at 320 ° C. for 1 hour in a nitrogen atmosphere, and then the film was peeled from the wafer. The peeled cured film was cut into a strip shape having a width of 1 cm and a length of about 9 cm as a sample for measuring elongation. “Tensilon” (RTM-100; manufactured by Orientec) was used for the elongation measurement, and the average value of the top 5 points was determined from the measurement results. Table 4 shows the measurement conditions. The value calculated | required at this time made 15% or more pass, and let it be unacceptable otherwise.

c) Adhesiveness with base material An aluminum substrate formed with a thickness of 500 nm on a silicon wafer was prepared. The heat-resistant resin precursor composition is spin-coated on this substrate, then baked on a hot plate at 120 ° C. for 3 minutes (SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.), and finally a prebaked film having a thickness of 8 μm. Was made. Under a nitrogen atmosphere, curing was carried out in an oven at 140 ° C. for 30 minutes and then at 320 ° C. for 1 hour to obtain a polyimide film. Cure was performed in nitrogen (oxygen concentration of 100 ppm or less). The cured film was cut into 10 rows and 10 columns at 2 mm intervals, and the adhesive properties between the metal material and the heat-resistant resin were determined according to how many squares were peeled off with cello tape (registered trademark). Evaluation was performed. First, a peeling test was performed immediately after curing, and a peeling test was performed again after heating and humidifying with PCT for 400 hours. A sample with a peeled number of less than 10 passed before and after the PCT treatment was accepted, and a sample with 10 or more was rejected. The PCT treatment was performed under a saturation condition of 121 ° C. and 2 atm.

  From the results in Table 3, it can be seen that the heat-resistant resin precursor composition of the present invention has a very small deterioration of the adhesive properties with the package material under high temperature and high humidity.

Claims (9)

A heat-resistant resin precursor composition comprising a resin having a repeating unit represented by the following general formula (1) or a repeating unit represented by the following general formula (2) as a main component.

(In General Formula (1), R ¹ represents a divalent to hexavalent organic group having 2 or more carbon atoms. Q represents an integer of 0 to 4. R ² represents a carbon containing an aromatic ring or an aromatic condensed ring. the ^.R 3 to R ⁶ which indicates the number 6-30 organic group may be the same or different, ^.R 7 ^{to R 10} showing an organic group having 6 to 30 carbon atoms containing an aromatic ring or aromatic fused ring It may be the same or different, and consists of —H, —F, —OH, —NHR ¹⁵ , —NHCOR ¹⁶ , —N═CHR ¹⁷ , an alkyl group having 1 to 20 carbon atoms, and a fluoroalkyl group having 1 to 10 carbon atoms. R ¹¹ and R ¹² are each an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring, and R ¹³ and R ¹⁴ are hydrogen or 1 to C carbon atoms. 20 represents an organic group, provided that COOR ¹³ represents —R ¹ —NHCO—R ^11. -Relative to the CO group in the main chain, COOR ¹⁴ is in the ortho position relative to the CO group in the main chain -R ¹² -CONH-R ^1, where a is 1 or 2, and b and c are 0 Or R ¹⁵ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ¹⁶ and R ¹⁷ represent a monovalent organic group having 1 to 20 carbon atoms.
In the general formula (2), R ¹⁸ represents a divalent to octavalent organic group having 2 or more carbon atoms. R ¹⁹ may be the same or different and represents hydrogen or an organic group having 1 to 20 carbon atoms. m represents an integer of 0 to 2, and p represents an integer of 0 to 4. R ²⁰ represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{21 to} R ²⁴ may be the same or different and each represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{25 to} R ²⁸ may be the same or different and are —H, —F, —OH, —NHR ²⁹ , —NHCOR ³⁰ , —N═CHR ³¹ , an alkyl group having 1 to 20 carbon atoms, and 1 to 10 carbon atoms. And a monovalent group selected from the group consisting of fluoroalkyl groups. d and e are 0 or 1, and f is 1 or 2. However, ^{R 25} when d is 0, ^{R 26} are each ^-NHR 29 when e is ^0, -NHCOR 30, a group selected from the group consisting of -N = ^{CHR 31.} R ²⁹ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ³⁰ and R ³¹ represent a monovalent organic group having 1 to 20 carbon atoms. ) Following general formula (3) and the tetracarboxylic dianhydride represented by the resistance Netsuju fat precursor composition characterized by containing a resin obtained by reacting a diamine compound.

(In General Formula (3), R ^{3 to} R ⁶ may be the same or different and each represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{7 to} R ¹⁰ may be the same. May be different from the group consisting of —H, —F, —OH, —NHR ¹⁵ , —NHCOR ¹⁶ , —N═CHR ¹⁷ , an alkyl group having 1 to 20 carbon atoms, and a fluoroalkyl group having 1 to 10 carbon atoms. R ¹¹ and R ¹² each represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring, a is 1 or 2, and b and c are 0 or 1. R ¹⁵ represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and R ¹⁶ and R ¹⁷ represent a monovalent organic group having 1 to 20 carbon atoms.) A diamine compound represented by the following general formula (4), tetracarboxylic dianhydride, anti Netsuju fat precursor composition characterized by containing a resin obtained by reacting a dicarboxylic acid or its diester object.

(In the general formula (4), R ²⁰ represents an organic group having 6 to 30 carbon atoms including an aromatic ring or an aromatic condensed ring. R ^{21 to} R ²⁴ may be the same or different, and may be an aromatic ring or aromatic group. An organic group having 6 to 30 carbon atoms including a condensed group ring, R ^{25 to} R ²⁸ may be the same or different, and —H, —F, —OH, —NHR ²⁹ , —NHCOR ³⁰ , —N═CHR ³¹ represents a monovalent group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a fluoroalkyl group having 1 to 10 carbon atoms, wherein d and e are 0 or 1, and f is 1 or 2. , ^{R 25} when d is 0, ^{R 26} are each ^-NHR 29 when e is ^0, -NHCOR ^{30, .R 29} 1 number of hydrogen or carbon that indicates a group selected from the group consisting of -N = ^{CHR 31} To 20 monovalent organic groups, R ³⁰ and And R ³¹ represents a monovalent organic group having 1 to 20 carbon atoms.) The diamine compound is resistant Netsuju fat precursor composition according to claim 3, characterized by being represented by at least one selected from the following structures.

The heat-resistant resin precursor composition according to any one of claims 1 to 4, wherein at least one of both ends of the main chain of the resin contains a phenol group and / or a thiophenol group. Furthermore, a photo-acid generator is contained, The heat-resistant resin precursor composition in any one of Claims 1-5 characterized by the above-mentioned. The heat-resistant resin precursor composition according to claim 6, wherein the photoacid generator contains an o-quinonediazide compound. The heat-resistant resin precursor composition according to claim 1, further comprising a photopolymerization initiator and a photopolymerizable compound. A semiconductor device comprising a cured film obtained by treating the heat-resistant resin precursor composition according to claim 1 at 200 ° C. or higher.