JP2018203959A - Polyimide and photosensitive resin composition - Google Patents

Abstract

To provide a material for an insulation film, from which a thin and high-definition adhesive pattern can be formed that allows continuous press-bonding in the process of fabricating a semiconductor device by stacking a plurality of semiconductor chips.SOLUTION: A polyimide is provided, which is soluble with an organic solvent and to be used for a photosensitive resin composition for an insulation film used in a semiconductor element. The polyimide contains a tetracarboxylic acid residue and a diamine residue, and contains, with respect to 100 pts.mol of the diamine residue, 40 pts.mol or more of a diamine residue derived from a dimer acid type diamine obtained by replacing two terminal carboxylic acid groups in a dimer acid by a primary aminomethyl group or an amino group, and the polyimide has no maleimide group.SELECTED DRAWING: None

Description

  The present invention relates to a polyimide applicable to a photosensitive resin composition for an insulating film used in a semiconductor element and a photosensitive resin composition using the polyimide.

  2. Description of the Related Art In recent years, in a semiconductor package having a multilayer structure in which a plurality of semiconductor chips are stacked, a method for separating a chip at the same time as thinning by previously half-cutting a thick semiconductor wafer and then performing back grinding (First dicing method) has been proposed (for example, Patent Document 1).

  In addition, a method of forming a photosensitive adhesive on a semiconductor wafer in advance in a semiconductor package having a multilayer structure and then dividing the chip has been proposed (for example, Patent Document 2). In this method, it is also possible to apply the above-mentioned dicing method after forming an adhesive layer on a thick semiconductor wafer in advance. However, when the photosensitive resin composition in the varnish state is used to form a thin photosensitive resin layer of, for example, 10 μm or less on the circuit surface of the semiconductor wafer, the adhesiveness of the photosensitive resin layer decreases, There has been a problem that the accuracy of formation tends to decrease.

  When a semiconductor device is manufactured by stacking a plurality of semiconductor chips, the adhesive layer surface of the divided semiconductor chip with an adhesive layer is picked up and picked up by a collet of a die bond device, and this is bonded to another semiconductor chip. This requires a process for forming a multilayer structure. However, if the process of laminating the semiconductor chips is repeated continuously, the heat of the hot plate of the die bond apparatus is transferred to the collet that adsorbs the chip, and the collet temperature becomes higher than the adhesive expression temperature of the adhesive layer and adheres to the collet. There has been a problem that the agent layer tends to adhere.

JP-A-5-335411 JP 2009-009110 A

  The present invention provides a material for an insulating film capable of continuous pressure bonding when a semiconductor device is manufactured by stacking a plurality of semiconductor chips and capable of forming a thin film and a high-definition adhesive pattern. Objective.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the continuous pressure bonding property and the adhesion during the formation of a thin film pattern. As a result, the inventors have found a polyimide that can be applied to a photosensitive resin composition having a continuous pressure bonding property and having a thin film and excellent adhesion during development, and has completed the present invention.

  That is, the polyimide of the present invention is a polyimide soluble in an organic solvent applied to a photosensitive resin composition for an insulating film used in a semiconductor element, and contains a tetracarboxylic acid residue and a diamine residue. 40 mol of a diamine residue derived from a dimer acid diamine in which two terminal carboxylic acid groups of dimer acid are substituted with primary aminomethyl groups or amino groups with respect to 100 mol parts of the diamine residue. It is characterized by containing at least part and having no maleimide group.

  In the polyimide of the present invention, the dimer acid diamine may be an aliphatic diamine having 36 carbon atoms.

  The photosensitive resin composition of the present invention contains the polyimide, a compound having a carbon-carbon unsaturated bond, an epoxy resin, and a photopolymerization initiator.

  By using the polyimide of the present invention, a photosensitive resin composition capable of continuous pressure bonding when forming a semiconductor device by laminating a plurality of semiconductor chips and forming a thin and high-definition adhesive pattern. Can be provided. Moreover, since the polyimide of this invention does not require a siloxane compound as a raw material, generation | occurrence | production of the volatile component which consists of cyclic siloxane which has a bad influence on an electronic component can be prevented. In addition, since the polyimide of the present invention is soluble in an organic solvent even in an imidized state, it does not require a ring-closing reaction and can realize a low heat treatment temperature. Moreover, since the polyimide of this invention does not have a maleimide group, there is no restriction | limiting in selection of the material as a photosensitive resin composition.

  Embodiments of the present invention will be described in detail.

  The polyimide according to the present embodiment is a polyimide soluble in an organic solvent applied to a photosensitive resin composition for an insulating film used in a semiconductor element, and contains a tetracarboxylic acid residue and a diamine residue. The diamine residue derived from a dimer acid type diamine in which two terminal carboxylic acid groups of the dimer acid are substituted with primary aminomethyl groups or amino groups with respect to 100 mole parts of the diamine residue. It is a polyimide containing at least a mole part and having no maleimide group. Here, since polyimide is produced by imidizing a precursor polyamic acid obtained by reacting a specific acid anhydride and a diamine compound, by explaining the acid anhydride and diamine compound, Specific examples of forms of polyimide are understood. In the present invention, the tetracarboxylic acid residue means a tetravalent group derived from tetracarboxylic dianhydride, and the diamine residue means a divalent group derived from a diamine compound. Means that.

(Tetracarboxylic acid residue)
The polyimide according to the present embodiment is a tetracarboxylic acid derived from a tetracarboxylic acid anhydride represented by the following general formula (1) and / or (2) with respect to 100 mole parts of the tetracarboxylic acid residue. It is preferable to contain 90 mol parts or more of acid residues (hereinafter sometimes referred to as “tetracarboxylic acid residues (1)” and “tetracarboxylic acid residues (2)”). In the present invention, solvent solubility is imparted to the polyimide by containing the tetracarboxylic acid residue (1) and / or (2) in a total of 90 mol parts or more with respect to 100 mol parts of the tetracarboxylic acid residues. At the same time, it is easier to achieve both flexibility and heat resistance of polyimide, which is more preferable. When the total of the tetracarboxylic acid residues (1) and / or (2) is less than 90 parts by mole, the solvent solubility of the polyimide tends to decrease.

  In general formula (1), X represents a single bond or a divalent group selected from the following formulas. In general formula (2), the cyclic moiety represented by Y is a 4-membered ring or 5-membered ring. , A cyclic saturated hydrocarbon group selected from a 6-membered ring, a 7-membered ring and an 8-membered ring is formed.

In the above formula, Z represents —C ₆ H ₄ —, — (CH ₂ ) n— or —CH ₂ —CH (—O—C (═O) —CH ₃ ) —CH ₂ —, where n is 1 Represents an integer of ~ 20.

  Examples of the tetracarboxylic dianhydride for deriving the tetracarboxylic acid residue (1) include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4′-oxydiphthalic anhydride (ODPA) 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (BPADA), p-phenylene Examples thereof include bis (trimellitic acid monoester anhydride) (TAHQ), ethylene glycol bisanhydro trimellitate (TMEG), and the like.

  Examples of the tetracarboxylic dianhydride for deriving the tetracarboxylic acid residue (2) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cycloheptanetetracarboxylic dianhydride, 1,2,5,6- And cyclooctane tetracarboxylic dianhydride.

  The polyimide may contain a tetracarboxylic acid residue derived from an acid anhydride other than the tetracarboxylic acid anhydride represented by the general formula (1) or (2) as long as the effects of the invention are not impaired. it can.

(Diamine residue)
In the polyimide according to the present embodiment, the dimer acid type diamine residue derived from the dimer acid type diamine is in the range of 40 mol part or more, for example, 40 mol part or more and 95 mol part or less with respect to 100 mol part of the diamine residue It is preferably contained in a range of 50 mol parts or more, for example, 50 mol parts or more and 95 mol parts or less, more preferably 80 mol parts or more, for example, 80 mol parts or more and 95 mol parts or less. By containing the dimer acid type diamine residue in the above-mentioned amount, the dielectric properties of the insulating film are improved, thermocompression characteristics are improved by lowering the glass transition temperature of the insulating film, and internal stress is reduced by lowering the elastic modulus. Can be relaxed. Further, by making the dimer acid type diamine residue 40 mol parts or more, it is possible to impart solubility and thermoplasticity to an organic solvent, and by setting the dimer acid type diamine residue to 50 mol parts or more, the water absorption of the insulating film Can be reduced. On the other hand, when the dimer acid type diamine residue exceeds 95 mole parts, the elastic modulus at the glass transition temperature or higher is too low, and there is a concern that the resin component will flow out. If the dimer acid type diamine residue is less than 40 mol parts with respect to 100 mol parts of the diamine residues, there is a concern that the solvent solubility as polyimide decreases and the elastic modulus increases.

Here, the dimer acid type diamine means that two terminal carboxylic acid groups (—COOH) of dimer acid are substituted with primary aminomethyl groups (—CH ₂ —NH ₂ ) or amino groups (—NH ₂ ). Means a diamine. Dimer acid is a known dibasic acid obtained by an intermolecular polymerization reaction of an unsaturated fatty acid, and its industrial production process is almost standardized in the industry, and an unsaturated fatty acid having 11 to 22 carbon atoms is converted into a clay catalyst. It is obtained by dimerization with the above. The dimer acid obtained industrially is mainly composed of a dibasic acid having 36 carbon atoms obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid or linoleic acid, depending on the degree of purification. , Containing any amount of monomeric acid (18 carbon atoms), trimer acid (54 carbon atoms), and other polymerized fatty acids having 20 to 54 carbon atoms. In the present invention, it is preferable to use dimer acid having a dimer acid content increased to 90% by weight or more by molecular distillation. In addition, although a double bond remains after the dimerization reaction, in the present invention, a dimer acid that is further reduced in the degree of unsaturation by hydrogenation reaction is included.

  As a feature of the dimer acid diamine, characteristics derived from the skeleton of the dimer acid can be imparted to the polyimide. That is, since the dimer acid type diamine is a macromolecular aliphatic having a molecular weight of about 560 to 620, the molecular molar volume can be increased and the polar groups of the polyimide can be relatively reduced. Such a feature of the dimer acid type diamine is considered to contribute to improving the dielectric characteristics by reducing the dielectric constant and the dielectric loss tangent while suppressing the decrease in the heat resistance of the polyimide. In addition, since it has two freely moving hydrophobic chains having 7 to 9 carbon atoms and two chain-like aliphatic amino groups having a length close to 18 carbon atoms, not only gives flexibility to the polyimide, Since polyimide can be made into a non-target chemical structure or non-planar chemical structure, it is possible to achieve a low dielectric constant and low dielectric loss tangent of polyimide, such as nonpolar organics such as alicyclic hydrocarbons. It is thought that the developability with respect to a solvent can be improved.

  The dimer acid type diamine is commercially available. For example, PRIAMINE 1073 (trade name), PRIAMINE 1074 (trade name), PRIAMINE 1075 (trade name) manufactured by Croda Japan, and Versamine 551 (trade name) manufactured by BASF Japan. ), Versamine 552 (trade name), and the like. Among these, CRIDA Japan Co., Ltd., PRIAMINE 1074 (trade name) and PRIAMINE 1075 (trade name), which are dimer acid type diamines having 36 carbon atoms, are particularly preferable.

  Moreover, the polyimide which concerns on implementation of this invention is a diamine residue derived from the at least 1 sort (s) of diamine compound chosen from the diamine compound represented by the following general formula (B1)-(B7). It is preferable to contain in the range of 1 mol part or more and 40 mol part or less in total with respect to a mol part, and it is more preferable to contain in the range of 1 mol part or more and 20 mol part or less. Since the diamine compounds represented by the general formulas (B1) to (B7) have a flexible molecular structure, polyimide molecules are obtained by using at least one diamine compound selected from these in an amount within the above range. The flexibility of the chain can be improved, and solvent solubility and thermoplasticity can be imparted. Moreover, the solvent solubility of a polyimide can be provided by using the diamine compound represented by general formula (B1)-(B7), the glass transition temperature of a polyimide can be raised, and the thermal weight at the time of the heating at high temperature There is an effect of suppressing the decrease. Accordingly, it is possible to suppress the flow of resin components and the generation of decomposition gas in the manufacturing process. When the total amount of the diamine compounds represented by the following general formulas (B1) to (B7) exceeds 40 mol parts with respect to 100 mol parts of all diamine components, the flexibility of the polyimide is insufficient, and the glass transition temperature. However, the residual stress due to thermocompression increases, and the adhesion tends to decrease.

In formulas (B1) to (B7), R ₁ independently represents a monovalent hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group, and the linking group A is independently —O—, —S—, —CO—. , —SO—, —SO ₂ —, —COO—, —CH ₂ —, —C (CH ₃ ) ₂ —, —NH— or —CONH—, wherein n ₁ is independently An integer of 0 to 4 is shown. However, in the formula (B3), those that overlap with the formula (B2) are excluded, and in the formula (B5), those that overlap with the formula (B4) are excluded.
Note that “independently” means that in one of the above formulas (B1) to (B7), or in two or more, a plurality of linking groups A, a plurality of R _{1 s,} or a plurality of n ₁ are the same. It means good or different. In the formulas (B1) to (B7), hydrogen atoms in the two terminal amino groups may be substituted. For example, —NR ₂ R ₃ (wherein R ₂ and R ₃ are independently alkyl Meaning an arbitrary substituent such as a group).

The diamine represented by the formula (B1) (hereinafter sometimes referred to as “diamine (B1)”) is an aromatic diamine having two benzene rings. This diamine (B1) has high flexibility because the degree of freedom of the polyimide molecular chain is increased because the amino group directly connected to at least one benzene ring and the divalent linking group A are in the meta position. It is thought that it contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the thermoplasticity of a polyimide increases by using diamine (B1). Here, as the linking group A, —O—, —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —SO ₂ —, —S—, and —COO— are preferable.

  Examples of the diamine (B1) include 3,3′-diaminodiphenylmethane, 3,3′-diaminodiphenylpropane, 3,3′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, and 3,3-diaminodiphenyl ether. , 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylpropane, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, (3,3'-bisamino ) Diphenylamine and the like.

  The diamine represented by the formula (B2) (hereinafter sometimes referred to as “diamine (B2)”) is an aromatic diamine having three benzene rings. This diamine (B2) has high flexibility because the degree of freedom of the polyimide molecular chain is increased because the amino group directly connected to at least one benzene ring and the divalent linking group A are in the meta position. It is thought that it contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B2) increases the thermoplasticity of the polyimide. Here, as the linking group A, —O— is preferable.

  Examples of the diamine (B2) include 1,4-bis (3-aminophenoxy) benzene, 3- [4- (4-aminophenoxy) phenoxy] benzenamine, 3- [3- (4-aminophenoxy) phenoxy] Examples thereof include benzeneamine.

  The diamine represented by the formula (B3) (hereinafter sometimes referred to as “diamine (B3)”) is an aromatic diamine having three benzene rings. This diamine (B3) has high flexibility because the degree of freedom of the polyimide molecular chain is increased because two divalent linking groups A directly connected to one benzene ring are in the meta position. Therefore, it is thought that it contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B3) increases the thermoplasticity of the polyimide. Here, as the linking group A, —O— is preferable.

  Examples of the diamine (B3) include 1,3-bis (4-aminophenoxy) benzene (TPE-R), 1,3-bis (3-aminophenoxy) benzene (APB), 4,4 ′-[2- Methyl- (1,3-phenylene) bisoxy] bisaniline, 4,4 '-[4-methyl- (1,3-phenylene) bisoxy] bisaniline, 4,4'-[5-methyl- (1,3-phenylene) ) Bisoxy] bisaniline and the like.

The diamine represented by the formula (B4) (hereinafter sometimes referred to as “diamine (B4)”) is an aromatic diamine having four benzene rings. This diamine (B4) has a high flexibility because the amino group directly connected to at least one benzene ring and the divalent linking group A are in the meta position, thereby improving the flexibility of the polyimide molecular chain. It is thought to contribute. Therefore, the use of diamine (B4) increases the thermoplasticity of the polyimide. Here, as the linking group A, —O—, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —CO—, and —CONH— are preferable.

  Examples of the diamine (B4) include bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy)] benzophenone, bis [4,4 ′-(3-aminophenoxy)] benzanilide and the like can be mentioned.

  The diamine represented by the formula (B5) (hereinafter sometimes referred to as “diamine (B5)”) is an aromatic diamine having four benzene rings. This diamine (B5) has high flexibility because the degree of freedom of the polyimide molecular chain is increased by having two divalent linking groups A directly connected to at least one benzene ring in the meta position. It is thought that it contributes to the improvement of the flexibility of the polyimide molecular chain. Therefore, the thermoplasticity of polyimide increases by using diamine (B5). Here, as the linking group A, —O— is preferable.

  Examples of the diamine (B5) include 4- [3- [4- (4-aminophenoxy) phenoxy] phenoxy] aniline, 4,4 ′-[oxybis (3,1-phenyleneoxy)] bisaniline, and the like. .

The diamine represented by the formula (B6) (hereinafter sometimes referred to as “diamine (B6)”) is an aromatic diamine having four benzene rings. This diamine (B6) has high flexibility by having at least two ether bonds, and is considered to contribute to the improvement of the flexibility of the polyimide molecular chain. Therefore, the use of diamine (B6) increases the thermoplasticity of the polyimide. Here, as the linking group A, —C (CH ₃ ) ₂ —, —O—, —SO ₂ —, and —CO— are preferable.

  Examples of the diamine (B6) include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (4-aminophenoxy) phenyl] ether (BAPE), and bis [4 -(4-Aminophenoxy) phenyl] sulfone (BAPS), bis [4- (4-aminophenoxy) phenyl] ketone (BAPK) and the like can be mentioned.

  The diamine represented by the formula (B7) (hereinafter sometimes referred to as “diamine (B7)”) is an aromatic diamine having four benzene rings. Since this diamine (B7) has divalent linking groups A having high flexibility on both sides of the diphenyl skeleton, it is considered that this diamine (B7) contributes to improvement in flexibility of the polyimide molecular chain. Therefore, the thermoplasticity of polyimide increases by using diamine (B7). Here, as the linking group A, —O— is preferable.

  Examples of the diamine (B7) include bis [4- (3-aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy)] biphenyl, and the like.

  The polyimide which concerns on this Embodiment can contain the diamine residue induced | guided | derived from diamine compounds other than the said dimer acid type diamine and diamine (B1)-(B7) in the range which does not impair the effect of invention.

  In addition, the polyimide according to the present embodiment selects the types of the tetracarboxylic acid residue and the diamine residue, and the respective molar ratios when two or more tetracarboxylic acid residues or diamine residues are applied. Thereby, a thermal expansion coefficient, a tensile elasticity modulus, a glass transition temperature, etc. can be controlled. Moreover, when it has multiple structural units of polyimide, it may exist as a block or may exist at random, but it is preferable to exist at random.

It is preferable that the imide group density | concentration of the polyimide of this Embodiment is 20 weight% or less. Here, the “imide group concentration” means a value obtained by dividing the molecular weight of the imide group (— (CO) ₂ —N—) in the polyimide by the molecular weight of the entire structure of the polyimide. When the imide group concentration exceeds 20% by weight, the solubility of polyimide in an organic solvent is lowered and the low hygroscopicity is also deteriorated due to the increase in polar groups, thereby increasing the elastic modulus.

  The weight average molecular weight of the polyimide according to the present embodiment is preferably in the range of 10,000 to 400,000, more preferably in the range of 20,000 to 350,000. When the weight average molecular weight is less than 10,000, the strength of the cured film tends to be reduced and it tends to become brittle. On the other hand, when the weight average molecular weight exceeds 400,000, the viscosity is excessively increased, and defects such as uneven thickness of the adhesive layer and streaks tend to occur during the coating operation.

Since the polyimide according to the present embodiment covers the conductor circuit layer, a completely imidized structure is most preferable in order to suppress copper diffusion. However, a part of the polyimide may be amic acid. The imidation ratio was measured at about 1015 cm ⁻¹ by measuring the infrared absorption spectrum of the polyimide thin film by a single reflection ATR method using a Fourier transform infrared spectrophotometer (commercial product: FT / IR620 manufactured by JASCO Corporation). It can be calculated from the absorbance of C═O stretching derived from an imide group of 1780 cm ⁻¹ with the benzene ring absorber as a reference.

  The polyimide of the present embodiment can be produced by reacting the above tetracarboxylic dianhydride and a diamine compound in a solvent to form a polyamic acid and then ring-closing with heating. For example, a precursor of polyimide by dissolving a tetracarboxylic dianhydride and a diamine compound in an organic solvent in an approximately equimolar amount, and stirring and polymerizing at a temperature in the range of 0 to 100 ° C. for 30 minutes to 24 hours. A polyamic acid is obtained. In the reaction, the reaction components are dissolved so that the precursor to be produced is in the range of 5 to 50% by weight, preferably in the range of 10 to 40% by weight in the organic solvent. Examples of the organic solvent used in the polymerization reaction include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2 -Butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triglyme, cresol and the like. Two or more of these solvents can be used in combination, and further, aromatic hydrocarbons such as xylene and toluene can be used in combination. Further, the amount of such an organic solvent used is not particularly limited, but it should be adjusted so that the concentration of the polyamic acid solution obtained by the polymerization reaction is about 5 to 50% by weight. Is preferred.

  The synthesized polyamic acid is usually advantageously used as a reaction solvent solution, but can be concentrated, diluted or replaced with another organic solvent as necessary. Moreover, since polyamic acid is generally excellent in solvent solubility, it is advantageously used. The viscosity of the polyamic acid solution is preferably in the range of 500 cps to 100,000 cps. If it is out of this range, defects such as uneven thickness and streaks are likely to occur in the film during coating by a coater or the like.

  The method for imidizing the polyamic acid to form the polyimide is not particularly limited. For example, a heat treatment such as heating in the solvent at a temperature within the range of 80 to 400 ° C. for 1 to 24 hours is suitably employed. Is done.

  The polyimide which concerns on this Embodiment can mix | blend the compound which has a carbon-carbon unsaturated bond, an epoxy resin, a photoinitiator, etc., for example, and can be set as the photosensitive resin composition. That is, the photosensitive resin composition of this Embodiment contains the compound which has a carbon-carbon unsaturated bond, an epoxy resin, a photoinitiator, etc. in addition to the said polyimide.

  Although there is no restriction | limiting in particular as a compound which has a carbon-carbon unsaturated bond, For example, the compound which has an ethylenically unsaturated group is mentioned, Especially, the monofunctional which has a (meth) acryl group as an ethylenically unsaturated group (Meth) acrylate, polyfunctional (meth) acrylate and the like are preferable. In addition, you may use the compound which has a carbon-carbon unsaturated bond in combination of 2 or more types.

  The epoxy resin is not particularly limited, but an epoxy resin having a fluorene skeleton in the molecule is preferable. In addition, you may use an epoxy resin in combination of 2 or more types.

  The photopolymerization initiator is not particularly limited, and examples thereof include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like are preferable. In addition, you may use a photoinitiator in combination of 2 or more types.

  The photosensitive resin composition of the present embodiment can further contain a curing agent, a curing accelerator, a filler, a coupling agent, an ion scavenger, a sensitizer, a thermal radical generator, an organic solvent, and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following examples, various measurements and evaluations are as follows unless otherwise specified.

[Measurement of weight average molecular weight (Mw)]
The weight average molecular weight was measured by gel permeation chromatograph (manufactured by Tosoh Corporation, using HLC-8220GPC). Polystyrene was used as a standard substance, and tetrahydrofuran was used as a developing solvent.

The abbreviations used in the examples represent the following compounds.
BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride BPDA: 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride ODPA: 4,4′-oxydiphthalic anhydride BPADA : 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride DSDA: 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride PMDA: pyromellitic anhydride Product BAPP: 2,2-bis (4-aminophenoxyphenyl) propane BAFL: bisaniline fluorene 3,4'-DAPE: 3,4'-diaminodiphenyl ether APB: 1,3-bis (3-aminophenoxy) benzene DDA : C36 aliphatic diamine (manufactured by CRODA JAPAN, trade name: PRIAMINE 1074, amine value: 210 mg KOH g, a mixture of dimer diamine cyclic structures and chain structures, the content of the dimer components; 95 wt% or higher)
A-LEN-10: Shin-Nakamura Chemical Co., Ltd., ethoxylated o-phenylphenol acrylate EG-250: Osaka Gas Chemical Co., Ltd .: fluorene skeleton-containing epoxy resin (epoxy equivalent 393)
LA-7052: manufactured by DIC, triazine skeleton-containing phenol novolac resin I-819: manufactured by Ciba Japan, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide I-OXE02: manufactured by Ciba Japan Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)
Park mill D: manufactured by NOF Corporation, dicumyl peroxide NMP: manufactured by Kanto Chemical Co., Inc., N-methyl-2-pyrrolidone

Example 1
<Preparation of polyimide soluble in organic solvent>
In a 500 mL four-necked flask equipped with a nitrogen inlet tube, a stirrer, a thermocouple, a Dean-Stark trap and a condenser tube, 38.67 g of BPADA (0.0743 mol), 23.05 g of ODPA (0.0743 mol), A polyamic acid solution was prepared by charging 32.01 g DDA (0.0599 mol), 26.27 g APB (0.0899 mol), 168 g NMP and 112 g xylene and mixing at 40 ° C. for 30 minutes. did. The polyamic acid solution was heated to 190 ° C., heated and stirred for 4 hours, and distilled water and xylene were removed from the system. Then, it cooled to 100 degreeC, 30 g NMP and 82 g xylene were added and stirred, and also the polyimide solution a which completed imidation was prepared by further cooling to 30 degreeC. The solid content in the polyimide solution a was 29.8% by weight, and the weight average molecular weight (Mw) of the polyimide contained in the polyimide solution a was 61,100.

<Preparation of photosensitive resin composition>
Polyimide solution a prepared above (100 parts by weight), A-LEN-10 (20 parts by weight), EG-250 (20 parts by weight), LA-7052 (10 parts by weight), I-819 (2 parts by weight) , I-OXE02 (1 part by weight), Parkmill D (1 part by weight), NMP (100 parts by weight), and xylene (100 parts by weight) were used to prepare a photosensitive resin composition.

<Formation of photosensitive resin layer>
A predetermined amount of the prepared photosensitive resin composition is dropped onto the mirror-finished side of a 50-μm thick 6-inch silicon wafer so that the film thickness after drying becomes 5 μm, and using a spin coater, 700 rpm for 10 seconds, and further 1200 rpm Was spin-coated for 30 seconds to form a thin film. Then, it was left to stand on a hot plate set at 100 ° C. for 10 minutes. Thus, the silicon wafer which has the insulating film formed from the photosensitive resin composition was prepared.

(Example 2)
<Preparation of polyimide soluble in organic solvent>
In a 500 mL four-necked flask equipped with a nitrogen inlet tube, a stirrer, a thermocouple, a Dean-Stark trap, and a condenser tube, 25.40 g BTDA (0.0788 mol), 24.45 g ODPA (0.0788 mol), A polyamic acid solution was prepared by charging 42.46 g DDA (0.0795 mol), 27.69 g BAFL (0.0795 mol), 168 g NMP and 112 g xylene and mixing at 40 ° C. for 30 minutes. did. The polyamic acid solution was heated to 190 ° C., heated and stirred for 4 hours, and distilled water and xylene were removed from the system. Then, it cooled to 100 degreeC, 30 g NMP and 82 g xylene were added and stirred, and also the polyimide solution b which completed imidation was prepared by further cooling to 30 degreeC. The solid content in the polyimide solution b was 29.5% by weight, and the weight average molecular weight (Mw) of the polyimide contained in the polyimide solution b was 68,600.

<Preparation of photosensitive resin composition>
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the polyimide solution b was used.

<Formation of photosensitive resin layer>
A silicon wafer having an insulating film was prepared in the same manner as in Example 1 except that the photosensitive resin composition prepared using the polyimide solution b was used.

Example 3
In a 500 mL four-necked flask equipped with a nitrogen inlet tube, a stirrer, a thermocouple, a Dean-Stark trap and a condenser tube, 19.17 g of BPDA (0.0652 mol), 33.91 g of BPADA (0.0652 mol), A polyamic acid solution was prepared by charging 56.14 g DDA (0.1051 mol), 26.27 g BAPP (0.0263 mol), 168 g NMP and 112 g xylene and mixing at 40 ° C. for 30 minutes. did. The polyamic acid solution was heated to 190 ° C., heated and stirred for 4 hours, and distilled water and xylene were removed from the system. Then, it cooled to 100 degreeC, 112 g of xylene was added and stirred, and also the polyimide solution c which completed imidation was prepared by further cooling to 30 degreeC. The solid content in the polyimide solution c was 30.2% by weight, and the weight average molecular weight (Mw) of the polyimide contained in the polyimide solution c was 72,300.

<Preparation of photosensitive resin composition>
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the polyimide solution c was used.

<Formation of photosensitive resin layer>
A silicon wafer having an insulating film was prepared in the same manner as in Example 1 except that the photosensitive resin composition prepared using the polyimide solution c was used.

(Example 4)
In a 500 mL four-necked flask equipped with a nitrogen inlet tube, a stirrer, a thermocouple, a Dean-Stark trap, and a condenser tube, 45.82 g BTDA (0.1422 mol), 72.75 g DDA (0.1362 mol), 1.435 g of 3,4′-DAPE (0.0072 mol), 168 g of NMP and 112 g of xylene were charged and mixed at 40 ° C. for 30 minutes to prepare a polyamic acid solution. The polyamic acid solution was heated to 190 ° C., heated and stirred for 4 hours, and distilled water and xylene were removed from the system. Then, it cooled to 100 degreeC, 112 g of xylene was added and stirred, and also the polyimide solution d which completed imidation was prepared by further cooling to 30 degreeC. The solid content in the polyimide solution d was 29.1% by weight, and the weight average molecular weight (Mw) of the polyimide contained in the polyimide solution d was 68,100.

<Preparation of photosensitive resin composition>
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the polyimide solution d was used.

<Formation of photosensitive resin layer>
A silicon wafer having an insulating film was prepared in the same manner as in Example 1 except that the photosensitive resin composition prepared using the polyimide solution d was used.

(Example 5)
In a 500 mL four-necked flask equipped with a nitrogen inlet tube, a stirrer, a thermocouple, a Dean-Stark trap, and a condenser tube, 15.99 g PMDA (0.0733 mol), 26.27 g DSDA (0.0733 mol), A polyamic acid solution was prepared by charging 75.02 g DDA (0.1404 mol), 2.72 g BAPB (0.0074 mol), 168 g NMP and 112 g xylene and mixing at 40 ° C. for 30 minutes. did. The polyamic acid solution was heated to 190 ° C., heated and stirred for 4 hours, and distilled water and xylene were removed from the system. Then, it cooled to 100 degreeC, 112 g of xylene was added and stirred, and also the polyimide solution e which completed imidation was prepared by cooling to 30 degreeC. The solid content in the polyimide solution e was 30.1% by weight, and the weight average molecular weight (Mw) of the polyimide contained in the polyimide solution e was 62,500.

<Preparation of photosensitive resin composition>
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the polyimide solution e was used.

<Formation of photosensitive resin layer>
A silicon wafer having an insulating film was prepared in the same manner as in Example 1 except that the photosensitive resin composition prepared using the polyimide solution e was used.

(Example 6)
In a 500 mL four-necked flask equipped with a nitrogen inlet tube, a stirrer, a thermocouple, a Dean Stark trap, and a condenser tube, 44.92 g of BTDA (0.1394 mol), 75.08 g of DDA (0.1405 mol), A polyamic acid solution was prepared by charging 168 g of NMP and 112 g of xylene and mixing at 40 ° C. for 30 minutes. The polyamic acid solution was heated to 190 ° C., heated and stirred for 4 hours, and distilled water and xylene were removed from the system. Then, it cooled to 100 degreeC, 112 g of xylene was added and stirred, and also the polyimide solution f which completed imidation was prepared by further cooling to 30 degreeC. The solid content in the polyimide solution f was 30.1% by weight, and the weight average molecular weight (Mw) of the polyimide contained in the polyimide solution f was 79,400.

<Preparation of photosensitive resin composition>
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the polyimide solution f was used.

<Formation of photosensitive resin layer>
A silicon wafer having an insulating film was prepared in the same manner as in Example 1 except that the photosensitive resin composition prepared using the polyimide solution f was used.

As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment, A various deformation | transformation is possible.

Claims (3)

A polyimide soluble in an organic solvent applied to a photosensitive resin composition for an insulating film used in a semiconductor element,
A dimer comprising a tetracarboxylic acid residue and a diamine residue, wherein two terminal carboxylic acid groups of the dimer acid are substituted with primary aminomethyl groups or amino groups with respect to 100 mole parts of the diamine residue. A polyimide containing 40 mole parts or more of a diamine residue derived from an acid-type diamine and having no maleimide group.   The polyimide according to claim 1, wherein the dimer acid diamine is an aliphatic diamine having 36 carbon atoms. A photosensitive resin composition comprising the polyimide according to claim 1 or 2, a compound having a carbon-carbon unsaturated bond, an epoxy resin, and a photopolymerization initiator.