JPH11209607A - Photosensitive and heat resistant polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat resistant polymer material which can keep the shrinkage on heat treatment to a minimum and has the photosensitivity with high stability. SOLUTION: A compsn. comprises (a) 100 pts.wt. of a polymer having the main component of the structural unit expressed by the formula: R0-(R1)n-R2 (wherein, R0 and R1 are each a silicon atom-contg. group having at least one unsatd. bond and alkoxy group; R1 is a group contg. an at least 6C or more aromatic group; and n is 10 to 100,000), and (b) 0.1-100 pts.wt. of a photopolymerization initiator and/or sensitizer. Alternatively, contains (a) 100 pts.wt. of a polymer having the main component of the structural unit expressed by the formula, (b) 0.1-100 pts.wt. of a polymerization initiator and/or a sensitizer, and (c) 10-300 pts.wt. of an amino compd. having at least one unsatd. bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to
The present invention relates to a photosensitive heat-resistant polymer material with a small weight loss due to heat treatment.

[0002]

2. Description of the Related Art A photosensitive polyimide precursor composition is widely used as a photosensitive heat-resistant material. As such, the following is known as a negative photosensitive polyimide precursor composition in which an exposed portion remains after development.

(A) A composition comprising a polyamic acid to which a carbon-carbon double bond and an amino group or a quaternized salt which can be dimerized or polymerized by actinic radiation are added (Japanese Patent Publication No. 59-5282).
No. 2). (B) A composition in which acrylamides are added to polyamic acid (JP-A-3-170555). (C) Compositions comprising a polyimide precursor having a carbon-carbon double bond group, a specific oxime compound, and a sensitizer (JP-A-61-118423, JP-A-62-162).
No. 184056, JP-A-62-273259).

[0004]

However, these prior arts have a problem that the obtained film has a large stress due to the shrinkage of about 50% during the heat treatment and a large change in the pattern. .

Further, a composition comprising a polyimide precursor and an alkoxysilane compound has been known (Japanese Patent Application Laid-Open No.
2-121179). However, the use of such a photoacid generator has a problem in that the stability of the composition is poor.

In view of the above, the present invention has made intensive studies to minimize the shrinkage during heat treatment and to develop a photosensitive and heat-resistant polymer material having higher stability. Silicon material and polyimide with a specific structure,
By finding a material having heat resistance and a small shrinkage after heat treatment by using a polyamide, a polybenzoxazole precursor or the like in combination, the present invention has been achieved.

It is an object of the present invention to solve such a problem and to provide a photosensitive heat-resistant polymer material having high stability while minimizing shrinkage during heat treatment. .

[0008]

According to the present invention, (a)
It is characterized by containing 100 parts by weight of a polymer having a structural unit represented by the general formula (1) as a main component and (b) 0.1 to 100 parts by weight of a photopolymerization initiator and / or a sensitizer. Photosensitive heat resistant polymer composition.

[0009]

Embedded image (R0 and R2 are a silicon atom-containing group having at least one unsaturated bond and an alkoxy group, and R1 is at least 6
An aromatic group having at least 10 carbon atoms, n is 10
To 100,000. )

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below.
The general formulas R0 and R2 represent a silicon-containing group having at least one unsaturated bond and an alkoxy group, and include a vinyltriethoxysilane residue, a vinyltrimethoxysilane residue, a vinylmethyldimethoxysilane residue, and a vinylmethyldimethoxysilane residue. A silicon-containing group having a vinyl group as an unsaturated bond such as a dimethylmethoxysilane residue, and further a 3-methacryloxypropyltrimethoxysilane residue, a 3-acryloxypropyltriethoxysilane residue, and a 3-methacryloxypropylmethyl Silicon atom-containing groups having an acryl group as an unsaturated bond, such as a dimethoxysilane residue and a 3-acryloxymethyldiethoxysilane residue, are more preferable than reactivity by light. This unsaturated bond is necessary for polymerization by light, and the alkoxy group is used to enhance the mechanical properties of the photosensitive polymer composition obtained by the condensation reaction of the silicon compounds during the subsequent heat treatment. It is effective for Specific examples of such a compound include a condensate of (3-aminopropyl) trimethoxysilane and methacryloxypropyltrimethoxysilane, and vinyltriethoxysilane and 1,3-bis (3-aminopropyl) -di Condensate with ethoxydimethyldisiloxane, N
-(3-acryloxy-2-hydroxypropyl) -3
-Aminopropyltriethoxysilane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisilazane, 3-aminopropoxy) -3,3'-dimethyl-1
Compounds having an unsaturated double bond with an amino group, such as -propenyltrimethoxysilane, are preferred.

Also, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyldimethylmethoxysilane, 2-acryloxypropylmethylbis (trimethylsiloxysilane), allyltriethoxysilane, Allyltrimethoxysilane, diphenylvinylethoxysilane, divinyltetraethoxydisiloxane, 3-methacryloxypropenyltrimethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropyldimethylmethoxylane, 3-methacryloxypropylditriethoxy Orchid, 3-methacryloxypropyltrimethoxylan, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxy Unsaturated bonds and alkoxy groups such as octane, oct-7-enyltrimethoxysilane, vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane and vinyltriphenoxysilane Silane compound having the formula: 4-aminobutyldimethylethoxysilane, N- (2-aminoethyl)-
3-aminopropylmethyldimethoxysilane, N- (2
Preferred examples include those obtained by condensing a silane compound having an amino group and an alkoxy group, such as -aminoethyl) -3-aminopropyltrimethoxysilane and 3-aminopropyldimethylethoxysilane. Such a condensation reaction is performed by adding a silane compound having an unsaturated bond and an alkoxy group, a silane compound having an amino group, water and, if necessary, an acid such as acetic acid, hydrochloric acid, or phosphoric acid, at 0 to 150 degrees for 10 minutes. It can be obtained by reacting for 6 hours.

R1 in the present invention is a polymer having a structural unit represented by the general formula (1) as a main component, and is heated, or an appropriate catalyst to form an imide ring, an oxazole ring, a thiazole ring, a quinoline ring, or the like. Or a polymer material such as polyphenylene, polyethersulfone, polyphenylene sulfide, aromatic polyester, aromatic polyamide, or a precursor thereof, but using any other polymer material Can also.

In the present invention, R3 represents a tricarboxylic acid or a tetracarboxylic acid constituting the polyamideimide precursor composition or the polyimide precursor composition, and preferred examples thereof include trimellitic acid, pyromellitic acid, and benzophenonetetracarboxylic acid. Aromatic carboxylic acids such as biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, bis (dicarboxyphenyl) hexafluoropropane, cyclobutanetetracarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, etc. Examples thereof include aliphatic carboxylic acids and their ester compounds such as methyl, ethyl, hexyl and ethoxy methacrylate. R3 may be composed of one kind of these compounds, or may be composed of two or more kinds.

In the present invention, R4 represents a diamine compound constituting a polyamideimide precursor composition or a polyimide precursor composition. Preferred examples thereof include phenylenediamine, diaminodiphenyl ether, diaminodiphenylsulfone, diaminodiphenylmethane, and bis ( Aminophenoxy) benzene, bis (aminophenoxyphenyl) sulfone, bis (aminophenoxyphenyl) propane, bis (trifluoromethyl) diaminobiphenyl, bis (aminophenoxyphenyl) hexafluoropropane, diaminobenzoic acid, ethyl diaminobenzoate, Ester compounds such as ethoxymethacrylate, aromatic diamine compounds such as bis (amino, hydroxyphenyl) hexafluoropropane, hexamethylenediamine, Njiamin, cyclohexyl diamine, can be mentioned methylenebis (aminocyclohexane) aliphatic diamine compounds such as. R4 is
These compounds may be composed of one kind or two or more kinds.

R5 in the present invention represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Such organic groups include methyl, ethyl, propyl, butyl, hexyl, decyl, allyl, hydroxyphenyl,
Ethoxymethyl, ethoxyethyl, ethoxypropyl,
Examples include groups such as ethoxybutyl, ethoxymethacrylate, ethoxyacrylate, 2-hydroxypropyl, 2-hydroxy-3-methacrylpropyl, and 2-hydroxy-3-acrylpropyl. R5 is
One of these may be used, or two or more may be used.

As the photopolymerization initiator and sensitizer in the present invention, aromatic secondary or tertiary amine compounds, thiol compounds and the like can be preferably used. Specific preferred examples thereof include N-phenylglycine, ethyl diethylaminobenzoate, isoamyl diethylaminobenzoate, N-phenylethanolamine, N-phenyldiethanolamine, N-ethylaniline, mercaptobenzothiazol, -Mercaptobenzimidazole, 1
-Phenyl-5-mercapto-1H-tetrazole and the like. From the standpoint of improving sensitivity, an N-arylglycine compound is particularly preferred. Examples of this compound include N-phenylglycine, N- (3-methoxyphenyl) glycine, N- (4-nitrophenyl) glycine,
N- (4-methoxyphenyl) glycine, N- (3-nitrophenyl) glycine, N-naphthylglycine, N-
Ethyl ester of phenylglycine, 3,3 ', 4
Examples include, but are not limited to, 4'-benzophenone tetracarboxyl peracid. Further, an aromatic secondary or tertiary amine compound and a thiol compound can be used in combination. The amount of addition of these compounds is
0.1 to 100 parts by weight, more preferably 0.2 to 10 parts by weight, per 100 parts by weight.

Coumarins may be used as a sensitizer to further improve the sensitivity to g-ray exposure. Specific examples of preferred coumarins include 3- (4-methoxybenzoylcoumarin), 7-diethylamino-3-benzoylcoumarin, 7-dimethylamino-3- (4-methoxybenzoylcoumarin), and 5,7-dimethoxy-3-.
(4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-dimethylaminobenzoyl) coumarin, 3,3′-carbonylbiscoumarin, 3,3′-carbonylbis (7-methoxycoumarin), 3,3 ′ -Carbonyl bis (7-diethylaminocoumarin), 9-
(7-diethylamino-3-cumanoyl) -1,2,2
4,5-tetrahydro-3H, 6H, 10H [1] benzopyrano [9,9a, 1-gh] quinolazin-10-one and the like, but are not limited thereto.
Any compound that actually absorbs at 436 nm, which is the g-line of a mercury lamp, can be used. Examples of the compounds other than the above include styryl compounds.
Such examples include 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) quinoline, 4- (p-dimethylaminostyryl) quinoline, 2- (p-dimethylaminostyryl) Benzothiazole, 2- (p-dimethylaminostyryl)
-3,3-dimethyl-3H-indole, 2- (p-dimethylaminostyryl) naphtho [1,2-d] thiazole and the like. Further, it is also preferable to increase the solubility of these compounds in water by introducing a hydroxyl group or a sulfonic acid group.

Further, Michler's ketone, fluorenone,
Aromatic carbonyl compounds such as benzanthrone, 2,
Azide compounds such as 6-bis (4-azidobenzylidene) -4-methylcyclohexanone, 4-azidobenzalacetophenone, 3- [4- (dimethylamino) phenyl] -1-phenyl-2-propen-1-one, 1-
Amino aromatic unsaturated ketones such as (3-chlorophenyl) -5- [4- (dimethylamino) phenyl] -1,4-pentadien-3-one, 1,3, -diphenyl-
1,2,3-propanetrione-2- (O-acetyl)
Oxime, 1-phenyl-1,2-butanedione-2-
Oximes such as (O-methoxycarbonyl) oxime and bis (α-isonitrosopropiophenone) isophthal, organometallic complexes such as titanocene, merocyanine dyes, and the like are effective, but not limited thereto. Also,
Two or more of these may be used in combination. The preferred amount of these additives is 0.1 to 100 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the polymer.

One of these photopolymerization initiators and sensitizers may be used alone, or two or more of them having different effects may be mixed and used.

In the present invention, at least one unsaturated bond is used.
The term "amino compound" refers to a compound such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, dimethylacrylamide, N-methylol methacrylamide, or vinylpyridine, and is compounded in the range of 10 to 300 parts by weight. Can be. When such a compound is added in an amount of 10 parts by weight or less with respect to 100 parts by weight of the polymer of the general formula (1), no change in performance is observed. There is a risk of remaining in the film without occurring and deteriorating the mechanical properties of the obtained film. From such a viewpoint, a more preferable range is 20 to 250 parts by weight.

The composition of the present invention further comprises, as a photoreactive monomer, acrylic monomers such as 2-hydroxyethyl methacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, and pentaerythritol trimethacrylate per polymer. To 20% by weight.

The solvent used in the present invention includes aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, dimethylacrylamide and the like. Esters such as ethyl lactate and propylene glycol monomethyl ether acetate; alcohols such as ethanol; ketones such as cyclohexanone and methyl isobutyl ketone; ethers such as tetrahydrofuran and dioxane; or a mixture thereof can be used.

If necessary, a surfactant may be mixed for the purpose of improving the wettability between the photosensitive heat-resistant polymer composition and the substrate. In addition, inorganic particles such as silicon dioxide and titanium oxide, or powder of polyimide can also be added.

Next, a method for forming a polyimide pattern using the photosensitive polymer composition of the present invention will be described.

The photosensitive heat-resistant polymer composition is applied on a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, or the like is used, but is not limited thereto. Spin coating using a spinner as a coating method,
There are methods such as spray coating and roll coating.
The coating thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like.
To 150 μm.

Next, the substrate coated with the photosensitive polymer composition is dried to obtain a photosensitive polymer composition film. Drying is preferably performed using an oven, a hot plate, an infrared ray, or the like, in the range of 50 to 120 degrees for 30 seconds to several hours.

Next, the photosensitive polyimide precursor composition film is exposed to actinic radiation through a mask having a desired pattern to expose the film. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i-line (365 nm) and g-line (436 nm) of a mercury lamp are used.
It is preferable to use

To form a pattern of the polymer composition,
After exposure, this is achieved by removing unexposed portions using a developing solution. Examples of the developer include polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide; and alcohols such as methanol, ethanol, and isopropanol. Such as ethyl lactate, esters such as propylene glycol monomethyl ether acetate, hydrocarbons such as xylene, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone, and water alone or in combination of several kinds. It is preferably used. Further, an alkaline aqueous solution such as an aqueous solution of tetramethylammonium, an aqueous solution of ammonia, an aqueous solution of diethylaminoethanol, or an aqueous solution of sodium hydroxide can also be used as the developer. When developing with an alkaline aqueous solution, N-methyl-2-pyrrolidone, N, N-
A developer in which solubility is adjusted by adding a polar solvent such as dimethylacetamide, alcohols such as methanol, ethanol and isopropanol, and ketones can also be used. After development, it is rinsed with alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate. When development is performed with an alkaline aqueous solution, rinsing is preferably performed using water.

After development, the film is converted into a heat-resistant film by applying a temperature of 200 to 500 degrees. This heat treatment is carried out for 5 minutes to 5 hours while selecting the temperature and increasing the temperature stepwise, or while selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130 degrees, 200 degrees, and 350 degrees for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be used.

The heat-resistant film formed from the photosensitive polymer composition according to the present invention is used for applications such as a passivation film of a semiconductor, a protective film of a semiconductor element, and an interlayer insulating film of a multilayer wiring for high-density mounting.

[0031]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Method of Measuring Characteristics Measurement of Film Thickness Using a SURFCOM 5000 surface step meter from Tokyo Seimitsu, the film thickness was measured from the step at a part without a pattern and at a part at a certain part. In the pattern before development, the film was scratched with a cutter knife, and the level difference was measured.

The film thickness after development is defined as T1. This is a clean inert oven CLH-21-C manufactured by Koyo Lindberg Co., Ltd.
D, using nitrogen, flowing at 140 ° C. for 30 minutes in an atmosphere having an oxygen concentration of 20 ppm or less,
Heat to 0 ° C. A heat treatment was performed at 350 ° C. for 1 hour, and then, when the temperature was lowered to 200 ° C. or less, the film was taken out, and its film thickness was measured to be T2.

The shrinkage rate was T2 / T1 × 100 (%). A contraction rate of 65% or more is good.

Synthesis Example 1 Synthesis of Photosensitive Silicon Compound (1) A nitrogen inlet tube, a thermometer and a condenser were attached to a 300 ml three-necked flask, and 19.1 g of 3-aminopropylmethyldiethoxysilane (AMES) (0.1 mL) was added. 1 mol) and 3-
Methacryloxypropylmethyldimethoxysilane (MM
MS) 23.2 g with N-methyl-2-pyrrolidone (NM
30 g of P) and 30 g of gamma-butyrolactone (GBL) were mixed with 1.8 g (0.1 mol) of water, and reacted at 50 ° C. for 2 hours. Thus, a solution of the photosensitive silicon compound in which AMES and MMMS were condensed one by one on average was obtained.

Synthesis Example 2 Synthesis of Photosensitive Silicon Compound (2) A nitrogen inlet tube, a thermometer and a condenser were attached to a 300 ml three-necked flask, and AMES 19.1 g (0.1 mol) was added.
And 2-hydroxyethyl methacrylate (HEMA) 1
3.0 g of NMP and 30 g of GBL were subjected to an alcohol exchange reaction at 50 ° C. for 3 hours. With this, AMES
And HEMA were condensed one by one on average to obtain a solution of a photosensitive silicon compound.

Synthesis Example 3 Synthesis of Photosensitive Silicon Compound (3) A nitrogen inlet tube, a thermometer and a condenser were attached to a 300 ml three-necked flask, and 38.2 g (0.2 mol) of AMES was added.
And 1.8 g (0.1 mol) of water and 50 g of NMP and GBL5
The reaction was carried out at 50 degrees with 0 g for 2 hours. This allows
A solution of the aminosilane compound in which AMES was condensed one by one on average was obtained. 21.4 g (0.1 mol) of 2-hydroxy-1-acryloxy-3-methacryloxypropane was added thereto, and the mixture was reacted at 50 ° C. for 2 hours to obtain a solution of a photosensitive silicon compound.

Example 1 A 500 ml four-necked flask was charged with bis (4
-Aminophenoxyphenyl) sulfone (BAPS) 4
1.1 g (0.095 mol) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (SiDA)
1.2 g (0.005 mol) was dissolved in 150 g of N-methyl-2-pyrrolidone (NMP). Here, 11.3 g (0.052 mol) of pyromellitic anhydride (PMDA) and 16.8 g (0.052 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) were added to 57 g of NMP. The reaction was carried out at room temperature for 1 hour and then at 50 ° C. for 2 hours. Here, 8 g of the photosensitive silicon compound (1) obtained in Synthesis Example 1 was added as a solution, and the mixture was further reacted at 50 ° C. for 1 hour to obtain a polyamic acid (polyimide precursor). 20 g of N, N-dimethylaminopropyl methacrylamide (DMA) (0.1
1 mol) (based on polymer 27% by weight), 1.25 g of N-phenylglycine (NPG) (1.7% by weight based on polymer), 0.2 g of 3,3'-carbonylbis (7-diethylaminocoumarin) (based on polymer) Polymer 0.3% by weight)
A varnish of a photosensitive polyimide precursor was added together with 30 g of MP.

On a 6-inch silicon wafer, a varnish of this photosensitive polyimide precursor was prebaked to a thickness of 2
0 μm, and then using a hot plate (SKW-636 manufactured by Dainippon Screen Co., Ltd.) for 100 μm.
By pre-baking for 5 minutes at a temperature, a photosensitive polyimide precursor film was obtained. Exposure machine (Nikon i-line stepper NSR
-1505-g6E), the reticle on which the pattern was cut was set, and g-ray exposure was performed at an exposure amount of 400 mJ / cm ² (intensity of 436 nm).

Immediately before the development, a heat treatment at 60 ° C. for 1 minute was performed using a hot plate (SKW-636 manufactured by Dainippon Screen). Developed by SK manufactured by Dainippon Screen Mfg.
Using a developing device of W-636, the developer DV is rotated at 100 rotations.
-308 (manufactured by Toray) was sprayed for 3 seconds. Thereafter, the developer is stopped for 80 seconds, and then the developer is sprayed at 1000 rotations for 5 seconds.
Rinse treatment was performed by spraying isopropyl alcohol at 5,000 rpm for 5 seconds, and shake-drying was performed at 3,000 rpm for 8 seconds.

As a result of visually observing the pattern after development with an optical microscope, a favorable pattern was obtained. At this time, the film thickness was 19 μm.

Further, this pattern was formed under a nitrogen stream at 140
At 30 ° C. for 30 minutes and then to 350 ° C. over 1 hour,
When the film thickness of the pattern after the heat treatment at 350 ° C. for 1 hour was measured, a very thick film of 15 μm remained, and the shrinkage due to curing was a good value of 79%. Further, the heat-treated film did not show cracks, decrease in film thickness, etc. in the NMP treatment and the treatment with the stripping solution 106 manufactured by Tokyo Ohka, and showed good solvent resistance.

Example 2 19.0 g (0.04 g) of 4,4'-diaminodiphenyl ether (4DAE) was placed in a 1-liter four-necked flask under a nitrogen stream.
95 mol) and 1.2 g (0.005 mol) of SiDA
MP was dissolved in 100 g. Here, BTDA35.
4 g (0.11 mol) was added together with 63 g of NMP and reacted at room temperature for 6 hours to obtain a polyamic acid (polyimide precursor). Here, the photosensitive silicon solution 10 of Synthesis Example 2 was used.
g was added and reacted at 50 ° C. for 1 hour. To this varnish, 5 g of ethylene glycol dimethacrylate (8.2% by weight based on polymer) and 2.5 g of N-phenylglycine (4.1% by weight based on polymer) were added together with 25 g of NMP to obtain a varnish B of a photosensitive polyimide.

On a 4-inch silicon wafer, a varnish of the photosensitive polyimide precursor was applied to a film thickness of 1 after prebaking.
2 μm, and then using a hot plate (SKW-636 manufactured by Dainippon Screen Co., Ltd.).
By pre-baking at a temperature of 3 minutes, a photosensitive polyimide precursor film was obtained. The mask with the pattern cut was set in an exposure machine (Canon contact aligner PLA-501), and exposure was performed at an exposure amount of 400 mJ / cm ² (405 nm intensity).

The development was carried out by SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a developing device of -636, a 0.5% aqueous solution of tetramethylammonium was sprayed for 10 seconds at 50 rotations. Thereafter, the sample was kept still for 80 seconds, then rinsed by spraying water at 400 rotations for 10 seconds, and shake-dried at 3000 rotations for 10 seconds.

As a result of visually observing the pattern after development with an optical microscope, a favorable pattern was obtained. At this time, the film thickness was 11 μm.

Further, this pattern was formed under a nitrogen stream at 140
At 30 ° C. for 30 minutes and then to 350 ° C. over 1 hour,
When the film thickness of the pattern after the heat treatment at 350 ° C. for 1 hour was measured, a very thick film of 7.5 μm remained, and the shrinkage due to curing was a good value of 68%. Further, the heat-treated film did not show cracks, decrease in film thickness, etc. in the NMP treatment and the treatment with the stripping solution 106 manufactured by Tokyo Ohka, and showed good solvent resistance.

Example 3 19.0 g (0.0%) of 3,4'-diaminodiphenyl ether (3DAE) was placed in a 1-liter four-necked flask under a nitrogen stream.
95 mol) and 1.2 g (0.005 mol) of SiDA were dissolved in 150 g of dimethylacrylamide. 30.93 g (0.105 mol) of BTDA was added thereto and reacted at room temperature for 6 hours to obtain a polyamic acid (polyimide precursor). The solution was heated to 50 ° C.
8 g of the photosensitive silicon solution was added and reacted at 50 ° C. for 1 hour.

After completion of the reaction, 10 g of dimethylamino methacrylate (18% by weight based on polymer), 5 g of ethylene glycol dimethacrylate (9% by weight based on polymer) and N-
2.5 g of phenylglycine (4.6% by weight based on polymer)
Was added together with 20 g of NMP to obtain a varnish C of photosensitive polyimide.

On a 6-inch silicon wafer, a varnish of this photosensitive polyimide precursor was prebaked to a film thickness of 1
2 μm, and then using a hot plate (SKW-636 manufactured by Dainippon Screen Co., Ltd.)
By pre-baking at a temperature of 3 minutes, a photosensitive polyimide precursor film was obtained. Exposure machine (Nikon i-line stepper NS
R-1755-i7A), the reticle with the cut pattern was set, and the exposure amount was 300 mJ / cm ² (365 nm).
I-ray exposure.

The development was carried out by SKW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a developing device of -636, a developer consisting of 70 parts by weight of NMP and 30 parts by weight of ethanol was sprayed for 10 seconds at 50 rotations. After this, the robot stands still for 80 seconds and then at 400 rotations for 1 second.
After spraying the developing solution for 0 second, propylene glycol monomethyl ether acetate was sprayed for 5 seconds at 1,000 rotations, rinsed, and shaken off at 3000 rotations for 10 seconds to dry.

As a result of visually observing the pattern after development with an optical microscope, a favorable pattern was obtained. At this time, the film thickness was 11 μm.

Further, this pattern was formed under a nitrogen stream at 140
At 30 ° C. for 30 minutes and then to 350 ° C. over 1 hour,
When the film thickness of the pattern after the heat treatment at 350 ° C. for 1 hour was measured, a very thick film of 7.4 μm remained, and the shrinkage by curing was a favorable value of 67%. Further, the heat-treated film did not show cracks, decrease in film thickness, etc. in the NMP treatment and the treatment with the stripping solution 106 manufactured by Tokyo Ohka, and showed good solvent resistance.

Example 4 In a nitrogen stream, 10.9 g (0.05 mol) of PMDA and B
16.1 g (0.05 mol) of TDA are added together with 13.0 g (0.1 mol) of 2-hydroxyethyl methacrylate, 9.2 g (0.1 mol) of ethanol, and 20 g of pyridine together with 20 g of γ-butyrolactone (GBL). 3 at ℃
Allowed to react for hours. After completion of the reaction, the temperature of the solution was cooled to 5 ° C. or less, and 41.2 g of dicyclohexylcarbodiimide was obtained.
(0.2 mol) dissolved in 50 g of GBL was added dropwise. After dropping, stirring was continued for 20 minutes.
19.4 g (0.045 mol) and 9.01 g of 4DAE
(0.045 mol), photosensitive silicon solution 1 of Synthesis Example 1
A solution in which 0 g was dissolved in 100 g of GBL was added dropwise. After the completion of the dropwise addition, the reaction was carried out at 5 ° C for 1 hour.
After continuing stirring for 1 hour, 1 g of ethanol was added and reacted at 40 ° C. for 1 hour.

After the completion of the reaction, the urea compound formed as a by-product in the obtained solution was removed by filtration, and the filtrate was poured into 5 l of ethanol.
The polymer was precipitated. The polymer is collected by filtration at 50 ° C.
For 24 hours under vacuum.

10 g of the polymer thus obtained was treated with 0.5 g of bis (1-phenyl-1,2-propanedione-2-oxime) isophthal (5% by weight based on the weight of the polymer) and N
0.2 g of phenyldiethanolamine (based on polymer 2)
Wt.), 0.05 g of Michler's ketone (vs. polymer 0.
5% by weight) and 1 g of ethylene glycol dimethacrylate
(10% by weight of polymer) with 15 g of NMP
Varnish D of a photosensitive polyimide precursor composition was obtained.

On a 6-inch silicon wafer, the varnish of this photosensitive polyimide precursor was prebaked to a film thickness of 1
2 μm, and then using a hot plate (SKW-636 manufactured by Dainippon Screen Co., Ltd.)
By pre-baking at a temperature of 3 minutes, a photosensitive polyimide precursor film was obtained. Exposure machine (Nikon i-line stepper NS
R-1755-i7A), the reticle with the cut pattern was set, and the exposure amount was 300 mJ / cm ² (365 nm).
I-ray exposure.

Development was carried out by SKW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a developing device of -636, a developing solution composed of cyclopentanone was sprayed at 2,000 rpm for 25 seconds. Then 20
After spraying propylene glycol monomethyl ether acetate with the above developer at 00 rotations for 10 seconds, propylene glycol monomethyl ether acetate was sprayed at 2000 rotations for 5 seconds, rinsed, and shaken off at 3000 rotations for 10 seconds to dry.

As a result of visually observing the pattern after development with an optical microscope, a favorable pattern was obtained. At this time, the film thickness was 11 μm.

Further, this pattern was formed under a nitrogen stream at 140
At 30 ° C. for 30 minutes and then to 350 ° C. over 1 hour,
When the film thickness of the pattern after the heat treatment at 350 ° C. for 1 hour was measured, a very thick film of 7.4 μm remained, and the shrinkage by curing was a favorable value of 67%. Further, the heat-treated film did not show cracks, decrease in film thickness, etc. in the NMP treatment and the treatment with the stripping solution 106 manufactured by Tokyo Ohka, and showed good solvent resistance.

Example 5 18.3 g (0.05 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added to 17.4 g (0.3 mol) of propylene oxide and NMP80m
1 and 20 ml of acetone. A solution prepared by dissolving 11.16 g (0.055 mol) of isophthalic acid dichloride in 50 ml of cyclohexanone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropping, 10 g of the photosensitive silicon solution synthesized in Synthesis Example 3 was added. Thereafter, stirring was continued at −15 ° C. for 2 hours, and then the temperature of the solution was gradually increased to 20 ° C., and stirring was continued. After stirring at 20 ° C. for 1 hour, the solution was poured into 5 l of water. The polymer precipitate obtained by the introduction was collected by filtration, and dried under vacuum at 100 ° C. for 24 hours. Polymer 10 thus obtained
g of N-phenylglycine (3% by weight based on polymer), bis (1-phenyl-1,2-propanedione-
0.3 g of 2-oxime) isophthal (3% by weight based on polymer), 0.05 g of Michler's ketone (0.5 based on polymer)
% By weight), 1 g of ethylene glycol dimethacrylate
(10% by weight of polymer) is dissolved in 20 g of NMP,
Varnish E, a photosensitive heat-resistant resin precursor, was obtained.

A varnish E of this photosensitive heat-resistant resin precursor was applied on a 4-inch silicon wafer so that the film thickness after prebaking was 7 μm, and then a hot plate (SKW-636 manufactured by Dainippon Screen Co., Ltd.) was used. ) To obtain 120
By pre-baking for 3 minutes at a temperature, a photosensitive heat-resistant resin precursor film was obtained. The mask with the pattern cut was set in an exposure machine (Canon contact aligner PLA-501), and exposure was performed at an exposure amount of 800 mJ / cm ² (intensity of 405 nm).

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a developing device of -636, a 1.2% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Thereafter, the plate was allowed to stand still for 50 seconds, then rinsed by spraying water at 400 rotations for 10 seconds, and shake-dried at 3000 rotations for 10 seconds.

As a result of visually observing the pattern after development with an optical microscope, a favorable pattern was obtained. At this time, the film thickness was 6.5 μm.

Further, this pattern was formed under a nitrogen stream at 140
At 30 ° C. for 30 minutes and then to 350 ° C. over 1 hour,
When the film thickness of the pattern after the heat treatment at 350 ° C. for 1 hour was measured, a very thick film of 5.5 μm remained, and the shrinkage by curing was a favorable value of 85%. Further, the heat-treated film did not show cracks, decrease in film thickness, etc. in the NMP treatment and the treatment with the stripping solution 106 manufactured by Tokyo Ohka, and showed good solvent resistance.

Comparative Example 1 19.0 g (0.095 mol) of 4DAE and SiDA1.
2 g (0.005 mol) was dissolved in 100 g of NMP. Here, 10.9 g (0.05 mol) of PMDA and BT
15.5 g (0.048 mol) of DA were added along with 30 g of NMP.

To the obtained solution, 37 g (0.2 mol) of diethylaminoethyl methacrylate (based on 79% by weight of polymer), 1.25 g of N-phenylglycine (based on 2.7% by weight of polymer), and 3 g of ethylene glycol dimethacrylate (based on Polymer 6.4% by weight), Michler's ketone 0.
2 g (0.4% by weight based on polymer) was added together with 30 g of NMP to obtain a varnish F of a photosensitive polyimide precursor composition.

This was applied in the same manner as in Example 1,
Exposure and development revealed a good pattern after development, with a film thickness of 11 μm. However, this pattern was heated at 140 ° C. for 30 minutes under a nitrogen stream, then heated to 350 ° C. over 1 hour, and then heat-treated at 350 ° C. for 1 hour. The film thickness was measured to be 5.6 μm. The decrease in thickness was large, and the shrinkage due to curing was 53%, which was not a good value.

[0069]

According to the present invention, a photosensitive heat-resistant polymer composition having a small shrinkage after curing can be obtained.

Claims (3)

[Claims] (1) 100 parts by weight of a polymer having a structural unit represented by the general formula (1) as a main component and (b) 0.1 to 100 parts by weight of a photopolymerization initiator and / or a sensitizer. A photosensitive heat-resistant polymer composition comprising: Embedded image (R0 and R2 are a silicon atom-containing group having at least one unsaturated bond and an alkoxy group, and R1 is at least 6
An aromatic group having at least 10 carbon atoms, n is 10
To 100,000. ) 2. The photosensitive heat-resistant polymer composition according to claim 1, wherein R1 is represented by the general formula (2). Embedded image (R3 is a trivalent or tetravalent organic group having two or more carbon atoms, R4 is a divalent organic group having two or more carbon atoms,
R5 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, m is an integer of 10 to 100,000, and p is 1 or 2. ) (3) 100 to 100 parts by weight of a polymer having a structural unit represented by the general formula (1) as a main component and (b) 0.1 to 100 parts by weight of a photopolymerization initiator and / or a sensitizer. And (c) an amino compound having at least one unsaturated bond in an amount of from 10 to 300 parts by weight.