KR102682046B1 - Manufacturing method of polyimide precursor composition and negative photosensitive polyimide composition including polyimide precursor composition prepared by using the same - Google Patents

Abstract

According to the present invention, a diamine monomer and a dianhydride monomer are polymerized to prepare a polyimide precursor containing a diamine monomer and a dianhydride monomer as polymerized units and a repeating unit represented by the following formula (1), wherein the polymerization reaction is A method for producing a polyimide precursor composition performed at less than 0°C can be provided.

Description

Method for producing a polyimide precursor composition and a negative photosensitive polyimide composition including a polyimide precursor composition manufactured using the same

The present invention relates to a method for producing a polyimide precursor composition and a negative photosensitive polyimide composition containing the polyimide precursor composition prepared using the same.

Polyimide is a polymer that has a heteroimide ring in the main chain, and is manufactured by condensation polymerization of tetracarboxylic acid and diamine. These polyimides have excellent light transmittance, mechanical properties, thermal properties, and adhesion to substrates, so they are widely used as replacements for metals and glass in various fields such as electricity, electronics, automobiles, and semiconductors. In particular, polyimide has excellent thermal and mechanical properties, so it is used in the production of photosensitive resin or printed circuit boards for modularized electronic circuit components such as surface protective films and insulating films for semiconductor devices.

Insoluble polyimide is difficult to apply as a photosensitive material, so it began to be used as a photosensitive polyimide precursor by introducing an ester bond or tertiary amine salt to the carboxyl group in the polyamic acid state. However, during the imidization reaction of the precursor, residual solvent or photoreactive groups were discharged, resulting in shrinkage of about 50%, causing problems such as distortion or stress of the phase. To overcome these problems, research on soluble polyimide synthesis is needed.

Meanwhile, conventional photosensitive polyimide compositions have a problem of low elongation.

Therefore, research is needed to manufacture a photosensitive polyimide composition with higher molecular weight and elongation by blocking the possibility of side reactions and lowering the content of impurities by strengthening the purification process.

Japanese Registered Patent No. 4,559,547

The technical problem to be achieved by the present invention is to prevent the possibility of side reactions by suppressing the activity of moisture in the polymerization solution by introducing a low-temperature polymerization method in the process of manufacturing a polyimide precursor composition, and to reduce the content of impurities by strengthening the purification process. This is to manufacture a photosensitive polyimide composition with higher molecular weight and elongation.

Since the present invention can make various changes and have various embodiments, specific embodiments will be illustrated in the drawings and described in detail. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

The terms used in this application are only used to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the technical field to which the present invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted in an ideal or excessively formal sense unless explicitly defined in the present application. No.

In order to achieve the above technical problem, an embodiment of the present invention provides a method for producing a polyimide precursor composition.

In one embodiment, the method for producing a polyimide precursor composition is to polymerize a diamine monomer and a dianhydride monomer to include the diamine monomer and the dianhydride monomer as polymerized units, and a polyimide comprising a repeating unit represented by the following formula (1) It includes preparing a precursor, and the polymerization reaction can be performed below 0°C.

[Formula 1]

The polymerization reaction of polymerizing diamine monomer and dianhydride monomer can be carried out below 0°C, -20°C to 0°C, -10°C to 0°C or -8°C to -2°C, for specific example -5°C. there is. When polymerization is performed at such a temperature, the possibility of side reactions is prevented by suppressing water activity in the polymerization solution, and the content of impurities is lowered by strengthening the purification process, thereby obtaining a photosensitive polyimide composition with a higher molecular weight and elongation rate. You can.

In Formula 1, X may be a tetravalent organic group, and in one example, X may be an organic group represented by Formula 2 below.

[Formula 2]

The dianhydride monomer constituting the polyimide precursor according to the present application may exhibit excellent mechanical properties by containing a structure with excellent rigidity as described above. On the other hand, in the case of other dianhydride monomers with excellent rigidity, their solubility in solvents is reduced, making it difficult to apply them as photosensitive materials. However, the dianhydride monomers of the specific structure according to the present application also show excellent solubility, so they have photosensitive properties. It may be suitable as a material.

Additionally, in Formula 1, Y may include two or more benzene rings, and may have a structure in which two or more benzene rings are directly connected to each other without a separate linker between them. Y may include 8 or less, 6 or less, or 4 or less benzene rings. As an example, but not limited thereto, Y may include a biphenyl group. Additionally, as an example, the benzene ring in Y may include 1 or more and 5 or less, 4 or less, 3 or less, or 2 or less substituents containing at least one fluoro group. The substituent including one or more fluoro groups substituted on the benzene ring is not limited thereto, but may be a fluoro group, an alkyl group having 1 to 4 carbon atoms substituted with one or more fluoro groups, or a perfluoro alkyl group.

In one example, Y in Formula 1 may be an organic group represented by Formula 3 below.

[Formula 3]

In Formula 3, A and B are each independently a fluoro group, an alkyl group having 1 to 4 carbon atoms substituted with one or more fluoro groups, a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, or a perfluoropropyl group. It may include any one of the groups.

In this way, the diamine monomer constituting the polyimide precursor according to the present application can exhibit excellent mechanical properties by containing a structure with excellent rigidity as described above. Furthermore, by including a fluoro group in the structural unit, water repellency is imparted to the surface of the film during development, suppressing absorption from the surface, etc., and excellent resolution can be exhibited. In addition, the present application can exhibit excellent properties in terms of dielectric constant and transmittance by including the specific diamine monomer.

Additionally, in Formula 1, Z ¹ or Z ² may each independently be -O- or -NH, and R ² and R ⁴ may each independently be hydrogen or a methyl group. In addition, in Formula 1, R ¹ and R ³ each independently contain a straight-chain or branched alkylene group having 1 to 20 carbon atoms, or a monocyclic ring or polycyclic ring having 3 to 20 carbon atoms. It represents a cycloalkylene group, and is preferably an alkylene group having 1 to 6 carbon atoms, and may be a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group.

That is, in the present invention, the polyimide precursor of Formula 1 includes a (meth)acrylic group, so that the photosensitive resin composition can realize excellent developability and photosensitivity.

As such, the present application includes monomers of a specific structure among the known monomers of diamine monomer and dianhydride monomer, so that it has excellent resolution and can be suitable for miniaturization for high integration, and has excellent light sensitivity, making it suitable for industrial use of semiconductor devices. In production, output can be significantly increased. In addition, the thermal expansion coefficient is low and the characteristics of dielectric constant, glass transition temperature, and transmittance can be excellent at the same time.

The polyimide precursor of Formula 1 of the present application may be derived from a photoreactive compound. The photoreactive compound may be a (meth)acrylate compound. Specifically, the (meth)acrylate compound may include at least one of alkyl group-containing (meth)acrylate, cycloalkyl group-containing (meth)acrylate, and polar functional group-containing (meth)acrylate.

As used herein, “alkyl group” may mean containing a carbon chain structure in which unsaturated bonds do not exist in the functional group, and may mean containing a straight or branched carbon chain structure having 1 to 20 carbon atoms. there is.

According to one embodiment of the present invention, the alkyl group-containing (meth)acrylate may be a (meth)acrylate having an alkyl group having 1 to 20 carbon atoms. Specifically, the alkyl group-containing (meth)acrylate monomer is methacrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n- Butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate It may include one or more selected from the group consisting of latex, n-octyl (meth)acrylate, and isooctyl (meth)acrylate.

As used herein, “cycloalkyl group” may include a carbon ring structure with no unsaturated bonds in the functional group, and may include a monocyclic ring or polycyclic ring having 3 to 20 carbon atoms. can do.

According to one embodiment of the present invention, the cycloalkyl group-containing (meth)acrylate is cyclohexyl acrylate (CHA), cyclohexyl methacrylate (CHMA), isobornyl acrylate (IBOA), isobornyl methacrylate ( It may include one or more selected from the group consisting of (IBOMA) and 3,3,5-trimethylcyclohexylacrylate (TMCHA).

According to one embodiment of the present invention, the polar functional group-containing (meth)acrylate monomer is at least one of a hydroxy group-containing (meth)acrylate monomer, a carboxyl group-containing (meth)acrylate monomer, and a nitrogen-containing (meth)acrylate monomer. It may include species.

According to an exemplary embodiment of the present invention, the hydroxy group-containing (meth)acrylate monomer is 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. A group consisting of 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, and 2-hydroxypropylene glycol (meth)acrylate It may include one or more selected from.

According to an exemplary embodiment of the present invention, the carboxyl group-containing (meth)acrylate monomer is acrylic acid, methacrylic acid, 2-ethyl acrylic acid, β-CEA (2-CARBOXYETHYL ACRYLATE), and 2-(meth)acryloyloxy acetic acid. , 3-(meth)acryloyloxy propylic acid, 4-(meth)acryloyloxybutyric acid, and acrylic acid doublet.

According to one embodiment of the present invention, the nitrogen-containing (meth)acrylate monomer is 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, and 4-isocynatopropyl (meth)acrylate. It may be one or more selected from the group consisting of anatobutyl (meth)acrylate.

The photoreactive compound according to the present application is introduced as a repeating unit in the polyimide precursor represented by Formula 1, and the repeating unit of the photoreactive compound in the polyimide precursor represented by Formula 1 may be 70 to 100%. As the polyimide precursor composition according to the present application includes a photoreactive compound having a repeating unit of 70 to 100% as described above, a large network structure is formed by a photoreaction later, resulting in a difference in solubility between the exposed and unexposed areas, It is possible to suppress deformation of the pattern profile or increase in line width roughness due to acid diffusion. Additionally, a pattern with improved line edge roughness and resolution can be obtained.

In one embodiment, the polyimide precursor composition may include a multifunctional photopolymerizable compound. A multifunctional photopolymerizable compound is a compound having at least two photopolymerizable groups, and the photopolymerizable group may be an ethylenically unsaturated bond. For example, a vinyl group containing at least one double bond between carbons, a (meth)allyl group, and (meth)acrylate groups.

As an example, the multifunctional photopolymerizable compound includes ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, tetraethylene glycol diacrylate, and propylene glycol. Diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1 , 6-hexanediol diacrylate, 1,9-nonanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl)ether, trimethylolethane triacrylate , pentaerythritol triacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acrylic Royloxyethyl)isocyanurate, isocyanuric acid ethylene oxide modified triacrylate, a product of Gongyoung Co., including PEG#200 diacrylate, PEG#400 diacrylate, or PEG#600 diacrylate. It can be done, and is not limited to this.

As described above, the polyimide precursor composition exhibits good compatibility with the multifunctional photopolymerizable compound, and by including the multifunctional photopolymerizable compound, excellent developability and photosensitivity of the photosensitive resin composition can be achieved.

In one example, the content of the multifunctional photopolymerizable compound may be 1 to 70 parts by weight, for example, 5 to 35 parts by weight, 10 to 30 parts by weight, 13 to 27 parts by weight, based on 100 parts by weight of the polyimide precursor. It may be included in 15 to 25 parts by weight, or 17 to 23 parts by weight. Here, the content of the multifunctional photopolymerizable compound may be measured based on the solid weight of the polyimide precursor.

Furthermore, the present application further includes a multifunctional photopolymerizable compound in a specific diamine monomer and a specific dianhydride monomer, so that the physical properties desired by the present invention can be realized, and thus, even if any of the combinations of the above compositions are not included, the present application It may be difficult to exhibit the physical properties intended for the invention.

In an embodiment of the present application, the polyimide precursor composition may include a photopolymerization initiator. As a photopolymerization initiator, any photopolymerization initiator that is known to be commonly used in photosensitive resin compositions may be used without any particular limitations, and may be appropriately selected in consideration of the wavelength of ultraviolet rays used. As an example, an acylphosphine oxide-based compound, an oxime ester-based compound, an acetophenone-based compound, or a triazine-based compound can be used as a photopolymerization initiator. One type may be used alone, or two or more types may be used in combination. It's okay too.

As an acylphosphine oxide photopolymerization initiator, specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, or bis(2,6- Dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. can be mentioned. Commercially available products include Omnirad TPO or Omnirad 819 manufactured by IGM Resins. As an oxime ester photopolymerization initiator, commercially available products include CGI-325 manufactured by BASF Japan, Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919 manufactured by Adeka Co., Ltd., and Adeka Ackles (registered trademark). ) NCI-831, etc. As an acetophenone photopolymerization initiator, specifically, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone , or N,N-dimethylaminoacetophenone. Commercially available products include Omnirad 907, Omnirad 369, or Omnirad 379 manufactured by IGM Resins.

As a triazine photopolymerization initiator, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 1,1,1,3,3,3 -Hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionate, ethyl-2-{4-[2, 4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 2-epoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine- 6-yl]phenylthio}acetate, cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, benzyl-2-{4- [2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazine- 6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionamide, 2,4-bis(trichloromethyl) Romethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3,-butadienyl- s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, etc. can be used.

In one example, the content of the photopolymerization initiator may be included in the range of 0.1 to 20 parts by weight or 0.5 to 10 parts by weight based on 100 parts by weight of the polyimide precursor. By satisfying the above range, a film manufactured from a polyimide precursor composition can sufficiently achieve the desired physical properties while having sufficiently excellent curing degree.

The polyimide precursor composition according to the present application may include an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent in which polyamic acid can be dissolved, but as an example, it may be an aprotic polar solvent.

Aprotic polar solvents include, for example, N-ethyl-pyrrolidone (NEP), N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone. , N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphotriamide, N-acetyl-ε-caprolactam, dimethylimidazolidinone, diethylene glycol dimethyl ether, trimethylene glycol It may be selected from the group consisting of ethylene glycol dimethyl ether, γ-butyrolactone, dioxane, dioxolane, tetrahydrofuran, chloroform, p-chlorophenol, o-chlorophenol, and methylene chloride, either alone or in a mixture of two or more. there is.

In this application, the solubility of polyamic acid may be adjusted by using auxiliary solvents such as toluene, tetrahydrofuran, acetone, methyl ethyl ketone, methanol, ethanol, or water, depending on the case.

In one example, the content of the solvent may be included in the range of 50 to 300 parts by weight, or 80 to 250 parts by weight, based on 100 parts by weight of the polyimide precursor. By satisfying the above range, a film manufactured from a polyimide precursor composition can sufficiently achieve the desired physical properties while maintaining sufficiently excellent curing properties.

In addition, in one specific example, the polyimide precursor composition has a solid content of 10 to 80% by weight, 15 to 75% by weight, 17 to 70% by weight, 20 to 60% by weight, 25 to 50% by weight, based on the total weight. Alternatively, it may contain 30 to 40% by weight. The present application adjusts the solid content of the polyamic acid composition to a relatively high level, thereby controlling the increase in viscosity while maintaining the physical properties after curing at the desired level, and preventing the increase in manufacturing cost and process time due to the need to remove a large amount of solvent during the curing process. can do.

The polyimide precursor composition of the present invention may further include a photocrosslinking sensitizer that promotes the generation of radicals and a curing accelerator that promotes curing as auxiliary components, if necessary.

In one example, at least one type from the group consisting of a photocrosslinking sensitizer and a curing accelerator may be additionally included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polyimide precursor. More preferably, it may contain 0.1 to 5 parts by weight based on 100 parts by weight of polyamic acid.

Photocrosslinking sensitizers include benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylaminobenzophenone, and methyl-o-benzoyl. Benzophenone-based compounds such as benzoate, 3,3-dimethyl-4-methoxybenzophenone, or 3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone; Fluorenone-based compounds such as 9-fluorenone, 2-chloro-9-fluorenone, and 2-methyl-9-fluorenone; Thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone, or diisopropyl thioxanthone. Thioxanthone-based compounds; xanthone-based compounds such as xanthone or 2-methylxanthone; Anthraquinone-based compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethylanthraquinone, t-butyl anthraquinone, or 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine (acridine), 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane) or 1,3-bis(9-acridinyl) Acridine-based compounds such as propane; dicarbonyl-based compounds such as benzyl, 1,7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-dione, and 9,10-phenanthrenequinone; phosphine oxide-based compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide or bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide; Benzoate-based compounds such as methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, or 2-n-butoxyethyl-4-(dimethylamino)benzoate; 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzal)cyclohexanone, or 2,6-bis(4-diethylaminobenzal)-4 -Amino synergist compounds such as methyl-cyclopentanone; 3,3-carbonylbis-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3 -benzoyl-7-methoxy-coumarin or 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]-benzo Coumarin-based compounds such as pyrano[6,7,8-ij]-quinolizin-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azidbenzalacetophenone; 2-benzoylmethylene, 3-methyl-b-naphthothiazoline, etc. can be used.

Typical curing accelerators include aromatic heterocyclic amine compounds, and examples of the aromatic heterocyclic amine compounds include pyridine, triazole, and pyridine substituted or unsubstituted with a hydrocarbon group having 3 to 12 carbon atoms. One or more types selected from the group consisting of imidazole, quinoline, triazine and their derivatives may be used.

Specifically, imidazole, benzoimidazole, 1-methyl imidazole, 2-methyl imidazole, ethyl imidazole, 1,2,4-triazole, 1,2,3-triazole, 2-mercaptobenzoxa Sol, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-4 ,6-dimethylaminopyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,4-dimethylpyridine, 4-pyridinemethanol, nicotinaldehyde oxime, isonicotinaldehyde oxime, ethyl picolinate, ethyl isopicotinate , 2,2'-bipyridyl, 4,4'-bipyridyl, 3-methylpyridazyl, quinoline, isoquinoline, phenanthridine, 2-mercaptobenzoimidazole, 2-mercaptobenzotriazole, Phthalazine or 1,10-phenanthroline may be used, but are not limited thereto.

Additionally, the polyimide precursor composition of the present invention may include a flame retardant. The flame retardant can be used without limitation as long as it is compatible with the polyamic acid solution and the polyamic acid solution containing the (meth)acrylate compound.

In addition, the polyimide precursor composition of the present invention may further include additives such as anti-foaming agents, leveling agents, or anti-gel agents, if necessary, to facilitate application or curing, or to improve other physical properties.

In one example, the polyimide precursor composition of the present application is

The weight average molecular weight may be in the range of 20,000 to 60,000, 25,000 to 55,000, 30,000 to 50,000, 20,000 to 50,000, or 20,000 to 40,000. In particular, the weight average molecular weight before curing may be in the range of 20,000 g/mol or more and 30,000 g/mol or less. In this application, the term weight average molecular weight refers to the converted value for standard polystyrene measured by GPC (Gel permeation Chromatograph). By satisfying the weight average molecular weight of the present application within a specific range, the desired viscosity can be achieved and excellent processability can be achieved.

The polyamic acid composition according to the present application may have a coefficient of thermal expansion (CTE) of 40 ppm/°C or less after curing. In one embodiment, the upper limit of the CTE may be less than or equal to 40 ppm/°C, 35 ppm/°C, 30 ppm/°C, 25 ppm/°C, 20 ppm/°C, 18 ppm/°C, or 15 ppm/°C, and the lower limit is, for example, 1 ppm/°C, 2 ppm/°C, 3 ppm/°C, 4 ppm/°C, 5 ppm/°C, 6 ppm/°C, 7 ppm/°C, 8 ppm/°C, 9 ppm/°C, It may be 10 ppm/°C, 11 ppm/°C, 12 ppm/°C, 13 ppm/°C, or 14 ppm/°C. In one example, the coefficient of thermal expansion may be measured at 100 to 450° C. using a thermomechanical analyzer (TA Q400) and may be measured according to the ASTM E831 standard. In detail, polyimide was manufactured into a film, cut into 2 mm wide and 10 mm long, and then the temperature was raised from room temperature to 500 ℃ at a rate of 10 ℃/min while applying a tension of 0.05 N under a nitrogen atmosphere, and then again at 10 ℃/min. The slope from 100 ℃ to 450 ℃ can be measured while cooling at a rate of .

The polyamic acid composition according to the present application may have a dielectric constant of 3.5 or less at 10 GHz after curing. The upper limit of the dielectric constant may be, for example, less than or equal to 3.45, 3.43, or 3.41, and the lower limit can be, for example, greater than or equal to 1, 2, or 3.

The polyamic acid composition according to the present application may have a 1% by weight thermal decomposition temperature of 400° C. or higher after curing. The thermal decomposition temperature can be measured using a thermogravimetric analysis (TA Q50). In a specific example, the polyimide obtained by curing the polyamic acid is heated to 150° C. at a rate of 10° C./min under a nitrogen atmosphere and then maintained isothermally for 30 minutes to remove moisture. Afterwards, the temperature is raised to 600°C at a rate of 10°C/min, and the temperature at which 1% weight loss occurs can be measured. The lower limit of the thermal decomposition temperature may be, for example, 410 °C, 415 °C, 425 °C, 435 °C, 445 °C, 450 °C, 455 °C, 460 °C, or 470 °C, and the upper limit may be, for example, 800 °C or 700 °C. It may be below ℃.

The polyamic acid composition according to the present application may have a transmittance in the range of 40 to 80% in any one wavelength range of the visible light range (300 to 900 nm) due to the UV light distribution after curing. As an example, the transmittance may be measured in a wavelength range of 300 to 900 nm and the average value may be expressed. The lower limit of the light transmittance may be, for example, 42%, 44%, 46%, 48%, or 50% or more, and the upper limit may be, for example, 90%, 80%, 70%, 65%, or 60% or less. there is.

The polyamic acid composition according to the present application may have an elongation rate of 10% or more, 15% or more, or 20% or more after curing. Since the polyamic acid composition according to the present application has a high elongation rate as described above, it can improve product reliability when introduced into displays or semiconductor equipment. In one embodiment, elongation refers to elongation at break, which can be measured according to ASTM D882.

Additionally, the present application relates to a method for producing the above-described polyamic acid composition.

In a specific example, the method for producing the polyamic acid composition of the present application may have, for example, the following polymerization method.

For example, (1) a method of polymerizing the entire amount of diamine monomer in a solvent and then adding dianhydride monomer and diamine monomer in substantially equimolar amounts;

(2) a method of polymerizing the entire amount of dianhydride monomer in a solvent and then adding diamine monomer in substantially equimolar amounts to the dianhydride monomer;

(3) After adding some of the diamine monomer components into the solvent, mixing some of the dianhydride monomer components in a ratio of about 95 to 105 mol% with respect to the reaction components, adding the remaining diamine monomer components, and then adding the remaining dianhydride monomer components continuously. A method of polymerizing by adding a dianhydride monomer component so that the diamine monomer and the dianhydride monomer are substantially equimolar;

(4) After adding the dianhydride monomer into the solvent, mixing some of the diamine compounds in a ratio of 95 to 105 mol% with respect to the reaction components, adding other dianhydride monomer components, and then adding the remaining diamine monomer components. A method of polymerizing by adding a diamine monomer and a dianhydride monomer such that the diamine monomer and the dianhydride monomer are substantially equimolar;

(5) reacting some diamine monomer components and some dianhydride monomer components in a solvent so that either one is in excess to form a first composition, and reacting some diamine monomer components with some dianhydride monomer components in another solvent. A method of forming a second composition by reacting in excess, mixing the first and second compositions, and completing polymerization. In this case, if the diamine monomer component is excessive when forming the first composition, the second composition In the first composition, the dianhydride monomer component is in excess, and when the dianhydride monomer component is in excess in the first composition, the diamine monomer component is in excess in the second composition, and the first and second compositions are mixed and used for these reactions. A method of polymerizing the total diamine monomer components and the dianhydride monomer components such that they are substantially equimolar is included.

The polymerization method is not limited to the above examples, and of course, any known method can be used.

The step of preparing the polyamic acid composition may be performed at a temperature of -20°C or more and less than 0°C. Preferably, it may be carried out at -10°C or higher and below 0°C. More preferably, it can be performed at -5°C.

Additionally, the present application relates to a photosensitive composition comprising a polyimide precursor composition. The photosensitive composition according to the present application may in particular be a negative photosensitive composition.

The negative photosensitive composition according to the present application includes a polyimide precursor composition, a photoinitiator, a multifunctional monomer containing two or more photoreactive functional groups, and a solvent.

The negative photosensitive composition according to the present application may include 30 to 50 parts by weight of a polyimide precursor composition, 0.1 to 5 parts by weight of a photoinitiator, 1 to 20 parts by weight of a polyfunctional monomer, and 30 to 70 parts by weight of a solvent.

The photoinitiator may be diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and the polyfunctional monomer may be tetra(ethylene glycol) diacrylate. The solvent may be γ-butyrolactone (GBL), but is not necessarily limited thereto.

Furthermore, the present application relates to polyimide containing a cured product of a polyimide precursor composition. A method for producing a polyimide film is provided, comprising forming a polyimide precursor composition prepared according to a method for producing a polyimide precursor composition onto a support, exposing, developing, and curing.

Specifically, the method for producing the polyimide film of the present invention is,

The support used in the film forming step may be, for example, an inorganic substrate. The inorganic substrate may include a glass substrate or a metal substrate, but it is preferable to use a glass substrate, and the glass substrate may be soda lime glass or borosilicate glass. Glass, alkali-free glass, etc. may be used, but are not limited to this. As an example, after the film forming step, a prebaking step may be further included at 70 to 130°C or 80 to 120°C for about 1 to 10 minutes.

The exposure step can be performed by irradiating ultraviolet rays or visible light with a wavelength of 200 to 500 nm using a photo mask on which the pattern to be processed is formed, and the exposure amount during irradiation is preferably 10 mJ/cm ² or 4,000 mJ/cm ² . In one example, after the exposure step, a post exposure bake step may be further included at 80 to 140° C. or 90 to 130° C. for about 1 to 6 minutes.

The development step may be performed in a commonly known manner, but is not limited thereto, and an organic solvent or an alkaline aqueous developer may be used.

The curing step can be carried out under an inert atmosphere, for example a nitrogen atmosphere. Specifically, the curing step involves heating the polyimide precursor composition starting at 20 to 28 °C or 23 to 27 °C and increasing the temperature to 80 to 150 °C, 90 to 130 °C, or 100 to 120 °C at a rate of 4 °C/min. , again increase the temperature at a rate of 4°C/min to a temperature of 300 to 450°C, 320 to 430°C, 340 to 410°C, or 360°C to 390°C, and then increase the temperature to 20 to 28°C or 23 to 27°C at a rate of 2°C/min. It may include cooling at a rate of minutes.

The thickness of the polyimide film may be 5 to 20 μm. For example, the polyimide film may have a thickness of 6 to 18 μm, 7 to 15 μm, 8 to 13 μm, or 9 to 12 μm.

The polyimide precursor composition according to the present application has excellent heat resistance and excellent photosensitivity and resolution, making it possible to form ultra-fine patterns.

Additionally, the negative pattern resolution can be implemented at 10㎛ or less. Additionally, a negative photosensitive polyimide composition including a polyimide precursor composition according to an embodiment of the present invention can achieve an elongation of 20% or more compared to a conventional photosensitive polyimide composition.

Additionally, the polyimide precursor composition according to one embodiment of the present invention has a molecular weight (Mw) of 20,000 g/mol or more.

However, the effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.

Below, a preferred experimental example (example) is presented to aid understanding of the present invention. However, the following experimental examples are only intended to aid understanding of the present invention, and the present invention is not limited by the following experimental examples.

Examples 1 to 2 and Comparative Examples 1 to 7 of polyimide precursor

60 g of BTDA, 300 g of NMP, and 0.1 g of hydroquinone were added to a 500 ml reaction vessel into which nitrogen was flowing, and stirred at room temperature until the solid content was dissolved. 53.01 g of HEMA and 60.39 g of pyridine were added to the above solution, and stirred at room temperature overnight. Then, the temperature of the solution was lowered to -5°C, and 360 g of NMP and 80.68 g of phenylphosphonic dichloride were slowly added dropwise and stirred for 2 hours. Afterwards, 59.63 g of TFMB was slowly added to the solution, the temperature of the solution was raised to 25°C, and the solution was stirred for 6 hours. The finally obtained solution was slowly dropped into two volumes of distilled water, and the resulting solid content was recovered. The obtained solid was washed in a solution of 1 part distilled water and 1 part ethanol, then washed twice in 2 parts distilled water, and then dried at a temperature of 40°C or lower for 3 days. In this way, polyimide precursors according to Examples 1 to 2 and Comparative Examples 1 to 7 were obtained.

Examples 1 to 2 of the present invention were obtained by conducting a polymerization reaction at a polymerization temperature of -5°C, and Comparative Examples 1 to 7 of the present invention were obtained by conducting a polymerization reaction at a polymerization temperature of 5°C.

division unit Comparative Example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Comparative Example 6 Comparative example 7 Example 1 Example 2 anhydride BTDA BTDA BTDA PMDA ODPA PMDA BTDA BTDA ODPA amine O.D.A. TFMB MDA TFMB O.D.A. O.D.A. HFBAPP TFMB O.D.A. photosensitive functional group HEMA HEMA HEMA HEMA HEMA HEMA HEMA HEMA HEMA polymerization
temperature ℃ 5 5 5 5 5 5 5 -5 -5 BTDA: 3,3',4,4'-benzophenonetetracarboxylic dianhydride
PMDA: pyromellitic dianhydride
ODPA: 4,4'-oxydiphthalic anhydride
ODA: 4,4'-oxydianiline
TFMB: 2,2'-bis(trifluoromethyl)benzidine
HFBAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane
MDA: 4,4'-methylenedianiline
HEMA: 2-hydroxyethyl methacrylate

Examples 1 to 2 and Comparative Examples 1 to 7 of polyimide precursor composition

36% by weight of solid polyimide precursor according to the Examples and Comparative Examples obtained above, 7.2% by weight of tetra(ethylene glycol) diacrylate as a multifunctional photopolymerizable compound, and TPO (diphenyl(2,4,6-trimethylbenzoyl) as a photoinitiator. )-phosphine oxide) 1.8% by weight was sufficiently dissolved in 55% by weight of gammabutyrolactone to obtain a polyimide precursor composition.

<Experimental example>

The experimental data obtained by measuring the physical properties according to the evaluation method below are summarized in Table 2 below.

Preparation of polyimide film specimens for physical property measurement

Air bubbles were removed from the polyimide precursor composition according to each of the Examples and Comparative Examples obtained above by rotating at a high speed of 1,500 rpm or more. Afterwards, it was uniformly applied to a thickness of 5 ㎛ on a glass substrate using spin coating.

Afterwards, it was prebaked at 100°C for 5 minutes, and exposure was performed using metal halide exposure equipment, covering the mask with a patterned pattern. Then, the exposed substrate was baked at 110°C for 3 minutes and developed using propylene glycol monomethyl ether acetate (PGMEA) and cyclopentanone.

Next, under a nitrogen atmosphere, the temperature was raised at a rate of 4°C/min from 25°C to 110°C and heat treated for 60 minutes, the temperature was raised at a rate of 4°C/min to 375°C and heat treated for 60 minutes, and then the temperature was raised to 25°C. The photosensitive polyimide film obtained by cooling at a rate of 4°C/min was peeled from the glass substrate to obtain a polyimide film specimen.

The physical properties were measured using the prepared polyimide film specimen in the following manner, and the results are shown in Table 2 below.

resolution

For the polyimide film specimen obtained above, the spacing of the narrowest pattern among the patterns observed using SEM equipment was measured and expressed as resolution. However, when a film is not formed or a pattern is not formed, it is indicated as X.

Elongation

The polyimide film specimen obtained above was measured according to ASTM D-882 standard. Specifically, the polyimide film specimen was cut into 10 mm wide and 40 mm long pieces and then measured using Instron's Instron5564 UTM equipment.

division unit Comparative Example 1 Comparative example 2 Comparative Example 3 Comparative example 4 Comparative Example 5 Comparative Example 6 Comparative example 7 Example 1 Example 2 Elongation % 4 4 4 2 3 3 9 22 33 Molecular weight (Mw) g/mol 10,600 11,955 10,915 10,034 6,644 3,334 17,149 21,000 28,000 resolution μm X 〈 10 X X X X 〈 10 〈 10 X

The polyimide precursor composition according to the present application has excellent heat resistance and excellent photosensitivity and resolution, making it possible to form ultra-fine patterns. Additionally, the negative pattern resolution can be implemented at 10㎛ or less.

In addition, Examples 1 to 2, which include the polyimide precursor composition according to an embodiment of the present invention, can achieve an elongation rate of 20% or more compared to Comparative Examples 1 to 7, which are conventional photosensitive polyimide compositions.

Additionally, Examples 1 to 2 including the polyimide precursor composition according to an embodiment of the present invention have a molecular weight (Mw) of 20,000 g/mol or more.

The present invention described above is not limited to the above-described embodiments, as various substitutions and changes can be made by those skilled in the art without departing from the technical spirit of the present invention. .

Claims (17)

3,3',4,4'-benzophenonetetracarboxyldianhydride (BTDA), 2,2'-bis(trifluoromethyl)benzidine (TFMB), and 2-hydroxyethyl methacrylate (HEMA) Comprising the step of producing a polyimide precursor by polymerizing,
A method for producing a polyimide precursor composition, wherein the polymerization reaction is performed at less than 0°C.
According to paragraph 1,
A method for producing a polyimide precursor composition in which the polymerization reaction is carried out at -10°C to 0°C.
delete delete delete delete delete According to paragraph 1,
A method for producing a polyimide precursor composition in which the content of 2-hydroxyethyl methacrylate (HEMA) is 1 to 40 parts by weight based on 100 equivalents of the polyimide precursor.
According to paragraph 1,
The method of producing a polyimide precursor composition further includes a photopolymerization initiator.
According to paragraph 1,
The polyimide precursor composition is a method of producing a polyimide precursor composition further comprising an organic solvent.
According to paragraph 1,
A method for producing a polyimide precursor composition containing 10 to 80% by weight of solid content based on the total weight.
According to paragraph 1,
A method for producing a polyimide precursor composition having a weight average molecular weight before curing in the range of 20,000 g/mol to 60,000 g/mol.
The polyimide precursor composition according to claim 1,
photoinitiator,
A multifunctional monomer containing two or more photoreactive functional groups and
A negative photosensitive composition comprising a solvent.
According to clause 13,
A negative photosensitive composition comprising 30 to 50 parts by weight of a polyimide precursor composition, 0.1 to 5 parts by weight of a photoinitiator, 1 to 20 parts by weight of a polyfunctional monomer, and 30 to 70 parts by weight of a solvent.
According to clause 13,
A negative photosensitive composition wherein the photoinitiator is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.
According to clause 13,
A negative photosensitive composition in which the multifunctional monomer is tetra(ethylene glycol) diacrylate.
A polyimide comprising a cured product of the polyimide precursor composition according to claim 1.