KR0166560B1 - Photoinitiator composition - Google Patents

Abstract

Photoinitiator composition (A) containing N-aryl-α-amino acid (I), 3-substituted coumarin (II) and azabenzalcyclohexanone (III), or N-aryl-α-amino acid (I) ), Photoinitiator composition (B) containing 3-substituted coumarin (II) and titanocene (IV), or photoinitiator composition containing 3-substituted coumarin (II), titanocene (IV) and oxime ester (V) C) is effective for improving the photosensitive properties of photosensitive materials containing poly (amic acid) and addition polymerizable compounds for pattern formation.

Description

Photoinitiator Composition

The present invention relates to photoinitiator compositions using N-aryl-α-amino acids, N-aryl-α-amino acids and 3-substituted coumarins and / or azabenzalcyclonucinonon and N-aryl-α-amisona, 3-substituted coumarins. And photoinitiator composition using titanocene, photoinitiator composition using 3-substituted coumarin, titanocene and oxime ester, photosensitive composition using at least one selected from the group consisting of these photoinitiator compositions, at least one selected from the group consisting of these photoinitiator compositions A photosensitive material and a method of forming a pattern using the photosensitive material.

The photosensitive composition is generally widely used to form typography, relief images, photoresists and the like using ultraviolet rays as a light source, and high sensitivity is required. In particular, when the photosensitive composition is used for scanning light exposure by laser light, it is necessary to have not only high sensitivity but also sufficiently high sensitivity to visible light (458, 488, 514, 5 nm) which is an output wavelength of argon light. Furthermore, in the case of the photosensitive polyimide for thick films usable in semiconductors, sufficient sensitivity and good sensitivity for g-line steppers with monochromatic light (rays of 435 nm), contact exposure devices with full lengths of mercury lamps, and mirror projection exposure devices. It is necessary to have photosensitive wavelength characteristics.

Various studies on photoinitiators have been conducted to enhance the sensitivity. As photoinitiators, benzoin and its derivatives, substituted or unsubstituted polynuclear quinones, and the like are known. However, no material with significant sensitivity that meets the above objectives is known.

On the other hand, a polyimide or a precursor thereof having light-pattern forming properties per se is called a "photosensitive plimite" and is used as a surface main film for semiconductors. In order to convey photosensitivity to polyimide, various methods are known. For example, Japanese Patent Publication (JP-B) No. 55-41422 describes a method of esterifying poly (amino acid) with hydroxy acrylate. Japanese Patent Laid-Open Nos. (JP-A) Nos. 57-170929 and 54-145794 propose introducing photosensitive groups by mixing salts of amino acrylate with poly (amic acid) to form salt bridges. In the former case (JP-B), the photo-pattern forming characteristic is relatively good, but since it is difficult to obtain a high polymer, the removal of the photosensitive group tends to be incomplete, thereby showing the disadvantage of poor film characteristics. On the other hand, in the latter case (2 JP-A) it is easy to obtain good film properties due to the high polymer and easy volatility, but the light pattern forming properties are not sufficient. Especially for photosensitive polyimide for thick films having a film thickness of 5 µm or more, after curing, exposure to a mirror projection type exposure apparatus using the full-wavelength fields of the i-line stepper (365 nm light) and g-line (435 nm light) mercury lamps In other words, there is a problem that good pattern characteristics cannot be obtained.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method of forming a pattern using a photosensitive material having a significant photosensitive property and a photoinitiator composition for the photosensitive composition, a photosensitive composition, a photosensitive material, a photosensitive material, that is, an N-aryl-α-amino acid, N, which is effective as a photoinitiator. Photoinitiator composition with -aryl-α-amino acids and 3-substituted coumarins and / or azabenzalcyclonucinonons and photoinitiator compositions with N-aryl-α-amisona, 3-substituted coumarins and titanocene, 3-substituted Photoinitiator compositions using coumarins, titanocene and oxime esters, photosensitive compositions using at least one selected from the group consisting of these photoinitiator compositions, photosensitive materials using at least one selected from the group consisting of these photoinitiator compositions and the aforementioned problems of the prior art To provide a pattern forming method using such a photosensitive material.

According to the novel composition of the present invention

The above-mentioned problem of not being able to obtain good pattern characteristics when exposed to light using a mirror projection type exposure apparatus using the i-line stepper, the g-line stepper, and the full wavelength of the water temperature lamp can be solved.

The present invention provides N-aryl-α-amino acids of Formula 1a:

[Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, an alkoxycarbonyl group having 2 to 10 carbon atoms, a carboxamido group or a carbon number 1 4, the alkyl moiety is an alkylsulfonyl group which may be substituted with a cyano group, and at least one of R ₁ to R ₅ is a sarano group or an alkylsulfonyl group having 1 to 4 carbon atoms; R ₆ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, or an aryl group; R 7 and R ₈ are independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]

The present invention is characterized in that the N-aryl-α-amino acid of Formula 1a, and 3-substituted gumarin compound of Formula 2 and azabenzacyclohexa of Formula 3 contain at least one compound selected from the group consisting of compounds A photoinitiator composition (A) is used.

[Wherein R ₉ , R ₁₀ , R ₁₁ , and R ₁₃ are each independently a hydrogen atom, an amino group substituted with an alkyl group having 1 to 5 carbon atoms, an amino group substituted with two alkyl groups having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms An alkoxy group, acyloxy group, aryl group, halogen atom, or a C1-5 taoalkyl group: R ₁₄ is an unsubstituted phenyl group, biphenyl group, naphthyl group, thiethyl group, benzofunyl group, furyl group, pyridyl group, kumari Nyl group, amino group, amino group substituted with one or more alkyl groups of 1 to 5 carbon atoms, cyno group, alkoxy group of 1 to 5 carbon atoms, alkyl group of 1 to 5 carbon atoms, halogen atom, haloalkyl group, formyl group, alkoxy of 1 to 5 carbon atoms A phenyl group substituted with a carbonyl group, an acyloxy group having 1 to 5 carbon atoms, an acyl organo group having 1 to 5 carbon atoms, a cyano group, an alkoxy group, or an acyl group having 1 to 5 carbon atoms, the biphenyl group, the naphthyl group, the thienyl group, The benzofuryl group, the furyl group, the fildil group or Group is Kumari group which may be substituted with acyl of 1 to 5 carbon atoms or an acyloxy group having 1 to 5 carbon atoms.]

[Wherein R ₁₅ , R ₁₆ , R ₁₇ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ are independently hydrogen, chlorine or bromine. An alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group having 1 to 12 carbon atoms; R ₂₃ , R ₂₄ , R ₂₅ , and R ₂₆ are each independently an alkyl group having 1 to 6 carbon atoms; X is an imino group which may be substituted with an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group, an acyl group having 2 to 12 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, and an alkoxy having 2 to 12 carbon atoms. Carbonyl group or aryloxycarbonyl group having 7 to 20 carbon atoms]

The present invention provides a photoinitiator composition (B) consisting of an N-aryl-α-amino acid of Formula 1b, a 3-substituted coumarin compound of Formula 2, and a titanocene compound of Formula 4;

[Wherein R ₂₇ to R ₃₆ independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic compound such as 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, imidazolyl, pyrazolyl, etc. Wherein the heterocyclic ring is capable of being bonded to the benzene ring directly or through an alkylene group, which may be substituted with one or more alkyl, amino, alkylamino or alkoxy groups]

The present invention provides a photoinitiator composition (C) consisting of a 3-substituted coumarin compound of formula (2), a titanocene compound of formula (4) and an oxime ester compound of formula (5):

[Wherein, R ₃₇ and R ₃₈ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a niko group; R ₃₉ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, a benzyl group, -0 CH ₂ CH ₂ OCH ₃ or -CO ₂ CH ₂ CH ₃ ;

The present invention also provides a photosensitive composition containing a compound capable of addition polymerization at a boiling point of 100 ° C. or higher at 1 atm, and a photoinitiator composition (A), (B) or (C).

The present invention

(a) poly (amic acid)

(b) compounds containing at least one carbon-carbon double bond and at least one amino group which are dimerizable or polymerizable by actinic rays or quaternary salts thereof, and

(c) A photosensitive material containing the photoinitiator composition (A), (B) or (C) is provided.

The present invention also provides a pattern forming method using the photosensitive material.

The N-aryl-α-amino acid of the present invention is represented by the following general formula (1a).

[Formula 1a]

[Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, an alkoxycarbonyl group having 2 to 10 carbon atoms, a carboxamido group or a carbon number 1 4, the alkyl moiety is an alkylsulfonyl group which may be substituted with a cyano group, and at least one of R ₁ to R ₅ is a sarano group or an alkylsulfonyl group having 1 to 4 carbon atoms; R ₆ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, or an aryl group; R 7 and R ₈ are independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]

For example, N-aryl-α-amino acids of the general formula (1a) can be prepared by aromatic nucleophilic substitution of the substituted halobenzenes with glycine compounds using similar methods.

When the compound of Formula 1a is used as the photoinitiator composition, the limitation of "at least one of R ₁ to R ₅ is a cyano group or an alkylsulfonyl group having 1 to 4 carbon atoms" is not essential and at least one of R ₁ to R ₅ is alkoxy It is selected from a carbonyl group, the carboxycyamido group, the alkylsulfonyl group, and the cyano group. These compounds are hereinafter referred to as "N-aryl-α-amino acids of Formula 1b."

More specifically, aromatic nucleophilic substitution is generally performed in the presence of a basic compound at room temperature to about 100 ° C. in acetone, dimethyl sulfoxide, N-methyl-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, It can be carried out by reacting the substituted halobenzene and glycine compounds in the same molar number in polar protic solvents such as tetrahydrofuran, sulfolane, methyl ethyl ketone, ethylene carbonate and the like. As the basic compound, natrium carbonate, potassium carbonate and the like can be used.

Examples of compounds of Formula 1a are as follows:

The compounds are effective as photoinitiators that generate active radicals by the action of ultraviolet and visible light in combination with one or more suitable photosensitizers.

The photoinitiator composition (A) of the present invention is at least one selected from the group consisting of the above-mentioned N-aryl-α-amino acid of Formula 1a, and the 3-substituted coumarin compound of Formula 2 and the Hazabenzalcyclonuxanon compound of Formula 3 It contains the above.

Examples of the 3-substituted coumarin compound of formula 2 are as follows:

These mixtures can be used alone or as mixtures thereof.

Examples of the azabelzalcyclonuxanon compound of the formula (3) are as follows.

The compounds can be synthesized by the method described in US Patent Application No. 4,987,057.

The compounds may be used alone or as a mixture thereof.

Although the N-aryl-α-amino acid of Formula 1a and the 3-substituted coumarin compound of Formula 2 and / or the azabenzalcyclohexanone compound of Formula 3 can be used in various ratios, the N-aryl-α-amino acid of Formula 1A Preference is given to using in larger quantities than the compound of the formula (2) and / or (3). In general, when using the compound of Formula 2 or Formula 3, the compound of Formula 2 or 3 is used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the chemical of Formula 1a, and both compounds of Formulas 2 and 3 are used. In this case, the total amount of the compounds of Formulas 2 and 3 is used in an amount of 1 to 100 parts by weight per 100 parts by weight of the compound of Formula 1a.

Other photoinitiator compositions (B) of the present invention contain an N-aryl-α-amino acid of Formula 1a, a 3-substituted coumarin compound of Formula 2 and a titanocene compound of Formula 4.

Examples of titanocene compounds of formula 4 are as follows:

The titanocene compound may be used alone or as a mixture thereof.

Compounds of formula (2) and compounds of formula (4) can be used in various ratios. Although the compound of Formula 1a may be used in various ratios, it is preferable to use the compound of Formula 2 in an amount of 1 to 100 parts by weight, and the compound of Formula 4 in an amount of 10 to 300 parts by weight per 100 parts by weight of the compound of Formula 1a. It is preferable to use.

The photoinitiator composition (C) of the present invention contains a 3-substituted coumarin compound of formula (2), a titanocene compound of formula (4) and an oxime ester compound of formula (5).

Examples of the oxime ester compound of the compound of formula 5 are as follows.

The compounds may be used alone or as a mixture thereof.

The compounds of the formulas (2), (4) and (5) may be used in various proportions, but it is preferable to use the titanocene compound and the oxime ester compound in an amount such that the weight ratio is greater than that of the 3-substituted coumarin compound. More specifically, it is preferable to use the compound of the formula (2) in 1 to 100 jungryab per 100 parts by weight of the compound of the formula (5), and it is preferable to use the compound of the formula (4) in the 10 to 300 parts by weight.

The photosensitive composition of the present invention contains an addition polymerizable compound having a boiling point of 100 ° C. or higher and a photoinitiator composition (A), (B) or (C) at 1 atmosphere.

The photosensitive composition may further contain one or more conventional photopolymerization initiators, if necessary.

Examples of the photopolymerization initiator are as follows.

The photopolymerization initiators can be used alone or as a mixture thereof.

The photopolymerization initiator can be used in various ratios.

The addition polymerizable compound should have a boiling point of at least 100 ° C. under 1 atmosphere. When the addition polymerizable compound has a boiling point of 100 ° C. or less under 1 atm, when the solvent is removed from the system, for example, it is evaporated during drying or actinic radiation, it has undesirable characteristics. Moreover, it is preferable to use those which are soluble in the organic solvents commonly used to obtain a uniform composition with the photoinitiator composition.

As a solvent useful for the photosensitive composition, acetone, methyl ethyl ketone, diethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, T-butanol, ethylene glycol monoethyl Ether, ethylene glycol monoethyl ether, xylene, tetrahydrofuran, dioxane, n, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, R-butyrolactone, dimethyl Sulfoxide, ethylene carbonate, propylene carbonate, sulfolane and the like can be used. The solvents may be used alone or as a mixture.

As the addition polymerizable compound having a boiling point of 100 ° C. or higher at 1 atm, it is preferable to use one obtained by condensation of a polyhydric alcohol with α, β-unsaturated carboxylic acid.

Examples of such compounds are as follows:

Ethylene Glycol Di (meth) Acrylate (Di (meth) -Acrylate is hereafter used to mean "diatrilate" or "dimethacrylate".

These compounds may be used alone or as mixtures thereof.

Photoinitiator composition (A). (B) or (C) is used in an amount of 0.01 to 30% by weight, preferably 0.05 to 10% by weight, in terms of photosensitivity and film strength, as a weight-based ability of the addition-polymerizable compound having a boiling point of 100 ° C. or higher at 1 atm.

The photosensitive composition of the present invention may further contain one or more organic polymers, if desired, preferably having a high molecular weight of 10,000 to 700,000.

Examples of such organic polymers are as follows.

(A) Mixed Polyester

For example, a polyhydric alcohol such as diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, neopentyl glycol and the like and a polyhydric carboxylic acid such as terephthalic acid, isophthalic acid, sebacic acid and adipic acid are reacted with each other. Hybrid Polyester Obtained

(B) vinyl polymer

Methacrylic acid, acrylic acid, for example methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyl ethyl (meth) acrylate, phenyl (meth) acrylate, Homopolymers or copolymers of vinyl monomers such as methacrylic acid or alkyl esters of acrylic acid such as benzyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like

(C) polyformaldehyde

(D) polyurethane

(E) polycarbonate

(F) polyamide

(G) poly (amic acid)

Poly (amic acid) can be produced by addition polymerization of tetracarboxylic dianhydride and a diamine compound.

Examples of tetracarboxylic dianhydride are as follows:

As the diamine compound, aromatic diamines, heterocyclic diamines and aliphatic diamines can be used.

Examples of aromatic diamines are as follows.

Examples of heterocyclic diamines are as follows:

Examples of aliphatic diamines are as follows.

Trimethylenediamine,

Tetramethylenediamine,

Hexamethylenediamine,

2,2-dimethylpropylenediamine,

Diaminopolysiloxanes of the formula:

Wherein n and m are the same or different integers from 1 to 10

These tetracarboxylic dianhydrides and diamine compounds can be used alone or as a mixture thereof.

(H) cellulose ester

Cellulose esters such as methyl cellulose and ethyl cellulose

By adding a high molecular weight organic polymer to the photosensitive composition, the adhesion to the substrate, chemical resistance, film forming properties and the like can be improved. It may be desirable to add a high molecular weight organic polymer in an amount of 20 to 80% by weight based on the total weight of the high molecular weight organic polymer and the addition polymerizable compound from the viewpoint of photocurability.

When adding a high molecular weight organic polymer to the photosensitive composition, the usage-amount of photoinitiator composition (A), (B) or (C) is the same as the usage-amount of said photoinitiator composition (A), (B) or (C).

Preferred examples of the photosensitive composition of the present invention are as follows:

The photosensitive composition may further contain one or more colorants such as dyes, pigments and the like, if necessary.

Examples of colorants include fuchsin, Crystal Viloet methyl orange, Nile Blue 2B, Victoria pure blue Malachite Green Night Green B, Pillon blue and the like.

In order to enhance the stability of the photosensitive composition during the storage period, a radical polymerization inhibitor or a radical polymerization inhibitor may be added. Examples of such inhibitors or inhibitors include p-methoxyphenol, p-benzoquinone, hydrokunone, pyroggarol, naphthylamine, phenolthiazine, aryl postife, nitrosoamine, and the like.

The photosensitive composition of this invention can be used as a photosensitive resin composition. Moreover, the photosensitive composition of the present invention may contain one or more additives such as plasticizers, adhesion promoters and the like.

The photosensitive material of the present invention is (a) a poly (amic acid) as described above, (b) a compound containing at least one carbon-carbon double bond and at least one amino group which is dimerizable or polymerizable by actinic rays or a quaternary salt thereof . (C) It contains photoinitiator composition (A), (B), or (C).

The poly (amic acid) (a) is preferably used in the same molar number based on the carboxyl group of the poly (amic acid) relative to the compound (b). The photoinitiator composition (c) is preferably used in an amount of 0.01 to 30% by weight, more preferably in an amount of 0.05 to 10% by weight, based on the weight of the compound (b).

Examples of compound (b) which is a compound containing at least one carbon-carbon double bond and at least one amino group or a quaternary salt thereof which are dimerizable or polymerizable by actinic radiation are as follows:

The photosensitive material may contain one or more bisazide compounds.

Examples of bisazide compounds are as follows:

The bisazide compound is preferably used in an amount of 0.01 to 10% by weight based on the weight of the poly (amic acid) (a).

N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, r-butyrolactone, dimethyl sulfoxide, sulfolane or the like as the solvent for the photosensitive material or one of the above-mentioned solvents Isayl mixtures and xylene, toluene, methyl ethyl ketone, diethyl ketone and the like can be used.

The pattern forming method of the present invention is characterized by coating a photosensitive material on a substrate, drying the photosensitive material, exposing the photosensitive material to light rays, and developing the photosensitive material to obtain a desired pattern.

More specifically, pattern formation is performed as follows. The photosensitive material is coated on a substrate such as a silicon wafer, a metallic substrate, a glass substrate, a ceramic substrate, or the like by immersion, spraying, screen printing, spin coating, or the like. Most of the solvent can be removed by heating to dryness and a coating film can be formed without sticky nature. A mask of the desired pattern is placed on the coating film and irradiated with actinic rays. Examples of actinic rays include ultraviolet rays, far ultraviolet rays, visible rays, electron beams, X-rays, and the like. After exposure to light, the unexposed part is removed with a suitable developing solution to obtain the desired pattern. As the developing solution, good solvents such as N, N-dimethylformamide, N, N-dimethyl acetamide, N-methyl-2-pyrrolidone and the like, and poor solvents such as lower alcohol, water and aromatic hydrocarbons are good. Mixtures of solvents can be used. After development, if necessary, washing with a poor solvent is followed by drying at about 100 ° C. to stabilize the pattern.

The invention is illustrated in the following examples, where all percentages are by weight unless otherwise indicated.

Example 1

Synthesis of N- (p-methylsulfonyl) -N-methyl-glycine (Compound No. 1)

Into a 500 ml flask, 4-fluoro-phenylmethylsulfone (15.01 g, 86.26 mmol), N-methyl-glycine (8.45 g, 94.89 mmol) and potassium carbonate (14.28 g, 103.48 mmol) were added and 1200 ml dimethyl as a solvent. Add sulfoxide. The water cooled pipe is attached to the flask and the reaction is carried out by heating in an oil bath at 100 ° C. for 9 hours with stirring using a magnetic stirrer. After cooling naturally, the reaction mixture is dissolved in 1 liter of water and further digested with 1/10 N HCl, after which the precipitate is filtered off. After washing well with water, the precipitate is washed with nucleic acid / benzene (4/1 volume ratio). After drying, the product yield is 12.13 G (49.92 mmol, 57.9%). Melting point is 161.2 ° C.

Example 2

Synthesis of N- (p-cyanophenyl) -glycine (Compound No. 2)

4-cyanoaniline (100 g, 847.4 mmol) was added to a 500 ml 3-neck flask, followed by 300 ml of water, and a water cooling pipe. A mechanical stirrer and dropping funnel are attached. The flask is heated in an oil bath heated to 100 ° C. To the flask was added dropwise an aqueous solution of monochloroacetic acid (104 g, 1116 mmol) (150 mL of water) for about 30 minutes and then refluxed with heating for 2.5 hours. After cooling naturally, about 100 ml ethyl acetate is added to the flask to dissolve the insoluble matter.

The organic layer is separated with a separatory funnel. The residual water layer and the aqueous layer obtained by extracting the organic layer with 100 ml 5 wt% NaOH solution are combined and then subjected to addition decomposition with 1/10 N HCl. The resulting precipitate is filtered off and washed several times. After drying for 3 hours in an oven heated to 60 ℃, the dried precipitate is dried overnight in a vacuum dryer. The resulting product is a beige powder which decomposes at 233.1 ° C. without melting point. 38.8 g (26%).

Example 3

N- (p-cyanophenyl) -N-methylglycine (Compound No. 3)

Into a 500 mL flask, 4-fluoro-benzonitrile (10.44 g, 86.26 mmol), N-methylglycine (8.45 g, 94.89 mmol) and potassium carbonate (14.28 g, 103.48 mmol) were added and 200 mL dimethyl sulfoxide as a solvent. Add. The water cooled pipe is attached to the flask and the reaction is carried out by heating in an oil bath at 100 ° C. for 9 hours with stirring using a magnetic stirrer. After cooling naturally, the reaction mixture is dissolved in 1 liter of water and further digested with 1/10 N HCl, after which the precipitate is filtered off. After washing well with water, the precipitate is washed with nucleic acid / benzene (4/1 volume ratio). After drying, the yield of product is 14.21 g (74.79 mmol, 86.7%). Melting point is 64.5 ° C.

The structure of Compound No. 1 and 2 are identified by the spectrum of the H ¹ -NMR shown in Table 1.

[Examples 4 to 8 Comparative Examples 1 and 2]

1.8 g 2-dimethyl 10 gN-methyl-2-pyrrolidone solution of poly (amic acid) (20% solids) obtained by reacting 4,4'-diaminodiphenyl ether with pyridellitic dianhydride in the same molar number Aminoethyl methacrylate and photoinitiator composition (A) as shown in Table 2 are mixed with stirring to prepare a photosensitive material.

After filtration using a filter, the photosensitive material is spin coated onto a silicon wafer. After heating for 200 seconds on a hot plate at 100 ° C., the solvent is removed to obtain a photosensitive coating film. The film thickness after drying is 10 μm,

The photosensitive coating film is exposed to light through a light mask using an ultra-high mercury lamp. The light dose is 500 mJ / cm 2 The resulting film is immersed in a mixed solution of N-methyl-2-pyrrolidone and methyl alcohol (4/1 volume ratio) and then washed with isopropanol. After development, the shape of the pattern is measured and observed. After development, normalized film thickness after development (NFTAD) (value obtained by dividing film thickness by initial film thickness) and minimum through-hole diamter are shown in Table 2.

In Example 4, N- (p-methylsulfonylphenyl) -N-methylglycine was used for the wafer, and heated at 350 ° C. for 20 minutes at 200 ° C. for 20 minutes at 100 ° C. under nitrogen atmosphere for 60 minutes, and then Obtain a cured film. The film thickness of the final cured film is 5 μm in a good polyimide pattern state.

As shown in Table 2, it can be evaluated that the photosensitive material of the present invention has excellent clarity according to the data of NFTAD and the pore diameter, and therefore, the photosensitive material of the present invention is superior in photosensitive specifications as compared with the comparison.

[Examples 9 to 14 and Comparative Examples 3 to 5]

N- (p-cyanophenyl) -glycine is synthesized in the same manner as described in Example 2.

N- (p-cyanophenyl) -N-methylglycine is synthesized in the same manner as described in Example 3.

1.8 g 2-dimethyl 10 gN-methyl-2-pyrrolidone solution of poly (amic acid) (20% solids) obtained by reacting 4,4'-diaminodiphenyl ether and pyridellitic dianhydride in the same molar number The aminoethyl methacrylate and the photoinitiator composition (A) as shown in Table 2 can be mixed with stirring to prepare a photosensitive material.

When the pattern is formed, the normalized film thickness (NEFAD) and the through hole diameter after development are measured in the same manner as described in Examples 4 to 8, and shown in Table 3. Table 3 also describes the form of the pattern.

The wafer of Example 12 was heated under nitrogen atmosphere for 15 minutes at 100 ° C. for 15 minutes, at 200 ° C. for 20 minutes, and at 350 ° C. for 60 minutes to obtain a final cured film. The film thickness of the final cured film is 10 μm in a good polyimide pattern state.

As shown in Table 3, according to the NFTAD and the pore diameter data, it can be evaluated that the photosensitive material of the present invention has excellent sharpness, and therefore the photosensitive material of the present invention is superior in photosensitive properties as compared with the comparative example.

Note) BC = 3,3'-carbonylbis-7- (diethylaminocoumarin)

MOBC-3,3'-carbonylbis- (7-methoxycoumarin)

Titanocene 1 = bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyrrole-1-yl) phenyl] titanium

[Examples 15-20 and Comparative Examples 6-8]

20 mg 4,4'-bisazido-3,3 '= dimethoxybiphenyl (AZ) was added to the same photosensitive material used in Examples 9 to 14 and Comparative Examples 3 to 5, and in Examples 15 to 20, Perform the same test as

The results are shown in Table 4.

As shown in Table 4, according to the data of NFTAD and the pore diameter, the sharpness of the photosensitive material of the present invention can be evaluated and the normalized film thickness after development is improved by adding a bisazide compound.

Examples 12 to 26 and Comparative Examples 9 to 14

1.8 g 2-dimethyl 10 gN-methyl-2-pyrrolidone solution of poly (amic acid) (20% solids) obtained by reacting 4,4'-diaminodiphenyl ether and pyridellitic dianhydride in the same molar number The aminoethyl methacrylate and the photoinitiator composition (C) as shown in Table 2 may be mixed with stirring to prepare a photosensitive material.

When the pattern is formed, the normalized film thickness (NEFAD) and the pore diameter after development are measured by the same method as described in Examples 4 to 8 and described in Table 5. Table 3 also describes the form of the pattern.

The wafer of Example 24 was heated under nitrogen atmosphere for 15 minutes at 100 ° C. for 15 minutes, at 200 ° C. for 20 minutes, and at 350 ° C. for 60 minutes to obtain a final cured film. The film thickness of the final cured film is 10 μm in a good polyimide pattern state.

As shown in Table 5, according to the NFTAD and the pore diameter data, it can be evaluated that the photosensitive material of the present invention has excellent sharpness, and therefore, the photosensitive material of the present invention is superior in photosensitive properties as compared with the comparative example.

Note) oxime ester 1 = 1.3-diphenyl-1,2,3-propanetrione-2- (0-ethoxycarbonyl) oxime

The photoinitiator composition of the present invention is effective for improving the photosensitive properties of photosensitive materials containing poly (amic acid) and addition polymerizable compounds for pattern formation.

Claims (7)

A photoinitiator composition (B) containing 1 to 100 parts by weight of the 3-substituted coumarin compound of Formula 2 and 10 to 300 parts by weight of the compound of Formula 4 per 100 parts by weight of N-aryl-α-amino acid of Formula 1b : [Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, an alkoxycarbonyl group having 2 to 10 carbon atoms, a carboxamido group or a carbon number 1 4, the alkyl moiety is an alkylsulfonyl group which may be substituted with a cyano group, and at least one of R ₁ to R ₅ is a sarano group or an alkylsulfonyl group having 1 to 4 carbon atoms; R ₆ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, or an aryl group; R 7 and R ₈ are independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms] [Wherein R ₉ , R ₁₀ , R ₁₁ , and R ₁₃ are each independently a hydrogen atom, an amino group substituted with an alkyl group having 1 to 5 carbon atoms, an amino group substituted with two alkyl groups having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms An alkoxy group, acyloxy group, aryl group, halogen atom, or a C1-5 taoalkyl group: R ₁₄ is an unsubstituted phenyl group, biphenyl group, naphthyl group, thiethyl group, benzofunyl group, furyl group, pyridyl group, kumari Nyl group, amino group, amino group substituted with one or more alkyl groups of 1 to 5 carbon atoms, cyno group, alkoxy group of 1 to 5 carbon atoms, alkyl group of 1 to 5 carbon atoms, halogen atom, haloalkyl group, formyl group, alkoxy of 1 to 5 carbon atoms A phenyl group substituted with a carbonyl group, an acyloxy group having 1 to 5 carbon atoms, an acyl organo group having 1 to 5 carbon atoms, a cyano group, an alkoxy group, or an acyl group having 1 to 5 carbon atoms, the biphenyl group, the naphthyl group, the thienyl group, The benzofuryl group, the furyl group, the fildil group or Group is Kumari group which may be substituted with acyl of 1 to 5 carbon atoms or an acyloxy group having 1 to 5 carbon atoms.] [Wherein R ₂₇ to R ₃₆ are independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, or can be directly bonded to the benzene ring via an alkylene group and at least one alkyl group, amino group, alkylamino group or alkoxy group Heterocyclic ring which may be substituted] A photosensitive composition containing an addition polymerizable compound having a boiling point of 100 ° C. or higher at 1 atm and a photoinitiator composition (B) according to claim 1 and 0.01 to 30% by weight of the photoinitiator composition (B) based on the weight of the polymerizable compound. Composition. The photosensitive composition according to claim 2, further comprising a high molecular weight at least one organic polymer in an amount of 20 to 80% by weight based on the total weight of the high molecular weight organic polymer and the addition polymerizable compound. (a) a poly (amic acid); (b) a compound containing at least one carbon-carbon double bond and at least one amino group capable of dimerization or polymerization by actinic radiation, or a quaternary salt thereof, and (c) a photoinitiator composition (B). Photosensitive material characterized in that. The photosensitive material according to claim 4, further comprising at least one bisazide compound. The photosensitive material of claim 4 for pattern formation. The pattern forming method of claim 4, wherein the photosensitive material is coated on a substrate, the photosensitive material is dried, the photosensitive material is exposed to light and the photosensitive material is developed.