KR20150073077A - Method for forming hole pattern, resin composition for forming hole pattern, and layered product - Google Patents

Abstract

The present invention relates to a method for forming a hole pattern, the method comprising Step 1 to Step 3: (Step 1) forming a resin film on a base material, wherein the resin film contains (A) an alkali soluble resin, (B) a compound having at least two structure represented by Formula (1) in one molecule, and (C) a photopolymerization initiator; (Step 2) selectively exposing the resin film to light to obtain a hole pattern; and (Step 3) contacting the resin film after being exposed to light with an alkaline solution. (R^1 represents a hydrogen atom or a methyl group, and * represents a combination chain.) In the method of the present invention, even when a developing speed is increased, a hole pattern can be formed without corrosion on a base material, especially, on a copper film formed on the surface of the base material. A resin composition for forming a hole pattern of the present invention can suitably form a resin film used for the method for forming a hole pattern.

Description

METHOD FOR FORMING HOLE PATTERN, RESIN COMPOSITION FOR FORMING HOLE PATTERN, AND LAYERED PRODUCT BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for forming a hole pattern,

TECHNICAL FIELD The present invention relates to a method for forming a hole pattern, a resin composition for forming a hole pattern, and a laminate comprising a hole pattern and a substrate, which can be suitably used for the production of a plating composition such as a bump.

2. Description of the Related Art Recently, in electronic apparatuses such as cellular phones, the integration and multilayering of large-scale integrated circuits (LSIs) have progressed rapidly. Therefore, a multi-pin mounting method for mounting an LSI on a substrate is required, and for example, a tape automated bonding (TAB) method or a flip chip mounting method of a bare chip . In this method, it is required to dispose a projecting electrode called a bump, which is a connection terminal, on the LSI with high accuracy.

Various precision parts such as bumps can be obtained by, for example, applying a radiation-sensitive resin composition onto a copper film of a substrate to form a resin film, patterning the resin film by photolithography, As a mask, electroplating or the like is performed (Patent Document 1). The patterned film for forming bumps and the like is a resist pattern having a plurality of fine holes (holes), that is, a hole pattern.

International Publication No. WO2008 / 114635

When bumps are formed using photolithography, it is necessary to raise the developing speed in order to improve the yield. However, it has been found that, when the development speed is raised, particularly when a fine resist pattern such as a hole pattern is formed, the copper film is corroded by an alkaline developing solution. This is presumably because, when forming a fine resist pattern, the alkaline developing solution stays in the fine voids of the resist pattern at the time of development, the contact time between the developing solution and the copper film becomes long and the copper film is corroded by the alkaline developing solution have.

The present invention provides a hole pattern forming method and a hole pattern forming method capable of forming a hole pattern without causing corrosion of a base material, particularly a copper film of a base material having a copper film on its surface, , And to provide a resin composition for forming a hole pattern which is used in a method of forming a hole pattern.

The method for forming a hole pattern of the present invention is characterized by having the following steps 1 to 3.

Step 1: A step of forming a resin film containing an alkali-soluble resin (A), a compound (B1) having at least two structures represented by the following formula (1) in one molecule, and a photopolymerization initiator (C) on a substrate.

Step 2: A step of selectively exposing the resin film so as to obtain a hole pattern.

Step 3: Step of bringing an alkaline aqueous solution into contact with the resin film after exposure:

(R ¹ represents a hydrogen atom or a methyl group; * represents a bond).

In the method of forming the hole pattern, it is preferable that the alkali-soluble resin (A) has a phenolic hydroxyl group.

In the method for forming the hole pattern, the content of the compound (B) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A).

In the hole pattern forming method, it is preferable that the substrate is a substrate having a copper film on its surface, and the resin film is formed on the copper film in the step 1.

Another hole pattern forming method of the present invention is characterized by having the following steps 1 to 3.

(1) A method for producing a photopolymerizable composition, comprising the steps of: (1) preparing a photopolymerization initiator (C) having at least two groups selected from alkali-soluble resin (A), hydroxyl group and carboxyl group and at least two (meth) acryloyl groups in one molecule, ) Is formed.

Step 2: A step of selectively exposing the resin film so as to obtain a hole pattern.

Step 3: Step of bringing an alkaline aqueous solution into contact with the resin film after exposure.

The resin composition for forming a hole pattern of the present invention is a resin composition for forming a hole pattern, which comprises (A) a compound (B) having at least one group selected from a hydroxyl group and a carboxyl group and at least two (meth) acryloyl groups in a molecule, (A), a compound (B1) having at least two structures represented by the following formula (1) in one molecule, and a photopolymerization initiator (C) C). ≪ RTI ID = 0.0 >

(R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; * represents a bond).

The laminate of the present invention comprises a substrate and a hole pattern formed on the substrate by the method of forming the hole pattern.

The method of forming a hole pattern of the present invention can form a hole pattern without increasing the substrate, particularly the copper film of the substrate having the copper film on the surface, even if the developing speed is increased. The resin composition for forming a hole pattern of the present invention can suitably form a resin film used in the method of forming the hole pattern.

1 is a schematic partial sectional view of a hole pattern and a silicon wafer including holes and holes.
2 is an electron micrograph of a cross section including holes and holes of a hole pattern and a silicon wafer.

(Mode for carrying out the invention)

[Method of forming hole pattern]

The method for forming a hole pattern of the present invention is characterized by having the following steps 1 to 3.

Step 1: A compound (B) having at least two groups selected from the alkali-soluble resin (A), hydroxyl group and carboxyl group and at least two (meth) acryloyl groups in one molecule B) "), and a photopolymerization initiator (C).

Step 2: A step of selectively exposing the resin film so as to form a hole pattern.

Step 3: Step of bringing an alkaline aqueous solution into contact with the resin film after exposure.

[Step (1)]

In the step (1), a compound (B) having at least two groups selected from an alkali-soluble resin (A), a hydroxyl group and a carboxyl group and a (meth) acryloyl group in a molecule, A resin film containing a photopolymerization initiator (C) is formed.

In the method of forming a hole pattern of the present invention, it is considered that the substrate is hardly corroded because the compound (B) contained in the resin film protects the substrate at the time of development. That is, when the base material is a base material having a copper film on the surface, when the exposed resin film is treated with a developing solution, in the conventional resin film, the unexposed portion is completely removed and as a result, The developing solution is liable to be corroded because the developing solution directly contacts the copper film portion under the gap. In contrast, in the forming method of the present invention, the compound (B Is not completely removed but adheres to a certain amount of the copper film and remains in the copper film. As a result, it can be considered that the developing solution flowing into the formed gap can prevent direct contact with the copper film portion under the gap . The fact that the compound (B) is not completely removed at the time of development and remains attached to the copper film and remains in the copper film due to the hydroxyl group or the carboxyl group of the compound (B) increases the affinity of the compound (B) I think it is because there is.

The substrate is not particularly limited as long as it is a substrate on which the resin film can be formed. Examples of the substrate include a semiconductor substrate, a glass substrate, a silicon substrate and a semiconductor plate, a glass plate, . The method of forming a hole pattern of the present invention is advantageous for a copper film which is susceptible to corrosion in an alkaline developing solution and can form a hole pattern without corroding the substrate. Therefore, when the substrate is a substrate having a copper film on its surface, Lt; / RTI >

The shape of the substrate is not particularly limited. The flat plate shape may be a shape formed by forming concave portions (holes) in the flat plate as in the substrate (silicon wafer) used in the later-described embodiments. In the case of a substrate having a concave portion and further having a copper film on its surface, a copper film is formed on a bottom portion of the concave portion like a TSV structure. When a hole pattern is formed on a substrate having a concave portion, a hole pattern is formed so that the space of the hole of the hole pattern is accommodated in the region of the hole extending in the extending direction of the hole.

The film thickness of the resin film is usually 1 to 100 占 퐉, preferably 10 to 50 占 퐉.

The resin film can be formed, for example, by applying a resin composition containing an alkali-soluble resin (A), a compound (B) and a photopolymerization initiator (C) onto a substrate and drying the resin composition.

The method of applying the resin composition is not particularly limited and a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, an ink jet method, or the like can be employed, Do. In the case of the spin coating method, the rotation speed is usually 800 to 3000 rpm, preferably 800 to 2000 rpm, and the rotation time is usually 1 to 300 seconds, preferably 5 to 200 seconds. After the resin composition is spin-coated, the resulting coating film is heated and dried, for example, at 50 to 250 캜 for about 1 to 30 minutes to form a resin film.

[Step (2)]

In the step (2), the resin film is selectively exposed so as to obtain a hole pattern. In order to perform selective exposure, the resin film is usually exposed using a contact aligner, a stepper or a scanner, for example, through a photomask suitable for a desired hole pattern. As the exposure light, light having a wavelength of 200 to 500 nm (for example, i-line (365 nm)) is used. The amount of exposure differs depending on the kind of the component in the resin film, the amount of the component, the thickness of the coating film, and the like. In the case of using i-line for exposure light, it is usually 1,000 to 100,000 mJ / m 2.

Further, a heat treatment may be performed after exposure. The conditions of the heat treatment after exposure are appropriately determined depending on the kind of the components in the resin film, the amount of the components to be mixed, the thickness of the coating film, and the like, but are usually 70 to 180 DEG C for 1 to 60 minutes.

[Step (3)]

In step (3), an alkaline aqueous solution is brought into contact with the resin film after exposure. That is, development is carried out in the step (3). In the step (3), the non-exposed portion of the resin film is dissolved by a developing solution, and the exposed portion is left to obtain a cured film having a predetermined pattern.

Examples of the developer include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di- 1,8-diazabicyclo [5.4.0] -7-undecene, 1, 2-diazabicyclo [5.4.0] -7-undecene, tetraethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, Diazabicyclo [4.3.0] -5-nonane, and the like can be used. In addition, an aqueous solution containing an appropriate amount of a water-soluble solvent such as methanol or ethanol or a surfactant may be used as the developing solution.

The developing time is usually from 10 to 600 seconds, preferably from 30 to 300 seconds, more preferably from 60 to 150 seconds, depending on the kind of each component in the composition, the blending ratio, the thickness of the coating film, The developing method may be any of a dipping method, a dipping method, a puddle method, a spray method, and a shower developing method.

The cured film thus prepared can further be cured by further performing additional exposure (hereinafter referred to as " post-exposure ") or heat treatment depending on the application.

The post exposure can be performed in the same manner as the exposure described above. The heating treatment may be performed at a predetermined temperature, for example, 60 to 100 占 폚 for a predetermined time, for example, 5 to 30 minutes in a hot plate, or 5 to 30 minutes in an oven, using a heating apparatus such as a hot plate or an oven. For 60 minutes. By this post-treatment, a cured film of a pattern having better characteristics can be obtained.

Depending on the developing time, the compound (B) contained in the unexposed portion of the resin film is not completely removed, and a certain amount of the resin (B) is adhered to the substrate and remained on the substrate. Thus, in the step (3), after the operation of bringing the alkaline aqueous solution into contact with the resin film, the cleaning may be performed in order to remove the compound (B) remaining on the substrate. The cleaning can be performed, for example, by bringing water into contact with the substrate and the cured film. The contact time of water is, for example, 60 to 180 seconds. The contact of water can be carried out, for example, by running water (running water) or spraying water.

Thereafter, air drying may be performed using an air gun or the like, or drying may be performed under heating such as a hot plate or an oven.

[Laminate]

By the above-mentioned method of forming a hole pattern, a laminate composed of a substrate and a hole pattern formed on the substrate can be obtained.

[Production of a plating composition]

A plating product such as a bump can be manufactured according to a regular method by using the hole pattern formed by the method of forming the hole pattern.

(Resin composition)

The resin composition is a resin composition for forming a hole pattern according to the present invention. (A), a compound (B) having at least one group selected from a hydroxyl group and a carboxyl group and at least two (meth) acryloyl groups in a molecule, and a photopolymerization initiator (C) (BR) having at least one ethylenically unsaturated double bond other than the compound (B), a solvent, and a surfactant, if necessary, in addition to the compound (B).

≪ Alkali-soluble resin (A) >

The alkali-soluble resin (A) is a resin having properties such that it is dissolved in an alkaline developer to such an extent that a desired development process can be carried out. For example, Japanese Unexamined Patent Application Publication No. 2008-276194, Japanese Unexamined Patent Publication No. 2003-241372, Japanese Patent Publication No. 2009-531730, International Patent Publication No. WO2010 / 001691, Japanese Unexamined Patent Publication No. 2011-123225, Alkali-soluble resins described in Japanese Patent Application Laid-Open No. 2009-222923 and Japanese Laid-Open Patent Publication No. 2006-243161. The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the alkali-soluble resin (A) is usually in the range of 1,000 to 1,000,000, preferably 2,000 to 50,000, and more preferably 3,000 to 20,000 .

Further, the alkali-soluble resin (A) preferably has a phenolic hydroxyl group in that the plating liquid resistance of the hole pattern is improved. As the alkali-soluble resin (A) having a phenolic hydroxyl group, an alkali-soluble resin (A ') having a structural unit represented by the following formula (2) (hereinafter also referred to as "structural unit (2)") is preferable.

In the formula (2), R ¹ represents a hydrogen atom or a methyl group.

By using the alkali-soluble resin (A ') having the structural unit (2), it is possible to obtain a hole pattern hardly swollen in the plating step. As a result, there is no lifting or peeling of the hole pattern from the substrate, so that even when the plating process is performed for a long time, the plating liquid can be prevented from leaking to the interface between the substrate and the hole pattern. In addition, resolution can be improved.

The content of the structural unit (2) in the alkali-soluble resin (A ') having the structural unit (2) is usually in the range of 1 to 40 mass%, preferably 10 to 30 mass%. When the content of the structural unit (2) is in the above range, that is, the monomer for deriving the structural unit (2) is used in such an amount, the molecular weight of the alkali-soluble resin (A ') can be sufficiently increased. Further, it is possible to obtain a hole pattern hard to swell in the plating process.

«Monomer (2 ')»

The alkali-soluble resin (A ') having the structural unit (2) can be obtained, for example, by reacting a hydroxyl group-containing aromatic vinyl compound such as o-hydroxystyrene, m-hydroxystyrene, p- (Hereinafter also referred to as " monomer (2 ') ") as a raw material monomer. These monomers (2 ') may be used singly or in combination of two or more.

Of these monomers (2 '), p-hydroxystyrene and p-isopropenylphenol are preferable, and p-isopropenylphenol is preferable because a resin composition capable of forming a hole pattern excellent in long- Phenol is more preferable.

«Monomer (I)»

The alkali-soluble resin (A ') having the structural unit (2) may also have a structural unit derived from another monomer (hereinafter also referred to as "monomer (I)") copolymerizable with the monomer (2').

Examples of the monomer (I) include aromatic vinyl compounds such as styrene,? -Methylstyrene, p-methylstyrene and p-methoxystyrene;

Hetero-containing alicyclic vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam;

(Meth) acrylate, phenoxyethyleneglycol (meth) acrylate, phenoxyethyleneglycol (meth) acrylate, phenoxyethyleneglycol (meth) acrylate, phenoxyethyleneglycol Acrylate, lauroyloxy triethylene glycol (meth) acrylate, lauroyloxy triethylene glycol (meth) acrylate, lauroyloxypropylene glycol (meth) acrylate, (Meth) acrylate such as lauroyloxytetraethylene glycol (meth) acrylate, lauroyloxydipropylene glycol (meth) acrylate, lauroyloxy tripropylene glycol (meth) acrylate, lauroyloxy tetrapropylene glycol (Meth) acrylic acid derivative having a glycol structure;

Cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitrile;

Conjugated diolefins such as 1,3-butadiene and isoprene;

Carboxyl group-containing vinyl compounds such as acrylic acid and methacrylic acid;

(Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethyleneglycol mono (meth) acrylate, (Meth) acrylates such as acrylate, isobornyl (meth) acrylate and tricyclodecanyl (meth) acrylate;

p-hydroxyphenyl (meth) acrylamide, and the like. These monomers (I) may be used singly or in combination of two or more.

Of these monomers (I), styrene, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tricyclodecanyl (Meth) acrylate, isobornyl (meth) acrylate, p-hydroxyphenyl (meth) acrylamide and the like.

The alkali-soluble resin (A ') can be produced, for example, by radical polymerization. Examples of polymerization methods include emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.

≪ Compound (B) >

The compound (B) is a compound having at least one group selected from a hydroxyl group and a carboxyl group and at least two (meth) acryloyl groups in one molecule. As the compound (B), it is preferable that the compound (B1) having at least two structures represented by the following formula (1) in one molecule is a compound represented by the formula It is possible to form a hole pattern without corroding the copper film.

In the formula (1), R ¹ represents a hydrogen atom or a methyl group. These alkyl groups may be either linear or branched. In Equation (1), * denotes a combined hand.

According to the method of forming a hole pattern of the present invention, it is possible to form a hole pattern without rubbing the substrate, especially the copper film of the substrate having the copper film on the surface, even if the developing speed is increased. With regard to this effect, it can be considered that the compound (B) contained in the resin film formed on the substrate characteristically acts.

When a hole pattern is formed on a substrate, the base portion under the hole formed in the resin film tends to corrode if the developing speed is increased. For example, in the case of a base material having a copper film on its surface, a needle-like defect is generated in the copper film portion under the hole. Particularly, when a hole pattern is formed on the TSV, a defect is remarkably generated. The cause of the defect is that as the developer is kept in the hole at the time of development, the defect is not discharged from the hole and therefore the copper film is contacted with the alkaline developer for a long time and the copper is corroded.

The compound (B) remaining in the copper film phase can be easily removed, for example, by a cleaning operation after development, for example, by bringing it into contact with water. For this reason, the compound (B) has no influence on the subsequent production of plating products such as bumps. It is considered that the reason why the compound (B) is easily removed by the washing operation is that the proportion of the hydroxyl group in the compound (B) is not high and the affinity of the compound (B) to the copper film is not excessively strong. Particularly, in the compound (B1), since the proportion of the hydroxyl group occupying in the compound (B1) is regulated within a certain range by the formula (1), it remains in the copper film in a certain amount at the time of development and is completely removed It is considered that the strength of the affinity for the copper film is realized.

As the compound (B), a compound obtained by reaction of an epoxy (meth) acrylate with a carboxylic acid, an alcoholic compound or a phenolic compound, and an alkylene glycol diglycidyl ether or a polyalkylene glycol diglycidyl ether (Meth) acrylic acid, and the like.

Examples of the carbonic acid compound include aliphatic saturated dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and cycloalkanedicarboxylic acid, aliphatic unsaturated dicarboxylic acids such as maleic acid, , Aromatic tetracarboxylic acids such as trimesic acid and hydrogenated products thereof, aromatic tetracarboxylic acids such as benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid and oxydiphthalic acid, and hydrogenated products thereof . Examples of the alcoholic and phenolic compounds include aliphatic dialcohols such as glycerol, alkylene glycols, polyalkylene glycols and alkane diols, biphenol and its substituents, bisphenol A and its derivatives, biphenol ether and its Derivatives, novolak oligomers and derivatives thereof, and the like.

The alkylene glycol diglycidyl ether includes, for example, ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether. The polyalkylene glycol diglycidyl ether includes, for example, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.

These may be used alone or in combination of two or more.

These reactions can be carried out according to a conventional method.

The content of the compound (B) in the resin composition is usually 1 to 100 parts, preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A) . If the content of the compound (B) is within this range, corrosion of the substrate can be more suitably prevented.

The content of the compound (B) in the resin film is also the same as described above. When a resin film is formed by using the resin composition, the content of the compound (B) relative to 100 parts by mass of the alkali-soluble resin (A) in the resin film is preferably 100 parts by mass or less per 100 parts by mass of the alkali- Is equal to the content of the compound (B).

≪ Photopolymerization initiator (C) >

The photopolymerization initiator (C) is a compound that generates radicals upon irradiation with light to initiate radical polymerization of the compound (B).

The content of the photopolymerization initiator (C) is usually 1 to 40 parts by mass, preferably 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). When the content of the photopolymerization initiator (C) is within the above range, it is easy to sufficiently cure the low-layer portions as well as the surface layer portions of the resin film to obtain a desired high-precision pattern.

The content of the photopolymerization initiator (C) in the resin film is also the same as described above. When the resin film is formed using the resin composition, the content of the photopolymerization initiator (C) in 100 parts by mass of the alkali-soluble resin (A) in the resin film is preferably 100 parts by mass (C) to the amount of the photopolymerization initiator (C).

As the photopolymerization initiator (C), there can be mentioned, for example, JP-A-2008-276194, JP-A-2003-241372, JP-A-2009-519991, JP-A-2009-531730, WO2010 / 001691 And a photopolymerization initiator described in JP-A-2011-132215.

Examples of the photopolymerization initiator (C) include a nonimidazole compound, an acylphosphine oxide compound, an alkylphenone compound, a triazine compound, an oxime ester compound, a benzoin compound, and a benzophenone compound.

Examples of the imidazole compound include 2,2'-bis (2,4-dichlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4- , 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dimethylphenyl) -4,5,4 ', 5'-tetraphenyl- Imidazole, 2,2'-bis (2-methylphenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole and 2,2'- 4 ', 5'-tetraphenyl-1,2'-biimidazole, and the like.

Examples of the alkylphenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- hydroxy- 1- [4- (2- ) Phenyl] -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (2-methylbenzyl) -2 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-ethylbenzyl) (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone and 2- Butanone, and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) 2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the oxime ester compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-ethoxycarbonyloxy- Imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy- 1- [ Yl] ethan-1-imine and N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3- Methyloxy) benzoyl} -9H-carbazol-3-yl] ethan-1-imine.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-bis (diethylamino) Benzophenone, 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, and 2,4,6-trimethylbenzophenone.

The photopolymerization initiator (C) may be used alone or in combination of two or more.

<Other components>

The resin composition may contain, in addition to the above components, at least one compound (BR) having at least one ethylenically unsaturated double bond other than the compound (B), a solvent, and a heat polymerization inhibitor A surfactant, an adhesion aid for improving the adhesion between the resin film and the substrate, a sensitizer for raising the sensitivity, an inorganic filler for improving the strength of the resin film, and the like can be used within a range that does not impair the objects and characteristics of the present invention It may be blended.

The compound (BR) having at least one ethylenically unsaturated double bond other than the compound (B)

When the compound (BR) (hereinafter also referred to as "compound (BR)") having at least one ethylenically unsaturated double bond other than the compound (B) is blended in the resin composition, the developing rate of the resin film is lowered, The developing speed of the film can be controlled. When the developing rate of the resin film is excessively high, the compounding of the compound (BR) is effective.

As the compound (BR), 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di , Diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, Di (meth) acrylate of ethoxylated bisphenol A, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3-methyl (Meth) acrylate such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxy (Meth) acrylates such as isocyanurate tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tetra Acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, dipentaerythritol tetra (Meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa And an acid anhydride, a reaction product of tripentaerythritol (meth) acrylate and anhydride caprolactone-modified trimethylolpropane tri Acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone- Acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone- Caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone- , A reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and an acid anhydride, A reaction product of a lactone-modified dipentaerythritol penta (meth) acrylate and an acid anhydride, a compound having three ethylenically unsaturated double bonds such as caprolactone-modified tripentaerythritol (meth) acrylate and an acid anhydride, . The compounding amount of the compound (BR) can be appropriately determined depending on the purpose, and is, for example, 10 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A).

«Solvent»

By containing a solvent, the resin composition of the present invention can improve handling properties, control viscosity, and improve storage stability of the resin composition.

As the solvent,

Alcohols such as methanol, ethanol, and propylene glycol;

Cyclic ethers such as tetrahydrofuran and dioxane;

Glycols such as ethylene glycol and propylene glycol;

Alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether;

Alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate;

Aromatic hydrocarbons such as toluene and xylene;

Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone;

Ethyl acetate, ethyl acetate, butyl acetate, ethyl ethoxyacetate, ethyl hydroxyacetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy- Esters such as methyl propionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate and ethyl lactate;

N-dimethylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, di Hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, Propylene, phenyl cellosolve acetate, and the like.

The amount of the ethylene glycol-based solvent used in the present invention is preferably 50% by mass or more, and more preferably 80% by mass or more, based on 100% by mass of the total solvent. By using an ethylene glycol-based solvent as the solvent within the above range, it becomes easier to form a resin film having a greatly different film thickness.

The amount of the solvent to be used is usually 50 parts by mass or more, preferably 60 to 300 parts by mass, more preferably 60 to 300 parts by mass, more preferably 100 parts by mass or more, per 100 parts by mass of the alkali-soluble resin (A) 80 to 200 parts by mass.

«Surfactant»

When a surfactant is added to the resin composition, the coating property, defoaming property, leveling property and the like can be improved.

As the surfactant, commercially available surfactants can be used. Examples of commercially available surfactants include NBX-15, FTX-204D, FTX-208D, FTX-212D, FTX-216D, FTX-218, FTX- (Manufactured by NEOS), BM-1000, BM-1100 (manufactured by BM KEMISA), MEGAFACE F142D, F172, F173 and F183 (manufactured by Dainippon Ink and Chemicals, Incorporated) (Manufactured by Sumitomo 3M Ltd.), SURFLON S-112 (manufactured by Sumitomo 3M Limited), Fluorad FC-135, FC-170C, FC- S-131, S-141, S-145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA, S-90, S-133, SZ-6032 and SF-8428 (Manufactured by Toray Dow Corning Silicone Co., Ltd.), and the like.

&Lt; Preparation method of resin composition >

The resin composition of the present invention can be prepared by uniformly mixing the respective components. Further, in order to remove the residue, the components may be uniformly mixed, and then the resulting mixture may be filtered with a filter or the like.

(Example)

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the description of the following examples and the like, &quot; part &quot; represents &quot; part by mass &quot;.

1. Measurement of physical properties

The weight average molecular weight of the alkali-soluble resin (A) Mw )

Mw was measured by gel permeation chromatography under the following conditions.

· Column: TSK-M and TSK2500 of Toso Manufacturing Column are connected in series.

Solvent: tetrahydrofuran

· Temperature: 40 ℃

Detection method: Refractive index method

Standard material: polystyrene

2. Synthesis of alkali-soluble resin (A)

[Synthesis Example 1] Synthesis of alkali-soluble resin (A1)

5.0 g of 2,2'-azobisisobutyronitrile as a polymerization initiator and 150 g of propylene glycol monomethyl ether as a polymerization solvent were placed in a flask equipped with a nitrogen-exchanged dry ice / methanol reflux and stirred.

To the obtained solution were added 11 g of methacrylic acid, 15 g of p-isopropenylphenol, 15 g of tricyclo [5.2.1.0 ^2,6 ] decaneyl methacrylate, 39 g of isobornyl acrylate and 20 g of phenoxypolyethylene glycol acrylate Stirring was started, and the temperature was raised to 80 캜. Thereafter, it was heated at 80 DEG C for 6 hours.

After the completion of the heating, the reaction product was dropped into a large amount of cyclohexane and solidified. This solidified product was subjected to water washing, and the solidified product was redissolved in the same amount of tetrahydrofuran as the solidified product. The resulting solution was added dropwise to a large amount of cyclohexane and solidified again. This redissolving and solidifying operation was carried out three times in total, and the obtained solidified product was vacuum-dried at 40 占 폚 for 48 hours to obtain an alkali-soluble resin (A1). The weight average molecular weight (Mw) of the alkali-soluble resin (A1) was 10,000.

[Synthesis Example 2] Synthesis of alkali-soluble resin (A2)

5.0 g of 2,2'-azobisisobutyronitrile as a polymerization initiator and 150 g of propylene glycol monomethyl ether as a polymerization solvent were placed in a flask equipped with a nitrogen-exchanged dry ice / methanol reflux and stirred.

10 g of methacrylic acid, 15 g of p-isopropenylphenol, 25 g of tricyclo [5.2.1.0 ^2,6 ] decaneyl methacrylate, 20 g of isobornyl acrylate and 30 g of n-butyl methacrylate were added to the obtained solution Stirring was started, and the temperature was raised to 80 캜. Thereafter, it was heated at 80 占 폚 for 7 hours.

After the completion of the heating, the reaction product was dropped into a large amount of cyclohexane and solidified. This solidified product was subjected to water washing, and the solidified product was redissolved in the same amount of tetrahydrofuran as the solidified product. The resulting solution was added dropwise to a large amount of cyclohexane and solidified again. This redissolving and solidifying operation was performed three times in total, and the obtained solidified product was vacuum-dried at 40 占 폚 for 48 hours to obtain an alkali-soluble resin (A2). The weight average molecular weight (Mw) of the alkali-soluble resin (A2) was 10,000.

3. Preparation of resin composition for forming a hole pattern

[Example 1A] Preparation of a resin composition for forming a hole pattern

100 parts of an alkali-soluble resin (A1) as the alkali-soluble resin (A) and 1 part of a reaction product of propylene glycol diglycidyl ether and acrylic acid as a compound (B1) having at least two structures of the formula (1) 8 parts of a compound (BR) having at least one ethylenically unsaturated double bond, 5 parts by weight of a polyester acrylate (trade name: Aronix (trade name, manufactured by Shin- 80 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one as a photopolymerization initiator (C) 10 parts of a commercial product (IRGACURE 907, manufactured by Chiba Specialty Chemicals) (C1), 10 parts of 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'- 3 parts of 4'-bis (diethylamino) benzophenone (C3) as a solvent, 200 parts of propylene glycol monomethyl ether acetate (D1) as a solvent, NBX as a surfactant -15 (manufactured by Neos Co., Ltd.) (E1) Were mixed and stirred to obtain a homogeneous solution. This solution was filtered with a capsule filter having a pore diameter of 10 mu m to obtain a resin composition for forming a hole pattern of Example 1A.

[Examples 2A to 8A, Comparative Examples 1A to 3A] Preparation of a resin composition for forming a hole pattern

A resin composition for forming a hole pattern in each of Examples 2A to 8A and Comparative Examples 1A to 3A was obtained in the same manner as in Example 1A, except that the components and the compounding amounts thereof shown in Table 1 were used.

Details of each component described in Table 1 are as follows.

A1: The alkali-soluble resin (A1) polymerized in Synthesis Example 1

A2: The alkali-soluble resin (A2) polymerized in Synthesis Example 2

B1-1: Reaction product of propylene glycol diglycidyl ether and acrylic acid (trade name &quot; NK Oligo EA-5920 &quot;, Shin Nakamura Kagaku Kogyo Co., Ltd.)

B1-2: 1,6-hexanediol diglycidyl ether acrylate

B1-3: Reaction product of phthalic acid and epoxy acrylate (trade name: DENACOL DA-721, manufactured by Nagase Chemtex Co., Ltd.)

B1-4: Reaction product of hydrogenated phthalic acid and epoxy acrylate (trade name &quot; Denacol DA-722 &quot;, manufactured by Nagase Chemtex Co., Ltd.)

B1-5: Reaction product of glycerol and epoxy acrylate (trade name &quot; Denacol DA-314 &quot;, manufactured by Nagase Chemtex Co., Ltd.)

BR1: polyester acrylate (trade name: Aronix M-8060, manufactured by Toagosei Co., Ltd.)

BR2: Tripropylene glycol diacrylate

(Trade name: IRGACURE 907, manufactured by Chiba Specialty Chemicals Co., Ltd.)

C2: 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole

C3: 4,4'-bis (diethylamino) benzophenone

D1: Propylene glycol monomethyl ether acetate

E1: diglycerin ethylene oxide (average addition mole number = 18) adducts Perfluorononenyl ether ("ftergent FTX-218", manufactured by Neos Co., Ltd.)

E2: Dimethyl, methyl (polyethylene oxide acetate) siloxane (CAS number: 70913-12-4)

4. Formation of hole pattern

[Example 1B] Formation of hole pattern

The hole pattern of Example 1A was formed on a 6-inch silicon wafer having a large number of columnar holes each having a diameter of 10 mu m and a depth of 40 mu m and further having copper sputtering films having a thickness of 0.3 mu m on the bottoms of the holes, The resin composition for forming was spin-coated and then heated on a hot plate at 110 DEG C for 5 minutes to form a resin film having a thickness of 25 mu m. Subsequently, using a stepper (model "NSR-2005 i10D", manufactured by Nikon Corporation), a resin coating film was exposed through a pattern mask so that holes could be formed on the respective holes of the silicon wafer. The exposed resin film was immersed in an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide for 90 seconds and then water was poured into the resin film for 60 seconds to form a hole pattern having holes with a diameter of 20 m. 1 is a schematic partial sectional view of the hole pattern and the silicon wafer including the hole and the hole. As shown in Fig. 1, a silicon wafer 1 having a hole 2 and a copper sputter film 3 on the bottom thereof is patterned so that the hole 2 is accommodated in a region of the hole pattern, (4) are formed.

The obtained hole pattern and the cross section of the silicon wafer were observed with an electron microscope and the presence or absence of corrosion of the copper sputter film and the presence or absence of residue of the resin coating film on the copper sputter film was evaluated based on the following criteria. The results are shown in Table 2. The electron microscope image is shown in Fig.

Residue  The presence or absence:

A: No residual resin coating film on the copper sputter film.

B: Remains of the resin coating film on the copper sputter film.

Copper sputter film of  Corrosiveness:

A: No corrosion of copper sputter film.

B: Corrosion of copper sputter film.

[Examples 2B to 16B and Comparative Examples 1B to 6B] Formation of a hole pattern

The resin compositions for hole pattern formation of Examples 2B to 16B and Comparative Examples 1B to 6B were obtained in the same manner as in Example 1B except that the resin composition for hole pattern formation and the developing time described in Table 2 were used. A hole pattern was formed in the same manner as in Example 1B, and the presence or absence of residue of the resin coating film on the copper sputter film and the corrosion of the copper sputter film was evaluated. The results are shown in Table 2. However, in Comparative Example 1B, there was a test for the presence or absence of corrosion of the copper sputter film because there was a residue of the resin coating film which was not developed on the copper sputter film.

1: Silicon wafer
2: hole
3: Copper sputter film
4: Hall pattern

Claims (8)

A hole pattern forming method characterized by comprising the following steps 1 to 3:
Step 1: A resin film containing an alkali-soluble resin (A), a compound (B1) having at least two structures represented by the following formula (1) in one molecule and a photopolymerization initiator (C) is formed in a base material ;
Step 2: selectively exposing the resin film so as to obtain a hole pattern;
Step 3: Step of bringing an alkaline aqueous solution into contact with the resin film after exposure:

(R ¹ represents a hydrogen atom or a methyl group; * represents a bond). The method according to claim 1,
Wherein the alkali-soluble resin (A) has a phenolic hydroxyl group. The method according to claim 1,
Wherein the content of the compound (B1) is 1 to 50 parts by mass based on 100 parts by mass of the alkali-soluble resin (A). The method according to claim 1,
Wherein the substrate is a substrate having a copper film on a surface thereof, and the resin film is formed on the copper film in the step (1). A hole pattern forming method characterized by comprising the following steps 1 to 3:
(1) A method for producing a photopolymerizable composition, comprising the steps of: (1) preparing a photopolymerization initiator (C) having at least two groups selected from alkali-soluble resin (A), hydroxyl group and carboxyl group and at least two (meth) acryloyl groups in one molecule, ) To form a resin film;
Step 2: selectively exposing the resin film so as to obtain a hole pattern;
Step 3: Step of bringing an alkaline aqueous solution into contact with the resin film after exposure. (B) having at least one group selected from the alkali-soluble resin (A), the hydroxyl group and the carboxyl group and the (meth) acryloyl group in each molecule and the photopolymerization initiator (C) To form a hole pattern. A resin composition for forming a hole pattern, which comprises an alkali-soluble resin (A), a compound (B1) having at least two structures represented by the following formula (1) and a photopolymerization initiator (C)

(R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; * represents a bond). A laminate comprising a substrate and a hole pattern formed on the substrate by the method of forming an hole pattern according to any one of claims 1 to 5.

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