JP5277968B2 - Radiation sensitive resin composition - Google Patents

Description

  The present invention relates to a radiation sensitive resin composition. More specifically, the present invention relates to a negative radiation-sensitive resin composition suitable for formation of a plated model by a photo application.

  Conventionally, a plating method using a radiation-sensitive composition as a resist is known as one method for forming copper wiring, solder bumps, and the like on a silicon wafer on which a semiconductor is formed. As a resist used in this plating method, for example, a positive resist containing naphthoquinone diazide (NQD) and a novolak resin, for example, a negative resist containing an acrylic monomer and a radiation sensitive initiator has been developed.

  The positive resist enables patterning by changing the polarity of the resin by irradiation with radiation such as ultraviolet rays and the subsequent chemical action to improve the solubility in an alkaline developer (see, for example, Patent Document 1). ). Therefore, the resin of the patterned portion in the positive resist is not crosslinked. Therefore, it is excellent in that the patterning portion can be peeled off by a general organic solvent after plating. However, the NQD positive resist has a problem that it cannot cope with a narrow pitch because of its low resolution. In addition, since the resin of the patterning portion of the positive resist is not cross-linked, the mechanical strength in the plating process is not sufficient, deformation during plating is likely to occur, and a desired shape cannot be obtained. Since the resin used in the positive resist is easily dissolved in an alkaline solution, there is a problem that plating is difficult under alkaline conditions.

The negative resist can be patterned by irradiating with radiation such as ultraviolet rays, for example, by cross-linking acrylic monomers to reduce solubility in an alkaline developer (see, for example, Patent Document 2). Therefore, the resin of the patterning portion in the negative resist is cross-linked, which is excellent in that the mechanical strength is high, deformation in the plating process can be suppressed, and a desired shape can be easily obtained. Further, since the resin in the patterning portion is crosslinked and insoluble in an alkaline solution, plating can be performed under alkaline conditions as well as acidic and neutral conditions. However, since the resin in the patterning portion is cross-linked, it is difficult to dissolve the resist when the resist is peeled off after plating. Therefore, it is necessary to remove the resist by a method in which the resist is finely dispersed in a solid state and then removed, or by a method using a special remover. In the former method, a minute peeling residue may reattach to the wafer and become a defect. On the other hand, in the latter method, since the special stripping solution is strongly alkaline, it may corrode copper wiring, solder bumps, etc. formed by plating.
JP 2004-309776 A JP 2004-302389 A

  An object of the present invention is to provide a negative resist that can be suitably used in a plating method and also has the advantages of a positive resist.

The negative radiation sensitive resin composition according to the present invention is
(A) an alkali-soluble resin,
(B) A divalent organic group having two or more ethylenically unsaturated double bonds and connecting at least two ethylenically unsaturated double bonds is represented by the following structural formula (1) or (2). A compound having at least one group
It contains (C) an acid generator and (D) a radiation-sensitive radical polymerization initiator.

(In the above formula (1), R ¹ and R ² each independently represents a monovalent hydrocarbon group having 1 to 4 carbon atoms.)

(In the above formula (2), R ³ and R ⁴ each independently represents a monovalent hydrocarbon group having 1 to 4 carbon atoms.)
As said monomer (B), the compound chosen from the monomer represented by the following general formula (4-1) and general formula (4-2) is preferable.

(In the above formulas (4-1) and (4-2), R ⁵ each independently represents a hydrogen atom or a methyl group, R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms, and Z ¹ And Z ² represents a methylene group which may have a substituent or an alkylene group having 2 to 4 carbon atoms.)
As said monomer (B), the monomer represented by following General formula (3) is preferable.

  As the acid generator (C), a thermal acid generator is preferable.

  The alkali-soluble resin (A) is preferably a resin having a structural unit derived from the monomer (B).

  By using a plating method using the negative radiation-sensitive resin composition as a resist, a plated shaped article such as a bump or a mask material for etching can be produced.

  When the negative shaped radiation-sensitive composition of the present invention is used as a resist when producing a plated model, the mechanical strength against the plating stress of the resin in the patterning portion is sufficiently high, and a desired plating shape can be easily obtained. In addition, when the resist is used, not only can the plating be performed under alkaline conditions, but also when the patterned portion of the resist is peeled off, the crosslinked structure that ensures the mechanical strength is decomposed by light treatment or heat treatment. It can be easily peeled off with a typical organic solvent. Therefore, it is possible to suppress the corrosion of the plated shaped article and the corrosion of the sputtered film by the general strong alkali stripping solution used for the stripping of the negative radiation sensitive resin composition, and the stripping cost can be stripped by an inexpensive process. Can be greatly reduced.

  Hereinafter, the present invention will be specifically described.

  First, each component of the negative radiation sensitive resin composition according to the present invention will be described.

<(A) Alkali-soluble resin>
The alkali-soluble resin (A) used in the radiation-sensitive resin composition of the present invention is a resin having a phenolic hydroxyl group that is soluble in alkali and an acrylic resin that is soluble in alkali.

  Here, in the present invention, being soluble in alkali means that it is soluble in an alkali developer to such an extent that it is dissolved in an alkali developer described later and the intended development processing is performed. .

[Resin having a phenolic hydroxyl group]
The resin having a phenolic hydroxyl group is not particularly limited as long as it is soluble in alkali. For example, a novolak resin, polyhydroxystyrene, a hydroxystyrene copolymer having no structural unit derived from at least one monomer selected from the group of monomers represented by formula (a1) and formula (a2) described later. Examples thereof include a polymer, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, and a phenol-dicyclopentadiene condensation resin.

  The novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3 -Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol , Catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.

  Specific examples of novolak resins obtained using these phenols and aldehydes as raw materials include phenol / formaldehyde condensed novolak resins, cresol / formaldehyde condensed novolak resins, phenol-naphthol / formaldehyde condensed novolak resins, and the like.

In the hydroxystyrene copolymer, examples of monomers copolymerizable with hydroxystyrene include aromatic vinyl compounds such as p-isopropenylphenol, styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene;
Heteroatom-containing alicyclic vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam;
Cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitrile;
1. conjugated diolefins such as 3-butadiene and isoprene;
Amide group-containing vinyl compounds such as acrylamide and methacrylamide;
Carboxyl group-containing vinyl compounds such as acrylic acid and methacrylic acid;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono ( (Meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) Examples include (meth) acrylic acid esters such as acrylate.

  Among these monomers, p-isopropenylphenol, styrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, tricyclodecanyl acrylate, benzyl acrylate, isobornyl acrylate, methyl methacrylate, Ethyl methacrylate, n-butyl methacrylate, tricyclodecanyl methacrylate, benzyl methacrylate, isobornyl methacrylate and the like are preferable, and styrene is particularly preferable. The above monomers may be used alone or in admixture of two or more.

  Further, when the resin having a phenolic hydroxyl group is a hydroxystyrene copolymer, at least a group having a specific structure having two or more ethylenically unsaturated double bonds described later and decomposing by the action of an acid. A copolymer obtained from a monomer containing one compound (B) and hydroxystyrene may be used.

  The resin having a phenolic hydroxyl group may contain a phenolic low molecular compound.

  Examples of the phenolic low molecular weight compound include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane. , Tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methyl Ethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- { 1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) Le) ethane and the like. These phenolic low molecular weight compounds may be contained in the resin having a phenolic hydroxyl group in a range of usually 0 to 40% by mass, preferably 0 to 30% by mass.

〔acrylic resin〕
The acrylic resin is not particularly limited as long as it is soluble in alkali. Among these acrylic resins soluble in alkali, a polymer having a structural unit derived from at least one monomer selected from the monomer group represented by the following formula (a1) and the following formula (a2) And a copolymer (hereinafter, these are also referred to as “alkali-soluble acrylic resin (a)”).

In the above formula (a1) and formula (a2), R ^a is a hydrogen atom or a methyl group, R ^b is — (CH ₂ ) _n —, and n is an integer of 0 to 3. R ^c is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 4.

  The structural unit derived from the monomer of the formula (a1) means a structural unit represented by the following formula (a1 ′), and the structural unit derived from the monomer of the formula (a2) This means a structural unit represented by the following formula (a2 ′).

In the above formula (a1 ′) and formula (a2 ′), R ^a is a hydrogen atom or a methyl group, R ^b is — (CH ₂ ) _n —, and n is an integer of 0 to 3. R ^c is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 4.

  Examples of the monomer (a1) include p-hydroxyphenylacrylamide, p-hydroxyphenylmethacrylamide, o-hydroxyphenylacrylamide, o-hydroxyphenylmethacrylamide, m-hydroxyphenylacrylamide, m-hydroxyphenylmethacrylamide, p. -Hydroxybenzylacrylamide, p-hydroxybenzylmethacrylamide, 3,5-dimethyl-4-hydroxybenzylacrylamide, 3,5-dimethyl-4-hydroxybenzylmethacrylamide, 3,5-tertbutyl-4-hydroxybenzylacrylamide, 3,5-tertbutyl-4-hydroxybenzylmethacrylamide, o-hydroxybenzylacrylamide, o-hydroxybenzylmethacrylamide and the like It is.

  Examples of the monomer (a2) include p-hydroxyphenyl (meth) acrylate, o-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p-hydroxybenzyl (meth) acrylate, 3,5- Examples thereof include dimethyl-4-hydroxybenzyl (meth) acrylate, 3,5-tertbutyl-4-hydroxybenzyl (meth) acrylate, and o-hydroxybenzyl (meth) acrylate.

  Among these monomers (a1) and (a2), p-hydroxyphenylacrylamide, p-hydroxyphenylmethacrylamide, 3,5-dimethyl-4-hydroxybenzylacrylamide, 3,5-dimethyl-4-hydroxybenzyl Methacrylamide is preferred.

  These monomers (a1) and (a2) may be used alone or in admixture of two or more, or may be used in combination of monomer (a1) and monomer (a2). Good.

  Further, when the alkali-soluble acrylic resin (a) is a copolymer, in addition to the structure derived from the monomers (a1) and (a2), two or more ethylenically unsaturated double bonds described later are used. It is also preferable to have a structure derived from the compound (B) having at least one group having a specific structure that has and decomposes by the action of an acid.

  Furthermore, in the case where the alkali-soluble acrylic resin (a) is a copolymer, the copolymer includes these monomers (a1) in addition to the structural units derived from the monomers (a1) and (a2). Alternatively, it may have a structural unit derived from a monomer copolymerizable with (a2) (hereinafter also referred to as “monomer (I)”) (excluding the compound (B)).

Examples of the monomer (I) include fragrances such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, p-isopropenylphenol, styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene. Group vinyl compounds;
Heteroatom-containing alicyclic vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam;
Cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitrile;
1. conjugated diolefins such as 3-butadiene and isoprene;
Amide group-containing vinyl compounds such as acrylamide and methacrylamide;
Carboxyl group-containing vinyl compounds such as acrylic acid and methacrylic acid;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono ( (Meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) Examples include (meth) acrylic acid esters such as acrylate.

  Among these monomers (I), p-hydroxystyrene, p-isopropenylphenol, styrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, tricyclodecanyl acrylate, benzyl acrylate, Isobornyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tricyclodecanyl methacrylate, benzyl methacrylate, isobornyl methacrylate and the like are preferable. Monomers (I) may be used alone or in admixture of two or more.

  The alkali-soluble acrylic resin (a) can be produced, for example, by radical polymerization. Examples of the polymerization method include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method, and a solution polymerization method is particularly preferable.

As a polymerization initiator used for radical polymerization of the acrylic resin (a), 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2 '-Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (2-methylbutyronitrile), 1,1'-azobis- (cyclohexane-1-carbonitrile), Azo compounds such as dimethyl-2,2′-azobis (2-methylpropionate);
Examples thereof include organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxypivalate, 1,1′-bis- (tert-butylperoxy) cyclohexane, and hydrogen peroxide. Moreover, when using the said organic peroxide for a radical polymerization initiator, it is good also as a redox type initiator combining a reducing agent.

  In addition, when the alkali-soluble acrylic resin (a) is produced by a solution polymerization method, the polymerization solvent to be used is not particularly limited as long as it does not react with the monomer and can dissolve the produced polymer.

Examples of such a polymerization solvent include alcohols such as methanol, ethanol, ethylene glycol, diethylene glycol, and propylene glycol;
Cyclic ethers such as tetrahydrofuran and dioxane;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Alkyl ethers of polyhydric alcohols such as ethers;
Alkyl ether acetates of polyhydric alcohols such as ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol;
Ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutane Examples include esters such as methyl acid, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate, butyl acetate, and ethyl lactate.

  Among these polymerization solvents, cyclic ethers, polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether acetates, ketones, and esters are preferable.

  The weight average molecular weight (Mw) of the alkali-soluble acrylic resin (a) obtained by the radical combination is usually in the range of 1,000 to 100,000, preferably 2,000 to 50, in terms of polystyrene by gel permeation chromatography. Is in the range of 3,000, more preferably in the range of 3,000 to 20,000.

  The total of structural units derived from the monomers represented by the above formulas (a1) and (a2) in the alkali-soluble acrylic resin (a) is the total structural unit constituting the alkali-soluble acrylic resin (a). As 100 mass%, it is 10-40 mass% normally, Preferably it is 10-20 mass%.

  When the total of the structural units derived from the monomers represented by the above formulas (1) and (2) in the alkali-soluble acrylic resin (a) is within the above range, the molecular weight of the resulting polymer is sufficiently The developability and resolution of the resulting radiation-sensitive resin film are improved.

  The alkali-soluble resin (A) of the present application may be a copolymer having a structural unit derived from the compound (B) described later. For example, a copolymer obtained from a monomer containing compound (B) and hydroxystyrene, an alkali-soluble compound obtained from a monomer containing compound (B) and the above formula (a1) and / or (a2) An acrylic resin (a) may be sufficient. By copolymerizing the polyfunctional monomer having the structure of the monomer (B), the cross-linked structure in the resin can be cut in the process of generating an acid by heat and light described below to cut the cross-linked structure. It can be easily removed with a typical organic solvent. When the alkali-soluble resin (A) has a structural unit derived from the compound (B), when the structural unit constituting the alkali-soluble resin (A) is defined as 100% by mass, usually in the range of 0.1 to 5% by mass, Preferably it is the range of 1-3 mass%.

  As such a polyfunctional monomer, 2,5-dimethyl-2,5-hexanediol diacrylate is preferable.

  These alkali-soluble resins (A) may be used alone or in combination of two or more.

<(B) Acid-decomposable compound having two or more ethylenically unsaturated double bonds>
The compound (B) used in the radiation-sensitive resin composition of the present invention has two or more ethylenically unsaturated groups in the molecule and connects at least two ethylenically unsaturated double bonds. The organic group is a compound having at least one group represented by the following structural formula (1) or (2).

(In the above formula (1), R ¹ and R ² each independently represents a monovalent hydrocarbon group having 1 to 4 carbon atoms.)
Examples of R ¹ and R ² include a methyl group, an ethyl group, a propyl group, and a butyl group.

(In the above formula (2), R ³ and R ⁴ each independently represents a monovalent hydrocarbon group having 1 to 4 carbon atoms.)
Examples of R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, and a butyl group.

  In the radiation-sensitive composition of the present application containing such a compound (B), the compound (B) acts as a cross-linking agent during pattern formation, imparts mechanical strength and heat resistance to the resulting patterned film, and forms a plated model. When used sometimes, it is possible to impart plating stress and resistance to a plating solution. Moreover, since the acid generated from the acid generator described later can decompose the crosslinked structure, the patterning film can be quickly removed with a general organic solvent after the formation of the plated model.

  As said compound (B), at least 1 sort (s) chosen from the monomer represented by the following general formula (4-1) and general formula (4-2) is mentioned.

(In the above formulas (4-1) and (4-2), R ⁵ each independently represents a hydrogen atom or a methyl group, R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms, and Z ¹ And Z ² represents a methylene group which may have a substituent or an alkylene group having 2 to 4 carbon atoms.)
Examples of R ⁶ include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a methyl group and an ethyl group are preferable. Examples of Z ¹ and Z ² include an ethylene group, a propylene group, and a butylene group. Among these, an ethylene group is preferable.

In Z ¹ and Z ² , hydrogen in the group may be substituted with another substituent. Examples of such a substituent include a methyl group, an ethyl group, a —R ⁷ —O—CO—CR ⁸ ═CH ₂ group, and a —O—CO—O—R ⁹ —CR ⁸ ═CH ₂ group. R ⁷ independently represents a single bond, a methylene group or an alkylene group having 2 to 4 carbon atoms, and R ⁸ independently represents a hydrogen atom or a methyl group.

Examples of the alkylene group having 2 to 4 carbon atoms of R ⁷ include an ethylene group, a propylene group, and a butylene group. However, when the substituent is —R ⁷ —O—CO—CR ⁸ ═CH ₂ group or —O—CO—O—R ⁹ —CR ⁸ ═CH ₂ group, it is the same as the carbon to which the substituent is bonded. A methyl group or an ethyl group is bonded to carbon.

  By using the above compound, when peeling the resist after plating while having a sufficient crosslinking density to suppress deformation of the pattern shape in the plating process, the strength of the coating film in the above plating process is ensured. Since the cross-linked structure that has been decomposed is decomposed by light treatment or heat treatment, it can be easily peeled off with a common organic solvent.

  The compound (B) is a divalent ester group represented by the structural formula (1) (hereinafter referred to as “ester group (B1)”) or a divalent carbonate represented by the structural formula (2). It has at least one group (hereinafter referred to as “carbonate group (B2)”).

  Among such compounds (B), the compound (B) having an ester group (B1) has, for example, a polyhydric alcohol having at least two tertiary hydroxyl groups and a polymerizable carbon-carbon double bond. It can synthesize | combine by carrying out esterification reaction with the monovalent carboxylic acid which has one.

  The esterification reaction includes, for example, (i) a method of reacting the acid chloride of the carboxylic acid with the polyhydric alcohol, and (ii) adding a condensing agent such as dicyclohexylcarbodiimide, and the carboxylic acid and the polyhydric alcohol. A method of reacting, (iii) a method of adding a strong acid anhydride such as trifluoroacetic anhydride as a dehydrating agent to react the carboxylic acid with the polyhydric alcohol, and (iv) a transesterification method. .

  Examples of the polyhydric alcohol having at least two tertiary hydroxyl groups used for the synthesis of the compound (B) having an ester group (1) include compounds represented by the following formulas (b1) to (b3). It is done.

(In the formula (b1), R is a monovalent hydrocarbon group having 1 to 4 carbon atoms which may be the same or different from each other, i is an integer of 2 to 4, and A ¹ is an i-valent organic group. (However, when i = 2, A ¹ is a divalent organic group or a single bond.)

(In the above formula (b2), R is a monovalent hydrocarbon group having 1 to 4 carbon atoms which may be the same or different from each other, and R ⁵ has 1 to 5 carbon atoms which may be the same or different from each other. An alkyl group, j is an integer of 2 to 4, m is an integer of 0 to 4, and j + m ≦ 6.)

(In the above formula (b3), R is a monovalent hydrocarbon group having 1 to 4 carbon atoms which may be the same or different from each other, and R ⁶ has 1 to 5 carbon atoms which may be the same or different from each other. An alkyl group, z is an integer of 2 to 4, A ² is a z-valent organic group, —O—, —S—, —CO— or —SO ₂ —, and k is 1 or 2. , N is an integer of 0-3.)
Examples of the compound represented by the formula (b1) include 2,3-dimethyl-2,3-butanediol, 2,3-diethyl-2,3-butanediol, and 2,3-di-n-propyl-2. , 3-butanediol, 2,3-diphenyl-2,3-butanediol, 2,4-dimethyl-2,4-pentanediol, 2,4-diethyl-2,4-pentanediol, 2,4-di -N-propyl-2,4-pentanediol, 2,4-diphenyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 2,5-diethyl-2,5-hexanediol 2,5-di-n-propyl-2,5-hexanediol, 2,5-diphenyl-2,5-hexanediol, 2,6-dimethyl-2,6-heptanediol, 2,6-diethyl- 2,6-hepta Diol, 2,6-di -n- propyl-2,6-heptane diol, divalent tertiary alcohols such as 2,6-diphenyl-2,6-heptane diol;
2,4-dimethyl-2,4-dihydroxy-3- (2-hydroxypropyl) pentane, 2,4-diethyl-2,4-dihydroxy-3- (2-hydroxypropyl) pentane, 2,5-dimethyl- Trivalent tertiary alcohols such as 2,5-dihydroxy-3- (2-hydroxypropyl) hexane and 2,5-diethyl-2,5-dihydroxy-3- (2-hydroxypropyl) hexane;
2,4-dimethyl-2,4-dihydroxy-3,3-di (2-hydroxypropyl) pentane, 2,4-diethyl-2,4-dihydroxy-3,3-di (2-hydroxypropyl) pentane, 2,5-dimethyl-2,5-dihydroxy-3,4-di (2-hydroxypropyl) hexane, 2,5-diethyl-2,4-dihydroxy-3,4-di (2-hydroxypropyl) hexane, And tetravalent tertiary alcohols such as 2,3,4,5-tetramethyl-2,3,4,5-tetrahydroxyhexane.

  Examples of the compound represented by formula (b2) include 1,4-di (2-hydroxypropyl) benzene, 1,3-di (2-hydroxypropyl) benzene, 1,3,5-tri (2-hydroxy). Propyl) benzene, 1,2,4,5-tetra (2-hydroxypropyl) benzene and the like.

  Examples of the compound represented by the formula (b3) include 2,2-bis {4- (2-hydroxypropyl) phenyl} propane, 1,2,2-tris {4- (2-hydroxypropyl) phenyl. } Propane, 1,2,3,4-tetra {4- (2-hydroxypropyl) phenyl} butane, bis {4- (2-hydroxypropyl) phenyl} ether, bis {4- (2-hydroxypropyl) phenyl } Sulfide, bis {4- (2-hydroxypropyl) phenyl} ketone, bis {4- (2-hydroxypropyl) phenyl} sulfone, and the like.

  Among the divalent to tetravalent tertiary alcohols represented by these formulas (b1) to (b3), 2,5-dimethyl-2,5-hexanediol, 2,3,4,5-tetramethyl-2 , 3,4,5-hexanetetraol acrylate, 2,5-dimethylhexane-2,5-bis (p-vinylphenyl carbonate), 1,4-di (2-hydroxypropyl) benzene, 1,3-di (2-Hydroxypropyl) benzene is preferred.

  The monovalent carboxylic acid having one polymerizable carbon-carbon double bond used for the synthesis of the compound (B) having an ester group (1) includes (meth) acrylic acid, crotonic acid, and cinnamic acid. , 2- (meth) acryloyloxyethyl carboxylic acid, 4- (meth) acryloyloxycyclohexyl carboxylic acid, and the like.

  Of the compounds (B) having an ester group represented by the above formula (1), the compound represented by the following formula (3) is preferable.

  When the monomer (B) having an ester group (1) is a compound represented by the above formula (3), the developability and resolution of the resulting radiation-sensitive resin film are improved. Further, since the viscosity is low, the solid content concentration of the resist can be increased, and the resist coating property is improved even at a high film thickness.

  In addition, the compound (B) having a carbonate group represented by the above formula (2) removes (2-1) 1-chloro-2chlorocarbonyloxyethane and 1-chloro-2chlorocarbonyloxy-2-methylethane. A method of synthesizing chlorocarbonyloxyethylene or 1-chlorocarbonyloxy-1-methylethene with hydrochloric acid and reacting it with, for example, a polyhydric alcohol having at least two tertiary hydroxyl groups, (2-2) Poly (chloroformate) polyhydric alcohol having at least two tertiary hydroxyl groups with phosgene or the like, and this poly (chloroformate) polyhydric alcohol is converted into one polymerizable carbon-carbon double bond. And a method of reacting with a compound having one hydroxyl group.

  As the polyhydric alcohol having at least two tertiary hydroxyl groups, the divalent to tetravalent tertiary used for the synthesis of the monomer (B) having an ester group represented by the above formula (1). Examples include alcohol. Among such 2- to 4-valent tertiary alcohols, 2,5-dimethyl-2,5-hexanediol, 1,4-di (2-hydroxypropyl) benzene, 1,3-di (2-hydroxypropyl) ) Benzene is preferred.

Examples of the compound having one polymerizable carbon-carbon double bond and one hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-isopropenylphenol, hydroxystyrenes such as m-isopropenylphenol and p-isopropenylphenol;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( And hydroxyalkyl (meth) acrylates such as (meth) acrylate.

  In this invention, the compounding quantity of the compound (B) with respect to alkali-soluble resin (A) is 20-90 mass parts normally with respect to 100 mass parts of alkali-soluble resin (A), Preferably it is 40-90 mass parts, More preferably Is 40-80 parts by mass. When the compounding amount of the compound (B) is less than the above range, the exposed area cannot be sufficiently insolubilized in the developer, so that no contrast can be obtained and the pattern cannot be formed. When the blending amount of (B) exceeds the above range, the low molecular weight increases and the remaining monomer increases, so that a good pattern shape tends not to be obtained.

<(C) Acid generator>
In the present invention, the acid generator means a heat-sensitive acid generator that generates an acid when heat is applied, and a photo-sensitive acid generator that generates an acid when irradiated with light.

  The heat-sensitive acid generator (hereinafter also referred to as “thermal acid generator (C1)”) is a compound that generates an acid by applying appropriate heat, for example, heating to 140 to 250 ° C. Although it does not restrict | limit in particular, A sulfonium salt, a diazonium salt, a halogen containing compound, a sulfonic acid ester compound, etc. are mentioned.

  Examples of the thermal acid generator (C1) that generates an acid by heating to 140 to 250 ° C. include benzylmethylphenylsulfonium hexafluoroantimonate, benzylmethylphenylsulfonium hexafluorophosphate, benzylmethylphenylsulfonium tetrafluoroborate, and benzylmethyl. Phenylsulfonium trifluoromethanesulfonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluoroantimonate, benzyl (4-hydroxyphenyl) methylsulfonium hexafluorophosphate, benzyl (4-hydroxyphenyl) methylsulfonium tetrafluoroborate, benzyl (4- Hydroxyphenyl) methylsulfonium trifluoromethanesulfonate (4-hydroxyphenyl) Nylmethyl-o-methylbenzylsulfonium trifluoromethanesulfonate), 4-acetoxyphenylbenzylmethylsulfonium trifluoromethanesulfonate, benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium tetrafluoroborate, Examples thereof include benzenediazonium trifluoromethanesulfonate, naphthalene diazonium hexafluoroantimonate, and naphthalene diazonium trifluoromethanesulfonate.

  In this invention, when using a thermal acid generator (C1) as an acid generator (C), the compounding quantity of a thermal acid generator (C1) is 100 mass parts of said alkali-soluble resin (A). Usually, 1 to 10 parts by mass, preferably 1 to 5 parts by mass. If the blending amount of the thermal acid generator (C1) is less than the above range, it may be difficult to cause sufficient chemical change due to the catalytic action of the generated acid. There is a risk of adverse effects.

  In the present invention, when a photo-sensitive acid generator (hereinafter also referred to as “photo acid generator (C2)”) is used as the acid generator (C), the acid is irradiated by irradiating with radiation having a wavelength of 300 nm to 380 nm. The resulting compound is used.

  Examples of the photoacid generator (C2) include onium salt compounds, halogen-containing compounds, diazoketone compounds, and sulfone compounds. Specific examples of these compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, and triphenyl. Examples include hexafluoroantimonate and triphenylsulfonium hexafluorophosphate.

  In this invention, when using a photo-acid generator (C2) as an acid generator (C), the compounding quantity of a photo-acid generator is 1 normally with respect to 100 mass parts of said alkali-soluble resin (A). -10 parts by mass, preferably 1-3 parts by mass. If the blending amount of the photoacid generator is less than the above range, it may be difficult to cause a chemical change due to the catalytic action of the generated acid, and if it exceeds the above range, the coatability and developability are adversely affected. There is a fear.

<(D) Radiation-sensitive radical polymerization initiator>
The radiation-sensitive radical polymerization initiator (D) used in the present invention is not particularly limited as long as the negative radiation-sensitive resin composition of the present invention can be cured with radiation.

  Here, the radiation in the present invention means ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron beams, and the like. Examples of radiation sources that generate such radiation include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, and argon gas lasers. Among these radiation sources, mercury lamps are generally used. Of the radiation emitted from the mercury lamp, i-line having a wavelength of 365 nm and h-line having a wavelength of 405 nm are most commonly used for curing the radiation-sensitive resin composition.

  Among these, i-line has high energy, high curability, is not easily inhibited by oxygen, but is easily absorbed because of its short wavelength, and cures a thick film formed from a radiation-sensitive resin composition. In this case, sufficient energy cannot reach the bottom of the thick film, and a desired pattern shape may not be obtained. Specifically, the shape of the cross section of the radiation-sensitive resin film after patterning is not a rectangle, but a trapezoid with a bottom that is more than the surface layer of the radiation-sensitive resin film, and a desired pattern shape may not be obtained. .

  On the other hand, the h-line has a lower energy than the i-line, and it takes time to cure, and the film surface formed from the radiation-sensitive resin composition is inhibited from curing by oxygen, and the residual film rate after patterning may be significantly reduced. However, since the wavelength is longer than the i-line, the radiation transmittance is high, and even in the case of a thick film, the energy easily reaches the bottom of the film, and the shape of the cross section of the film after patterning becomes a rectangular shape. There is a feature that it is easy to obtain the shape.

  In the present invention, in consideration of such i-line and h-line characteristics, among the above-mentioned radiation-sensitive radical polymerization initiators (D), the negative-type radiation-sensitive resin composition of the present invention has a dry film thickness of 70 μm. When a cured coating film is formed, the radiation transmittance of 365 nm of the coating film is 10% or more, preferably 12-30%, and the radiation transmittance of 405 nm is 60% or more, preferably 65-80. % Of the radiation-sensitive radical polymerization initiator (D) is preferred. However, when a photoacid generator is used as the acid generator, the i-line is cut by a filter and patterning is performed by irradiation with h-line, so that the h-line transmittance is 30 to 80%. Radiation radical polymerization initiators are preferred. When such a radiation-sensitive radical polymerization initiator (D) is used in a specific amount to be described later, even if a coating film having a film thickness of 50 μm or more is formed on the substrate, the surface layer portion of the coating film In addition, the bottom portion can be sufficiently cured, and a desired pattern can be formed with high accuracy.

  That is, by improving the transmittance at the wavelength in the above-described region, the attenuation of radiation transmitted from the surface of the coating film formed from the radiation-sensitive resin composition is suppressed, and the entire film is uniformly cured. It is also possible to form a cured film having a patterning shape in which the bottom side and the side wall are substantially perpendicular. For example, by using a predetermined amount of such a radiation-sensitive radical polymerization initiator (D), a straight-shaped high bump can be formed with high accuracy.

  In addition, the measurement of the transmittance | permeability of the dry coating film mentioned above is implemented with the following method.

  First, the alkali-soluble resin (A) has at least two ethylenically unsaturated double bonds, has at least two ethylenically unsaturated double bonds, and has at least two ethylenically unsaturated double bonds. A compound (B) having at least one group represented by a specific structure in which a divalent organic group to be linked is decomposed by the action of an acid, an acid generator (C), a radiation-sensitive radical polymerization initiator (D), and A composition containing lactic acid, which is an example of a solvent to be described later, is prepared (the total mass of (A), (B), (C), and (D) is 65 mass%), and the thickness is determined by spin coating. A coating film is formed on a 1 mm quartz substrate, and then baked on a hot plate at 110 ° C. for 5 minutes to remove the solvent and form a coating film. In this case, the number of rotations during spin coating is controlled in advance so that the film thickness of the coating film after baking is 70 μm.

  Thus, the transmittance | permeability in wavelength 300nm -500nm is measured for the coating film formed on the quartz substrate using the spectrophotometer (for example, HITACHI Spectrophotometer U-2010) with reference to the quartz substrate which does not have a coating film. To do.

Also, the measured transmittance can be applied to the equation ε = log (I ₀ / I) / L to determine the extinction coefficient ε (where ε is the extinction coefficient (m ⁻¹ ), and I is transmitted through the coating film). The light intensity (cd) immediately after exposure, I ₀ is the light intensity (cd) before passing through the coating film, and L is the dry film thickness (m) of the coating film. From the viewpoint of the extinction coefficient, the radiation-sensitive radical polymerization initiator (D) used in the present invention usually has an extinction coefficient of radiation having a wavelength of 365 nm in the above-mentioned uncured coating film having a dry film thickness of 70 μm. It is preferably 15000 m ⁻¹ or less and the extinction coefficient of radiation having a wavelength of 405 nm is usually 4000 m ⁻¹ or less.

However, when a photoacid generator is used as the acid generator, patterning is performed by h-ray irradiation, so that the radiation sensitive radical polymerization initiator is combined such that the extinction coefficient at a wavelength of 405 nm is 8000 m ⁻¹ or less. It is preferable to adjust to.

As such a radiation sensitive radical polymerization initiator (D), for example,
Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; 2,2-dimethoxy-1, 2-diphenylethane-1-one, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 2,2′-bis (2 -Chlorophenyl) -4,5-4 ', 5'-tetraphenyl-1-2'bisimidazole and the like. Moreover, as a commercial item, Lucilin TPO (made by BASF Corporation), Irgacure 651 (made by Ciba Specialty Chemicals Co., Ltd.), etc. are mentioned. These compounds can be used alone or in combination of two or more.

  Among these radiation-sensitive radical polymerization initiators (D), the combined use of 2,2-dimethoxy-1,2-diphenylethane-1-one and 2,4,6-trimethylbenzoyldiphenylphosphine oxide is preferable. When a photoacid generator is used as the acid generator, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (2-chlorophenyl) -4,5-4 ′, 5′-tetraphenyl The use of -1-2 'bisimidazole is desirable.

  The radiation-sensitive radiation radical polymerization initiator (D) is usually 1 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). Used in the amount of.

  When using a photo-acid generator as an acid generator, a radiation sensitive radical polymerization initiator (D) is 5-50 mass parts normally with respect to 100 mass parts of alkali-soluble resin (A), Preferably it is 10-30. Used in parts by mass. When the radiation-sensitive radical polymerization initiator (D) is used in an amount within the above range, the transmittance at the wavelength in the above-described region becomes sufficient, and not only the surface layer of the film formed from the resin composition of the present invention. The bottom part can be cured sufficiently. Furthermore, the influence (deterioration of sensitivity) of radical deactivation due to oxygen can be suppressed, and a desired pattern can be formed from the film with high accuracy.

  When 2,2-dimethoxy-1,2-diphenylethane-1-one and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are used in combination, 100 parts by mass of the alkali-soluble resin (A) is used. On the other hand, 2,2-dimethoxy-1,2-diphenylethane-1-one is usually added in an amount of 10 to 30 parts by mass, preferably 10 to 15 parts by mass, and said (f) 2,4,6-trimethylbenzoyl. Diphenylphosphine oxide is usually used in an amount of 3 to 10 parts by mass, preferably 3 to 5 parts by mass.

<Other ingredients>
In the present invention, the above-described alkali-soluble resin (A) has two or more ethylenically unsaturated double bonds and a divalent organic group that links at least two ethylenically unsaturated double bonds is formed by the action of an acid. In addition to the compound (B) having at least one group represented by the specific structure to be decomposed, the acid generator (C), and the radiation-sensitive radical polymerization initiator (D), an organic solvent, various Components such as additives can be used.

  As the organic solvent, a solvent that can uniformly dissolve the alkali-soluble resin (A) and other components and does not react with the components is used. As such an organic solvent, the solvent similar to the polymerization solvent used for manufacture of alkali-soluble resin (A) can be used. Further, these organic solvents include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl. Ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, A high boiling point solvent such as phenyl cellosolve acetate may be added and used.

Among these organic solvents, alkyl ethers of polyhydric alcohols such as ethylene glycol monoethyl ether and diethylene glycol monomethyl ether;
Alkyl ether acetates of polyhydric alcohols such as ethyl cellosolve acetate and propylene glycol monomethyl ether acetate;
Esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 2-hydroxypropionate, ethyl lactate;
Ketones such as diacetone alcohol are preferred. When the organic solvent is the above solvent, each component can be dissolved uniformly and does not react with each component, and a coating film can be easily formed from the resin composition of the present invention.

  Moreover, the resin composition of the present invention may contain a thermal polymerization inhibitor. Examples of such thermal polymerization inhibitors include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4. '-(1-methylethylidene) bis (2-methylphenol), 4,4'-(1-methylethylidene) bis (2,6-dimethylphenol), 4,4 '-[1- [4- (1 -(4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] bisphenol, 4,4 ', 4 "-ethylidenetris (2-methylphenol), 4,4', 4" -ethylidenetrisphenol, 1, 1,3-tris (2,5-dimethyl-4-hydroxy Eniru) -3-phenyl propane. The blending amount of these thermal polymerization inhibitors is preferably 5 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A).

  In addition, the resin composition of the present invention may contain a surfactant for the purpose of improving coating properties, antifoaming properties, leveling properties and the like. As the surfactant, for example, NBX-15 (manufactured by Neos Co., Ltd.) BM-1000, BM-1100 (manufactured by BM Chemie), MegaFac F142D, F172, F173, F183 (and above, Dainippon) Ink Chemical Industry Co., Ltd.), FLORARD FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 (made by Asahi Glass Co., Ltd.), SH-28PA, -190, -193, SZ-6032, SF-8428 (above, Toray Dow Corning Silicone ( Fluorosurfactants marketed under trade names such as “manufactured by Co., Ltd.” can be used. The compounding amount of these surfactants is preferably 5 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (A).

  The resin composition of the present invention may contain an adhesion assistant in order to improve the adhesion to the substrate. Examples of the adhesion assistant include functional silane coupling agents. Here, the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group.

  Functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltri Examples include methoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. As for the compounding quantity of an adhesion assistant, 20 mass parts or less are preferable with respect to 100 mass parts of alkali-soluble resin (A).

In order to finely adjust the solubility of the resin film formed from the resin composition of the present invention in an alkaline developer, acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid Monocarboxylic acids such as benzoic acid and cinnamic acid;
Lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxy Hydroxymonocarboxylic acids such as isophthalic acid, syringic acid;
Oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, Polyvalent carboxylic acids such as trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid;
Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetra Acid anhydrides such as carboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride, glycerin tris anhydrous trimellitate May be added to the resin composition of the present invention.

  Further, the resin composition of the present invention may further contain other additives such as a filler, a colorant, and a viscosity modifier as necessary.

  Examples of the filler include silica, alumina, talc, bentonite, zirconium silicate, and powdered glass.

  Colorants include alumina white, clay, barium carbonate, barium sulfate and other extender pigments; zinc white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, carbon black, etc. Pigments; organic pigments such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, and phthalocyanine green; basic dyes such as magenta and rhodamine; direct dyes such as direct scarlet and direct orange; Examples include acid dyes such as yellow.

  Examples of the viscosity modifier include bentonite, silica gel, and aluminum powder. The blending amount of these other additives may be within a range that does not impair the object of the present invention. Preferably, the total amount of the components (A), (B), (C), and (D) is 100 masses. It is 50 mass parts or less with respect to a part.

  The resin composition of the present invention is produced by mixing the components described above.

  In the resin composition of the present invention, when the filler and the pigment are not added, each of the above components (A), (B), (C), and (D), and other components as necessary Can be mixed and produced by a usual method. In addition, in the resin composition of the present invention, when adding a filler and a pigment, first, the components other than the filler and the pigment are mixed, and then the mixture is mixed with a dissolver, a homogenizer, a three-roll mill, etc. It can manufacture by dispersing a filler and a pigment using a disperser. Moreover, you may filter the product obtained by the said mixing using a mesh, a membrane filter, etc. as needed.

<Radiation-sensitive resin film and cured film comprising the same>
A radiation-sensitive resin film is formed on a substrate using the resin composition of the present invention thus obtained.

  This radiation sensitive resin film can be formed on a substrate by, for example, applying the resin composition of the present invention on the substrate and removing the solvent by heating. Alternatively, after applying the resin composition of the present invention on a flexible base film in advance, a transfer film is prepared by drying, and the transfer film is adhered to the substrate, and the radiation-sensitive resin film is formed on the substrate. And a radiation sensitive resin film can be formed on the substrate.

  In the transfer film, it is preferable that the surface of the radiation-sensitive resin film on the base film is covered with a protective film until just before transferring to the base material.

  As the base film, synthetic resin films such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyether sulfone, and polyvinyl chloride can be used. The thickness of the base film is preferably in the range of 15 to 125 μm.

  For forming the radiation sensitive resin film, an applicator, a bar coater, a roll coater, a curtain flow coater, a die coater, a spin coater, screen printing, or the like is used. The film thickness of the obtained radiation-sensitive resin film is usually 50 μm or more, preferably 50 to 150 μm, more preferably 50 to 100 μm in terms of the dry film thickness after removal of the solvent. When the dry film thickness of the radiation sensitive resin film thus obtained is 50 μm or more, it is suitable for forming high bumps by photo application.

  In addition, when forming the said radiation sensitive resin film, although it changes with the kind of each component in a resin composition, a mixture ratio, the thickness of a coating film, etc., after apply | coating the composition, it is usually 60-120 degreeC. And preferably at a temperature in the range of 80 to 110 ° C. for about 5 to 20 minutes. If the drying time is too short, the adhesion state at the time of development deteriorates, and if it is too long, the resolution may be lowered due to heat fogging.

  In addition, when plating a base material using the said radiation sensitive resin film and forming a plated modeling thing, for example, a high bump, it is necessary for the base material surface to be coated with the metal. The method for coating the surface of the substrate with a metal is not particularly limited, and examples thereof include a method for depositing a metal and a method for sputtering.

  In this way, the radiation sensitive resin film provided on the substrate is irradiated with radiation such as ultraviolet light having a wavelength of 300 to 500 nm or visible light through a photomask having a predetermined pattern, thereby exposing the exposed portion. Is cured by radiation. By irradiation with radiation such as ultraviolet rays, the compound (B) having at least two ethylenically unsaturated double bonds crosslinks the resin film in the exposed area, so that the resin film in the exposed area has higher mechanical strength. Thus, thermal deformation is suppressed and heat resistance is increased.

As such a radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used. . The amount of radiation irradiation varies depending on the type of each component in the composition, the blending amount, the thickness of the coating film, and the like, but is, for example, 100 to 1500 mJ / cm ² when a high-pressure mercury lamp is used.

  As described above, after radiation-curing the exposed portion of the radiation-sensitive resin film, a non-exposed portion is removed by alkali development, whereby a cured film having a desired pattern can be obtained. The alkali development treatment is performed by dissolving and removing unnecessary non-exposed portions using an alkaline aqueous solution as a developer, and leaving only the exposed portions.

  As the developer, an aqueous solution containing an alkali is used. Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, Triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5 -Nonane etc. are mentioned.

  The developer may further contain an appropriate amount of a water-soluble organic solvent such as methanol and ethanol, and a surfactant.

  The development time of the alkali development treatment varies depending on the type of each component in the resin composition, the blending ratio, the thickness of the coating film, etc., but is usually 30 to 360 seconds. Examples of the developing method include a liquid piling method, a dipping method, a paddle method, a spray method, and a shower developing method. After the development treatment, the substrate on which the cured film has been formed is usually washed with running water for 30 to 90 seconds, air-dried with an air gun or the like, and then heat-dried with a hot plate or oven as necessary.

The radiation-sensitive resin film can be sufficiently cured only by the above-mentioned radiation irradiation, but is further cured by additional radiation irradiation (hereinafter referred to as post-exposure) or heating depending on the application. Also good. Post-exposure can be performed in the same manner as the above-described radiation irradiation. The amount of radiation irradiation at the time of post-exposure is not particularly limited, but when a high-pressure mercury lamp is used, 100 to 2000 mJ / cm ² is preferable. When the photoacid generator (C2) is used as the acid generator (C), a condition that does not generate an acid by light, usually a filter that cuts a wavelength around 365 nm, and around 405 nm of a high-pressure mercury lamp Is cured with a radiation dose of 1000 to 3000 mJ / cm ² .

  In the case of further curing by heating, a heating device such as a hot plate or an oven is used, for example, at a temperature of 60 to 100 ° C. for 5 to 30 minutes on the hot plate and 5 to 60 in the oven. Heat for minutes. In the case where the thermal acid generator (C1) is used as the acid generator (C), it is 5 to 5 on the hot plate under conditions where no acid is generated by heat, usually 60 to 130 ° C. Heat in oven for 5 to 60 minutes.

  By this post-treatment, a cured film having a predetermined pattern having even better characteristics can be obtained.

  When a substrate having a cured film on which the above-described pattern is formed is immersed in various plating solutions for electroplating, and a current value and an energization time are set so as to obtain a desired plating thickness, a plated model is formed on the substrate. Is formed.

  And after a plated modeling thing is formed, when a thermal acid generator (C1) is used as an acid generator (C), it heats. In addition, when the photoacid generator (C2) is used as the acid generator (C), light irradiation is performed.

  When the thermal acid generator (C1) is used as the acid generator (C), the acid generator (C1) may be heated under conditions that generate an acid depending on the thermal acid generator (C1) to be used. And preferably at a temperature in the range of 140 to 180 ° C. for 3 to 20 minutes. By heating under the above conditions, a chemical change due to the catalytic action of the generated acid can be sufficiently caused.

When the photoacid generator (C2) is used as the acid generator (C), light irradiation may be performed under conditions that generate an acid depending on the photoacid generator (C2) used. Is irradiated with light having a light amount of 500 to 2000 mJ / cm ² . Then, it heats for 3 to 20 minutes at the temperature of the range of 100-180 degreeC as needed. By irradiating with light under the above conditions, a chemical change due to the catalytic action of the generated acid can be sufficiently caused.

  By this heating or light irradiation, an acid is generated from the acid generator (C), and the group represented by the formula (1) or (2) derived from the monomer (B) is dissociated by the acid. Wake up. For example, the structure represented by the formula (1) separates a part having a carboxylic acid and a part having an alcohol.

  Then, the board | substrate which has a plated modeling thing can be formed by immersing this base material in peeling liquid on the temperature conditions of 50-80 degreeC, for example for 5 to 30 minutes, for example, and peeling a cured film.

  As the stripping solution used for the stripping operation, N-methylpyrrolidone, propylene glycol monomethyl ether acetate, dimethyl sulfoxide and the like are preferably used.

  In this peeling operation, as described above, the portion cured by radiation is reduced in molecular weight by the catalytic action of acid generated by heat or light irradiation, the solubility is improved, and it is easy to peel off. Without using a strong alkaline stripping solution having a pH of 12 to 14 such as an aqueous solution of a quaternary ammonium salt or a mixed solution of a quaternary ammonium salt, dimethyl sulfoxide and water, Peeling can be done easily without depending on it.

  According to such a method, straight plated high bumps in which the bottom and the side wall of the cross-sectional shape are substantially perpendicular can be easily formed on the substrate among the plated shaped objects.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

[Synthesis Example 1]
<Synthesis of alkali-soluble resin A1>
The flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then 5 g of 2,2′-azobisisobutyronitrile as a polymerization initiator and 150 g of ethyl lactate as a solvent were added and stirred until the polymerization initiator was dissolved. . Subsequently, 10 g of methacrylic acid, 15 g of 4-hydroxyphenyl methacrylate, 50 g of n-butyl methacrylate, and 25 g of tricyclo [5.2.1.0 ^2,6 ] decanyl methacrylate were charged, and then gently stirring was started. Subsequently, the temperature of the solution was raised to 85 ° C., and polymerization was carried out at this temperature for 6 hours. Thereafter, the temperature of the solution was raised to 100 ° C., and polymerization was further performed at this temperature for 1 hour.

  Then, this solution was cooled to room temperature to stop the polymerization reaction, and an ethyl lactate solution of the desired alkali-soluble resin A1 was obtained. The ethyl lactate solution of the alkali-soluble resin A1 was concentrated using an evaporator, so that the mass concentration of the resin was 70%.

[Synthesis Example 2]
<Synthesis of alkali-soluble resin A2>
An alkali-soluble resin A2 was synthesized in the same manner as the synthesis of the alkali-soluble resin A1 of Synthesis Example 1 except that the type and amount of the compound were changed according to the composition shown in Table 1 below.

[Synthesis Example 3]
<Synthesis of p-hydroxystyrene / styrene copolymer A5>
100 parts by weight of pt-butoxystyrene and styrene in a molar ratio of 85:15 were dissolved in 150 parts by weight of propylene glycol monomethyl ether, and the reaction temperature was maintained at 70 ° C. in a nitrogen atmosphere. Polymerization was carried out for 10 hours using 4 parts by weight of isobutyronitrile. Thereafter, sulfuric acid was added to the reaction solution, and the reaction temperature was kept at 90 ° C. for reaction for 10 hours, and pt-butoxystyrene was deprotected and converted to hydroxystyrene. Ethyl acetate was added to the obtained copolymer, washing with water was repeated 5 times, the ethyl acetate phase was separated, the solvent was removed, and a p-hydroxystyrene / styrene copolymer was obtained.

When the molecular weight of this copolymer was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) in terms of polystyrene was 10,000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). (Mw / Mn) was 3.5. As a result of ¹³ C-NMR analysis, the molar ratio of copolymer A5 of p-hydroxystyrene and styrene was 85:15.

<Synthesis of alkali-soluble resin A6>
[Synthesis Example 4]
In the same manner as the alkali-soluble resin A5, an alkali-soluble resin A6 having hydroxystyrene / styrene = 80/20 (molar ratio) weight average molecular weight = 10000 was synthesized.

[Synthesis Example 5]
<Synthesis of alkali-soluble resin A7>
The flask equipped with a dry ice / methanol reflux was purged with nitrogen, and then 5 g of 2,2′-azobisisobutyronitrile as a polymerization initiator and 150 g of ethyl lactate as a solvent were added and stirred until the polymerization initiator was dissolved. . Subsequently, 9 g of methacrylic acid, 15 g of 4-hydroxyphenyl methacrylate, 25 g of n-butyl methacrylate, 25 g of isobornyl acrylate, and 24 g of tricyclo [5.2.1.0 ^2,6 ] decanyl methacrylate were slowly added. Stirring started. Subsequently, the temperature of the solution was raised to 85 ° C., and polymerization was carried out at this temperature for 6 hours. Thereafter, the temperature of the solution was raised to 90 ° C., and polymerization was further performed at this temperature for 2 hours. Thereafter, the temperature of the solution was raised to 100 ° C., and polymerization was further performed at this temperature for 1 hour.

a: methacrylic acid b: 4-hydroxyphenyl methacrylate c: isobornyl acrylate d: n-butyl acrylate e: n-butyl methacrylate f: tricyclo [5.2.1.0 ^2,6 ] decanyl methacrylate i: hydroxy Styrene j: Styrene k: 2,5-Dimethyl-2,5-hexanediol diacrylate [Example 1]
<Preparation of resin composition>
100 g of alkali-soluble resin A1 obtained in Synthesis Example 1 above, 70 g of 2,5-dimethyl-2,5-hexanediol diacrylate as a monomer having two ethylenically unsaturated double bonds, thermal acid generator Acetoxyphenylbenzylmethylsulfonium trifluoromethanesulfonate 3 g, 2,2-dimethoxy-1,2-diphenylethane-1-one 18 g as a radiation-sensitive radical polymerization initiator, 2,4,6-trimethylbenzoyldiphenyl 6 g of phosphine oxide, 0.3 g of NBX-15 (manufactured by Neos Co., Ltd.) as a surfactant, and 260 g of ethyl lactate as a solvent were mixed and stirred to obtain a uniform solution.

  This solution was filtered through a capsule filter having a pore size of 10 μm to obtain a negative radiation sensitive resin composition.

<Pattern formation>
The resin composition was applied to a copper sputter substrate using a spin coater, and then heated on a hot plate at 110 ° C. for 5 minutes to form a resin film having a thickness of 70 μm. Next, ultraviolet light of 1000 to 1500 mJ / cm ² was irradiated using an ultra high pressure mercury lamp (HBO manufactured by OSRAM, output 1,000 W) through a pattern mask. However, when using a photoacid generator (C2) as an acid generator, a filter that cuts off a wavelength near 365 nm was used, and exposure was performed at 2000 to 4000 mJ / cm ² using only g and h lines. The exposure amount was confirmed with an illuminometer (a probe UV-42 (light receiver) connected to UV-M10 (illuminometer) manufactured by Oak Manufacturing Co., Ltd.)). Development was performed using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, developed at room temperature, washed with running water, and blown with nitrogen to form a pattern. Hereinafter, the substrate on which this pattern is formed is referred to as a “patterning substrate”.

<Formation of plated objects>
The patterning substrate was subjected to an ashing treatment (output 100 W, oxygen flow rate 100 ml, treatment time 1 minute) by oxygen plasma as a pretreatment for electroplating to perform a hydrophilic treatment. Next, this substrate was subjected to electrolytic copper plating. Regarding <Examples 1 to 12, 15 to 17>, in order to dissociate the bond of the cured product with acid and heat, heat treatment was performed on a hot plate at 150 ° C. for 10 minutes. Regarding <Examples 13 and 14>, the substrate after plating was irradiated with light at a light amount of 2000 mJ / cm ² using light having a wavelength of around 365 nm of a high-pressure mercury lamp. Thereafter, heating was performed at a temperature in the range of 150 ° C. for 10 minutes. Thereafter, N-methylpyrrolidone was used as a stripping solution, and immersion was carried out at 50 to 70 ° C. with stirring for 10 to 20 minutes to obtain a test object. In addition, about Comparative Examples 1-4, it immersed while stirring for 10-20 minutes at 60 degreeC using THB-S2 (alkaline concentration 2%) by JSR Corporation, and obtained the to-be-tested object. For electrolytic plating, MicrofabCu300 manufactured by Tanaka Kikinzoku Co., Ltd. was used as the plating solution, and electrolytic plating was performed at room temperature, 3 A / dm ² for 60 minutes to form bumps having a height of about 50 μm. Hereinafter, the substrate having the plated model is referred to as “plated substrate”.

<Resolution evaluation>
The patterning substrate was observed at 1000 times using a scanning electron microscope, and the resolution was measured. Here, the resolution is “AA” when a 75 μm × 75 μm square pattern is resolved without residual resist and the side wall angle is 85 to 95 °, and a 100 μm × 100 μm square pattern has no residual resist. The case where the image was resolved and the side wall angle was 85 to 95 ° was designated as “BB”, and the case other than this was designated as “CC”.

<Adhesion evaluation>
Evaluation of adhesion between the substrate and the resist film formed from the resin composition was performed by observing a cross section of the cured resist film after development at a magnification of 1500 times using a scanning electron microscope.

  “AA” when no resist lift is observed around the opening or at the edge of the wafer, “BB” when the open pattern is less than 1 μm, and more than 1 μm, and resist lift or resist peeling. The observed case was designated as “CC”.

<Evaluation of plating resistance>
Evaluation of plating resistance is based on the fact that after the resist cured film is peeled off from the plated substrate, the shape of the plated model has transferred the resist pattern, that is, the bump width is within 103% of the resist pattern. It was carried out based on the fact that it did not ooze out from the opening. The case where the plated shaped object satisfying these two conditions is 95% or more is “AA”, the case where it is 90 to 95% is “BB”, and the case where it is 90% or less is “CC”.

<Evaluation of peelability>
Evaluation of peelability was carried out by observing a test specimen from which the cured film was peeled off with N-methylpyrrolidone at room temperature at 1500 times with a scanning electron microscope.

The case where no residue was observed after 10 minutes of peeling time was indicated as “AA”, the case where no residue was observed after 20 minutes was indicated as “BB”, and the case where the residue was observed after 20 minutes was indicated as “CC”.
These evaluation results are summarized in Table 3.

[Examples 2 to 17]
According to Table 2, the radiation sensitive resin composition was prepared like Example 1 except having changed the composition. A radiation-sensitive resin film and a cured film were formed from the obtained resin composition in the same manner as in Example 1, and the characteristics were evaluated. The results are shown in Table 3.

[Comparative Examples 1-4]
According to Table 2, the radiation sensitive resin composition was prepared like Example 1 except having changed the composition. A radiation-sensitive resin film and a cured film were formed from the obtained resin composition in the same manner as in Example 1, and the characteristics were evaluated. The results are shown in Table 3.

A3: Sumilite resin S-2 (manufactured by Sumitomo Bakelite: m-cresol / p-cresol = 60/40, weight average molecular weight in terms of polystyrene = 6000)
A4: Sumilite resin S-3 (manufactured by Sumitomo Bakelite: m-cresol / p-cresol = 60/40, weight average molecular weight in terms of polystyrene = 9400)
B1: 2,5-dimethyl-2,5-hexanediol diacrylate B2: 2,3,4,5-tetramethyl-2,3,4,5-hexanetetraol tetraacrylate B3: 2,5-dimethylhexane -2,5-bis (p-vinylphenyl carbonate)
CB1: Toa Gosei Co., Ltd. Aronix M8060 (mixture of trimethylolpropane, acrylic acid, tetrahydroxyphthalic anhydride condensation ester, trimethylolpropane triacrylate, and propylene glycol monomethyl ether acetate)
CB2: Toa Gosei Co., Ltd. Aronix M320 (Propylene oxide modified triacrylate of trimethylolpropane)
CB3: Ethylene oxide of isocyanuric acid Modified triacrylate C1-1: Acetoxyphenylbenzylmethylsulfonium trifluoromethanesulfonate C1-2: Hydroxyphenyl-o-methylbenzylmethylsulfonium trifluoromethanesulfonate C2-1: 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate D1: 2,2-dimethoxy-1,2-diphenylethane-1-one D2: 2-methyl-1- [4- (Methylthio) phenyl] -2-monforinopropanone-1
D3: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

Claims (8)

(A) an alkali-soluble resin,
(B) A divalent organic group having two or more ethylenically unsaturated double bonds and connecting at least two ethylenically unsaturated double bonds is represented by the following structural formula (1) or (2). A compound having at least one group
A negative radiation-sensitive resin composition comprising (C) a thermal acid generator , and (D) a radiation-sensitive radical polymerization initiator.

(In the above formula (1), R ¹ and R ² each independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.)

(In the above formula (2), R ³ and R ⁴ each independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.) 2. The negative radiation-sensitive radiation according to claim 1, wherein the compound (B) is at least one selected from the compounds represented by the following general formulas (4-1) and (4-2). Resin composition.

(In the above formulas (4-1) and (4-2), R ⁵ each independently represents a hydrogen atom or a methyl group, each R ⁶ independently represents a C 1-4 alkyl group, and Z ¹ And Z ² represents a methylene group which may have a substituent or an alkylene group having 2 to 4 carbon atoms.) The negative radiation-sensitive resin composition according to claim 1 or 2, wherein the compound (B) is represented by the following general formula (3).

The negative according to any one of claims 1 to 3, wherein the alkali-soluble resin (A) is a copolymer having a structural unit derived from the compound (B) according to claim 1. Type radiation sensitive resin composition. The negative radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the negative radiation-sensitive resin composition is for producing a plated model. The negative radiation-sensitive resin composition according to claim 5, wherein the plated model is a bump. The negative radiation sensitive resin composition according to any one of claims 1 to 4, wherein the negative radiation sensitive resin composition is a mask material for etching. The manufacturing method of the plating molded article on the board | substrate including following process (i)-(vi).
(I ) The process of forming the radiation sensitive resin film obtained from the negative radiation sensitive resin composition of any one of Claims 1-4 on a board | substrate.
(Ii) A step of irradiating the radiation-sensitive resin film formed in the step (i) with radiation through a photomask and radiation-curing the exposed portion.
(Iii) The process of forming a pattern in a radiation sensitive resin film by carrying out the alkali image development of the radiation sensitive resin film which passed through the process of the process (ii), and removing a non-exposed part.
(Iv) A step of forming a plated shaped article on a substrate having a radiation-sensitive resin film on which a pattern is formed by the treatment of step (iii).
(V) A step of generating an acid from the thermal acid generator (C) in the radiation- sensitive resin film that has undergone the treatment in the step (iv).
(Vi) A step of removing the radiation-sensitive resin film that has undergone the treatment of step (v) from the substrate.