JP5251470B2 - Negative photosensitive insulating resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a negative photosensitive insulating resin composition used for a surface protective film (passivation film, overcoat film), an interlayer insulating film, a planarizing film, a photosensitive adhesive, a pressure sensitive adhesive, etc. The present invention relates to an insulating cured product obtained by curing. More specifically, since a specific block copolymer is contained, it is possible to suppress warping of the substrate when forming the insulating film, and as a permanent film resist, the resolution is excellent and the remaining film ratio is high. The present invention relates to a negative photosensitive insulating resin composition that can form a cured product such as an insulating film that is high and has good electrical insulation and thermal shock properties, and a cured product obtained by curing the same.

  Conventionally, polyimide-based resins having excellent heat resistance, mechanical properties, and the like have been widely used as surface protective films, interlayer insulating films, and the like used in semiconductor devices of electronic devices. Also, various photosensitive polyimide resins having photosensitivity have been proposed in order to improve film formation accuracy with the high integration of semiconductor elements. For example, in Patent Document 1 and Patent Document 2, a composition containing a photosensitive polyimide resin in which a photocrosslinking group is introduced into a polyimide precursor by ionic bonding, and a photocrosslinking group by an ester bond in the polyimide precursor, respectively. A composition containing the introduced photosensitive polyimide resin is described. Furthermore, Patent Document 3 describes a negative photosensitive composition in which a polyfunctional acrylic compound is added to an aromatic polyimide precursor. In addition, as another resin composition that is not a composition containing a polyimide resin, Patent Document 4 discloses a photosensitive insulation containing an alkali-soluble resin having a phenolic hydroxyl group, a crosslinking agent, a photosensitive acid generator, and the like. A resin composition is described.

JP 54-145794 A Japanese Patent Laid-Open No. 03-186847 Japanese Patent Application Laid-Open No. 08-50354 JP 2003-215802 A

  However, the compositions described in Patent Documents 1 and 2 require a ring-closing step for imidization, and are solvent development, so that there is a drawback that the resolution is not sufficient. Further, the same problem as described above is pointed out even in the composition described in Patent Document 3. Furthermore, in the insulating film formed using the composition described in Patent Document 4, warpage of the substrate that occurs when the insulating film is formed is a problem.

  The present invention solves the above-mentioned problems of the prior art, more specifically, a negative photosensitive insulating resin composition for forming an insulating film or the like, and a substrate for forming the insulating film The present invention aims to provide a negative photosensitive insulating resin composition having excellent resolution, electrical insulation, and the like, and a cured product such as an insulating film formed by curing the composition. To do.

［式（１）のＲは水素原子又は炭素数１〜４のアルキル基を表す。また、式（２）のＲ^１及びＲ^２は炭素数１〜４のアルキル基を表す。］
２．前記構造単位（ａ１）と前記構造単位（ａ２）との合計を１００モル％とした場合に、該構造単位（ａ１）の含有割合が２０〜９０モル％である前記１．に記載のネガ型感光性絶縁樹脂組成物。
３．前記ブロック共重合体（Ａ）のゲルパーミエーションクロマトグラフィーで測定したポリスチレン換算の重量平均分子量が、３，０００〜３０，０００である前記１．又は２．に記載のネガ型感光性絶縁樹脂組成物。
４．前記光感応性酸発生剤（Ｂ）がヒドロキシル基含有オニウム塩である前記１．乃至３．のうちのいずれか１項に記載のネガ型感光性絶縁樹脂組成物。
５．更に密着助剤（Ｅ）を含有する前記１．乃至４．のうちのいずれか１項に記載のネガ型感光性絶縁樹脂組成物。
６．更に架橋微粒子（Ｆ）を含有し、
前記架橋微粒子は、不飽和重合性基を２個以上有する架橋性単量体と、架橋微粒子のＴｇが０℃以下となるように選択される１種又は２種以上の他の単量体とを共重合させた共重合体からなる前記１．乃至５．のうちのいずれか１項に記載のネガ型感光性絶縁樹脂組成物。
７．前記１．乃至６．のうちのいずれか１項に記載のネガ型感光性絶縁樹脂組成物が硬化されてなることを特徴とする硬化物。 The present invention is as follows.
1. (A) a block copolymer having a structural unit (a1) represented by the following formula (1) and a structural unit (a2) represented by the following formula (2);
(B) at least one compound selected from a compound (b1) having two or more alkyl etherified amino groups in the molecule, an oxirane ring-containing compound (b2), and an oxetanyl ring-containing compound (b3);
(C) a photosensitive acid generator,
(D) A negative photosensitive insulating resin composition, comprising a solvent.

[R in Formula (1) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Further, ^{R 1} and ^{R 2} of formula (2) represents an alkyl group having 1 to 4 carbon atoms. ]
2. 1. When the total of the structural unit (a1) and the structural unit (a2) is 100 mol%, the content of the structural unit (a1) is 20 to 90 mol%. Negative photosensitive insulating resin composition as described in 1.
3. The polystyrene-converted weight average molecular weight measured by gel permeation chromatography of the block copolymer (A) is 3,000 to 30,000. Or 2. Negative photosensitive insulating resin composition as described in 1.
4). 1. The light-sensitive acid generator (B) is a hydroxyl group-containing onium salt. To 3. The negative photosensitive insulating resin composition of any one of these.
5. Furthermore, the said 1. containing adhesion assistant (E). To 4. The negative photosensitive insulating resin composition of any one of these.
6). Furthermore, it contains crosslinked fine particles (F) ,
The crosslinked fine particles include a crosslinkable monomer having two or more unsaturated polymerizable groups, and one or more other monomers selected so that the Tg of the crosslinked fine particles is 0 ° C. or lower. 1. A copolymer obtained by copolymerizing To 5. The negative photosensitive insulating resin composition of any one of these.
7. 1 above. To 6. A cured product obtained by curing the negative photosensitive insulating resin composition according to any one of the above.

Since the negative photosensitive insulating resin composition of the present invention contains a specific block copolymer, warping of the substrate when forming the insulating film is sufficiently suppressed, and excellent resolution and electrical properties are achieved. A cured product having insulation or the like can be formed.
Further, when the total content of the structural unit (a1) and the structural unit (a2) is 100 mol%, when the content ratio of the structural unit (a1) is 20 to 90 mol%, excellent alkali developability is obtained. As a result, the stress of the obtained insulating film can be sufficiently reduced.
Furthermore, when the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of the block copolymer (A) is 3,000 to 30,000, the resolution, thermal shock resistance, and heat resistance of the insulating film And the remaining film rate can be further improved.
Further, when the photosensitive acid generator (C) is a hydroxyl group-containing onium salt, the reaction between the compound (B) and the block copolymer (A) or the phenolic low molecular compound is promoted, and the negative type This pattern can be easily formed.
Furthermore, when the adhesion assistant (E) is contained, the adhesion between the substrate and the cured product (cured film) can be further improved.
Moreover, when a crosslinked fine particle (F) is contained, durability, thermal shock property, etc. of hardened | cured material (cured film) can be improved more.
The cured product of the present invention is obtained by curing the negative photosensitive insulating resin composition of the present invention, and has excellent resolution, electrical insulation and the like.

  The present invention will be described in detail below. In the present specification, “(meth) acryl” means “acryl” or “methacryl”. “(Meth) acrylate” means “acrylate” or “methacrylate”.

[1] Negative photosensitive insulating resin composition The negative photosensitive insulating resin composition of the present invention (hereinafter sometimes referred to as “resin composition”) is represented by (A) the above formula (1). A block copolymer having the structural unit (a1) and the structural unit (a2) represented by the formula (2), (B) at least two alkyl etherified amino group-containing compounds in the molecule ( b1), at least one compound selected from the oxirane ring-containing compound (b2) and the oxetanyl ring-containing compound (b3), (C) a light-sensitive acid generator, and (D) a solvent.

(A) Block copolymer The “block copolymer (A)” in the present invention is an alkali-soluble resin, represented by the structural unit (a1) represented by the formula (1) and the formula (2). Structural unit (a2). The structural unit (a1) is a hydroxystyrene unit or a hydroxystyrene alkyl derivative unit (provided that the alkyl group is a methyl group, an ethyl group, a propyl group, or a butyl group, and may be linear when it is a propyl group and a butyl group). And the structural unit (a2) is a dialkylsiloxane unit (provided that the alkyl group is a methyl group, an ethyl group, a propyl group or a butyl group, and is a propyl group or a butyl group). May be linear or branched.).

  The block copolymer (A) is AB type, that is, the other block is bonded to one end of one of the block consisting of the structural unit (a1) and the block consisting of the structural unit (a2). A block copolymer may be used, and the other block is bonded to both ends of either one of the ABA type, that is, the block composed of the structural unit (a1) and the block composed of the structural unit (a2). A block copolymer may be used. Of these, AB type block copolymers are preferred because of their higher resolution. The block copolymer (A) is usually an AB type block copolymer in which a block composed of the structural unit (a1) and a block composed of the structural unit (a2) are combined.

Examples of the monomer used for forming the structural unit (a1) include 4-hydroxystyrene and 4-hydroxy-α-methylstyrene.
In addition, R ^x ₂ Si (OR ^y ) ₂ can be used as a monomer used for forming the structural unit (a2). Here, R ^x is a methyl group, an ethyl group, a propyl group, or a butyl group, and the two R ^{x s} may be the same group or different. Moreover, when it is a propyl group and a butyl group, it may be linear and may be branched. R ^x is an alkyl group that becomes R ¹ and R ^{2 of} the structural unit (a2) after polymerization. Furthermore, R ^{y is} also a methyl group, an ethyl group, a propyl group or a butyl group, and the two R ^{x s} may be the same group or different. Moreover, when it is a propyl group and a butyl group, it may be linear and may be branched. Examples of the monomer represented by R ^x ₂ Si (OR ^y ) ₂ include dimethyldimethoxysilane, diethyldimethoxysilane, and dipropyldimethoxysilane.

  The content ratio of the structural unit (a1) and the structural unit (a2) constituting the block copolymer (A) is not particularly limited, but the total of the structural unit (a1) and the structural unit (a2) is 100 mol%. In this case, the structural unit (a1) is preferably 20 to 90 mol%, more preferably 40 to 80 mol%. Moreover, it is preferable that it is 10-80 mol%, and, as for a structural unit (a2), it is more preferable that it is 20-60 mol%.

  Furthermore, the weight average molecular weight measured by gel permeation chromatography of the block copolymer (A) is not particularly limited, but from the viewpoints of resolution, thermal shock, heat resistance, and remaining film ratio of the insulating film, 3 3,000 or more, more preferably 3,000 to 30,000.

  Furthermore, the content ratio of the block copolymer (A) contained in the negative photosensitive insulating resin composition is not particularly limited, but when the total amount of other components excluding the solvent (D) is 100% by mass. 30 to 90% by mass, and more preferably 40 to 80% by mass. When the content ratio of the block copolymer (A) is 30 to 90% by mass, the insulating film formed using the negative photosensitive insulating resin composition has sufficient developability with an alkaline aqueous solution. Therefore, it is preferable.

  Moreover, the phenolic low molecular weight compound may be mix | blended with the resin composition. As this phenolic low molecular weight compound, for example, 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 -Methylethyl] 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-hydro Shifeniru) ethane and the like. These phenolic low molecular weight compounds may be used alone or in combination of two or more.

  The compounding amount of the phenolic low molecular compound is preferably 40 parts by mass or less, and more preferably 1 to 30 parts by mass, when the block copolymer (A) is 100 parts by mass.

  The block copolymer (A) can be produced by a radical polymerization method using a polymer radical polymerization initiator having the structure of the structural unit (a2). Examples of commercially available polymer radical polymerization initiators include trade name “VPS-1001” manufactured by Wako Pure Chemical Industries, Ltd.

Polymerization solvents include amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, hydrocarbon solvents such as benzene, toluene, xylene, hexane and cyclohexane, ester solvents such as γ-butyrolactone and ethyl lactate, cyclohexyl Ketone solvents such as benzophenone and cyclohexanone can be used.
Moreover, the usage-amount of a radical polymerization initiator can be suitably determined with the ratio of the structural unit (a2) to introduce | transduce. The reaction temperature is determined by the energy required to cleave the end-protected living group and can be, for example, 60-200 ° C.

(B) Specific compound acting as a crosslinking agent Compound having two or more alkyl etherified amino groups in the molecule (hereinafter referred to as “amino group-containing compound”) (b1), oxirane ring-containing compound (b2 ) And the oxetanyl ring-containing compound (b3) act as a crosslinking agent, and as this compound (B), at least one compound selected from (b1), (b2) and (b3) can be used.

The amino group-containing compound (b1) is not particularly limited. For example, the activity in nitrogen compounds such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea, etc. Examples thereof include compounds in which all or part (at least two) of methylol groups (CH ₂ OH groups) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, and these may be the same as or different from each other. In addition, the methylol group that is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.

The oxirane ring-containing compound (b2) is not particularly limited as long as it contains an oxirane ring in the molecule. For example, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol type epoxy resin, a trisphenol type Epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. Is mentioned.
The oxetanyl ring-containing compound (b3) is not particularly limited as long as the oxetanyl ring is contained in the molecule, and examples thereof include a compound represented by the following general formula (b3-1), the following general formula ( Examples thereof include compounds represented by b3-3) and compounds represented by the following general formula (b3-2).

In each of the general formulas (b3-1) to (b3-3), R ³ is an alkyl group such as a methyl group, an ethyl group, or a propyl group, and R ⁴ is an alkylene such as a methylene group, an ethylene group, or a propylene group. R ⁵ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a hexyl group; an aryl group such as a phenyl group or a xylyl group; a dimethylsiloxane residue represented by the following formula (i); a methylene group; An alkylene group such as an ethylene group or a propylene group; a phenylene group; or a group represented by the following formulas (ii) to (vi): i is an integer of 1 to 4, which is equal to the valence of R ⁵ .

In the formulas (i) and (ii), x and y are each independently an integer of 0 to 50.
Z in the formula (iii) is a single bond or a divalent group represented by —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or —SO ₂ —. It is a group.

  Specific examples of the compounds represented by the general formulas (b3-1) to (b3-3) include 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene (trade name “ OXT-121 ", manufactured by Toa Gosei Co., Ltd.), 3-ethyl-3-{[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (trade name" OXT-221 ", manufactured by Toa Gosei Co., Ltd.), bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] propane, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl ] Sulfone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ketone, bis [(3-ethyl-3-oxetanylmethoxy) methyl- Nenyl] hexafluoropropane, tri [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, tetra [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and the following chemical formulas (b3-4) to (b3) -8) and the like.

  In addition to these compounds, compounds having a high molecular weight polyvalent oxetane ring can be used. Specific examples include oxetane oligomers (trade name “Oligo-OXT”, manufactured by Toagosei Co., Ltd.) and compounds represented by the following chemical formulas (b3-9) to (b3-11). .

  P, q, and s in the formulas (b3-9) to (b3-11) are each independently an integer of 0 to 10,000.

  Among these oxetanyl ring-containing compounds (b3), 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene (trade name “OXT-121”, manufactured by Toagosei Co., Ltd.), 3-ethyl-3-{[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (trade name “OXT-221”, manufactured by Toagosei Co., Ltd.) is preferable.

  As the compound (B), an amino group-containing compound (b1) and an oxirane ring-containing compound (b2) are preferable, and an amino group-containing compound (b1) and an oxirane ring-containing compound (b2) are more preferably used in combination. Moreover, when using together, when a sum total is 100 mass%, it is preferable that an oxirane ring containing compound (b2) is 50 mass% or less, and it is more preferable that it is 5-40 mass%. The combined use at such a mass ratio is preferable because a cured product such as an insulating film excellent in chemical resistance can be formed without impairing high resolution.

  The content of the compound (B) is preferably 1 to 100 parts by mass and more preferably 5 to 50 parts by mass when the block copolymer (A) is 100 parts by mass. When the content of the compound (B) is 1 to 100 parts by mass, the curing reaction proceeds sufficiently, the formed insulating film has a high resolution and a good pattern shape, and has heat resistance and electrical insulation. It is preferable because of its superiority.

(C) Photosensitive acid generator Photosensitive acid generator (C) [hereinafter referred to as “acid generator (C)”. ] Is a compound that generates an acid upon irradiation with radiation or the like, and by the catalytic action of this acid, the alkyl ether group in the compound (B) and the phenol in the block copolymer (A) or the phenolic low molecular compound A negative pattern is formed when the ring reacts with dealcoholization. The acid generator (C) is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation or the like. For example, an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and diazomethane. Compounds and the like.

  Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Specific examples of preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluorochlorosulfonate, Phenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7-di-n- Butoxynaphthyltetrahydrothiophenium trifluorolo Tan sulfonate, and the like.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -s-triazine. S-triazine derivatives such as 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, and the like.

  Examples of diazoketone compounds include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and specific examples include 1,2-naphthoquinonediazide-4-sulfonic acid esters of phenols. Compounds and the like.

  Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (Phenacylsulfonyl) methane and the like.

  Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred specific examples include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl p-toluene sulfonate, and the like.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like.

Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.
As the acid generator (C), an onium salt compound is preferable, and a hydroxyl group-containing onium salt compound is more preferable.
These acid generators (C) may be used alone or in combination of two or more.

  The content of the acid generator (C) is blended with a block copolymer (A) or a phenolic low molecular weight compound from the viewpoint of ensuring the sensitivity, resolution, pattern shape, etc. of the negative photosensitive insulating resin composition. When the total is 100 parts by mass, it can be 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass. When the content of the acid generator (C) is less than 0.1 parts by mass, curing may be insufficient and heat resistance may be reduced. On the other hand, when it exceeds 10 parts by mass, the transparency to radiation is lowered, and the pattern shape may be deteriorated.

(D) Solvent By including the solvent (D) in the negative photosensitive insulating resin composition, the handleability of the resin composition can be improved, and the viscosity and storage stability can be adjusted. The solvent (D) is not particularly limited, and examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Propylene glycol monoalkyl ethers such as ether and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether; Propylene glycol monomethyl ether acetate and propylene glycol Propylene glycol monoalkyl ether acetates such as rumonoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; methyl lactate, ethyl lactate Lactic acid esters such as ethyl acetate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate Aliphatic carboxylic acid esters such as isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and 3-ethoxypropionate , Other esters such as ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolacun. These solvents may be used alone or in combination of two or more.

(E) Adhesion aid The negative photosensitive insulating resin composition may further contain an adhesion aid (E) in order to improve the adhesion to the substrate. Examples of the adhesion assistant (E) include a functional silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate and the like. These adhesion assistants may be used alone or in combination of two or more.

  The content of the adhesion aid (E) is not particularly limited, but when the block copolymer (A) is 100 parts by mass, it is preferably 0.2 to 10 parts by mass, and 0.5 to 8 parts by mass. More preferably, it is a part. If the content of the adhesion assistant (E) is 0.2 to 10 parts by mass, it is preferable because the resin composition has excellent storage stability and good adhesion.

(F) Crosslinked fine particles The negative photosensitive insulating resin composition may further contain crosslinked fine particles (F) in order to improve the durability and thermal shock resistance of the cured product. Crosslinked fine particles (F) has a glass transition temperature (Tg) of Ri der 0 ℃ less, crosslinkable monomer having two or more unsaturated polymerizable group (hereinafter, simply referred to as "crosslinking monomer".) When, composed of one or more "other monomer" and copolymers obtained by copolymerizing a Tg are selected such that 0 ℃ less crosslinked fine particles (F). In particular, two or more other monomers are used in combination, and at least one of the other monomers is a functional group other than a polymerizable group such as a carboxyl group, an epoxy group, an amino group, an isocyanate group, or a hydroxyl group. It is more preferable to have a group.

  Examples of the crosslinkable monomer include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene Examples thereof include compounds having a plurality of polymerizable unsaturated groups such as glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate. Of these, divinylbenzene is preferred.

  The crosslinkable monomer used for producing the crosslinked fine particles (F) is preferably 1 to 20% by mass, based on 100% by mass of all monomers used for copolymerization, and 2 to 10%. More preferably, it is mass%.

  Examples of other monomers include diene compounds such as butadiene, isoprene, dimethylbutadiene, chloroprene and 1,3-pentadiene; (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxy. Unsaturated nitrile compounds such as acrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumarate dinitrile; (meth) acrylamide, N, N′-methylenebis (meth) acrylamide N, N′-ethylenebis (meth) acrylamide, N, N′-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide Unsaturated amides such as N, N-bis (2-hydroxyethyl) (meth) acrylamide, crotonic acid amide, cinnamic acid amide; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylate compounds such as propyl, butyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate; styrene, α- Aromatic vinyl compounds such as methylstyrene, o-methoxystyrene, p-hydroxystyrene, p-isopropenylphenol; diglycidyl ether of bisphenol A, diglycidyl ether of glycol, (meth) acrylic acid, hydroxyalkyl (meth) With acrylate etc. Epoxy groups such as epoxy (meth) acrylates obtained by reaction, urethane (meth) acrylates obtained by reaction of hydroxyalkyl (meth) acrylate and polyisocyanate, glycidyl (meth) acrylate, (meth) allyl glycidyl ether, etc. Containing unsaturated compounds; (meth) acrylic acid, itaconic acid, succinic acid-β- (meth) acryloxyethyl, maleic acid-β- (meth) acryloxyethyl, phthalic acid-β- (meth) acryloxyethyl, Unsaturated acid compounds such as hexahydrophthalic acid-β- (meth) acryloxyethyl; Amino group-containing unsaturated compounds such as dimethylamino (meth) acrylate and diethylamino (meth) acrylate; (meth) acrylamide, dimethyl (meth) Insaturation containing amide groups such as acrylamide Japanese compounds; hydroxyl group-containing unsaturated compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.

  Among these other monomers, butadiene, isoprene, (meth) acrylonitrile, (meth) acrylic acid alkyl esters, styrene, p-hydroxystyrene, p-isopropenylphenol, glycidyl (meth) acrylate, (meth ) Acrylic acid, hydroxyalkyl (meth) acrylates and the like are preferable.

In the production of the crosslinked fine particles (F), at least one diene compound, specifically, butadiene is preferably used as the other monomer. Such a diene compound is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass, when the total amount of monomers used for copolymerization is 100% by mass. If the diene compound is 20 to 80% by mass, the crosslinked fine particles (F) become rubbery soft fine particles, and it is possible to prevent cracks from occurring in a cured product such as an insulating film formed. It can be set as the insulating film etc. which are excellent in durability.
These crosslinked fine particles (F) may be used alone or in combination of two or more.

Moreover, the average particle diameter of crosslinked fine particles (F) is 30-500 nm normally, Preferably it is 40-200 nm, More preferably, it is 50-120 nm. The method for controlling the particle size of the crosslinked fine particles (F) is not particularly limited. For example, when the crosslinked fine particles are synthesized by emulsion polymerization, the number of micelles during emulsion polymerization is controlled by the amount of the emulsifier used. The diameter can be adjusted.
The average particle diameter of the crosslinked fine particles (F) was measured by diluting the dispersion of the crosslinked fine particles according to a conventional method using a light scattering flow distribution measuring device (manufactured by Otsuka Electronics Co., Ltd., model “LPA-3000”). Value.

  Furthermore, the content of the crosslinked fine particles (F) is preferably 0.5 to 50 parts by mass and preferably 1 to 30 parts by mass when the block copolymer (A) is 100 parts by mass. More preferred. When the content of the crosslinked fine particles (F) is 0.5 to 50 parts by mass, the compatibility with other components or dispersibility is excellent, and the thermal shock resistance and heat resistance of the formed insulating film and the like are improved. be able to.

Other Additives The negative photosensitive insulating resin composition of the present invention can contain other additives to the extent that the characteristics of the present invention are not impaired, if necessary. Examples of such other additives include inorganic fillers, sensitizers, quenchers, and leveling agents.

Manufacturing method The manufacturing method of the negative photosensitive insulating resin composition of this invention is not specifically limited, It can manufacture by a well-known method. Moreover, it can manufacture also by throwing in each sample ingredient | tool and stirring the sample bottle on the wave rotor.

[2] Cured product The cured product of the present invention is obtained by curing the negative photosensitive insulating resin composition of the present invention.
The cured product using the negative photosensitive insulating resin composition of the present invention is excellent in electrical insulation, thermal shock, etc., and the insulating film, which is one type of cured product, has a high residual film ratio and excellent resolution. It has sex etc. Therefore, the cured product can be suitably used as a surface protective film, a planarizing film, an interlayer insulating film, a photosensitive adhesive, a pressure sensitive adhesive, and the like for electronic components such as semiconductor elements and semiconductor packages.

  The cured product of the present invention is obtained by coating the negative photosensitive insulating resin composition of the present invention on a support (a copper foil with resin, a copper-clad laminate, a silicon wafer provided with a metal sputtered film, an alumina substrate, or the like). , Dried, volatilized solvent, etc. to form a coating film, and then exposed through a desired mask pattern, heat-treated (hereinafter referred to as “PEB”), The reaction between the union (A) and the compound (B) is promoted, and then developed with an alkaline developer to dissolve and remove the unexposed areas to form a desired pattern. It can be formed by heat treatment for expression.

  As a method of applying the resin composition to the support, for example, various coating methods such as a dipping method, a spray method, a bar coating method, a roll coating method, or a spin coating method can be employed. Further, the thickness of the coating film can be appropriately controlled by adjusting the coating means, the solid content concentration of the resin composition solution, the viscosity, and the like.

Examples of radiation used for exposure include ultraviolet rays, electron beams, and laser beams emitted from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, h-line steppers, i-line steppers, gh-line steppers, and ghi-line steppers. Etc. The exposure amount can be appropriately set by the light source and the resin film thickness and the like to be used, for example, when the ultraviolet light emitted from a high pressure mercury lamp, the resin thickness 1~50μm, 100~20,000J / ^{m 2} Can be about.

  After the exposure, the PEB treatment is carried out in order to accelerate the curing reaction between the block copolymer (A) and the compound (B) by the generated acid. The PEB conditions vary depending on the blending amount and film thickness of the negative photosensitive insulating resin composition, but are usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes. Thereafter, development is performed with an alkaline developer, and a desired pattern is formed by dissolving and removing unexposed portions. Examples of the developing method include shower developing method, spray developing method, immersion developing method, paddle developing method and the like. The development conditions are usually about 20 to 40 ° C. and about 1 to 10 minutes.

  Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, and choline is dissolved in water so as to have a concentration of 1 to 10% by mass. Can be mentioned. In addition, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol, a surfactant, and the like can be blended in the alkaline aqueous solution. In addition, after developing with an alkaline developer, it is washed with water and dried.

  Furthermore, in order to fully develop the characteristics as an insulating film after development, it can be sufficiently cured by heat treatment. Such curing conditions are not particularly limited, but can be cured by heating at a temperature of 50 to 250 ° C. for about 30 minutes to 10 hours depending on the use of the cured product. Moreover, in order to advance hardening fully or to prevent the deformation | transformation of the formed pattern shape, it can also heat in two steps, for example, at the temperature of 50-120 degreeC in a 1st step, 5 minutes-2 It can also be cured by heating for about an hour and further heating for about 10 minutes to 10 hours at a temperature of 80 to 250 ° C. Under such curing conditions, a general oven, an infrared furnace, or the like can be used as a heating facility.

  If the negative photosensitive insulating resin composition of the present invention is used, an electronic component such as a semiconductor element (substrate with circuit) as shown in FIGS. 1 and 2 can be formed. That is, the metal pad 2 is formed in a pattern on the substrate 1, and then the cured insulating film 3 is formed in a pattern using the resin composition, and then the metal wiring 4 is formed in the pattern. 1 can be produced. Further, by forming a cured insulating film 5 on the substrate, a circuit board as shown in FIG. 2 can be produced.

Hereinafter, the present invention will be described specifically by way of examples.
[1] Production of block copolymer Production Example 1
Polymer mass polymerization having a dimethylsiloxane structure was initiated by dissolving 50 parts by mass of pt-butoxystyrene in 150 parts by mass of propylene glycol monomethyl ether under a nitrogen stream and maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. Polymerization was performed for 10 hours using 10 parts by mass of an agent (trade name “VPS-1001” manufactured by Wako Pure Chemical Industries, Ltd.). 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 4-hydroxystyrene. Next, 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 the block copolymer [4-hydroxystyrene / dimethylsiloxane copolymer ( Hereinafter, "copolymer (A-1)") was obtained.
When the composition of the copolymer (A-1) was analyzed by ¹³ C-NMR, the proportion of the structural unit (a1) derived from 4-hydroxystyrene was 80 mol%, and the structural unit (a2) derived from dimethylsiloxane. The ratio was 20 mol%. Moreover, the polystyrene equivalent weight average molecular weight (Mw) of the copolymer (A-1) was 5,000, and molecular weight distribution was 1.3.

For ¹³ C-NMR analysis, a model “JNM-EX270” manufactured by JEOL Ltd. was used. For measurement of Mw and Mn, GPC of the model “HLC-8220GPC” manufactured by Tosoh Corporation was used. Specifically, two G2000HXL, one G3000HXL and one G4000HXL were used as columns, flow rate: 1.0 ml / min, elution solvent; tetrahydrofuran, column temperature; It was measured by GPC using dispersed polystyrene as a standard. The molecular weight distribution (Mw / Mn) was calculated based on the measured values of Mw and Mn.

Production Examples 2-3 and Comparative Production Example 1
Production Example 2
Except having changed the quantity ratio with pt-butoxystyrene and the polymer radical polymerization initiator which has a dimethylsiloxane structure (the product name "VPS-1001" by Wako Pure Chemical Industries, Ltd.), it carried out similarly to manufacture example 1 Then, an AB type block copolymer was produced [referred to as “copolymer (A-2)”. ]. When the copolymer (A-2) was analyzed in the same manner as in Production Example 1, the proportion of the structural unit (a1) derived from 4-hydroxystyrene was 80 mol%, and the structural unit (a2 derived from dimethylsiloxane). The copolymer (A-2) had a polystyrene equivalent weight average molecular weight of 10,000 and a molecular weight distribution of 1.4.

Production Example 3
Except having changed the quantity ratio with pt-butoxystyrene and the polymer radical polymerization initiator which has a dimethylsiloxane structure (the product name "VPS-1001" by Wako Pure Chemical Industries, Ltd.), it carried out similarly to manufacture example 1 An AB type block copolymer was produced [referred to as “copolymer (A-3)”. ]. When the copolymer (A-3) was analyzed in the same manner as in Production Example 1, the proportion of the structural unit (a1) derived from 4-hydroxystyrene was 60 mol%, and the structural unit (a2 derived from dimethylsiloxane). ) Was 40 mol%. The copolymer (A-3) had a polystyrene equivalent weight average molecular weight of 5,000 and a molecular weight distribution of 1.3.

Comparative production example 1
An AB type block copolymer was produced in the same manner as in Production Example 1 except that styrene and a radical polymerization initiator [AIBN (azobisisobutyronitrile)] were used instead of the polymer radical polymerization initiator. This is designated as “Copolymer AR-1.” ]. When the copolymer (AR-1) was analyzed in the same manner as in Production Example 1, the proportion of the structural unit (ar1) derived from 4-hydroxystyrene was 80 mol%, and the structural unit (ar2) derived from styrene. The ratio was 20 mol%. The copolymer (AR-1) had a polystyrene equivalent weight average molecular weight of 10,000 and a molecular weight distribution of 1.5.

[2] Production of negative photosensitive insulating resin composition Example 1
As shown in Table 1, 100 parts by mass of copolymer (A-1), 15/5 parts by mass of specific compound (crosslinking agent) (B-1 / B-2), and acid generator (C-1) 1 part by mass, 150 parts by mass of the solvent (D-1), 3 parts by mass of the adhesion assistant (E-1), and 0.1 part by mass of the surfactant (G-1). The components were dissolved in a solvent to produce a negative photosensitive insulating resin composition.

Examples 2 to 6 and Comparative Example 1
The copolymer shown in Table 1, a specific compound (crosslinking agent), an acid generator, a solvent, an adhesion aid, and a surfactant are blended so as to have the mass ratio shown in Table 1, and negative photosensitive properties are obtained. An insulating resin composition was produced.
In addition to the above components, in Example 5, 5 parts by mass of a phenolic low molecular compound [phenol compound (a-1)] was blended. Moreover, in Example 6, 5 mass parts of crosslinked fine particles (F-1) were mix | blended.

Details of the other components excluding the copolymer among the components described in Table 1 are as follows.
(A) Phenol compound a-1: 1,1-bis (4-hydroxyphenyl) -1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethane (B) Specific compound (Crosslinking agent)
B-1: Hexamethoxymethylated melamine (Mitsui Cytec Co., Ltd., trade name “Cymel 300”)
B-2: Propylene glycol diglycidyl ether (manufactured by Kyoeisha, trade name “Epolite 70P”)
B-3: Pentaerythritol glycidyl ether (manufactured by Nagase Chemtech, trade name “Denacol EX411”)
B-4: 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene (trade name “OXT-121” manufactured by Toagosei Co., Ltd.)
(C) Photosensitive acid generator C-1: 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine (trade name “manufactured by Sanwa Chemical Co., Ltd.” TFE-triazine ")
C-2: 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate (manufactured by Sun Apro, trade name “CPI-210S”)
(D) Solvent D-1: Ethyl lactate (E) Adhesion aid E-1: γ-glycidoxypropyltrimethoxysilane (trade name “S-510” manufactured by Chisso Corporation)
(F) Crosslinked fine particles F-1: butadiene / styrene / hydroxybutyl methacrylate / methacrylic acid /
Divinylbenzene = 60/20/12/6/2 (mass%), average particle size; 65 nm
(G) Surfactant G-1: Neos, trade name “FTX-218”

[3] Evaluation of photosensitive insulating resin composition The characteristics of the negative photosensitive insulating resin compositions of Examples 1 to 6 and Comparative Example 1 were evaluated according to the following methods. The results are shown in Table 2.
(1) Resolution A 6-inch silicon wafer was spin-coated with a negative photosensitive insulating resin composition, and then heated at 110 ° C. for 3 minutes using a hot plate to produce a uniform resin film having a thickness of 20 μm. . Next, using an aligner (model “MA-100” manufactured by Karl Suss), UV light irradiated from a high-pressure mercury lamp through a pattern mask was exposed so that the exposure amount at a wavelength of 365 nm was 500 mJ / cm ² . . Thereafter, the substrate was heated (PEB) at 110 ° C. for 3 minutes using a hot plate, and immersed and developed at 23 ° C. for 120 seconds using a 2.38 mass% aqueous tetramethylammonium hydroxide solution. The minimum dimension of the pattern thus obtained is taken as the resolution.

(2) Stress of insulating film A negative photosensitive insulating resin composition is spin-coated on an 8-inch silicon wafer, and then heated at 110 ° C. for 3 minutes using a hot plate to form a uniform resin film having a thickness of 20 μm. Was made. Next, using an aligner (manufactured by Karl Suss, model “MA-100”), ultraviolet light irradiated from a high-pressure mercury lamp was exposed so that the exposure amount at a wavelength of 365 nm was 500 mJ / cm ² . Thereafter, the substrate was heated (PEB) at 110 ° C. for 3 minutes using a hot plate, and immersed and developed at 23 ° C. for 120 seconds using a 2.38 mass% aqueous tetramethylammonium hydroxide solution. Then, it heated at 190 degreeC for 1 hour using the convection type oven, the resin coating film was hardened, and the insulating film was formed. And the stress difference of the board | substrate before and behind insulating film formation was measured with the stress measuring device (FLX-2320-s by the TOHO technology (old technology possession KLA-Tencor) company), and the stress was evaluated.

(3) Electrical Insulation As shown in FIG. 3, a negative photosensitive insulating resin composition is applied to a base material 8 for insulation evaluation having a patterned copper foil 7 on a substrate 6, and hot The substrate was heated at 110 ° C. for 3 minutes using a plate to prepare a substrate having a resin coating film having a thickness of 10 μm on the copper foil 7. Then, it heated at 190 degreeC for 1 hour using the convection-type oven, the resin coating film was hardened, and the cured film was formed. This base material 8 is put into a migration evaluation system (model “AEI, EHS-221MD” manufactured by Tabai Espec Co., Ltd.) and treated for 200 hours under conditions of a temperature of 121 ° C., a humidity of 85%, a pressure of 1.2 atmospheres, and an applied voltage of 5V. did. Next, the resistance value (Ω) of the test substrate was measured to evaluate the insulation.

  According to the result of Table 2, it turned out that Examples 1-6 are small in the stress of an insulating film, and are excellent in resolution and electrical insulation.

It is a schematic diagram explaining the cross section of a semiconductor element. It is a schematic diagram explaining the cross section of a semiconductor element. It is a schematic diagram explaining the base material for electrical insulation evaluation.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1; Board | substrate, 2; Metal pad, 3; Curing insulating film, 4; Metal wiring, 5; Curing insulating film, 6: Board | substrate, 7; Copper foil, 8: Base material for insulation evaluation.

Claims (7)

(A) a block copolymer having a structural unit (a1) represented by the following formula (1) and a structural unit (a2) represented by the following formula (2);
(B) at least one compound selected from a compound (b1) having two or more alkyl etherified amino groups in the molecule, an oxirane ring-containing compound (b2), and an oxetanyl ring-containing compound (b3);
(C) a photosensitive acid generator,
(D) A negative photosensitive insulating resin composition, comprising a solvent.

[R in Formula (1) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Further, ^{R 1} and ^{R 2} of formula (2) represents an alkyl group having 1 to 4 carbon atoms. ]   2. The negative type according to claim 1, wherein the content ratio of the structural unit (a1) is 20 to 90 mol% when the total of the structural unit (a1) and the structural unit (a2) is 100 mol%. Photosensitive insulating resin composition.   The negative photosensitive insulating resin composition according to claim 1 or 2, wherein the block copolymer (A) has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of 3,000 to 30,000. .   The negative photosensitive insulating resin composition according to any one of claims 1 to 3, wherein the photosensitive acid generator (B) is a hydroxyl group-containing onium salt.   Furthermore, the negative photosensitive insulating resin composition of any one of Claims 1 thru | or 4 containing a close_contact | adherence adjuvant (E). Furthermore, it contains crosslinked fine particles (F) ,
The crosslinked fine particles include a crosslinkable monomer having two or more unsaturated polymerizable groups, and one or more other monomers selected so that the Tg of the crosslinked fine particles is 0 ° C. or lower. The negative photosensitive insulating resin composition according to any one of claims 1 to 5, comprising a copolymer obtained by copolymerizing the above.   A cured product obtained by curing the negative photosensitive insulating resin composition according to any one of claims 1 to 6.

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