Patent Application
20200326624
The present invention relates to a positive photosensitive resin composition, a patterning process capable of developing with an alkaline aqueous solution that uses the positive photosensitive resin composition, a method of forming a cured film, an interlayer insulation film, a surface protective film, and an electronic component.
As miniaturization and higher performance of various electronic devices such as personal computers, digital cameras, and mobile phones advance, a demand for further miniaturization, thinning and higher density rapidly are increasing. Accompanying these, it is demanded for interlayer insulation films and surface protective films of semiconductor devices to combine excellent electric characteristics, heat resistance, mechanical characteristics and the like.
In a high-density mounting technology such as a three-dimensional lamination, as a photosensitive insulation material capable of forming a pattern on a substrate, a polyimide film has been utilized as a protective film or an insulation layer, its insulation property, mechanical characteristics, and adhesiveness with a substrate are kept drawing attention, and its development is active even now.
So far, as a photosensitive polyimide material, a material that utilizes polyamic acid that is a precursor of the polyimide, for example, one in which a photosensitive group is introduced in a carboxyl group of the polyamic acid by an ester bond (Patent Document 1, Patent Document 2) has been proposed. However, in these proposals, since in order to obtain a polyimide film that is a target, an imidization treatment at a high temperature exceeding 300° C. after a patterned film is formed is necessary, in order to endure the high temperature, there were problems such that an undercoat base material is restricted, or copper of a wiring is oxidized.
As an improvement of this, in order to make a post-curing temperature lower, a photosensitive polyimide that uses a pre-imidized and solvent-soluble resin has been proposed (Patent Document 3, Patent Document 4). In the Patent Document 3, a negative photosensitive composition having a closed-ring polyimide has been proposed and the pattern-forming property and the adhesiveness are described. However there is no description of the mechanical strength.
Although the Patent Document 4 proposes a positive photosensitive resin composition that uses an alkali-soluble and closed-ring polyimide, a photoacid generator and a heat crosslinking agent having a methylol group, there was room for improving a value of breaking elongation when cured at low temperatures.
Furthermore, in the Patent Document 5, a positive photosensitive resin composition that uses an alkali-soluble polyimide containing a diamine residue having a triazine or diazine skeleton in a molecular skeleton, an alkali-soluble polyimide having a glass transition temperature different from that of the polyimide, and a photoacid generator have been proposed. Although the resin composition is a material having excellent adhesiveness with copper wire, there was room for improving the mechanical characteristics, in particular, the breaking elongation.
Furthermore, although Patent Document 6 proposes a polyimide resin composition in which a polyimide having a carboxyl group in a molecule skeleton and a polyimide containing a heterocyclic skeleton having a nitrogen atom at a molecular terminal are combined, there is no description of a photosensitive resin composition. Furthermore, in the case of using the composition described in the Patent Document 6 as an insulation material that is used in the surface protective film or the interlayer insulation film, the carboxyl group contained in the resin which remains in a cured film causes copper migration, therefore, it is necessary to completely block the carboxyl group. There, in order to block the carboxyl group, for example, an epoxy type crosslinking agent or the like is used. However, since the carboxyl group and the epoxy type crosslinking agent are very reactive to cause a problem of storage stability, application of the relevant composition in the present field is difficult.
Furthermore, in Patent Document 7, a positive photosensitive resin composition that uses an alkali-soluble polyamide-imide, and a photoacid generator has been proposed. Although the resin composition is a material excellent in solvent solubility and resolution, there was a room for improving the mechanical characteristics, in particular, the breaking elongation.
Thus, hereafter, since as higher densification and higher integration of chips proceed, the miniaturization of patterns in a rewiring technology of the insulation protective film further proceeds, as the photosensitive resin composition, a composition that can realize high resolution without damaging excellent features such as the mechanical characteristics of a pattern and a protective film and adhesiveness obtained by heating is demanded strongly.
Patent Literature 1: Japanese Patent Laid-Open Publication No. S49-115541
Patent Literature 2: Japanese Patent Laid-Open Publication No. S55-45746
Patent Literature 3: Japanese Patent No. 3232022
Patent Literature 4: Japanese Patent Laid-Open Publication No. 2006-313237
Patent Literature 5: WO 2018/159384 A1
Patent Literature 6: Japanese Patent Laid-Open Publication No. 2001-106911
Patent Literature 7: Japanese Patent Laid-Open Publication No. 2018-158966
The present invention was performed in view of the above situations and intends to provide a positive photosensitive resin composition that is soluble in an alkaline aqueous solution, can form a fine pattern and can obtain high resolution, and has excellent mechanical characteristics even when cured at low temperatures.
To solve the problem, the present invention provides a positive photosensitive resin composition comprising:
(A-1) an alkali-soluble resin containing at least one or more structures selected from a polyimide structure, a polybenzoxazole structure, a polyamide-imide structure, and a precursor structure thereof;
(A-2) a resin containing at least one or more structures selected from a polyimide structure, a polybenzoxazole structure, a polyamide-imide structure, and a precursor structure thereof, each of which has no alkali-soluble group and contains a heterocyclic skeleton having at least one or more nitrogen atoms at a molecular end;
(B) a compound having a quinonediazide structure for serving as a photosensitizer to generate an acid by light and increase a dissolution speed to an alkaline aqueous solution; and
(D) a solvent.
The positive photosensitive resin composition like this is soluble in an alkaline aqueous solution, enables a fine pattern and high resolution, and has excellent mechanical characteristics even when cured at low temperatures.
Furthermore, the positive photosensitive resin composition of the present invention may contain a polyimide structure in which the (A-2) is represented by the following general formula (1).
In the formula, W is a monovalent organic group having a heterocyclic skeleton having at least one or more nitrogen atoms, X1 is a tetravalent organic group, X2 is a divalent organic group, and “1” represents an integer of 1 to 1000.
Since the positive photosensitive resin composition like this may improve the elongation of a cured film of the photosensitive composition, the mechanical characteristics may be excellent even when cured at low temperatures.
Furthermore, the positive photosensitive resin composition of the present invention preferably contains 5 parts by mass or larger and 50 parts by mass or smaller of the (A-2) relative to 100 parts by mass of the (A-1).
The positive photosensitive resin composition like this may make a desirable intermolecular interaction between resins (A-1), and the resin (A-1) and the resin (A-2), and may obtain an effect of improving the elongation of the cured film of the photosensitive composition, and does not cause the problem such as residues during lithography patterning.
Furthermore, in the positive photosensitive resin composition of the present invention, the (A-1) preferably contains a structure represented by the following general formulae (2) and/or (3),
wherein X3 is a tetravalent organic group, “s” represents 0 or 1, Z is a divalent linking group, and when s=0, two aromatic rings in the formula are directly bonded without a linking group,
wherein X4 is a divalent organic group, and “s” and Z are the same as the above.
The positive photosensitive resin composition like this may have more preferable solubility to the alkaline aqueous solution, and may become more excellent in the mechanical characteristics of the cured product.
In this case, Z in the general formulae (2) and (3) is preferable to be a divalent group represented by the following general formula (4) or (5),
wherein a dotted line represents a bond.
When Z is a group like this, it is preferable that the solubility to a developer of an alkaline aqueous solution be improved.
Furthermore, in the positive photosensitive resin composition of the present invention, the (A-1) is, furthermore, preferable to contain a structural unit represented by the following general formulae (6) and/or (8),
wherein X5 is a tetravalent organic group, R1 is a group represented by the following general formula (7), “s” represents 0 or 1, Z is a divalent linking group, and, when s=0, two aromatic rings in the formula are directly linked without a linking group,
wherein a dotted line represents a bond, Y1 is an organic group with a valency of (k+1), Rf is a linear branched, or cyclic alkyl group having 1 to 20 carbon atoms or an aromatic group optionally substituted with an alkyl group in which a part or all of hydrogen atoms are substituted with fluorine atoms, “k” represents 1, 2 or 3, and “n” represents 0 or 1,
wherein X6 is a tetravalent organic group, and X7 is a group shown by the following general formula (9),
wherein R2 to R5 each is independently a linear or branched alkylene group having 2 to 10 carbon atoms, m1 is an integer of 1 to 40, and m2, m3 each is independently an integer of 0 to 40.
By containing the structural unit like this, the positive photosensitive resin composition of the present invention has improved solubility to a general-purpose organic solvent, may be used without limiting a solvent of the composition, may generate flexibility, and may obtain a cured film having high elongation and low warpage.
In this case, the R1 in the general formula (6) is preferably an organic group selected from any one of groups represented by the following general formulae (10), (11), (12) and (13),
wherein a dotted line represents a bond, Rf is the same as the above, Ra and Rb are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Y2 and Y3 are a linear or branched alkylene group having 1 to 6 carbon atoms, n1 represents an integer of 0 to 6, n2 represents an integer of 1 to 6, n3 represents an integer of 0 to 6, n4 represents an integer of 1 to 6, n5 represents an integer of 0 to 6, n6 represents 0 or 1, and n7 represents an integer of 0 to 6.
From the easy availability of a compound that is a raw material for introducing R1, the R1 is preferable to be a group like this.
Furthermore, the positive photosensitive resin composition of the present invention preferably furthermore contains (C) one or two or more kinds of crosslinking agents selected from an amino condensate modified by formaldehyde or formaldehyde-alcohol; a phenol compound having two or more methylol groups or alkoxymethylol groups by average in one molecule; a compound in which a hydrogen atom of a phenolic hydroxy group is substituted with a glycidyl group; a compound in which a hydrogen atom of a phenolic hydroxy group is substituted with a substituent represented by the following formula (C-1); and a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2),
wherein a dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and “v” represents 1 or 2.
The (C) component like this causes a crosslinking reaction in the post-curing after a pattern of the positive photosensitive resin composition of the present invention is formed to improve the strength of the cured product further and to form a more preferable cured film.
Furthermore, the positive photosensitive resin composition of the present invention is preferable to contain (E) a compound to generate an acid by heating.
The (E) component like this may further improve the mechanical strength, chemical resistance, adhesiveness and the like of an obtained pattern or a film, by furthermore advancing the crosslinking and curing reaction.
Furthermore, the present invention provides a patterning process comprising steps of:
(1) forming a photosensitive material film by coating the positive photosensitive resin composition according to any one of claim 1 to 9 on a substrate;
(2) subsequently, after a heat treatment, exposing the photosensitive material film with a high energy beam having a wavelength of 190 to 500 nm or an electron beam via a photomask; and
(3) developing with a developer of an alkaline aqueous solution.
According to the patterning process like this, since the positive photosensitive resin composition becomes alkali-soluble, a fine pattern may be formed and high resolution may be obtained.
Furthermore, the present invention provides a method of forming a cured film comprising a step of heating and post-curing a film on which a pattern is formed by the patterning process according to claim 10 at a temperature of 100 to 300° C.
The method of forming a cured film enables a cured film (pattern) to have excellent mechanical characteristics even when cured at low temperatures.
Furthermore, the present invention provides an interlayer insulation film or a surface protective film being a cured film by curing the positive photosensitive resin composition.
The cured film obtained by curing the positive photosensitive resin composition of the present invention has excellent adhesiveness with a substrate, heat resistance, electric property, mechanical strength and chemical resistance to an alkaline release liquid or the like, and a semiconductor element having the cured film as a protective coating has excellent reliability. Therefore, the cured film is suitable as a protective coating (an interlayer insulation film or surface protective film) of electric and electronic components, semiconductor elements and the like.
Furthermore, the present invention provides an electronic component having the interlayer insulation film or the surface protective film.
The protective coating like this (interlayer insulation film or surface protective film) is effective for an insulation film for semiconductor elements including rewiring use, an insulation film for multilayer printed board and so on from the viewpoint of heat resistance, chemical resistance, and insulation property, and may give electronic components having excellent reliability.
As was described above, the present invention may provide a positive photosensitive resin composition that is soluble in an alkaline aqueous solution, enables a fine pattern and high resolution, and has excellent mechanical characteristics even when cured at low temperatures.
As was described above, a photosensitive resin composition that is soluble in an alkaline aqueous solution, enables a fine pattern and high resolution, and has excellent mechanical characteristics even when cured at low temperatures has been demanded.
The present inventors studied hard to achieve the above object and found that a pattern obtained by using a positive photosensitive resin composition comprising (A-1) an alkali-soluble resin containing a specific structure, (A-2) a resin not having an alkali-soluble group but containing a specific structure, (B) a specific photosensitizer, and (D) a solvent is fine and has an excellent pattern shape.
Furthermore, it was found that a protective film obtained by using the positive photosensitive resin composition, by forming a pattern, and by heating has excellent mechanical characteristics, in particular, the breaking elongation. That is, it was found that a cured film with a pattern formed by using the positive photosensitive resin composition is excellent as an electric, electronic component protective film, and an insulation protective film, thus the present invention was completed. In the present specification, the electric and electronic components are called summarized also as “electronic component”.
That is, the present invention is a positive photosensitive resin composition including: (A-1) an alkali-soluble resin containing at least one or more structures selected from a polyimide structure, a polybenzoxazole structure, a polyamide-imide structure, and a precursor structure thereof;
(A-2) a resin containing at least one or more structures selected from a polyimide structure, a polybenzoxazole structure, a polyamide-imide structure, and a precursor structure thereof, each of which has no alkali-soluble group and contains a heterocyclic skeleton having at least one or more nitrogen atoms at a molecular end;
(B) a compound having a quinonediazide structure for serving as a photosensitizer to generate an acid by light and increase a dissolution speed to an alkaline aqueous solution; and
(D) a solvent.
In what follows, the present invention will be detailed, but the present invention is not limited to these.
The positive photosensitive resin composition of the present invention will be described.
The positive photosensitive resin composition of the present invention includes:
(A-1) an alkali-soluble resin containing at least one or more structures selected from a polyimide structure, a polybenzoxazole structure, a polyamide-imide structure, and a precursor structure thereof;
(A-2) a resin containing at least one or more structures selected from a polyimide structure, a polybenzoxazole structure, a polyamide-imide structure, and a precursor structure thereof, each of which has no alkali-soluble group and contains a heterocyclic skeleton having at least one or more nitrogen atoms at a molecular end;
(B) a compound having a quinonediazide structure for serving as a photosensitizer to generate an acid by light and increase a dissolution speed to an alkaline aqueous solution; and (D) a solvent. The positive photosensitive resin composition may be alkali-developed. Furthermore, the positive photosensitive resin composition may furthermore contain, as needs arise, (C) a crosslinking agent, (E) a compound (thermal acid generator) that generates an acid by heat and so on, other than the (A-1) component, (A-2) component, (B) component and (D) component.
An alkali-soluble resin (A-1) of the present invention is an alkali-soluble resin containing at least one or more structures selected from a polyimide structure, a polybenzoxazole structure, a polyamide-imide structure, and a precursor structure thereof. Although the resin (A-1) is not particularly restricted as long as an alkali-soluble resin containing the above structures, one containing the structure represented by the following general formula (2) and/or (3) is preferable.
In the formula, X3 is a tetravalent organic group, “'s” represents 0 or 1, Z is a divalent linking group, and when s=0, two aromatic rings in the formula are directly bonded without a linking group.
In the formula, X4 is a divalent organic group, and “s” and Z are the same as those described above.
Although X3 in the general formula (2) is a tetravalent organic group, it is not restricted as long as it is a tetravalent organic group. Preferably, X3 is a tetravalent organic group of a cyclic aliphatic group having 4 to 40 carbon atoms or an aromatic group, and more preferably, a tetravalent organic group represented by the following formula (14). Furthermore, a structure of X3 may be a combination of one or two or more kinds.
In the formulae, a dotted line represents a bond.
The s in the general formula (2) represents 0 or 1, and when s is 0, two aromatic rings in the general formula (2) are bonded directly without the divalent linking group Z.
When s is 1, two aromatic rings in the general formula (2) are bonded via the divalent linking group Z. Z is not restricted as long as it is a divalent group. Preferably, the Z is a divalent organic group of an alicyclic aliphatic group having 4 to 40 carbon atoms or aromatic group, and more preferably a divalent linking group represented by the following formula (15). The structure of Z may be one kind or a combination of two or more kinds.
In the formulae, q1, q2, and q3 represent an integer of 1 to 6, and q4 and q5 represent an integer of 1 to 10. A dotted line represents a bond.
In particular, a preferable divalent linking group Z is a divalent group represented by the following general formula (4) or (5).
In the formulae, a dotted line represents a bond.
As a structural unit represented by the general formula (2), when Z in the general formula (2) is a group represented by the formula (4), a structural unit represented by the following general formula (2-1) is preferable, and when Z in the general formula (2) is a group represented by the general formula (5), a structural unit represented by the following general formula (2-2) is preferable.
In the formulae, X3 is the same as that described above.
As shown by the general formula (2-1), when the divalent linking group Z is a hexafluoropropylidene group shown by the formula (4) and is located at a p-position of a phenolic hydroxy group, since the hexafluoropropylidene group is an electron withdrawing group, the acidity of the phenolic hydroxy group becomes high, and the solubility to a developer of an alkaline aqueous solution increases. Therefore, it is preferred that the Z be the group shown by the formula (4).
Similarly, as shown by the general formula (2-2), when the divalent linking group Z is a sulfonic group shown by the formula (5) and is located at a p-position of a phenolic hydroxy group, since the sulfonic group is also an electron withdrawing group, the acidity of the phenolic hydroxy group becomes high, and the solubility to a developer of an alkaline aqueous solution increases. Therefore, it is also preferred that the Z be the group shown by the formula (5).
The X4 in the general formula (3) is a divalent organic group and is not restricted as long as it is the divalent organic group. Preferably, it is a divalent organic group of an aliphatic chain length structure or an alicyclic aliphatic group having 4 to 40 carbon atoms, or an aromatic group. Furthermore preferably, it is a divalent organic group represented by the following formula (16). The structure of the X4 may be one kind or a combination of two or more kinds.
In the formulae, R6 and R7 each independently a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, q6 is an integer of 1 to 30, and a dotted line represents a bond.
When the X4 in the general formula (3) is a divalent organic group that is an aliphatic chain length structure, the mechanical strength, in particular, the elongation of a cured film of the positive photosensitive resin composition of the present invention is improved. Therefore, this case is preferred.
The s and Z in the general formula (3) are the same as the above, the Z is preferable to be the general formula (4) or (5) from the viewpoint of the solubility to a developer of an alkaline aqueous solution. Also in this case, in the same manner as the case of the formulae (2-1) and (2-2), the acidity of the phenolic hydroxy group becomes higher, and the solubility to the developer that is an alkaline aqueous solution is improved. Therefore, this case is preferred.
The alkali-soluble resin (A-1) of the present invention may furthermore contain a structural unit represented by the following general formula (17) (hereinafter, also referred to as a structural unit (17)), in addition to the structural units shown by the general formulae (2) and (3).
In the formula, the X4 is the same as the above. X8 is a divalent organic group.
The X8 in the general formula (17) is a divalent organic group, as long as it is a divalent organic group, there is no restriction, and it is preferable to be a divalent organic group having 6 to 40 carbon atoms, and a cyclic organic group having an aromatic ring having a substitution group or a cyclic organic group containing 1 to 4 aliphatic rings, or an aliphatic group or a siloxane group not having a cyclic structure. Furthermore, as the preferable X8, a structure shown by the following formula (18) or (19) is exemplified. The structure of the X8 may be one kind or a combination of two or more kinds.
In the formulae, a dotted line represents a bond.
In the formulae, a dotted line represents a bond with an amino group, R8s each represent independently a methyl group, an ethyl group, a propyl group, an n-butyl group, or a trifluoromethyl group, and q7 represents a positive number of 2 to 20.
Furthermore, the alkali-soluble resin (A-1) of the present invention may furthermore contain a structural unit shown by the following general formula (20) (hereinafter, also referred to as structural unit (20)), in addition to the structural units shown by the general formulae (2) and (3).
In the formula, X3 and X8 are the same as those shown above.
The alkali-soluble resin (A-1) of the present invention is preferable to furthermore contain a structural unit shown by the following general formula (6) (hereinafter, also referred to as structural unit (6)), in addition to the structural units shown by the general formulae (2) and (3).
In the formula, X8 is the same tetravalent organic group as or different from the X3, R1 is a group represented by the following general formula (7), and s and Z are the same as the above.
In the formula, a dotted line represents a bond, Y1 is an organic group with a valency of (k+1), Rf is a linear branched, or cyclic alkyl group having 1 to 20 carbon atoms or an aromatic group optionally substituted with an alkyl group in which a part or all of hydrogen atoms are substituted with fluorine atoms, “k” represents 1, 2 or 3, and “n” represents 0 or 1.
The alkali-soluble resin (A-1) which is contained in the structural unit (6) improves the solubility to a general-purpose organic solvent such as propylene glycol monomethyl ether acetate, and thus a solvent of the composition may be used limitlessly.
As the Y1 in the general formula (7), a linear or branched divalent organic group (for example, alkylene group) having 1 to 6 carbon atoms is preferable.
Furthermore, R1 in the general formula (6) is preferable to be an organic group selected from groups shown by the following formulae (10), (11), (12), and (13). Regarding the following formula (11), an organic group represented by the following formula (11′) is more preferable.
In the formulae, a dotted line represents a bond, Rf is the same as the above, Ra and Rb each are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Y2 and Y3 each are a linear or branched alkylene group having 1 to 6 carbon atoms, n1 represents an integer of 0 to 6, n2 represents an integer of 1 to 6, n3 represents an integer of 0 to 6, n4 represents an integer of 1 to 6, n5 represents an integer of 0 to 6, n6 represents 0 or 1, and n7 represents an integer of 0 to 6.
In the organic group shown by the general formula (10), as a preferred organic group, the followings may be exemplified. However, there is no restriction to these.
In the formulae, a dotted line represents a bond.
In the organic group shown by the general formula (11), as a preferred organic group, the followings may be exemplified. However, there is no restriction to these.
In the formulae, a dotted line represents a bond, “n2” represents an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2, and most preferably 1.
In the organic group shown by the general formula (12), as a preferred organic group, the followings may be exemplified. However, there is no restriction to these.
In the formula, a dotted line represents a bond, “n4” represents an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2, and most preferably 1.
In the organic group shown by the general formula (13), as a preferred organic group, the followings may be exemplified. However, there is no restriction to these.
In the formula, a dotted line represents a bond.
Here, after performing the patterning with the positive photosensitive resin composition of the present invention, in the heating of the post-curing, in a structural unit of a polyimide precursor shown by the general formula (6), a ring-closure reaction for imidization proceeds. At this time, the introduced R1 is eliminated and removed from a system to observe a thickness of a formed film decrease. Accordingly, in order to keep a thickness reduction at a minimum level during the post-curing, the more preferred R1 may have a small molecular weight.
The alkali-soluble resin (A-1) of the present invention preferably furthermore contains a structural unit shown by the following general formula (8) (hereinafter, referred to as a structural unit (8)) in addition to the structural units shown by the general formulae (2) and (3).
In the formula, X6 is the same tetravalent organic group as or different from X3, and X7 is a group represented by the following general formula (9).
In the formula, R2 to R5 each is independently a linear or branched alkylene group having 2 to 10 carbon atoms, m1 is an integer of 1 to 40, m2, m3 each is independently an integer of 0 to 40.
X6 in the formula (8) may be a tetravalent organic group cited as X3, for example, a tetravalent organic group shown by the above formula (14). With regard to X7 (a group shown by the general formula (9)), the followings may be exemplified as a preferred organic group. There is no restriction to these.
When the alkali-soluble resin (A-1) contains a structural unit (8) like this, the flexibility is generated to obtain a cured film having high elongation and low warpage.
The alkali-soluble resin (A-1) of the present invention contains structures represented by the following general formula (2) and/or (3).
In the formulae, X3, X4, s and Z are the same as the above.
An alkali-soluble resin containing the structural unit represented by the general formula (2) may be obtained by reacting tetracarboxylic dianhydride represented by the following general formula (21) and a diamine represented by the following general formula (22). Firstly, the tetracarboxylic dianhydride shown by the following general formula (21) and the diamine shown by the following general formula (22) are reacted to synthesize amide acid, followed by heating and dehydrating to form an imide ring to be able to obtain a polymer containing the structural unit (2).
The structural unit (2) may be produced by performing the following steps in sequence: dissolving diamine in a solvent having a high boiling point and high polarity such as γ-butyrolactone or N-methyl-2-pyrrolidone, adding an acid anhydride, reacting at 0 to 80° C., preferably 10 to 50° C. to form an amide acid, adding a nonpolar solvent such as xylene, and heating to 100 to 200° C., preferably to 130 to 180° C. to perform an imidization reaction while removing water from a reaction system.
In the formula, X3 is the same as the above.
In the formula, s and Z are the same as the above.
Preferred examples of tetracarboxylic dianhydrides shown by the general formula (21) include an aromatic dianhydride, an alicyclic dianhydride, an aliphatic dianhydride and the like. Examples of the aromatic dianhydride include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,2′,3′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-terphenyltetracarboxylic dianhydride, 3,3′,4,4′-oxydiphthalic dianhydride, 2,3,3′,4′-oxypdihthalic dianhydride, 2,3,2′,3′-oxydiphthalic dianhydride, diphenylsulfone-3,3′,4,4′-tetracarboxylic dianhydride, benzophenone-3,3′,4,4′-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, p-phenylene bis (trimellitic acid monoester anhydride), bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)-1,4-phenylene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzoyloxy)phenyl)hexafluoropropane dianhydride, 1,6-difluoropyromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1,6-ditrifluoromethylpyromellitic dianhydride, 2,2′-bis (trifluoromethyl)-4,4′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2′-bis[(dicarboxyphenoxy)phenyl]propane dianhydride, 2,2′-bis[(dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, and acid dianhydride compounds obtained by substituting the aromatic rings of these by an alkyl group, an alkoxy group, a halogen atom or the like, but are not limited to these.
Examples of the alicyclic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4.3.0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4.4.0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4.4.0]decane-2,4,8,10-tetracarboxylic dianhydride, tricyclo[6.3.0.02,6]undecane-3,5,9,11-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1]heptanetetracarboxylic dianhydride, bicyclo[2.2.1]heptane-5-carboxymethyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2.2.1]heptane-2,4,6,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecahydroanthracene-1,2,8,9-tetracarboxylic dianhydride, 3,3′,4,4′-dicyclohexanetetracarboxylic dianhydride, 3,3′,4,4′-oxydicyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and “RIKACID” (Registered trademark) BT-100 (all tradenames, available from New Japan Chemical Co., Ltd.) and their derivatives, or an acid dianhydride compound in which an alicyclic ring of the above is substituted with an alkyl group, an alkoxy group, a halogen atom, and the like, but are not limited to these.
Examples of the aliphatic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and derivatives thereof, without limiting to these.
These aromatic dianhydrides, alicyclic dianhydrides, or aliphatic dianhydrides may be used singularly or in a combination of two or more kinds.
In the general formula (22), s represents 0 or 1, in the case of s=0, two aromatic rings in the general formula (22) are directly bonded without the divalent linking group Z.
In the case of s=1 in the general formula (22), Z in the general formula (22) is not restricted as long as Z is a divalent group. As was described above, a divalent organic group of an alicyclic aliphatic group having 4 to 40 carbon atoms or aromatic group is preferred, and a divalent linking group shown by the formula (15) is more preferred. Furthermore, a structure of the Z may be one kind or a combination of two or more kinds.
Furthermore, preferable examples of the diamine shown by the general formula (22) are compounds shown by the following general formulae (23), (24).
An alkali-soluble resin obtained by reacting the diamine shown by the general formula (23) and tetracarboxylic dianhydride shown by the general formula (21) becomes a polymer containing a structural unit shown by the general formula (2-1) that is a preferable structural unit.
Alternatively an alkali-soluble resin obtained by reacting the diamine shown by the general formula (24) and tetracarboxylic dianhydride shown by the general formula (21) becomes a polymer containing a structural unit shown by the general formula (2-2) that is a preferable structural unit.
The alkali-soluble resin containing the structural unit (3) may be obtained by reacting a dicarboxylic acid compound shown by the following general formula (25) and diamine shown by the general formula (22).
In the formula, X4 is the same as the above.
Here, a polymer containing a structural unit (3) may be obtained by reacting, for example, a dicarboxylic acid compound shown by the general formula (25) and diamine shown by the general formula (22) under the presence of a dehydration condensation agent. That is, the polymer containing the structural unit (3) may be produced by performing the following steps in sequence: dissolving the dicarboxylic acid compound shown by the general formula (25) in a reaction solvent to use a resultant in a reaction, charging and mixing a well-known dehydration condensation agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinone, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N′-discuccinimidyl carbonate in the reaction solution with icing to convert the dicarboxylic acid compound shown by the general formula (25) to an acid anhydride, and adding dropwise solution or dispersion of diamine shown by the general formula (22) separately in a solvent to the acid anhydride to cause a polycondensation.
As another method of obtaining a polymer containing the structural unit (3) by reacting the dicarboxylic acid compound shown by the general formula (25) and diamine (a diamine compound) shown by the general formula (22), there is an exemplary method in which a dicarboxylic acid compound shown by the general formula (25) is converted to an acid chloride by using a chlorinating agent such as thionyl chloride or dichlorooxalic acid, followed by reacting with diamine shown by the general formula (22) to synthesize.
In a reaction in which the dicarboxylic acid compound described above is converted to an acid chloride with a chlorinating agent, a basic compound may be used together. As the basic compound, for example, pyridine, 4-dimethylaminopyridine, triethyl amine or the like may be used.
Next, the obtained acid chloride of the dicarboxylic acid compound and the diamine shown by the general formula (22) are reacted under the presence of a basic catalyst, so that a polymer containing a structural unit (3) of a target is able to be obtained. At this time, as the basic catalyst such as pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene or 1,5-diazabicyclo[4.3.0]nona-5-ene may be used.
Among methods of producing the alkali-soluble resin of the present invention, as a solvent used in a method that undergoes the acid chloride, one that well dissolves the dicarboxylic acid compound and their acid chlorides, and furthermore the polymer obtained by a polycondensation reaction with diamines is preferable. Specifically, N-methyl-2-pyrohlidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone and the like may be used. Other than the polar solvent, also ketones, esters, lactones, ethers, halogenated hydrocarbons or hydrocarbons may be used. For example, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dicycloethane, 1,4-dicyclobutane, trichloroethylene, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene or the like may be used. These organic solvents may be used singularly or in a combination of two or more kinds.
Suitable examples of the X4 in the dicarboxylic acid compounds shown by the general formula (25), the same as the above may be used.
Furthermore, examples of the dicarboxylic acid compound shown by the general formula (25) include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosane-dioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and the like.
Examples of the dicarboxylic acid compound having an aromatic ring include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-diphenyl ether dicarboxylic acid, 3,4′-diphenyl ether dicarboxylic acid, 3,3′-diphenyl ether dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, 3,4′-biphenyl dicarboxylic acid, 3,3′-biphenyl dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 3,4′-benzophenone dicarboxylic acid, 3,3′-benzophenone dicarboxylic acid, 4,4′-hexafluoroisopropylidene dibenzoic acid, 4,4′-dicarboxydiphenylamide, 1,4-phenylenediethanoic acid, bis(4-carboxyphenyl)sulfide, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-carboxyphenyl)tetraphenyldisiloxane, bis(4-carboxyphenyl)tetramethyldisiloxane, bis(4-carboxyphenyl)sulfone, bis(4-carboxyphenyl)methane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,2-bis-(p-carboxyphenyl)propane, 2,6-naphthalene dicarboxylic acid, and the like, but are not limited to these. Furthermore, these materials may be used singularly or in a combination of these.
As preferable examples as s and Z in the general formula (22), the same as the above examples may be used.
As was described above, the alkali-soluble resin (A-1) of the present invention may furthermore contain the following structural units (17) and/or (20).
In the formula, X4 and X8 are the same as the above.
In the formula, X3 and X8 are the same as the above.
The alkali-soluble resin containing the structural unit (17) may be obtained by simultaneously reacting a dicarboxylic acid compound shown by the general formula (25) and both of diamine shown by the general formula (22) and diamine shown by the following formula (26). Exemplarily, the alkali-soluble resin containing the structural unit (17) may be obtained by the similar method of producing the polymer containing the structural unit (3). Specifically, the method includes performing a reaction under the presence of the dehydration condensation agent or a reaction of converting to an acid chloride with a chlorinating agent, followed by reacting with the diamine.
H
2
N—X
8
—NH
2 (26)
In the formula, X8 is the same as the above.
As the diamine shown by the general formula (26), an aromatic diamine, an alicyclic diamine and an aliphatic diamine may be exemplified. Examples of the preferable aromatic diamine include 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,4-bis(4-aminophenoxy)benzene, benzidine, 2,2′-bis(trifluoromethyl)benzidine, 3,3′-bis(trifluoromethyl)benzidine, 2,2′-dimethylbenzidine, 3,3′-dimethylbenzidine, 2,2′3,3′-tetramethylbenzidine, 2,2′-dichlorobenzidine, 3,3′-dichlorobenzidine, 2,2′3,3′-tetrachlorobenzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis[4-(3-amino-phenoxy)phenyl]sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl} ether, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)fluorene, 2,2′-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane, 4-aminophenyl-4′-aminobenzoate, 4,4′-diaminobenzanilide, or a diamine compound in which the aromatic ring of the above is substituted with an alkyl group, an alkoxyl group, a halogen atom, and the like, but are not limited to these.
Examples of the alicyclic diamine include cyclobutanediamine, isophoronediamine, bicyclo[2.2.1]heptanebismethylamine, tricyclo[3.3.1.13,7]decane-1,3-diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-diaminocyclohexane, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 3,3′-diethyl-4,4′-diaminodicyclohexylmethane, 3,3′,5,5′-tetramethyl-4,4′-diaminodicyclohexylmethane, 3,3′,5,5′-tetraethyl-4,4′-diaminodicyclohexylmethane, 3,5-diethyl-3′,5′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexyl ether, 3,3′-dimethyl-4,4′-diaminodicyclohexyl ether, 3,3′-diethyl-4,4′-diaminodicyclohexyl ether, 3,3′,5,5′-tetramethyl-4,4′-diaminodicyclohexyl ether, 3,3′,5,5′-tetraethyl-4,4′-diaminodicyclohexyl ether, 3,5-diethyl-3′,5′-dimethyl-4,4′-diaminodicyclohexyl ether, 2,2-bis(4-amino-cyclohexyl)propane, 2,2-bis(3-methyl-4-aminocyclohexyl)-propane, 2,2-bis(3-ethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-dimethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-diethyl-4-aminocyclohexyl) propane, 2,2-(3,5-diethyl-3′,5′-dimethyl-4,4′-diaminodicyclohexyl)propane, or a diamine compound in which an aliphatic ring of the above is substituted with an alkyl group, an alkoxyl group, a halogen atom, and the like, but are not limited to these.
Examples of the aliphatic diamine include: alkylene diamines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and the like; ethylene glycol diamines such as bis(aminomethyl) ether, bis(2-aminoethyl) ether, bis(3-aminopropyl) ether, and the like; and siloxanediamines such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, and the like, but are not limited to these.
These aromatic diamines, alicyclic diamines, or aliphatic diamines may be used singularly or in a combination of two or more kinds.
Preferably, siloxanediamines may be also used.
The alkali-soluble resin containing the structural unit (20) may be obtained by performing the same reaction procedure for the structural unit (2). Exemplarily, a mixture of a diamine shown by the general formula (22) and a diamine shown by the general formula (26) reacts with a tetracarboxylic dianhydride shown by the general formula (21) to synthesize an amide acid, followed by performing a heating and dehydrating step to form an imide ring to obtain the alkali-soluble resin containing the structural unit (20).
As was described above, the alkali-soluble resin (A-1) of the present invention may furthermore contains the following structural unit (6).
A polymer having the structural unit shown by the general formula (6) may be obtained by reacting a tetracarboxylic acid diester compound shown by the following formula (27) and a diamine shown by the general formula (22). Exemplarily, the polymer may be obtained by the similar method of producing a polymer containing the structural unit (3), the method including a reaction under the presence of the dehydration condensation agent or a reaction for converting to an acid chloride by using a chlorinating agent, followed by reacting with the diamine.
In the formula, X5, R1, s, and Z are the same as the above.
In the formula, R1 and X5 are the same as the above.
As a method of producing the tetracarboxylic acid diester compound shown by the general formula (27), a method of introducing R1 is exemplified. In the method, the tetracarboxylic dianhydride shown by the general formula (28) reacts with a compound having a hydroxy group at a terminal shown by the general formula (29) under the presence of a basic catalyst such as pyridine. Here, the tetracarboxylic dianhydride shown by the following general formula (28) is an origin of the tetravalent organic group X5 in the general formula (6), for example, shown by the formula (14). The compound having a hydroxy group at a terminal shown by the following general formula (29) allows to introduce a group shown by the general formula (7).
In the formula, X5 is the same as the above.
In the formula, Y1, Rf, k and n are the same as the above.
As the tetracarboxylic dianhydride shown by the general formula (28), examples shown by the tetracarboxylic dianhydride shown by the general formula (21) are cited as preferred examples.
In a reaction between the tetracarboxylic dianhydride shown by the general formula (28) and a compound having a hydroxy group at a terminal shown by the general formula (29), both of them are stirred, dissolved and mixed over 4 to 10 hours at a reaction temperature of 20 to 50° C., in a reaction solvent, under the presence of a basic catalyst such as pyridine or the like to forward a half esterification reaction of the acid dianhydride. A solution in which the desired tetracarboxylic acid diester compound shown by the general formula (27) is dissolved in a reaction solvent may be obtained.
The obtained tetracarboxylic acid diester compound may be isolated, or the obtained solution may be used as it is in a reaction with diamine in the next step described below.
The preferred reaction solvent is one that well dissolves the tetracarboxylic acid diester compound and a polymer having a structural unit of a polyimide precursor obtained by a polycondensation reaction performed next between the tetracarboxylic acid diester compound and the diamines. For example, N-methyl-2-pyrolidone, N,N-dimethyl acetamide, N,N-dimethyl formamide, dimethylsulfoxide, tetramethyl urea, and γ-butyrolactone may be used. Furthermore, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like may be used, specific example include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, and the like. These may be used, as needs arise, singularly or in a combination of two or more kinds.
Preferable examples of the general formula (22) are the same as the above.
As was described above, the alkali-soluble resin (A-1) of the present invention may furthermore contain the following structural unit (8).
In the formula, X6 and X7 are the same as the above.
In the formula, R2 to R8, m1, m2 and m3 are the same as the above.
The alkali-soluble resin containing the structural unit (8) may be obtained by performing the same reaction procedure as performed for the structural unit (2). Exemplarily, after an amide acid is synthesized by reaction between the tetracarboxylic dianhydride shown by the following general formula (30) and a mixture of the diamine shown by the general formula (22) and the diamine shown by the following general formula (31), an imide ring is formed by performing a heating and dehydration step to obtain the alkali-soluble resin containing the structural unit (8).
In the formula, X6 is the same as the above.
In the formula, R2 to R5, m1, m2 and m3 are the same as the above.
As the tetracarboxylic dianhydride shown by the general formula (30), a preferable example includes one cited as the tetracarboxylic dianhydride shown by the general formula (21).
Examples of the diamine shown by the general formula (31) include 1,2-bis(aminoetoxy)ethane, HK-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-230, D-400, D-2000, THE-100, THF-140, THE-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, and HT-1700 (all trade names, manufactured by Huntsman Corporation), but are not limited to these.
A preferable molecular weight of the alkali-soluble, resin is preferably 5,000 to 100,000, and more preferably 7,000 to 30,000. When the molecular weight is 5,000 or larger, a photosensitive resin composition that includes the alkali-soluble resin as a base resin may be readily formed into a film having a desired film thickness on a substrate. When the molecular weight is 100,000 or smaller, the viscosity of the photosensitive resin composition does not become remarkable high, and there is no fear of failing to form a film.
The alkali-soluble resin may be blocked with an end blocking agent at both ends to control a molecular weight in the polycondensation reaction, and to suppress a temporal variation in molecular weight of the obtained polymer, that is, to suppress gelling. As the end blocking agent reacting with the acid dianhydride, a monoamine or monovalent alcohol may be exemplified. As the end blocking agent reacting with the diamine compound, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a mono-active ester compound, dicarbonic acid esters, vinyl ethers and the like may be exemplified. In addition, reaction of the end blocking agent allows various organic groups to be introduced into the terminal.
Examples of the monoamines used as a blocking agent for the terminal group of the acid anhydride include aniline, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, ammelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-aminonaphthalene and the like, but are not limited to these. These may be used singularly or in a combination of two or more kinds.
Examples of the monohydric alcohol used as a blocking agent for the terminal group of the acid anhydride include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2-nonanol, 1-decanol, 2-decanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol, 1-eicosanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-propyl-1-pentanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,4,4-trimethyl-1-hexanol, 2,6-dimethyl-4-heptanol, isononyl alcohol, 3,7-dimethyl-3-octanol, 2,4-dimethyl-1-heptanol, 2-heptylundecanol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol 1-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane monomethylol, norborneol, terpineol and the like, but are not limited to these. These may be used singularly or in combination of two or more kinds.
Examples of the acid anhydride, the monocarboxylic acid, the monoacid chloride compound and the mono-active ester compound to be used as the blocking agent for the terminal amino group include: acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride and the like; monocarboxylic acids such as 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, 8-ethynyl-2-naphthoic acid, and monoacid chloride compounds obtained by chlorination of carboxyl groups of the above; monoacid chloride compounds in which one carboxyl group of the dicarboxylic acids is chlorinated such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, 2,7-dicarboxynaphthalene and the like; and active ester compounds obtained by the reaction of a monoacid chloride compound and either N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide.
Examples of the dicarbonic acid ester used as the blocking agent for terminal amino groups include di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.
Examples of the vinyl ether compound used as the blocking agent for terminal amino groups include butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, tert-butyl vinyl ether, and benzyl vinyl ether.
Examples of other compounds used as the blocking agent for terminal amino groups include: chloroformate esters such as fluorenylmethyl chloroformate, 2,2,2-trichloroethyl chloroformate, tert-butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate, isopropyl chloroformate; isocyanate compounds such as butyl isocyanate, 1-naphthyl isocyanate, octadecyl isocyanate, phenyl isocyanate; benzoyl chloride, methanesulfonyl chloride, and p-toluenesulfonyl chloride.
An introduction rate of the blocking agent for the terminal group of the acid anhydride is preferably in the range 0.1 to 60 mol %, more preferably in the range of 5 to 50 mol %, and furthermore preferably in the range of 5 to 20 mol % relative to the tetracarboxylic dianhydride component shown by the general formula (21).
The component is a raw material of the alkali-soluble resin of the present invention. An introduction rate of the blocking agent for the terminal group of the amino group is preferably in the range of 0.1 to 100 mol % and particularly preferably in the range of 5 to 90 mol % relative to a diamine component. In addition, different terminal groups may be introduced by reacting with two or more of the end blocking agents.
((A-2) Resin Containing Heterocyclic Skeleton with Nitrogen Atom)
The (A-2) component of the present invention is a resin that contains at least one or more structures selected from a polyimide structure, a polybenzoxazole structure, a polyamide-imide structure, and precursor structures thereof, each of which has no alkali-soluble group and contains a heterocyclic skeleton having at least one or more nitrogen atoms at a molecular terminal. The resin is not particularly limited as long as it doesn't have the alkali-soluble group but contains the specific structure. The resin may contain a structure represented by the following general formula (1).
W is a monovalent organic group comprising a heterocyclic skeleton having at least one or more nitrogen atoms, X1 is a tetravalent organic group which is the same as or different from the X3, X2 is a divalent organic group which is the same as or different from the X2, and “l” represents an integer of 1 to 1000.
Here, the alkali-soluble group indicates a functional group that interacts or reacts with an alkali to increase the solubility of the resin to an alkali solution, specifically, an acidic group may be exemplified. Examples of the preferable alkali-soluble group include a carboxyl group, a phenolic hydroxy group, a hydroxy alkyl group in which a carbon atom at an alpha-position of an alcoholic hydroxy group is substituted with an electron drawing group, a sulfonic acid group, and a thiol group. Exemplarily, the alkali-soluble group includes a group having an acid dissociation constant (pKa) of the same degree as the phenolic hydroxy group, for example, one having the pKa in the range of 6 to 12.
The (A-2) component of the present invention doesn't have the alkali-soluble group like this in the structural unit and/or at the main chain terminal of the resin.
The W in the general formula (1) is a monovalent organic group having a heterocyclic skeleton having at least one or more nitrogen atoms. Preferably, the W includes a monovalent organic group represented by the following formula (32), but is not restricted to these. A structure of the W may be one kind or a combination of two or more kinds.
In the formulae, a dotted line represents a bond.
When the W in the general formula (1) has the organic group like the above at a molecular terminal, the elongation of a cured film of the photosensitive resin composition including the alkali-soluble resin (A-1) and the resin (A-2) of the present invention is improved. This is considered that the alkali-soluble group in the alkali-soluble resin (A-1) and an organic group shown by the W in the resin (A-2) form a hydrogen bond between molecules, and the resin (A-1) and the resin (A-2) properly tangle to improve the intermolecular interaction between the resin (A-1)s, and the resin (A-1) and the resin (A-2).
When a monovalent organic group having a heterocyclic skeleton having at least one or more nitrogen atoms in the resin (A-2) (a functional group shown by the W) is present not at a molecular terminal but in a molecular skeleton, a molecular interaction due to a hydrogen bond with the resin (A-1) becomes excessive to be unable to obtain a desired effect. Therefore, it is necessary for the organic group to be present at least one or more at the molecular terminal.
When the resin (A-2) has the alkali-soluble group, a hydrogen bond has been formed within the molecule in the resin (A-2), or between molecules of the resin (A-2) to cause an undesirable effect and further proceeding gelation during resin synthesis. Consequently, the resin (A-2) is necessary not to have the alkali-soluble group.
“1” in the general formula (1) represents an integer from 1 to 1000, preferably an integer from 1 to 100, and furthermore preferably an integer from 1 to 50. When “1” is larger than 1000, an amount of terminal organic group W interacting with the alkali-soluble resin (A-1) becomes relatively smaller. Consequently “l” is preferably 1000 or smaller, and particularly preferably 50 or smaller.
An addition amount of the resin (A-2) is preferably 5 parts by mass or larger and 50 parts by mass or smaller relative to 100 parts by mass of the alkali-soluble resin (A-1). When the addition amount is 5 parts by mass or larger, an interaction effect with the alkali-soluble resin (A-1) as was described above is obtained. When it is 50 parts by mass or smaller, a problem of such a residue during lithography patterning doesn't occur due to the (A-2) itself not having the alkali-solubility, and consequently the addition amount of the resin (A-2) is preferably set to the above range. The addition amount of the resin (A-2) is preferably 5 parts by mass or larger and 30 parts by mass or smaller. By setting the addition amount in the range, the balance between the interaction effect and the lithography patterning becomes excellent.
A (B) component in the positive photosensitive resin composition of the present invention is a photosensitizer that generates an acid by light to increase the dissolution speed to an alkaline aqueous solution, and is a compound having a quinonediazide structure. As the (B) component, a compound having a 1,2-naphtoquinone diazide sulfonyl group in a molecule may be exemplified.
Examples of the compound having a 1,2-naphthoquinone diazide sulfonyl group in its molecule include compounds having a 1,2-naphthoquinone diazide sulfonyl group shown by the following general formula (33) or (34)
Illustrative examples of a preferable compound into which the 1,2-naphthoquinone diazide sulfonyl group is introduced include trihydroxybenzophenone or tetrahydroxybenzophenone, a ballast molecule shown by the following general formula (35) having a phenolic hydroxy group and a novolac resin having a repeating unit represented by the following formula (40) with a weight average molecular weight in the range of 2,000 to 20,000, preferably 3,000 to 10,000. That is, those obtained by substituting a hydrogen atom(s) of the phenolic hydroxy group of the following resin or compound which has the phenolic hydroxy group with the 1,2-naphthoquinone diazide sulfonyl group are suitable to the (B) component.
Here, R101 to R106 each independently represents a hydrogen atom, a methyl group, a group represented by the following formula (36) or a group represented by the following formula (37). “w” is an integer of 0 to 2, and “z” is an integer of 0 to 2. When “z” is 0, “w” is 1 or 2. A is represented as follows: when “z” is 0 and “w” is 1, A is a hydrogen atom, a methyl group, or a group represented by the following formula (36); when “z” is 0 and “w” is 2, one of A's is a methylene group or a group represented by the following formula (38), and the other is a hydrogen atom, a methyl group or a group shown by the following formula (36); when “z” is 1, A is a methylene group or a group represented by the following formula (38); when “z” is 2 and “w” is 1, A is a methyne group or a group represented by the following formula (39); and when “z” is 2 and “w” is 2, one of A's is a methylene group or a group represented by the following formula (38), and the other is a methyne group or a group represented by the following formula (39).
In the formulae, a1, a2, a3, a4, a5, a6, and a7 each is an integer of 0 to 3, a1+a2≤5, a3+a4≤4 and a6+a7≤3.
In this case, a low nucleus body (ballast molecule) of the formula (35) has the number of benzene rings of 2 to 20, more preferably 2 to 10, still more preferably 3 to 6, and a ratio of the number of the phenolic hydroxy groups to the number of the benzene rings is 0.5 to 2.5, more preferably 0.7 to 2.0, and still more preferably 0.8 to 1.5.
As the low nucleus body (ballast molecule) like this, specifically, the followings may be exemplified.
Among the low nucleus bodies (ballast molecules) illustrated above, (B-3), (B-29), (B-33), (B-38) and the like are preferred. Compounds obtained by substituting a hydrogen atom of the phenolic hydroxy group of these ballast molecules with the 1,2-naphthoquinone diazide sulfonyl group are suited for the (B) component of the positive photosensitive resin composition of the present invention.
“mm” is an integer of 0 to 3.
The novolac resin having a repeating unit represented by the formula (40) may be synthesized by making condense aldehydes and the phenols shown by the following formula (41), specifically, at least one kind of phenols of o-cresol, m-cresol, p-cresol, 3,5-xylenol, and the like according to an ordinary method.
“mm” is an integer of 0 to 3.
In this case, as the aldehydes, for example, formaldehyde, para-formaldehyde, acetaldehyde, benzaldehyde and the like may be exemplified, but the formaldehyde is preferable.
A ratio of the phenols represented by the formula (41) to the aldehydes is preferably 0.2 to 2, particularly preferably 0.3 to 2, by molar ratio.
As a method of introducing the 1,2-naphthoquinone diazide sulfonyl group into a compound in which the group is introduced, it is preferable to perform a dehydrochlorination condensation reaction between the 1,2-naphthoquinone diazide sulfonyl chloride and the phenolic hydroxy group with a basic catalyst. In the case of reacting with the ballast molecule represented by the formula (35), trihydroxybenzophenone or tetrahydroxybenzophenone, a ratio of substituting hydrogen atoms of the phenolic hydroxy group with the 1,2-naphthoquinone diazide sulfonyl group is 10 to 100 mol %, and preferably 50 to 100 mol %. In the case of reacting with the novolac resin having a repeating unit represented by the formula (40), a ratio of substituting hydrogen atoms of the phenolic hydroxy group with the 1,2-naphthoquinone diazide sulfonyl group is 2 to 50 mol %, and preferably 3 to 27 mol %.
An addition amount of the (B) component is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass relative to 100 parts by mass of the (A-1) component. Furthermore, one kind or two or more kinds of the (B) components in combination may be used.
By blending the (B) component like this, before exposure, the solubility to the alkali aqueous solution is suppressed due to the dissolution preventing effect of the (B) component, the system becomes alkali-insoluble, and when exposed, the photosensitizer of the (B) component generates an acid by light, a dissolution rate to the alkaline aqueous solution increases, and the system becomes alkali-soluble.
That is, when an alkaline aqueous solution is used as a developer, an unexposed part is not dissolved in the developer and an exposed part is soluble in the developer. As a result, a positive pattern may be formed.
The (D) component in the positive photosensitive resin composition is a solvent. The solvent of the (D) component is not limited as long as it can dissolve the (A-1) component, the (A-2) component and the (B) component. Examples of the solvents includes: ketones such as cyclohexanone, cyclopentanone, methyl-2-n-amyl ketone, and the like; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and the like; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and the like; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol-mono-tert-butyl ether acetate, γ-butyrolactone, and the like. One or more kinds thereof may be used. In particular, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone or a mixed solvent thereof is preferable.
A blending amount of the (D) component is preferably 50 to 2,000 parts by mass, particularly preferably 100 to 1,000 parts by mass relative to 100 parts by mass of a total of the blending amounts of the (A-1) component, the (A-2) component and the (B) component.
The positive photosensitive resin composition of the present invention preferably contains furthermore, in addition to the (A-1), (A-2), (B), and (D) components that are necessary components, (C) one kind or two or more kinds of crosslinking agents selected from an amino condensate modified by formaldehyde or formaldehyde-alcohol; a phenol compound having two or more methylol groups or alkoxymethylol groups by average in one molecule; a compound in which a hydrogen atom of a phenolic hydroxy group is substituted with a glycidyl group; a compound in which a hydrogen atom of a phenolic hydroxy group is substituted with a substituent represented by the following formula (C-1); and a compound having two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2).
In the formulae, a dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v represents 1 or 2.
Examples of the (C) component in the positive photosensitive resin composition according to the present invention is one or two or more kinds of crosslinking agent(s) selected from an amino condensate modified by formaldehyde or formaldehyde-alcohol, a phenol compound having two or more methylol groups or alkoxymethylol groups by average in one molecule, a compound in which a hydrogen atom of a hydroxy group of a polyhydric phenol is substituted with a glycidyl group, a compound in which a hydrogen atom of a hydroxy group of a polyhydric phenol is substituted with a group represented by the following formula (C-1), and a compound having two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2).
In the formula, a dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v represents 1 or 2.
Examples of the amino condensates modified by the formaldehyde or formaldehyde-alcohol include a melamine condensate modified by the formaldehyde or formaldehyde-alcohol, and a urea condensate modified by the formaldehyde or formaldehyde-alcohol.
The melamine condensate modified by the formaldehyde or formaldehyde-alcohol is prepared in such a manner that, firstly, according to a well-known method, a melamine monomer is modified by methylol reaction with formalin, or this is furthermore modified by alkoxylation with alcohol, thus modified melamine represented by the following general formula (42) is obtained. As the alcohol, a lower alcohol, for example alcohols having 1 to 4 carbon atoms is preferable.
In the formula, R10s may be the same or different from each other, and is a methylol group, an alkoxymethyl group containing an alkoxy group having 1 to 4 carbon atoms or a hydrogen atom, and at least one of them is a methylol group or the alkoxymethyl group.
Examples of the R10 include a hydrogen atom, and alkoxymethyl groups such as a methylol group, a methoxymethyl group, and an ethoxymethyl group.
Specific examples of the modified melamine represented by the general formula (42) include trimethoxymethylmonomethylol melamine, dimethoxymethylmonomethylol melamine, trimethylol melamine, hexamethylol melamine, and hexamethoxymethylol melamine. Next, the modified melamine represented by the general formula (42) or its multimer (for example, an oligomer such as a dimer or a trimer) is subjected to addition condensation polymerization with formaldehyde until a desired molecular weight is obtained according to the conventional method to obtain a melamine condensate modified by formaldehyde or formaldehyde-alcohol.
The urea condensate modified by the formaldehyde or formaldehyde-alcohol is prepared, according to, for example, a well-known method, by modifying a urea condensate having a desired molecular weight by methylol reaction with formaldehyde, or by further modifying by alkoxylation with alcohol.
Specific examples of the urea condensate modified by the formaldehyde or formaldehyde-alcohol include a methoxymethylated urea condensate, an ethoxymethylated urea condensate, a propoxymethylated urea condensate, and the like.
These modified melamine condensates and modified urea condensates may be used by one king or by mixing two or more kinds.
Next, examples of the phenol compound having two or more methylol groups or alkoxymethylol groups in average in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2′,6,6′-tetramethoxymethylbisphenol A, compounds represented by the following formulae (C-3) to (C-7), and the like.
The crosslinking agents may be used singularly or in combination of two or more kinds.
Examples of the compounds in which a hydrogen atom of a hydroxy group of polyhydric phenol is substituted with a glycidyl group include a compound obtained by reaction of the hydroxy group of bisphenol A, tris(4-hydroxyphenyl)methane, and 1,1,1-tris(4-hydroxyphenyl)ethane with epichlorohydrin in the presence of a base. Suitable examples of the compound in which a hydrogen atom of a hydroxy group of a polyhydric phenol is substituted with a glycidyl group include the compounds represented by the following formulae (C-8) to (C-14).
In the formulae, t is 2≤t≤3.
One kind or two kinds of the compounds (a compound in which a hydrogen atom of a phenolic hydroxy group is substituted with a glycidyl group) obtained by substituting a hydroxy group of the polyhydric phenol with a glycidyl group may be used as a crosslinking agent.
Examples of the compound in which a hydrogen atom of a phenolic hydroxy group is substituted with a substituent represented by the following formula (C-1) include ones containing two or more of the substituents and represented by the following formula (C-15).
In the formula, a dotted line represents a bond.
In the formula, 1≤u≤3.
Examples of the compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2) include ones represented by the following formulae (C-16).
In the formula, a dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and v represents 1 or 2.
In the formula, W represents a linear, branched or cyclic alkylene group having 2 to 12 carbon atoms, or a divalent aromatic group. The W here is applied only in the above formula.
Examples of the compounds represented by the formula (C-16) include compounds represented by the following formulae (C-17) to (C-20).
As the compound containing two or more nitrogen atoms each of which has a glycidyl group(s) represented by the formula (C-2), a compound represented by the following formula (C-21) may be suitably used.
One kind or two kinds of these compounds containing two or more nitrogen atoms each of which has a glycidyl group(s) represented by the formula (C-2) may be used as a crosslinking agent.
The (C) component is a component that causes a crosslinking reaction in the post-curing after forming a pattern of the positive photosensitive resin composition of the present invention to further increase the strength of a cured product. A weight average molecular weight of the (C) component like this is preferable to be 150 to 10,000, and particularly preferable to be 200 to 3,000, from the viewpoint of the photocurability and heat resistance.
In the positive photosensitive resin composition of the present invention, a blending amount of the (C) component is preferably 0.5 to 50 parts by mass, and particularly preferably 1 to 30 parts by mass relative to 100 parts by mass of the (A-1) component.
((E) Compound that Generates Acid by Heat)
The positive photosensitive resin composition of the present invention may further contain (E) a compound that generates an acid by heat. The compound generating an acid by heat of the (E) component may be added to thermally expedite a crosslinking reaction with the (A-1) component in a step of heating and post-curing in a temperature of 100 to 300° C. performed after the pattern formation.
In particular, as the (E) component, one that doesn't encourage the curing of a film and doesn't disturb the pattern formation until a pattern is formed by development. In order to realize this, the (E) component is preferably one that, after the photosensitive resin composition is coated, doesn't generate an acid at a temperature in a step of removing a solvent and drying, but generates an acid by a heat treatment after pattern formation to encourage the curing of the pattern or a film of the photosensitive resin composition. Specifically, a compound that is decomposed by a heat treatment at 100° C. to 300° C., preferably at 150° C. to 300° C. to generate an acid is preferable. By containing such component (E), crosslinking and curing reaction of the pattern or the film of the positive photosensitive resin composition can be further promoted in the step of heating and post-curing at 100 to 300° C. after patterning. The (E) component makes it possible to further improve the mechanical strength, the chemical resistance, the adhesiveness or the like of the obtained pattern or film, by further forwarding the crosslinking, and the curing reaction.
As the compound that generates an acid by a suitable heat, compounds described in paragraphs [0061] to [0085] of the publication of JP 2007-199653 A may be exemplified.
A Blending Amount of the Compound that Generates an acid by heat is preferably 0.1 part by mass or larger, more preferably 0.5 part by mass or larger, and, preferably 30 parts by mass or smaller, and more preferably 10 parts by mass or smaller relative to 100 parts by mass of the (A-1) component in the positive photosensitive resin composition of the present invention.
(Other components)
In the positive photosensitive resin composition of the present invention, components other than the (A-1), (A-2), (B), (C), (D) and (E) component may be further contained. As such other components, for example, an adhesive aide, (G) a surfactant and the like may be contained. As the (G) surfactant, compounds illustrated below may be preferably contained.
As the (G) surfactant, a nonionic surfactant is preferable. Examples thereof include fluorinated surfactants, specifically, perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, and a fluorine-containing organosiloxane compound.
As these surfactants, commercially available ones may be used. Example thereof include Fluorad “FC-4430” (manufactured by Sumitomo 3M Limited), Surflon “S-141” and “S-145” (all manufactured by ASAHI GLASS CO., LTD.), UNIDYNE “DS-401”, “DS-4031” and “DS-451” (all manufactured by DAIKIN INDUSTRIES, LTD.), Megafac “F-8151” (manufactured by DIC Corporation), “X-70-093” (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Among these, preferred are Fluorad “FC-4430” (manufactured by Sumitomo 3M Limited) and “X-70-093” (manufactured by from Shin-Etsu Chemical Co., Ltd.).
(Patterning process)
The present invention provides a patterning process comprising the following steps.
(1) A step of coating the positive photosensitive resin composition on a substrate to form a photosensitive material film,
(2) subsequently, after a heat treatment, a step of exposing a photosensitive material film with a high energy beam having a wavelength of 190 to 500 nm or an electron beam via a photomask, and,
(3) a step of developing with a developer of an alkaline aqueous solution.
In the following, a patterning process using the positive photosensitive resin composition of the present invention will be described.
In the positive photosensitive resin composition of the present invention, in order to form a pattern, a well-known lithography technology may be adopted and performed. For example, on a silicon wafer, a SiO2 substrate, a SiN substrate, or a substrate on which a pattern such as copper wiring is formed, the photosensitive resin composition is coated by a technique of spin-coating (spin-coating method), followed by prebaking under the condition at 80 to 130° C., and about for 50 to 600 seconds to form a photosensitive film having a thickness of 1 to 50 μm, preferably 1 to 30 μm, and furthermore preferably 5 to 20 μm.
According to the spin-coating method, after dispensing about 5 mL of the photosensitive resin composition on such a silicon substrate, by rotating the substrate, the photosensitive resin composition may be coated on the substrate. At this time, by adjusting the rotation rate, a film thickness of the photosensitive film on the substrate may be readily adjusted.
Subsequently, by holding a mask for forming a target pattern over the photosensitive material film, a high energy beam of a wavelength of 190 to 500 nm such as an i-line and a g-line or an electron beam is irradiated such that an exposure dose is about 1 to 5,000 mJ/cm2, preferably about 100 to 2,000 mJ/cm2.
Subsequently, as needs arise, at 60 to 150° C. for 1 to 10 minutes, preferably at 80 to 120° C. for 1 to 5 minutes on such a hot plate, a post-exposure heat treatment (post exposure baking (PEB)) may be applied.
After that, the development is applied. In the positive photosensitive resin composition of the present invention, an alkaline development using an alkaline aqueous solution may be applied.
Examples of the aqueous alkaline solution that can be favorably used for the alkali development include 2.38% aqueous tetramethylammonium hydroxide (TMAH) solution. The development may be performed according to an ordinary method such as a spray method and a paddle method, or by dipping in the developer, or the like. After that, as needs arise, by performing cleaning, rinsing, drying or the like, a resist film having a desired pattern may be obtained.
The film having a pattern obtained by the patterning process may be baked and post-cured with an oven or a hot plate at 100 to 300° C., preferably 150 to 300° C., more preferably 180 to 250° C. to form a cured film. In this post-curing step, the post-curing temperature of 100 to 300° C. allows the film of the photosensitive resin composition to increase the crosslinking density and to remove remaining volatile components. Thus, this temperature range is preferable in view of adhesiveness to a substrate, heat resistance, strength, and electronic characteristics. The time for the post-curing can be 10 minutes to 10 hours.
The formed pattern is used for the purpose of a protective film for covering wirings, circuits and substrates, and the like. The formed patterns and protective films, while having excellent insulation property, have excellent adhesive force on a metal layer such as Cu of wirings and circuits to be covered, on a metal electrode existing on the substrate, or on an insulating substrate such as SiN existing in wirings and circuits to be covered, and make it possible, while having the mechanical strength appropriate as a protective film, to remarkably improve the resolution performance for enabling a finer pattern formation.
The cured film thus obtained is excellent in the adhesiveness to the substrate, heat resistance, electric characteristics, mechanical strength and chemical resistance to an alkaline peeling solution, and the like, and also excellent in reliability of a semiconductor device using the film as a protective film, in particular, it is possible to prevent occurrence of cracks in the temperature cycle test, it can be suitably used as a protective film (an interlayer insulating film or a surface protective film) for electric and electronic parts, a semiconductor device, and the like.
That is, the present invention provides an interlayer insulation film or a surface protective film made of the cured film obtained by curing the positive photosensitive resin composition.
The above protective film is useful for an insulator film for a semiconductor device including rewiring use, an insulator film for a multilayer printed substrate, a solder mask, and a cover lay film, because of its heat resistance, chemical resistance, and insulating property.
Furthermore, the present invention provides an electronic component having the interlayer insulation film or the surface protective film.
The electronic component like this becomes excellent in reliability because the electronic component has the protective film (interlayer insulation film or surface protective film) having heat resistance, chemical resistance, and the insulation property.
In what follows, with reference to synthesis examples, comparative synthesis examples, examples and comparative examples, the present invention will be specifically described. However, the present invention is not limited to the following examples.
1. Synthesis of Resin In the following synthesis examples, chemical structures and names of the used compounds are shown below.
Into a 1 L flask provided with a stirrer and a thermometer, 30 g (81.9 mmol) of 2,2,-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9 g (8.6 mmol) of 4-aminophenol(PAP) and 125 g of N-methyl-2-pyrollidone were added, followed by dissolving by stirring at room temperature. Next, under room temperature, a solution in which 26.7 g (86.2 mmol) of 3,3′,4,4′-oxydiphthalic dianhydride (s-ODPA) was dissolved in 270 g of N-methyl-2-pyrrolidone was dropped thereto, after dropping, followed by stirring for 3 hours under room temperature. Thereafter, 40 g of xylene was added to the reaction liquid, followed by heating and refluxing for 3 hours while removing water generated at 170° C. outside the system. After cooling to the room temperature, the reaction liquid was dropped into 2 L of ultrapure water under stirring, a precipitate was filtered to be washed appropriately with water, followed by drying under reduced pressure at 40° C. for 48 hours, a polyimide resin (A1-1) was obtained. A molecular weight of the polymer was measured by GPC. A weight average molecular weight was 35,000 in terms of polystyrene.
As a diamine compound, a monoamine compound, and a tetracarboxylic dianhydride, compounds of the weights shown in the following Table 1 were used, and, according to the same formulation as the synthesis example 1, polyimide resins (A1-2) to (A1-8), and (B-1) were obtained. A molecular weight of each of polymers was measured according to the GPC, weight average molecular weights in terms of polystyrene are shown in the following Table 1.
Diester Dichloride (X-1)) Into a 3 L flask provided with a stirrer and a thermometer, 100 g (322 mmol) of 3,3′,4,4′-oxydiphthalic dianhydride (s-ODPA), 65.2 g (644 mmol) of triethylamine, 39.3 g (322 mmol) of N,N-dimethyl-4-aminopyridine, and 400 g of γ-butyrolactone were added, under stirring at room temperature, 114.7 g (644 mmol) of 4,4,5,5,5-pentafluoropentanol (Rf-1) was dropped thereto, followed by stirring for 24 hours under room temperature. After that, 370 g of a 10% aqueous solution of hydrochloric acid was dropped under ice cooling to stop the reaction. To the reaction liquid, 800 g of 4-methyl-2-pentanone was added to sample an organic layer, followed by washing 6 times with 600 g of ultrapure water. A solvent of the obtained organic layer was distilled and 193 g of a tetracarboxylic diester compound was obtained. To the obtained tetracarboxylic diester compound, 772 g of N-methyl-2-pyrolidone was added, followed by dissolving by stirring at room temperature. Next, under ice cooling, 75.8 g (637 mmol) of thionyl chloride was added such that a temperature of the reaction liquid keeps 10° C. or lower, after the end of the dropping, followed by stirring for 2 hours under ice cooling, and a N-methyl-2-pyrolidone solution of tetracarboxylic diester dichloride (X-1) was obtained.
In the Synthesis Example 9, 3,3′,4,4′-oxydiphthalic dianhydride (s-ODPA) was substituted with 94.8 g (322 mmol) of 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (s-BPDA), and the others are in the same procedures, a N-methyl-2-pyrolidone solution of tetracarboxylic diester dichloride (X-2) was obtained.
In the Synthesis Example 9, 4,4,5,5,5-pentafluoropentanol (Rf-1) was substituted with 170.1 g (644 mmol) of 1H, 1H, 2H, 2H-nonafluoro-1-hexanol (Rf-2), and the others are in the same procedures, a N-methyl-2-pyrolidone solution of tetracarboxylic diester dichloride (X-3) was obtained.
In the Synthesis Example 9, 4,4,5,5,5-pentafluoropentanol (Rf-1) was substituted with 136.6 g (644 mmol) of 1-trifluoromethyl-2,2,2-trifluoroethyl-2′-hydroxyethyl ether (Rf-3), and the others are in the same procedures, a N-methyl-2-pyrolidone solution of tetracarboxylic diester dichloride (X-4) was obtained.
In the Synthesis Example 9, 4,4,5,5,5-pentafluoropentanol (Rf-1) was substituted with 112.2 g (644 mmol) of 3,3,3-trifluoropropyl-2′-hydroxyethyl ether (Rf-4), and the others are in the same procedures, a N-methyl-2-pyrolidone solution of tetracarboxylic diester dichloride (X-5) was obtained.
In the Synthesis Example 9, 4,4,5,5,5-pentafluoropentanol (Rf-1) was substituted with 101.8 g (644 mmol) of 2-hydroxyethyl trifluoroacetate (Rf-5), and the others are in the same procedures, an N-methyl-2-pyrolidone solution of tetracarboxylic diester dichloride (X-6) was obtained.
In the Synthesis Example 9, 4,4,5,5,5-pentafluoropentanol (Rf-1) was substituted with 101.8 g (644 mmol) of 3-hydroxy-2,2-dimethylpropyl trifluoroacetate (Rf-6), and the others are in the same procedures, an N-methyl-2-pyrolidone solution of tetracarboxylic diester dichloride (X-7) was obtained.
In the Synthesis Example 9, 4,4,5,5,5-pentafluoropentanol (Rf-1) was substituted with 189.4 g (644 mmol) of 4,4,5,5,6,6,7,7,7-nonafluoro-1,2-heptane diol (Rf-7), and the others are in the same procedures, a N-methyl-2-pyrolidone solution of tetracarboxylic diester dichloride (X-8) was obtained.
Into a 500 ml flask provided with a stirrer and a thermometer, 28.5 g (77.9 mmol) of 2,2,-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.4 g (4.1 mmol) of 4-aminophenol(PAP), and 125 g of N-methyl-2-pyrollidone were added, followed by dissolving by stirring at room temperature. Next, under room temperature, a solution in which 15.3 g (49.2 mmol) of 3,3′,4,4′-oxydiphthalic dianhydride (s-ODPA) was dissolved in 155 g of N-methyl-2-pyrrolidone was dropped thereto, after the end of dropping, followed by stirring for 3 hours under room temperature. Thereafter, 40 g of xylene was added to the reaction liquid, followed by heating and refluxing for 3 hours while removing water generated at 170° C. outside the system. After cooling to the room temperature, 1.4 g (18.0 mmol) of pyridine was added thereto, and a mixed liquid of 14.7 g (4.1 mmol as tetracarboxylic diester dichloride) of a separately prepared N-methyl-2-pyrolidone solution (X-1) of tetracarboxylic diester dichloride and 6.9 g (28.7 mmol) of sebacoyl dichloride (DC-1) was dropped thereto so as to keep the temperature to 5° C. or lower. After the end of the dropping, the temperature is returned to the room temperature, the reaction liquid was dropped into 2 L of ultrapure water under stirring, a precipitate was filtered to be washed appropriately with water, followed by drying under reduced pressure at 40° C. for 48 hours, and a polyamide-imide resin (A1-9) was obtained. A molecular weight of the polymer was measured by GPC. A weight average molecular weight was 35,000 in terms of polystyrene.
As a diamine compound, a monoamine compound, a tetracarboxylic dianhydride, and a tetracarboxylic diester dichloride, compounds of the weights shown in the following Table 2 were used, with the same procedures as that of Synthesis Example 17, polyamide-imide resins (A1-10) to (A1-21) were obtained. By measuring a molecular weight of each of polymers by GPC, weight average molecular weights in terms of polystyrene are shown in the following Table 2.
(2) Tetracarboxylic dianhydride
(3) Dicarboxy acid dichloride
(4) NMP solution of Tetracarboxylic diester dichloride: in ( ), number of moles as tetracarboxylic diester dichloride
Into a 1 L flask provided with a stirrer and a thermometer, 30 g (93.7 mmol) of 2,2,-bis(trifluormethyl)benzidine (TFMB), 5.9 g (62.5 mmol) of 4-aminopyridine (4APY), and 144 g of N-methyl-2-pyrolidone were added, followed by dissolving by stirring at room temperature. Next, under room temperature, a solution obtained by dissolving 38.8 g (125.0 mmol) of 3,3′,4,4′-oxydiphthalic dianhydride (s-ODPA) in 390 g of N-methyl-2-pyrrolidone was dropped thereto, after the end of the dropping, followed by stirring for 3 hours under room temperature. After that, 40 g of xylene was added to the reaction liquid, followed by heating and refluxing for 3 hours while removing water generated at 170° C. outside of the system. After cooling to the room temperature, the reaction liquid was dropped into 2 L of ultrapure water under stirring, followed by filtering a precipitate, followed by properly washing with water, further followed by drying under reduced pressure at 40° C. for 48 hours, thus a polyimide resin (A2-1) was obtained. By measuring a molecular weight of the polymer by GPC, a weight average molecular weight was 6,500 in terms of polystyrene.
As a diamine compound, a monoamine compound, and a tetracarboxylic dianhydride, compounds of the weights shown in the following Table 3 were used, with the same procedures as that of Synthesis Example 30, polyimide resins (A2-2) to (A2-8) were obtained. By measuring a molecular weight of each of polymers by GPC, weight average molecular weights in terms of polystyrene are shown in the following Table 3.
Polyimide resins (A1-1) to (A1-8), (B-1) synthesized in the Synthesis Example 1 to Synthesis Example 8 and Comparative Synthesis Example 1, polyamide-imide resins (A1-9) to (A1-21) synthesized in Synthesis Examples 17 to Synthesis Example 29, and nitrogen-containing heterocycle-containing polyimide resins (A2-2) to (A2-8) synthesized according to Synthesis example 31 to Synthesis example 37 were used as a base resin, with compositions and blending amounts described in Table 4A to 4C, resin compositions of 30 mass % in terms of resin were prepared. Thereafter, after stirring, mixing, and dissolving, micro-filtering was applied with a Teflon (registered trade mark) 0.5 μm filter, and a photosensitive resin composition was obtained. In Table, PGMEA of a solvent represents propylene glycol monomethyl ether acetate and GBL represents γ-butyrolactone.
In the Table 4A to 40, details of the photosensitizer (photosensitizer 1) which are quinonediazide compounds, the crosslinking agents (CL-1, (CL-2), and the acid generator (E-1), are as shown below.
In the formula, Q represents a 1,2-naphthoquinone diazidosulfonyl group represented by the following formula (40) or a hydrogen atom, and 90% of the Q is substituted with the 1,2-naphthoquinone diazidosulfonyl group represented by the following formula (40).
Epoxy resin: EP4000L manufactured by ADEKA Corporation
By rotating a substrate after each of the photosensitive resin compositions 1 to 34, and comparative photosensitive resin compositions 1 to 3 was dispensed by 5 mL on a silicon substrate, that is, by a spin coating method, the photosensitive resin composition was coated such that a film thickness is 10 μm after patterning and heating for the post-curing. That is, by studying in advance that after the post-curing step, the film thickness decreases, the number of rotation during coating was adjusted such that a finishing film thickness after the post-curing is 10 μm.
Subsequently, prebaking was applied on a hot plate at 100° C. for 2 minutes. Then, i-line exposure and patterning was performed with an i-line stepper NSR-2205ill manufactured by Nikon Corporation. In the patterning, a mask for a positive pattern was used. The mask has a pattern which can form a hole of 20 μm in lengthwise and breadthwise arrangement of 1:1, and can form a hole pattern of 10 μm in increments from 50 μm to 20 μm, 5 μm in increments from 20 μm to 10 μm, and 1 μm in increments from 10 μm to 1 μm.
In the development step, an alkaline aqueous solution was used as a developer, and a 2.38% tetramethyl ammonium hydroxide aqueous solution was used as the developer. After performing three times paddle development with the 2.38% tetramethyl ammonium hydroxide (TMAH) aqueous solution for 1 minute, followed by rinsing with ultrapure water.
Next, the obtained pattern on the substrate was post-cured with an oven at 180° C. for 2 hours while purging with nitrogen.
Subsequently, each substrate was cutout such that a shape of the obtained hole pattern may be observed, followed by observing a shape of the hole pattern with a scanning electron microscope (SEM). A minimum aperture diameter of the opening holes was measured on the post-cured film having a thickness of 10 μm, followed by evaluating a shape of the pattern. The sensitivity at which the minimum pattern was formed was shown in Table 5A and 5B together with these results.
The pattern shape of hole was evaluated based on the following criteria, and evaluation results are shown in Table 5A and 5B.
good: It was observed as a rectangular shape or a forward tapered shape (a dimension of a hole upper part is larger than a dimension of a bottom part).
poor: It was observed as an inversely tapered shape (a shape where a dimension of a hole upper part is smaller than a dimension of a bottom part), an overhang shape (a shape where a hole upper part protrudes), one having drastic thickness reduction, or one having a residue on a bottom surface.
The photosensitive resin compositions 1 to 34 and comparative photosensitive resin compositions 1 to 3 each was spin-coated on an aluminum substrate such that a finishing film thickness after curing is 10 μm. Subsequently, prebaking was applied on a hot plate at 100° C. for 3 minutes, and a photosensitive resin film was obtained.
Thereafter, curing was performed with an oven at 180° C. for 2 hours while purging with nitrogen and a photosensitive resin cured film was obtained. Next, a wafer with a cured film was cut in strips of a width of 10 mm and a length of 60 mm, followed by peeling the cured film from the substrate by dipping in hydrochloric acid of 20 mass %. The obtained cured film was subjected to a measurement of the rupture elongation using an Autograph AGX-1KN manufactured by Shimadzu Corporation. The measurement was performed 10 times a sample, and an average value thereof is shown in Table 5A and 5B.
As shown in Table 5A and 5B, since the positive photosensitive resin compositions of the present invention show an excellent pattern shape in the alkali solvent development, and the minimum hole dimension shows a value smaller than the finishing film thickness of 10 μm, it was found that an aspect ratio of 1 or larger can be achieved.
Furthermore, even when the positive photosensitive resin compositions of the present invention were cured at low temperatures, cured films having excellent mechanical strength were obtained.
On the contrary, the cured films obtained by using the comparative photosensitive resin compositions 1 to 3 resulted in poor mechanical characteristics than the cured films obtained from the compositions of the present invention.
It is to be noted that the present invention is not restricted to the foregoing embodiment. The embodiment is just an exemplification, and any examples that have substantially the same feature and demonstrate the same functions and effects as those in the technical concept described in claims of the present invention are included in the technical scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-77383 | Apr 2019 | JP | national |
