Patent Application
20220144745
This application claims priority to Japanese Patent Application No. 2020-185798, filed Nov. 6, 2020, the entire content of which is incorporated herein by reference.
The present invention relates to an energy-sensitive composition, a cured product, a forming method of a cured product, thermal base generator, and a compound.
Polysilanes having a silicon-silicon bond have been used in applications, for example, ceramic precursors, optoelectronic materials (for example, optoelectronic photographic materials such as photoresists and organic photoreceptors, optical transmission materials such as optical waveguides, optical recording materials such as optical memories, materials for electroluminescence elements), interlayer insulating films and protective films in various elements, sealing materials of light-emitting elements such as LED elements and organic EL elements, coating films for diffusion of impurities to semiconductor substrates, gap filling materials for semiconductor process and the like.
Various compositions containing a polysilane have been developed. For example, an energy-sensitive composition containing a polysilane, and a base generator has been developed (see, Patent Document 1, etc.). In such an energy-sensitive composition, an increase in molecular weight of the polysilane occurs by an action of a base generated from the base generator, to give a cured product. The cured product can be used for the materials mentioned above.
After the cured product of the energy-sensitive composition is formed, the cured product is heated in some cases. For example, in some cases, the heating is conducted to form other member after the cured product is formed, and/or further heating is conducted for an annealing treatment to relieve the residual stress of the cured product, etc. Thus, it is desirable for the cured product to be resistant to cracking upon heating, in other words, to have excellent crack resistance.
However, some of cured products obtained using conventionally-known polysilane-containing compositions as disclosed in Patent Document 1, etc. have insufficient crack resistance.
In light of the above problems of the prior art, an object of the present invention is to provide an energy-sensitive composition that yields a cured product with excellent crack resistance, a cured product of the energy-sensitive composition, a forming method of a cured product, a thermal base generator, and a compound.
The present inventors have found that an energy-sensitive composition containing a polysilane (A), and a thermal base generator (B), in which the thermal base generator (B) includes a compound represented by the following formula (b1), solves the problem, thus completing the present invention. Specifically, the present invention provides the following.
A first aspect of the present invention relates to an energy-sensitive composition containing a polysilane (A), and a thermal base generator (B), wherein the thermal base generator (B) includes a compound represented by the following formula (b1):
wherein in the formula (b1), Rb1 and Rb2 each independently represent a halogen atom, a nitro group, an alkyl group, an aryl group, an arylalkyl group, or an alkoxy group;
Rb3 represents a hydrogen atom or an alkyl group;
n1 and n2 each independently represent an integer of 0 or more and 4 or less;
Zq+ represents a q-valent organic cation composed of a base having a pKa of greater than 15; and
q represents an integer of 1 or more.
A second aspect of the present invention relates to a cured product of the energy-sensitive composition according to the first aspect.
A third aspect of the present invention relates to a method for forming a cured product, including applying the energy-sensitive composition according to the first aspect onto a substrate to form a coating film, and heating the coating film for curing.
A fourth aspect of the present invention relates to a thermal base generator including a compound represented by the following formula (b1a):
wherein in the formula (b1a), Rb1 and Rb2 each independently represent a halogen atom, a nitro group, an alkyl group, an aryl group, an arylalkyl group, or an alkoxy group;
Rb3 represents a hydrogen atom or an alkyl group;
n1 and n2 each independently represent an integer of 0 or more and 4 or less;
Xq+ represents a q-valent counter cation composed of a base having a pKa of greater than 15,
q represents an integer of 1 or more.
A fifth aspect of the present invention relates to a compound represented by the following formula (b1a):
wherein in the formula (b1a), Rb1 and Rb2 each independently represent a halogen atom, a nitro group, an alkyl group, an aryl group, an arylalkyl group, or an alkoxy group;
Rb3 represents a hydrogen atom or an alkyl group;
n1 and n2 each independently represent an integer of 0 or more and 4 or less;
Xq+ represents a q-valent counter cation composed of a base having a pKa of greater than 15; and
q represents an integer of 1 or more.
According to the present invention, it is possible to provide an energy-sensitive composition which yields a cured product with excellent crack resistance, a cured product of the energy-sensitive composition, and a forming method of a cured product, as well as a thermal base generator and a compound which can be used in the energy-sensitive composition.
Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be implemented by appropriately introducing variations within the object of the present invention. “To” in phrases of the type of “a lower limit to an upper limit” as used herein means a range between the lower limit and the upper limit inclusive, unless otherwise specified.
An energy-sensitive composition contains a polysilane (A), and a thermal base generator (B). The thermal base generator (B) includes a compound represented by formula (b1). Hereinafter, essential components and optional components contained in the energy-sensitive composition, as well as a production method and applications of the energy-sensitive composition will be described.
The structure of the polysilane (A) contained in the energy-sensitive composition is not particularly limited. The polysilane (A) may be linear, branched, network-like, or cyclic, and a linear or branched chain structure is preferable. The polysilane (A) may contain a silanol group or an alkoxy group. A suitable polysilane (A) is exemplified by a polysilane which includes at least one of the units represented by the following formulas (a1) and (a2) as an essential unit, and may contain at least one unit selected from the units represented by the following formulas (a3) to (a5). Such a polysilane may contain a silanol group, or an alkoxy group bonded to a silicon atom.
In the formulas (a1) to (a5), Ra1 and Ra2 each independently represent a hydrogen atom, an organic group or a silyl group; and Ra3 represents a hydrogen atom or an alkyl group.
When Ra3 is an alkyl group, an alkyl group having 1 or more and 4 or less carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.
With regard to Ra1 and Ra2, examples of the organic group include a hydrocarbon group such as an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group and an aralkyl group, an alkoxy group, an alkenyloxy group, a cycloalkoxy group, a cycloalkenyloxy group, an aryloxy group, an aralkyloxy group, and the like. Among these groups, an alkyl group, an aryl group, and an aralkyl group are preferable. The alkyl group is preferably a linear or branched alkyl group having 1 or more and 20 or less carbon atoms, and more preferably a linear or branched alkyl group having 1 or more and 4 or less carbon atoms. Suitable examples of the aryl group include the following groups.
In the above formulas, Ra4 represents: a hydrogen atom; a hydroxyl group; an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group, and a propoxy group; or a hydrocarbon group such as a methyl group, an ethyl group, a butyl group, or a propyl group. In the above formulas, Ra5 represents an alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group.
Suitable specific examples of the aryl group or aralkyl group include a benzyl group, a phenethyl group, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenylyl group, a fluorenyl group, a pyrenyl group, and the like.
When Ra1 and Ra2 are each a silyl group, examples of the silyl group include Si1-10 silanyl groups (Si1-6 silanyl groups, etc.) such as a silyl group, a disilanyl group, and a trisilanyl group. The polysilane preferably includes any of the following units (a6) to (a9):
wherein in the formulas (a6) to (a9), Ra1 and Ra2 are the same as Ra1 and Ra2 in the formulas (a1), (a3) and (a4); and the symbols a, b, and c are each an integer of 2 or more and 1,000 or less. The symbols a, b, and c are each preferably 3 or more and 500 or less, and more preferably 5 or more and 100 or less. Each constituent unit may be included at random, or in a block-like manner.
Among the polysilanes described hereinabove, a polysilane including an alkyl group in combination with an aryl group or an aralkyl group, wherein the alkyl group, the aryl group and the aralkyl group are each bonded to a silicon atom, or a polysilane having only an alkyl group bonded to a silicon atom is preferable. More particularly, a polysilane including a methyl group in combination with a benzyl group, wherein the methyl group and the benzyl group are each bonded to a silicon atom, a polysilane including a methyl group in combination with a phenyl group, wherein the methyl group and the phenyl group are each bonded to a silicon atom, or a polysilane having only a methyl group bonded to a silicon atom is preferably used.
The mass average molecular weight of the polysilane is preferably 300 or more and 100,000 or less, more preferably 500 or more and 70,000 or less, and even more preferably 800 or more and 30,000 or less, in terms of polystyrene. Two or more types of polysilanes having different mass average molecular weights may be mixed.
The content of the polysilane (A) in the energy-sensitive composition is not particularly limited, and may be adjusted according to a desired film thickness. In view of film-forming properties, the content of the polysilane (A) in the energy-sensitive composition is preferably 1% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 40% by mass or less, and particularly preferably 5% by mass or more and 35% by mass or less.
The energy-sensitive composition contains a compound represented by the following formula (b1) as the thermal base generator (B). The thermal base generator (B) is composed of a compound that generates a base upon heating. The base generated by the thermal base generator (B) upon heating causes an increase in molecular weight of the polysilane (A) to occur, resulting in the formation of a cured product. It should be noted that the thermal base generator (B) may be a compound capable of generating a base with the assistance of light (i.e. the thermal base generator (B) may be a compound capable of generating a base upon exposure to light), so long as the compound generates a base upon heating.
In the formula (b1), Rb1 and Rb2 each independently represent a halogen atom, a nitro group, an alkyl group, an aryl group, an arylalkyl group, or an alkoxy group;
Rb3 represents a hydrogen atom or an alkyl group;
n1 and n2 each independently represent an integer of 0 or more and 4 or less;
Zq+ represents a q-valent organic cation composed of a base having a pKa of greater than 15; and
q represents an integer of 1 or more.
Examples of the halogen atom of Rb1 and Rb2 in the formula (b1) include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and the halogen atom is preferably a chlorine atom or a bromine atom. Examples of the alkyl group of Rb1 and Rb2 include alkyl groups having 1 or more and 12 or less carbon atoms (preferably having 1 or more and 10 or less carbon atoms, and more preferably having 1 or more and 6 or less carbon atoms) which may have a substituent or not, and may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, a 2-methylbutyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a cyclopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a neohexyl group, a 2-methylpentyl group, a 1,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 1-ethylbutyl group, a cyclohexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, a neoheptyl group, a cycloheptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, a neooctyl group, a 2-ethylhexyl group, a cyclooctyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, a neononyl group, a cyclononyl group, an n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, a neodecyl group, a cyclodecyl group, an n-undecyl group, a cycloundecyl group, an n-dodecyl group, a cyclododecyl group, a nonylbonyl group (norbornan-χ-yl group), a bornyl group (bornan-χ-yl group), a menthyl group (menth-χ-yl group), an adamantyl group, a decahydronaphthyl group and the like.
Among the above-mentioned alkyl groups, for example, linear, branched or cyclic alkyl groups having 1 or more and 4 or less carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and a cyclobutyl group are preferable, and alkyl groups having 1 carbon atom such as a methyl group are more preferable.
Examples of the aryl group of Rb1 and Rb2 include aryl groups having 6 or more and 14 or less carbon atoms which may be monocyclic or fused polycyclic and may have a substituent or not, such as a phenyl group, a naphthyl group, an anthracenyl group (anthryl group) and a phenanthrenyl group (phenanthryl group). Among these aryl groups, for example, aryl groups having 6 or more and 10 or less carbon atoms, such as a phenyl group and a naphthyl group are preferable, and aryl groups having 6 carbon atoms such as a phenyl group are more preferable.
Examples of the arylalkyl group of Rb1 and Rb2 include arylalkyl groups having 7 or more and 15 or less carbon atoms which may have a substituent or not and may be monocyclic or fused polycyclic, such as a benzyl group, a phenethyl group, a methylbenzyl group, a phenylpropyl group, a 1-methylphenylethyl group, a phenylbutyl group, a 2-methylphenylpropyl group, a tetrahydronaphthyl group, a naphthylmethyl group, a naphthylethyl group, an indenyl group, a fluorenyl group, an anthracenylmethyl group (anthrylmethyl group) and a phenanthrenylmethyl group (phenanthrylmethyl group). Among these arylalkyl groups, arylalkyl groups having 7 carbon atoms such as a benzyl group are preferable.
Examples of the alkoxy group of Rb1 and Rb2 include alkoxy groups having 1 or more and 12 or less carbon atoms (preferably having 1 or more and 6 or less carbon atoms, and more preferably having 1 or more and 4 or less carbon atoms) which may have a substituent or not and may be linear, branched or cyclic such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a cyclobutoxy group, an n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a neopentyloxy group, a 2-methylbutoxy group, a 1,2-dimethylpropoxy group, a 1-ethylpropoxy group, a cyclopentyloxy group, an n-hexyloxy group, an isohexyloxy group, a sec-hexyloxy group, a tert-hexyloxy group, a neohexyloxy group, a 2-methylpentyloxy group, a 1,2-dimethylbutoxy group, a 2,3-dimethylbutoxy group, a 1-ethylbutoxy group, a cyclohexyloxy group, an n-heptyloxy group, an isoheptyloxy group, a sec-heptyloxy group, a tert-heptyloxy group, a neoheptyloxy group, a cycloheptyloxy group, an n-octyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, a neooctyloxy group, a 2-ethylhexyloxy group, a cyclooctyloxy group, an n-nonyloxy group, an isononyloxy group, a sec-nonyloxy group, a tert-nonyloxy group, a neononyloxy group, a cyclononyloxy group, an n-decyloxy group, an isodecyloxy group, a sec-decyloxy group, a tert-decyloxy group, a neodecyloxy group, a cyclodecyloxy group, an n-undecyloxy group, a cycloundecyloxy group, an n-dodecyloxy group, a cyclododecyloxy group, a norbornyloxy group (norbornan-χ-yloxy group), a bornyloxy group (bornan-χ-yloxy group), a menthyloxy group (menth-χ-yloxy group), an adamantyloxy group and a decahydronaphthyloxy group. Among these alkoxy groups, for example, linear, branched or cyclic alkoxy groups having 1 or more and 4 or less carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, isobutoxy group, a sec-butoxy group, a tert-butoxy group and a cyclobutoxy group are preferable, and alkoxy groups having 1 carbon atom such as a methoxy group are more preferable.
Examples of the alkyl group of Rb3 include alkyl groups having 1 or more and 4 or less carbon atoms which may have a substituent or not, and may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Rb1 and Rb2 are preferably an alkyl group having 1 or more and 12 or less carbon atoms. n1 and n2 is each preferably 0. q is preferably an integer of 1 or more and 3 or less, more preferably an integer of 1 or 2, and still more preferably 1.
Preferable specific examples of an anion moiety of the compound represented by the formula (b1) include the following anions.
In the formula (b1), the q-valent counter cation Zq+ is composed of an organic cation (organic base) composed of a base having a pKa value of greater than 15 (pKa of the conjugate acid), preferably 20 or more, more preferably 24 or more, and still more preferably 30 or more. This allows for the acceleration of the crosslinking reaction of the polysilane in a film. The upper limit of pKa is not particularly limited and is, for example, 50 or less, preferably 45 or less, more preferably 40 or less, and particularly preferably 35 or less.
As used herein, “pKa” means a pKa in an acetonitrile (CH3CN) solvent and is, for example, mentioned in Fourth Revision of Kagaku-Binran II (1993) edited by The Chemical Society of Japan, Maruzen Co., Ltd. The lower this value, the larger the acid strength. Regarding the pKa in CH3CN, it is also possible to determine the value based on a database of Hammett's substituent constant and known literature values by calculation (J. Org. Chem. 2016, 81, 7349-7361).
From a viewpoint of basicity and nucleophilicity to a silicon atom, the base having a pKa of greater than 15 which constitutes the q-valent counter cation Zq+ preferably includes at least one base selected from the group consisting of a phosphazene compound and an amidine compound, namely, the above q-valent counter cation Zq+ preferably includes at least one cation selected from the group consisting of a phosphazene compound cation and an amidine compound cation.
As used herein, “phosphazene compound” means “organic compound having a —P═N— bond in the molecule”. The number of —P═N— bonds in the above phosphazene compound is not particularly limited so long as the pKa of greater than 15 is achieved and includes 1 or more and 10 or less, and is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, still more preferably 2 or more and 4 or less, particularly preferably 2 or 3, and most preferably 2. The phosphazene compound is preferably a compound represented by the following formula (bc-1) or a compound in which at least two structures represented by the following formula (bc-1) are connected to each other, and more preferably a compound in which at least two structures represented by the following formula (bc-1) are connected to each other,
wherein, in the above formula (bc-1), Rbc1 to Rbc7 each independently represent a hydrogen atom or a monovalent organic group which may include a hetero atom, wherein at least two of Rbc1 to Rbc7 may be bonded to each other to form a ring. The monovalent organic group which may include a hetero atom of Rbc1 to Rbc7 preferably has 1 or more and 20 or less carbon atoms, more preferably 1 or more and 10 or less carbon atoms, and still more preferably 1 or more and 6 or less carbon atoms. Examples of the organic group include an alkyl group, an arylalkyl group and the like, which may include a hetero atom. The alkyl group which may include a hetero atom may be linear, branched or cyclic, and examples thereof include alkyl groups having 1 or more and 12 or less carbon atoms (preferably having 1 or more and 10 or less carbon atoms, and more preferably having 1 or more and 6 or less carbon atoms), and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, a 2-methylbutyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a cyclopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a neohexyl group, a 2-methylpentyl group, a 1,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 1-ethylbutyl group, a cyclohexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, a neoheptyl group, a cycloheptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, a neooctyl group, a 2-ethylhexyl group, a cyclooctyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, a neononyl group, a cyclononyl group, an n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, a neodecyl group, a cyclodecyl group, an n-undecyl group, a cycloundecyl group, an n-dodecyl group, a cyclododecyl group, a nonylbonyl group (norbornan-χ-yl group), a bornyl group (bornan-χ-yl group), a menthyl group (menth-χ-yl group), an adamantyl group, a decahydronaphthyl group and the like.
Among the above-mentioned alkyl groups, for example, linear, branched or cyclic alkyl groups having 1 or more and 4 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and a cyclobutyl group are preferable.
Examples of the arylalkyl group which may include a hetero atom include arylalkyl groups having 7 or more and 15 or less carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, a methylbenzyl group, a phenylpropyl group, a 1-methylphenylethyl group, a phenylbutyl group, a 2-methylphenylpropyl group, a tetrahydronaphthyl group, a naphthylmethyl group, a naphthylethyl group, an indenyl group, a fluorenyl group, an anthracenylmethyl group (anthrylmethyl group), a phenanthrenylmethyl group (phenanthrylmethyl group) and the like. Among these arylalkyl groups, arylalkyl groups having 7 carbon atoms, such as a benzyl group are preferable.
Examples of the hetero atom which can be possessed by the monovalent organic group of Rbc1 to Rbc7 include a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. It is preferable that the hetero atom is bonded to a carbon atom and does not constitute an acid functional group such as a carboxyl group or a sulfone group. It is preferable that Rbc7 is not a hydrogen atom. Examples of the ring which can be formed by at least two of Rbc1 to Rbc7 include a five-membered ring, a six-membered ring or a seven-membered ring, and the ring is preferably a six-membered ring.
The compound in which at least two structures represented by the above formula (bc-1) are connected to each other is preferably a compound in which two or more and six or less structures represented by the above formula (bc-1) are connected to each other, more preferably a compound in which two or more and four or less structures represented by the above formula (bc-1) are connected to each other, and still more preferably a compound in which two or three structures represented by the above formula (bc-1) are connected to each other. The aspect in which at least two structures represented by the above formula (bc-1) are connected to each other is preferably an aspect in which one structure represented by the above formula (bc-1) and the other structure represented by the above formula (bc-1) are connected so as to share one nitrogen atom in the above formula (bc-1). A molecular weight (Mw) of the phosphazene compound is, for example, 120 or more and 900 or less, and is preferably 250 or more and 600 or less, and more preferably 300 or more and 500 or less, from the viewpoint of curability or residual film properties.
Preferred specific examples of the phosphazene compound will be exemplified below, but are not limited thereto.
The amidine compound is preferably a compound represented by the following formula (bc-2):
wherein, in the above formula (bc-2), Rbc11 to Rbc14 each independently represent a hydrogen atom or a monovalent organic group which may include a hetero atom, wherein at least one of Rbc11 to Rbc14 represents a monovalent organic group which may include a hetero atom, and at least two of Rbc11 to Rbc14 may be bonded to each other to form a ring. Specific examples and preferred examples of the monovalent organic group which may include a hetero atom of Rbc11 to Rbc14 include those which are the same as mentioned above as the monovalent organic group which may include a hetero atom of Rbc1 to Rbc7. Examples of the hetero atom which can be possessed by the monovalent organic group of Rbc11 to Rbc14 include a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. It is preferable that the hetero atom is bonded to a carbon atom and does not constitute an acid functional group such as a carboxyl group or a sulfone group. It is preferable that Rbc14 is not a hydrogen atom. Examples of the ring which can be formed by at least two of Rbc11 to Rbc14 include a five-membered ring, a six-membered ring or a seven-membered ring, and the ring is preferably a six-membered ring or a seven-membered ring. Amidine including at least one ring structure (i.e., cyclic amidine) is preferable. Cyclic amidine including two ring structures (i.e., dicyclic amidine) is more preferable. The amidine compound is more preferably a compound represented by the following formula.
In the formula, r represents an integer of 1 or more and 3 or less.
Specific examples of the amidine compound include 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-diethyl-1,4,5,6-tetrahydropyrimidine, 1-n-propyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-isopropyl-2-methyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-n-propyl-1,4,5,6-tetrahydropyrimidine, 1-ethyl-2-isopropyl-1,4,5,6-tetrahydropyrimidine, DBU (i.e., 1,8-diazabicyclo[5.4.0]-7-undecene), DBN (i.e., 1,5-diazabicyclo[4.3.0]-5-nonene), TBD (i.e., 1,5,7-triazabicyclo[4.4.0]deca-5-ene) and those analogous thereto, and combinations thereof.
The compound represented by the formula (b1) can be produced by mixing an acid represented by the following formula with a base having a pKa of greater than 15 under arbitrary conditions to cause a reaction (for example, neutralization reaction),
wherein, in the formula, Rb1, Rb2, Rb3, n1 and n2 are each as defined in the formula (b1).
In the compound represented by the formula (b1), with regard to a constitutional molar ratio of the cation moiety and the anion moiety, the cation moiety:anion moiety is, for example, in a range of 1:1 to 1:2, and preferably 1:1 to 1:1.5.
The energy-sensitive composition may contain only one type of the compound represented by the formula (b1) alone, or a combination of two or more types thereof.
Since the energy-sensitive composition thus contains the compound represented by the formula (b1) as the thermal base generator (B) along with the polysilane (A), a cured product with excellent crack resistance can be formed. Therefore, a cured product formed from the energy-sensitive composition is less prone to cracking upon heating. Accordingly, after the formation of the cured product of the energy-sensitive composition, even when the cured product is heated to form other members, and/or further heated for an annealing treatment to relieve the residual stress of the cured product, the generation of cracks is suppressed. On the other hand, when the energy-sensitive composition contains no compound represented by the formula (b1), cracks are likely to be generated in the cured product upon heating.
In addition, the compound represented by the formula (b1) can generate the base at lower temperatures (for example, 90° C. or higher and below 200° C., and further 150° C. or lower) as well as at elevated temperatures (for example, 200° C. or higher). Therefore, the energy-sensitive composition containing the compound represented by the formula (b1) exhibits excellent curability even at lower temperatures, and allows the heating step in the formation of the cured product to be performed at lower temperatures. On the other hand, in the energy-sensitive composition containing the compound represented by the formula (b1), the heating step at elevated temperatures would reduce the amount of the residual compound represented by the formula (b1) in the cured product formed, leading to favorable film properties of the cured product (for example, the hardness and the lower dielectric constant of the film, and the like).
The content of the compound represented by the formula (b1) in the energy-sensitive composition is preferably 0.001% by mass or more and 10% by mass or less, more preferably 0.005% by mass or more and 5% by mass or less, and even more preferably 0.1% by mass or more and 3% by mass or less. Further, in the energy-sensitive composition, the mass of the compound represented by the formula (b1) is preferably 0.01 parts by mass or more and 30 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less, and even more preferably 1 part by mass or more and 15 parts by mass or less, when the mass of the polysilane (A) is 100 parts by mass.
[Thermal Base Generator Other than Compound Represented by Formula (b1)]
The thermal base generator (B) may further include a thermal base generator other than the compound represented by the formula (b1) (hereinafter, may be also referred to as “other thermal base generator”). The other thermal base generator can decompose by heat and generate a base. When the other thermal base generator is contained, an increase in molecular weight of the polysilane (A), and the like occurs by an action of the base generated from the compound represented by the formula (b1) as well as the base generated from the other thermal base generator, leading to curing of the energy-sensitive composition.
The other thermal base generator is exemplified by a nonionic compound. When the energy-sensitive composition contains, as the thermal base generator (B), the nonionic compound along with the compound represented by the formula (b1), a cured product with excellent thermal resistance can be formed. Therefore, a cured product formed from the energy-sensitive composition is less prone to deforming upon heating. Accordingly, after the formation of the cured product of the energy-sensitive composition, even when the cured product is heated to form other members, and/or further heated for an annealing treatment to relieve the residual stress of the cured product, the shape of the cured product can be maintained before the heating.
The nonionic compound is exemplified by a compound that generates an imidazole compound represented by the following formula (i) upon heating:
wherein in the formula (i), Rb11 to Rb13 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a phosphino group, a sulfonato group, a phosphinyl group, a phosphonato group, or an organic group.
The organic group in Rb11 to Rb13 is exemplified by an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and the like. The organic group may include a bond other than a hydrocarbon group such as a hetero atom, or substituent, therein. In addition, the organic group may be linear, branched or cyclic. This organic group is typically monovalent, and may be a divalent or higher multivalent organic group when the organic group forms a cyclic structure, or the like.
Rb11 and Rb12 may be bonded to each other to form a cyclic structure, and may further include a bond of a hetero atom. The cyclic structure is exemplified by a heterocycloalkyl group, a heteroaryl group, and the like, and may be a fused ring.
The bond included in the organic group represented by each of Rb11 to Rb13 is not particularly limited so long as the effects of the invention are not impaired, and the organic group may include a bond that includes a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. Specific examples of the bond that includes a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (—N═C(—R)—, —C(═NR)—, wherein R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.
The bond that includes a hetero atom, which may be included in the organic group represented by each of Rb11 to Rb13, is preferably an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (—N═C(—R)—, —C(═NR)—, wherein R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond in view of the heat-resistance of the imidazole compound.
When the organic group represented by each of Rb11 to Rb13 is a substituent other than a hydrocarbon group, Rb11 to Rb13 are not particularly limited so long as the effects of the invention are not impaired. Specific examples of the atom or group represented by Rb11 to Rb13 include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxylato group, an acyl group, an acyloxy group, a sulfino group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, an alkylether group, an alkenylether group, an alkylthioether group, an alkenylthioether group, an arylether group, an arylthioether group, and the like. The hydrogen atom(s) included in the substituent may be substituted with a hydrocarbon group. In addition, the hydrocarbon group included in the substituent may be linear, branched or cyclic.
As Rb11 to Rb13, a hydrogen atom, an alkyl group having 1 or more and 12 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, an alkoxy group having 1 or more and 12 or less carbon atoms, and a halogen atom are preferable, and a hydrogen atom is more preferable.
The compound that generates the imidazole compound represented by the formula (i) upon heating is obtained from a compound (thermal base generator) that generates an amine by an action of heat, which has been conventionally added to various compositions, by substituting the skeleton derived from an amine generated upon heating with a skeleton derived from the imidazole compound represented by the formula (i).
The compound that generates the imidazole compound represented by the formula (i) upon heating is exemplified by a compound represented by the following formula (b2):
wherein, in the formula (b2), Rb11 to Rb13 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group;
Rb14 and Rb15 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group; and
Rb16 to Rb20 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group,
wherein two or more of Rb16 to Rb20 may be bonded to each other to form a cyclic structure, and Rb16 to Rb20 may each include a bond of a hetero atom.
In the formula (b2), Rb11 to Rb13 are as defined in the formula i).
In the formula (b2), Rb14 and Rb15 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group.
Examples of the organic group in Rb14 and Rb15 include those listed for Rb11 to Rb13 by way of example. The organic group may include a hetero atom therein, similarly to Rb11 to Rb13. In addition, the organic group may be linear, branched or cyclic.
It is preferable that Rb14 and Rb15 each independently represent a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, a cycloalkyl group having 4 or more and 13 or less carbon atoms, a cycloalkenyl group having 4 or more and 13 or less carbon atoms, an aryloxyalkyl group having 7 or more and 16 or less carbon atoms, an aralkyl group having 7 or more and 20 or less carbon atoms, an alkyl group having 2 or more and 11 or less carbon atoms and a cyano group, an alkyl group having 1 or more and 10 or less carbon atoms and a hydroxyl group, an alkoxy group having 1 or more and 10 or less carbon atoms, an amide group having 2 or more and 11 or less carbon atoms, an alkylthio group having 1 or more and 10 or less carbon atoms, an acyl group having 1 or more and 10 or less carbon atoms, an ester group having 2 or more and 11 or less carbon atoms (—COOR, —OCOR, wherein R represents a hydrocarbon group), an aryl group having 6 or more and 20 or less carbon atoms, an aryl group having 6 or more and 20 or less carbon atoms and substituted with an electron-donating group and/or an electron-withdrawing group, a benzyl group substituted with an electron-donating group and/or an electron-withdrawing group, a cyano group, or a methylthio group, among the atoms and groups described above. More preferably, both of Rb14 and Rb is represent a hydrogen atom, or Rb14 represents a methyl group and Rb is represents a hydrogen atom.
In the formula (b2), Rb16 to Rb20 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group.
Examples of the organic group in Rb16 to Rb20 include those listed for Rb11 to Rb13 by way of example. The organic group may include a bond other than a hydrocarbon group such as a hetero atom, or substituent, therein, similarly to Rb11 and Rb12. In addition, the organic group may be linear, branched or cyclic.
Two or more of Rb16 to Rb20 may be bonded to each other to form a cyclic structure, and Rb16 to Rb20 may each include a bond of a hetero atom. The cyclic structure is exemplified by a heterocycloalkyl group, a heteroaryl group, and the like, and may be a fused ring. For example, two or more of Rb16 to Rb20 may be bonded to each other to form a fused ring such as naphthalene, anthracene, phenanthrene, and indene by sharing atoms of the benzene ring to which Rb16 to Rb20 are bonded.
It is preferable that Rb16 to Rb20 each independently represent a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, a cycloalkyl group having 4 or more and 13 or less carbon atoms, a cycloalkenyl group having 4 or more and 13 or less carbon atoms, an aryloxyalkyl group having 7 or more and 16 or less carbon atoms, an aralkyl group having 7 or more and 20 or less carbon atoms, an alkyl group having 2 or more and 11 or less carbon atoms and a cyano group, an alkyl group having 1 or more and 10 or less carbon atoms and a hydroxyl group, an alkoxy group having 1 or more and 10 or less carbon atoms, an amide group having 2 or more and 11 or less carbon atoms, an alkylthio group having 1 or more and 10 or less carbon atoms, an acyl group having 1 or more and 10 or less carbon atoms, an ester group having 2 or more and 11 or less carbon atoms, an aryl group having 6 or more and 20 or less carbon atoms, an aryl group having 6 or more and 20 or less carbon atoms and substituted with an electron-donating group and/or an electron-withdrawing group, a benzyl group substituted with an electron-donating group and/or an electron-withdrawing group, a cyano group, a methylthio group, or a nitro group, among the atoms and groups described above.
It is also preferable that two of Rb16 to Rb20 are bonded to form a fused ring such as naphthalene, anthracene, phenanthrene, and indene by sharing atoms of the benzene ring to which Rb16 to Rb20 are bonded.
Among the compounds represented by the above formula (b2), a compound represented by the following formula (b2-1) is preferable,
wherein, in the formula (b2-1), Rb11 to Rb13 are as defined in the formulas (i) and (b2);
Rb14 to Rb19 are as defined in the formula (b2); and
Rb21 represents a hydrogen atom or an organic group,
wherein Rb16 and Rb17 do not represent a hydroxyl group, and two or more of Rb16 to Rb19 may be bonded to each other to form a cyclic structure, and Rb16 to Rb19 may each include a bond of a hetero atom.
The compound represented by the formula (b2-1) has excellent solubility in an organic solvent because of the presence of the substituent —O—Rb21.
In the formula (b2-1), Rb21 represents a hydrogen atom or an organic group. When Rb21 is an organic group, examples of the organic group include those listed for Rb11 to Rb13 by way of example. The organic group may include a hetero atom therein. In addition, the organic group may be linear, branched or cyclic. As Rb21, a hydrogen atom, an alkyl group having 1 or more and 12 or less carbon atoms and an alkoxyalkyl group having 1 or more and 12 or less carbon atoms are preferable, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxymethyl group, and a butoxymethyl group are more preferable.
Specific examples of a particularly suitable compound as the compound that generates the imidazole compound represented by the formula (i) upon heating are shown below.
The energy-sensitive composition may contain only one type of the other thermal base generator or a combination of two or more types thereof.
When the thermal base generator (B) includes the other thermal base generator, the proportion of the mass of the compound represented by the formula (b1) is preferably 10% by mass or more and 95% by mass or less, and more preferably 15% by mass or more and 90% by mass or less, based on the sum of the mass of the compound represented by the formula (b1) and the mass of the other thermal base generator.
The proportion of the mass of the thermal base generator (B) is preferably 0.01% by mass or more and 15% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, and even more preferably 1% by mass or more and 5% by mass or less, based on the mass of the energy-sensitive composition. Further, in the energy-sensitive composition, the mass of the thermal base generator (B) is preferably 0.01 parts by mass or more and 30 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less, and even more preferably 1 part by mass or more and 15 parts by mass or less, when the mass of the polysilane (A) is 100 parts by mass.
The energy-sensitive composition may further contain an acid so as to improve the stability. From the viewpoint of the homogeneity (compatibility, affinity), the acid is preferably a conjugate acid of the anion moiety in the base generator represented by the above formula (b1), and specifically an acid represented by the following formula:
wherein, in the above formula, Rb1, Rb2, Rb3, n1, and n2 are the same as Rb1, Rb2, Rb3, n1, and n2 defined in the above formula (b1).
Examples of the acid other than the conjugate acid include any organic acid or inorganic acid, and the acid is preferably an organic acid. Examples of the acid other than the conjugate acid include monovalent or divalent or higher multivalent organic acid having 1 or more and 30 or less carbon atoms, and specific examples thereof include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, citric acid and the like. To maintain the stability, two or more acids may be used in combination.
The energy-sensitive composition may include the above acid or not and, and when including the acid, the amount of the acid used is usually 0.001% by mass or more and 10% by mass or less, and preferably 0.01% by mass or more and 5% by mass or less, based on the mass of the solid component (the mass of the energy-sensitive composition excluding the mass of a solvent) of the energy-sensitive composition.
A use ratio of the thermal base generator (B) to the acid in the energy-sensitive composition, for example, in terms of the thermal base generator (B):acid is 1:0.003 to 1:3.5, and preferably 1:0.01 to 1:3, in terms of a molar ratio. When the cation moiety is phosphazene, the use ratio of the thermal base generator (B) to the acid in terms of the thermal base generator (B):acid is more preferably 1:0.003 to 1:1, in terms of a molar ratio from the viewpoint of the stability of the energy-sensitive composition. Regarding use of the thermal base generator (B) and the acid, an adjustment may be made such that the pH of the energy-sensitive composition is, for example, in a range of 4 or higher and 9 or lower, and preferably 5 or higher and 7 or lower.
The energy-sensitive composition preferably contains a solvent. Examples of the solvent include cyclic skeleton-containing acetate compounds represented by the below-mentioned formula (S1), such as cycloalkyl acetate, alcohols such as methanol, ethanol, propanol and n-butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol;
ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone and 2-heptanone; lactone ring-containing organic solvents such as γ-butyrolactone;
derivatives of polyhydric alcohols, for example, compounds having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate, and compounds having an ether bond, such as monoalkyl ethers or monophenyl ethers, such as monomethyl ether, monoethyl ether, monopropyl ether and monobutyl ether of the polyhydric alcohols or the compounds having the ester bond;
cyclic ethers such as dioxane, and esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate;
aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, amylbenzene, isopropylbenzene, toluene, xylene, cymene and mesitylene;
nitrogen-containing organic solvents such as N,N,N′,N′-tetramethylurea, N,N,2-trimethylpropionamide, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylacetamide, N,N-diethylformamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and N-ethylpyrrolidone; and the like.
Among these solvents, cycloalkyl acetate represented by the below-mentioned formula (S1), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), N,N,N′,N′-tetramethylurea (TMU) and butanol are preferable, cyclopropyl acetate, cyclobutyl acetate, cyclopentyl acetate, cyclohexyl acetate, cycloheptyl acetate or cyclooctyl acetate is more preferable, and cyclohexyl acetate is still more preferable. These solvents may be used alone or in combination of two or more thereof.
In the formula (S1), Rs1 each independently represent an alkyl group; p is an integer of 1 or more and 6 or less; and q is an integer of 0 or more and (p+1) or less. Examples of the alkyl group represented by Rs1 include alkyl groups having 1 or more and 3 or less carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group and an i-propyl group.
Specific examples of the cycloalkyl acetate represented by the formula (S1) include cyclopropyl acetate, cyclobutyl acetate, cyclopentyl acetate, cyclohexyl acetate, cycloheptyl acetate and cyclooctyl acetate. Among these, cyclooctyl acetate is preferable from the viewpoint of availability and the like.
The content of the solvent in the energy-sensitive composition is not particularly limited so long as it does not interfere with the object of the present invention. In view of film-forming properties, the solvent is used such that the solid component concentration of the energy-sensitive composition is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 1% by mass or more and 40% by mass or less. The solid component refers to components other than the solvent. The solvent may be used alone or in combination of two or more.
The energy-sensitive composition may contain, as a stabilizer, a monohydric or dihydric or higher polyhydric alcohol which has a cyclic ether as a substituent, or an ether compound. Specific examples of a usable stabilizer include stabilizers mentioned in Japanese Unexamined Patent Application, Publication No. 2009-126940, paragraphs (0180) to (0184).
The energy-sensitive composition may contain water. The addition of water leads to an improvement in lithographic performance. The content of water in a solvent component in the energy-sensitive composition is, for example, 0% by mass or more and less than 50% by mass, and preferably 0.5% by mass or more and 5% by mass or less.
The energy-sensitive composition may optionally contain a surfactant. Specific examples of a usable surfactant include surfactants mentioned in Japanese Unexamined Patent Application, Publication No. 2009-126940, paragraph (0185).
A production method of the energy-sensitive composition is not particularly limited. For example, the energy-sensitive composition is produced by mixing each component described above with a stirrer or the like. It should be noted that the energy-sensitive composition produced thus may be filtered through a membrane filter, etc. such that the energy-sensitive composition is homogeneous.
The energy-sensitive composition can be used, for example, in various elements, in applications for formation of a protective film which protects various substrates (including a metal oxide-containing film, a film containing various metals), a sealing material for OLED display element, OLED lightings, hard coats, insulating films, antireflective films, interlayer insulating films, carbon hard masks, display panel materials (flattened films, pixels for color filter, barrier ribs for organic EL, spacers), or a transparent coating film covering a metal wiring in display elements such as touch panels. Examples of various substrates include semiconductor substrates; substrates for display materials (including a metal oxide-containing film, a film containing various metals) such as a liquid crystal display, an organic light-emitting display (OLED), an electrophoretic display (electronic paper), a touch panel, a color filter, and a back light; substrates for solar cells (including a metal oxide-containing film, a film containing various metals); substrates for photoelectric conversion elements (including a metal oxide-containing film, a film containing various metals) such as an optical sensor; and substrates for photoelectric elements (including a metal oxide-containing film, a film containing various metals). In particular, a cured product formed using the energy-sensitive composition exhibits excellent crack resistance. Therefore, the energy-sensitive composition described above is suitably used in applications including the step of, after the formation of the cured product using the energy-sensitive composition, heating the cured product to form other members, and/or further heating the cured product for an annealing treatment to relieve the residual stress of the cured product, etc.
The energy-sensitive composition described hereinabove may be used to form a cured product. Such a cured product is typically formed according to a method including applying the energy-sensitive composition described above onto a substrate to form a coating film, and heating the coating film for curing. Hereinafter, each step will be described. The step of applying the energy-sensitive composition onto a substrate to form a coating film is referred to as “coating-film-forming step”. The step of heating the coating film for curing is referred to as “heating step”.
A method of applying the energy-sensitive composition to form a coating film is not particularly limited so long as the effects of the present invention are not impaired, and includes a method that involves applying the energy-sensitive composition onto the substrate, using optionally contact transfer coating applicators such as a roll coater, a reverse coater, a bar coater and an inkjet; and non-contact applicators such as a spinner (rotary applicator) and a curtain flow coater. Examples of the substrate include, but are not limited to, a glass substrate, a quartz substrate, a transparent or translucent resin substrate (for example, heat-resistant materials such as polycarbonate, polyethylene terephthalate, polyether sulfone, polyimide, and polyamideimide), metal, a silicon substrate and the like. The substrate may be various substrates, for example, semiconductor substrates; substrates for display materials (including a metal oxide-containing film, a film containing various metals) such as a liquid crystal display, an organic light-emitting display (OLED), an electrophoretic display (electronic paper), a touch panel, a color filter, and a back light; substrates for solar cells (including a metal oxide-containing film, a film containing various metals); substrates for photoelectric conversion elements (including a metal oxide-containing film, a film containing various metals) such as an optical sensor; and substrates for photoelectric devices (including a metal oxide-containing film, a film containing various metals). The thickness of the substrate is not particularly limited and can be appropriately selected according to embodiment of usage of a cured product.
After the application of the energy-sensitive composition, drying (prebaking) is preferably performed. A drying method is not particularly limited and includes, for example, (1) a method that involves drying with a hot plate at a temperature of 80° C. or higher and 180° C. or lower, and preferably 90° C. or higher and 160° C. or lower, for 60 seconds or more and 120 seconds or less, (2) a method that involves allowing to stand at room temperature for several hours to several days, (3) a method that involves placing in a hot-air heater or an infrared heater for several tens of minutes to several hours to remove the solvent, and the like.
When the coating film formed using the energy-sensitive composition is heated (baked), a base is generated from the thermal base generator (B). The base generated thus causes an increase in molecular weight of the polysilane (A), etc. to occur, leading to the formation of a cured product (cured film). It should be noted that the formation of the cured product usually omits the step of curing the coating film by exposure, since the energy-sensitive composition described above is cured upon heating.
The heating temperature (baking temperature) may be higher than or equal to a temperature at which the compound represented by the formula (b1) decomposes to generate a base, and is, for example, 90° C. or higher, preferably 100° C. or higher, and more preferably 130° C. or higher. The upper limit of the heating temperature is not particularly limited and may be adjusted appropriately according to the substrate or the applications, and is, for example, 1,000° C. or lower, preferably 700° C. or lower, and more preferably 600° C. or lower. In this regard, the compound represented by the formula (b1) can generate the base at lower temperatures as well as at elevated temperatures, as described above. Thus, the heating temperature may be set to an elevated temperature (for example, 200° C. or higher), or a lower temperature (for example, 90° C. or higher and below 200° C., and further 150° C. or lower). The heating atmosphere is not particularly limited and may be an inert gas atmosphere such as a nitrogen atmosphere or argon atmosphere, or may be under vacuum or reduced pressure. The heating atmosphere may be under an atmospheric air, or the oxygen concentration may be appropriately controlled. The heating time may be appropriately changed, and is 10 minutes or more and 120 minutes or less.
The thickness of the cured product formed thus is preferably 10 nm or more and 10,000 nm or less, and more preferably 50 nm or more and 5,000 nm or less.
Since the energy-sensitive composition described above contains, as the thermal base generator (B), the compound represented by the formula (b1) along with the polysilane (A), a cured product formed using the energy-sensitive composition exhibits excellent crack resistance. Thus, the crack generation in the cured product upon heating is suppressed.
The compound represented by the formula (b1) is a novel compound. The compound represented by the formula (b1) can be used as the thermal base generator (B) including the compound represented by the formula (b1), i.e., a thermal base generator composed of the compound represented by the formula (b1), or a thermal base generator including the compound represented by the formula (b1) and other thermal base generator, as described above.
Further, the compound represented by the formula (b1) in which Zq+ represents a counter cation other than the organic cation is also a novel compound. This compound is a compound represented by the following formula (b1a). It is to be noted that H+ does not fall under the counter cation. The compound represented by the formula (b1a) may be used as a thermal base generator including the compound represented by the formula (b1a), i.e., a thermal base generator composed of the compound represented by the formula (b1a), or a thermal base generator including the compound represented by the formula (b1a) and other thermal base generator, similarly to the compound represented by the formula (b1),
wherein, in the formula (b1a), Rb1 and Rb2 each independently represent a halogen atom, a nitro group, an alkyl group, an aryl group, an arylalkyl group, or an alkoxy group;
Rb3 represents a hydrogen atom or an alkyl group;
n1 and n2 each independently represent an integer of 0 or more and 4 or less;
Xq+ represents a q-valent counter cation composed of a base having a pKa of greater than 15; and
q represents an integer of 1 or more.
In the formula (b1a), Rb1, Rb2, Rb3, n1, n2, and q are as defined in the formula (b1). In the formula (b1a), the q-valent counter cation Xq+ composed of the base having a pKa of greater than 15 is composed of an organic cation or a metal cation.
The organic cation is similar to Zq+ in the formula (b1). The metal cation is exemplified by a cation of a metal atom selected from the group consisting of a main group metal element (a typical metal element), a transition metal element and a metalloid element, or a cation of an atomic group including the metal atom. Examples of the main group metal element include alkali metal elements (metal elements consisting of elements of group 1 of the periodic table excluding hydrogen, for example, sodium and potassium), alkaline earth metal elements (metal elements consisting of elements of group 2 of the periodic table, for example, magnesium), metal elements consisting of elements of group 12 of the periodic table (for example, zinc), metal elements consisting of elements of group 13 of the periodic table excluding boron (for example, aluminum), metal elements consisting of elements of group 14 of the periodic table excluding carbon and silicon (for example, tin), metal elements consisting of elements of group 15 of the periodic table excluding nitrogen, phosphorus and arsenic (for example, antimony), and metal elements consisting of elements of group 16 of the periodic table excluding oxygen, sulfur, selenium and tellurium (for example, polonium). Examples of the transition metal element include metal elements consisting of elements of groups 3 to 11 of the periodic table (for example, hafnium). Examples of the metalloid element include boron, silicon, arsenic, selenium, tellurium, and the like. The cation of the atomic group including the metal atom is exemplified by atomic groups including both of a metal atom and a non-metal atom, and more specifically, [ZrO]2+, [(C2H5O)Al]2+, and [(n-C4H9)2Sn—O—Sn (n-C4H9)2]2+, and the like. The counter cation Xq+ may be a cation of an atomic group including phosphorus, sulfur or iodine.
The present invention will be described in more detail by way of Examples, but the present invention is not limited to these Examples.
[Synthesis of Compound Represented by Formula (b1)]
To a 20 mL eggplant-shaped flask were added the carboxylic acid shown in the above scheme (0.24 g) and tetrahydrofuran (9 g). The atmosphere inside the eggplant-shaped flask was substituted with nitrogen gas, and then the eggplant-shaped flask was warmed in an oil bath at 60° C., to dissolve the carboxylic acid in tetrahydrofuran. Next, the phosphazene compound (0.30 g) was added dropwise, and the carboxylic acid was reacted with the phosphazene compound at 60° C. for 30 minutes according to the above scheme. After the completion of the reaction, the reaction solution was cooled to room temperature. Subsequently, the solvent was distilled off from the reaction solution using a rotary evaporator, to give the compound b1. (amount=0.44 g, yield=97.78%, yellow solid)
1H-NMR (deuterated DMSO, 400 MHz):
cation δ (ppm)=1.24 (—C(CH3)3, 9H), 2.60 (—NH2, 30H)
anion δ (ppm)=7.20-7.95 (Ar—H, 8H), 4.95 (Ar—CH—Ar, H)
To a 50 mL three-neck flask were added the carboxylic acid shown in the above scheme (0.24 g) and tetrahydrofuran (20 g). The atmosphere inside the flask was substituted with nitrogen gas, and then the flask was warmed in a water bath at 60° C., to dissolve the carboxylic acid in tetrahydrofuran. Next, diazabicycloundecene (DBU; 0.12 g) was added dropwise, and the carboxylic acid was reacted with DBU at 60° C. for 4 h according to the above scheme. After the completion of the reaction, the reaction solution was cooled to room temperature (25° C.). Subsequently, the solvent was distilled off from the reaction solution using a rotary evaporator, to give the compound b2. (amount=0.30 g, yield=90.90%, yellow viscous liquid)
1H-NMR (deuterated DMSO, 400 MHz):
cation δ (ppm)=3.48 (NH—CH2—, 2H), 3.40 (N—CH2—, 2H), 3.15 (N—CH2—, 2H), 2.65 (—CH2—, 2H), 1.82 (—CH2—, 2H), 1.70-1.45 (—CH2—, 6H)
anion δ (ppm)=7.20-7.95 (Ar—H, 8H), 4.95 (Ar—CH—Ar, H)
To a 20 mL eggplant-shaped flask were added the carboxylic acid shown in the above scheme (0.24 g) and tetrahydrofuran (9 g). The atmosphere inside the eggplant-shaped flask was substituted with nitrogen gas, and then the eggplant-shaped flask was warmed in an oil bath at 60° C., to dissolve the carboxylic acid in tetrahydrofuran. Next, 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD; 0.12 g) was added dropwise, and the carboxylic acid was reacted with TBD at 60° C. for 30 minutes according to the above scheme. After the completion of the reaction, the reaction solution was cooled to room temperature. Subsequently, the solvent was distilled off from the reaction solution using a rotary evaporator, to give the compound b3. (amount=0.31 g, yield=93.94%, yellow solid)
1H-NMR (deuterated DMSO, 500 MHz):
cation δ (ppm)=10.48 (—NH—, 2H), 3.22-3.17 (NH—CH2—, 4H), 3.10-3.07 (N—CH2—, 4H), 1.86-1.81 (—CH2—, 4H)
anion δ (ppm)=7.20-7.95 (Ar—H, 8H), 4.95 (Ar—CH—Ar, H)
In Examples and Comparative Example, a linear polysilane including a silanol group, a phenyl group and a methyl group, in which the silanol group, the phenyl group and the methyl group are each bonded to a silicon atom (mass average molecular weight: 1,500) was used as the polysilane (A).
In Examples and Comparative Example, the compounds b1 to b3 as described above were used as the compound represented by the formula (b1). It should be noted that pKa of the cation moiety of each compound is as follows.
b1: pKa=33.0
b2: pKa=24.3
b3: pKa=26.0
In Examples and Comparative Example, compounds b4 and b5 represented by the following formulas were used as the compound represented by the formula (b2).
In Examples and Comparative Example, the following s1 and s2 were used as a solvent.
s1: cyclohexyl acetate (CHXA)
s2: N,N,N′,N′-tetramethylurea (TMU)
Each of energy-sensitive compositions of Examples and Comparative Example was prepared by dissolving 18.3 parts by mass of the polysilane (A), and the compound represented by the formula (b1) and the compound represented by the formula (b2) of the type and amount (parts by mass) specified in Table 1 in 80 parts by mass of the solvent of the type specified in Table 1, followed by filtration through a filter having a pore size of 0.1 μm made of fluororesin.
Each of the energy-sensitive compositions of the Examples and Comparative Example was applied onto a glass substrate (100 mm×100 mm) using a spin coater, followed by prebaking at 100° C. for 120 seconds, to form a coating film. The coating film obtained thus was heated in atmospheric for 30 minutes, to obtain a cured product having a thickness of 4.0 μm. The heating temperature was 250° C. for Examples 1 to 8 and Comparative Example 1, and 150° C. for Example 9.
The cured product obtained in the section [Preparation of Cured Product] was heated at 350° C. for 30 minutes using a hot plate, and then cooled to room temperature (25° C.). This operation was repeated five times. The surface of the cured product was observed with an optical microscope at 50× magnification, and inspected for the presence or absence of a crack, and the crack resistance was evaluated according to the following criteria. The results are shown in Table 1.
⊚: no crack was found after completing the operation five times repetition of the operation;
◯: no crack was found after completing the operation three times, but cracks were found after completing the operation four times;
Δ: no crack was found after completing the operation once, but cracks were found after completing the operation twice; and
X: cracks were found after completing the operation once.
The cured product obtained in the section [Preparation of Cured Product] was heated at 350° C. for 30 minutes using a hot plate, and then cooled to room temperature (25° C.). This operation was repeated five times. Subsequently, the thickness of the cured product was measured, and the thermal resistance was evaluated according to the following criteria. The results are shown in Table 1.
⊚: thickness of 3.6 μm or more and 4.0 μm or less;
◯: thickness of 3.2 μm or more and less than 3.6 μm;
Δ: thickness of 2.8 μm or more and less than 3.2 μm; and
X: thickness of less than 2.8 μm.
According to Examples 1 to 9, it can be found that the energy-sensitive composition containing the polysilane (A) and the thermal base generator (B), in which the thermal base generator (B) includes the compound represented by the formula (b1), exhibits extremely excellent crack resistance. In addition, the energy-sensitive compositions of Examples 1 to 7 and 9 also exhibit excellent thermal resistance. In particular, the energy-sensitive compositions of Examples 1 to 7 exhibit more excellent thermal resistance than the energy-sensitive composition of Example 9. The reason for this can be presumed as follows: the temperature (decomposition temperature) at which a mass loss of the compound b1 by the heating starts is 100° C., and thus a base is generated in Example 9 where the heating was conducted at 150° C., and in Examples 1 to 7 where the heating was conducted at 250° C., a larger amount of the base is generated and thermal curing proceeds more favorably. On the other hand, the energy-sensitive composition of Comparative Example 1, which does not contain the compound represented by the formula (b1), can be found to exhibit lower crack resistance.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-185798 | Nov 2020 | JP | national |
