JP2004231660A - Acid decomposable compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an easily disposable material and to provide a compound servable as a new photosensitive material. <P>SOLUTION: The acid decomposable compound has an acid decomposing atomic group which decomposes by an acid, and an atomic group forming a new bond by heating. The acid decomposable compound uses Diels-Alder reaction, ene reaction or metathesis reaction for forming the new bond by heating. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to novel degradable compounds. These decomposable compounds are useful as decomposable plastics, decomposable thermosetting resins, photosensitive resins, and photoresists. For example, decomposable plastics, photoresist materials, inks, paints, sealants, lenses, optical disks, etc. It is expected to be used for various applications.

  Disposal of synthetic resins such as plastics has a very large impact on the environment. Therefore, in recent years, researches for imparting decomposability and recyclability to synthetic resins have been actively conducted.

  The Diels-Alder reaction is known as a reversible reaction. When a polymer synthesized by using this reaction is subjected to a heat treatment, the polymer is decomposed by the retro-Diels-Alder reaction or rearrangement of bonds occurs. For example, Macromolecules, Vol. 31, pp. 314 to 321 (1998) reports a thermally crosslinkable polymer composed of a polymer having furan in the side chain and a low molecule having maleimide. In this polymer composition, the Diels-Alder reaction and the retro-Diels-Alder reaction occur when heat is applied. However, since the polymer itself hardly changes, it is not degradable. Chen et al., Science, vol. 295, pp. 1698-1702 (2002), synthesized a low molecule having a plurality of furans and a low molecule having a plurality of maleimides, and mixed them with heat. It is reported that a reversible cross-linking / dissociation-forming network polymer is formed and becomes a material capable of repairing. The materials in this report can be used mainly as structural materials.

  The present inventor thought that a new functional material could be obtained by using a heat-crosslinking reaction such as the Diels-Alder reaction. For example, it can be used as a photoresist material. Here, a conventional technique for a photoresist will also be described.

  Today, chemically amplified resists are generally used in the process of manufacturing highly integrated LSIs. The chemically amplified resist contains a polymer serving as a matrix, a photoacid generator that generates an acid upon irradiation with light, and the like. The structural feature of the polymer serving as the matrix is that a part or all of the alkali-soluble portion of the alkali-soluble resin is protected with an appropriate acid-labile group.

  The photoreaction mechanism of a photoresist made of such a polymer will be briefly described below. When a portion of the photoresist is irradiated with light, the acid generated by the light releases the acid-labile groups of the polymer, rendering the polymer readily soluble in alkali. If alkali development is performed thereafter, only the light-irradiated portion will be dissolved, and the portion not irradiated with light will remain.

  However, in the conventional photoresist, only the solubility of the light-irradiated portion is increased, and the reaction of the light-unirradiated portion is hardly considered, and there is room for improvement in the contrast of the formed pattern. That is, when the acid-decomposable compound of the present invention is used as a photoresist material, a reaction in which the solubility is reduced occurs in a portion not irradiated with light, and the contrast is improved.

  A first object of the present invention is to provide a material that can be easily disposed of. A second object of the present invention is to provide a compound that can be a new photosensitive resin material.

  As a means for solving the above problems, a first aspect of the present invention is an acid-decomposable compound having an acid-decomposable atomic group that decomposes by an acid and an atomic group that generates a new bond by heat.

  The acid-decomposable atomic group is preferably one that can be decomposed by an acid having a pKa of 10 or less at a temperature of 200 ° C. or less from the viewpoint of its properties. More preferably, it can be decomposed at a temperature of 150 ° C. or lower.

  Next, the structure of the acid-decomposable atomic group will be specifically described. For example, those known as atomic groups in which various functional groups are protected with an acid-dissociable protecting group can be applied.

  In the present invention, all or a part of the atomic groups that generate a new bond by heat may constitute all or a part of the acid-decomposable atomic group.

  More specifically, examples of the acid-decomposable atomic group include a tertiary ester bond, a secondary aryl ester bond, a tertiary oxycarbonyloxy bond, a secondary aryloxycarbonyloxy bond, a thioester bond, an acetal bond, and a tertiary ether. Examples include, but are not limited to, bonds, secondary aryl ether bonds, tertiary thioether bonds, secondary aryl ether bonds, and those substituted with an electron donating group.

  For more specific description, a structure that is a particularly preferable example of an atomic group decomposed by an acid is illustrated below, but the present invention is not limited to this example.

In the formulas (16) to (22), R ⁴⁵ , R ⁴⁶ , R ⁴⁹ , R ⁵⁵ , R ⁵⁶ , R ⁵⁹ , R ⁶⁵ , and R ⁶⁶ each independently represent a C 1 to C 20 which may have a substituent. Chain, cyclic or branched alkyl group, C5-C20 aryl group which may have a substituent, alkoxy group which may have a substituent, thioalkoxy which may have a substituent A group, a vinyl group which may have a substituent, a saturated or unsaturated heterocyclic group which may have a substituent, and a silyl group which may have a substituent.

More specifically, R ⁴⁵ , R ⁴⁶ , R ⁴⁹ , R ⁵⁵ , R ⁵⁶ , R ⁵⁹ , R ⁶⁵ and R ⁶⁶ each independently represent a methyl group, an ethyl group, an n-propyl group, a 1-methylethyl group, Propyl group, n-butyl group, 1-methyl-propyl group, 2-methylpropyl group, cyclobutyl group n-pentyl group, branched pentyl group, cyclopentyl group, n-hexyl group, branched hexyl group, cyclohexyl group , A C7-C20 linear, cyclic or branched alkyl group, allyl group, and the above-mentioned groups such as alkyl group, alkoxy group, ester group, nitro group, halogen group, cyano group, hydroxyl group, thiol group, etc. Those having a substituent, a methyloxy group, an ethyloxy group, an n-propyloxy group, a 1-methylethyloxy group, a cyclopropyloxy N-butyloxy group, 1-methyl-propyloxy group, 2-methylpropyloxy group, cyclobutyloxy group, n-pentyloxy group, branched pentyloxy group, cyclopentyloxy group, n-hexyloxy group, branched A hexyloxy group, a cyclohexyloxy group, a C7-C20 linear or cyclic or branched alkyloxy group, and further, an alkyl group, an alkoxy group, an ester group, a nitro group, a halogen group, a cyano group , A group having a substituent such as a hydroxyl group or a thiol group, or an aryl group such as a phenyl group, a furanyl group, a thionyl group, a pyridyl group, or a naphthyl group; and further, an alkyl group, an alkoxy group, an ester group, or a nitro group. Group, halogen group, cyano group, hydroxyl group, thiol group, phenyl group, furanyl group Includes those to which substituents such as aryl groups such as thionyl group, pyridyl group and naphthyl group are bonded, and further silyl groups substituted with alkylsilyl, dialkylsilyl, trialkylsilyl, and aryl groups. May be.

R ⁴⁷ , R ⁴⁸ R ⁵¹ , R ⁵³ , R ⁵⁷ , R ⁶³ , and R ⁶⁴ are each independently a divalent organic group or a silylene group, or an oxygen atom, a sulfur atom, or a nitrogen atom; It represents an alkylene group which may have a substituent, a vinylene group which may have a substituent, a carbonyl group, and an arylene group which may have a substituent. Or an atomic group consisting of the above-mentioned divalent organic group or silylene group, or any combination of an oxygen atom, a sulfur atom, or a secondary or tertiary nitrogen atom or boron atom. Alternatively, R ⁴⁷ , R ⁴⁸ , R ⁵¹ , R ⁵³ , R ⁵⁷ , R ⁶³ , and R ⁶⁴ each independently represent an atom containing a part or all of an atomic group that forms a new bond by heat of the present invention. It may represent a group.

  In the present invention, the valence described as divalent includes a covalent bond with a hydrogen atom. For example, an aryl group is synonymous with a divalent arylene group that has a hydrogen atom attached thereto.

Particularly preferred examples of R ⁴⁷ , R ⁴⁸ , R ⁵¹ , R ⁵³ , R ⁵⁷ , R ⁶³ , and R ⁶⁴ are, for example, a methylene group, a C2-C10 alkylene group, and a total number of atoms excluding hydrogen of 20 or less. Constituent ether group, thioether group composed of 20 or less total atoms excluding hydrogen, phenylene group, naphthylene group, anthranylene group, furanylene group, pyridylene group, thiophenylene group, arylene group such as phenyleneoxy group, Arylene vinyl groups such as naphthyleneoxy group, anthranylene oxy group, furanylene oxy group, pyridylene oxy group, thiophenylene oxy group, etc. Group, carbonyl group, oxygen atom, sulfur atom It is an atomic group consisting of combinations such as

Further particularly preferred examples are a furanyl group, a furanyloxy group and a furanylenevinylene group.
Then, in the formula (16), a ring may be formed by any two or more of the atomic groups further bonded to R ^{45 to} R ⁴⁷ and R ⁴⁷ . Also, a ring may be formed with R ⁴⁸ and any of a plurality of atomic groups further bonded to R ⁴⁸ .
In Formulas (17) and (20), R ⁵⁰ and R ⁶⁰ each independently represent an arylene group that may have a substituent or a vinylene group that may have a substituent.

  Further, a vinylene group having a conjugated multiple bond is also preferable. A methylene group or a methine group substituted with an electron donating group, for example, a methoxymethylene group, a methylthiomethylene group, a methoxyethoxymethylene group, a 2- (trimethylsilyl) ethoxymethylene group, or the like, or a 2-tetrahydropyranylene group An aryloxymethylene group which may have a substituent such as a furanylene group having an electron-donating group, a thionylene group, a phenylene group, a vinylene group, or a benzyloxymethylene group, a furanyloxymethylene group, or a thionyloxymethylene group; A vinyloxylene group which may have a group, an N-phthalimidomethylene group which may have a substituent, a 9-anthrylmethylene group which may have a substituent, or a trimethylsilylene group, a triethylsilylene group, Has a substituent such as phenyldimethylsilylene Even though it may be a good silylene group.

  Particularly preferably, an arylene group such as a phenylene group, a naphthylene group, an anthranylene group, a furanylene group, a pyridylene group, a thiophenylene group, or a phenyleneoxy group, a phenylenevinylene group, a furanylenevinylene group, a pyridylenephenylene group, or a thiphenylenevinylene group. It is an atomic group such as an arylenevinylene group. Further particularly preferred examples are a furanylene group, a furanyloxylene group and a furanylenevinylene group.

Then, in the formula (17), a ring may be formed by an arbitrary plurality of atomic groups among the atomic groups further bonded to R ⁴⁹ , R ⁵⁰ and R ⁵⁰ . Further, R ⁵¹ and an atomic group further bonded to R ⁵¹ may form a ring.

In the formulas (18) and (21), R ⁵² and R ⁶² each independently represent a tetrahydropyranylene group, an arylene group having an electron donating group, a vinylene group having an electron donating group, or a benzyloxymethylene group, or furanyloxy. Aryloxymethylene group which may have a substituent such as methylene group and thionyloxymethylene group, vinyloxylen group which may have a substituent and N-phthalimidomethylene which may have a substituent Represents a group, a 9-anthrylmethylene group which may have a substituent, or a silylene group which may have a substituent such as a trimethylsilylene group, a triethylsilylene group, or a phenyldimethylsilylene group.
Then, in the formula (18), R ⁵² and an atomic group further bonded to R ⁵² may form a ring. Further, a ring may be formed by R ⁵³ and an atomic group further bonded to R ⁵³ .

In the formulas (19) to (22), X ⁵ and X ⁶ each independently represent an oxygen atom or a sulfur atom.

In the formulas (19), (20) and (21), R ⁵⁴ , R ⁵⁸ and R ⁶¹ each independently have a substituent conjugated to an arylene group or an aryl group which may have a divalent substituent. Represents a vinylene group which may be substituted.

However, the bond between R ⁵⁴ , R ⁵⁸ , or R ⁶¹ and X ⁵ is an aromatic structure constituting R ⁵⁴ , R ^58, or R ⁶¹ or a double bond structure conjugated to an aromatic, and a single bond to X ^5. It is.
Then, in the formula (19), a ring may be formed by an arbitrary plurality of atomic groups among the atomic groups further bonded to R ^{55 to} R ⁵⁷ and R ⁵⁷ . Further, R ⁵⁴ and an atomic group further bonded to R ⁵⁴ may form a ring.

Further, in the formula (20), a ring may be formed by any two or more of the atomic groups further bonded to R ⁵⁹ , R ⁶⁰ and R ⁶⁰ . Further, R ⁵⁸ and an atomic group further bonded to R ⁵⁸ may form a ring.
Further, in the formula (21), R ⁶¹ and an atomic group further bonded to R ⁶¹ may form a ring. Further, R ⁶² and an atomic group further bonded to R ⁶² may form a ring.

Further, in the formula (22), a ring may be formed by an arbitrary plurality of atomic groups among the atomic groups further bonded to R ⁶³ , R ⁶⁵ , R ⁶⁶ and R ⁶³ . Further, a ring may be formed by an arbitrary plurality of atomic groups among the atomic groups further bonded to R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁴ . However, when R ⁶⁵ forms a ring with R ⁶³ or an atomic group further bonded to R ⁶³ , R ⁶⁵ and R ⁶⁶ form a ring with an atomic group further bonded to R ⁶⁴ or R ^64. I will not. When R ⁶⁵ forms a ring with R ⁶⁴ or an atomic group further bonded to R ⁶⁴ , R ⁶⁵ and R ⁶⁶ form a ring with an atomic group further bonded to R ⁶³ or R ^63. I will not. And, when R ⁶⁶ forms a ring with R ⁶³ or an atomic group further bonded to R ⁶³ , R ⁶⁶ can form a ring with an atomic group further bonded to R ⁶⁴ or R ⁶⁴ Absent.

  Part or all of the above acid-decomposable atomic groups may form part or all of the atomic groups that generate new bonds by heat described below.

  An atomic group that forms a new bond by heat means that the reaction rate is slow at 0 ° C or lower, but the temperature required for the reaction falls within a practical temperature range of 0 ° C or higher and 300 ° C or lower, preferably 5 ° C or higher and 200 ° C or lower. It is an atomic group that generates a bond by increasing the reaction rate when heated or maintained in a temperature range necessary for the reaction. Therefore, the phrase "by heat" in the present invention means not only that the compound of the present invention is heated at a constant temperature, such as by leaving it at room temperature, but also by raising the temperature using a heat source. And so on.

  In addition to a device in which two atomic groups generate a bond without a catalyst, a device in which a new bond is generated by the action of a catalyst may be used. In addition, it includes generation of a bond again after the bond in the atomic group is decomposed by heat.

  However, it is a necessary condition that the acid-decomposable atomic group is not decomposed during the bond formation reaction due to heat, and it is difficult to apply a cross-linking reaction using a usual acid catalyst. In other words, any atomic group that causes a new bond by heat may be used as long as it is an atomic group involved in a reaction that does not decompose the acid-decomposable atomic group during a bond-forming reaction by heat.

  For example, an atomic group involved in the Diels-Alder reaction, an atomic group involved in the ene reaction, an atomic group involved in the metathesis reaction, and the like are preferable. In addition, a bond forming reaction using a base catalyst is also applicable. Further, a bond forming reaction by a radical reaction is also preferable. However, the present invention is not limited to these.

  More specifically, preferred examples of the structure of the atomic group include, for example, an atomic group involved in the Diels-Alder reaction, which has a furan ring structure, a maleimide ring structure, a diene structure, particularly a conjugated cyclic diene structure, a double bond, particularly an electron withdrawing group Examples include a double bond, an anthracene structure, and various fullerene structures. Preferred examples of the structure of the atomic group in the ene reaction are, for example, various double bonds, and examples of the atomic group involved in the metathesis reaction are various double bonds. Further, for example, a radical reaction between a benzyl position and a stable radical is also preferable because it generates a bond by heat.

    For more specific description, a structure that is a particularly preferred example of an atomic group that generates a new bond by heat is illustrated below, but the present invention is not limited to this example.

In the formulas (23) to (28), R ^{67 to} R ⁸⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group, or a C1 to C20 chain which may have a substituent. , Cyclic or branched alkyl group, C5-C20 aryl group which may have a substituent, alkoxy group which may have a substituent, thioalkoxy group which may have a substituent A vinyl group which may have a substituent, a saturated or unsaturated heterocyclic group which may have a substituent, and a silyl group which may have a substituent. R ^{87 to} R ⁹⁰ each independently represent a C1 to C20 linear, cyclic or branched alkyl group which may have a substituent, or a C5 to C20 aryl group which may have a substituent. .

More specifically, R ^{67 to} R ⁸⁴ each independently represent a methyl group, an ethyl group, an n-propyl group, a 1-methylethyl group, a cyclopropyl group, an n-butyl group, a 1-methyl-propyl group, a 2-methyl Propyl group, cyclobutyl group n-pentyl group, pentyl group having a branch, cyclopentyl group, n-hexyl group, hexyl group having a branch, cyclohexyl group, C7 to C20 linear or cyclic or branched alkyl group, Allyl group, further having an alkyl group, an alkoxy group, an ester group, a nitro group, a halogen group, a cyano group, a hydroxyl group, a substituent such as a thiol group, a methyloxy group, an ethyloxy group, an n-propyloxy group , 1-methylethyloxy group, cyclopropyloxy group, n-butyloxy group, 1-methyl-propyloxy group, 2- Tylpropyloxy group, cyclobutyloxy group, n-pentyloxy group, branched pentyloxy group, cyclopentyloxy group, n-hexyloxy group, branched hexyloxy group, cyclohexyloxy group, C7-C20 straight chain Or an alkyloxy group having a cyclic or branched form, and those having a substituent such as an alkyl group, an alkoxy group, an ester group, a nitro group, a halogen group, a cyano group, a hydroxyl group, a thiol group, or a phenyl group , Furanyl group, thionyl group, pyridyl group, aryl groups such as naphthyl group, further alkyl group, alkoxy group, ester group, nitro group, halogen group, cyano group, hydroxyl group, thiol group and phenyl group, Aryl groups such as furanyl group, thionyl group, pyridyl group, naphthyl group, etc. It includes those substituents are bonded, furthermore, alkylsilyl group, a dialkyl silyl group, a trialkylsilyl group or a silyl group substituted with an aryl group.

Then, in the formula (23), a ring may be formed by an arbitrary plurality of atomic groups among R ^{67 to} R ⁷⁰ .
However, at least one of the atomic groups of R ^{67 to} R ⁷⁰ is directly or indirectly bonded to the acid-decomposable atomic group of the present invention, or is at least a part of the acid-decomposable atomic group. There must be.

Further, in the formula (24), a ring may be formed by any two or more of R ^{71 to} R ⁷⁶ .
Then, at least one of the atomic groups of R ^{71 to} R ⁷⁶ is directly or indirectly bonded to the acid-decomposable atomic group of the present invention, or is at least a part of the acid-decomposable atomic group. There must be.

Then, in the formula (25), a ring may be formed by an arbitrary plurality of atomic groups among R ^{77 to} R ⁸⁰ .
Further, at least one of the groups R ^{77 to} R ⁸⁰ is directly or indirectly bonded to the acid-decomposable group of the present invention or is at least a part of the acid-decomposable group. There must be.

Then, in the formula (26), a ring may be formed by an arbitrary plurality of atomic groups among R ^{81 to} R ⁸³ .
Further, at least one of the atomic groups of R ^{81 to} R ⁸³ is directly or indirectly bonded to the acid-decomposable atomic group of the present invention, or is at least a part of the acid-decomposable atomic group. There must be.

In the formula (23), X ⁷ represents a methylene group, an ethylene group, an oxygen atom or a sulfur atom which may have a substituent. Particularly, a methylene group and an oxygen atom which may have a substituent are preferable, and an oxygen atom is more preferable.

In the formula (27), R ⁸⁵ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. It represents a thioalkoxy group which may be possessed and a vinyl group which may be substituted.
Further, R ⁸⁶ represents an aryl group which may have a substituent. Preferably, it is a phenyl group which may have a substituent.

Then, a ring may be formed by any of a plurality of atomic groups among R ^{84 to} R ⁸⁶ .
In addition, at least one of R ^{84 to} R ⁸⁶ must be directly or indirectly bonded to the acid-decomposable atomic group of the present invention or be at least a part of the acid-decomposable atomic group. .

In the formula (28), R ⁹¹ represents an organic group which may have a divalent or higher valent substituent, and is preferably an ethylene or propylene group.

Then, a ring may be formed by an arbitrary plurality of atomic groups among R ^{87 to} R ⁹¹ .
In addition, at least one of R ^{87 to} R ⁹¹ must be directly or indirectly bonded to the acid-decomposable atomic group of the present invention or be at least a part of the acid-decomposable atomic group. .

  Further, part or all of the atomic groups that generate bonds by heat according to the present invention may be part or all of the acid-decomposable atomic groups.

  As described above, since it is an acid-decomposable compound having an atomic group that decomposes by an acid and an atomic group that generates a new bond by heat, it can generate a crosslinked structure by heat or cause a structural change by heat. For example, while it can be used as a thermosetting resin, it can be dissolved in a solvent by decomposing into a low molecular weight or changing polarity by acid decomposition, and can be easily disposed of. In addition, as described later, it is an unprecedented excellent photosensitive resin constituent material.

  Here, the solvent in the present invention includes not only a mere liquid but also a liquid in which various substances are dissolved or a liquid mixture in which various substances are dispersed while maintaining fluidity.

  A second aspect of the present invention is the acid-decomposable compound according to claim 1, wherein a change in solubility in the solvent due to decomposition by an acid is increased or decreased, and a change in solubility in the solvent caused by a new bond generated by heat. It is characterized in that the increase and decrease are reversed.

  Here, the change in solubility in a solvent due to decomposition by an acid means that a change in solubility in various solvents occurs due to an increase or decrease in polarity before and after decomposition of an atomic group decomposed by an acid, and a decrease in molecular weight due to decomposition by an acid. When the solubility increases, another group that is easily soluble in the solvent is bonded to the group that is decomposed by the acid in advance, and the group that is easily dissolved in the solvent is cut off by the acid. This includes the case where it becomes insoluble in the solvent.

  For example, a phenolic hydroxyl group protected with a t-butyl group is decomposed by an acid to generate a phenolic hydroxyl group (and butene). In this case, since a highly polar phenolic hydroxyl group is generated from t-butylphenyl ether having almost no polarity, the solubility in an alkaline solvent increases. Conversely, the solubility in non-polar solvents such as various alkanes decreases.

  In addition, polyesters having ester groups of tertiary type are decomposed by an acid and become soluble in a solvent, and the like is an example in which the solubility in a solvent changes due to a change in molecular weight.

  In addition, when the solubility in a solvent changes due to a new bond generated by heat, the molecular weight increases due to crosslinking between the same or different molecules and the solubility in various solvents decreases. For example, when the steric structure changes and the solubility in various solvents changes, and when the solubility changes due to the formation of a new bond between substances that are easily or poorly soluble in various solvents. Including.

  According to the fourth aspect of the present invention, for example, a part of the acid-decomposable compound according to the present invention can be decomposed by an acid, and at the same time, the remaining part can be cross-linked by heat. In other words, the solubility of the acid-treated part is very high, while the remaining part is cross-linked by heat and the solubility is remarkably reduced. Can be removed. Or, conversely, it is conceivable to reduce the solubility by treating a part with an acid, and to impart the solubility by heating the remaining part.

  The acid-decomposable atomic group is generally used in a positive photosensitive resin, and it is clear that the solubility in an alkali developing solution increases and decreases. Therefore, the present invention is also used as a positive photosensitive resin. Can be applied.

  A third aspect of the present invention is the acid-decomposable compound according to claim 1 or 2, wherein the solubility in a solvent is increased by decomposition with an acid, while the solubility in the solvent is reduced by a new bond due to heat. It is an acid-decomposable compound characterized by the following.

In the reaction in a normal positive photosensitive resin, the protective group of an alkali-soluble group is removed based on a reaction caused by an acidic compound generated in a portion irradiated with light, thereby increasing the solubility in an alkali developer. In addition, no reaction occurs in a part where light is not irradiated.
However, when the acid-decomposable compound according to the present invention is applied as a positive photosensitive resin, a reaction such as a cross-linking reaction or the like that reduces solubility can be caused by applying heat to a portion not irradiated with light. That is, the present invention can be applied to a positive photosensitive resin having a feature that the difference in solubility (dissolution rate) between a light-irradiated portion and an unirradiated portion is extremely large.

A fourth aspect of the present invention is the acid-decomposable compound according to any one of claims 1 to 3, wherein the pKa is at least 10% by an acid in a reaction within a temperature range of 0 ° C to 200 ° C within 72 hours with an acid having a pKa of 10 or less. An acid-decomposable compound characterized in that 5% of the decomposing atomic groups are decomposed.
The fourth invention is a compound whose decomposition by an acid is highly sensitive.

A fifth aspect of the present invention is the acid-decomposable compound according to any one of claims 1 to 4, wherein the atom group decomposed by the acid is a tertiary ester bond, a secondary aryl ester bond, a tertiary oxycarbonyloxy bond, or a secondary oxycarbonyloxy bond. An atomic group selected from an aryloxycarbonyloxy bond, a thioester bond, an acetal bond, a tertiary ether bond, a secondary aryl ether bond, a tertiary thioether bond, a secondary aryl ether bond and those substituted with an electron donating group. It is an acid-decomposable compound characterized by the above.
The fifth aspect of the present invention relates to an acid-decomposable compound having an acid-dissociable atomic group, which is particularly promising as a positive photosensitive resin.

  A sixth aspect of the present invention is the acid-decomposable compound according to any one of claims 1 to 5, wherein the reaction for generating a new bond by heat is a reversible reaction.

  In the sixth aspect of the invention, various effects occur because the reaction for generating a bond by heat is a reversible reaction. For example, when considering the disposal of the acid-decomposable compound of the present invention after use, it may be possible to recover the acid-decomposable compound in heating and the subsequent isolation step. Even after curing, for example, the chemical bond forming the cross-link is reversible, so that it can be further processed by heat and processed. That is, the recyclability is excellent. When application to a positive photosensitive resin is considered, edge line roughness generated in a light-irradiated portion and a light-unirradiated portion can be reduced by annealing with heat. Further, as apparent from the references, the composition containing the acid-decomposable compound of the present invention has a self-healing function when reversibility is further added.

As the reversible reaction which is the sixth important constituent factor of the present invention, for example, as described in the seventh embodiment of the present invention described below, a Diels-Alder reaction, an ene reaction or a metathesis reaction is promising.
In particular, a Diels-Alder reaction between a furan and a maleimide, a Diels-Alder reaction between an anthracene and a maleimide, and a fullerene, and a metathesis reaction using a metathesis catalyst represented by a Grubbs catalyst are preferable.

  However, the seventh aspect of the present invention also includes a Diels-Alder reaction, an ene reaction, and a metathesis reaction, which are not substantially reversible. For example, among the Diels-Alder reactions, those in which the corresponding retro-Diels-Alder reaction can only occur at a high temperature have many side reactions and are hardly reversible in a strict sense. The present invention is applicable to other inventions except the invention.

  Accordingly, as described in the eighth aspect of the present invention, an acid-decomposable compound in which an atomic group which forms a new bond by heat contains a double bond, a furan structure, a maleimide structure, an anthracene structure, a cyclopentadiene structure or a butadiene structure is used. The present invention can be applied to the whole invention.

  Double bonds are active in Diels-Alder reactions, ene reactions, metathesis reactions, and the like, and can be widely used in the present invention. Considering the easiness of application to the Diels-Alder reaction, which is a particularly preferable reaction, those having an electron-withdrawing group bonded to a double bond are more preferable. Examples of such electron withdrawing groups include, for example, carbonyl group, carbonyloxy group, nitro group, nitrile group, halogen group, and thiocarbonyloxy group. And those linked via a methylene group or a methine group.

It is known that the furan compound and the maleimide compound and the anthracene compound and the maleimide compound undergo a reversible Diels-Alder reaction without other additives, and are particularly preferable in the present invention.
Cyclopentadiene and butadiene also perform a Diels-Alder reaction with compounds having various double bonds. The Diels-Alder reaction does not require a catalyst such as a metal complex. This is particularly preferable when forming a positive photosensitive resin required to have a low metal content.

The ninth aspect of the present invention is the acid-decomposable compound according to any one of claims 1 to 8, which has a plurality of acid-decomposable atomic groups in one molecule.
As described above, since it is an acid-decomposable compound having a plurality of acid-decomposable atomic groups in one molecule, it can be decomposed even by a small amount of acid. Particularly, an acid-decomposable compound having a plurality of acid-decomposable atomic groups as an atomic group constituting a branched substance such as a dendrimer is preferable.

A tenth aspect of the present invention is the acid-decomposable compound according to any one of claims 1 to 9, which has an atomic group that forms a new bond by a plurality of heats in one molecule. is there.
As described above, since the acid-decomposable compound has a plurality of atomic groups that generate a bond by a plurality of heats in one molecule, a change in solubility due to heat is large.
An eleventh aspect of the present invention is the acid-decomposable compound according to any one of claims 1 to 10, wherein an acid-decomposable atomic group is bonded to an atom or an atomic group serving as a core, and the acid-decomposable atomic group is newly added by heat. An acid-decomposable compound represented by the following general formula (1) to which an atomic group that forms a natural bond is bonded.

  In the formula (1), the core represents an atom such as a carbon atom, a silicon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a boron atom having a difference in electronegativity with carbon of 2.0 or less, or an organic group. The organic group has a structure mainly containing a normal carbon skeleton, but the structure is not particularly limited, and a very wide range of atomic groups is applicable. Preferred examples of the core structure include a branched structure and a dendrimer structure used at the center of a branched substance such as a dendrimer. Further, a compound or a polymer having a molecular weight of 1,000 or more is also preferable.

  The acid-decomposable atomic group is the same as the acid-decomposable atomic group described in the first embodiment of the present invention, and the atomic group that generates a new bond by heat is described in the first embodiment of the present invention. It is the same as the atomic group that generates a new bond by the heat generated, and is particularly preferably an atomic group containing a furan structure or a maleimide structure.

Further, as described in the first aspect of the present invention, an atomic group that generates a new bond by heat may also serve as part or all of the acid-decomposable atomic group.
Then, in Expression (1), a represents a natural number.

  A twelfth aspect of the present invention is the acid-decomposable compound according to the eleventh aspect, wherein the formula weight of the atomic group forming the core is 1000 or more.

13 of the present invention is the acid-decomposable compound according to claim 12, wherein the core is at least one unit of an acrylic acid derivative, a methacrylic acid derivative, a hydroxystyrene derivative, a norbornene derivative, a maleic acid derivative, and a maleimide derivative. An acid-decomposable compound characterized by having a structure.
There have been many reports on polymers containing these unit structures as photosensitive polymers, and they are promising as materials for photosensitive resin compositions.

  Item 14 of the present invention is the acid-decomposable compound according to claims 11 to 13, wherein the core comprises a branched structure having three or more branches.

For example, the core has a 1,3,5-3 branched benzene derivative, a 3,5,3 ', 5'-4 branched diphenylbenzene derivative, a three or more branched 1,3,5-triphenylbenzene derivative, a carbon number of 4 or more. Since it contains a structure having three or more branches such as a multi-branched cycloalkyl derivative, a multi-branched adamantane derivative, and a three-branched tertiary amine derivative which may have a bridge structure of 12 or less, an acid-decomposable compound having a branched structure It becomes. A highly branched compound can be imparted with properties such as solubility and homogeneity as a dendrimer, as well as amorphous properties.
In the following, among the three or more branched structures included in the core, particularly preferred structures are exemplified, but the present invention is not limited to these examples.

  The fifteenth aspect of the present invention is the acid-decomposable compound according to any one of claims 11 to 14, wherein the acid-decomposable atomic group is an atomic group represented by the following general formulas (2) to (8), An acid group that forms a new bond is an acid-decomposable compound that is an atomic group represented by the following general formula (9) or (10).

In the formulas (2) to (8), R ¹ , R ² , R ⁵ , R ¹¹ , R ¹² , R ¹⁵ , R ²¹ , and R ²² each independently have a C1 to C20 chain which may have a substituent. , Cyclic or branched alkyl group, C5-C20 aryl group which may have a substituent, alkoxy group which may have a substituent, thioalkoxy group which may have a substituent A vinyl group which may have a substituent, a saturated or unsaturated heterocyclic group which may have a substituent, and a silyl group which may have a substituent.

More specifically, R ¹ , R ² , R ⁵ , R ¹¹ , R ¹² , R ¹⁵ , R ²¹ , and R ²² are each independently a methyl group, an ethyl group, an n-propyl group, a 1-methylethyl group, Propyl group, n-butyl group, 1-methyl-propyl group, 2-methylpropyl group, cyclobutyl group n-pentyl group, branched pentyl group, cyclopentyl group, n-hexyl group, branched hexyl group, cyclohexyl group , A C7-C20 linear, cyclic or branched alkyl group, allyl group, and the above-mentioned groups such as alkyl group, alkoxy group, ester group, nitro group, halogen group, cyano group, hydroxyl group, thiol group, etc. Those having a substituent, methyloxy group, ethyloxy group, n-propyloxy group, 1-methylethyloxy group, cyclopropyloxy group, n Butyloxy group, 1-methyl-propyloxy group, 2-methylpropyloxy group, cyclobutyloxy group, n-pentyloxy group, branched pentyloxy group, cyclopentyloxy group, n-hexyloxy group, branched hexyl An oxy group, a cyclohexyloxy group, a C7 to C20 linear or cyclic or branched alkyloxy group, and further, an alkyl group, an alkoxy group, an ester group, a nitro group, a halogen group, a cyano group, a hydroxyl group, A group having a substituent such as a thiol group, or an aryl group such as a phenyl group, a furanyl group, a thionyl group, a pyridyl group, or a naphthyl group; and an alkyl group, an alkoxy group, an ester group, a nitro group, or a halogen group. Group, cyano group, hydroxyl group, thiol group, phenyl group, furanyl group, thio group Aryl, pyridyl, naphthyl, and other aryl groups, and other substituents, and further include alkylsilyl, dialkylsilyl, trialkylsilyl, and aryl-substituted silyl groups. May be.
R ³ , R ⁴ , R ⁷ , R ⁹ , R ¹³ , R ¹⁹ , and R ²⁰ are each independently a divalent organic group or a silylene group, or an oxygen atom, a sulfur atom, or a nitrogen atom; Represents an alkylene group which may have a substituent, a vinylene group which may have a substituent, a carbonyl group, or an arylene group which may have a substituent. Or an atomic group consisting of the above-mentioned divalent organic group or silylene group, or any combination of an oxygen atom, a sulfur atom, or a secondary or tertiary nitrogen atom or boron atom. Alternatively, R ³ , R ⁴ , R ⁷ , R ⁹ , R ¹³ , R ¹⁹ , and R ²⁰ each independently represent an atomic group that forms a new bond by heat represented by the formula (9) or the formula (10). Represents an atomic group including part or all.

Then, in the formula (2), a ring may be formed by an arbitrary plurality of atomic groups among the atomic groups further bonded to R ^{1 to} R ³ and R ³ . Further, R ⁴ and an atomic group further bonded to R ⁴ may form a ring.

In the formulas (3) and (6), R ⁶ and R ¹⁶ each independently represent an arylene group which may have a substituent or a vinylene group which may have a substituent. Alternatively, R ⁶ and R ¹⁶ each independently represent an atomic group including a part or all of an atomic group that forms a new bond by heat represented by the formula (9) or (10).

  Further, a vinylene group having a conjugated multiple bond is also preferable. A methylene group or a methine group substituted with an electron donating group, for example, a methoxymethylene group, a methylthiomethylene group, a methoxyethoxymethylene group, a 2- (trimethylsilyl) ethoxymethylene group, or the like, or a 2-tetrahydropyranylene group An aryloxymethylene group which may have a substituent such as a furanylene group having an electron donating group, a thionylene group, a phenylene group, a vinylene group, or a benzyloxymethylene group, a furanyloxymethylene group, or a thionyloxymethylene group; A vinyloxylene group which may have a group, an N-phthalimidomethylene group which may have a substituent, a 9-anthrylmethylene group which may have a substituent, or a trimethylsilylene group, a triethylsilylene group, Has a substituent such as phenyldimethylsilylene Even though it may be a good silylene group.

  Particularly preferably, an arylene group such as a phenylene group, a naphthylene group, an anthranylene group, a furanylene group, a pyridylene group, a thiophenylene group, or a phenyleneoxy group, a phenylenevinylene group, a furanylenevinylene group, a pyridylenephenylene group, or a thiphenylenevinylene group. It is an atomic group such as an arylenevinylene group. Further particularly preferred examples are a furanylene group, a furanyloxylene group and a furanylenevinylene group.

Then, in the formula (3), among the atomic groups further bonded to R ⁵ , R ⁶ and R ⁶ , a ring may be formed by an arbitrary plurality of atomic groups. Further, R ⁷ and an atomic group further bonded to R ⁷ may form a ring.

In the formulas (4) and (7), R ⁸ and R ¹⁸ are each independently a tetrahydropyranylene group, an arylene group having an electron donating group, a vinylene group having an electron donating group, a benzyloxymethylene group, or a furanyloxy group. Aryloxymethylene group which may have a substituent such as methylene group and thionyloxymethylene group, vinyloxylen group which may have a substituent and N-phthalimidomethylene which may have a substituent Represents a group, a 9-anthrylmethylene group which may have a substituent, or a silylene group which may have a substituent such as a trimethylsilylene group, a triethylsilylene group, or a phenyldimethylsilylene group.

Then, in the formula (4), R ⁸ and an atomic group further bonded to R ⁸ may form a ring. Further, R ⁹ and an atomic group further bonded to R ⁹ may form a ring.
In the formulas (5) to (8), X ¹ and X ² each independently represent an oxygen atom or a sulfur atom.

Further, in the formulas (5), (6) and (7), R ¹⁰ , R ¹⁴ and R ¹⁷ are each independently conjugated to a divalent arylene group or an aryl group which may have a substituent. It represents a divalent vinylene group which may have a substituent.

^However, the bond between R ^{10, R 14} or ^{R 17} and ^{X 1 is} a double bond structure conjugated to the aromatic structure or aromatic constituting R ^{10, R 14} or ^{R 17,} a single bond and ^{X 1} It is.

In the formula (5), a ring may be formed by an arbitrary plurality of atomic groups among the atomic groups further bonded to R ^{11 to} R ¹³ and R ¹³ . Further, R ¹⁰ and an atomic group further bonded to R ¹⁰ may form a ring.

Further, in the formula (6), a ring may be formed by any two or more of the atomic groups further bonded to R ¹⁵ , R ¹⁶ and R ¹⁶ . Further, R ¹⁴ and an atomic group further bonded to R ¹⁴ may form a ring.

Further, in the formula (7), R ¹⁷ and an atomic group further bonded to R ¹⁷ may form a ring. Further, R ¹⁸ and an atomic group further bonded to R ¹⁸ may form a ring.

Further, in the formula (8), any two or more of the atomic groups further bonded to R ²¹ , R ²² , R ¹⁹ and R ¹⁹ may form a ring. In addition, any two or more of the atomic groups further bonded to R ²¹ , R ²² , R ²⁰ , and R ²⁰ may form a ring. However, when R ²¹ forms a ring with R ¹⁹ or an atomic group further bonded to R ¹⁹ , R ²¹ and R ²² form a ring with an atomic group further bonded to R ²⁰ or R ^20. I will not. When R ²¹ forms a ring with R ²⁰ or an atomic group further bonded to R ²⁰ , R ²¹ and R ²² form a ring with an atomic group further bonded to R ¹⁹ or R ^19. I will not. And, when R ²² forms a ring with R ¹⁹ or an atomic group further bonded to R ¹⁹ , R ²² may form a ring with an atomic group further bonded to R ²⁰ or R ^20. Absent.

X ³ and X ⁴ in the formula (9) or (10) each independently represent an oxygen atom or a methylene group.

R ^{23 to} R ²⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group, a C1 to C20 chain, cyclic or branched alkyl group which may have a substituent, C5-C20 aryl group which may have a substituent, vinyl group which may have a substituent, alkoxy group which may have a substituent, and saturated which may have a substituent Or an unsaturated heterocyclic group or a silyl group which may have a substituent. Then, in the formula (9), a ring may be formed by an arbitrary plurality of atomic groups among R ^{23 to} R ²⁵ .

Furthermore atomic group R ²³ to R ^25, the among the atomic group constituting an acid-decomposable atomic groups from the bond that is degraded attached to the formula (9) side any atomic group and form a ring and an acid May be.

In Formula (10), a ring may be formed by a plurality of arbitrary atomic groups among R ^{26 to} R ²⁸ .

Further, the atomic groups R ^{26 to} R ²⁸ form a ring with any of the atomic groups constituting the acid-decomposable atomic group, which are bonded to the formula (10) side from the bond decomposed by the acid. May be. )

The atomic group generating a new bond by the heat of the present invention have a substituent group ^R 23 ^{to R 25} or ^R 26 ^{to R 28,} represented by the formula (9) or (10) Good cyclic diene structure. And, as described in the first aspect of the present invention, the cyclic diene structure itself can be a part of the acid-decomposable atomic group. Examples of such a structure in which the cyclic diene becomes a part of the acid-decomposable atomic group are shown below as Formulas (39) to (42).

Formulas (39) to (42) correspond to an example in which R ⁶ or R ¹⁶ in Formula (3) or Formula (6) is Formula (9) or Formula (10). Therefore, in Formulas (39) to (42), R ⁵ , R ⁷ , R ¹⁵ , R ¹⁴ , and X ¹ are the same atomic groups as those described in Formulas (3) and (6), and In formulas (39) to (42), R ^{23 to} R ²⁶ , R ^{27 to} R ²⁸ , X ³ and X ⁴ are the same atomic groups as those described in formulas (9) and (10). Since the conjugated cyclic diene structure, particularly the aromatic furan ring structure, stabilizes cations generated by acid decomposition from the acid-decomposable atomic group, the conjugated cyclic diene structure is used in the above formulas (39) to (42). Can be said to be a part of the acid-decomposable atomic group.
16 of the present invention is the acid-decomposable compound according to claim 15, which comprises a unit structure represented by the following general formula (11) or (12).

In Formula (11) or (12), X ³ , X ⁴ , and R ^{23 to} R ²⁸ represent the same atomic groups as those described in the above-mentioned claim 15. h and i each independently represent an integer.
R ²⁹ and R ³³ each independently represent an acid-decomposable atomic group represented by formulas (2) to (8) according to claim 15. H and i each independently represent a natural number.

In the formula (11) or (12), R ^{30 to} R ³² and R ^{34 to} R ³⁶ each independently represent a C1 to C20 chain, cyclic or branched alkyl group which may have a substituent. A C5 to C20 aryl group which may have a substituent, an alkoxy group which may have a substituent, a thioalkoxy group which may have a substituent, and a substituent It represents a vinyl group, a saturated or unsaturated heterocyclic group which may have a substituent, or a silyl group which may have a substituent. In the formula (11), a ring may be formed by an arbitrary plurality of atomic groups of R ^{30 to} R ³² . Further among the atomic groups constituting the acid decomposable atomic group, may form an arbitrary atomic group and ring attached to the atomic group R ³⁰ side than the binding to be decomposed with acid.

In the formula (12), a ring may be formed by any of a plurality of atomic groups represented by R ^{34 to} R ³⁶ . Further, among the atomic groups constituting the acid-decomposable atomic group, a ring may be formed with an arbitrary atomic group bonded to the atomic group ^R34 side from the bond decomposed by the acid.
A seventeenth aspect of the present invention is the acid-decomposable compound according to claim 15, represented by the following general formula (13).

In the formula (13), R ³⁷ and R ⁴⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an amino group, a C1 to C20 chain, cyclic or cyclic group which may have a substituent. A branched alkyl group, a C5-C20 aryl group which may have a substituent, an alkoxy group which may have a substituent, a thioalkoxy group which may have a substituent, It represents a vinyl group which may have, a saturated or unsaturated heterocyclic group which may have a substituent, and a silyl group which may have a substituent. R ³⁸ has a C1 to C20 chain, cyclic or branched alkyl group which may have a substituent, a C5 to C20 aryl group which may have a substituent, and a substituent. A substituted or unsubstituted thioalkoxy group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted saturated or unsaturated heterocyclic group, It represents a silyl group which may be possessed. And d is an integer of 0 or more and 10 or less. R ³⁹ has a C1 to C20 chain, cyclic or branched alkyl group which may have a substituent, a C5 to C20 aryl group which may have a substituent, and a substituent. An alkoxy group, a vinyl group which may have a substituent, a saturated or unsaturated heterocyclic group which may have a substituent, a silyl group which may have a substituent, and the like. When = 0, it also represents a hydrogen atom. b, c, and e are integers, 1 <= c <= 6, 0 <= b <= (6-c), and 0 <= e <= 3. When 2 <= b, a plurality of R3 may be different from each other; when 2 <= e, a plurality of R4 may be different from each other; when 2 <= c, a plurality of parentheses related to c May be different. )

A seventeenth aspect of the present invention is an acid-decomposable compound having a core structure having a branched structure containing a benzene ring. Particularly preferred are trimesic acid derivatives, which can be synthesized, for example, from trimesic acid chloride and furyl-2-methyl alcohol or 2-furyl-2-methylalkoxide.
An eighteenth aspect of the present invention is the acid-decomposable compound according to claim 16, which comprises a structural unit represented by the following general formula (14) or (15).

In Formula (14) or (15), R ^{23 to} R ²⁸ , R ^{30 to} R ³² , and R ^{34 to} R ³⁶ represent the same atomic groups as those described in the above-described Claim 16. j and k each independently represent an integer.
R ⁴¹ and R ⁴³ are each independently a C1 to C20 linear, cyclic or branched alkyl group which may have a substituent, a C5 to C20 aryl group which may have a substituent, An alkoxy group which may have a group, a thioalkoxy group which may have a substituent, a vinyl group which may have a substituent, and a saturated or unsaturated group which may have a substituent It represents a heterocyclic group or a silyl group which may have a substituent.

F is an integer of 10 or less. g is an integer of 10 or less.
R ⁴² has a C1 to C20 chain, cyclic or branched alkyl group which may have a substituent, a C5 to C20 aryl group which may have a substituent, and a substituent. A substituted or unsubstituted thioalkoxy group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted saturated or unsaturated heterocyclic group, It represents a silyl group or the like which may be possessed, and when f = 0, also represents a hydrogen atom.

R ⁴⁴ has a C1 to C20 chain, cyclic or branched alkyl group which may have a substituent, a C5 to C20 aryl group which may have a substituent, and a substituent. A substituted or unsubstituted thioalkoxy group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted saturated or unsaturated heterocyclic group, It represents a silyl group or the like which may be possessed, and when g = 0, also represents a hydrogen atom.

Particularly preferred are, in the formula (14), R ³⁰ = hydrogen atom or methyl group, R ³¹ , R ³² = hydrogen atom, R ⁴¹ = methyl group, R ⁴² = hydrogen atom, f = 0, R ²³ , R ²⁴ , In the case of R ²⁵ = hydrogen atom, or in the formula (15), R ³⁴ = hydrogen atom or methyl group, R ³⁵ , R ³⁶ = hydrogen atom, R ⁴³ = methyl group, R ⁴⁴ = hydrogen atom, g = 0, When R ²⁶ , R ²⁷ , and R ^{28 are} hydrogen atoms, that is, acrylic acid or methacrylic acid derivatives. In the formula (14), R ³⁰ = hydrogen atom or methyl group, R ³¹ , R ³² = hydrogen atom, R ⁴¹ = alkyl group of C1 to C10, R ⁴² = alkyl group of C1 to C10, 0 <= f <= 10, R ²³ , R ²⁴ , R ²⁵ = hydrogen atom or alkyl group or aryl group, or in the formula (15), R ³⁴ = hydrogen atom or methyl group, R ³⁵ , R ³⁶ = hydrogen atom, It is also preferred that R ⁴³ = C 1 to C 10 alkyl group, R ⁴⁴ = C 1 to C 10 alkyl group, 0 <= g <= 10, R ²⁶ , R ²⁷ , R ²⁸ = hydrogen atom or alkyl group or aryl group.

  For the synthesis of a polymerizable compound having a particularly preferred structural unit, for example, for example, acrylic acid chloride or methacrylic acid chloride and furyl-alkyl-alcohol such as furyl-2-methyl alcohol or 2-furyl-2-methylalkoxide It can be synthesized from derivatives. As another example, it can also be synthesized by dehydrating acrylic acid or methacrylic acid with furyl-2-methyl alcohol or furyl-3-methyl alcohol in the presence of an acid catalyst. Further, among the acid-decomposable compounds according to the present invention, a compound containing a 1- (2-furyl) ethyloxycarbonyl group was examined in detail, and as a result, it was very stable up to a certain temperature, but at a certain temperature or higher. It has been found that it shows a very characteristic thermal decomposition property that it decomposes quickly. For this reason, the compound of the present invention can be discarded by utilizing its thermal decomposability.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Synthesis of 1- (2-furyl) ethyl methacrylate

200 ml of dried tetrahydrofuran was charged into a 1-liter flask purged with nitrogen, and 138 ml (0.414 mol) of a 3M methylmagnesium chloride solution in tetrahydrofuran was added. The flask was stirred with a stirrer while being cooled in an ice bath, and 35.8 g of furfural was dropped into the solution over 1 hour. After stirring was continued for another 0.5 hour after the completion of the dropwise addition, 42 ml (0.430 mol) of methacrylic acid chloride was added dropwise over 1 hour. After further stirring for 16 hours, 100 ml of water was added, and the mixture was stirred for 10 minutes, and separated into an organic phase and an aqueous phase using a separating funnel. Next, the organic phase was washed with 100 ml of 5.6% NH3 water. After 200 ml of diethyl ether was added to the organic phase, the mixture was washed three times with 100 ml of water, separated, and dried by adding magnesium sulfate. After removing the solvent under reduced pressure, vacuum distillation was performed under reduced pressure of 40 Pa, and steam at about 50 ° C. was collected to obtain 66.89 g of 1- (2-furyl) ethyl methacrylate. The yield was about 72.3%. The NMR spectrum is shown in FIG.
Synthesis of poly (1- (2-furyl) ethyl methacrylate)

  28.43 g (0.158 mol) of 1- (2-furyl) ethyl methacrylate was added to 56 ml of diglyme, and 1.00 g (0.0030 mol) of N, N'-azoisobutyronitrile was further added. This mixed solution was charged into a pressure-resistant tube having a capacity of 500 ml. While the pressure tube was cooled with liquid nitrogen, the pressure was reduced to 0.5 Pa with an oil rotary pump, and then the pump was removed from the pump while maintaining the reduced pressure and returned to room temperature to perform degassing. After repeating this deaeration operation three times, the mixture was stirred in an oil bath at 80 ° C. using a stirrer. After the reaction was completed for 5 hours, the reaction solution was added dropwise to 2500 ml of methanol over 1 hour, and a white solid was precipitated. The white solid was collected by filtration. Further, it was dried in a vacuum dryer at 20 ° C. for 16 hours to obtain 26.24 g of poly (2-furyl) -1′-ethyl methacrylate as a white powder. The yield was about 92%. FIG. 2 shows the NMR chart. In addition, when the thermal decomposition reaction was examined under nitrogen at a heating temperature of 10 ° C./min, almost no change in weight was observed up to 232 ° C., but when the temperature was raised to 239 ° C., the weight loss was reduced by 40%. Had been reached.

Confirmation of acid decomposability 0.21 g (0.0011 mol) of 1- (2-furyl) ethyl methacrylate and 0.1 g of p-methoxyphenol were dissolved in 2.0 g of heavy chloroform, and heavy water containing 10% sulfuric acid was added. And stirred at 60 ° C. for 12 hours. After stirring, the heavy chloroform phase was subjected to NMR measurement. As a result, (2-furyl) -1′-methacrylate-1′-yl was reduced to ３ mol equivalent before the reaction, and methacrylic acid was charged instead (2). -Furyl) -1'-methacrylate-1'-yl was produced in about 2/3 equivalents. In Comparative Example 2 described later, 2-methyltricyclo [5.2.1.0 ^2,6 ] dodecanyl methacrylate-2-yl, which is an acid-decomposable component of the ArF exposure photoresist, does not decompose under the same conditions. From these results, it is apparent that the poly (1- (2-furyl) ethyl methacrylate) according to the present invention exhibits sufficient acid solubility as an acid-soluble component of a photoresist.
Synthesis of 1,3,5-tris (methylfurfuryloxycarbonyl) benzene

A 1.5 M methylmagnesium chloride / tetrahydrofuran solution was charged into a flask purged with nitrogen. The flask was cooled in an ice bath, and 35.6 g of furfural was added dropwise over 80 minutes while stirring with a stirrer. After the addition, the mixture was further stirred for 10 minutes. Next, a solution in which 20.63 g of trimesic acid chloride was dissolved in 60 ml of tetrahydrofuran was added dropwise over 80 minutes. Thereafter, 200 ml of diethyl ether and 200 ml of a 4M aqueous solution of ammonium chloride were added, and the mixture was sufficiently stirred and then separated. The organic phase thus obtained was washed three times with 200 ml of water and dried over 10 g of anhydrous magnesium chloride, after which the solvent was distilled off under reduced pressure. 45.5 g of a mixture of 1,3,5-tris (methylfurfuryloxycarbonyl) benzene and methylfurfuryl alcohol in a molar ratio of 3: 1 was obtained. FIG. 3 shows the NMR spectrum of this mixture of 1,3,5-tris (methylfurfuryloxycarbonyl) benzene and methylfurfuryl alcohol at a molar ratio of 3: 1.
Comparative Example 1

0.20 g (0.0012 mol) of furfuryl methacrylate and 0.1 g of p-methoxyphenol are dissolved in 2.0 g of heavy chloroform, mixed with 1.0 g of heavy water containing 10% sulfuric acid, and stirred at 60 ° C. for 12 hours. did. After stirring, the heavy chloroform phase was subjected to NMR measurement, but no decomposition of furfuryl methacrylate was observed.
Comparative Example 2

0.25 g (0.0027 mol) of 2-methyltricyclo [5.2.1.0 ^2,6 ] dodecanyl methacrylate-2-yl reported to have acid-decomposability and 0.1 g of p-methoxyphenol Was dissolved in 2.0 g of heavy chloroform, mixed with 1.0 g of heavy water containing 10% sulfuric acid, and stirred at 60 ° C. for 12 hours. After stirring, the heavy chloroform phase was subjected to NMR measurement, but no decomposition of 2-methyltricyclo [5.2.1.0 ^2,6 ] dodecanyl methacrylate-2-yl was observed.

  As described above, according to the acid-decomposable compound of the present invention, a compound having both thermal crosslinking property and acid-decomposability can be provided. And since it is an acid-decomposable compound that has an atomic group that decomposes with an acid and an atomic group that generates a new bond with heat, it generates a crosslinked structure by heat or causes a structural change by heat. While its properties can be changed, for example, it can be used as a thermosetting resin, on the other hand, it can be dissolved in a solvent by decomposing into a low molecular weight or changing its polarity by acid decomposition, and can be easily disposed of. In addition, it becomes an unprecedented excellent photosensitive resin constituent material.

      NMR chart of 1- (2-furyl) ethyl methacrylate       NMR chart of poly (1- (2-furyl) ethyl methacrylate)       NMR chart of 1,3,5-tris (methylfurfuryloxycarbonyl) benzene

Claims (18)

  An acid-decomposable compound having an acid-decomposable atomic group that is decomposed by an acid and an atomic group that generates a new bond by heat.   The acid-decomposable compound according to claim 1, wherein the change in solubility in the solvent due to decomposition by an acid is opposite to the change in solubility in the solvent caused by a new bond generated by heat. An acid-decomposable compound, which is characterized in that:   The acid-decomposable compound according to claim 1 or 2, wherein the solubility in a solvent is increased by decomposition with an acid, while the solubility in the solvent is reduced by generation of a new bond by heat. Acid-decomposable compounds.   The acid-decomposable compound according to any one of claims 1 to 3, wherein at least 5 of the atomic groups decomposed by the acid with a pKa of 10 or less in a temperature range of 0 ° C to 200 ° C within 72 hours. % Is decomposed by an acid-decomposable compound.   The acid-decomposable compound according to claim 1, wherein the acid-decomposable atomic group is a tertiary ester bond, a secondary aryl ester bond, a tertiary oxycarbonyloxy bond, a secondary aryloxycarbonyloxy bond, or a thioester bond. Acid decomposability characterized by an atomic group selected from an acetal bond, a tertiary ether bond, a secondary aryl ether bond, a tertiary thioether bond, a secondary aryl ether bond and those substituted with an electron donating group. Compound.   The acid-decomposable compound according to claim 1, wherein a reaction for generating a new bond by heat is a reversible reaction.   The acid-decomposable compound according to claim 1, wherein the reaction for generating a new bond by heat is based on a Diels-Alder reaction, an ene reaction, or a metathesis reaction.   The acid-decomposable compound according to any one of claims 1 to 7, wherein the atomic group generating a new bond by heat includes a double bond, a furan structure, a maleimide structure, an anthracene structure, a cyclopentadiene structure, or a butadiene structure. A characteristic acid-decomposable compound.   The acid-decomposable compound according to claim 1, wherein the compound has a plurality of acid-decomposable atomic groups in one molecule.   The acid-decomposable compound according to any one of claims 1 to 9, wherein one molecule has an atomic group that forms a new bond by a plurality of heats in one molecule. The acid-decomposable compound according to any one of claims 1 to 10, wherein the acid-decomposable atomic group is bonded to a core atom or atomic group, and a new bond is generated in the acid-decomposable atomic group by heat. And an acid-decomposable compound represented by the following general formula (1).

(In the formula (1), the core represents an atom such as a carbon atom, a silicon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a boron atom whose difference in electronegativity with carbon is 2.0 or less, or an organic group. , The core may be part or all of the acid-decomposable atomic group, and the atomic group that forms a new bond by heat may be part or all of the acid-decomposable atomic group. a represents a natural number.)   The acid-decomposable compound according to claim 11, wherein a formula weight of an atomic group forming a core is 1,000 or more.   The acid-decomposable compound according to claim 12, wherein the core is at least one of an acrylic acid derivative unit, a methacrylic acid derivative unit, a hydroxystyrene derivative unit, a norbornene derivative unit, a maleic acid derivative unit, and a maleimide derivative unit. An acid-decomposable compound comprising a unit structure.   14. The acid-decomposable compound according to claim 11, wherein the core comprises a branched structure having three or more branches. The acid-decomposable compound according to claim 11, wherein the acid-decomposable atomic group is an atomic group represented by the following general formulas (2) to (8), or an atomic group that generates a new bond by heat. An acid-decomposable compound which is an atomic group represented by the following general formula (9) or (10).

(In the formulas (2) to (8), R ¹ , R ² , R ⁵ , R ¹¹ , R ¹² , R ¹⁵ , R ²¹ , and R ²² each independently may have a substituent. A chain, cyclic or branched alkyl group, a C5-C20 aryl group which may have a substituent, an alkoxy group which may have a substituent, and a thio which may have a substituent Examples thereof include an alkoxy group, a vinyl group which may have a substituent, a saturated or unsaturated heterocyclic group which may have a substituent, and a silyl group which may have a substituent.
R ³ , R ⁴ , R ⁷ , R ⁹ , R ¹³ , R ¹⁹ , and R ²⁰ are each independently a divalent organic group or a silylene group, or an oxygen atom, a sulfur atom, or a nitrogen atom; Represents an alkylene group which may have a substituent, a vinylene group which may have a substituent, a carbonyl group, or an arylene group which may have a substituent. Or an atomic group consisting of the above-mentioned divalent organic group or silylene group, or any combination of an oxygen atom, a sulfur atom, or a secondary or tertiary nitrogen atom or boron atom. Alternatively, R ³ , R ⁴ , R ⁷ , R ⁹ , R ¹³ , R ¹⁹ , and R ²⁰ each independently represent an atomic group that forms a new bond by heat represented by the formula (9) or the formula (10). Represents an atomic group including part or all.
Then, in the formula (2), a ring may be formed by an arbitrary plurality of atomic groups among the atomic groups further bonded to R ^{1 to} R ³ and R ³ . Further, R ⁴ and an atomic group further bonded to R ⁴ may form a ring.
In the formulas (3) and (6), R ⁶ and R ¹⁶ are each independently an arylene group which may have a substituent, a vinylene group which may have a substituent, or an electron donating group. And a divalent organic group having, on the acid-decomposable bond side, a methylene group, a vinyleneoxy group which may have a substituent, and a silylene group which may have a substituent. Alternatively, R ⁶ and R ¹⁶ each independently represent an atomic group including a part or all of an atomic group that forms a new bond by heat represented by the formula (9) or (10).
Then, in the formula (3), among the atomic groups further bonded to R ⁵ , R ⁶ and R ⁶ , a ring may be formed by an arbitrary plurality of atomic groups. Further, R ⁷ and an atomic group further bonded to R ⁷ may form a ring.
In the formulas (4) and (7), R ⁸ and R ¹⁸ are each independently a tetrahydropyranylene group, an arylene group having an electron donating group, a vinylene group having an electron donating group, or a benzyloxymethylene group, furanyl. Aryloxymethylene group which may have a substituent such as oxymethylene group, thionyloxymethylene group, vinyleneoxylen group which may have a substituent, N-phthalimide which may have a substituent An acid-decomposable bond of a methylene group, a 9-anthrylmethylene group which may have a substituent, or a silylene group which may have a substituent such as a trimethylsilylene group, a triethylsilylene group, or a phenyldimethylsilylene group. Represents a divalent organic group on the side.
Then, in the formula (4), R ⁸ and an atomic group further bonded to R ⁸ may form a ring. Further, R ⁹ and an atomic group further bonded to R ⁹ may form a ring.
In the formulas (5) to (8), X ¹ and X ² each independently represent an oxygen atom or a sulfur atom.
In the formulas (5), (6) and (7), R ¹⁰ , R ¹⁴ and R ¹⁷ each independently represent a substituent conjugated to a divalent arylene group or an aryl group which may have a substituent. Represents a divalent organic group having a divalent vinylene group which may have a group on the acid-decomposable bond side.
^However, the bond between R ^{10, R 14} or ^{R 17} and ^{X 1 is} a double bond structure conjugated to the aromatic structure or aromatic constituting R ^{10, R 14} or ^{R 17,} a single bond and ^{X 1} It is.
In the formula (5), a ring may be formed by an arbitrary plurality of atomic groups among the atomic groups further bonded to R ^{11 to} R ¹³ and R ¹³ . Further, R ¹⁰ and an atomic group further bonded to R ¹⁰ may form a ring.
Further, in the formula (6), a ring may be formed by any two or more of the atomic groups further bonded to R ¹⁵ , R ¹⁶ and R ¹⁶ . Further, R ¹⁴ and an atomic group further bonded to R ¹⁴ may form a ring.
Further, in the formula (7), R ¹⁷ and an atomic group further bonded to R ¹⁷ may form a ring. Further, R ¹⁸ and an atomic group further bonded to R ¹⁸ may form a ring.
Further, in the formula (8), any two or more of the atomic groups further bonded to R ²¹ , R ²² , R ¹⁹ and R ¹⁹ may form a ring. In addition, any two or more of the atomic groups further bonded to R ²¹ , R ²² , R ²⁰ , and R ²⁰ may form a ring. However, when R ²¹ forms a ring with R ¹⁹ or an atomic group further bonded to R ¹⁹ , R ²¹ and R ²² form a ring with an atomic group further bonded to R ²⁰ or R ^20. I will not. When R ²¹ forms a ring with R ²⁰ or an atomic group further bonded to R ²⁰ , R ²¹ and R ²² form a ring with an atomic group further bonded to R ¹⁹ or R ^19. I will not. And, when R ²² forms a ring with R ¹⁹ or an atomic group further bonded to R ¹⁹ , R ²² may form a ring with an atomic group further bonded to R ²⁰ or R ^20. Absent.
X ³ and X ⁴ in the formula (9) or (10) each independently represent an oxygen atom or a methylene group.
R ^{23 to} R ²⁸ each independently have a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, and a C1 to C20 chain, cyclic or branched group which may have a substituent. An alkyl group, a C5-C20 aryl group which may have a substituent, a vinyl group which may have a substituent, an alkoxy group which may have a substituent, And a saturated or unsaturated heterocyclic group, a silyl group which may have a substituent, and the like. Then, in the formula (9), a ring may be formed by an arbitrary plurality of atomic groups among R ^{23 to} R ²⁵ .
Furthermore atomic group R ²³ to R ^25, the among the atomic group constituting an acid-decomposable atomic groups from the bond that is degraded attached to the formula (9) side any atomic group and form a ring and an acid May be.
In the formula (10), a ring may be formed by a plurality of arbitrary atomic groups among R ^{26 to} R ²⁸ .
Further, the atomic groups R ^{26 to} R ²⁸ form a ring with any of the atomic groups constituting the acid-decomposable atomic group, which are bonded to the formula (10) side from the bond decomposed by the acid. It may be. ) The acid-decomposable compound according to claim 15, comprising a unit structure represented by the following general formula (11) or (12).

(In formula (11) or (12), X ³ , X ⁴ , R ^{23 to} R ²⁸ represent the same atomic group as described in the above-mentioned claim 15. h and i each independently represent an integer.) .
R ²⁹ and R ³³ each independently represent an acid-decomposable atomic group represented by formulas (2) to (8) according to claim 15.
In the formula (11) or (12), R ^{30 to} R ³² and R ^{34 to} R ³⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, and a substituent. C1-C20 chain, cyclic or branched alkyl group which may have, C5-C20 aryl group which may have a substituent, alkoxy group which may have a substituent, substituent A thioalkoxy group which may have a substituent, a vinyl group which may have a substituent, a saturated or unsaturated heterocyclic group which may have a substituent, and a substituent Shows a silyl group. In the formula (11), a ring may be formed by an arbitrary plurality of atomic groups of R ^{30 to} R ³² . Further among the atomic groups constituting the acid decomposable atomic group, may form an arbitrary atomic group and ring attached to the atomic group R ³⁰ side than the binding to be decomposed with acid.
In the formula (12), a ring may be formed by any of a plurality of atomic groups represented by R ^{34 to} R ³⁶ . Further, among the atomic groups constituting the acid-decomposable atomic group, a ring may be formed with an arbitrary atomic group bonded to the atomic group ^R34 side from the bond decomposed by the acid. ) The acid-decomposable compound according to claim 15, represented by the following general formula (13).

(In the formula (13), R ³⁷ and R ⁴⁰ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, and a C1 to C20 chain which may have a substituent. , Cyclic or branched alkyl group, C5-C20 aryl group which may have a substituent, alkoxy group which may have a substituent, thioalkoxy group which may have a substituent R ³⁸ represents a substituent, a vinyl group which may have a substituent, a saturated or unsaturated heterocyclic group which may have a substituent, or a silyl group which may have a substituent. A C1-C20 chain, cyclic or branched alkyl group which may have a C5-C20 aryl group which may have a substituent, an alkoxy group which may have a substituent, Thioalkoxy optionally having a substituent And d represents a silyl group, a vinyl group which may have a substituent, a saturated or unsaturated heterocyclic group which may have a substituent, and a silyl group which may have a substituent. Is an integer of 0 to 10. R ³⁹ is a C1 to C20 chain-like, cyclic or branched alkyl group which may have a substituent, or a C5 to C20 which may have a substituent. An aryl group, an alkoxy group which may have a substituent, a vinyl group which may have a substituent, a saturated or unsaturated heterocyclic group which may have a substituent, And d represents a hydrogen atom when d = 0, b, c and e are integers, and 1 <= c <= 6 and 0 <= b <= (6-c) , 0 <= e <= 3 In the case of 2 <= b, a plurality of R3s may be different from each other, and in the case of 2 <= e, The numbers R4 may be different from each other, and when 2 <= c, the atomic groups in parentheses related to c may be different.) The acid-decomposable compound according to claim 16, comprising a structural unit represented by the following general formula (14) or (15).

(In the formula (14) or (15), R ^{23 to} R ²⁸ , R ^{30 to} R ³² , and R ^{34 to} R ³⁶ represent the same atomic group as that described in the above-mentioned claim 16. j and k are respectively. Independently represents an integer.
R ⁴¹ and R ⁴³ are each independently a C1 to C20 linear, cyclic or branched alkyl group which may have a substituent, a C5 to C20 aryl group which may have a substituent, An alkoxy group which may have a group, a thioalkoxy group which may have a substituent, a vinyl group which may have a substituent, and a saturated or unsaturated group which may have a substituent It represents a heterocyclic group or a silyl group which may have a substituent. F is an integer of 10 or less. g is an integer of 10 or less.
R ⁴² has a C1 to C20 chain, cyclic or branched alkyl group which may have a substituent, a C5 to C20 aryl group which may have a substituent, and a substituent. A substituted or unsubstituted thioalkoxy group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted saturated or unsaturated heterocyclic group, It represents a silyl group or the like which may be possessed, and when f = 0, also represents a hydrogen atom.
R ⁴⁴ has a C1 to C20 chain, cyclic or branched alkyl group which may have a substituent, a C5 to C20 aryl group which may have a substituent, and a substituent. A substituted or unsubstituted thioalkoxy group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted saturated or unsaturated heterocyclic group, It represents a silyl group or the like which may be possessed, and when g = 0, also represents a hydrogen atom. )

Images