JP2016204283A - Novel compound, photo-base generator, and method for producing novel compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound and a photo-base generator, being photosensitive materials, serving as an initiator for polymerization reaction and chemical reaction when used in photoresist and the like, as well as suitable as a photo-base generator and having an excellent base generation rate, and a method for producing the compound.SOLUTION: The present invention provides a compound represented by formula (1) (R-Rindependently represent H, a hydrocarbon group or a hydrocarbon oxy group; one of R-Ris a -Y-Z group; Y is a bivalent linking group; Z is a monovalent photosensitization group; X is -NRR, -N=CRRor -N=PRRR).SELECTED DRAWING: None

Description

  The present invention relates to a novel compound, a photobase generator, and a method for producing the novel compound.

  Photoacid generators have been widely used as photosensitive materials for resins such as polyimides and epoxies used in the field of electronic devices such as high density printed circuit boards. In the insulation treatment with a resin such as polyimide or epoxy, by adding this photoacid generator, the pattern of the connecting portion and the insulating portion can be formed by utilizing the curing reaction of the resin by ultraviolet irradiation.

  As a photoresist material made of a photosensitive material using the photoacid generator, various materials are provided aiming at high sensitivity and high resolution. However, when this photoacid generator is used, for example, as a cationic polymerization material that generates acid by the action of light and uses the acid as a catalyst, the acid remains even after curing, causing the presence of the strong acid. As a result, there are problems such as corrosion of the metal wiring and modification of the resin. In the future, it is predicted that this problem will become more apparent in consideration of further miniaturization of the wiring of electronic devices.

  Against this background, in order to obtain a resist material that can form a pattern with high resolution and high sensitivity and high etching resistance, a curing technology that instantly solidifies a liquid substance by irradiating active energy rays has a higher performance. Therefore, development of a new photosensitive system that solves the above problems has been desired.

  As a method of solving the above problem, a method using a base-catalyzed polymerization reaction or chemical reaction, for example, a base generated by light using a method in which a base is generated by the action of light and a resin is chemically modified using this as a catalyst. Means for applying a photosensitive resin composition using NO as a catalyst to a photoresist material, a photo-curing material or the like has been studied. Examples of such a photobase generator include carbamate-based (urethane-based) photobase generators (for example, Patent Documents 1 to 5), α-aminoketone-based photobase generators (for example, Patent Document 6), Quaternary ammonium-based photobase generator (for example, Patent Document 7), O-acyloxime-based photobase generator (for example, Patent Document 8), photobase generator comprising an amine having a cyclopropenone ring (Patent Various photobase generators such as a photobase generator composed of [9] and [[(2-nitrobenzyl) oxy] carbonyl] alkylamine (Non-patent Document 1) are known.

  However, for example, the photobase generators of Patent Documents 1 to 6, 8, 9 and Non-Patent Document 1 have a relatively low basicity because the base generated by ultraviolet irradiation is a primary or secondary amine, and is particularly patentable. The photobase generators of Literatures 1-3, 6, 8, and 9 have a problem that they do not sufficiently exhibit the effect as a base generator in terms of base generation efficiency. In addition, the photobase generators of Patent Documents 4 and 5 are sensitive to the wavelength region of light rays called so-called h-rays (wavelength of about 405 nm), which has a longer wavelength than the ultraviolet rays that are usually used to form patterns. There is a problem that the area is specified. The quaternary ammonium salt-based photobase generator of Patent Document 7 has insufficient catalytic activity for curing the epoxy group, and the base generated by ultraviolet irradiation contains an ionic component, so that the insulation reliability is improved. There is concern in terms of.

  Furthermore, since the conventional photobase generator has a low base generation rate, there is also a problem that it takes a long time to reach a desired pH.

  Therefore, it is desired to develop a photobase generator having an excellent base generation rate as compared with conventional photobase generators by devising the molecular structure.

Japanese Patent Laid-Open No. 10-77264 Japanese Patent Publication No. 51-46159 Japanese Patent Laid-Open No. 6-345711 International Publication No. 2010-38828 International Publication No. 2010-38837 JP-A-11-71450 JP 2005-264156 A JP 2006-36895 A

J. Am. Chem. Soc., 113, 4303-4313 (1991)

  An object of the present invention is to provide a compound, a photobase generator, and a method for producing the compound, which are suitable as a photobase generator and have an excellent base generation rate.

  Now, the present inventor has focused on a compound having an excellent base generation rate and found that, when irradiated with active energy rays, the compound having a strong base is liberated in a short time to solve the above-mentioned problems. Completed.

式（１）中、Ｒ^１〜Ｒ^７は、それぞれ独立に、水素原子、炭化水素基または炭化水素オキシ基を表し、Ｒ^１とＲ^２、Ｒ^２とＲ^３、Ｒ^３とＲ^４、Ｒ^４とＲ^５、またはＲ^５とＲ^６とは、それぞれ共同して飽和または不飽和の環構造を形成してもよく、ただし、Ｒ^１〜Ｒ^７の一つは−Ｙ−Ｚ基であり、ここでＹは二価の連結基を表し、Ｚは一価の光増感基を表し、Ｘは−ＮＲ^８Ｒ^９、−Ｎ＝ＣＲ^１０Ｒ^１１又は−Ｎ＝ＰＲ^１２Ｒ^１３Ｒ^１４（Ｒ^８およびＲ^９は、それぞれ独立に、水素原子または炭素原子数１〜５のアルキル基を表し、Ｒ^８およびＲ^９は共同して窒素原子を含む環構造を形成してもよく、Ｒ^１０およびＲ^１１はそれぞれ独立にアミノ基を表し、Ｒ^１２〜Ｒ^１４は、それぞれ独立に、窒素原子を含む環構造を表す。）を表す。 According to one embodiment of the present invention, a compound represented by the following formula (1) is provided.

In formula (1), R ^{1 to} R ⁷ each independently represent a hydrogen atom, a hydrocarbon group or a hydrocarbon oxy group, and R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may jointly form a saturated or unsaturated ring structure, provided that one of R ^{1 to} R ⁷ is a —YZ group. Where Y represents a divalent linking group, Z represents a monovalent photosensitizing group, and X represents —NR ⁸ R ⁹ , —N═CR ¹⁰ R ^11, or —N═PR ¹² R ¹³ R ^14. (R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁸ and R ⁹ may jointly form a ring structure containing a nitrogen atom; ¹⁰ and ^{R 11} each independently represent an amino ^group, R 12 ^{to R 14} are independently ring structure containing a nitrogen atom Representing a representative.) A.

  According to another aspect of the present invention, a photobase generator comprising the above compound is provided.

According to another aspect of the present invention, a compound represented by the following formula (2) is provided.
Z-R ¹⁵ -Q ¹ (2)
In formula (2), Z is as defined above, R ¹⁵ represents a divalent hydrocarbon group, and Q ¹ is selected from the group consisting of a hydroxyl group, a carboxyl group, a halogenated alkyl group, and an amino group. Represents a group.

式（３）中、Ｒ^１７〜^２３は、それぞれ独立に、水素原子、炭化水素基または炭化水素オキシ基を表し、Ｒ^１７とＲ^１８、Ｒ^１８とＲ^１９、Ｒ^１９とＲ^２０、Ｒ^２０とＲ^２１、またはＲ^２１とＲ^２２とは、それぞれ共同して飽和または不飽和の環構造を形成してもよく、ただし、Ｒ^１７〜Ｒ^２３の一つは−Ｒ^１６−Ｑ^３基であり、ここでＲ^１６は上記で定義した通りであり、Ｑ^３は水酸基、カルボキシル基、ハロゲン化アルキル基、およびアミノ基からなる群から選択され、かつＱ^１とエステル結合、エーテル結合、およびアミド結合からなる群から選択される結合を形成し得る基を表し、Ｘは上記で定義した通りである。 According to another aspect of the present invention, there is provided a method for producing a compound represented by the above formula (1), wherein Y is a -R ¹⁶ -Q ² -R ¹⁵ -group in the formula (1), Here, R ¹⁵ and R ¹⁶ represent a divalent hydrocarbon group, Q ² represents a bond selected from the group consisting of an ester bond, an ether bond, and an amide bond, and is a compound represented by the following formula (3) And a method for producing a compound, comprising reacting the compound represented by the above formula (2).

In the formula (3), R ¹⁷ to ²³ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon oxy group, and R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , R ²⁰ And R ²¹ , or R ²¹ and R ²² may jointly form a saturated or unsaturated ring structure, provided that one of R ^{17 to} R ²³ is a -R ¹⁶ -Q ³ group Wherein R ¹⁶ is as defined above, Q ³ is selected from the group consisting of a hydroxyl group, a carboxyl group, a halogenated alkyl group, and an amino group, and Q ¹ and an ester bond, an ether bond, and an amide Represents a group capable of forming a bond selected from the group consisting of bonds, and X is as defined above.

  Since the compound of one embodiment of the present invention contains a photosensitizing group, an excellent base generation rate can be achieved by the photosensitizing action.

4- [Tetramethylguanidylcarbamoyloxy- (8-nitro-1-naphthyl) methyl] benzoic acid-N-methyl-N- (2-hydroxyethyl) -N′N′-dimethyl-4,4 ′ - is a chart showing ¹ H-NMR spectrum of aminobenzophenone ester. 4- [Tetramethylguanidylcarbamoyloxy- (8-nitro-1-naphthyl) methyl] benzoic acid-N-methyl-N- (2-hydroxyethyl) -N′N′-dimethyl-4,4 ′ It is a figure which shows the ¹³ C-NMR spectrum of -aminobenzophenone ester. 4- [Tetramethylguanidylcarbamoyloxy- (8-nitro-1-naphthyl) methyl] benzoic acid-N-methyl-N- (2-hydroxyethyl) -N′N′-dimethyl-4,4 ′ -It is a figure which shows the UV-Vis spectrum of aminobenzophenone ester. 4- [Tetramethylguanidylcarbamoyloxy- (8-nitro-1-naphthyl) methyl] benzoic acid-N-methyl-N- (2-hydroxyethyl) -N′N′-dimethyl-4,4 ′ It is a figure which shows the mass spectrum of -amino benzophenone ester.

<Compound>
Hereinafter, the compound represented by the formula (1) of the present invention (hereinafter also referred to as “compound (1)”) will be described in detail.

ただし、前記式（１）中、Ｒ^１〜Ｒ^７は、それぞれ独立に、水素原子、炭化水素基又は炭化水素オキシ基を表すが、Ｒ^１〜Ｒ^７の一つは−Ｙ−Ｚ基である。ここで、炭化水素基は、炭素原子数１〜５のアルキル基であり、炭化水素オキシ基は、炭素原子数１〜５のアルコキシ基であることが好ましい。なお、前記炭化水素基又は炭化水素オキシ基は、本発明の目的を損なわない範囲内で、１個又は２個以上の窒素原子、酸素原子、ケイ素原子等の炭素以外の原子又は該原子を含む置換基を有していてもよい。

However, in said formula (1), R < ¹ > -R < ⁷ > represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon oxy group each independently, but ^{one of} R < ¹ > -R < ⁷ > is -YZ group. is there. Here, the hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and the hydrocarbon oxy group is preferably an alkoxy group having 1 to 5 carbon atoms. The hydrocarbon group or hydrocarbon oxy group includes one or two or more atoms other than carbon such as nitrogen atom, oxygen atom, silicon atom or the like within a range not impairing the object of the present invention. It may have a substituent.

  Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, and neopentyl group. 1-ethylpropyl group, s-pentyl group, 1-methylbutyl group, 2-methylbutyl group and 1,2-dimethylpropyl group.

  Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, pentyloxy group, isopentyloxy Group, neopentyloxy group, 1-ethylpropyloxy group, s-pentyloxy group, 1-methylbutyloxy group, 2-methylbutyloxy group and 1,2-dimethylpropyloxy group.

  Among these, a hydrogen atom, a methoxy group, an ethoxy group, or a t-butyl group is preferable in terms of handling and availability.

As described above, in Formula (1), R ^{1 to} R ⁷ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon oxy group, and one of R ^{1 to} R ⁷ is —Y—. Z group. Specifically, for example, compounds represented by the following formulas (1-1) to (1-7) are included in the compound (1).

R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may jointly form a saturated or unsaturated ring structure. . To form a saturated or unsaturated ring structure, specifically, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are respectively combined. , Forming a saturated or unsaturated 5-, 6- or 7-membered ring.

In particular, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ form an unsaturated ring structure, whereby It is preferable to form a polycyclic fused aromatic ring together with the naphthalene structure. Specifically, the formula (1) includes polycyclic fused aromatic rings as shown in the following formulas (5-1) to (5-9). In the examples of the following formulas (5-1) to (5-9), R ⁷ is a —YZ group.

すなわち、前記多環縮合芳香環は、アセナフテン環、アントラセン環、ナフタセン環、ペンタセン環、クリセン環、ピレン環、ベンゾピレン環、フェナントレン環又は２Ｈ−ベンゾ［ｃｄ］ピレン等であることが好ましい。

That is, the polycyclic fused aromatic ring is preferably an acenaphthene ring, anthracene ring, naphthacene ring, pentacene ring, chrysene ring, pyrene ring, benzopyrene ring, phenanthrene ring or 2H-benzo [cd] pyrene.

  The polycyclic fused aromatic ring has one or more nitrogen atoms, oxygen atoms, silicon atoms and other non-carbon atoms or substituents containing the atoms within a range not impairing the object of the present invention. Specifically, it may have one or more substituents such as a methoxy group, an amino group, a nitrile group, or a t-butyl group.

R ⁷ represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 15 carbon atoms. The aliphatic hydrocarbon group is preferably an alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group. , Isopentyl group, s-amyl group, t-amyl group, 2-methylbutyl group, hexyl group, 1,1′-dimethylbutyl group, 2,2′-dimethylbutyl group, 3,3′-dimethylbutyl group, 1 -A methylpentyl group, a 1,2,2'-trimethylpropyl group, etc. are mentioned. Further, the aliphatic hydrocarbon group may have an atom other than carbon, such as a nitrogen atom, an oxygen atom, or a silicon atom, or a substituent containing the atom within a range not impairing the object of the present invention.

  The aromatic hydrocarbon having 6 to 15 carbon atoms is preferably a phenyl group, a biphenylenyl group, a fluorenyl group, a naphthyl group, an acenaphthenyl group or an anthracenyl group, and within a range not impairing the object of the present invention, , An atom other than carbon, such as an oxygen atom or a silicon atom, or a substituent containing the atom.

  Among these, a methyl group, a phenyl group, or a naphthyl group is preferable in terms of synthesis and easy handling.

In formula (1), X represents a group represented by —NR ⁸ R ⁹ , —N═CR ¹⁰ R ¹¹ or —N═PR ¹² R ¹³ R ¹⁴ , and R ⁸ and R ⁹ are each independently Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁸ and R ⁹ may jointly form a ring structure containing a nitrogen atom, and R ¹⁰ and R ¹¹ each independently represents an amino group; R ^{12 to} R ¹⁴ each independently represents a ring structure containing a nitrogen atom.

The alkyl group having 1 to 5 carbon atoms is the same as that described in the definition of R ^{1 to} R ⁶ . Examples of the amino group include an amino group or a linear or cyclic primary, secondary, or tertiary amino group having 1 to 6 carbon atoms, specifically, a cyclohexylamino group, an ethyleneimino group, or azacyclobutyl. Group, pyrrolidinyl group, piperidinyl group, hexamethyleneimino group, pyrrolidinyl group or pyridazinyl group.

  Examples of the ring structure containing a nitrogen atom include 3- to 7-membered rings containing a nitrogen atom such as ethyleneimine, azacyclobutane, pyrrolidine, piperidine and hexamethyleneimine. Among the above, X is preferably a group represented by the following formulas (6-1) to (6-6). Here, n ′ and n ″ are integers of 1 to 5.

これらのうち、紫外線を照射したときに、効率的に強塩基を生成するという観点から、上記式（６−２）〜（６−４）および（６−６）で表される基が特に好ましい。

Of these, groups represented by the above formulas (6-2) to (6-4) and (6-6) are particularly preferable from the viewpoint of efficiently producing a strong base when irradiated with ultraviolet rays. .

  In formula (1), Y represents a divalent linking group. Y is preferably a divalent hydrocarbon group. The divalent hydrocarbon group preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms, from the viewpoint of photosensitization.

  This divalent hydrocarbon group may contain at least one bond selected from the group consisting of an ester bond, an ether bond, and an amide bond. Among these, an ester bond is preferable from the viewpoint of stability.

  The divalent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group is preferably an alkylene group, specifically, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, an s-butylene group, a t-butylene group, or a pentylene. Group, isopentylene group, s-amylene group, t-amylene group, 2-methylbutylene group, hexylene group, 1,1'-dimethylbutylene group, 2,2'-dimethylbutylene group, 3,3'-dimethylbutylene group 1-methylpentylene group, 1,2,2′-trimethylpropylene group, and the like.

  The aromatic hydrocarbon group is preferably a phenyl group, a biphenylenyl group, a fluorenyl group, a naphthyl group, an acenaphthenyl group or an anthracenyl group.

Y is preferably a group of the following formula (7).

In formula (1), Z represents a monovalent photosensitizing group. Z is not particularly limited as long as it is a group showing a photosensitizing action, but Z is benzene, naphthalene, anthracene, anthraquinone, benzophenone, acridone, quinoxaline, ketocoumarin and derivatives thereof from the viewpoint of high triplet energy. And a monovalent group derived from any one of the compounds. As Z, (1) the wavelength of the irradiated light, the molecular absorption coefficient is larger than that of nitronaphthalene, (2) the triplet energy is larger than the triplet energy of nitronaphthalene, and (3) the quantum yield of intersystem crossing. Is preferable, and a monovalent group derived from a benzophenone derivative is more preferable. Specific examples of Z include monovalent groups derived from compounds of the following formulas (8-1) to (8-13).

  Among these, 4,4′-bis (dimethylamino) benzophenone represented by the formula (8-10) (also known as Michler's ketone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone) Monovalent groups derived from

  Specific examples of the compound represented by the above formula (1) include compounds represented by the following formula (9).

  Any of these compounds, for example, emits or generates a strong base such as a guanidine or a phosphazene derivative in a short time by irradiation with active energy rays such as ultraviolet rays, and exhibits high basicity for a long time.

<Method for producing compound>
Although the manufacturing method of a compound (1) is not specifically limited unless the objective of this invention is impaired, For example, it can manufacture with the following method. In the present embodiment, an example of producing a compound in which Y in the compound (1) is a -R ¹⁶ -Q ² -R ¹⁵ -group will be described. R ¹⁵ and R ¹⁶ represent a divalent hydrocarbon group, and Q ² represents a bond selected from the group consisting of an ester bond, an ether bond, and an amide bond.

式（１０）中、Ｒ^１７〜Ｒ^２３は、それぞれ独立に、水素原子、炭化水素基または炭化水素オキシ基を表し、Ｒ^１７とＲ^１８、Ｒ^１８とＲ^１９、Ｒ^１９とＲ^２０、Ｒ^２０とＲ^２１、またはＲ^２１とＲ^２２とは、それぞれ共同して飽和または不飽和の環構造を形成してもよく、ただし、Ｒ^１７〜Ｒ^２３の一つは−Ｒ^１６−Ｑ^３基である。Ｒ^１７〜Ｒ^２３における炭化水素基または炭化水素オキシ基は、Ｒ^１〜Ｒ^７において説明した炭化水素基または炭化水素オキシ基と同様であり、また飽和または不飽和の環構造もＲ^１〜Ｒ^７において説明した飽和または不飽和の環構造と同様であるので、説明を省略するものとする。Ｒ^１６は上記で定義した通りであり、Ｑ^３は水酸基、カルボキシル基、ハロゲン化アルキル基、およびアミノ基からなる群から選択され、かつ後述するＱ^１とエステル結合、エーテル結合、およびアミド結合からなる群から選択される結合を形成し得る基を表す。 In order to produce the compound (1) in which Y is a —R ¹⁶ —Q ² —R ¹⁵ — group, first, a compound of the following formula (10) is prepared.

In the formula (10), R ^{17 to} R ²³ each independently represents a hydrogen atom, a hydrocarbon group or a hydrocarbon oxy group, and R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , R ²⁰ and R ²¹ , or R ²¹ and R ²² may jointly form a saturated or unsaturated ring structure, provided that one of R ^{17 to} R ²³ is a —R ¹⁶ —Q ³ group It is. The hydrocarbon group or hydrocarbon oxy group in R ^{17 to} R ²³ is the same as the hydrocarbon group or hydrocarbon oxy group described in R ^{1 to} R ⁷ , and the saturated or unsaturated ring structure is also R ^{1 to} R. ^Since this is the same as the saturated or unsaturated ring structure described in ⁷ , the description is omitted. R ¹⁶ is as defined above, Q ³ is selected from the group consisting of a hydroxyl group, a carboxyl group, a halogenated alkyl group, and an amino group, and from Q ¹ described later and an ester bond, an ether bond, and an amide bond Represents a group capable of forming a bond selected from the group consisting of

The compound represented by the formula (10) can be produced, for example, as follows. The following example illustrates a compound in which Q ³ is a carboxyl group among the compounds represented by formula (10). First, 1-naphthaldehyde is put into a flask containing concentrated nitric acid and reacted to obtain 8-nitro-1-naphthaldehyde. Next, 8-nitro-1-naphthaldehyde is charged into a flask containing tetrahydrofuran, ethyl 4-bromobenzoate, 1,2-dibromoethane, and magnesium, and reacted. Then, when the product is put into a flask containing methanol and a sodium hydroxide solution and reacted, a compound represented by the formula (10) is obtained.

式（３）中、Ｒ^１７〜Ｒ^２３、Ｒ^１６、Ｑ^３およびＸは上記で定義した通りである。 After preparing the compound represented by the formula (10), the compound represented by the formula (10) is charged into a flask containing toluene, and sodium hydride is further charged. Then, carbon dioxide gas is blown into this solution, and then mesyl chloride is added, and HX is further added and reacted to obtain a compound represented by the following formula (3).

In the formula (3), R ^{17 to} R ²³ , R ¹⁶ , Q ³ and X are as defined above.

The compound represented by the formula (3) is dissolved in dichloromethane, and thionyl chloride is added to the solution and refluxed. The solution is then concentrated to remove any remaining thionyl chloride. Then, after adding new dichloromethane to the residue and dissolving it, the compound represented by the formula (2) is added and reacted to give a compound (1) in which Y is a -R ¹⁶ -Q ² -R ¹⁵ -group Get.
Z-R ¹⁵ -Q ¹ (2)
In the formula (2), R ¹⁵ and Z are as defined above, and Q ¹ represents a group selected from the group consisting of a hydroxyl group, a carboxyl group, a halogenated alkyl group, and an amino group.

  In addition, the said reaction example shows an example of the manufacturing method of a compound (1), and can manufacture it not only using the said manufacturing method but using a various well-known method.

  When a compound obtained by dissolving the compound represented by the above formula (1) in, for example, dichloromethane is irradiated with ultraviolet rays having a wavelength of 250 to 350 nm, a compound represented by HX is generated. For example, when the compound represented by the formula (9) is used as the compound represented by the above formula (1), tetramethylguanidine is generated by ultraviolet irradiation. In addition, when piperidine is used as HX, piperidine is generated by ultraviolet irradiation.

  When the compound (1) is irradiated with active energy rays, the photosensitizing group Z is excited and photochemical release of HX occurs easily in a short time.

  In this embodiment, since the compound (1) has the photosensitizing group Z, the base generation rate can be increased by the photosensitizing action of the photosensitizing group Z. Thereby, compared with the photobase generator which does not have a photosensitizer group, the base generation rate outstanding can be obtained. Here, it is also conceivable to use a photobase generator having no photosensitizer group and a photosensitizer in combination. In this case, the photosensitizer is excited, but other substances are used. Since it is necessary to propagate energy to the photobase generator, it takes time to propagate energy to the photobase generator. On the other hand, in this embodiment, when the photosensitizing group Z is excited, an internal reaction occurs in the compound (1) to generate a compound represented by the base HX. It is considered that the base generation rate is superior to the case of using a mixture of a non-photobase generator and a photosensitizer.

  The compound represented by HX exhibits a high basicity with a pH value of 11 to 13, and can exist stably in an air atmosphere.

  In the present invention, examples of the solvent for dissolving the compound (1) include polar organic solvents such as chloroform, acetone, methanol, ethanol, toluene, and acetonitrile, in addition to dichloromethane. Further, for example, a mixed solvent in which acetone and water are mixed at a volume ratio of 3: 1 may be used.

  As described above, the compound (1) has a high quantum yield, and the compound represented by HX is very easily generated by irradiation with ultraviolet rays having a wavelength of 250 to 350 nm. Among the compounds represented by HX, phosphazenes, in particular, are strong bases having a pH value of around 12, and thus sufficiently exhibit the effect as a base generator in terms of base generation efficiency.

The compound represented by HX produced by irradiating the solution of compound (1) with ultraviolet rays is confirmed, for example, using the method described below. A solution in which compound (1) is dissolved in dichloromethane or the like is prepared, and the pH value at room temperature is measured. Subsequently, the solution is irradiated with ultraviolet rays (wavelength 254 nm; illuminance 614 μW / cm ² ), and the pH value thereafter is measured.

  A change in pH is observed before and after UV irradiation, and when the pH value increases before and after UV irradiation, specifically, a base is generated when the pH value is less than 7.0 to a value higher than 7.0. It is recognized that the basicity increased when the pH value before light irradiation was 7.0 or higher and became higher after irradiation.

  In the present embodiment, since the compound represented by the formula (2) is used, a compound having a photosensitizing group Z can be easily produced.

  By the way, compound (1) has an effect | action as a dissolution inhibitor with respect to aqueous alkali solution. A dissolution inhibitor refers to a substance having an action of reducing the solubility of an alkali-soluble compound in an alkali by mixing with the alkali-soluble compound. Compound (1) decomposes as shown in the above formula by irradiating with ultraviolet rays having a wavelength of 250 to 350 nm to produce a compound represented by HX as a base. The solubility is higher than that of a soluble polymer alone system. This is presumably because the produced compound represented by HX acts as a dissolution accelerator.

  Compound (1) can be used together with an alkali-soluble polymer. Specific examples of the alkali-soluble polymer include poly (p-hydroxy-α-methylstyrene), poly (p-hydroxystyrene), poly (p-vinylbenzoic acid), polyacrylic acid, and polymethacrylic acid. A styrene / maleic acid copolymer, a styrene / acrylic acid copolymer, a styrene / methacrylic acid copolymer, a novolac resin, and the like are used, but the invention is not limited thereto.

  However, as will be described later, in the method for producing a negative resist, a carboxyl group-containing alkali-soluble polymer is particularly used as the alkali-soluble polymer. Examples of such a carboxyl group-containing alkali-soluble polymer include poly (p-vinylbenzoic acid), polyacrylic acid, polymethacrylic acid, styrene / maleic acid copolymer, styrene / acrylic acid copolymer, and styrene / acrylic acid copolymer. A methacrylic acid copolymer or the like is used.

  The compounding ratio of the alkali-soluble polymer (hereinafter also simply referred to as “A”) and the photobase generator (hereinafter also simply referred to as “B”) in the resist pattern forming material is A / B (weight ratio). ) Is usually 100/50 to 100/5, preferably about 100/35 to 100/5.

  In addition to the photobase generator and the alkali-soluble polymer, the resist pattern forming material may contain a diluent, a sensitizer, a dye, or the like as long as the object of the present invention is not impaired.

From the resist pattern forming material, both positive and negative resist patterns can be prepared. In the method for producing a positive resist, the resist pattern forming material is applied and dried on a substrate to be processed made of Si, Ga, As, or the like to produce a coating film. The thickness of the coating film is usually about 0.5 to 10 μm, preferably about 0.5 to 5 μm, and particularly preferably about 0.5 to 2 μm. Next, the coating film is irradiated with ultraviolet rays having a wavelength of 250 to 350 nm in a desired pattern. Irradiation with ultraviolet rays is performed through a mask, for example. UV exposure is usually 0.5 J / cm ² or more, preferably 1~100J / cm ^2. In the coating film of the part irradiated with ultraviolet rays (hereinafter referred to as “ultraviolet irradiation part”), as described above, the compound (1) is decomposed to generate a base and the dissolution inhibitory property disappears, and the alkali-soluble property. Rises. On the other hand, in the coating film in the part not irradiated with ultraviolet rays (hereinafter referred to as “ultraviolet non-irradiated part”), the dissolution inhibition property remains, so that the alkali solubility remains lowered. Therefore, when the coating film is developed with an alkaline aqueous solution in this state, the ultraviolet irradiation part is washed away and the ultraviolet non-irradiation part remains, and a positive resist is obtained.

  In the negative resist preparation method, the coating film is prepared and exposed in the same manner as in the positive resist preparation method, and the carboxyl group-containing alkali-soluble polymer described above is used as the alkali-soluble polymer. And, prior to development, the coating film is usually heat treated. The heat treatment is usually performed at 80 to 180 ° C, preferably 110 to 150 ° C, particularly preferably 115 to 140 ° C for about 1 to 30 minutes. By performing the heat treatment, the base generated by the decomposition of the photobase generator reacts with the carboxyl group of the carboxyl group-soluble polymer in the ultraviolet irradiation part, and the carboxyl group is eliminated. As a result of elimination of the carboxyl group, the polymer loses alkali solubility. Accordingly, the ultraviolet irradiation part is insoluble in alkali. On the other hand, although the ultraviolet non-irradiated part has reduced solubility in alkali due to compound (1), it does not completely lose alkali solubility, so the developer or development time is appropriately set. Can be removed. Specifically, as a developing solution, a 2 to 4% aqueous solution of strong alkaline trimethylammonium hydroxide or the like is used, or the development time is increased to, for example, 60 seconds or more, so that the ultraviolet non-irradiated part Can be removed. By such treatment, the ultraviolet non-irradiated part is washed away, and the ultraviolet irradiated part remains, and a negative resist is obtained.

  In the above, the compound (1) is used for the resist pattern forming material, but is not limited to the resist pattern forming material, and the compound (1) may be used as a sealing agent for sealing an adhesive or liquid crystal. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this. The method for identifying the reaction product and evaluating the basicity is as follows.

[1] Identification of reaction product (1) Nuclear magnetic resonance method ( ¹ H- and ¹³ C-NMR)
Apparatus: JNM-AL400 FT-NMR (manufactured by JEOL Ltd.)
Measurement conditions Internal standard: Tetramethylsilane (TMS)
¹ H resonance frequency: 400 MHz
(2) Ultraviolet / visible (UV-Vis) spectroscopy apparatus: SLUV-4 (manufactured by ASONE Corporation)
Measurement conditions Wavelength: 254nm
Light intensity: 614 μW / cm ²

[2] Basic evaluation device: pH meter (product name “PHM-103” manufactured by Toa DKK Co., Ltd.)
Measurement method: Glass electrode method According to the method described in International Publication No. 2008/072651, the following confirmation was made.

  The pH value at room temperature of a solution in which compound (1) is dissolved in dichloromethane, acetone or acetonitrile is measured. Subsequently, the solution is irradiated with ultraviolet rays, and the subsequent pH value is measured after 30 minutes.

  When the pH changes before and after the light irradiation and the pH value increases before and after the light irradiation, specifically, when the pH value is less than 7.0 and higher than the pH value 7.0, the base is It is recognized that the basicity has increased when the pH value before light irradiation is 7.0 or higher and becomes higher after irradiation.

<Example>
4- [Tetramethylguanidylcarbamoyloxy- (8-nitro-1-naphthyl) methyl] benzoic acid-N-methyl-N- (2-hydroxyethyl) -N′N′-dimethyl-4,4 ′ -Synthesis of aminobenzophenone ester 60 g of concentrated nitric acid was weighed into a flask and cooled to 0 ° C or lower with an ice bath while stirring with a stirrer, and 12.7 g of 1-naphthaldehyde represented by the following formula (14) (81 .3 mmol) was added in 5 portions. The mixture was stirred vigorously for about 30 minutes, ice water having the same amount as the amount of solution was prepared, and the reaction solution was slowly added while stirring.

  The product was extracted three times with the same amount of diethyl ether as this aqueous solution. The organic layer was washed with the same amount of tap water and saturated aqueous sodium bicarbonate, dehydrated with anhydrous sodium sulfate, and concentrated to distill off the ether. Silica gel chromatography was performed with 30 mass times silica gel / toluene / chloroform of the obtained syrupy substance to extract the target spot. Then, the effluent from the target spot was concentrated to obtain 14.7 g of a compound represented by the following formula (15).

  Next, 100 g of tetrahydrofuran (THF), 18.5 g (81.0 mmol) of ethyl 4-bromobenzoate, 1,2-dibromoethane (catalytic amount), and 1.96 g of magnesium pieces were charged into the flask until the temperature reached around 0 ° C. Cooled and stirred for 1 hour. Thereafter, a solution prepared by dissolving the compound of the formula (15) obtained above in 50 g of tetrahydrofuran was slowly added dropwise to the flask. After completion of the reaction, the reaction solution was poured into ice water and extracted with the same amount of ethyl acetate. Thereafter, the organic layer was washed with the same amount of tap water, saturated aqueous sodium hydrogen carbonate, and saturated brine, dehydrated with anhydrous sodium sulfate, concentrated to distill off ethyl acetate, and 18.7 g of the following formula (16). The indicated compound was obtained.

  Next, 200 ml of methanol and 4N aqueous sodium hydroxide solution were added to the flask and stirred. Thereto, the compound of the formula (16) obtained above was added in three portions and stirred for about 1 hour. After confirming the completion of the reaction, 150 ml of chloroform was added and extracted. Thereafter, the organic layer was washed with 4N aqueous hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and saturated brine, dehydrated with anhydrous sodium sulfate, and then the solvent was removed by concentration to obtain a compound represented by the following formula (17). .

  100 g of toluene is weighed into a flask, 2.3 g of sodium hydroxide (60% oil dispersion) is added, and the compound of formula (17) is added in three portions, and the external temperature is set to 80 ° C. And stirred for about 3 hours. Then, after cooling a container to room temperature, it cooled to 5 degrees C or less with the ice bath. Carbon dioxide gas was sufficiently blown into this solution until the shape became jelly. Thereafter, 5.67 g of mesyl chloride was added and stirred for 30 minutes, and then 5.7 g (49.5 mmol) of 1,1,3,3-tetramethylguanidine was added and stirred for about 5 hours. After the reaction was completed, the product was washed with the same amount of tap water as the solvent, dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off by concentration to obtain a syrup-like compound represented by the following formula (18). .

Then, the compound of the formula (18) obtained above was dissolved in dichloromethane, and 8.7 g of thionyl chloride was added and stirred. At this time, heat was applied from the outside to reflux. After stirring for a predetermined time, all the solution was concentrated to remove the remaining thionyl chloride, and then 100 g of new dichloromethane was added to the residue to dissolve it. Further, 12 g (42.5 mmol) of N-methyl-N- (2-hydroxyethyl) -N′N′-dimethyl-4,4′-diaminobenzophenone was added thereto and stirred. After confirming the completion of the reaction, the reaction solution was washed with the same amount of tap water and saturated sodium bicarbonate water as the solution, dehydrated with anhydrous sodium sulfate, and then the solvent was removed by concentration. The obtained crude product was subjected to column chromatography using a 30-fold weight silica gel and a solvent in which hexane: ethyl acetate was mixed at a volume ratio of 1: 1, the target product was isolated, and the compound of formula (9) 14.1 g of 4- [tetramethylguanidylcarbamoyloxy- (8-nitro-1-naphthyl) methyl] benzoic acid-N-methyl-N- (2-hydroxyethyl) -N′N′-dimethyl -4,4'-aminobenzophenone ester was obtained.

When the structure of this compound was analyzed by nuclear magnetic resonance spectroscopy, the results shown in FIGS. 1 and 2 were obtained. The peaks were as follows.
¹ HNMR (400 MHz, CDCl ₃ ) δ: 2.73 (tetramethylguanidine-methyl, 12H, S), 3.05-3.14 (trimethylbenzophenone, 9H, S), 3.81-3.83 (methylene hydrogen, 2H, T), 4.50-4.53 (Methylene hydrogen, 2H, T), 7.14 (naphthyl methine, 1H, S), 6.67-8.06 (naphthalene, benzene, 10H)
¹³ C NMR (400 MHz, CDCl ₃ ) δ: 39.0-40.08 (benzophenone methyl group), 50.8 (methylene), δ 61.9 (methylene), 74.2 (naphthyl α-position), 110.55 (benzophenone 2 and 6-position), 122.92-136.08 (Naphthalene, benzene, benzophenone), 146.99 (benzene ring 1st), 148.66 (naphthalene 8th), 151.30 (benzophenone 1st), 152.70 (benzophenone 8th), 158.40 (carbamate ketone), 166.37 (guanidine carbon), 166.67 (Ester carbon), 193.85 (benzophenone ketone)

Compound (9) was analyzed by UV-Vis spectroscopy, and as a result, an absorption maximum (λ _max ) was observed at around 350 nm as shown in FIG. Further, when the mass spectrum of the compound (9) was measured, the result as shown in FIG. 4 was obtained.

Evaluation of base generation efficiency 774 mg of the compound represented by the above formula (9) was dissolved in 1 mL of dichloromethane. The dichloromethane solution was placed in a quartz cell for UV measurement, and irradiated with ultraviolet rays having a wavelength of 254 nm in a light-shielded / air atmosphere. Table 1 shows the results of changes in pH value with time when irradiated with ultraviolet rays.

  For comparison, the pH value of dichloromethane (blank) was measured and found to be 6.82.

  From the results in Table 1, the solution in which 774 mg of the compound represented by the above formula (9) was dissolved in 1 mL of dichloromethane had a pH of 7.37 before UV irradiation, but the pH value was 12 or more after 40 minutes. It can be seen that high basicity is obtained.

Further, the compound of the above formula (9) is dissolved in deuterated benzene, the solution is put into a sample tube for NMR measurement, and the sample tube and a high-pressure mercury lamp (manufactured by Toshiba Corp., 300) in a light-shielded and atmospheric atmosphere. Place a slide of nickel sulfate aqueous solution (light transmissive container filled with nickel sulfate aqueous solution) between ˜400 nm and 100 W) and use a high-pressure mercury lamp while cutting active energy rays with a wavelength of 400 nm or more. Then, active energy rays were irradiated, and ¹ HNMR measurement was performed every 0.5 hour to trace the decomposition reaction shown in the following scheme.

<Comparative example>
Synthesis of α-methyl-8-nitronaphthalenyloxycarbonyltetramethylguanidine In a 100 ml four-necked flask, 1.64 mg (10.12 mmol) of 1,1′-carbodiimidazole, 563 mg (5.5 mmol) of triethylamine and dimethyl 5 mL of formamide (DMF) was added and stirred, and a solution of 1.1 g (5.06 mmol) of α-methyl-8-nitronaphthalenyl alcohol dissolved in 5 mL of DMF was added dropwise thereto.

  After stirring for about 30 minutes, the progress of the reaction was confirmed by thin layer chromatography (TLC), and 1.74 g (15.18 mmol) of 1,1,3,3-tetramethylguanidine was added dropwise.

  After further stirring for about 20 minutes, it was confirmed by TLC that the reaction had progressed again. When it was confirmed that the intermediate between 1,1′-carbodiimidazole and α-methyl-8-nitronaphthalenyl alcohol had disappeared, stirring was stopped, and the reaction solution was poured into a 200 ml separatory funnel. 15 ml of ethyl and 45 ml of water were added, and the mixture was shaken vigorously to separate the layers.

After extracting the aqueous layer, 20 ml of saturated saline was added to the organic layer, and the liquids were separated again. The organic layer was taken out and dried with sodium sulfate, and then the solution was concentrated under reduced pressure to obtain 1.2 g of a crude product. Using silica gel having a weight 15 times that of this crude product, thin layer chromatography was performed with an eluent mixed with hexane: ethyl acetate at a volume ratio of 1: 1, and α-methyl- represented by the following formula (21) was obtained. 8-Nitronaphthalenyloxycarbonyltetramethylguanidine was obtained.

Evaluation of base generation efficiency 358.93 mg of the compound represented by the above formula (21) was dissolved in 1 mL of dichloromethane. The dichloromethane solution was placed in a quartz cell for UV measurement, and irradiated with ultraviolet rays having a wavelength of 254 nm in a light-shielded / air atmosphere. Table 2 shows the results of changes in pH value with time when irradiated with ultraviolet rays.

From the results in Table 2, a solution in which 358.93 mg of the compound represented by the above formula (21) was dissolved in 1 mL of dichloromethane had a pH of 7.0 to 7.5 before irradiation with ultraviolet light, and a pH of 12 or more. It took more than 2 hours to become. From this result, it is understood that α-methyl-8-nitronaphthalenyloxycarbonyltetramethylguanidine according to the comparative example has a lower base generation rate than the compound represented by the above formula (9) according to the example. it can.

Claims (11)

A compound represented by the following formula (1).

(In the formula ^(1), R 1 ~R ⁷ are independently a hydrogen atom, a hydrocarbon group or a hydrocarbon oxy group, ^{R 1} and ^R 2, ^{R 2} and ^R 3, ^{R 3} and ^R 4, R ⁴ and R ⁵ , or R ⁵ and R ⁶ may jointly form a saturated or unsaturated ring structure, provided that one of R ^{1 to} R ⁷ is a —YZ group. Yes, where Y represents a divalent linking group, Z represents a monovalent photosensitizing group,
X represents —NR ⁸ R ⁹ , —N═CR ¹⁰ R ^11, or —N═PR ¹² R ¹³ R ¹⁴ (R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R ⁸ and R ⁹ may jointly form a ring structure containing a nitrogen atom, R ¹⁰ and R ¹¹ each independently represent an amino group, and R ^{12 to} R ¹⁴ each independently represent nitrogen. Represents a ring structure containing an atom). )   2. The formula (1), wherein Z is a monovalent group derived from a compound of any one of benzene, naphthalene, anthracene, anthraquinone, benzophenone, acridone, quinoxaline, ketocoumarin, and derivatives thereof. Compound.   The compound according to claim 2, wherein Z is a monovalent group derived from a benzophenone derivative in the formula (1).   In the formula (1), Y is a divalent hydrocarbon group which may contain at least one bond selected from the group consisting of an ester bond, an ether bond, and an amide bond. 4. The compound according to any one of 3.   The compound according to claim 1, wherein in the formula (1), Y is a divalent hydrocarbon group containing an ester bond, and Z is a monovalent group derived from a benzophenone derivative. In Formula (1), R ^{1 to} R ⁶ are a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and R ⁷ is a —YZ group. The compound according to item. In the formula (1), R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ form an unsaturated ring structure. The compound according to any one of claims 1 to 5, which forms a polycyclic fused aromatic ring.   The compound according to claim 6, wherein the polycyclic fused aromatic ring is an acenaphthene ring, anthracene ring, naphthacene ring, pentacene ring, chrysene ring, pyrene ring, benzopyrene ring or phenanthrene ring.   The photobase generator which consists of a compound as described in any one of Claims 1-8. A compound represented by the following formula (2).
Z-R ¹⁵ -Q ¹ (2)
(In formula (2), Z is as defined above, R ¹⁵ represents a divalent hydrocarbon group, and Q ¹ is selected from the group consisting of a hydroxyl group, a carboxyl group, a halogenated alkyl group, and an amino group. Represents a group to be It is a manufacturing method of the compound represented by Formula (1) of Claim 1, Comprising:
In the formula (1), Y is a —R ¹⁶ —Q ² —R ¹⁵ — group, wherein R ¹⁵ and R ¹⁶ represent a divalent hydrocarbon group, Q ² represents an ester bond, an ether bond, and Represents a bond selected from the group consisting of amide bonds,
The manufacturing method of a compound including reacting the compound represented by following formula (3), and the compound represented by Formula (2) of Claim 10.

(In the formula (3), R ^{17 to} R ²³ each independently represents a hydrogen atom, a hydrocarbon group or a hydrocarbon oxy group, R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , R ²⁰ and R ²¹ , or R ²¹ and R ²² may jointly form a saturated or unsaturated ring structure, provided that one of R ^{17 to} R ²³ is —R ¹⁶ -Q ³ Wherein R ¹⁶ is as defined above, Q ³ is selected from the group consisting of a hydroxyl group, a carboxyl group, a halogenated alkyl group, and an amino group, and Q ¹ and an ester bond, an ether bond, And a group capable of forming a bond selected from the group consisting of an amide bond, and X is as defined above.

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