JP6243718B2 - Compound and photobase generator comprising said compound - Google Patents

Description

  The present invention relates to a novel compound and a photobase generator comprising the 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 a 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.

  Therefore, it is desired to develop a photobase generator that generates a base having a higher base generation efficiency than a conventional photobase generator 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)

  The present invention is a novel compound suitable as a photobase generator, a compound capable of generating a strong base very efficiently by irradiation with active energy rays and maintaining high basicity for a long time. The issue is to provide.

Now, the present inventor has focused on a compound having a high quantum yield (photodecarboxylation efficiency) and found that a compound that decarboxylates and releases a strong base upon irradiation with active energy rays solves the above problem. The present invention has been completed.
That is, the compound of the present invention is represented by the following formula (1).

式（１）中、Ｒ¹〜Ｒ⁶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し、Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、又はＲ⁵とＲ⁶とは、それぞれ共同して飽和又は不飽和の環構造を形成してもよく、Ｒ⁷は炭素原子数１〜６の炭化水素基又は炭素原子数６〜１５の芳香環を表し、Ｑは−ＮＲ ⁸ Ｒ ⁹ 、−Ｎ＝ＣＲ ¹⁰ Ｒ ¹¹ 又は−Ｎ＝ＰＲ ¹² Ｒ ¹³ Ｒ ¹⁴ （Ｒ ⁸ 及びＲ ⁹ は、それぞれ独立に、水素原子又は炭素原子数１〜５のアルキル基を表し、Ｒ ⁸ 及び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 及び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。

In formula (1), R ^{1 to} R ⁶ each independently represents 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, and R ⁷ is a hydrocarbon group having 1 to 6 carbon atoms or 6 carbon atoms. Represents an aromatic ring of ˜15, Q is —NR ⁸ R ⁹ , —N═CR ¹⁰ R ¹¹ or —N═PR ¹² R ¹³ R ¹⁴ (R ⁸ and R ⁹ are each independently a hydrogen atom or a carbon atom; Represents an alkyl group of 1 to 5, 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 9 ¹⁴ each independently represent a representative.) a ring structure containing a nitrogen atom.

In the formula (1), R ^{1 to} R ⁶ are preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.
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, It is preferable to form a polycyclic fused aromatic ring.

The polycyclic fused aromatic ring is preferably an acenaphthene ring, anthracene ring, naphthacene ring, pentacene ring, chrysene ring, pyrene ring, benzopyrene ring or phenanthrene ring.
The photobase generator of the present invention comprises the compound represented by the above formula (1).

  The compound represented by the formula (1) of the present invention has a high quantum yield (photodecarboxylation efficiency). For this reason, the compound is extremely highly efficient by irradiation with active energy rays such as ultraviolet rays or light irradiation with a high-pressure mercury lamp. Can be liberated.

  That is, a base (compound represented by the formula (3) described later) photochemically liberated from the compound represented by the formula (1) of the present invention by irradiation with an active energy ray such as ultraviolet rays is extremely basic. It is high and can exist stably in an air atmosphere, so that high basicity is maintained for a long time.

  Therefore, the compound represented by the formula (1) of the present invention is suitable as a photobase generator.

FIG. 1 is a diagram showing a ¹ H-NMR spectrum of α-methyl-8-nitronaphthalenyloxycarbonyltetramethylguanidine. FIG. 2 is a diagram showing a ¹³ C-NMR spectrum of α-methyl-8-nitronaphthalenyloxycarbonyltetramethylguanidine. FIG. 3 is a diagram showing an IR spectrum of α-methyl-8-nitronaphthalenyloxycarbonyltetramethylguanidine. FIG. 4 is a diagram showing a UV-Vis spectrum of α-methyl-8-nitronaphthalenyloxycarbonyltetramethylguanidine. FIG. 5 is a diagram showing a ¹ H-NMR spectrum of the compound (6). FIG. 6 is a diagram showing a ¹³ C-NMR spectrum of the compound (6). FIG. 7 is an IR spectrum of the compound (6). FIG. 8 is a diagram showing a UV-Vis spectrum of the compound (6). FIG. 9 is a diagram showing a DSC thermogram of the compound (6).

  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、Ｒ¹〜Ｒ⁶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。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 < ⁶ > represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon oxy group each independently. 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.
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. .

The formation of a saturated or unsaturated ring structure specifically means that 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 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, thereby forming It is preferable to form a polycyclic fused aromatic ring together with the naphthalene structure.
Specifically, the polycyclic condensed aromatic ring as shown below is included in the formula (1).

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 a hydrocarbon group having 1 to 6 carbon atoms or an aromatic ring having 6 to 15 carbon atoms.
The 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. 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-methyl A pentyl group, a 1,2,2'-trimethylpropyl group, etc. are mentioned. The 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, as long as the object of the present invention is not impaired.

  The aromatic ring 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. You may have atoms other than carbon, such as an atom and a silicon atom, or a substituent containing this atom.

Among these, a methyl group, a phenyl group, or a naphthyl group is preferable in terms of synthesis and easy handling.
Q 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 each independently represents a hydrogen atom or a carbon atom number. 1 to 5 alkyl groups, 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 represents a ring structure containing a nitrogen atom.

The alkyl group having 1 to 5 carbon atoms is the same as those 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.
Of the above, Q is preferably the following group. 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、

Among these, from the viewpoint of efficiently generating a strong base when irradiated with ultraviolet rays,

が特に好ましい。

Is particularly preferred.

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

これらの化合物はいずれも、例えば、紫外線等の活性エネルギー線の照射により、グアニジン類又はホスファゼン誘導体等の強塩基を効率的に脱離又は生成し、長時間に渡って高い塩基性を示す。

All of these compounds, for example, efficiently desorb or generate strong bases such as guanidines or phosphazene derivatives by irradiation with active energy rays such as ultraviolet rays, and show high basicity over a long period of time.

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.
As an example, a production method of compound (1) using α-methyl-8-nitronaphthalenyloxycarbonyltetramethylguanidine is shown.

  A solution prepared by dissolving α-methyl-8-nitronaphthalenyl alcohol, which is a starting material, in N, N′-dimethylformamide (DMF) was added in a molar amount of 1,1′-carbodi with respect to the starting material. The solution is dropped into a flask containing imidazole, triethylamine and DMF, and stirred at room temperature for a while. After confirming the completion of the reaction by thin layer chromatography (TLC), 3 mole times the amount of 1,1,3,3-tetramethylguanidine (TMG) is added to the starting material. After stirring at room temperature for a while, it was confirmed by TLC that the intermediate product of α-methyl-8-nitronaphthalenyl alcohol and 1,1′-carbodiimidazole had disappeared, and the reaction was terminated. Extract with water, dry with sodium sulfate, and purify by silica gel column chromatography to obtain the desired product.

なお、上記反応例は、化合物（１）の製造方法の一例を示すものであり、上記製造方法に限らず、種々の公知の方法を使って製造することができる。

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.

The structure of the compound (1) can be confirmed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR and ¹³ C-NMR), infrared spectroscopy (IR) and elemental analysis.
That is, in the ¹ H-NMR spectrum, a peak based on α-methyl group is observed at 1.71 ppm, a peak based on methyl group derived from TMG is observed at 2.63 ppm, and a peak derived from methine is 5.90 ppm. And a peak derived from hydrogen in the naphthalene ring is observed at 7.44 to 7.9 ppm.

^{In the 13} C-NMR spectrum, a peak based on the α-methyl group was observed at 22.59 ppm, a peak based on the methyl group derived from TMG was observed at 39.52 ppm, and a peak based on methine was observed at 68.56 ppm. A peak based on a carbonyl group is observed at 159.06 ppm, a peak derived from guanidine carbon is observed at 165.80 ppm, and a peak derived from naphthalene ring carbon is observed at 121.97 to 147.96 ppm.

The results of the ¹ H- and ¹³ C-NMR spectra were obtained under the measurement conditions of ¹ H resonance frequency of 400 MHz using tetramethylsilane (TMS) as an internal standard substance.

The infrared (IR) spectrum, a peak derived from a naphthalene ring was observed at 1521cm ^-1, a peak derived from a carbonyl group was observed at 1660 cm ^-1, a peak derived from a (C = O) N group 3233Cm ^- Observed at ¹ .

  When a compound in which the compound represented by the above formula (1) is dissolved in, for example, dichloromethane, is irradiated with ultraviolet rays having a wavelength of 250 to 350 nm, compounds represented by the following formulas (2) and (3) are generated, Carbon dioxide is generated.

化合物（１）に活性エネルギー線を照射すると、式（２）及び（３）で表される化合物の光化学的な遊離が容易に起こる。これは、化合物（１）の構造において、電子吸引基であるニトロ基により、ナフタレン環中に正電荷が共鳴によって分散していると考えられ、活性エネルギー線が照射されると、ナフタレン環への電子移動が誘起され、脱炭酸が起きるためであると考えられる。

When the compound (1) is irradiated with active energy rays, photochemical release of the compounds represented by the formulas (2) and (3) occurs easily. In the structure of the compound (1), it is considered that a positive charge is dispersed in the naphthalene ring by resonance due to the nitro group which is an electron-withdrawing group. This is probably because electron transfer is induced and decarboxylation occurs.

The compound represented by the above formula (3) exhibits a high basicity with a pH value of 11 to 12, 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) of the present invention has a high quantum yield, and the compound represented by the formulas (2) and (3) can be very easily irradiated with ultraviolet rays having a wavelength of 250 to 350 nm. Generate. Among the compounds represented by the formula (3), phosphazenes 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 the formula (3) generated by irradiating the solution of the compound (1) with ultraviolet rays is confirmed using, for example, 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. Next, 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.

  By the way, the compound (1) of this invention has an effect | action as a dissolution inhibitor with respect to alkaline aqueous 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 formula (3) which is a base, and the dissolution inhibitory property disappears accordingly. In addition, the solubility is higher than that of a system of an alkali-soluble polymer alone. This is considered because the produced | generated compound represented by Formula (3) acts as a solubility promoter.

The compound (1) of the present invention 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 developing 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.

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
(3) Infrared (IR) spectroscopy apparatus: FT / IR-4200 (manufactured by JASCO Corporation)
Measuring method: KBr method (4) Differential scanning calorimetry (DSC)
Apparatus: DSC-60 (manufactured by Shimadzu Corporation)

[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 1]
Synthesis of α-methyl-8-nitronaphthalenyloxycarbonylpiperidine In a 100 ml 4-neck flask, 3.1 g (19.33 mmol) of 1,1′-carbodiimidazole, 1.07 g (10.63 mmol) of triethylamine and N , N′-dimethylformamide (DMF) 15 mL was added and stirred, and a solution of α-methyl-8-nitronaphthalenyl alcohol 2.1 g (9.67 mmol) dissolved in DMF 15 mL was added dropwise thereto.

  After stirring for about 30 minutes, the progress of the reaction was confirmed by thin layer chromatography (TLC), and 2.47 g (29 mmol) of piperidine was added dropwise. At this time, stirring was performed without stopping.

  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 had disappeared, the stirring was stopped, the reaction solution was put into a 200 ml separatory funnel, 40 ml of ethyl acetate and 20 ml of water were added, and the mixture was shaken vigorously to separate.

  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 3.2 g of a crude product. Silica gel having a weight 15 times that of the crude product was used, and thin layer chromatography was performed with an eluent in which dichloromethane: hexane was mixed at a volume ratio of 3: 2 to obtain the desired product.

Evaluation of base generation efficiency 358.2 mg of α-methyl-8-nitronaphthalenyloxycarbonylpiperidine was dissolved in 1 mL of dichloromethane. The pH value at this time was 7.32.

  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 6.24.

表１の結果から、α−メチル−８−ニトロナフタレニルオキシカルボニルピペリジンをジクロロメタンに溶解させた溶液は、紫外線照射前はｐＨが７．０〜７．５であったのが、紫外線照射１時間後には、ｐＨ値が１２まで上昇、３時間経過しても高い塩基性を維持していることがわかる。

From the results shown in Table 1, the solution of α-methyl-8-nitronaphthalenyloxycarbonylpiperidine dissolved in dichloromethane had a pH of 7.0 to 7.5 before the ultraviolet irradiation. It can be seen that after a period of time, the pH value increased to 12, and high basicity was maintained even after 3 hours.

Further, α-methyl-8-nitronaphthalenyloxycarbonylpiperidine is dissolved in deuterated benzene, and the solution is put into a sample tube for NMR measurement. The sample tube and a high-pressure mercury lamp (Toshiba) Place a slide of nickel sulfate aqueous solution (light transmissive container filled with nickel sulfate aqueous solution) between the product and 300-400 nm (100 W), and cut active energy rays with a wavelength of 400 nm or more. However, active energy rays were irradiated using a high-pressure mercury lamp, and ¹ HNMR measurement was performed every 0.5 hour to follow the decomposition reaction shown in the following scheme.

¹Ｈ−ＮＭＲ測定により、メチル−８−ニトロソナフチルケトンの生成量を測定し、量子収率０．１２を算出した。

^The amount of methyl-8-nitrosonaphthyl ketone produced was measured by ¹ H-NMR measurement, and the quantum yield of 0.12 was calculated.

[Example 2]
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. Ethyl (15 ml) and water (45 ml) 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. Silica gel having a weight 15 times that of the crude product was used, and thin layer chromatography was carried out with an eluent in which hexane: ethyl acetate was mixed at a volume ratio of 1: 1 to obtain the desired product.

¹ HNMR (400 MHz, CDCl ₃ ) δ: 1.71 (α-methyl, 3H, s), 2.63 (tetramethyl, 12H, s), 5.90 (methine, 1H, s), 7.44 ( Naphthalene 2nd, 1H), 7.57 (Naphthalene 7th, 1H), 7.71 (Naphthalene 3rd, 1H), 7.79 (Naphthalene 6th, 1H), 7.97-8.01 ppm (Naphthalene 4 And 5th place, 2H)
¹³ C NMR (400 MHz, CDCl ₃ ) δ: 22.59 (α-methyl), 39.52 (tetramethyl), 68.56 (methine), 121.97 (naphthalene 8a position), 122.80 (naphthalene 7 position) ), 123.35 (6th naphthalene), 126.93 (3rd naphthalene), 127.77 (2nd and 4th naphthalene), 133.17 (4th naphthalene), 134.37 (1st naphthalene), 139.66 (5th naphthalene), 147.96 (8th naphthalene), 159.06 (-O (C = O) N-), 165.80 ppm (guanidine carbon)
IR spectrum: 1521 (naphthalene), 1660 (carbonyl), 3233 cm ⁻¹ ((C═O) N)
UV-Vis spectrum: around 317 nm (absorption maximum λ _max )
Elemental analysis: C, 60.32; H6.19; N, 15.55 (theoretical value)
C, 62.84; H6.24; N, 13.33 (actual measured value)
Melting point: 141.2 ° C
The melting point was determined by DSC measurement under the following conditions.
Start temperature: 65 ° C

Evaluation of base generation efficiency 358.39 mg of α-methyl-8-nitronaphthalenyloxycarbonyltetramethylguanidine 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 3 shows the results of changes in pH value with time when irradiated with ultraviolet rays.

  From the results in Table 3, a solution of 358.39 mg of α-methyl-8-nitronaphthalenyloxycarbonyltetramethylguanidine in 1 mL of dichloromethane had a pH of 7.0 to 7.5 before UV irradiation. However, it is understood that the basicity of 11 to 12 is maintained even after 2 hours.

In addition, α-methyl-8-nitronaphthalenyloxycarbonyltetramethylguanidine was dissolved in deuterated benzene and irradiated with active energy rays using a high-pressure mercury lamp in the same manner as in Example 1 for 0.5 hours. The decomposition reaction shown in the following scheme was followed by measuring ¹ HNMR every time.

¹ＨＮＭＲ測定により、α−メチル−８−ニトロソナフチルケトンの生成量を測定した。量子収率の２回の測定結果は０．３５及び０．４０であった。

^The amount of α-methyl-8-nitrosonaphthyl ketone produced was measured by ¹ HNMR measurement. The two measurement results of the quantum yield were 0.35 and 0.40.

Example 3
Synthesis of α-methyl-8-nitronaphthalenyloxycarbonylbispiperidinoguanidine (compound (6)) In a 100 ml four-necked flask, 1.64 mg (10.12 mmol) of 1,1′-carbodiimidazole, triethylamine 1.12 g (11.13 mmol) and 5 mL of dimethylformamide (DMF) were added and stirred, and a solution of 1.86 g (11.13 mmol) of bispyrrolidinoguanidine 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 2.41 g (11.13 mmol) of α-methylnitronaphthyl alcohol 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 bispyrrolidinoguanidine had disappeared, stirring was stopped, the reaction solution was put into a 200 ml separatory funnel, and 15 ml of ethyl acetate and 45 ml of water were added. , Shaken vigorously to separate.

  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. Silica gel having a weight 15 times that of the crude product was used, and thin layer chromatography was carried out with an eluent in which hexane: ethyl acetate was mixed at a volume ratio of 1: 1 to obtain the desired product.

  Compound (4) was synthesized using pyrrolidine instead of dimethylamine in the method described in JP-A No. 2000-212155.

¹ＨＮＭＲ（４００ＭＨｚ、ＣＤＣｌ₃）δ：１．７１（α−メチル，３Ｈ，ｓ）、ピロリジン１位及び４位，８Ｈ，s）、３．０７−３．０８（ピロリジン２位，４Ｈ，ｔ）、３．２１−３．２２（ピロリジン３位，４Ｈ，ｑ）、７．４０−８．０５ｐｐｍ（ナフタレン，６Ｈ）
¹³ＣＮＭＲ（４００ＭＨｚ、ＣＤＣｌ₃）δ：２２．４２（α−メチル）、２５．１８（ピロリジン２位及び３位）、４８．９５（ピロリジン１位及び４位）、６８．７７（メチン）、１２２．３５（ナフタレン８ａ位）、１２２．８１（ナフタレン７位）、１２３．３３（ナフタレン６位）、１２７．２４（ナフタレン３位）、１２７．７４及び１２８．０４（ナフタレン２位及び４位）、１３３．２２（ナフタレン４ａ位）、１３４．５８（ナフタレン１位）、１４０．７３（ナフタレン５位）、１４８．３３（ナフタレン８位）、１５７．４０（−Ｏ（Ｃ＝Ｏ）Ｎ−）、１６０．１５ｐｐｍ（グアニジン炭素）

¹ HNMR (400 MHz, CDCl ₃ ) δ: 1.71 (α-methyl, 3H, s), pyrrolidine 1-position and 4-position, 8H, s), 3.07-3.08 (pyrrolidine 2-position, 4H, t ), 3.21-3.22 (pyrrolidine 3-position, 4H, q), 7.40-8.05 ppm (naphthalene, 6H)
¹³ C NMR (400 MHz, CDCl ₃ ) δ: 22.42 (α-methyl), 25.18 (pyrrolidine 2 and 3 positions), 48.95 (pyrrolidine 1 and 4 positions), 68.77 (methine), 122.35 (Naphthalene 8a position), 122.81 (Naphthalene 7 position), 123.33 (Naphthalene 6 position), 127.24 (Naphthalene 3 position), 127.74 and 128.04 (Naphthalene 2 position and 4 position) ) 133.22 (Naphthalene 4a position), 134.58 (Naphthalene 1 position), 140.73 (Naphthalene 5 position), 148.33 (Naphthalene 8 position), 157.40 (-O (C = O) N -), 160.15 ppm (guanidine carbon)

IR spectrum: 1400-1519 (pyrrolidine), 1300-1370 (nitro group), 1652 (carbonyl), 2800-3000 (naphthalene), around 3400 cm ^-1 (pyrrolidine)
UV-Vis spectrum: around 285 nm and 318 nm (absorption maximum λ _max )
Melting point: 155.92 ° C
The melting point was determined by DSC measurement under the following conditions.
Start temperature: 125 ° C

Evaluation of base generation efficiency 2 mL of a solution obtained by dissolving 410.19 mg of compound (6) in a mixture of 4.5 mL of acetone and 0.5 mL of distilled water was taken, and a mixture of acetone and water (9: 1 (volume ratio)) ) To 10 mL.

  The acetone aqueous solution was put in a quartz cell for UV measurement, and irradiated with ultraviolet rays having a wavelength of 254 nm in a light-shielded and atmospheric atmosphere. Table 5 shows the results of changes over time in pH value when irradiated with ultraviolet rays.

  From the results of Table 5, the aqueous acetone solution of compound (6) had a pH of 7.5 to 7.8 before UV irradiation, but a high base of pH 11.5 to 12.2 even after 2 hours. It can be seen that the sex is maintained.

The compound (6) is considered to be decomposed as shown in the following scheme.
Further, the compound (6) was dissolved in deuterated benzene, irradiated with active energy rays using a mercury lamp, and ¹ HNMR measurement was performed every 0.5 hour to follow the decomposition reaction shown in the following scheme.

¹ＨＮＭＲ測定により、メチル−８−ニトロソナフチルケトンの生成量を測定した。量子収率の測定結果は０．３６であった。

^The amount of methyl-8-nitrosonaphthyl ketone produced was measured by ¹ HNMR measurement. The measurement result of the quantum yield was 0.36.

[Comparative Example 1]
328.36 mg of α-methyl-2-nitrobenzyloxycarbonylpiperidine was dissolved in 1 mL of dichloromethane. The pH value at this time was 7.23.

α-Methyl-2-nitrobenzyloxycarbonylpiperidine was dissolved in deuterated benzene and irradiated with active energy rays using a high-pressure mercury lamp in the same manner as in Example 1, and ¹ HNMR measurement was performed every hour. The decomposition reaction shown in the following scheme was followed.

^The amount of methyl-2-nitrosophenyl ketone produced was measured by ¹ HNMR measurement, and a quantum yield of 0.05 was calculated.

実施例１〜３に比べて、比較例１では量子収率が低く、塩基発生効率に劣ることがわかる。

Compared with Examples 1-3, it turns out that the quantum yield is low in Comparative Example 1, and the base generation efficiency is inferior.

[Comparative Example 2]
A solution in which 1 mmol of N- (2-nitrobenzyloxycarbonyl) piperidine is dissolved in a mixture of 98 mL of acetone and 2 mL of water is placed in a quartz cell for UV measurement, and ultraviolet light having a wavelength of 254 nm is irradiated in a light-shielded and atmospheric atmosphere. Irradiated. N- (2-nitrobenzyloxycarbonyl) piperidine is considered to be decomposed as shown in the following scheme.

  N- (2-nitrobenzyloxycarbonyl) piperidine was synthesized according to the method described in Japanese Patent Application No. 2013-1059.

上記のように紫外線を照射しながら、石英セル中の溶液のｐＨ値を測定したところ、紫外線照射前にはｐＨ６．５９だったのが、紫外線照射３時間後に再びｐＨ値を測定したところｐＨ９．６１であった。
実施例１〜３に比べて、比較例２では塩基性が弱く、塩基発生効率に劣ることがわかる。

When the pH value of the solution in the quartz cell was measured while irradiating with ultraviolet rays as described above, the pH value was 6.59 before the ultraviolet irradiation, but when the pH value was measured again 3 hours after the ultraviolet irradiation, the pH was 9. 61.
Compared to Examples 1 to 3, it can be seen that Comparative Example 2 is weak in basicity and inferior in base generation efficiency.

Claims (5)

A compound represented by the following formula (1).

(In the formula ^(1), R 1 ~R ⁶ 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, and R ⁷ is a hydrocarbon group having 1 to 6 carbon atoms or the number of carbon atoms 6 to 15 aromatic rings, Q is —NR ⁸ R ⁹ , —N═CR ¹⁰ R ^11, or —N═PR ¹² R ¹³ R ¹⁴ (R ⁸ and R ⁹ are each independently a hydrogen atom or carbon; Represents an alkyl group having 1 to 5 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, R ¹² to R ¹⁴ each independently represents a ring structure containing a nitrogen atom.) The compound of Claim ^{1 in which} R < ¹ > -R < ⁶ > represents a hydrogen atom or a C1-C5 hydrocarbon group in said Formula (1). 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 claim 1 or 2, which forms a polycyclic fused aromatic ring.   The compound according to claim 3, 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 1-4.

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