JP2001163971A - Alkoxymethyl ester dendrimer and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel acid-sensitive polymer. SOLUTION: An alkoxymethyl ester dendrimer represented by formula I a: -(CH2-CH2-N-(CH2-CH2-CH2-N-R2)2)2 or by formula Ib: -(CH2-CH2-N-CH2-(-CH2- CH2-N-(CH2-CH2-CH2-N-R2)2)2)2 (wherein R is R2-O-CH(R1)-O-C(=O)-CH2-CH2-) and its production method are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to novel (alkoxymethyl) ester dendrimers. The polymer compound of the present invention is an acid-sensitive polymer, and is used, for example, as a resist photosensitizer in combination with a photoacid generator.

Conventionally, acid-sensitive polymers include linear
(Alkoxymethyl) acrylic acid polymers are known. However, such a polymer may be entangled with a molecular chain, and the resolution of an image which has undergone development processing or the like may be limited. Therefore, the present inventors have studied to obtain a new acid-sensitive polymer. As a result, the present inventors have found that the above-mentioned problem can be solved by modifying the terminal of a dendrimer, which is a polymer having a highly branched three-dimensional structure, with a functional low molecule, and completed the present invention.

[0003]

SUMMARY OF THE INVENTION That is, the present invention provides the following:

Embedded imageOr(Where R isMeans R¹And R²Are each independently a carbon number of 1 to 6
Alkyl having a chain or branch, or 3 to 8 carbon atoms
Shows alicyclic alkyl. Also R₁And R₂Contact me
May be formed. (Alkoxymethyl)
Regarding the Stelldendrimer. R¹, R²Has 1 to 1 carbon atoms
6 When there is a linear or branched alkyl, for example,
Methyl, ethyl, isobutyl, t-butyl, 1-octy
And the like. Also, R¹, R²Is alicyclic alkyl
Cyclopentyl, cyclohexyl
And alicyclic alkyl having 3 to 8 carbon atoms such as
Also, R¹, R ²Are linked to form a ring
2-tetrahydrofuranyl, 2-tetrahydropyranyl
Is mentioned.

Further, the present invention provides the following formula:

Embedded image Or And a polyfunctional amine compound represented by the following formula:

[0005]

Embedded image Reacting the acrylic acid (alkoxymethyl) ester derivative represented by (R ¹ and R ² are the same as above) in an organic solvent in the presence or absence of a catalyst (alkoxymethyl) The present invention relates to a method for producing an ester dendrimer.

The (alkoxymethyl) dendrimer thus obtained is an acid-sensitive molecule. That is, the (alkoxymethyl) ester derivative introduced at the terminal of the dendrimer causes the decomposition of the ester portion by an acid catalyst, thereby generating a carboxylic acid functional group. In addition, the polymer of the present invention has a poly (propylene imine) dendrimer as a basic skeleton, and an acrylic acid (alkoxymethyl) ester is bonded thereto, so that it is presumed that entanglement of a molecular chain is small.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The (alkoxymethyl) ester dendrimer of the present invention has a polyfunctional amine compound as a core. Examples of such a core include polypropylene imine dendrimer DAB-Am-4, poly (propylene imine) dendrimer first generation (Poly (propyleneimine) Dendrimer,
Generation 1.0) (Formula (IIIa)), DAB-Am-8, poly (propylene imine) dendrimer second generation (Poly (pro
pyleneimine) Dendrimer, Generation 2.0) (Formula (IIIb))
(All manufactured by DSM) can be used. These compounds can also be synthesized using ethylenediamine and acrylonitrile as starting materials.

The terminal of the poly (propylene imine) dendrimer, which is a polyfunctional amine compound, is modified with an acrylate derivative having an alkoxymethyl group.
Such acrylic acid (alkoxymethyl) ester derivatives include, for example, acrylic acid (1-ethoxyethyl), acrylic acid (2-tetrahydrofuranyl), acrylic acid (2
-Tetrahydropyranyl), (1-isobutyroxyethyl) acrylate, (1- (t-butoxy) ethyl) acrylate, (1-cyclopentyloxyethyl) acrylate,
Acrylates such as acrylic acid (1-cyclohexyloxyethyl) are exemplified. These may be used alone or in combination of two or more.

The (alkoxymethyl) ester dendrimer of the present invention can be obtained by reacting a polyfunctional amine compound with an acrylic acid (alkoxymethyl) ester derivative in an organic solvent. The amount of the acrylic acid (alkoxymethyl) ester derivative used is 16 to 80 mol, preferably 16 to 20 mol for DAB-Am-8, relative to 1 mol of the polyfunctional amine compound or poly (propylene imine) dendrimer. 8 for DAB-Am-4
40 mol, preferably 8 to 10 mol, or 2 to 10 equivalents, preferably 2 to 2.5 equivalents (Am
-8 and Am-4).

As the reaction solvent, any of those conventionally known as solvents for the above compounds may be used. Specifically, halogenated hydrocarbons such as tetrachloroethylene, 1,2-dichloroethane and chloroform; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; cyclic ether solvents such as tetrahydrofuran and dioxane; toluene and xylene Aromatic hydrocarbon solvents; N-methyl-2-pyrrolidone,
An aprotic polar solvent such as N, N-dimethylformamide and N, N-dimethylacetamide can be used. These may be used alone or in combination of two or more.

[0011] The reaction temperature is -50 to 150 ° C, preferably 25 to 80 ° C. If the reaction temperature is lower than −50 ° C., the reaction rate is remarkably reduced, which is not preferable. Also, 15
At reaction temperatures above 0 ° C., polyfunctional amine compounds and
It is not preferable in view of the stability of the (alkoxymethyl) acrylate derivative.

The reaction time is 2 to 200 hours, preferably
48 to 100 hours. If the reaction time is shorter than this, the reaction does not proceed completely, which is not preferable.

After completion of the reaction, the desired (alkoxymethyl) ester dendrimer can be obtained by concentrating and removing the solvent. Alternatively, purification may be carried out by adding a poor solvent such as hexane or toluene, heating and removing the supernatant.

[0014]

The present invention will be described more specifically with reference to examples and comparative examples. All syntheses were performed under a stream of nitrogen. The properties of the obtained (alkoxymethyl) ester dendrimer were measured as follows.

[0015] ¹ H NMR  It was measured using JNM-LA300 (manufactured by JEOL Ltd.).
Was.IR  Measured using FT / IR-230 (manufactured by JASCO Corporation)
Was.

[Example 1] First generation (1-ethoxyethoxy)
Cyl) ester-poly (propylene imine) dendrimer
Acrylic acid (1-ethoxyethyl) was placed in a 20 ml reaction vessel.
(0.88 mmol, 126.9 mg), poly (propylene)
Reimine) dendrimer DAB-Am-4 (0.10
mmol, 31.6 mg) and 1 ml of dichloromethane
The mixture was stirred at 40 ° C. for 18 hours. Cooled to room temperature
Thereafter, the desired product is obtained by removing the solution under reduced pressure.
Was. Yield 93%.¹2.38, 2.7 by 1 H NMR
0 (m, 32H, -N-CH_TwoCH_Two-C = O)
1730.8cm by IR ^-1(CO) characteristics
Absorption was observed.

Example 2 Synthesis of Second Generation (2-Tetrahydropyranyl) Ester-Poly (propylene imine) Dendrimer In a 20 ml reaction vessel, acrylic acid (2-tetrahydropyranyl) (0.88 mmol, 137.80 g) was used. 4 mg), poly (propylene imine) dendrimer DAB-Am-4
(0.10 mmol, 31.6 mg), 1 ml of dichloromethane was added, and the mixture was stirred at 40 ° C. for 18 hours. After cooling to room temperature, the target product was obtained by removing this solution under reduced pressure. Yield 98%. 2.4 by ¹ H NMR
2,2.73 (m, 32H, -N- CH 2 CH 2 -C = O) to generate the peak, and by IR, 1731.8cm ^-1 (C
O) characteristic absorption was observed.

Example 3 Synthesis of Second-Generation (1-Isobutyroxyethyl) ester-Poly (propyleneimine) Dendrimer In a 20 ml reaction vessel, (1-isobutyroxyethyl) acrylate (0.88 mmol, 151.6 mg), poly (propylene imine) dendrimer DAB-Am-4
(0.10 mmol, 31.6 mg), 1 ml of dichloromethane was added, and the mixture was stirred at 40 ° C. for 18 hours. After cooling to room temperature, the target product was obtained by removing this solution under reduced pressure. 95% yield. 2.3 by ¹ H NMR
8,2.70 (m, 32H, -N- CH 2 CH 2 -C = O) to generate the peak, and by IR, 1730.8cm ^-1 (C
O) characteristic absorption was observed.

Example 4 Synthesis of 2nd generation (1- (t-butoxy) ethyl) ester-poly (propyleneimine) dendrimer In a 20 ml reaction vessel, (1- (t-butoxy) ethyl acrylate) ( 0.88 mmol, 151.6 mg), poly (propylene imine) dendrimer DAB-Am-4
(0.10 mmol, 31.6 mg), 1 ml of dichloromethane was added, and the mixture was stirred at 40 ° C. for 18 hours. After cooling to room temperature, the target product was obtained by removing this solution under reduced pressure. 95% yield. 2.3 by ¹ H NMR
4,2.68 (m, 32H, -N- CH 2 CH 2 -C = O) to generate the peak, and by IR, 1730.8cm ^-1 (C
O) characteristic absorption was observed.

Example 5 Second generation (1-cyclohexyloxyethyl) ester-poly (propylene imine)
Synthesis of Dendrimer In a 20 ml reaction vessel, (1-cyclohexyloxyethyl acrylate) (0.88 mmol, 348.9 mg), poly (propylene imine) dendrimer DAB-Am-4
(0.10 mmol, 31.6 mg), 1 ml of dichloromethane was added, and the mixture was stirred at 40 ° C. for 18 hours. After cooling to room temperature, the target product was obtained by removing this solution under reduced pressure. Yield 98%. 2.3 by ¹ H NMR
5,2.72 (m, 32H, -N- CH 2 CH 2 -C = O) to generate the peak, and by IR, 1725.0cm ^-1 (C
O) characteristic absorption was observed.

Example 6 Synthesis of 2nd generation (1-ethoxyethyl) ester-poly (propyleneimine) dendrimer In a 20 ml reaction vessel, (1-ethoxyethyl) acrylate (1.76 mmol, 253.7 mg) was added. , Poly (propylene imine) dendrimer DAB-Am-8 (0.10 mmol, 7
7.3 mg), add 1 ml of dichloromethane, and add
Stirred at 18 ° C. for 18 hours. After cooling to room temperature, the target product was obtained by removing this solution under reduced pressure. Yield 97
%. ^{According to 1} H NMR, 2.39, 2.71 (m, 64H,
-N-CH ₂ CH ₂ -C = O), and the peak was
A characteristic absorption of 730.8 cm ^-1 (CO) was observed.

Example 7 Synthesis of Second Generation (2-Tetrahydropyranyl) Ester-Poly (propylene imine) Dendrimer In a 20 mL reaction vessel, acrylic acid (2-tetrahydropyranyl) (1.76 mmol, 274. 8 mg), poly (propylene imine) dendrimer DAB-Am-8 (0.10 mmol
l, 77.3 mg), 1 ml of dichloromethane was added, and the mixture was stirred at 40 ° C for 18 hours. After cooling to room temperature,
The desired product was obtained by removing this solution under reduced pressure.
Yield 100%. 2.43, 2.74 by ¹ H NMR
(m, 64H, -N-CH 2 CH 2 -C = O) is the generation of the peak, by also IR, the characteristic absorption of 1731.7cm ^-1 (CO) was observed.

Example 8 Synthesis of Second-Generation (1-Isobutyroxyethyl) Ester-Poly (propylene imine) Dendrimer In a 20 mL reaction vessel, (1-isobutyroxyethyl) acrylate (1.76 mmol, 303.1 mg), poly (propylene imine) dendrimer DAB-Am-8 (0.10 mmol
l, 77.3 mg), 1 ml of dichloromethane was added, and the mixture was stirred at 40 ° C for 18 hours. After cooling to room temperature,
The desired product was obtained by removing this solution under reduced pressure.
Yield 93%. ^{According to 1} H NMR, 2.39, 2.71 (m,
_{64H, -N-CH 2 CH 2} -C = O) to generate the peak, the addition IR, the characteristic absorption of 1730.8cm ^-1 (CO) was observed.

Example 9 Synthesis of 2nd generation (1- (t-butoxy) ethyl) ester-poly (propyleneimine) dendrimer In a 20 mL reaction vessel, (1- (t-butoxy) ethyl acrylate) ( 1.76 mmol, 303.1 mg), poly (propylene imine) dendrimer DAB-Am-8 (0.10 m
mol, 77.3 mg), 1 ml of dichloromethane was added, and the mixture was stirred at 40 ° C. for 18 hours. After cooling to room temperature,
The desired product was obtained by removing this solution under reduced pressure.
95% yield. ^{According to 1} H NMR, 2.33, 2.69 (m,
_{64H, -N-CH 2 CH 2} -C = O) to generate the peak, the addition IR, the characteristic absorption of 1724.0cm ^-1 (CO) was observed.

Example 10 Second generation (1-cyclohexyloxyethyl) ester-poly (propyleneimine)
Synthesis of Dendrimer In a 20 mL reaction vessel, (1-cyclohexyloxyethyl) acrylate (1.76 mmol, 348.9 mg), poly (propylene imine) dendrimer DAB-Am-8 (0.1
0 mmol, 77.3 mg), 1 ml of dichloromethane was added, and the mixture was stirred at 40 ° C. for 18 hours. After cooling to room temperature, the target product was obtained by removing this solution under reduced pressure. Yield 100%. 2.37, 2.7 by ¹ H NMR
1 (m, 64H, -N- CH 2 CH 2 -C = O) is the generation of the peak, and by IR, the characteristic absorption of 1726.9cm ^-1 (CO) was observed.

[0026]

The (alkoxymethyl) dendrimer of the present invention is an acid-sensitive molecule, which decomposes the ester moiety by the reaction of the (alkoxymethyl) ester derivative introduced at the terminal under acidic conditions to form a carboxylic acid functional group. I do.
Since the entanglement of the molecular chains of the dendrimer structure is small, the boundary between the region in which the ester is decomposed and the region in which the ester is not decomposed can be clearly distinguished and used as a resist photosensitizer.

 ──────────────────────────────────────────────────の Continuation of front page (72) Inventor Masahiro Yoshioka 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation F-term (reference) 4H006 AA01 AA02 AB80 AB92 AB99 AC52 BB10 BJ20 BP10 BP20 BT12 BU32 BU42 4J043 PA02 PB11 PC076 PC116 QC02 QC28 RA02 SA08 SA09 SB01 TA06 TA31 TA72 TB01 UB011 YB19 YB21 YB24 ZA05 ZB22

Claims (4)

[Claims] [Claim 1] The following formula: (Where R is And R ¹ and R ² each independently represent a straight-chain or branched alkyl having 1 to 6 carbon atoms or an alicyclic alkyl having 3 to 8 carbon atoms. R ₁ and R ₂ may be linked to form a ring. )) (Alkoxymethyl) ester dendrimer. 2. The following formula: And a polyfunctional amine compound represented by the following formula: (R ¹ and R ² each independently represent a straight-chain or branched alkyl having 1 to 6 carbons or an alicyclic alkyl having 3 to 8 carbons. In addition, R ₁ and R ₂ are linked to each other to form a ring. (Alkoxymethyl) represented by
2. The method according to claim 1, wherein the ester derivative is reacted in an organic solvent in the presence or absence of a catalyst.
A method for producing an (alkoxymethyl) ester dendrimer. 3. The following formula: (Where R is And R ¹ and R ² each independently represent a straight-chain or branched alkyl having 1 to 6 carbon atoms or an alicyclic alkyl having 3 to 8 carbon atoms. R ₁ and R ₂ may be linked to form a ring. )) (Alkoxymethyl) ester dendrimer. 4. The following formula: And a polyfunctional amine compound represented by the following formula: (R ¹ and R ² each independently represent a straight-chain or branched alkyl having 1 to 6 carbons or an alicyclic alkyl having 3 to 8 carbons. In addition, R ₁ and R ₂ are linked to each other to form a ring. (Alkoxymethyl) represented by
4. The method according to claim 3, wherein the ester derivative is reacted in an organic solvent in the presence or absence of a catalyst.
A method for producing an (alkoxymethyl) ester dendrimer.