Acid- and radical-generating agent and method for generating acid and radical

A technology of carbonyloxy and carbonylamino, which is applied in the direction of chemical instruments and methods, photographic plate-making process of patterned surface, photosensitive material used in optomechanical equipment, etc., can solve the problems of poor stability, dimensional change, and easy resist performance. Changes and other problems, to achieve the effect of heat resistance, good efficiency, high sensitivity

Active Publication Date: 2016-07-13
FUJIFILM WAKO PURE CHEM CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In addition, in order to increase the sensitivity to active energy rays in the long-wavelength region, for example, an aromatic ring such as an anthracene ring or a pyrene ring as a substituent is bonded to an aryl group such as an arylsulfonium salt to extend the conjugated system. Ionic acid generators have the following problems: Generally, their solubility becomes poor, they are easily precipitated as solids in resin compositions, and their stability in organic solvents is poor. Therefore, they cannot be stored for several weeks and are resistant to Etch properties are prone to changes (e.g., dimensional changes, sensitivity changes, shape changes, etc.), etc.

Method used

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  • Acid- and radical-generating agent and method for generating acid and radical
  • Acid- and radical-generating agent and method for generating acid and radical
  • Acid- and radical-generating agent and method for generating acid and radical

Examples

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Embodiment

[0412] Hereinafter, the present invention will be specifically described based on examples and comparative examples. However, the present invention is not limited by these examples.

Synthetic example 12

[0413] Synthesis Example 12, Synthesis of 4-bis(1-bromoethyl)thioxanth-9-one

[0414] 26.8 g (100 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of 2,4-diethylthioxanth-9-one was dissolved in 300 mL of ethyl acetate, and N-bromosuccinimide 19.6 g (110mmol; manufactured by Wako Pure Chemical Industries, Ltd.) and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) 1.54g (5.0mmol; Wako Pure Chemical Industries ( Co., Ltd.), stirred at 45°C for 30 minutes. Next, the reaction liquid was temporarily cooled to room temperature, and then, 19.6 g (110 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of N-bromosuccinimide and 2,2'-azobis( 4-methoxy-2,4-dimethylvaleronitrile) 1.54 g (5.0 mmol; manufactured by Wako Pure Chemical Industries, Ltd.), and stirred at 45° C. for 1 hour. After the reaction was completed, methanol was added to the reaction liquid, cooled to 5° C., and the obtained crystals were deliquified, thereby obtaining 28.9 g (micro Yellow powder, yie...

Embodiment 12

[0417] Example 12, Synthesis of 4-bis(1-tosylethyl)thioxanth-9-one (compound represented by formula (1))

[0418] 4.26 g (10.0 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of 2,4-bis(1-bromoethyl)thioxanth-9-one obtained in Synthesis Example 1 and p-sodium toluenesulfinate 5.0 g (20.0 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of 4 water mixtures was dissolved in 20 mL of dimethylformamide (DMF), and stirred at room temperature for 1 hour. After the reaction was completed, water was added to the reaction solution, and the precipitate generated by adding water was obtained by filtration, and the obtained filtrate was recrystallized in dioxane, thereby obtaining 2,4-bis(1-toluenesulfonate Acylethyl)thioxanth-9-one 0.84 g (light yellow powder, yield: 19%). Below, the 1 H-NMR measurement results and structural formula of 2,4-bis(1-tosylethyl)thioxanth-9-one.

[0419] 1 H-NMR (400MHz, CDCl 3 )δ (ppm): 1.63 (3H, d), 1.82 (3H, d), 2.28 (3H, s), 2.38...

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Abstract

The present invention addresses the problem of providing: an acid- and radical-generating agent which has high sensitivity to an active energy ray having a wavelength of about 300 to 450 nm, can exhibit both high acid-generating ability and high radical-generating ability, and has heat resistance; and a method for producing an acid and a radical. The present invention relates to: a compound represented by general formula (A); an acid- and radical-generating agent comprising the compound; and a method for producing an acid and a radical. (In the formula, n R1's independently represent an alkyl group which may have a specific functional group in the chain and may be substituted by a halogen atom, an alkoxy group which may be substituted by a halogen atom, an aryl or aryloxy group which may be substituted by a halogen atom, an alkyl group or a haloalkyl group, or an arylalkyl or arylalkyloxy group which may be substituted by a halogen atom, an alkyl group or a haloalkyl group; n R2's and n R3's independently represent a hydrogen atom, an alkyl group or an alkoxycarbonyl group; R4 to R7 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an alkoxycarbonyl group, a dialkylamino group or a nitro group; Y represents an oxygen atom, a sulfur atom or a carbonyl group; n Z's independently represent a sulfonyl group or an alkoxyphosphoryl group; and n represents 1 or 2.)

Description

technical field [0001] The present invention relates to compounds useful as acid generators and radical generators used in the field of resists, etc., and more specifically, to compounds capable of generating acids and radicals when irradiated with active energy rays around a wavelength of 300 to 450 nm. Compounds of the nature, acids and free radical generators containing these compounds, and acid and free radical generating methods. Background technique [0002] Conventionally, as a resist material used in a photolithography process, for example, a resin composition containing a resin and a photoacid generator is known. The resin is tert-butyl ester of carboxylic acid or tert-butyl ester of phenol. Ethers, silyl ethers, etc. are reacted with carboxylic acid derivatives or phenol derivatives by the action of acid to form alkali-soluble resins. In such a resin composition, for example, when irradiated with active energy rays such as ultraviolet rays, the photoacid generator...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C317/24C07C317/44C07D335/16C09K3/00G03F7/004H01L21/027
CPCC07C317/24C07C317/44C07D335/16C07C2603/24G03F7/0045G03F7/029G03F7/031B01J19/127C07C317/14
Inventor 酒井信彦簗场康佑
Owner FUJIFILM WAKO PURE CHEM CORP
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