RU2646088C1 - Photopolymer composition for the production of thermal-resistant objects by the method of laser stereolithography - Google Patents

Photopolymer composition for the production of thermal-resistant objects by the method of laser stereolithography Download PDF

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RU2646088C1
RU2646088C1 RU2016151979A RU2016151979A RU2646088C1 RU 2646088 C1 RU2646088 C1 RU 2646088C1 RU 2016151979 A RU2016151979 A RU 2016151979A RU 2016151979 A RU2016151979 A RU 2016151979A RU 2646088 C1 RU2646088 C1 RU 2646088C1
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diacrylamide
phenyl
laser
oxide
stereolithography
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Виталий Федорович Бурдуковский
Бато Чингисович Холхоев
Борис Дамбаевич Очиров
Елена Николаевна Горенская
Петр Сергеевич Тимашев
Никита Владимирович Минаев
Дарья Сергеевна Дудова
Ксения Николаевна Бардакова
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Федеральное государственное бюджетное учреждение науки Байкальский институт природопользования Сибирского отделения Российской академии наук (БИП СО РАН)
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Abstract

FIELD: chemistry.
SUBSTANCE: invention relates to photopolymerizable compositions for use in manufacturing techniques using the method of laser stereolithography. Composition includes poly(N-allyl(2,2'-m-phenylene)-5,5'-dibenzimidazole oxide), N,N'-dimethylacrylamide, an acrylamide component selected from 4,4'-diphenylphthalide diacrylamide, 4,4'-oxydiphenyl diacrylamide, diacrylamide[di(4,4'-diphenyloxydisophthaloylamido)]-phenyl-4'-phenyloxide, diacrylamide [penta(4,4'-diphenyloxydisophthaloylamido)]-phenyl-4'-phenyloxide, and a photoinitiator of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1.
EFFECT: proposed composition has sufficient photosensitivity for the manufacture of three-dimensional products with a thermal stability of 380–440 °C from an arbitrary shape under laser 3D stereolithography using economical and small-sized lasers with λ= 405 nm.
1 cl, 4 ex

Description

Изобретение относится к фотополимеризующимся композициям (ФПК) на основе поли(N-аллил (2,2'-м-фенилен)-5,5'-дибензимидазолоксида) и различных акриламидных компонентов, способных под действием лазерного импульсного излучения образовывать трехмерные структуры заданной архитектуры с повышенной термо- и теплостойкостью, которые могут быть использованы в различных отраслях промышленности.The invention relates to photopolymerizable compositions (FPKs) based on poly (N-allyl (2,2'-m-phenylene) -5,5'-dibenzimidazole oxide) and various acrylamide components capable of forming three-dimensional structures of a given architecture with laser pulses increased heat and heat resistance, which can be used in various industries.

Наиболее пригодными ФПК для лазерной стереолитографии традиционно являются составы на основе акриловых и метакриловых кислот, описанные, например, в патентах США 6468711, РФ 2127444, РФ 2515991, РФ 2477290. Однако общим недостатком таких ФПК является низкие значения термо- и теплостойкости получаемых изделий на их основе.The most suitable FPAs for laser stereolithography are traditionally compositions based on acrylic and methacrylic acids, described, for example, in US patents 6468711, RF 2127444, RF 2515991, RF 2477290. However, a common disadvantage of such FPAs is the low heat and heat resistance of the products obtained on them basis.

Техническим результатом настоящего изобретения является создание ФПК, которая при действии лазерного излучения с длинной волны 405 нм, образует трехмерные изделия с температурой эксплуатации до 380-440°С. Такой результат достигается за счет использования ФПК на основе поли(N-аллил(2,2'-м-фенилен)-5,5'-дибензимидазолоксида) следующего видаThe technical result of the present invention is the creation of FPK, which under the action of laser radiation with a wavelength of 405 nm, forms three-dimensional products with operating temperatures up to 380-440 ° C. This result is achieved through the use of FPK based on poly (N-allyl (2,2'-m-phenylene) -5,5'-dibenzimidazoloxide) of the following form

Figure 00000001
Figure 00000001

с добавлением различных акриламидных производных в качестве дополнительных сшивающих компонентов, активного растворителя - диметилакриламида и фотоинициатора - 2-бензил-2-диметиламино-1-(4-морфолинофенил)-бутанона-1.with the addition of various acrylamide derivatives as additional crosslinking components, the active solvent is dimethyl acrylamide and the photoinitiator 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1.

В качестве дополнительных сшивающих компонентов используются:As additional crosslinking components are used:

Figure 00000002
Figure 00000002

диакриламид [ди(4,4'-дифенилоксидизофталоиламидо)]-фенил-4'-фенилоксидаdiacrylamide [di (4,4'-diphenyloxyisophthaloylamido)] - phenyl-4'-phenyl oxide

Figure 00000003
Figure 00000003

диакриламид [пента(4,4'-дифенилоксидизофталоиламидо)]-фенил-4'-фенилоксидаdiacrylamide [penta (4,4'-diphenyloxyisophthaloylamido)] - phenyl-4'-phenyl oxide

Figure 00000004
Figure 00000004

4,4'-дифенилфталиддиакриламид4,4'-diphenylphthalide diacrylamide

Figure 00000005
Figure 00000005

4,4'-оксидифенилдиакриламид4,4'-oxydiphenyl diacrylamide

Фотоотверждение композиций осуществляли с использованием твердотельного лазерного модуля с диодной накачкой MDL-III-405 (CNIlaser) со следующими характеристиками: длина волны 405 нм, мощность излучения от 1 до 100 мВт, диаметр пучка на выходной апертуре ~2,5 мм, расходимость пучка (полный угол) 0,5 мрад. Подвод лазерного излучения производили снизу, перпендикулярно поверхности фотокомпозиции. Фокусировку лазерного излучения осуществляли при помощи F-theta объектива (фокусное расстояние 160 мм), а для перемещения лазерного излучения использовали однозеркальный гальваносканер LScanH-10 (Атеко) с основными параметрами: диапазон сканирования ±6°; максимальная скорость сканирования - до 480°/с; поле обработки (в текущем эксперименте) 30×30 мм.Photo curing of the compositions was carried out using an MDL-III-405 solid-state diode pumped laser module (CNIlaser) with the following characteristics: wavelength 405 nm, radiation power from 1 to 100 mW, beam diameter at the output aperture ~ 2.5 mm, beam divergence ( full angle) 0.5 mrad. Laser radiation was supplied from below, perpendicular to the surface of the photocomposition. Laser radiation was focused using an F-theta lens (focal length 160 mm), and LScanH-10 (Ateko) single-mirror galvanoscanner with basic parameters was used to move laser radiation: scanning range ± 6 °; maximum scanning speed - up to 480 ° / s; processing field (in the current experiment) 30 × 30 mm.

Полученные таким образом материалы заданной геометрической формы согласно данным синхронного термического анализа (ТГ-ДТА/ДСК STA 449 C14/G Jupiter (Netzsch), на воздухе при скорости нагревания 5°/мин) не плавятся вплоть до начала деструкции, которая начинается при 380-440°С, что свидетельствует об их высокой термостойкости.Thus obtained materials of a given geometric shape according to the data of synchronous thermal analysis (TG-DTA / DSC STA 449 C14 / G Jupiter (Netzsch), in air at a heating rate of 5 ° / min) do not melt until the start of destruction, which begins at 380- 440 ° C, which indicates their high heat resistance.

Предлагаемый способ подтверждается следующими нижеприведенными примерами.The proposed method is confirmed by the following examples.

Пример 1. В 58 мас.ч. (5 г) N,N'-диметилакриламида добавляли 20 мас.ч. (1,724 г) поли(N-аллил (2,2'-м-фенилен)-5,5'-дибензимидазолоксида), 20 мас.ч. (1,724 г) 4,4'-дифенилфталиддиакриламида и смешивали с 2 мас.ч. (0,1724 г) инициатора фотополимеризации 2-бензил-2-диметиламино-1-(4-морфолинофенил)-бутанона-1. и интенсивно перемешивали до полной гомогенизации. Полученную композицию подвергали лазерной стереолитографии с λ=405 нм. В результате получали изделие, которое после тщательного промывания и сушки начинало деструктировать на воздухе при 410°С.Example 1. In 58 parts by weight (5 g) N, N'-dimethylacrylamide was added 20 wt.h. (1.724 g) poly (N-allyl (2,2'-m-phenylene) -5,5'-dibenzimidazole oxide), 20 parts by weight (1.724 g) of 4,4'-diphenylphthalide diacrylamide and mixed with 2 parts by weight (0.1724 g) of the initiator of photopolymerization of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1. and vigorously stirred until complete homogenization. The resulting composition was subjected to laser stereolithography with λ = 405 nm. As a result, a product was obtained which, after thorough washing and drying, began to degrade in air at 410 ° C.

Пример 2. В 58 мас.ч. (5 г) N,N'-диметилакриламида добавляли 20 мас.ч. (1,724 г) поли(N-аллил (2,2'-м-фенилен)-5,5'-дибензимидазолоксида), 20 мас.ч. (1,724 г) 4,4'-оксидифенилдиакриламида) и смешивали с 2 мас.ч. (0,1724 г) инициатора фотополимеризации 2-бензил-2-диметиламино-1-(4-морфолинофенил)-бутанона-1 и интенсивно перемешивали до полной гомогенизации. Полученную композицию подвергали лазерной стереолитографии с λ=405 нм. В результате получали изделие, которое после тщательного промывания и сушки начинало деструктировать на воздухе при 380°С.Example 2. In 58 parts by weight (5 g) N, N'-dimethylacrylamide was added 20 wt.h. (1.724 g) poly (N-allyl (2,2'-m-phenylene) -5,5'-dibenzimidazole oxide), 20 parts by weight (1.724 g) of 4,4'-oxydiphenyl diacrylamide) and mixed with 2 parts by weight (0.1724 g) of a photopolymerization initiator of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 and was intensively mixed until complete homogenization. The resulting composition was subjected to laser stereolithography with λ = 405 nm. As a result, a product was obtained which, after thorough washing and drying, began to degrade in air at 380 ° C.

Пример 3. В 58 мас.ч. (5 г) N,N'-диметилакриламида добавляли 20 мас.ч. (1,724 г) поли(N-аллил (2,2'-м-фенилен)-5,5'-дибензимидазолоксида), 20 мас.ч. диакриламида [ди(4,4'-дифенилоксидизофталоиламидо)]-фенил-4'-фенилоксида (1,724 г) и смешивали с 2 мас.ч. (0,1724 г) инициатора фотополимеризации 2-бензил-2-диметиламино-1-(4-морфолинофенил)-бутанона-1 и интенсивно перемешивали до полной гомогенизации. Полученную композицию подвергали лазерной стереолитографии с λ=405 нм. В результате получали изделие, которое после тщательного промывания и сушки начинало деструктировать на воздухе при 420°С.Example 3. In 58 parts by weight (5 g) N, N'-dimethylacrylamide was added 20 wt.h. (1.724 g) poly (N-allyl (2,2'-m-phenylene) -5,5'-dibenzimidazole oxide), 20 parts by weight diacrylamide [di (4,4'-diphenyloxyisophthaloylamido)] phenyl-4'-phenyl oxide (1,724 g) and mixed with 2 parts by weight (0.1724 g) of a photopolymerization initiator of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 and was intensively mixed until complete homogenization. The resulting composition was subjected to laser stereolithography with λ = 405 nm. As a result, a product was obtained which, after thorough washing and drying, began to degrade in air at 420 ° C.

Пример 4. В 58 мас.ч. (5 г) N,N'-диметилакриламида добавляли 20 мас.ч. (1,724 г) поли(N-аллил (2,2'-м-фенилен)-5,5'-дибензимидазолоксида), 20 мас.ч. (1,724 г) диакриламида [пента(4,4'-дифенилоксидизофталоиламидо)]-фенил-4'-фенилоксида и смешивали с 2 мас.ч. (0,1724 г) инициатора фотополимеризации 2-бензил-2-диметиламино-1-(4-морфолинофенил)-бутанона-1 и интенсивно перемешивали до полной гомогенизации. Полученную композицию подвергали лазерной стереолитографии с λ=405 нм. В результате получали изделие, которое после тщательного промывания и сушки начинало деструктировать на воздухе при 440°С.Example 4. In 58 parts by weight of (5 g) N, N'-dimethylacrylamide was added 20 wt.h. (1.724 g) poly (N-allyl (2,2'-m-phenylene) -5,5'-dibenzimidazole oxide), 20 parts by weight (1.724 g) of diacrylamide [penta (4,4'-diphenyloxyisophthaloamido)] -phenyl-4'-phenyl oxide and mixed with 2 parts by weight of (0.1724 g) of a photopolymerization initiator of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 and was intensively mixed until complete homogenization. The resulting composition was subjected to laser stereolithography with λ = 405 nm. The result was a product that, after thorough washing and drying, began to degrade in air at 440 ° C.

Как видно из приведенных примеров, фотополимерная композиция выгодно отличается тем, что проста в получении, не требует эксикатора и вакуума для удаления пузырьков. В процессе фотополимеризации отсутствует выделение побочных продуктов. Полученные структуры после сшивки по кратным связям в трехмерный полимер обладают термостойкостью до 440°С.As can be seen from the above examples, the photopolymer composition favorably differs in that it is easy to obtain, does not require a desiccator and vacuum to remove bubbles. In the process of photopolymerization, no by-products are isolated. The structures obtained, after crosslinking via multiple bonds into a three-dimensional polymer, are heat resistant up to 440 ° C.

Вышеперечисленный комплекс практически полезных свойств, полученных ФПК определяет положительный эффект изобретения. Полученные ФПК могут быть использованы в стериолитографии для получения термо- и теплостойких изделий заданной архитектуры.The above complex of practically useful properties obtained by FPK determines the positive effect of the invention. The obtained FPKs can be used in sterolithography to obtain thermally and heat-resistant products of a given architecture.

Claims (2)

Фотополимеризующаяся композиция для изготовления термостойких материалов лазерной стериолитографией с использованием излучения λ=405 нм следующего состава, мас.%:Photopolymerizable composition for the manufacture of heat-resistant materials by laser sterolithography using radiation λ = 405 nm of the following composition, wt.%: поли(N-аллил(2,2'-м-фенилен)-5,5'-дибензимидазолоксид)poly (N-allyl (2,2'-m-phenylene) -5,5'-dibenzimidazole oxide) 20twenty акриламидный компонент, в качестве которого могут выступатьacrylamide component, which may be 4,4'-дифенилфталиддиакриламид; 4,4'-оксидифенилдиакриламид;4,4'-diphenylphthalide diacrylamide; 4,4'-oxydiphenyl diacrylamide; диакриламид[ди(4,4'-дифенилоксидизофталоиламидо)]-фенил-4'-фенилоксид;diacrylamide [di (4,4'-diphenyloxyisophthaloylamido)] phenyl-4'-phenyl oxide; диакриламид[пента(4,4'-дифенилоксидизофталоиламидо)]-фенил-4'-фенилоксид diacrylamide [penta (4,4'-diphenyloxyisophthaloylamido)] - phenyl-4'-phenyl oxide 20twenty N,N'-диметилакриламид N, N'-dimethylacrylamide 5858 2-бензил-2-диметиламино-1-(4-морфолинофенил)-бутанон-1 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 22
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WO2020189712A1 (en) * 2019-03-19 2020-09-24 三菱瓦斯化学株式会社 Film forming material for lithography, composition for forming film for lithography, underlayer film for lithography, pattern forming method, and purification method
RU2760736C1 (en) * 2021-04-19 2021-11-30 Федеральное государственное бюджетное учреждение науки Байкальский институт природопользования Сибирского отделения Российской академии наук (БИП СО РАН) Curable resins for making heat-resistant 3d objects using dlp 3d printing

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