KR102422539B1 - Photocurable composition for imprint - Google Patents
Photocurable composition for imprint Download PDFInfo
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- KR102422539B1 KR102422539B1 KR1020207033547A KR20207033547A KR102422539B1 KR 102422539 B1 KR102422539 B1 KR 102422539B1 KR 1020207033547 A KR1020207033547 A KR 1020207033547A KR 20207033547 A KR20207033547 A KR 20207033547A KR 102422539 B1 KR102422539 B1 KR 102422539B1
- Authority
- KR
- South Korea
- Prior art keywords
- component
- mass
- meth
- parts
- ethylenically unsaturated
- Prior art date
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- DKPFODGZWDEEBT-QFIAKTPHSA-N taxane Chemical class C([C@]1(C)CCC[C@@H](C)[C@H]1C1)C[C@H]2[C@H](C)CC[C@@H]1C2(C)C DKPFODGZWDEEBT-QFIAKTPHSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000011043 treated quartz Substances 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- JLQFVGYYVXALAG-CFEVTAHFSA-N yasmin 28 Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.C([C@]12[C@H]3C[C@H]3[C@H]3[C@H]4[C@@H]([C@]5(CCC(=O)C=C5[C@@H]5C[C@@H]54)C)CC[C@@]31C)CC(=O)O2 JLQFVGYYVXALAG-CFEVTAHFSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
[과제] 신규한 임프린트용 광경화성 조성물을 제공한다.
[해결수단] 하기 (a)성분, 하기 (b)성분, 하기 (c)성분, 및 하기 (d)성분을 포함하는 임프린트용 광경화성 조성물로서, 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해, 이 (a)성분이 10질량부 내지 40질량부, 이 (b)성분이 10질량부 내지 50질량부, 이 (c)성분이 1질량부 내지 10질량부, 이 (d)성분이 0.1질량부 내지 5질량부인, 임프린트용 광경화성 조성물이다.
(a): 일차입자경이 1nm 내지 100nm인, 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자 (b): 에틸렌성 불포화기를 갖는 단관능(메트)아크릴레이트 화합물 (c): 에틸렌성 불포화기를 갖는 폴리로탁세인 (d): 광라디칼개시제[Problem] To provide a novel photocurable composition for imprinting.
[Solutions] A photocurable composition for imprint comprising the following (a) component, the following (b) component, the following (c) component, and the following (d) component, the compound having an ethylenically unsaturated group contained in the composition. With respect to 100 mass parts in total, 10 mass parts - 40 mass parts of this (a) component, this (b) component 10 mass parts - 50 mass parts, this (c) component 1 mass part - 10 mass parts, this (d) It is a photocurable composition for imprints whose component is 0.1 mass part - 5 mass parts.
(a): a primary particle diameter of 1 nm to 100 nm, surface-modified silica particles with a functional group having an ethylenically unsaturated group (b): a monofunctional (meth) acrylate compound having an ethylenically unsaturated group (c): having an ethylenically unsaturated group Polyrotaxane (d): photoradical initiator
Description
본 발명은, 에틸렌성 불포화기를 갖는 관능기로 표면수식(修飾)된 실리카입자, 에틸렌성 불포화기를 갖는 단관능(메트)아크릴레이트 화합물, 에틸렌성 불포화기를 갖는 폴리로탁세인(ポリロタキサン), 및 광라디칼개시제를 포함하는 임프린트용 광경화성 조성물에 관한 것이다. 상세하게는, 광학특성(고굴절률, 고아베수, 저복굴절)이 우수하고, 경화물 및 성형체의 상층에 반사방지층(AR층)을 성막 후, 열처리를 거쳐도 이 반사방지층에 크랙이 발생하지 않고, 나아가 유기용매에 의한, 세정 또는 현상 후여도 경화물에 크랙이 발생하지 않는, 광경화성 조성물에 관한 것이다.The present invention relates to silica particles surface-modified with a functional group having an ethylenically unsaturated group, a monofunctional (meth)acrylate compound having an ethylenically unsaturated group, polyrotaxane having an ethylenically unsaturated group, and a photoradical It relates to a photocurable composition for imprint comprising an initiator. Specifically, it has excellent optical properties (high refractive index, high Abbe number, low birefringence), and cracks do not occur in this antireflection layer even after heat treatment after forming an antireflection layer (AR layer) on the upper layer of the cured product and the molded body Furthermore, it relates to a photocurable composition in which cracks do not occur in the cured product even after washing or development with an organic solvent.
수지렌즈는, 휴대전화, 디지털카메라, 차재카메라 등의 전자기기에 이용되고 있으며, 그 전자기기의 목적에 따른, 우수한 광학특성을 갖는 것이 요구된다. 또한, 사용태양에 맞춰, 높은 내구성, 예를 들어 내열성 및 내후성, 그리고 수율좋게 성형할 수 있는 높은 생산성이 요구되고 있다. 이러한 요구를 만족하는 수지렌즈용의 재료로는, 예를 들어, 폴리카보네이트수지, 시클로올레핀폴리머, 메타크릴수지 등의 열가소성의 투명수지가 사용되어 왔다.Resin lenses are used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical properties according to the purpose of the electronic devices. In addition, high durability, for example, heat resistance and weather resistance, and high productivity capable of molding with good yield are required according to the usage mode. As a material for a resin lens that satisfies these requirements, for example, a thermoplastic transparent resin such as a polycarbonate resin, a cycloolefin polymer, or a methacrylic resin has been used.
또한, 고해상도 카메라모듈에는 복수매의 렌즈가 이용되는데, 파장분산성이 낮은, 즉 고아베수를 갖는 렌즈가 주로 사용되고 있으며, 그것을 형성하는 광학재료가 요구되고 있다. 나아가, 수지렌즈의 제조에 있어서, 수율이나 생산효율의 향상, 더 나아가서는 렌즈적층시의 광축어긋남의 억제를 위해, 열가소성 수지의 사출성형으로부터, 실온에서 액상인 경화성 수지를 사용한 압착(押付)성형에 의한 웨이퍼레벨성형으로의 이행이 활발히 검토되고 있다. 웨이퍼레벨성형에서는, 생산성의 관점으로부터, 유리기판 등의 지지체 상에 렌즈를 형성하는 하이브리드렌즈방식이 일반적이다.In addition, although a plurality of lenses are used in the high-resolution camera module, a lens having a low wavelength dispersion, that is, a high Abbe number, is mainly used, and an optical material forming the lens is required. Furthermore, in the manufacture of resin lenses, in order to improve the yield and production efficiency, and furthermore, to suppress the optical axis shift during lens lamination, from injection molding of a thermoplastic resin to compression molding using a liquid curable resin at room temperature. The transition to wafer-level molding by In wafer level molding, from the viewpoint of productivity, a hybrid lens method in which a lens is formed on a support such as a glass substrate is common.
웨이퍼레벨성형이 가능한 광경화성 수지로는, 종래, 고투명성, 내열황변색성 및 금형으로부터의 이형성의 관점으로부터, 라디칼경화성 수지 조성물이 이용되고 있다(특허문헌 1). 성형체가 렌즈인 경우, 그 상층에 산화규소, 산화티탄 등의 무기물로 이루어지는 반사방지층이 형성된다. 그러므로, 이 반사방지층으로 피복된 렌즈를 열처리함에 따라, 그 반사방지층에 크랙이 발생한다는 과제를 갖고 있다.As a photocurable resin capable of wafer level molding, a radically curable resin composition is conventionally used from the viewpoint of high transparency, heat yellowing resistance, and releasability from a mold (Patent Document 1). When the molded object is a lens, an antireflection layer made of an inorganic material such as silicon oxide or titanium oxide is formed on the upper layer. Therefore, as the lens coated with this antireflection layer is heat treated, there is a problem that cracks are generated in the antireflection layer.
또한, 실란 화합물로 표면수식된 실리카입자, 분산제로 표면수식된 산화지르코늄입자 등의, 표면수식된 산화물입자를 함유함으로써, 높은 아베수의 경화물이 얻어지는 경화성 조성물이 알려져 있다(예를 들어, 특허문헌 2 및 특허문헌 3). 이러한 산화물입자를 포함하는 경화성 조성물은, 임프린트 후에 복수의 렌즈패턴이 형성된 웨이퍼상성형체의 외주부 등의 미경화부를 유기용매에 의해 세정하는 현상공정에 있어서, 이 유기용매의 상기 웨이퍼상성형체에의 침식이 현저해져서, 이 웨이퍼상성형체에 크랙이 발생한다는 과제를 갖고 있다.In addition, curable compositions are known that contain surface-modified oxide particles such as silica particles surface-modified with a silane compound and zirconium oxide particles surface-modified with a dispersing agent, thereby obtaining a cured product having a high Abbe's number (for example, in the patent Document 2 and Patent Document 3). In the developing step of cleaning uncured parts such as the outer periphery of the wafer-shaped molded body on which a plurality of lens patterns are formed after imprinting with an organic solvent, the curable composition containing such oxide particles is eroded by the organic solvent on the wafer-like molded body. This becomes remarkable, and it has the subject that a crack generate|occur|produces in this wafer-shaped molded object.
더 나아가서는, 일반적인 라디칼경화성 수지 조성물로부터 성형된 경화물은, 경화수축에 기인한 응력이 경화물 중에 축적되어, 복굴절을 발생시킨다. 복굴절이 높은 경화물을 고화소카메라모듈용의 렌즈로서 이용하면, 얻어지는 화상은 왜곡(歪み)이 발생하므로, 렌즈용의 경화성 수지 조성물로서 저복굴절인 재료가 요구되고 있다.Furthermore, in a cured product molded from a general radical-curable resin composition, stress due to curing shrinkage is accumulated in the cured product to cause birefringence. When a cured product having high birefringence is used as a lens for a high-pixel camera module, distortion occurs in the obtained image. Therefore, a material having low birefringence is required as a curable resin composition for lenses.
한편, 개구부를 갖는 환상분자, 직쇄상분자, 및 봉쇄기(스토퍼)를 가지며, 이 환상분자의 개구부가 이 직쇄상분자에 의해 꼬챙이(串刺し)상으로 포접된 의(擬)폴리로탁세인의 양 단에 이 봉쇄기가 배치되고, 이 환상분자가 (메트)아크릴기를 갖는 폴리로탁세인이 알려져 있다(예를 들어, 특허문헌 4). 상기 직쇄상분자는 상기 환상분자의 개구부를 관통하고, 상기 봉쇄기는 이 환상분자가 이 직쇄상분자로부터 이탈하지 않도록 마련되어 있다. 한편, “포접”이란 환상분자의 개구부의 공간에 다른 분자를 취입하는 것을 의미하고, “의폴리로탁세인”이란 상기 봉쇄기를 갖지 않는 폴리로탁세인을 의미한다. 상기 폴리로탁세인을 포함하는 광경화성 조성물은, 고강도, 고탄성률, 및 우수한 인성을 갖는 광경화물을 제작할 수 있다.On the other hand, a cyclic molecule having an opening, a linear molecule, and a pseudopolyrotaxane having a blocking group (stopper), in which the opening of the cyclic molecule is entrapped in a skewer shape by the linear molecule Polyrotaxane in which this blocking group is disposed at both ends and the cyclic molecule has a (meth)acryl group is known (for example, Patent Document 4). The linear molecule passes through the opening of the cyclic molecule, and the blocking group is provided so that the cyclic molecule does not depart from the linear molecule. On the other hand, "inclusion" means introducing other molecules into the space of the opening of the cyclic molecule, and "polyrotaxane" means polyrotaxane having no blocking group. The photocurable composition containing the polyrotaxane can produce a photocured having high strength, high modulus of elasticity, and excellent toughness.
고아베수(예를 들어 53 이상)와 낮은 복굴절을 가지며, 고해상도 카메라모듈용 렌즈로서 사용할 수 있는 성형체가 얻어지고, 이 성형체의 상층에 성막된 반사방지층이, 그 후의 열처리에 의해 크랙이 발생하지 않고, 더 나아가서는, 유기용매에 의해 상기 웨이퍼상성형체의 외주부 등의 미경화부를 세정하는 현상공정에 있어서, 이 웨이퍼상성형체에 크랙이 발생하지 않는, 경화성 수지재료는 아직 없어, 그 개발이 요망되고 있었다. 본 발명은, 이러한 사정을 감안하여 이루어진 것으로, 고아베수, 고굴절률, 및 저복굴절을 나타내는 성형체를 형성할 수 있고, 또한 이 성형체를 열처리함으로써 그 상층의 반사방지층에 크랙이 발생하지 않고, 현상공정에 노출되어도 크랙이 발생하지 않는 높은 내크랙성을 갖는 성형체를 형성할 수 있는, 광경화성 조성물을 제공하는 것을 과제로 한다.A molded article having a high Abbe number (for example, 53 or more) and low birefringence, which can be used as a lens for a high-resolution camera module, is obtained. Furthermore, in the developing step of cleaning the uncured parts such as the outer periphery of the wafer-shaped molded body with an organic solvent, there is still no curable resin material that does not generate cracks in the wafer-like molded body, and its development is desired was becoming The present invention has been made in view of such circumstances, and it is possible to form a molded article exhibiting a high Abbe number, a high refractive index, and a low birefringence, and by heat-treating the molded article, cracks do not occur in the antireflection layer of the upper layer, and the development An object of the present invention is to provide a photocurable composition capable of forming a molded article having high crack resistance that does not generate cracks even when exposed to a process.
본 발명의 제1 태양은, 하기 (a)성분, 하기 (b)성분, 하기 (c)성분, 및 하기 (d)성분을 포함하는 임프린트용 광경화성 조성물로서, 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해, 이 (a)성분이 10질량부 내지 40질량부, 이 (b)성분이 10질량부 내지 50질량부, 이 (c)성분이 1질량부 내지 10질량부, 이 (d)성분이 0.1질량부 내지 5질량부인, 임프린트용 광경화성 조성물이다.A first aspect of the present invention is a photocurable composition for imprints comprising the following component (a), the following component (b), the following component (c), and the following component (d), wherein the ethylenically unsaturated composition is contained in the composition. With respect to 100 mass parts of sum total of the compound which has a group, this (a) component is 10 mass parts - 40 mass parts, this (b) component is 10 mass parts - 50 mass parts, this (c) component is 1 mass part - 10 mass parts It is a photocurable composition for imprints whose mass part and this (d)component are 0.1 mass part - 5 mass parts.
(a): 일차입자경이 1nm 내지 100nm인, 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자(a): silica particles having a primary particle diameter of 1 nm to 100 nm, surface-modified with a functional group having an ethylenically unsaturated group
(b): 에틸렌성 불포화기를 갖는 단관능(메트)아크릴레이트 화합물(b): monofunctional (meth)acrylate compound having an ethylenically unsaturated group
(c): 에틸렌성 불포화기를 갖는 폴리로탁세인(c): polyrotaxane having an ethylenically unsaturated group
(d): 광라디칼개시제(d): photoradical initiator
본 발명의 임프린트용 광경화성 조성물은 추가로, 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해, 5질량부 내지 50질량부의 하기 (e)성분 및/또는 하기 (f)성분을 함유할 수도 있다.The photocurable composition for imprint of the present invention further comprises 5 parts by mass to 50 parts by mass of the following (e) component and/or (f) with respect to 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition. It may contain ingredients.
(e): 에틸렌성 불포화기를 갖는, 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물(단, 상기 (c)성분의 폴리로탁세인 및 (f)성분의 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물을 제외한다.)(e): a polyfunctional (meth) acrylate compound having an ethylenically unsaturated group and not containing an aromatic ring (provided that the polyrotaxane of the component (c) and the urethane (meth) acrylate compound of the component (f)) or an epoxy (meth) acrylate compound.)
(f): 에틸렌성 불포화기를 갖는, 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물(단, 상기 (c)성분의 폴리로탁세인을 제외한다.)(f): a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound having an ethylenically unsaturated group (however, the polyrotaxane of the component (c) is excluded.)
본 발명의 임프린트용 광경화성 조성물은 추가로, 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해 0.05질량부 내지 3질량부의 하기 (g)성분 및/또는 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해 0.1질량부 내지 3질량부의 하기 (h)성분을 함유할 수도 있다.The photocurable composition for imprint of the present invention further comprises from 0.05 parts by mass to 3 parts by mass of the following (g) component and/or the composition with respect to 100 parts by mass of the compound having an ethylenically unsaturated group contained in the composition. You may contain the following (h) component of 0.1 mass parts - 3 mass parts with respect to total 100 mass parts of the compound which has an ethylenically unsaturated group.
(g): 페놀계 산화방지제(g): phenolic antioxidant
(h): 설파이드계 산화방지제(h): sulfide-based antioxidant
상기 (a)성분의 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자가, 예를 들어 2가의 연결기를 개재하여 규소원자와 결합한 (메트)아크릴로일옥시기로 표면수식된 실리카입자이다. 이 2가의 연결기는, 예를 들어, 탄소원자수 1 내지 5의 알킬렌기, 바람직하게는 탄소원자수 2 또는 3의 알킬렌기이다.The silica particles surface-modified with a functional group having an ethylenically unsaturated group of the component (a) are, for example, silica particles surface-modified with a (meth)acryloyloxy group bonded to a silicon atom via a divalent linking group. This divalent linking group is, for example, an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms.
상기 (e)성분의 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물이, 2종 이상의 화합물로 구성될 수도 있다. 그 경우, 이 2종 이상의 화합물 중 적어도 1종의 화합물은 지환식 탄화수소기를 갖는다.The polyfunctional (meth)acrylate compound which does not contain the aromatic ring of the said (e) component may be comprised from 2 or more types of compounds. In that case, at least 1 type of compound among these 2 or more types of compounds has an alicyclic hydrocarbon group.
상기 임프린트용 광경화성 조성물은, 그 경화물의 파장 589nm에 있어서의 굴절률nD가 1.49 이상이고, 또한 이 경화물의 아베수νD가 53 이상이다. 상기 굴절률nD, 상기 아베수νD는 모두 높은 값일수록 바람직하나, 예를 들어, 굴절률nD는 1.49 이상 1.55 이하, 아베수νD는 53 이상 60 이하의 범위이면 된다.The photocurable composition for imprint has a refractive index n D of the cured product at a wavelength of 589 nm of 1.49 or more, and an Abbe number ν D of the cured product is 53 or more. The refractive index n D and the Abbe's number ν D are preferably higher values, for example, the refractive index n D may be in the range of 1.49 or more and 1.55 or less, and the Abbe's number ν D may be in the range of 53 or more and 60 or less.
본 발명의 제2 태양은, 상기 임프린트용 광경화성 조성물의 경화물이다.A second aspect of the present invention is a cured product of the photocurable composition for imprinting.
본 발명의 제3 태양은, 상기 임프린트용 광경화성 조성물을 임프린트성형하는 공정을 포함하는, 수지렌즈의 제조방법이다.A third aspect of the present invention is a method for manufacturing a resin lens, comprising the step of imprint molding the photocurable composition for imprinting.
본 발명의 제4 태양은, 임프린트용 광경화성 조성물의 성형체의 제조방법으로서, 상기 임프린트용 광경화성 조성물을, 접합하는 지지체와 주형 사이의 공간, 또는 분할가능한 주형의 내부의 공간에 충전하는 공정, 및 이 공간에 충전된 임프린트용 광경화성 조성물을 노광하여 광경화하는 공정을 포함하는, 성형체의 제조방법이다. 상기 주형은 몰드라고도 칭한다.A fourth aspect of the present invention provides a method for producing a molded article of a photocurable composition for imprint, the step of filling the space between the support to be joined and the mold or the space inside the splittable mold with the photocurable composition for imprinting; and exposing the photocurable composition for imprinting filled in the space to photocuring. The mold is also referred to as a mold.
본 발명의 성형체의 제조방법에 있어서, 상기 광경화하는 공정의 후, 얻어진 광경화물을 취출하여 이형하는 공정, 그리고, 이 광경화물을, 이 이형하는 공정의 전, 중도 또는 후에 있어서 가열하는 공정을 추가로 포함할 수도 있다.In the manufacturing method of the molded object of this invention, after the said photocuring process, the process of taking out and releasing the obtained photocured, and the process of heating this photocured before, during, or after this releasing process, It may further include.
상기 이형하는 공정 후, 상기 가열하는 공정의 전에 유기용매를 이용한 현상공정을 추가로 포함할 수도 있다.After the releasing step, before the heating step, a developing step using an organic solvent may be further included.
본 발명의 성형체의 제조방법에 있어서, 이 성형체는, 예를 들어 카메라모듈용 렌즈이다.In the manufacturing method of the molded object of this invention, this molded object is a lens for camera modules, for example.
본 발명의 임프린트용 광경화성 조성물은, 상기 (a)성분 내지 상기 (d)성분을 포함하고, 추가로 임의로, 상기 (e)성분 및/또는 상기 (f)성분, 그리고 상기 (g)성분 및/또는 상기 (h)성분을 포함한다. 그러므로, 이 광경화성 조성물로부터 얻어지는 경화물 및 성형체가, 광학디바이스, 예를 들어, 고해상도 카메라모듈용의 렌즈로서 바람직한 광학특성, 즉 고아베수, 고굴절률 및 저복굴절을 나타낸다. 또한, 본 발명의 광경화성 조성물로부터 얻어지는 경화물 및 성형체는, 이 경화물 및 성형체의 상층의 반사방지층이 175℃에서의 열처리에 의해 크랙, 주름이 모두 발생하지 않고, 나아가 유기용매를 이용한 현상공정에 있어서 크랙이 발생하지 않는다.The photocurable composition for imprint of the present invention comprises the component (a) to the component (d), and further optionally, the component (e) and/or the component (f), and the component (g) and / or said (h) component is included. Therefore, the cured product and molded article obtained from this photocurable composition exhibit optical properties desirable as lenses for optical devices, for example, high-resolution camera modules, i.e., high Abbe's number, high refractive index, and low birefringence. In addition, in the cured product and the molded product obtained from the photocurable composition of the present invention, the anti-reflection layer of the upper layer of the cured product and the molded product does not generate any cracks or wrinkles by heat treatment at 175°C, and furthermore, a developing process using an organic solvent No cracks occur in
본 발명의 임프린트용 광경화성 조성물의 각 성분에 대하여, 보다 상세하게 설명한다. 한편, 본 발명에 있어서, 에틸렌성 불포화기란, 2개의 탄소원자간에 이중결합을 갖는 기, 예를 들어, (CH2=CH)-기 및 [CH2=C(CH3)]-기를 들 수 있다. 본 발명의 임프린트용 광경화성 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물은, (a)성분 내지 (c)성분이고, 이 조성물이 상기 (e)성분 및 (f)성분 중 적어도 일방을 함유하는 경우 이들 성분도 해당한다.Each component of the photocurable composition for imprints of this invention is demonstrated in more detail. Meanwhile, in the present invention, the ethylenically unsaturated group refers to a group having a double bond between two carbon atoms, for example, (CH 2 =CH)-group and [CH 2 =C(CH 3 )]-group. have. The compound having an ethylenically unsaturated group contained in the photocurable composition for imprint of the present invention is component (a) to component (c), and the composition contains at least one of component (e) and component (f). These ingredients are also included.
[(a)성분: 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자][(a) component: silica particles surface-modified with a functional group having an ethylenically unsaturated group]
본 발명의 임프린트용 광경화성 조성물의 (a)성분으로서 사용가능한, 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자는, 일차입자경이 1nm 내지 100nm이다. 여기서, 일차입자란, 분체를 구성하는 입자이고, 이 일차입자가 응집한 입자를 이차입자라 한다. 상기 일차입자경은, 가스흡착법(BET법)에 의해 측정되는 상기 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자의 비표면적(단위질량당 표면적)S, 이 표면수식된 실리카입자의 밀도ρ, 및 일차입자경D간에 성립되는 관계식: D=6/(ρS)으로부터 산출할 수 있다. 이 관계식으로부터 산출되는 일차입자경은, 평균입자경이며, 일차입자의 직경이다. 또한, 상기 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자는, 예를 들어, 2가의 연결기를 개재하여 규소원자와 결합한 (메트)아크릴로일옥시기로 표면수식되어 있다. 상기 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자를 이용할 때에는, 이 표면수식된 실리카입자를 그대로 이용할 수도 있고, 이 표면수식된 실리카입자를 분산매인 유기용제에 미리 분산시킨 콜로이드상태의 것(콜로이드입자가 분산매에 분산된 졸)을 이용할 수도 있다. 이 표면수식된 실리카입자를 포함하는 졸을 이용하는 경우, 고형분의 농도가 10질량% 내지 60질량%의 범위인 졸을 이용할 수 있다.The silica particles surface-modified with a functional group having an ethylenically unsaturated group usable as component (a) of the photocurable composition for imprint of the present invention have a primary particle diameter of 1 nm to 100 nm. Here, the primary particles are particles constituting the powder, and the particles in which the primary particles are aggregated are called secondary particles. The primary particle diameter is the specific surface area (surface area per unit mass) S of the silica particles surface-modified with a functional group having an ethylenically unsaturated group as measured by the gas adsorption method (BET method), the density of the surface-modified silica particles ρ, and It can be calculated from the relational expression established between the primary particle diameters D: D=6/(ρS). The primary particle diameter calculated from this relational expression is an average particle diameter, and is the diameter of a primary particle. In addition, the surface-modified silica particles with a functional group having an ethylenically unsaturated group are, for example, surface-modified with a (meth)acryloyloxy group bonded to a silicon atom via a divalent linking group. When using the surface-modified silica particles with a functional group having an ethylenically unsaturated group, the surface-modified silica particles may be used as they are, and the surface-modified silica particles are previously dispersed in an organic solvent as a dispersion medium in a colloidal state (colloids). A sol in which particles are dispersed in a dispersion medium) may also be used. In the case of using the sol containing the surface-modified silica particles, the sol having a solid content in the range of 10% by mass to 60% by mass may be used.
상기 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자를 포함하는 졸로서, 예를 들어, MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L(이상, 닛산화학공업(주)제), 및 ELCOM(등록상표) V-8802, 동(同) V-8804(이상, 닛키촉매화성(주)제)를 채용할 수 있다.As a sol comprising silica particles surface-modified with a functional group having the ethylenically unsaturated group, for example, MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC -4130Y, MIBK-AC-2140Z, MIBK-SD-L (above, manufactured by Nissan Chemical Industry Co., Ltd.), and ELCOM (registered trademark) V-8802, the same V-8804 (above, Nikki Catalyst Chemical Co., Ltd.) Note) can be employed.
본 발명의 임프린트용 광경화성 조성물의 (a)성분의 함유량은, 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해, 10질량부 내지 40질량부, 바람직하게는 15질량부 내지 35질량부이다. 이 (a)성분의 함유량이 10질량부보다 적으면, 상기 임프린트용 광경화성 조성물로부터 얻어진 경화물 및 성형체의 상층에 성막되는 반사방지층의 크랙을 억제하지 못할 우려가 있고, 40질량부보다 많으면, 이 경화물 및 성형체에 헤이즈가 발생하여, 투과율이 저하될 우려가 있다.The content of component (a) in the photocurable composition for imprint of the present invention is 10 parts by mass to 40 parts by mass, preferably 15 parts by mass, based on 100 parts by mass of the total of the compounds having an ethylenically unsaturated group contained in the composition. to 35 parts by mass. When the content of the component (a) is less than 10 parts by mass, there is a fear that cracks in the antireflection layer formed on the upper layer of the cured product and the molded article obtained from the photocurable composition for imprint cannot be suppressed, and when it is more than 40 parts by mass, A haze may generate|occur|produce in this hardened|cured material and a molded object, and there exists a possibility that the transmittance|permeability may fall.
상기 (a)성분의 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자는, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The silica particles surface-modified with a functional group having an ethylenically unsaturated group of the component (a) may be used alone or in combination of two or more.
[(b)성분: 에틸렌성 불포화기를 갖는 단관능(메트)아크릴레이트 화합물][(b) component: monofunctional (meth)acrylate compound having an ethylenically unsaturated group]
본 발명의 임프린트용 광경화성 조성물의 (b)성분으로서 사용가능한, 에틸렌성 불포화기를 갖는 단관능(메트)아크릴레이트 화합물은, 이 화합물 1분자 중에 (메트)아크릴로일옥시기를 1개 갖는 화합물이다. 이 단관능(메트)아크릴레이트 화합물로서, 예를 들어, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, n-부틸(메트)아크릴레이트, tert-부틸(메트)아크릴레이트, n-헥실(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, 스테아릴(메트)아크릴레이트, 이소스테아릴(메트)아크릴레이트, 시클로펜틸(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 3,3,5-트리메틸시클로헥실(메트)아크릴레이트, 4-tert-부틸시클로헥실(메트)아크릴레이트, 멘틸(메트)아크릴레이트, 이소보닐(메트)아크릴레이트, 노보닐(메트)아크릴레이트, 1-아다만틸(메트)아크릴레이트, 2-아다만틸(메트)아크릴레이트, 2-메틸아다만탄-2-일(메트)아크릴레이트, 2-에틸아다만탄-2-일(메트)아크릴레이트, 트리시클로[5.2.1.0(2,6)]데카닐(메트)아크릴레이트, 트리시클로[5.2.1.0(2,6)]데카닐옥시에틸(메트)아크릴레이트를 들 수 있다. 그 중에서도, 굴절률의 관점으로부터, 지환구조를 갖는 지환식 (메트)아크릴레이트 화합물을 이용하는 것이 바람직하다.The monofunctional (meth)acrylate compound having an ethylenically unsaturated group usable as component (b) of the photocurable composition for imprint of the present invention is a compound having one (meth)acryloyloxy group in one molecule of the compound. . As this monofunctional (meth)acrylate compound, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 3 , 3,5-trimethylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, menthyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantan-2-yl (meth) ) acrylate, tricyclo[5.2.1.0(2,6)]decanyl (meth)acrylate, and tricyclo[5.2.1.0(2,6)]decanyloxyethyl (meth)acrylate. Especially, it is preferable to use the alicyclic (meth)acrylate compound which has an alicyclic structure from a viewpoint of a refractive index.
상기 에틸렌성 불포화기를 갖는 단관능(메트)아크릴레이트 화합물로서 시판품을 이용할 수도 있고, 예를 들어, 비스코트#155, IBXA, ADMA(이상, 오사카유기화학공업(주)제), NK에스테르 A-IB, 동 IB, A-S, S, S-1800A, A-1800M(이상, 신나카무라화학공업(주)제), 및 판크릴(등록상표) FA-511AS, 동 FA-512AS, 동 FA-513AS, 동 FA-512M, 동 FA-512MT, 동 FA-513M(이상, 히타치화성(주)제)을 들 수 있다.A commercial item can also be used as a monofunctional (meth)acrylate compound which has the said ethylenically unsaturated group, For example, Viscot #155, IBXA, ADMA (above, Osaka Organic Chemical Co., Ltd. product), NK ester A- IB, Copper IB, A-S, S, S-1800A, A-1800M (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), and Pancryl (registered trademark) FA-511AS, Copper FA-512AS, Copper FA-513AS, Copper FA-512M, copper FA-512MT, and copper FA-513M (above, Hitachi Chemical Co., Ltd. product) are mentioned.
본 발명의 임프린트용 광경화성 조성물의 (b)성분의 함유량은, 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해, 10질량부 내지 50질량부, 바람직하게는 20질량부 내지 45질량부이다. 이 (b)성분의 함유량이 10질량부보다 적으면, 상기 임프린트용 광경화성 조성물로부터 얻어진 경화물 및 성형체의 복굴절의 저감효과가 불충분해질 우려가 있고, 50질량부보다 많으면, 이 경화물 및 성형체의 가교밀도가 저하되어 가열처리시에 경화물 및 성형체의 형상이 변형될 우려가 있다.The content of component (b) in the photocurable composition for imprint of the present invention is 10 parts by mass to 50 parts by mass, preferably 20 parts by mass, based on 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition. to 45 parts by mass. When the content of the component (b) is less than 10 parts by mass, the effect of reducing the birefringence of the cured product and the molded article obtained from the photocurable composition for imprinting may become insufficient, and when it is more than 50 parts by mass, the cured product and the molded article of the crosslinking density is lowered, there is a possibility that the shape of the cured product and the molded article may be deformed during heat treatment.
상기 (b)성분의 에틸렌성 불포화기를 갖는 단관능(메트)아크릴레이트 화합물은, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The monofunctional (meth)acrylate compound which has an ethylenically unsaturated group of the said (b) component can be used individually by 1 type or in combination of 2 or more type.
[(c)성분: 에틸렌성 불포화기를 갖는 폴리로탁세인][(c) component: polyrotaxane having an ethylenically unsaturated group]
본 발명의 임프린트용 광경화성 조성물의 (c)성분으로서 사용가능한 에틸렌성 불포화기를 갖는 폴리로탁세인은, 환상분자의 개구부가 직쇄상분자에 의해 꼬챙이상으로 포접된 의폴리로탁세인의 양 단에 상기 환상분자가 탈리하지 않도록 봉쇄기가 배치되고, 이 환상분자가 에틸렌성 불포화기를 갖는다. 이 환상분자가 에틸렌성 불포화기를 갖는 폴리로탁세인의 구성요소인, 환상분자, 직쇄상분자 및 봉쇄기에 대하여, 설명한다.Polyrotaxane having an ethylenically unsaturated group usable as component (c) of the photocurable composition for imprint of the present invention is a pseudopolyrotaxane in which the openings of the cyclic molecules are clasped over skewers by linear molecules at both ends of the polyrotaxane. A blocking group is disposed on the cyclic molecule to prevent the cyclic molecule from detaching, and the cyclic molecule has an ethylenically unsaturated group. The cyclic molecule, the linear molecule, and the blocking group, which are components of the polyrotaxane in which the cyclic molecule has an ethylenically unsaturated group, will be described.
<c-1. 환상분자><c-1. Cyclic Molecules>
(c)성분의 에틸렌성 불포화기를 갖는 폴리로탁세인의 환상분자는, 환상이며 또한 개구부를 가지며, 직쇄상분자에 의해 꼬챙이상으로 포접되는 것이면, 특별히 한정되지 않는다. 이 에틸렌성 불포화기를 갖는 폴리로탁세인의 구성요소는, 환상분자가 바람직하고, 이 에틸렌성 불포화기는 이 환상분자에 직접결합되어 있을 수도, 스페이서를 개재하여 결합되어 있을 수도 있다. 이 스페이서로는, 특별히 한정되지 않으나, 예를 들어, 알킬렌기, 알킬렌옥사이드기, 하이드록시알킬렌기, 카바모일기, 아크릴산에스테르쇄, 폴리알킬렌에테르쇄, 및 폴리알킬렌카보네이트쇄를 들 수 있다. 상기 환상분자로서, 예를 들어, α-시클로덱스트린, β-시클로덱스트린 및 γ-시클로덱스트린으로 이루어지는 군으로부터 선택하는 것이 바람직하다.The cyclic molecule of polyrotaxane having an ethylenically unsaturated group as component (c) is not particularly limited as long as it is cyclic and has an opening and is encapsulated more than a skewer by a linear molecule. A component of the polyrotaxane having an ethylenically unsaturated group is preferably a cyclic molecule, and the ethylenically unsaturated group may be directly bonded to the cyclic molecule or may be bonded via a spacer. The spacer is not particularly limited, and examples thereof include an alkylene group, an alkylene oxide group, a hydroxyalkylene group, a carbamoyl group, an acrylic acid ester chain, a polyalkylene ether chain, and a polyalkylene carbonate chain. have. The cyclic molecule is preferably selected from the group consisting of, for example, ?-cyclodextrin, ?-cyclodextrin, and ?-cyclodextrin.
<c-2. 직쇄상분자><c-2. straight-chain molecules>
(c)성분의 에틸렌성 불포화기를 갖는 폴리로탁세인의 직쇄상분자는, 이용하는 환상분자의 개구부에 꼬챙이상으로 포접될 수 있는 것이면, 특별히 한정되지 않는다. 예를 들어, 이 직쇄상분자로서, 특허문헌 4에 예시된 화합물(폴리머)을 들 수 있고, 그들 중에서, 폴리에틸렌글리콜, 폴리이소프렌, 폴리이소부틸렌, 폴리부타디엔, 폴리프로필렌글리콜, 폴리테트라하이드로푸란, 폴리디메틸실록산, 폴리에틸렌, 폴리프로필렌, 폴리비닐알코올 및 폴리비닐메틸에테르로 이루어지는 군으로부터 선택되는 폴리머가 바람직하고, 특히 폴리에틸렌글리콜이 바람직하다.The linear molecule of polyrotaxane having an ethylenically unsaturated group as the component (c) is not particularly limited as long as it can be entrapped more than a skewer in the opening of the cyclic molecule to be used. For example, as this linear molecule, the compound (polymer) illustrated in patent document 4 is mentioned, Among them, polyethyleneglycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran Polymers selected from the group consisting of , polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether are preferable, and polyethylene glycol is particularly preferable.
상기 직쇄상분자는, 그의 중량평균분자량이 1,000 이상, 바람직하게는 3,000~100,000, 보다 바람직하게는 6,000~50,000이다. (c)성분의 에틸렌성 불포화기를 갖는 폴리로탁세인에 있어서, (환상분자, 직쇄상분자)의 조합이, (α-시클로덱스트린유래, 폴리에틸렌글리콜유래)인 것이 바람직하다.The linear molecule has a weight average molecular weight of 1,000 or more, preferably 3,000 to 100,000, and more preferably 6,000 to 50,000. In polyrotaxane having an ethylenically unsaturated group as component (c), it is preferable that the combination of (cyclic molecule, linear molecule) is (derived from α-cyclodextrin, derived from polyethylene glycol).
<c-3. 봉쇄기><c-3. blockade>
(c)성분의 에틸렌성 불포화기를 갖는 폴리로탁세인의 봉쇄기는, 의폴리로탁세인의 양 단에 배치되며, 이용하는 환상분자가 탈리하지 않도록 작용하는 기이면, 특별히 한정되지 않는다. 예를 들어, 봉쇄기로서, 특허문헌 4에 예시된 봉쇄기를 들 수 있고, 그들 중에서, 디니트로페닐기류, 시클로덱스트린류, 아다만틸기류, 트리틸기류, 플루오레세인(フルオレセイン)류, 실세스퀴옥산류, 및 피렌류로 이루어지는 군으로부터 선택되는 봉쇄기가 바람직하고, 보다 바람직하게는 아다만틸기류 또는 시클로덱스트린류이다. 이 봉쇄기는, 예를 들어 -NH-C(=O)-기를 개재하여, 상기 직쇄상분자와 결합되어 있다.The blocking group of polyrotaxane having an ethylenically unsaturated group in the component (c) is not particularly limited as long as it is a group that is disposed at both ends of the polyrotaxane and acts so that the cyclic molecule used does not detach. For example, as a blocking group, the blocking group illustrated in patent document 4 is mentioned, Among them, dinitrophenyl group, cyclodextrins, adamantyl group, trityl group, fluorescein (fluorescein), and a thread A blocking group selected from the group consisting of sesquioxanes and pyrenes is preferable, and adamantyl groups or cyclodextrins are more preferable. This blocking group is bonded to the linear molecule via, for example, a -NH-C(=O)- group.
상기 에틸렌성 불포화기를 갖는 폴리로탁세인으로서 시판품을 이용할 수도 있고, 예를 들어, 세름(SeRM, セルム)(등록상표) 슈퍼폴리머 SA1303P, 동 SA2403P, 동 SA3403P, 동 SM1303P, 동 SM2403P, 동 3403P(이상, 어드밴스드·소프트머테리얼즈(주)제)를 들 수 있다.As the polyrotaxane having an ethylenically unsaturated group, a commercially available product may be used, for example, SeRM (SeRM, Serm) (registered trademark) superpolymer SA1303P, SA2403P, SA3403P, SM1303P, SM2403P, 3403P ( As mentioned above, Advanced Soft Materials Co., Ltd. product) is mentioned.
본 발명의 임프린트용 광경화성 조성물의 (c)성분의 함유량은, 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해, 1질량부 내지 10질량부, 바람직하게는 3질량부 내지 7질량부이다. 이 (c)성분의 함유량이 1질량부보다 적으면, 유기용매를 이용한 현상공정에 있어서 경화물에 크랙이 발생하는 것을 억제하는 효과가 불충분해질 우려가 있고, 10질량부보다 많으면, 저탄성률화로 인해 가열시의 이 경화물 및 성형체의 형상변화가 증가할 우려가 있다.The content of component (c) in the photocurable composition for imprints of the present invention is 1 to 10 parts by mass, preferably 3 parts by mass, based on 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition. to 7 parts by mass. When the content of the component (c) is less than 1 part by mass, the effect of suppressing the occurrence of cracks in the cured product in the developing step using an organic solvent may become insufficient. For this reason, there is a possibility that the shape change of the cured product and the molded product upon heating may increase.
상기 (c)성분의 에틸렌성 불포화기를 갖는 폴리로탁세인은, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The polyrotaxane which has an ethylenically unsaturated group of the said (c) component can be used individually by 1 type or in combination of 2 or more type.
[(d)성분: 광라디칼개시제][(d) component: photoradical initiator]
본 발명의 임프린트용 광경화성 조성물의 (d)성분으로서 사용가능한 광라디칼개시제로서, 예를 들어, 알킬페논류, 벤조페논류, 미힐러(Michler)의 케톤류, 아실포스핀옥사이드류, 벤조일벤조에이트류, 옥심에스테르류, 테트라메틸티우람모노설파이드류 및 티옥산톤류를 들 수 있고, 특히, 광개열형의 광라디칼중합개시제가 바람직하다. 상기 광라디칼개시제로서 시판품, 예를 들어, IRGACURE(등록상표) 184, 동 369, 동 651, 동 500, 동 819, 동 907, 동 784, 동 2959, 동 CGI1700, 동 CGI1750, 동 CGI1850, 동 CG24-61, 동 TPO, 동 1116, 동 1173(이상, BASF재팬(주)제), 및 ESACURE KIP150, 동 KIP65LT, 동 KIP100F, 동 KT37, 동 KT55, 동 KTO46, 동 KIP75(이상, Lamberti사제)를 채용할 수 있다.As a photoradical initiator usable as (d) component of the photocurable composition for imprint of the present invention, for example, alkylphenones, benzophenones, Michler's ketones, acylphosphine oxides, benzoylbenzoate and oxime esters, tetramethylthiuram monosulfides and thioxanthones, and in particular, photo-cleavage-type photo-radical polymerization initiators are preferable. Commercial products as the photoradical initiator, for example, IRGACURE (registered trademark) 184, copper 369, copper 651, copper 500, copper 819, copper 907, copper 784, copper 2959, copper CGI1700, copper CGI1750, copper CGI1850, copper CG24 -61, copper TPO, copper 1116, copper 1173 (above, manufactured by BASF Japan), and ESACURE KIP150, copper KIP65LT, copper KIP100F, copper KT37, copper KT55, copper KTO46, copper KIP75 (above, manufactured by Lamberti) can be hired
본 발명의 임프린트용 광경화성 조성물의 (d)성분의 함유량은, 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해 0.1질량부 내지 5질량부, 바람직하게는 0.5질량부 내지 3질량부이다. 이 (d)성분의 함유량이 0.1질량부보다 적으면, 상기 임프린트용 광경화성 조성물로부터 얻어지는 경화물 및 성형체의 강도가 저하될 우려가 있고, 5질량부보다 많으면, 이 경화물 및 성형체의 내열황변성이 악화될 우려가 있다.The content of component (d) in the photocurable composition for imprint of the present invention is 0.1 parts by mass to 5 parts by mass, preferably 0.5 parts by mass to 100 parts by mass of the total of the compounds having an ethylenically unsaturated group contained in the composition. 3 parts by mass. When the content of the component (d) is less than 0.1 parts by mass, there is a fear that the strength of the cured product obtained from the photocurable composition for imprint and the molded body may decrease, and when it is more than 5 parts by mass, the heat-resistant sulfur of the cured product and the molded product There is a risk that degeneration may worsen.
상기 (d)성분의 광라디칼개시제는, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The photoradical initiator of the said (d)component can be used individually by 1 type or in combination of 2 or more type.
[(e)성분: 에틸렌성 불포화기를 갖는, 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물][(e) component: the polyfunctional (meth)acrylate compound which has an ethylenically unsaturated group and does not contain an aromatic ring]
본 발명의 임프린트용 광경화성 조성물의 (e)성분으로서 사용가능한, 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물은, 이 화합물 1분자 중에 (메트)아크릴로일옥시기를 적어도 2개 가지며, 상기 (c)성분의 폴리로탁세인 및 후술하는 (f)성분의 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물을 제외하는, 방향환을 포함하지 않는 화합물이다. 여기서 방향환이란, 휘켈규칙을 만족하는 탄소환 또는 복소환, 예를 들어, 벤젠, 나프탈렌, 아줄렌, 안트라센, 테트라센, 펜타센, 페난트렌, 피렌, 푸란, 티오펜, 피롤, 피라졸, 이미다졸, 옥사졸, 티아졸, 피리딘, 피리다진, 피리미딘, 피라진 및 트리아진을 들 수 있다. 따라서, 방향환을 포함하지 않는다는 것은, 휘켈규칙을 만족하는 탄소환 또는 복소환을 포함하지 않는 것을 의미한다. 이 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물로서, 예를 들어, 에틸렌글리콜디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 에톡시화트리메틸올프로판트리(메트)아크릴레이트, 에톡시화글리세린트리(메트)아크릴레이트, 에톡시화펜타에리스리톨테트라(메트)아크릴레이트, 에톡시화디펜타에리스리톨헥사(메트)아크릴레이트, 폴리글리세린모노에틸렌옥사이드폴리(메트)아크릴레이트, 디펜타에리스리톨헥사(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 펜타에리스리톨트리(메트)아크릴레이트, 트리메틸올프로판트리(메트)아크릴레이트, 트리시클로데칸디메탄올디(메트)아크릴레이트, 1,3-아다만탄디올디(메트)아크릴레이트, 1,4-시클로헥산디메탄올디(메트)아크릴레이트, 1,4-부탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 1,9-노난디올디(메트)아크릴레이트, 및 이소시아눌산트리스(2-아크릴로일옥시에틸)을 들 수 있다.The polyfunctional (meth)acrylate compound not containing an aromatic ring, which can be used as component (e) of the photocurable composition for imprint of the present invention, has at least two (meth)acryloyloxy groups in one molecule of the compound. It is a compound which does not contain an aromatic ring except the polyrotaxane of the said (c) component, and the urethane (meth)acrylate compound or epoxy (meth)acrylate compound of the (f) component mentioned later. Here, the aromatic ring refers to a carbocyclic or heterocyclic ring satisfying Hückel's rule, for example, benzene, naphthalene, azulene, anthracene, tetracene, pentacene, phenanthrene, pyrene, furan, thiophene, pyrrole, pyrazole, imidazole, oxazole, thiazole, pyridine, pyridazine, pyrimidine, pyrazine and triazine. Accordingly, the absence of an aromatic ring means that the carbocyclic or heterocyclic ring satisfying the Hückel rule is not included. As a polyfunctional (meth)acrylate compound which does not contain this aromatic ring, For example, ethylene glycol di(meth)acrylate, polyethyleneglycol di(meth)acrylate, ethoxylated trimethylol propane tri(meth)acrylate , ethoxylated glycerin tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, polyglycerol monoethylene oxide poly (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,3 -Adamantanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylic rate, 1,9-nonanediol di(meth)acrylate, and tris(2-acryloyloxyethyl) isocyanurate.
상기 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물로서 시판품을 이용할 수도 있고, 예를 들어, NK에스테르 A-200, 동 A-400, 동 A-600, 동 A-1000, 동 A-9300, 동 A-9300-1CL, 동 1G, 동 2G, 동 3G, 동 4G, 동 9G, 동 14G, 동 23G, 동 A-GLY-3E, 동 A-GLY-9E, 동 A-GLY-20E, 동 A-TMPT-3EO, 동 A-TMPT-9EO, 동 ATM-4E, 동 ATM-35E, 동 A-DPH, 동 A-TMPT, 동 A-DCP, 동 A-HD-N, 동 A-NOD-N, 동 AD-TMP, 동 A-DOG, 동 TMPT, 동 DCP, 동 NPG, 동 HD-N, 동 NOD-N, 동 D-TMP(이상, 신나카무라화학공업(주)제), KAYARAD(등록상표) DPHA, 동 NPGDA, 동 PET30, 동 DPEA-12, 동 PEG400DA, 동 RP-1040(이상, 일본화약(주)제), M-210, M-350(이상, 토아합성(주)제)을 들 수 있다.A commercial item can also be used as a polyfunctional (meth)acrylate compound which does not contain the said aromatic ring, For example, NK ester A-200, copper A-400, copper A-600, copper A-1000, copper A- 9300, Building A-930-1CL, Building 1G, Building 2G, Building 3G, Building 4G, Building 9G, Building 14G, Building 23G, Building A-GLY-3E, Building A-GLY-9E, Building A-GLY-20E , A-TMPT-3EO, A-TMPT-9EO, ATM-4E, ATM-35E, A-DPH, A-TMPT, A-DCP, A-HD-N, A- NOD-N, copper AD-TMP, copper A-DOG, copper TMPT, copper DCP, copper NPG, copper HD-N, copper NOD-N, copper D-TMP (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) DPHA, copper NPGDA, copper PET30, copper DPEA-12, copper PEG400DA, copper RP-1040 (above, manufactured by Nippon Kayaku Co., Ltd.), M-210, M-350 (above, Toa Synthetic Co., Ltd.) ) can be mentioned.
본 발명의 임프린트용 광경화성 조성물이 (e)성분을 포함하는 경우, 그 함유량은, 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해, 5질량부 내지 50질량부, 바람직하게는 5질량부 내지 30질량부이다. 이 (e)성분의 함유량이 5질량부보다 적으면, 상기 임프린트용 광경화성 조성물로부터 얻어진 경화물 및 성형체의 가교밀도가 저하되어 가열처리시에 경화물 및 성형체의 형상이 변형되고, 50질량부보다 많으면, 이 경화물 및 성형체의 복굴절의 저감효과가 불충분해질 우려가 있다.When the photocurable composition for imprints of the present invention contains component (e), the content thereof is preferably 5 parts by mass to 50 parts by mass, with respect to 100 parts by mass of the total of the compounds having an ethylenically unsaturated group contained in the composition. Preferably, it is 5 mass parts - 30 mass parts. When the content of the component (e) is less than 5 parts by mass, the crosslinking density of the cured product and the molded product obtained from the photocurable composition for imprint is lowered, and the shape of the cured product and the molded product is deformed during heat treatment, and 50 parts by mass When more, there exists a possibility that the effect of reducing the birefringence of this hardened|cured material and a molded object may become inadequate.
상기 (e)성분의 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물은, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The polyfunctional (meth)acrylate compound which does not contain the aromatic ring of the said (e) component can be used individually by 1 type or in combination of 2 or more type.
[(f)성분: 에틸렌성 불포화기를 갖는, 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물][(f) component: urethane (meth)acrylate compound or epoxy (meth)acrylate compound having an ethylenically unsaturated group]
본 발명의 임프린트용 광경화성 조성물의 (f)성분으로서 사용가능한 우레탄(메트)아크릴레이트 화합물은, 1분자 중에 (메트)아크릴로일옥시기를 적어도 2개 및 “-NH-C(=O)O-”로 표시되는 우레탄구조를 적어도 2개 갖는 화합물이다. 이 우레탄(메트)아크릴레이트 화합물로서, 예를 들어, EBECRYL(등록상표) 230, 동 270, 동 280/15IB, 동 284, 동 4491, 동 4683, 동 4858, 동 8307, 동 8402, 동 8411, 동 8804, 동 8807, 동 9270, 동 8800, 동 294/25HD, 동 4100, 동 4220, 동 4513, 동 4738, 동 4740, 동 4820, 동 8311, 동 8465, 동 9260, 동 8701, KRM7735, 동 8667, 동 8296(이상, 다이셀·올넥스(주)제), UV-2000B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA, UV-3300B, UV-3310B, UV-3500B, UV-3520EA, UV-3700B, UV-6640B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE(이상, 일본합성화학(주)제), UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G(이상, 쿄에이샤화학(주)제), M-1100, M-1200(이상, 토아합성(주)제), 및 NK올리고 U-2PPA, 동 U-6LPA, 동 U-200PA, U-200PA, 동 U-160TM, 동 U-290TM, 동 UA-4200, 동 UA-4400, 동 UA-122P, 동 UA-7100, 동 UA-W2A(이상, 신나카무라화학공업(주)제)를 들 수 있다.The urethane (meth)acrylate compound usable as component (f) of the photocurable composition for imprint of the present invention contains at least two (meth)acryloyloxy groups and “-NH-C(=O)O” in one molecule. -" is a compound having at least two urethane structures. As this urethane (meth)acrylate compound, For example, EBECRYL (trademark) 230, copper 270, copper 280/15IB, copper 284, copper 4491, copper 4683, copper 4858, copper 8307, copper 8402, copper 8411, 8804, 8807, 9270, 8800, 294/25HD, 4100, 4220, 4513, 4738, 4740, 4820, 8311, 8465, 9260, 8701, KRM7735, KRM7735 8667, Copper 8296 (above, manufactured by Daicel Allnex Co., Ltd.), UV-2000B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA, UV-3300B, UV-3310B, UV-3500B, UV-3520EA, UV-3700B, UV-6640B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE (above, manufactured by Nippon Synthetic Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I , UA-510H, UF-8001G (above, manufactured by Kyoeisha Chemical Co., Ltd.), M-1100, M-1200 (above, manufactured by Toa Synthesis Co., Ltd.), and NK oligo U-2PPA, copper U-6LPA U-200PA, U-200PA, U-160TM, U-290TM, UA-4200, UA-4400, UA-122P, UA-7100, UA-W2A (above, Shin-Nakamura Chemical) Industrial Co., Ltd. product) is mentioned.
본 발명의 임프린트용 광경화성 조성물의 (f)성분으로서 사용가능한 에폭시(메트)아크릴레이트 화합물은, 1분자 중에 에폭시환을 적어도 2개 갖는 화합물과 (메트)아크릴산을 반응시킨 에스테르이다. 이 에폭시(메트)아크릴레이트 화합물로서, 예를 들어, EBECRYL(등록상표) 645, 동 648, 동 860, 동 3500, 동 3608, 동 3702, 동 3708(이상, 다이셀·올넥스(주)제), DA-911M, DA-920, DA-931, DA-314, DA-212(이상, 나가세켐텍스(주)제), HPEA-100(케이에스엠(주)제), 및 유니딕(등록상표) V-5500, 동 V-5502, 동 V-5508(이상, DIC(주)제)을 들 수 있다.The epoxy (meth)acrylate compound usable as component (f) of the photocurable composition for imprint of the present invention is an ester obtained by reacting (meth)acrylic acid with a compound having at least two epoxy rings in one molecule. As this epoxy (meth)acrylate compound, For example, EBECRYL (trademark) 645, copper 648, copper 860, copper 3500, copper 3608, copper 3702, copper 3708 (above, Daicel Allnex Co., Ltd. product) ), DA-911M, DA-920, DA-931, DA-314, DA-212 (above, manufactured by Nagase Chemtex Co., Ltd.), HPEA-100 (manufactured by KSM Co., Ltd.), and Unidic (registered) Trademarks) V-5500, V-5502, V-5508 (above, manufactured by DIC Corporation).
상기 (f)성분의 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물로서, 이 화합물 1분자 중에 (메트)아크릴로일옥시기를 2개 또는 3개 갖는 화합물이 바람직하게 이용된다.As the urethane (meth)acrylate compound or epoxy (meth)acrylate compound of the component (f), a compound having two or three (meth)acryloyloxy groups in one molecule of the compound is preferably used.
본 발명의 임프린트용 광경화성 조성물이 (f)성분을 포함하는 경우, 그 함유량은, 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해, 5질량부 내지 50질량부, 바람직하게는 5질량부 내지 30질량부이다. 이 (f)성분의 함유량이 5질량부보다 적으면, 상기 임프린트용 광경화성 조성물로부터 얻어진 경화물 및 성형체가 취성화함으로써 가열시에 이 경화물 및 성형체의 내크랙성이 저하될 우려가 있고, 50질량부보다 많으면, 가교밀도의 저하로 인해 가열시의 이 경화물 및 성형체의 형상변화가 증가할 우려가 있다.When the photocurable composition for imprints of the present invention contains component (f), the content thereof is preferably 5 parts by mass to 50 parts by mass, with respect to 100 parts by mass of the total of the compounds having an ethylenically unsaturated group contained in the composition. Preferably, it is 5 mass parts - 30 mass parts. When the content of the component (f) is less than 5 parts by mass, the cured product and the molded product obtained from the photocurable composition for imprinting become brittle, so that the crack resistance of the cured product and the molded product during heating may decrease, When it is more than 50 mass parts, there exists a possibility that the shape change of this hardened|cured material and a molded object at the time of heating may increase due to the fall of a crosslinking density.
상기 (f)성분의 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물은, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The urethane (meth)acrylate compound or the epoxy (meth)acrylate compound of the said (f) component can be used individually by 1 type or in combination of 2 or more type.
[(g)성분: 페놀계 산화방지제][(g) component: phenolic antioxidant]
본 발명의 임프린트용 광경화성 조성물의 (g)성분으로서 사용가능한 페놀계 산화방지제로서, 예를 들어, IRGANOX(등록상표) 245, 동 1010, 동 1035, 동 1076, 동 1135(이상, BASF재팬(주)제), SUMILIZER(등록상표) GA-80, 동 GP, 동 MDP-S, 동 BBM-S, 동 WX-R(이상, 스미토모화학(주)제), 및 아데카스타브(등록상표) AO-20, 동 AO-30, 동 AO-40, 동 AO-50, 동 AO-60, 동 AO-80, 동 AO-330(이상, (주)ADEKA제)을 들 수 있다.As a phenolic antioxidant usable as (g) component of the photocurable composition for imprint of the present invention, for example, IRGANOX (registered trademark) 245, 1010, 1035, 1076, and 1135 (above, BASF Japan) Co., Ltd.), SUMILIZER (registered trademark) GA-80, copper GP, copper MDP-S, copper BBM-S, copper WX-R (above, manufactured by Sumitomo Chemical Co., Ltd.), and ADEKA STAB (registered trademark) AO-20, copper AO-30, copper AO-40, copper AO-50, copper AO-60, copper AO-80, copper AO-330 (above, manufactured by ADEKA) are mentioned.
본 발명의 임프린트용 광경화성 조성물이 (g)성분을 함유하는 경우, 그 함유량은, 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해, 0.05질량부 내지 3질량부, 바람직하게는 0.1질량부 내지 1질량부이다.When the photocurable composition for imprints of the present invention contains component (g), the content thereof is 0.05 parts by mass to 3 parts by mass, preferably 0.1 parts by mass, based on 100 parts by mass of the total of the compounds having an ethylenically unsaturated group. to 1 part by mass.
상기 (g)성분의 페놀계 산화방지제는, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The phenolic antioxidant of the said (g) component can be used individually by 1 type or in combination of 2 or more type.
[(h)성분: 설파이드계 산화방지제][(h) component: sulfide-based antioxidant]
본 발명의 임프린트용 광경화성 조성물의 (h)성분으로서 사용가능한 설파이드계 산화방지제로서, 예를 들어, 아데카스타브(등록상표) AO-412S, 동 AO-503(이상, (주)ADEKA제), IRGANOX(등록상표) PS802, 동 PS800(이상, BASF사제), 및 SUMILIZER(등록상표) TP-D(스미토모화학(주)제)를 들 수 있다.As a sulfide-based antioxidant usable as component (h) of the photocurable composition for imprint of the present invention, for example, ADEKASTAB (registered trademark) AO-412S, AO-503 (above, manufactured by ADEKA Corporation) , IRGANOX (trademark) PS802, copper PS800 (above, manufactured by BASF), and SUMILIZER (registered trademark) TP-D (manufactured by Sumitomo Chemical Co., Ltd.).
본 발명의 임프린트용 광경화성 조성물이 (h)성분을 포함하는 경우, 그 함유량은, 이 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해, 0.1질량부 내지 3질량부, 바람직하게는 0.1질량부 내지 1질량부이다.When the photocurable composition for imprint of the present invention contains component (h), the content thereof is 0.1 parts by mass to 3 parts by mass, preferably with respect to 100 parts by mass of the total of the compounds having an ethylenically unsaturated group contained in the composition. Preferably it is 0.1 mass part - 1 mass part.
상기 (h)성분의 설파이드계 산화방지제는, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The sulfide-type antioxidant of the said (h) component can be used individually by 1 type or in combination of 2 or more type.
<기타 첨가제><Other additives>
추가로 본 발명의 임프린트용 광경화성 조성물은, 본 발명의 효과를 손상시키지 않는 한, 필요에 따라, 연쇄이동제, 산화방지제, 자외선흡수제, 광안정화제, 레벨링제, 레올로지조정제, 실란커플링제 등의 접착보조제, 안료, 염료, 소포제 등을 함유할 수 있다.In addition, the photocurable composition for imprint of the present invention may contain, if necessary, a chain transfer agent, antioxidant, ultraviolet absorber, light stabilizer, leveling agent, rheology modifier, silane coupling agent, etc., as long as the effects of the present invention are not impaired. Adhesive aids, pigments, dyes, antifoaming agents and the like may be contained.
<임프린트용 광경화성 조성물의 조제방법><Method for preparing photocurable composition for imprint>
본 발명의 임프린트용 광경화성 조성물의 조제방법은, 특별히 한정되지 않는다. 조제법으로는, 예를 들어, (a)성분, (b)성분, (c)성분 및 (d)성분, 그리고 필요에 따라 (e)성분 및/또는 (f)성분, (g)성분 및/또는 (h)성분을 소정의 비율로 혼합하여, 균일한 용액으로 하는 방법을 들 수 있다.The preparation method of the photocurable composition for imprints of this invention is not specifically limited. As a preparation method, for example, (a) component, (b) component, (c) component, and (d) component, and as needed (e) component and/or (f) component, (g) component and/ Or the method of mixing (h) component in a predetermined ratio to make a uniform solution is mentioned.
또한, 용액으로 조제한 본 발명의 임프린트용 광경화성 조성물은, 구멍직경이 0.1μm 내지 5μm인 필터 등을 이용하여 여과한 후, 사용하는 것이 바람직하다.Moreover, it is preferable to use the photocurable composition for imprints of this invention prepared as a solution after filtering using the filter etc. which are 0.1 micrometer - 5 micrometers in pore diameter.
<경화물><Cured material>
본 발명의 임프린트용 광경화성 조성물을, 노광(광경화)하여, 경화물을 얻을 수 있으며, 본 발명은 이 경화물도 대상으로 한다. 노광하는 광선으로는, 예를 들어, 자외선, 전자선 및 X선을 들 수 있다. 자외선조사에 이용하는 광원으로는, 예를 들어, 태양광선, 케미칼램프, 저압수은등, 고압수은등, 메탈할라이드램프, 크세논램프, 및 UV-LED를 사용할 수 있다. 또한, 노광 후, 경화물의 물성을 안정화시키기 위해 포스트베이크를 실시할 수도 있다. 포스트베이크의 방법으로는, 특별히 한정되지 않으나, 통상, 핫플레이트, 오븐 등을 사용하여, 50℃ 내지 260℃, 1분 내지 24시간의 범위에서 행해진다.A cured product can be obtained by exposing (photocuring) the photocurable composition for imprints of the present invention, and the present invention also covers this cured product. As a light beam to be exposed, an ultraviolet-ray, an electron beam, and X-ray are mentioned, for example. As a light source used for ultraviolet irradiation, for example, sunlight, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, and UV-LED can be used. In addition, after exposure, a post-baking may be performed in order to stabilize the physical properties of the cured product. Although it does not specifically limit as a method of a post-baking, Usually, using a hotplate, oven, etc., 50 degreeC - 260 degreeC, it is performed in the range of 1 minute - 24 hours.
본 발명의 임프린트용 광경화성 조성물을 광경화함으로써 얻어지는 경화물은, 아베수νD가 53 이상으로 높은 것이며, 파장 589nm(D선)에 있어서의 굴절률nD가 1.49 이상이다. 그러므로, 본 발명의 임프린트용 광경화성 조성물은, 수지렌즈형성용으로서 호적하게 사용할 수 있다.The hardened|cured material obtained by photocuring the photocurable composition for imprints of this invention is a thing as high as an Abbe's number (nu) D 53 or more, and refractive index n D in wavelength 589 nm (D line) is 1.49 or more. Therefore, the photocurable composition for imprint of the present invention can be suitably used for forming a resin lens.
<성형체><Molded article>
본 발명의 임프린트용 광경화성 조성물은, 예를 들어 임프린트성형법을 사용함으로써, 경화물의 형성과 병행하여 각종 성형체를 용이하게 제조할 수 있다. 성형체를 제조하는 방법으로는, 예를 들어 접합하는 지지체와 주형 사이의 공간, 또는 분할가능한 주형의 내부의 공간에 본 발명의 임프린트용 광경화성 조성물을 충전하는 공정, 이 공간에 충전된 임프린트용 광경화성 조성물을 노광하여 광경화하는 공정, 이 광경화하는 공정에 의해 얻어진 광경화물을 취출하여 이형하는 공정, 그리고, 이 광경화물을, 이 이형하는 공정의 전, 중도 또는 후에 있어서 가열하는 공정을 포함하는 방법을 들 수 있다. 그 때, 상기 광경화하는 공정에 의해 얻어진 광경화물을 취출하여 이형하는 공정의 후, 상기 가열하는 공정의 전에 유기용매로 미경화부를 세정·제거하는 현상공정을 추가로 포함할 수도 있다. 상기 미경화부를 제작하는 수법으로는, 특별히 제한은 없으나, 마스크노광, 투영노광 등에 의해 소정의 위치만을 노광함으로써, 노광되지 않는 부분 즉 미경화부를 제작할 수 있다. 추가로, 필요에 따라, 상기 현상공정 후의 광경화물을, 재차 노광하여 광경화할 수도 있다.The photocurable composition for imprint of the present invention can easily manufacture various molded articles in parallel with formation of a cured product by using, for example, an imprint molding method. As a method of manufacturing a molded article, for example, a step of filling the space between the support to be joined and the mold or the space inside the divisible mold with the photocurable composition for imprint of the present invention, the imprinting sight filled in this space A step of exposing the chemical composition to photocuring, a step of taking out the photocured obtained by the photocuring step and releasing it, and a step of heating the photocured before, during or after the releasing step. how to do it In that case, after the step of taking out and releasing the photocured obtained by the photocuring step, a developing step of washing and removing the uncured portion with an organic solvent before the heating step may be further included. There is no particular limitation on a method for producing the uncured portion, but an unexposed portion, that is, an uncured portion, can be produced by exposing only a predetermined position by mask exposure, projection exposure, or the like. In addition, if necessary, the photocured material after the above-mentioned developing step may be exposed again to photocuring.
상기 노광하여 광경화하는 공정은, 상기 서술한 경화물을 얻기 위한 조건을 적용하여 실시할 수 있다. 나아가, 상기 광경화물을 가열하는 공정의 조건으로는, 특별히 한정되지 않으나, 통상, 50℃ 내지 260℃, 1분 내지 24시간의 범위에서 적당히 선택된다. 또한, 가열수단으로는, 특별히 한정되지 않으나, 예를 들어, 핫플레이트 및 오븐을 들 수 있다. 이러한 방법에 의해 제조된 성형체는, 카메라모듈용 렌즈로서 호적하게 사용할 수 있다.The said process of exposing and photocuring can apply and implement the conditions for obtaining the hardened|cured material mentioned above. Furthermore, the conditions of the step of heating the photocured material are not particularly limited, but are usually appropriately selected in the range of 50°C to 260°C and 1 minute to 24 hours. In addition, the heating means is not particularly limited, and examples thereof include a hot plate and an oven. The molded article produced by such a method can be suitably used as a lens for a camera module.
실시예Example
이하, 실시예를 들어, 본 발명을 보다 구체적으로 설명하나, 본 발명은 하기의 실시예로 한정되는 것은 아니다. 한편, 하기 실시예 및 비교예에 있어서, 시료의 조제 및 물성의 분석에 이용한 장치 및 조건은, 이하와 같다.Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. In addition, in the following Examples and Comparative Examples, the apparatus and conditions used for preparation of a sample and analysis of physical properties are as follows.
(1) 교반탈포기(1) Stirred degassing machine
장치: (주)싱키제 자전·공전믹서 아와토리렌타로(등록상표) ARE-310 Apparatus: Rotating and revolving mixer Awatori Rentaro (registered trademark) ARE-310 made by Thinky Co., Ltd.
(2) UV노광(2) UV exposure
장치: 씨씨에스(주)제 배치식 UV-LED조사장치(파장 365nm)Device: CCS Co., Ltd. batch type UV-LED irradiation device (wavelength 365nm)
(3) 굴절률nD, 아베수νD (3) refractive index n D , Abbe number ν D
장치: 안톤파르사제 다파장굴절계 Abbemat MWApparatus: Abbemat MW multi-wavelength refractometer manufactured by Antonfar Inc.
측정온도: 23℃Measured temperature: 23℃
(4) 복굴절측정(4) Birefringence measurement
장치: (주)포토닉래티스제, WPA-100Device: manufactured by Photonic Lattice Co., Ltd., WPA-100
조건: 파장=543nm, 온도=실온Condition: Wavelength=543nm, Temperature=Room Temperature
(5) 디지털마이크로스코프(유기용매를 이용한 현상공정에 있어서의 내크랙성의 평가)(5) Digital microscope (evaluation of crack resistance in developing process using organic solvent)
장치: (주)하이록스제 KH-7700, MXG-2500REZDevice: Hyrox KH-7700, MXG-2500REZ
조건: 반사(암시야), Low-Range, 100배Conditions: Reflection (darkfield), Low-Range, 100x
(6) 반사방지층의 성막(6) Formation of antireflection layer
장치: 신코정기(주)제 SRV4300시리즈Device: SRV4300 series made by Shinko Seiki Co., Ltd.
방식: RF스퍼터·마그네트론방식Method: RF sputter/magnetron method
조건: 타겟재=SiO2, 타겟·기판간의 수직거리=100mm,Conditions: target material = SiO 2 , vertical distance between target and substrate = 100 mm,
온도=실온, 스퍼터시간=29분Temperature = room temperature, sputtering time = 29 minutes
(7) 광학현미경(반사방지막의 관찰)(7) Optical microscope (observation of anti-reflection film)
장치: (주)키엔스제 VHX-1000, VH-Z1000RDevice: VHX-1000, VH-Z1000R manufactured by Keyence Co., Ltd.
조건: 반사(명시야), 대물 500배Conditions: reflection (brightfield), 500x objective
(8) 렌즈성형(8) Lens molding
장치: 메이쇼기공(주)제 6인치 대응 나노임프린터Apparatus: Meisho Machinery Co., Ltd. 6-inch compatible nanoimprinter
광원: 고압수은등, i선밴드패스필터 HB0365(아사히분광(주)제)를 개재하여 노광Light source: high pressure mercury lamp, exposure through i-line band pass filter HB0365 (manufactured by Asahi Spectroscopy Co., Ltd.)
성형조건: 압착압 100N, 20mW/cm2×300초Molding conditions: 100N compression pressure, 20mW/cm 2 × 300 seconds
(9) 렌즈높이 측정(9) Lens height measurement
장치: 미타카광기(주)제 비접촉 표면성상 측정장치 PF-60Apparatus: PF-60, non-contact surface property measurement device manufactured by Mitaka Kwang Ki Co., Ltd.
각 제조예, 실시예 및 비교예에 있어서 사용한 화합물의 공급원은 이하와 같다.The supply source of the compound used in each manufacture example, an Example, and a comparative example is as follows.
A-DCP: 신나카무라화학공업(주)제 상품명: NK에스테르 A-DCPA-DCP: Shin-Nakamura Chemical Industry Co., Ltd. Product name: NK Ester A-DCP
MEK-AC-2140Z: 닛산화학공업(주)제 상품명: 오가노실리카졸 MEK-AC-2140ZMEK-AC-2140Z: Nissan Chemical Industry Co., Ltd. product name: Organosilicasol MEK-AC-2140Z
FA-513AS: 히타치화성(주)제 상품명: 판크릴(등록상표) FA-513ASFA-513AS: Hitachi Chemical Co., Ltd. Product name: Pancryl (registered trademark) FA-513AS
FA-512AS: 히타치화성(주)제 상품명: 판크릴(등록상표) FA-512ASFA-512AS: Hitachi Chemical Co., Ltd. Product name: Pancryl (registered trademark) FA-512AS
SA1303P: 어드밴스드·소프트머테리얼즈(주)제 상품명: 세름(등록상표) 슈퍼폴리머 SA1303PSA1303P: Advanced Soft Materials Co., Ltd. Product name: Serum (registered trademark) Superpolymer SA1303P
IBA: 오사카유기화학공업(주)제 상품명: IBXAIBA: Osaka Organic Chemical Industry Co., Ltd. Product name: IBXA
UA-4200: 신나카무라화학공업(주)제 상품명: NK올리고 UA-4200UA-4200: Shin-Nakamura Chemical Industry Co., Ltd. Product Name: NK Oligo UA-4200
I184: BASF사제 상품명: Irgacure(등록상표) 184I184: BASF Corporation Product name: Irgacure (registered trademark) 184
I245: BASF사제 상품명: Irganox(등록상표) 245I245: BASF company brand name: Irganox (registered trademark) 245
AO-503: (주)ADEKA제 상품명: 아데카스타브(등록상표) AO-503AO-503: ADEKA Co., Ltd. Product name: ADEKA STAB (registered trademark) AO-503
[제조예 1][Production Example 1]
500mL 가지형 플라스크에, (e)상기 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물로서 A-DCP 200g을 칭량하고, 메틸에틸케톤(이하, 본 명세서에서는 MEK라 약칭한다.) 200g으로 용해시켰다. 그 후, (a)상기 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자로서, MEK-AC-2140Z((메트)아크릴로일옥시기로 표면수식된 일차입자경 10nm~15nm의 실리카입자, 고형분 45질량%의 MEK분산액) 441g을 첨가하고, 교반하여 균일화하였다. 그 후, 이배퍼레이터를 이용하여, 50℃, 감압도 133.3Pa 이하의 조건으로 MEK를 유거하여, 상기 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자의 A-DCP분산액(이 표면수식된 실리카입자함유량 50질량%)을 얻었다.In a 500 mL eggplant-type flask, (e) 200 g of A-DCP as a polyfunctional (meth) acrylate compound that does not contain the aromatic ring is weighed, and 200 g of methyl ethyl ketone (hereinafter, referred to as MEK in this specification) is used. dissolved. After that, (a) silica particles surface-modified with a functional group having an ethylenically unsaturated group, MEK-AC-2140Z ((meth)acryloyloxy group surface-modified silica particles having a primary particle diameter of 10 nm to 15 nm, solid content 45 mass % MEK dispersion) was added and stirred to homogenize. Thereafter, using an evaporator, MEK was distilled off at 50° C. and a reduced pressure of 133.3 Pa or less, and an A-DCP dispersion of silica particles surface-modified with a functional group having an ethylenically unsaturated group (this surface-modified silica 50 mass % of particle content) was obtained.
[제조예 2][Production Example 2]
500mL 가지형 플라스크에, (b)단관능(메트)아크릴레이트 화합물로서 FA-513AS 100g을 칭량하고, MEK 100g으로 용해시켰다. 그 후, (a)상기 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자로서, MEK-AC-2140Z((메트)아크릴로일옥시기로 표면수식된 일차입자경 10nm~15nm의 실리카입자, 고형분 45질량%의 MEK분산액) 222g을 첨가하고, 교반하여 균일화하였다. 그 후, 이배퍼레이터를 이용하여, 50℃, 감압도 133.3Pa 이하의 조건으로 MEK를 유거하여, 상기 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자의 FA-513AS분산액(이 표면수식된 실리카입자함유량 50질량%)을 얻었다.In a 500 mL eggplant-type flask, (b) 100 g of FA-513AS as a monofunctional (meth) acrylate compound was weighed and dissolved with 100 g of MEK. After that, (a) silica particles surface-modified with a functional group having an ethylenically unsaturated group, MEK-AC-2140Z ((meth)acryloyloxy group-modified primary particle diameter of 10 nm to 15 nm silica particles, solid content 45 mass % MEK dispersion) was added and stirred to homogenize. Thereafter, using an evaporator, MEK was distilled off under the conditions of 50° C. and a reduced pressure of 133.3 Pa or less, and the FA-513AS dispersion of silica particles surface-modified with a functional group having an ethylenically unsaturated group (this surface-modified silica A particle content of 50 mass %) was obtained.
[제조예 3][Production Example 3]
500mL 가지형 플라스크에, (f)우레탄(메트)아크릴레이트 화합물로서 UA-4200 50.0g을 칭량하고, MEK 50.0g으로 용해시켰다. 그 후, (a)상기 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자로서, MEK-AC-2140Z((메트)아크릴로일옥시기로 표면수식된 일차입자경 10nm~15nm의 실리카입자, 고형분 45질량%의 MEK분산액) 111g을 첨가하고, 교반하여 균일화하였다. 그 후, 이배퍼레이터를 이용하여, 60℃, 감압도 133.3Pa 이하의 조건으로 MEK를 유거하여, 상기 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자의 UA-4200분산액(이 표면수식된 실리카입자함유량 50질량%)을 얻었다.In a 500 mL eggplant-type flask, (f) 50.0 g of UA-4200 as a urethane (meth) acrylate compound was weighed and dissolved in MEK 50.0 g. After that, (a) silica particles surface-modified with a functional group having an ethylenically unsaturated group, MEK-AC-2140Z ((meth)acryloyloxy group-modified primary particle diameter of 10 nm to 15 nm silica particles, solid content 45 mass % MEK dispersion) was added and stirred to homogenize. Then, using an evaporator, the MEK was distilled off at 60° C. and a reduced pressure of 133.3 Pa or less, and a UA-4200 dispersion of silica particles surface-modified with a functional group having an ethylenically unsaturated group (this surface-modified silica) A particle content of 50 mass %) was obtained.
[제조예 4][Production Example 4]
500mL 가지형 플라스크에, (e)상기 에틸렌성 불포화기를 갖는, 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물로서 A-DCP 20.0g을 칭량하였다. 그 후, (c)상기 에틸렌성 불포화기를 갖는 폴리로탁세인으로서, SA1303P(시클로덱스트린으로 이루어지는 환상분자의 측쇄에 아크릴기를 갖는 폴리로탁세인, 고형분 50질량%의 MEK분산액) 40.0g을 첨가하고, 교반하여 균일화하였다. 그 후, 이배퍼레이터를 이용하여, 50℃, 감압도 133.3Pa 이하의 조건으로 MEK를 유거하여, 상기 에틸렌성 불포화기를 갖는 폴리로탁세인의 A-DCP용액(이 에틸렌성 불포화기를 갖는 폴리로탁세인함유량 50질량%)을 얻었다.In a 500 mL eggplant-type flask, (e) 20.0 g of A-DCP was weighed as a polyfunctional (meth)acrylate compound having the ethylenically unsaturated group and not containing an aromatic ring. Thereafter, (c) as the polyrotaxane having an ethylenically unsaturated group, 40.0 g of SA1303P (polyrotaxane having an acryl group in the side chain of a cyclic molecule made of cyclodextrin, MEK dispersion having a solid content of 50% by mass) was added, , and homogenized by stirring. Then, using an evaporator, MEK was distilled off under the conditions of 50° C. and a reduced pressure of 133.3 Pa or less, and an A-DCP solution of polyrotaxane having an ethylenically unsaturated group (polyrotaxane having an ethylenically unsaturated group) 50 mass % of taxane content) was obtained.
[실시예 1][Example 1]
(a)에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자로서 제조예 1에서 얻은 상기 A-DCP분산액의 고형분, 및 제조예 2에서 얻은 상기 FA-513AS분산액의 고형분, (b)에틸렌성 불포화기를 갖는 단관능(메트)아크릴레이트 화합물로서 FA-513AS, (c)에틸렌성 불포화기를 갖는 폴리로탁세인으로서, 제조예 4에서 얻은 상기 A-DCP용액의 고형분, (d)광라디칼개시제로서 I184, (e)에틸렌성 불포화기를 갖는, 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물로서 A-DCP, (f)에틸렌성 불포화기를 갖는 우레탄(메트)아크릴레이트 화합물로서 UA-4200, (g)페놀계 산화방지제로서 I245, 및 (h)설파이드계 산화방지제로서 AO-503을, 각각 하기 표 1에 기재된 비율로 배합하였다. 한편, 하기 표 1에 나타내는 A-DCP의 비율은 상기 A-DCP분산액 및 상기 A-DCP용액에 포함되는 A-DCP성분을, FA-513AS의 비율은 상기 FA-513AS분산액에 포함되는 FA-513AS를 포함한다. 그 후, 배합물을 50℃에서 16시간 진탕시키고, 상기 교반탈포기를 이용하여 10분간 교반탈포함으로써, 임프린트용 광경화성 조성물1을 조제하였다. 한편, 하기 표 1 중, 「부」는 「질량부」를 나타낸다.(a) the silica particles surface-modified with a functional group having an ethylenically unsaturated group, the solid content of the A-DCP dispersion obtained in Preparation Example 1, and the solid content of the FA-513AS dispersion obtained in Preparation Example 2, (b) the ethylenically unsaturated group FA-513AS as a monofunctional (meth)acrylate compound having, (c) polyrotaxane having an ethylenically unsaturated group, the solid content of the A-DCP solution obtained in Preparation Example 4, (d) I184 as a photoradical initiator, (e) A-DCP as a polyfunctional (meth)acrylate compound having an ethylenically unsaturated group and not containing an aromatic ring, (f) UA-4200 as a urethane (meth)acrylate compound having an ethylenically unsaturated group, (g ) I245 as a phenol-based antioxidant and (h) AO-503 as a sulfide-based antioxidant were blended in the proportions shown in Table 1 below, respectively. On the other hand, the ratio of A-DCP shown in Table 1 below is the A-DCP component included in the A-DCP dispersion and the A-DCP solution, and the ratio of FA-513AS is FA-513AS included in the FA-513AS dispersion. includes Thereafter, the mixture was shaken at 50° C. for 16 hours, and stirred and defoamed for 10 minutes using the stirring degassing machine, thereby preparing a photocurable composition 1 for imprinting. In addition, in Table 1 below, "part" shows "part by mass".
[실시예 2 내지 실시예 5, 비교예 1][Examples 2 to 5, Comparative Example 1]
상기 실시예 1과 동일한 수순으로, (a)성분 내지 (h)성분을 하기 표 1에 나타내는 비율로 혼합함으로써, 임프린트용 광경화성 조성물2 내지 6을 조제하였다. 단, 비교예 1은 (b)성분 및 (c)성분을 사용하지 않는다.In the same procedure as in Example 1, by mixing the components (a) to (h) in the proportions shown in Table 1 below, photocurable compositions 2 to 6 for imprints were prepared. However, Comparative Example 1 does not use (b) component and (c) component.
[표 1][Table 1]
[경화막의 제작][Production of cured film]
실시예 1 내지 실시예 5 및 비교예 1에서 조제한 각 임프린트용 광경화성 조성물을, 500μm두께의 실리콘고무제 스페이서와 함께, NOVEC(등록상표) 1720(쓰리엠재팬(주)제)을 도포하고 건조함으로써 이형처리한 유리기판 2매로 끼워넣었다. 이 끼워넣은 임프린트용 광경화성 조성물을, 상기 UV-LED조사장치를 이용하여 30mW/cm2로 200초간 UV노광하였다. 노광 후 얻어진 경화물을, 상기 이형처리한 유리기판으로부터 박리한 후, 100℃의 핫플레이트에서 10분간 가열함으로써, 직경 1cm, 두께 0.5mm의 경화막을 제작하였다.Each of the photocurable compositions for imprints prepared in Examples 1 to 5 and Comparative Example 1 was coated with NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) together with a silicone rubber spacer having a thickness of 500 μm and dried. It was sandwiched between two molded glass substrates. This embedded photocurable composition for imprint was UV-exposed for 200 seconds at 30 mW/cm 2 using the UV-LED irradiation device. After peeling the hardened|cured material obtained after exposure from the said mold release process, the cured film of diameter 1cm and thickness 0.5mm was produced by heating for 10 minutes on a 100 degreeC hotplate.
[굴절률nD·아베수νD 평가][Evaluation of refractive index n D Abbe number ν D ]
상기의 방법으로 제작한 경화막의 파장 589nm에 있어서의 굴절률nD, 및 아베수νD를, 상기 다파장굴절계를 이용하여 측정하였다. 결과를 하기 표 2에 함께 나타낸다.Refractive index n D and Abbe's number (nu) D in wavelength 589 nm of the cured film produced by said method were measured using the said multi-wavelength refractometer. The results are shown together in Table 2 below.
[유기용매를 이용한 현상공정에 있어서의 경화막의 내크랙성의 평가][Evaluation of the crack resistance of the cured film in the developing step using an organic solvent]
실시예 1 내지 실시예 5 및 비교예 1에서 조제한 각 임프린트용 광경화성 조성물을 적량, NOVEC(등록상표) 1720(쓰리엠재팬(주)제)을 도포하고 건조함으로써 이형처리한 포토마스크기판(개구부 가로세로 1cm) 상에 적하하였다. 그 후, 500μm두께의 실리콘고무제 스페이서를 개재하여, 4인치 유리웨이퍼(0.7mm두께)로, 상기 이형처리한 포토마스크기판 상의 임프린트용 광경화성 조성물을 끼워넣었다. 상기 4인치 유리웨이퍼는, 신에쓰화학공업(주)제 접착보조제(제품명: KBM-5103)를 프로필렌글리콜모노메틸에테르아세테이트(이하, 본 명세서에서는 PGMEA라 약칭한다.)로 30질량%로 희석한 용액을 도포하고 건조함으로써 밀착처리한 것이다. 이 끼워넣은 광경화성 조성물을, 상기 UV-LED조사장치를 이용하여 115mW/cm2로 2.2초간 UV노광하였다. 노광 후 얻어진 경화물을, 상기 이형처리한 포토마스크기판으로부터 박리한 후, 교반된 PGMEA 중에 침지(현상)하고, 다시 PGMEA로 린스하여 미노광부를 제거함으로써, 상기 밀착처리한 4인치 유리웨이퍼 상에, 가로세로 1cm, 두께 0.5mm의 경화막을 제작하였다. 얻어진 경화막을, 상기 (주)하이록스제 디지털마이크로스코프로 경화막의 측면을 관찰하여, 크랙이 확인되는 것을 ×, 크랙이 관측되지 않는 것을 ○로 판정하였다. 결과를 하기 표 2에 함께 나타낸다.An appropriate amount of each photocurable composition for imprint prepared in Examples 1 to 5 and Comparative Example 1 was coated with NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) and dried to release the photomask plate (opening width). 1 cm in length). Thereafter, the photocurable composition for imprint on the photomask substrate subjected to the release treatment was sandwiched with a 4-inch glass wafer (0.7 mm thick) through a 500 μm-thick silicone rubber spacer. The 4-inch glass wafer was prepared by diluting an adhesion aid (product name: KBM-5103) manufactured by Shin-Etsu Chemical Industry Co., Ltd. with propylene glycol monomethyl ether acetate (hereinafter, abbreviated as PGMEA in this specification) to 30% by mass. Adhesive treatment was carried out by applying the solution and drying it. The embedded photocurable composition was UV-exposed for 2.2 seconds at 115 mW/cm 2 using the UV-LED irradiation device. The cured product obtained after exposure was peeled off from the photomask substrate subjected to the release treatment, and then immersed (developed) in stirred PGMEA, rinsed again with PGMEA to remove the unexposed portion, and then on the closely-treated 4-inch glass wafer. , A cured film having a length of 1 cm and a thickness of 0.5 mm was produced. For the obtained cured film, the side surface of the cured film was observed with the digital microscope manufactured by Hyrox Co., Ltd., and that in which a crack was observed was judged as x and that in which a crack was not observed was evaluated as (circle). The results are shown together in Table 2 below.
[경화막의 복굴절측정][Measurement of birefringence of cured film]
실시예 1 내지 실시예 5 및 비교예 1에서 조제한 각 임프린트용 광경화성 조성물 0.030g을, NOVEC(등록상표) 1720(쓰리엠재팬(주)제)을 도포하고 건조함으로써 이형처리한 유리기판 상에 칭량하였다. 그 후, 500μm두께의 실리콘고무제 스페이서를 개재하여, 석영기판(가로세로 4cm, 1mm두께)으로, 상기 이형처리한 유리기판 상의 임프린트용 광경화성 조성물을 끼워넣었다. 상기 석영기판은, 신에쓰화학공업(주)제 접착보조제(제품명: KBM-5103)를 PGMEA로 30질량%로 희석한 용액을 도포하고 건조함으로써 밀착처리한 것이다. 이 끼워넣은 광경화성 조성물을, 상기 UV-LED조사장치를 이용하여 30mW/cm2로 200초간 UV노광하였다. 노광 후 얻어진 경화물을, 상기 이형처리한 유리기판으로부터 박리한 후, 100℃의 핫플레이트에서 10분간 가열함으로써, 상기 밀착처리한 석영기판 상에, 직경 1cm, 두께 0.5mm 및 질량 0.030g의 경화막을 제작하였다. 얻어진 경화막을, 상기 (주)포토닉래티스제 위상차측정장치로, 경화막 내의 위상차를 측정하였다. 경화막 내에서 최대가 되는 위상차(단, 외주부로부터 약 1mm의 부분은, 단면구조에 기인한 위상차가 발생하므로, 해석에서는 제외한다.)를, 경화물의 막두께 0.5mm로 나눔으로써, 각 경화물의 복굴절을 산출하였다. 복굴절이 2.5×10-5 이하가 되는 경우를 ○, 2.5×10-5보다 높은 경우를 ×로 판정하였다. 각각의 결과를 하기 표 2에 함께 나타낸다.0.030 g of each imprint photocurable composition prepared in Examples 1 to 5 and Comparative Example 1 was coated on NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) and dried on a glass substrate subjected to release treatment. did. Thereafter, the photocurable composition for imprint on the glass substrate subjected to the release treatment was sandwiched with a quartz substrate (width 4 cm, 1 mm thickness) through a silicone rubber spacer having a thickness of 500 μm. The quartz substrate was adhered to by applying a solution obtained by diluting an adhesion aid (product name: KBM-5103) manufactured by Shin-Etsu Chemical Industry Co., Ltd. to 30% by mass with PGMEA, followed by drying. This embedded photocurable composition was UV-exposed for 200 seconds at 30 mW/cm 2 using the UV-LED irradiation device. The cured product obtained after exposure was peeled from the glass substrate subjected to the release treatment, and then heated on a hot plate at 100° C. for 10 minutes to cure the cured quartz substrate with a diameter of 1 cm, a thickness of 0.5 mm, and a mass of 0.030 g on the contact-treated quartz substrate. membrane was made. The phase difference in the cured film was measured for the obtained cured film with the phase difference measuring apparatus made from the said Co., Ltd. Photonic Lattice. By dividing the maximum retardation within the cured film (however, in the part of about 1 mm from the outer periphery, the phase difference due to the cross-sectional structure occurs, so it is excluded from the analysis) by the film thickness of the cured product of 0.5 mm. Birefringence was calculated. The case where the birefringence was 2.5×10 -5 or less was judged as ○, and the case where the birefringence was higher than 2.5×10 -5 was judged as x. Each result is shown together in Table 2 below.
[반사방지층(AR층)의 성막과 그의 내크랙성 평가][Film formation of antireflection layer (AR layer) and evaluation of its crack resistance]
실시예 1, 2 및 4 그리고 비교예 1에서 조제한 각 임프린트용 광경화성 조성물 0.017g을, NOVEC(등록상표) 1720(쓰리엠재팬(주)제)을 도포하고 건조함으로써 이형처리한 유리기판 상에 칭량하였다. 그 후, 300μm두께의 실리콘고무제 스페이서를 개재하여, 석영기판(가로세로 6cm, 1mm두께)으로, 상기 이형처리한 유리기판 상의 임프린트용 광경화성 조성물을 끼워넣었다. 상기 석영기판은, 신에쓰화학공업(주)제 접착보조제(제품명: KBM-5103)를 PGMEA로 30질량%로 희석한 용액을 도포하고 건조함으로써 밀착처리한 것이다. 이 끼워넣은 광경화성 조성물을, 상기 UV-LED조사장치를 이용하여 30mW/cm2로 200초간 UV노광하였다. 노광 후 얻어진 경화물을, 상기 이형처리한 유리기판으로부터 박리한 후, 100℃의 핫플레이트에서 10분간 가열함으로써, 상기 석영기판 상에, 직경 1cm, 두께 0.3mm 및 질량 0.017g의 경화막을 제작하였다.0.017 g of each photocurable composition for imprint prepared in Examples 1, 2 and 4 and Comparative Example 1 was weighed on a glass substrate subjected to release treatment by applying NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) and drying. did. Thereafter, the photocurable composition for imprint on the glass substrate subjected to the release treatment was sandwiched with a quartz substrate (length 6 cm, 1 mm thickness) through a silicon rubber spacer having a thickness of 300 μm. The quartz substrate was adhered to by applying a solution obtained by diluting an adhesion aid (product name: KBM-5103) manufactured by Shin-Etsu Chemical Industry Co., Ltd. to 30% by mass with PGMEA, followed by drying. This embedded photocurable composition was UV-exposed for 200 seconds at 30 mW/cm 2 using the UV-LED irradiation device. The cured product obtained after exposure was peeled from the glass substrate subjected to the release treatment, and then heated on a hot plate at 100° C. for 10 minutes to prepare a cured film having a diameter of 1 cm, a thickness of 0.3 mm and a mass of 0.017 g on the quartz substrate. .
상기 석영기판 상에 제작된 경화막 상에, 상기 RF스퍼터장치를 이용하여 상기 성막조건으로, 막두께 200nm의 산화규소층을 반사방지층으로서 성막하였다. 상기 (주)키엔스제 광학현미경을 이용하여, 상기 경화막 상의 반사방지층을 관찰하여 크랙의 유무를 확인한 후, 상기 석영기판을 175℃의 핫플레이트에서 2분 30초간 가열함으로써 내열성 시험을 행하였다. 내열성 시험 후의 상기 석영기판에 대해서도, 상기 (주)키엔스제 광학현미경을 이용하여 상기 경화막 상의 반사방지층의 크랙의 유무를 관찰하고, 이 반사방지층의 내크랙성을 판정하였다. 상기 경화막 상의 반사방지층에서 크랙이 시인되는 경우를 ×, 이 경화막 상의 반사방지층에서 크랙, 주름이 모두 시인되지 않는 경우를 ○로 판정하였다. 각각의 결과를 하기 표 2에 함께 나타낸다.On the cured film prepared on the quartz substrate, a silicon oxide layer having a thickness of 200 nm was formed as an antireflection layer by using the RF sputtering apparatus under the above film formation conditions. Using the optical microscope manufactured by Keyence Co., Ltd., the antireflection layer on the cured film was observed to confirm the presence or absence of cracks, and then the quartz substrate was heated on a hot plate at 175° C. for 2 minutes and 30 seconds to perform a heat resistance test. Also for the quartz substrate after the heat resistance test, the presence or absence of cracks in the antireflection layer on the cured film was observed using the optical microscope manufactured by Keyence Co., Ltd., and the crack resistance of the antireflection layer was judged. The case where cracks and wrinkles were not visually recognized by x in the antireflection layer on this cured film was judged as (circle) the case where a crack was visually recognized in the antireflection layer on the said cured film. Each result is shown together in Table 2 below.
[표 2][Table 2]
(b)성분과 (c)성분을 포함하지 않는 비교예 1의 임프린트용 광경화성 조성물로부터 제작한 경화막은, 유기용매를 이용한 현상공정 후, 이 경화막의 측면에 크랙이 발생함과 함께, 경화물의 복굴절도 높은 결과가 되었다. 상기의 결과로부터, 본 발명의 임프린트용 광경화성 조성물로부터 얻어진 경화막은, 고아베수, 고굴절률, 저복굴절을 나타냄과 함께, 이 경화막의 상층의 반사방지층이 175℃에서의 열처리에 의해 크랙, 주름이 모두 발생하지 않고, 유기용매에 노출되어도 경화막에 크랙이 발생하지 않는, 고해상도 카메라모듈용의 렌즈로서 바람직한 특성을 갖는 것으로 나타났다.The cured film produced from the photocurable composition for imprint of Comparative Example 1 which does not contain the component (b) and the component (c), after the developing process using an organic solvent, cracks occur on the side surface of the cured film, and the cured product The result was also high in birefringence. From the above results, the cured film obtained from the photocurable composition for imprint of the present invention exhibits high Abbe's number, high refractive index, and low birefringence, and the upper antireflection layer of the cured film is cracked and wrinkled by heat treatment at 175°C. All of these did not occur, and cracks did not occur in the cured film even when exposed to organic solvents, and it was found to have desirable properties as a lens for high-resolution camera modules.
[렌즈의 제작][Production of lenses]
실시예 1, 2 및 4에서 조제한 각 임프린트용 광경화성 조성물을, 각각, 니켈제의 주형(2mm직경×300μm깊이의 렌즈형을, 종 3열×횡 5열의 합 15개 배치) 및 나노임프린터를 이용하고, 상기 서술한 성형체의 제조방법에 따라서, 지지체인 석영기판 상에서 렌즈형상으로 성형하였다. 한편, 사용한 주형은, 미리 NOVEC(등록상표) 1720(쓰리엠재팬(주)제)으로 이형처리하였다. 또한, 사용한 유리기판은, 미리 신에쓰화학공업(주)제 접착보조제(제품명: KBM-5103)를 PGMEA로 30질량%로 희석한 용액을 도포하고 건조함으로써 밀착처리하였다. 상기 주형으로부터 경화물을 분리한 후, 이 경화물을 100℃의 핫플레이트에서 10분간 가열함으로써, 상기 밀착처리한 유리기판 상에 볼록렌즈를 제작하였다.Each of the photocurable compositions for imprints prepared in Examples 1, 2, and 4 was applied to a nickel mold (a 2 mm diameter × 300 μm deep lens type, 15 pieces in 3 vertical rows × 5 horizontal rows) and a nanoimprinter, respectively. was used and molded into a lens shape on a quartz substrate as a support according to the manufacturing method of the molded body described above. On the other hand, the mold used was previously subjected to a mold release treatment with NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.). The glass substrate used was subjected to adhesion treatment by applying a solution obtained by diluting an adhesion aid (product name: KBM-5103) manufactured by Shin-Etsu Chemical Industry Co., Ltd. to 30% by mass with PGMEA in advance and drying. After separating the cured product from the mold, the cured product was heated on a hot plate at 100° C. for 10 minutes to prepare a convex lens on the glass substrate subjected to the adhesion treatment.
상기 유리기판 상에 얻어진 볼록렌즈에 대하여, 가열시험 전후의 렌즈높이(두께)를 상기 비접촉 표면성상 측정장치로 측정하고, 그 변화율을 다음식 “[(가열 전의 렌즈높이-가열 후의 렌즈높이)/가열 전의 렌즈높이]×100”으로부터 산출하여, 가열에 의한 치수안정성을 평가하였다. 또한, 가열시험 후의 볼록렌즈에 있어서의 크랙의 발생의 유무를, 상기 비접촉 표면성상 측정장치에 부속된 마이크로스코프로 관찰하였다. 한편, 가열시험이란, 유리기판 상에 얻어진 볼록렌즈를 175℃의 핫플레이트에서 2분 30초간 가열한 후, 실온(약 23℃)까지 방랭하는 시험이다. 결과를 하기 표 3에 나타낸다.For the convex lens obtained on the glass substrate, the lens height (thickness) before and after the heating test was measured with the non-contact surface property measuring device, and the rate of change was calculated using the following formula “[(lens height before heating - lens height after heating)/ Lens height before heating] x 100", and dimensional stability by heating was evaluated. Further, the presence or absence of cracks in the convex lens after the heating test was observed with a microscope attached to the non-contact surface property measuring apparatus. On the other hand, the heating test is a test in which a convex lens obtained on a glass substrate is heated on a hot plate at 175°C for 2 minutes and 30 seconds, and then allowed to cool to room temperature (about 23°C). The results are shown in Table 3 below.
[표 3][Table 3]
표 3에 나타내는 바와 같이, 본 발명의 임프린트용 광경화성 조성물로부터 얻어진 볼록렌즈는, 175℃, 2분 30초간의 열이력을 거쳐도 렌즈높이의 변화가 작고(변화율 0.30% 미만), 치수안정성이 높다는 결과가 얻어졌다.As shown in Table 3, the convex lenses obtained from the photocurable composition for imprint of the present invention exhibited a small change in lens height (less than 0.30% change rate) and dimensional stability even after a thermal history at 175° C. for 2 minutes and 30 seconds. high results were obtained.
Claims (12)
(a): 일차입자경이 1nm 내지 100nm인, 에틸렌성 불포화기를 갖는 관능기로 표면수식된 실리카입자
(b): 에틸렌성 불포화기를 갖는 단관능(메트)아크릴레이트 화합물
(c): 에틸렌성 불포화기를 갖는 폴리로탁세인
(d): 광라디칼개시제A photocurable composition for imprint comprising the following (a) component, the following (b) component, the following (c) component, and the following (d) component, wherein a total of 100 parts by mass of a compound having an ethylenically unsaturated group contained in the composition This (a) component is 10 mass parts - 40 mass parts, this (b) component is 10 mass parts - 50 mass parts, this (c) component is 1 mass part - 10 mass parts, this (d) component The photocurable composition for imprints which is this 0.1 mass part - 5 mass parts.
(a): silica particles having a primary particle diameter of 1 nm to 100 nm, surface-modified with a functional group having an ethylenically unsaturated group
(b): monofunctional (meth)acrylate compound having an ethylenically unsaturated group
(c): polyrotaxane having an ethylenically unsaturated group
(d): photoradical initiator
상기 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해, 5질량부 내지 50질량부의 하기 (e)성분 및/또는 하기 (f)성분을 추가로 포함하는, 임프린트용 광경화성 조성물.
(e): 에틸렌성 불포화기를 갖는, 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물(단, 상기 (c)성분의 폴리로탁세인 및 (f)성분의 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물을 제외한다.)
(f): 에틸렌성 불포화기를 갖는, 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물(단, 상기 (c)성분의 폴리로탁세인을 제외한다.)According to claim 1,
With respect to 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition, 5 parts by mass to 50 parts by mass of the following (e) component and/or the following (f) component further comprising a photocurable composition for imprints .
(e): a polyfunctional (meth) acrylate compound having an ethylenically unsaturated group and not containing an aromatic ring (provided that the polyrotaxane of the component (c) and the urethane (meth) acrylate compound of the component (f)) or an epoxy (meth) acrylate compound.)
(f): a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound having an ethylenically unsaturated group (however, the polyrotaxane of the component (c) is excluded.)
상기 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해 0.05질량부 내지 3질량부의 하기 (g)성분 및/또는 상기 조성물에 포함되는 에틸렌성 불포화기를 갖는 화합물의 합 100질량부에 대해 0.1질량부 내지 3질량부의 하기 (h)성분을 추가로 포함하는, 임프린트용 광경화성 조성물.
(g): 페놀계 산화방지제
(h): 설파이드계 산화방지제3. The method of claim 1 or 2,
Based on 100 parts by mass of the total of the compound having an ethylenically unsaturated group contained in the composition, 0.05 parts by mass to 3 parts by mass of the following (g) component and/or 100 parts by mass of the compound having an ethylenically unsaturated group contained in the composition The photocurable composition for imprints which further comprises the following (h) component with respect to 0.1 mass parts - 3 mass parts.
(g): phenolic antioxidant
(h): sulfide-based antioxidant
상기 (a)성분이, 2가의 연결기를 개재하여 규소원자와 결합한 (메트)아크릴로일옥시기로 표면수식된 실리카입자인, 임프린트용 광경화성 조성물.3. The method of claim 1 or 2,
The photocurable composition for imprint, wherein the component (a) is a silica particle surface-modified with a (meth)acryloyloxy group bonded to a silicon atom via a divalent linking group.
상기 (e)성분의 방향환을 포함하지 않는 다관능(메트)아크릴레이트 화합물이 2종 이상의 화합물로 구성되고, 이 2종 이상의 화합물 중 적어도 1종의 화합물은 지환식 탄화수소기를 갖는, 임프린트용 광경화성 조성물.3. The method of claim 2,
The polyfunctional (meth)acrylate compound not containing an aromatic ring of the component (e) is composed of two or more compounds, and at least one of these two or more compounds has an alicyclic hydrocarbon group. Mars composition.
상기 임프린트용 광경화성 조성물은, 그 경화물의 파장 589nm에 있어서의 굴절률nD가 1.49 이상이고, 또한 이 경화물의 아베수νD가 53 이상인, 임프린트용 광경화성 조성물.3. The method of claim 1 or 2,
The photocurable composition for imprints has a refractive index n D of the cured product at a wavelength of 589 nm of 1.49 or more, and an Abbe number ν D of the cured product is 53 or more.
상기 광경화하는 공정의 후, 얻어진 광경화물을 취출하여 이형하는 공정, 그리고, 이 광경화물을, 이 이형하는 공정의 전, 중도 또는 후에 있어서 가열하는 공정을 추가로 포함하는, 성형체의 제조방법.10. The method of claim 9,
The manufacturing method of a molded object which further includes the process of taking out and releasing the obtained photocured material after the said photocuring process, and the process of heating this photocured material before, during, or after this releasing process.
상기 이형하는 공정 후, 상기 가열하는 공정의 전에 유기용매를 이용한 현상공정을 추가로 포함하는, 성형체의 제조방법.11. The method of claim 10,
After the step of releasing, and before the step of heating, a method for producing a molded article further comprising a developing step using an organic solvent.
상기 성형체가 카메라모듈용 렌즈인, 성형체의 제조방법.10. The method of claim 9,
The method for producing a molded body, wherein the molded body is a lens for a camera module.
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