KR20170001561A - Thermochromic micro particles and thermochromic ink composition, writing apparatus and smart window using the same - Google Patents
Thermochromic micro particles and thermochromic ink composition, writing apparatus and smart window using the same Download PDFInfo
- Publication number
- KR20170001561A KR20170001561A KR1020160048338A KR20160048338A KR20170001561A KR 20170001561 A KR20170001561 A KR 20170001561A KR 1020160048338 A KR1020160048338 A KR 1020160048338A KR 20160048338 A KR20160048338 A KR 20160048338A KR 20170001561 A KR20170001561 A KR 20170001561A
- Authority
- KR
- South Korea
- Prior art keywords
- thermochromic
- carbon atoms
- fine particles
- ink composition
- resin
- Prior art date
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K7/00—Ball-point pens
- B43K7/02—Ink reservoirs; Ink cartridges
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
- C09D11/17—Writing inks characterised by colouring agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
Abstract
Description
본 발명은 열변색성 미세 입자 및 이를 이용한 열변색성 잉크 조성물, 필기구 및 스마트 윈도우에 관한 것이다. 보다 상세하게는, 온도 변화에 따라 높은 발색성 및 소색성을 안정적으로 구현할 수 있고, 소거성, 내열성 및 내화학성이 향상된 열변색성 미세 입자 및 이를 이용한 열변색성 잉크 조성물, 필기구 및 스마트 윈도우에 관한 것이다.The present invention relates to thermochromic fine particles and a thermochromic ink composition using the same, a writing implement and a smart window. More particularly, the present invention relates to a thermochromic fine particle which can stably realize coloring and decoloring properties according to a change in temperature and has improved smear resistance, heat resistance and chemical resistance, and a thermochromic ink composition using the same, will be.
일반적으로 필기용 잉크는 수성잉크와 유성잉크로 나뉘어지며, 필기면에 흡수 또는 접착되어 정착되는 것에 의하여 장기간 필기된 상태를 유지하도록 이루어진다. 상기 필기용 수성잉크 및 유성잉크는 필기면(예를 들면 종이나 합성수지 등)에 흡수 또는 접착되어 정착되고, 쉽게 지워지지 않는다.Generally, the writing ink is divided into water-based ink and oil-based ink, and is absorbed or adhered to the writing surface to be fixed, thereby maintaining the written state for a long time. The water-based ink for writing and the oily ink are absorbed or adhered to a writing surface (for example, paper or synthetic resin) and fixed, and are not easily erased.
필기용 수성잉크 및 유성잉크를 사용하는 필기구를 이용하여 작성한 문서에 있어서, 문안을 수정하거나 오기를 정정해야 하는 일이 발생하면, 쓰여진 문안을 지워야하는 데, 일반 연필용 지우개로는 잘 지워지지 않는다. 또한, 볼펜용 지우개로 지우는 경우에는 수성잉크 및 유성잉크가 정착된 표면을 갈아 벗겨내기 때문에, 종이가 찢어지거나 변형되는 일이 발생할 수 있다.In a document created using a writing instrument using water-based ink or oil-based ink, if it is necessary to correct or correct the text, it is necessary to erase the written text, which is not easily erased by a general pencil eraser. Further, in the case of erasing with a ballpoint pen eraser, since the water-based ink and the oil-based ink are shaved off the fixed surface, the paper may be torn or deformed.
이에, 최근에는 외부자극에 의해서 무색의 화합물이 색깔을 나타내게 되거나, 거꾸로 유색의 화합물이 무색으로 변하는 변색성을 갖는 물질을 이용하여 잉크를 제조하는 기술이 제안되었다. 상기 외부자극으로는 열, 빛, 압력 등을 들 수 있으며, 특히, 열을 가하면 유색에서 무색으로의 변색성을 나타내는 열변색성 화합물을 이용하여 잉크의 소거성을 확보하려는 연구가 활발히 진행되고 있다.In recent years, there has been proposed a technique for producing an ink using a substance in which a colorless compound exhibits a color due to an external stimulus or a substance having a discoloration property in which a colorless compound changes colorlessly upside down. Examples of the external stimuli include heat, light, and pressure. Particularly, studies have been actively carried out to secure the fade-resistance of ink using a thermochromic compound that exhibits discoloration from color to color when heat is applied .
그러나, 비교적 높은 온도에서 변색이 진행되는 열변색성 물질의 경우, 잉크의 소거에 있어 헤어 드라이어나 온수 등의 가열 장치가 요구되어, 휴대성을 만족시키지 못하는 한계가 있었다.However, in the case of a thermochromic material in which discoloration proceeds at a relatively high temperature, a heating device such as a hair dryer or hot water is required to erase the ink, which has a limitation in not satisfying portability.
또한, 체온이나, 지우개에 의한 마찰열 등에 의해서 열변색이 가능한 물질을 사용하는 경우에는, 여름철 기온에 의해서도 변색이 진행되는 등, 발색성이 충분히 유지되지 못하는 한계가 있었다. In addition, in the case of using a material capable of thermochromic change due to body temperature or frictional heat caused by an eraser, there is a limit in that color development can not be sufficiently maintained, for example, discoloration progresses due to summer temperature.
이에, 우수한 발색성을 유지하면서, 간단하고 휴대성을 갖춘 소거 방법에 의해서 신속하게 소거될 수 있는 변색온도범위를 갖는 열변색성 조성물의 개발이 요구되고 있다.Accordingly, development of a thermochromic composition having a discoloration temperature range that can be quickly erased by a simple and portable erasing method while maintaining excellent coloring property is required.
본 발명은 높은 발색성 및 소색성을 안정적으로 구현할 수 있고, 소거성, 내열성 및 내화학성이 향상된 열변색성 미세 입자를 제공하기 위한 것이다. Disclosed is a thermochromic microparticle which can stably realize high coloring and decoloring properties and has improved smear resistance, heat resistance and chemical resistance.
또한, 본 발명은 상기 열변색성 미세 입자를 이용한 열변색성 잉크 조성물, 필기구 및 스마트 윈도우를 제공하기 위한 것이다.The present invention also provides a thermochromic ink composition, writing implement and smart window using the thermochromic fine particles.
본 명세서에서는, 탄소수 8이상의 사슬형 탄화수소 1종 이상, 수화 무기염, 탄소수 5이상의 알코올 및 폴리알킬렌글리콜로 이루어진 군에서 선택된 1종 이상을 포함한 상전이 물질, 염료, 및 현색제를 포함하는 코어부; 및 고분자 수지를 포함한 쉘층;을 포함하는 열변색성 미세 입자가 제공된다. In the present specification, a core material containing a phase transition material containing at least one kind of chain-like hydrocarbon having at least 8 carbon atoms, at least one selected from the group consisting of inorganic hydrated salts, alcohols having 5 or more carbon atoms and polyalkylene glycols, dye, ; And a shell layer comprising a polymeric resin.
본 명세서에서는 또한, 상기 열변색성 미세 입자를 포함하는 열변색성 잉크 조성물이 제공된다. In this specification, there is also provided a thermochromic ink composition comprising the thermochromic fine particles.
본 명세서에서는 또한, 상기 열변색성 잉크 조성물이 충전된 잉크저장용기를 포함하는 열변색성 필기구가 제공된다. In this specification, there is also provided a thermochromic writing implement including the ink storage container filled with the thermochromic ink composition.
본 명세서에서는 또한, 상기 열변색성 미세 입자가 분산된 코팅층을 포함하는, 스마트 윈도우가 제공된다. In this specification, a smart window is also provided, wherein the thermochromic fine particle comprises a coating layer dispersed therein.
이하 발명의 구체적인 구현예에 따른 열변색성 미세 입자 및 이를 이용한 열변색성 잉크 조성물, 필기구 및 스마트 윈도우에 대하여 보다 상세하게 설명하기로 한다. Hereinafter, the thermochromic fine particles according to the specific embodiment of the present invention and the thermochromic ink composition using the same, the writing implement and the smart window will be described in detail.
발명의 일 구현예에 따르면, 탄소수 8이상의 사슬형 탄화수소1종 이상, 수화 무기염, 탄소수 5이상의 알코올 및 폴리알킬렌글리콜로 이루어진 군에서 선택된 1종 이상을 포함한 상전이 물질, 염료, 및 현색제를 포함하는 코어부; 및 고분자 수지를 포함한 쉘층;을 포함하는 열변색성 미세 입자가 제공될 수 있다. According to one embodiment of the present invention, there is provided a process for producing a phase change material, dye, and developer comprising at least one chain hydrocarbon having at least 8 carbon atoms, at least one selected from the group consisting of inorganic hydrated salts, alcohols having 5 or more carbon atoms and polyalkylene glycols ; And a shell layer containing a polymer resin can be provided.
본 발명자들은 상술한 열변색성 미세 입자를 이용하면, 높은 발색성을 나타내면서 온도변화에 따라 소색성을 구현할 수 있으며, 상기 상전이 물질에 의해 열변색이 진행되는 온도 범위가 조절되어, 상기 발색성 및 소색성을 유지하기가 용이하며, 간단하고 휴대성을 갖춘 소거 방법에 의해서 신속하게 소거될 수 있다는 점을 실험을 통하여 확인하고 발명을 완성하였다.The inventors of the present invention have found that when the thermochromic fine particles described above are used, it is possible to realize decolorization according to a temperature change while exhibiting a high coloring property, and a temperature range in which thermal coloring progresses by the phase transition material is controlled, And it can be quickly erased by a simple and portable erase method, and completed the invention through experiments.
또한, 상기 열변색성 미세 입자를 사용하게 되면, 산성 물질, 염기성 물질, 과산화물 등의 화학적으로 활성인 물질 또는 다른 용제 성분과 접촉하더라도, 기능의 저하를 방지할 수 있고, 내열 안정성을 확보할 수 있다.Further, by using the thermochromic fine particles, it is possible to prevent the deterioration of the function even when brought into contact with a chemically active substance such as an acidic substance, a basic substance or a peroxide or other solvent component, have.
상술한 일 구현예의 열변색성 미세 입자는 열변색성이 요구되는 다양한 분야에서 활용될 수 있으며, 예를 들어 잉크 조성물, 잉크, 펜, 코팅 조성물, 섬유, 건축 자재 등에서 사용될 수 있다.The thermochromic fine particles of one embodiment described above can be utilized in various fields requiring heat discoloration and can be used in, for example, ink compositions, inks, pens, coating compositions, fibers, building materials and the like.
특히, 상기 열변색성 미세 입자는 상전이 물질을 포함할 수 있다. 상기 상전이 물질은 상변화온도에 따라 고체-액체, 액체-기체로 상이 변화하게 되면서 잠열을 흡수 저장하는 물질로서, 화학결합을 통해 열을 저장하거나 또는 방출할 수 있다. In particular, the thermochromic fine particle may include a phase transition material. The phase change material is a material that absorbs and stores latent heat as the phase changes to a solid-liquid or a liquid-gas depending on a phase change temperature, and can store or release heat through chemical bonding.
상기 상전이 물질(phase change material: PCM) 은 탄소수 8이상의 사슬형 탄화수소 1종 이상, 수화 무기염, 탄소수 5이상의 알코올 및 폴리알킬렌글리콜로 이루어진 군에서 선택된 1종 이상을 포함할 수 있다. 즉, 상기 상전이 물질은 탄소수 8이상, 또는 탄소수 10 내지 50, 또는 12 내지 40, 또는 19내지 30, 또는 21 내지 30의 사슬형 탄화수소 1종 이상, 수화 무기염, 탄소수 5이상, 또는 탄소수 6 내지 50, 또는 8 내지 40, 또는 10 내지 30, 또는 12 내지 18의 알코올, 폴리알킬렌글리콜 또는 이들의 2종 이상의 혼합물을 포함할 수 있다.The phase change material (PCM) may include at least one selected from the group consisting of at least one of chain hydrocarbons having at least 8 carbon atoms, an inorganic hydrate, an alcohol having 5 or more carbon atoms, and a polyalkylene glycol. That is, the phase change material may include at least one kind of chain hydrocarbons having 8 or more carbon atoms, 10 to 50 carbon atoms, or 12 to 40, 19 to 30, or 21 to 30 carbon atoms, an inorganic hydrated salt, 50, or 8 to 40, or 10 to 30, or 12 to 18 alcohols, polyalkylene glycols, or mixtures of two or more thereof.
상기 혼합물의 경우, 예를 들면, 상기 탄소수 8이상의 사슬형 탄화수소 및 탄소수 5이상의 알코올의 혼합물을 들 수 있고, 이 경우, 상기 탄소수 8이상의 사슬형 탄화수소 및 탄소수 5이상의 알코올의 중량비가 1:1.2 내지 1:5, 또는 1:1.3 내지 1:3일 수 있다.In this case, the weight ratio of the chain-like hydrocarbon having 8 or more carbon atoms to the alcohol having 5 or more carbon atoms is preferably 1: 1.2 to 1: 1: 5, or 1: 1.3 to 1: 3.
상기 탄소수 8이상의 사슬형(chain structure) 탄화수소는 8이상, 또는 10 이상, 또는 19이상의 탄소 원자가 사슬 모양으로 이어진 화합물을 의미한다. 상기 탄소수 8이상의 사슬형 탄화수소는 1종 이상, 즉 단독 또는 혼합물로 존재할 수 있으며, 상기 탄소수 8 이상의 사슬형 탄화수소 혼합물은 탄소수를 기준으로 구분되는 적어도 2 종 이상의 사슬형 탄화수소의 혼합물을 의미한다. The above-mentioned chain structure hydrocarbon having 8 or more carbon atoms means a compound having 8 or more, or 10 or more, or 19 or more carbon atoms in a chain. The above-mentioned chain-like hydrocarbons having a carbon number of 8 or more may be present in one or more, alone or in a mixture, and the above-mentioned chain-like hydrocarbon mixture having at least 8 carbon atoms means a mixture of at least two or more kinds of chain-like hydrocarbons classified on the basis of the number of carbon atoms.
상기 탄소수 8이상의 사슬형 탄화수소는 탄소수 10 내지 50, 또는 12 내지 40, 또는 20 내지 40의 직쇄 포화탄화수소를 포함할 수 있다. 상기 탄소수 10 내지 50의 직쇄 포화탄화수소의 예로는 노말 도데칸(n-dodecane), 노말 테트라데칸(n-tetradecane), 노말 펜타데칸(n-pentadecane), 노말 헥사데칸(n-hexadecane), 노말 헵타데칸(n-heptadecane), 노말 옥타데칸(n-octadecane), 노말 아이코센(n-eicosane), 노말 도코센(n-docosane) 등을 들 수 있다.The chain hydrocarbon having 8 or more carbon atoms may include a linear saturated hydrocarbon having 10 to 50 carbon atoms, or 12 to 40 carbon atoms, or 20 to 40 carbon atoms. Examples of the straight chain saturated hydrocarbons having 10 to 50 carbon atoms include n-dodecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, N-heptadecane, n-octadecane, n-eicosane, n-docosane, and the like.
상기 탄소수 20 내지 40의 직쇄 포화탄화수소 또는 이들의 혼합물을 흔히 파라핀(paraffin)으로 불리며, 고체 상태로 존재하는 경우, 파라핀 왁스(paraffin wax)라고 한다.The above-mentioned straight chain saturated hydrocarbons having a carbon number of 20 to 40 or a mixture thereof are often called paraffin. When they exist in a solid state, they are called paraffin wax.
상기 수화 무기염은 무기염의 수화물을 의미하며, 구체적으로 무기산 금속염의 수화물 또는 유기산 금속염의 수화물을 포함할 수 있다. 상기 무기산 금속염은 금속의 황산염, 질산염, 탄산염, 인산염, 싸이오황산염 또는 할로겐화물을 포함할 수 있다. 또한, 상기 유기산 금속염은 금속의 아세트산염을 포함할 수 있다. 상기 금속은 전형금속 또는 전이금속을 모두 포함할 수 있으며, 구체적으로, 리튬, 나트륨, 칼륨 등의 알칼리 금속, 마그네슘, 칼슘, 바륨 등의 알칼리토 금속, 또는 망간, 철, 니켈, 구리, 아연, 은 등의 전이금속을 사용할 수 있다.The hydrated inorganic salt means a hydrate of an inorganic salt, specifically, a hydrate of an inorganic acid metal salt or a hydrate of an organic acid metal salt. The inorganic metal salt may include a sulfate, a nitrate, a carbonate, a phosphate, a thiosulfate or a halide of a metal. In addition, the organic acid metal salt may include a metal acetate. The metal may include both a typical metal or a transition metal and may be an alkali metal such as lithium, sodium or potassium, an alkaline earth metal such as magnesium, calcium or barium, or a metal such as manganese, iron, nickel, copper, A transition metal such as silver can be used.
이러한 상기 수화무기염의 구체적인 예로는 Na2SO4·10H2O, Na2HPO4·12H2O, Zn(NO3)2·6H2O, Na2S3O3·5H2O 및 CH3COONa·3H2O 등을 들 수 있다.Specific examples of the hydrated inorganic salt include Na 2 SO 4 .10H 2 O, Na 2 HPO 4 .12H 2 O, Zn (NO 3 ) 2 .6H 2 O, Na 2 S 3 O 3 .5H 2 O and CH 3 COONa · 3H 2 O, and the like.
상기 탄소수 5이상의 알코올은 탄소수 6 내지 50, 또는 8 내지 40, 또는 14 내지 30, 또는 18 내지 25의 지방족 알코올 또는 탄소수 3 내지 20의, 또는 3 내지 15, 또는 4 내지 10의 방향족 알코올을 포함할 수 있다. The alcohols having 5 or more carbon atoms include aliphatic alcohols having 6 to 50, or 8 to 40, or 14 to 30, or 18 to 25 carbon atoms, or aromatic alcohols having 3 to 20 carbon atoms, or 3 to 15, or 4 to 10 carbon atoms .
상기 탄소수 6 내지 50의 지방족 알코올은 탄소수 6 내지 50의 사슬형 포화 탄화수소를 주쇄로 포함하며, 상기 주쇄 또는 말단에 적어도 하나 이상의 히드록시기가 결합한 화합물을 포함할 수 있으며, 바람직하게는 탄소수 6 내지 50의 직쇄의 포화 탄화수소를 포함한 주쇄의 말단에 하나의 히드록시기가 결합한 화합물을 포함할 수 있다.The aliphatic alcohol having 6 to 50 carbon atoms may include a compound having a main chain of a chain saturated hydrocarbon having 6 to 50 carbon atoms and having at least one hydroxyl group bonded to the main chain or terminal thereof, And a compound in which one hydroxy group is bonded to the end of the main chain containing a straight chain saturated hydrocarbon.
상기 탄소수 6 내지 50의 사슬형 포화 탄화수소를 포함한 주쇄의 말단에 하나의 히드록시기가 결합한 화합물의 예로는 노말 옥틸 알코올(n-octyl alcohol), 노말 데킬 알코올(n-decyl alcohol), 노말 라우릴 알코올(n-lauryl alcohol), 노말 미리스틸 알코올(n-myristyl alcohol), 노말 세틸 알코올(n-cetyl alcohol), 노말 스테아릴 알코올(n-stearyl alcohol) 등을 들 수 있다.Examples of the compound having one hydroxyl group bonded to the end of the main chain containing the chain saturated hydrocarbon having 6 to 50 carbon atoms include n-octyl alcohol, n-decyl alcohol, n-lauryl alcohol n-lauryl alcohol, n-myristyl alcohol, n-cetyl alcohol and n-stearyl alcohol.
상기 탄소수 3 내지 20의 방향족 알코올은 탄소수 3 내지 20의 방향족 탄화수소 또는 탄소수 3 내지 20의 헤테로 방향족 화합물; 및 적어도 하나 이상의 히드록시기;를 포함할 수 있으며, 바람직하게는 탄소수 3 내지 20의 헤테로 방향족 화합물 및 적어도 하나 이상의 히드록시기를 포함한 화합물을 포함할 수 있으며, 상기 탄소수 3 내지 20의 헤테로 방향족 화합물에 적어도 하나 이상의 히드록시기가 직접 결합할 수 있다.The aromatic alcohol having 3 to 20 carbon atoms is preferably an aromatic hydrocarbon having 3 to 20 carbon atoms or a heteroaromatic compound having 3 to 20 carbon atoms; And a compound containing at least one hydroxy group, preferably at least one heteroaromatic compound having 3 to 20 carbon atoms and at least one hydroxy group, wherein the heteroaromatic compound having 3 to 20 carbon atoms may include at least one A hydroxy group can be bonded directly.
상기 탄소수 3 내지 20의 헤테로 방향족 화합물의 예가 크게 한정되는 것은 아니나, 예를 들어, 퓨란, 티오펜, 피롤, 이미다졸, 피리딘, 피리미딘, 인돌 또는 이들의 유도체를 들 수 있다.Examples of the above heteroaromatic compound having 3 to 20 carbon atoms are not particularly limited, but include, for example, furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, indole or derivatives thereof.
상기 폴리알킬렌글리콜은 하기 화학식1로 표시되는 반복단위를 포함할 수 있다.The polyalkylene glycol may include a repeating unit represented by the following general formula (1).
[화학식1][Chemical Formula 1]
상기 화학식1에서, R1은 탄소수 1 내지 10의 알킬렌기이고, n은 1 내지 1000의 정수이다. 상기 탄소수 1 내지 10의 알킬렌기의 예로는 메틸렌기, 에틸렌기, 프로필렌기, 부틸렌기 등을 들 수 있고, 상기 화학식1에서 '*'는 직접 결합을 의미할 수 있다.Wherein R 1 is an alkylene group having 1 to 10 carbon atoms and n is an integer of 1 to 1000. Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group and a butylene group. In the above formula (1), '*' may mean a direct bond.
상기 폴리알킬렌글리콜은 폴리옥시알킬렌을 포함한 주쇄 및 상기 주쇄의 양말단에 결합한 히드록시기를 포함할 수 있다. 상기 폴리옥시알킬렌을 포함한 주쇄의 양말단에 히드록시기가 결합한 화합물은 하기 화학식 2로 표시될 수 있다.The polyalkylene glycol may include a main chain including a polyoxyalkylene and a hydroxy group bonded to both ends of the main chain. The compound having a hydroxy group at both ends of the main chain including the polyoxyalkylene may be represented by the following general formula (2).
[화학식2](2)
상기 화학식2에서, R1은 탄소수 1 내지 10의 알킬렌기이고, n은 1 내지 1000의 정수이다.In
상기 폴리알킬렌글리콜의 구체적인 예가 크게 한정되는 것은 아니나, 예를 들어, 폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리부틸렌글리콜 등을 들 수 있다.Specific examples of the polyalkylene glycol include, but are not limited to, polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like.
상기 열변색성 미세 입자에서는, 하기 일반식 1로 정의되는 변색 온도 범위가 50 이상일 수 있다. 이에 따라, 상기 염료의 열변색이 조절되어, 우수한 발색성을 유지하면서, 간단하고 소거 방법에 의해서 신속하게 소거될 수 있다. 구체적으로, 상기 열변색성 미세 입자는 하기 일반식 1로 정의되는 변색 온도 범위가 50℃ 이상으로 크게 나타나, 상전이 물질의 고체상과 액체상이 공존하는 상전이 구간이 넓어져, 변색 전후의 발색 또는 소색 상태 각각을 유지시키기가 용이하다.In the thermochromic fine particle, the color temperature range defined by the following general formula (1) may be 50 or more. As a result, the heat discoloration of the dye is controlled and can be quickly and easily erased by the erasing method while maintaining excellent coloring property. Specifically, the thermochromic fine particles have a discoloration temperature range of 50 DEG C or more as defined by the following general formula (1), and the phase transition period in which the solid phase and the liquid phase of the phase transition material coexist is widened, It is easy to keep each.
[일반식1][Formula 1]
변색온도범위(T) = 상전이 물질의 녹는점과 결정화 온도의 차이의 절대값The discoloration temperature range (T) = the absolute value of the difference between the melting point of the phase transition material and the crystallization temperature
상기 녹는점(melting temperature, Tm)은 고체에서 액체로 상태변화가 일어날 때의 온도로서, 구체적으로 상기 상전이 물질이 완전한 액체 상태로 존재할 수 있는 가장 낮은 온도를 의미한다. 또한, 상기 결정화 온도(crystallization temperature, Tc)는 결정화가 일어나는 온도나 결정화에 필요한 열처리 온도를 의미하며, 구체적으로 상기 상전이 물질이 완전한 고체 상태로 존재할 수 있는 가장 높은 온도를 의미한다.The melting temperature (Tm) is a temperature at which a state transition from solid to liquid occurs, and specifically refers to the lowest temperature at which the phase transition material can exist in a completely liquid state. The crystallization temperature Tc means a temperature at which crystallization occurs or a heat treatment temperature required for crystallization. Specifically, the crystallization temperature Tc means the highest temperature at which the phase transition material can exist in a completely solid state.
상기 상전이 물질은 -20℃ 내지 0℃, 또는 -10℃ 내지 5℃의 결정화 온도를 가질 수 있다. 또한, 상기 상전이 물질은 50℃ 이상, 또는 50℃ 내지 80℃의 녹는점을 가질 수 있다. The phase change material may have a crystallization temperature of -20 ° C to 0 ° C, or -10 ° C to 5 ° C. The phase change material may have a melting point of 50 ° C or higher, or 50 ° C to 80 ° C.
또한, 상기 열변색성 미세 입자는 염료를 포함할 수 있다. 상기 염료는 락톤계 염료일 수 있고, 상기 락톤계 염료는 류코(leuco)염료로서, 열변색성을 나타낼 수 있으며, 상기 락톤계 염료의 예로는 프탈리드(phthalide)계 화합물 또는 플루오란(fluoran)계 화합물 등을 들 수 있다. In addition, the thermochromic fine particles may include a dye. The dye may be a lactone dye, and the lactone dye may be a leuco dye and may exhibit thermal discoloration. Examples of the lactone dye include phthalide-based compounds or fluoran- Based compounds and the like.
상기 프탈리드(phthalide)계 화합물은 프탈리드(phthalide) 화합물 또는 그 유도체 화합물을 포함할 수 있으며, 상기 플루오란계(fluoran)계 화합물 또한 플루오란계(fluoran) 화합물 또는 그 유도체 화합물을 포함할 수 있다.The phthalide-based compound may include a phthalide compound or a derivative thereof, and the fluororan-based compound may also include a fluororan compound or a derivative thereof. have.
상기 프탈리드계 화합물의 예로는 디페닐메탄 프탈리드계 화합물, 페닐 인돌릴 프탈리드계 화합물, 인돌릴 프탈리드계 화합물, 디페닐메탄 아자프탈리드계 화합물 등을 들 수 있다.Examples of the phthalide-based compounds include diphenylmethanephthalide-based compounds, phenylindolylphthalide-based compounds, indolylphthalide-based compounds, and diphenylmethaneazaphthalide-based compounds.
보다 구체적으로 상기 락톤계 염료의 예를 들면, 3,3-비스(p-디메틸아미노 페닐)-6-디메틸아미노 프탈리드, 3-(4-디에틸 아미노 페닐)-3-(1-에틸-2-메틸인돌-3-일) 프탈리드, 3,3-비스(1-n-부틸-2-메틸인돌-3-일) 프탈리드, 3,3-비스(2-에톡시-4-디에틸 아미노 페닐)-4-아자프탈리드, 3-〔2-에톡시-4-(N-에틸 아닐리노) 페닐〕-3-(1-에틸-2-메틸인돌-3-일)-4-아자프탈리드, 3,6-디페닐 아미노 플루오란, 3,6-디메톡시 플루오란, 3,6-디-n-부톡시 플루오란, 2-메틸-6-(N-에틸-N-p-트릴 아미노) 플루오란, 3-클로로-6-시클로헥실아미노 플루오란, 2-메틸-6-시클로헥실아미노 플루오란, 2-(2-클로로 아닐리노)-6-디-n-부틸 아미노 플루오란, 2-(3-트리플루오로메틸 아닐리노)-6-디에틸 아미노 플루오란, 2-(N-메틸아닐리노)-6-(N-에틸-N-p-트릴 아미노) 플루오란, 1,3-디메틸-6-디에틸 아미노 플루오란, 2-클로로-3-메틸-6-디에틸 아미노플루오란, 2-아닐리노-3-메틸-6-디에틸 아미노 플루오란, 2-아닐리노-3-메틸-6-디-n-부틸 아미노 플루오란, 2-키시리지노3-메틸 -6-디에틸 아미노 플루오란, 1,2-벤츠-6-디에틸 아미노 플루오란, 1,2-벤츠-6-(N-에틸-N-이소부틸 아미노) 플루오란, 1,2-벤츠-6-(N-에틸-N-이소아밀 아미노) 플루오란, 스피로〔5H-(1) 벤조피라노(2,3-d) 피리미딘-5,1´(3´H) 이소벤조푸란〕-3´-온,2-(디에틸 아미노)-8-(디에틸아미노)-4-메틸-, 스피로〔5H-(1) 벤조피라노(2,3-d) 피리미딘-5,1´(3´H) 이소벤조푸란〕-3´-온,2-( 디-n-부틸아미노)-8-( 디-n-부틸 아미노)-4-메틸-, 스피로〔5H-(1) 벤조피라노(2,3-d) 피리미딘-5,1´(3´H) 이소벤조푸란〕-3´-온,2-( 디-n-부틸 아미노)-8-(디에틸 아미노)-4-메틸-, 스피로〔5H-(1) 벤조피라노(2,3-d) 피리미딘-5,1´(3´H) 이소벤조푸란〕-3´-온,2-(디-n-부틸 아미노)-8-(N-에틸-N-i-아밀 아미노)-4-메틸-, 스피로〔5H-(1)벤조피라노(2,3-d) 피리미딘-5,1´(3´H) 이소벤조푸란〕-3´-온,2-( 디-n-부틸 아미노)-8-( 디-n-부틸 아미노)-4-페닐,3-(2-메톡시-4-디메틸아미노 페닐)-3-(1-부틸-2-메틸인돌-3-일)-4,5,6,7-테트라클로로프탈라이드,3-(2-에톡시-4-디에틸 아미노 페닐)-3-(1-에틸-2-메틸인돌-3-일)-4,5,6,7-테트라클로로프탈라이드,3-(2-에톡시-4-디에틸 아미노 페닐)-3-(1-펜틸-2-메틸인돌-3-일)-4,5,6,7-테트라클로로프탈라이드 등을 들 수 있다. More specifically, examples of the lactone dyes include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- 2-methylindol-3-yl) phthalide, 3,3-bis (1-n-butyl- Ethyl-2-methylindol-3-yl) -4- (2-ethoxyphenyl) Di-n-butoxyfluororane, 2-methyl-6- (N-ethyl-Np-trityl, 3,6- Amino) fluorane, 3-chloro-6-cyclohexylaminofluorane, 2- methyl-6-cyclohexylaminofluorane, 2- (2-chloroanilino) -6- 2- (3-trifluoromethylanilino) -6-diethylaminofluorane, 2- (N-methylanilino) -6- Dimethyl-6-diethylaminofluorane, 2- 3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino- Methyl-6-diethylaminofluorane, 1,2-benz-6-diethylaminofluorane, 1,2-benz-6- (N-ethyl-N-isobutylamino (1-benzopyrano (2,3-d) pyrimidine-5, 1 ') fluororane, 1,2-benz- (3'H) isobenzofuran] -3'-one, 2- (diethylamino) -8- (diethylamino) -4-methyl-, spiro [5H- (1) benzopyrano (di-n-butylamino) -4-methylpyridine, -, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3'- ) -8- (diethylamino) -4-methyl-, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5,1 '(3'H) isobenzofuran] -3 ≪ RTI ID = 0.0 > 2- (di-n- Amino) -8- (N-ethyl-N-amylamino) -4-methyl-, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine- (Di-n-butylamino) -4-phenyl, 3- (2-methoxy-4-dimethylaminophenyl) 3- (1-butyl-2-methylindole-3-yl) -4,5,6,7-tetrachlorophthalide, 3- (1-ethyl-2-methylindole-3-yl) -4,5,6,7-tetrachlorophthalide, 3- Pentyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide.
또한, 상기 열변색성 미세 입자는 피리딘계, 퀴나졸린계, 비스퀴나졸린계 화합물을 더 포함할 수 있다.In addition, the thermochromic fine particles may further include pyridine-based, quinazoline-based, and bisquinazoline-based compounds.
또한, 상기 열변색성 미세 입자는 현색제를 포함할 수 있다. 상기 현색제(Developer)는 상기 열변색성 미세 입자에 포함된 락톤계 염료를 발색시키는 화합물로서, 그 예가 크게 한정되는 것은 아니나, 예를 들어, 페놀계 화합물을 포함할 수 있다. 상기 페놀계 화합물은 페놀 화합물 또는 그 유도체 화합물을 포함할 수 있다.In addition, the thermochromic fine particles may include a developing agent. The developer (developer) is a compound for coloring a lactone-based dye contained in the thermochromic fine particle, and examples thereof are not limited, but may include, for example, a phenol compound. The phenolic compound may include a phenol compound or a derivative thereof.
상기 페놀계 화합물의 구체적인 예가 크게 한정되는 것은 아니나, 예를 들어, 비스페놀계 화합물, 갈레이트(gallate) 화합물 또는 파라벤(paraben) 화합물 등을 사용할 수 있다.Although specific examples of the phenol compound are not limited in any way, for example, a bisphenol compound, a gallate compound or a paraben compound can be used.
보다 구체적으로 상기 현색제의 예를 들면, 2,2-비스(4´-하이드록시페닐) 헥사플루오로프로판, 2,2-비스(4´-하이드록시페닐) 프로판, 에틸 갈레이트, 메틸 p-하이드록시벤조에이트, 페놀, o-크레졸, 제3 부틸카테콜, 노닐 페놀, n-옥틸 페놀, n-도데실페놀, n-스테아릴 페놀, p-클로로 페놀, p-브로모 폐놀, o-페닐 페놀, p-하이드록시 안식향산 n-부틸, p-하이드록시 안식향산 n-옥틸, 레조르시놀, 4,4-디히드록시 디페닐 설폰, 1,1-비스(4´-하이드록시페닐) 에탄, 2,2-비스(4´-하이드록시-3-메틸 페닐) 프로판, 비스(4-하이드록시페닐) 설파이드,1-페닐-1,1-비스(4´-하이드록시페닐)에탄, 1,1-비스(4´-하이드록시페닐)-3-메틸 부탄, 1,1-비스(4´-하이드록시페닐)-2-메틸 프로판, 1,1-비스(4´-하이드록시페닐) n-헥산, 1,1-비스(4´-하이드록시페닐) n-헵탄, 1,1-비스(4´-하이드록시페닐) n-옥탄, 1,1-비스(4´-하이드록시페닐) n-노난, 1,1-비스(4´-하이드록시페닐) n-데칸, 1,1-비스(4´-하이드록시페닐) n-도데칸, 2,2-비스(4´-하이드록시페닐) 부탄, 2,2-비스(4´-하이드록시페닐) 에틸프로피오네이트, 2,2-비스(4´-하이드록시페닐)-4-메틸 펜탄, 2,2-비스(4´-하이드록시페닐) 헥사플루오로프로판, 2,2-비스(4´-하이드록시페닐) n-헵탄, 2,2-비스(4´-하이드록시페닐) n-노난, 4,4´,4˝-메틸리덴 트리스페놀, 2,6-비스〔(2-하이드록시-5-메틸페놀) 메틸〕-4-메틸페놀, 4,4´-〔1-［4-［1-(4-하이드록시페닐)-1-메틸 에틸］페닐］에틸리덴〕비스페놀, 4,4´,4˝-에틸리덴 트리스〔2-메틸페놀〕, 4,4´-〔(2-하이드록시페닐) 메틸렌〕비스［2,3,6-트리페닐 페놀］, 2,2-메틸렌비스［6-［(2-하이드록시-5-메틸 페닐) 메틸］-4-메틸페놀］, 2,4,6-트리스(4-히드록시페닐메틸) 1,3-벤젠 디올, 4,4´,4˝-에틸리덴 트리스페놀, 4,4´-［(4-하이드록시페닐)메틸렌］비스［2-메틸페놀］, 4,4´-［(4-하이드록시페닐) 메틸렌］비스［2,6-디메틸페놀］, 4,4´-［(4-하이드록시페닐) 메틸렌］비스［2-메틸페놀］, 4,4´-［(4-하이드록시페닐］메틸렌］비스［2,6-디메틸페놀］, 4,4´-［(4-하이드록시-3-메톡시페닐) 메틸렌］비스［2,6-디메틸페놀］, 2,4-비스［(5-메틸-2-하이드록시페닐) 메틸］-6-사이클로헥실 페놀, 4,4´-［1-［4-［1-(4-하이드록시-3-메틸페놀)-1-메틸 에틸］페닐］에틸리덴］비스［2-메틸페놀］, 4,4´-［(4-하이드록시페닐) 메틸렌］비스［2-사이클로헥실-5-메틸페놀］, 4,6-비스［(4-하이드록시페닐)메틸］1,3-벤젠 디올, 4,4´-［(3,4-디-히드록시 페닐) 메틸렌］비스［2,6-디메틸페놀］, 4,4´-(1-페닐에틸리덴)비스페놀, 5,5´-(1-메틸에틸리덴) 비스［1-페닐-2-올］, 4,4´,4˝-메틸리덴 트리스페놀, 4,4´-［1-［4-［1-(4-하이드록시페닐)-1-메틸 에틸］페닐］에틸리덴］비스페놀, 4,4´-(페닐메틸렌) 비스페놀, 4,4´-［1,4-페닐렌비스(1-메틸에틸리덴)］비스［2-메틸페놀］, 5,5´-(1,1-사이클로헥실리덴) 비스-［1-비페닐-2-올］, 비스(3,5-디메틸-4-하이드록시페닐), 비스(3-에틸-4-하이드록시페닐) 설파이드, 비스(3,5-디에틸-4-하이드록시페닐) 설파이드, 비스(3-프로필-4-하이드록시페닐) 설파이드, 비스(3,5-디프로필-4-하이드록시페닐) 설파이드, 비스(3-t-부틸-4-하이드록시페닐) 설파이드, 비스(3,5-t-부틸-4-하이드록시페닐) 설파이드, 비스(3-펜틸-4-하이드록시페닐) 설파이드, 비스(3-헥실-4-하이드록시페닐) 설파이드, 비스(3-헵틸-4-하이드록시 페닐) 설파이드, 비스(5-옥틸-2-하이드록시페닐) 설파이드 등을 들 수 있다. 이외에도 종래 현색제로 사용될 수 있는 것으로 알려진 다양한 물질들을 사용할 수 있다.More specifically, examples of the developer include 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 2,2-bis (4'-hydroxyphenyl) propane, ethyl gallate, methyl p N-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromohexanol, o (4'-hydroxyphenyl) phenoxyphenol, n-butyl p-hydroxybenzoate, n-octyl p-hydroxybenzoate, resorcinol, 4,4-dihydroxy diphenylsulfone, Ethane, 2,2-bis (4'-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, Bis (4'-hydroxyphenyl) -3-methylbutane, 1,1-bis (4'-hydroxyphenyl) n-heptane, 1,1-bis (4'-hydroxyphenyl) n-heptane, (4'-hydroxyphenyl) n-nonane, 1,1-bis (4'-hydroxyphenyl) n-decane, 1,1- (4'-hydroxyphenyl) butane, 2,2-bis (4'-hydroxyphenyl) ethyl propionate, 2,2-bis (4'-hydroxyphenyl) n-heptane, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 2,2- Hydroxyphenyl) n-nonane, 4,4 ', 4'-methylidene trisphenol, 2,6-bis [(2-hydroxy-5-methylphenol) Methylphenyl] ethylidene] bisphenol, 4,4 ', 4'-ethylidene tris (2-methylphenol), 4,4'- Triphenylphenol], 2,2-methylenebis [6 - [(2-hydroxy-5-methylphenyl) methyl] - 4-methylphenol], 2,4,6-tris (4-hydroxyphenylmethyl) 1,3-benzenediol, 4, (4-hydroxyphenyl) methylene] bis [2-methylphenol], 4,4 '- [(4-hydroxyphenyl) methylene] bis [4-hydroxyphenyl] methylene] bis [2-methylphenol], 4,4 '- [(4-hydroxyphenyl) methylene] , 6-dimethylphenol], 4,4'- [(4-hydroxy-3-methoxyphenyl) methylene] bis [2,6- Hydroxyphenyl) methyl] -6-cyclohexylphenol and 4,4'- [1- [4- [1- (4-hydroxy-3- methylphenol) (4-hydroxyphenyl) methyl] bis [2-cyclohexyl-5-methylphenol], 4,6'- Benzene diol, 4,4'- [(3,4-dihydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4'- (1-phenylethylidene) bisphenol , 5,5'- (1-methylethylidene) bis [1-phenyl-2-ol], 4, 4 '- [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4'- (Phenylmethylene) bisphenol, 4,4'- [1,4-phenylenebis (1-methylethylidene)] bis [2-methylphenol], 5,5'- (1,1-cyclohexylidene Bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-di Bis (3-propyl-4-hydroxyphenyl) sulfide, bis (3-propyl-4-hydroxyphenyl) sulfide, bis Hydroxyphenyl) sulfide, bis (3,5-t-butyl-4-hydroxyphenyl) sulfide, bis (3-pentyl- ) Sulfide, bis (3-heptyl-4-hydroxyphenyl) sulfide, bis (5-octyl-2-hydroxyphenyl) sulfide and the like. In addition, various materials known to be usable as conventional color developers can be used.
상기 열변색성 미세 입자에 포함된 상전이 물질의 함량이 상기 열변색성 미세 입자의 중량을 기준으로 10 중량% 내지 70 중량%, 또는 30 중량% 내지 60 중량%일 수 있다. 이에 따라, 상기 열변색성 미세 입자는 상전이 물질의 고체상과 액체상이 공존하는 상전이 구간이 넓어져, 변색 전후의 발색 또는 소색 상태 각각을 유지시키기가 용이하다. The content of the phase change material contained in the thermochromic fine particles may be 10 wt% to 70 wt%, or 30 wt% to 60 wt% based on the weight of the thermochromic fine particles. As a result, the thermochromic fine particles have a wider phase transition period in which the solid phase and the liquid phase of the phase transition material coexist, so that it is easy to maintain each of the coloring or decoloring state before and after the discoloration.
또한, 상기 염료에 대한 현색제의 중량비율이 1 내지 10, 또는 2 내지 5일 수 있다.In addition, the weight ratio of the developer to the dye may be 1 to 10, or 2 to 5.
상기 열변색성 미세 입자의 직경은 0.1 ㎛ 내지 10 ㎛일 수 있다. 상기 열변색성 미세 입자의 직경이 10 ㎛ 초과로 지나치게 증가하면, 잉크 등에 적용시 분산 안정성이 감소할 수 있다. 반면, 상기 열변색성 미세 입자의 직경이0.1 ㎛ 미만으로 지나치게 감소하면, 고농도의 발색성을 나타내기 어려울 수 있다.The diameter of the thermochromic fine particles may be 0.1 μm to 10 μm. If the diameter of the thermochromic fine particles is excessively increased to more than 10 占 퐉, dispersion stability upon application to an ink or the like may be reduced. On the other hand, if the diameter of the thermochromic fine particles is excessively reduced to less than 0.1 占 퐉, it may be difficult to exhibit the high coloring property.
상기 열변색성 미세입자에 포함된 코어부 또는 쉘층은 팽창제 또는 수축제를 더 포함할 수 있다. 상기 팽창제 또는 수축제는 외부의 특정 작용에 의해 팽창 또는 수축이 가능한 물질을 의미하며, 상기 코어부, 쉘층 또는 코어부 및 쉘층 모두에 포함되어, 상기 열변색성 미세 입자의 직경을 증가 또는 감소시킬 수 있다. 이와 같이, 상기 열변색성 미세입자의 크기를 온도에 따라 변형 시킴으로써, 상기 열변색성 미세 입자의 발색 농도를 특정 온도 이상에서 가역적 또는 비가역적으로 조절하기가 용이해져 우수한 발색성을 구현할 수 있다.The core or shell layer included in the thermochromic fine particles may further include a swelling agent or a swelling agent. The swelling agent or swelling agent means a material capable of expanding or shrinking by a specific external action and is included in both the core portion, the shell layer or the core portion and the shell layer to increase or decrease the diameter of the thermochromic fine particles . By modifying the size of the thermochromic fine particles according to the temperature, it is easy to reversibly or irreversibly regulate the color density of the thermochromic fine particles at a specific temperature or higher, thereby realizing excellent color development.
상기 팽창제의 예가 크게 한정되는 것은 아니나, 예를 들어, 저비점 유기 용매를 사용할 수 있다. 상기 저비점 유기 용매는 비점이 90℃이하, 또는 80℃이하인 용매로서, 예를 들어, 이소부탄(비점: 약 -11.7℃), 펜탄(비점: 약 36℃), 석유 에테르(비점: 약 30~70℃), 헥산(비점: 약 69℃) 등을 들 수 있고, 상기 저비점 유기 용매는 가열 시에 쉽게 휘발하여 가스를 발생시킴으로써, 상기 열변색성 미세 입자를 팽창시킬 수 있다. Examples of the swelling agent are not particularly limited, but low-boiling organic solvents can be used, for example. (Boiling point: about -11.7 占 폚), pentane (boiling point: about 36 占 폚), petroleum ether (boiling point: about 30 占 폚, 70 ° C) and hexane (boiling point: about 69 ° C). The low-boiling organic solvent easily volatilizes upon heating to generate gas, thereby expanding the thermochromic fine particles.
상기 수축제의 예가 크게 한정되는 것은 아니나, 예를 들어, 고분자 전해질(polyelectrolyte)을 사용할 수 있다. 상기 고분자 전해질은 전하를 가지고 있는 고분자를 의미하며, 이온성 또는 이온화 가능 작용기가 함유된 반복단위를 포함하며, 상기 해리기의 해리도나 용매의 이온강도에 의해 고분자사슬의 형태를 변화시킬 수 있다. Although the example of the water-shrinking agent is not limited to a great extent, for example, a polyelectrolyte may be used. The polymer electrolyte refers to a polymer having a charge and includes a repeating unit containing an ionizable or ionizable functional group. The shape of the polymer chain can be changed by dissociation of the dissociation group or ionic strength of the solvent.
상기 고분자 전해질은 양이온성 고분자 전해질과 음이온성 고분자 전해질을 모두 포함하며, 상기 양이온성 고분자 전해질의 예로는, 폴리(디알릴디메틸암모늄 클로라이드)[Poly(diallyldimethylammonium chloride), (PDADMA-Cl)]; 폴리(N,N-디메틸-3,5-이메틸렌 피페리디늄 클로라이드[Poly(N,N-dimethyl-3,5-dimethylene piperidinium chloride)]; 폴리(에틸렌이민)[Poly(ethylenimine),(PEI)]; 폴리(비닐아민)[Poly(vinylamine),(PVAH)]; 폴리(N-메틸 비닐아민)[Poly(N-methyl vinylamine)]; 폴리(알릴아민)[Poly(allylamine), (PAH)]; 폴리(4-비닐-1-메틸피리디늄 브로마이드)[Poly(4-vinyl-1-methylpyridinium bromide)]; 폴리(알릴암모늄 플루오라이드)[Poly(allylammonium fluoride)]; 폴리(디메틸아민-코-에피클로로하이드린)[Poly(dimethylamine-co-epichlorohydrin)]; 폴리(리신)[Poly(lysine)]; Poly(N,N,N',N′'-테트라메틸-N-트리메틸렌헥사메틸렌디암모늄 디브로마이드)[Poly(N,N,N',N′'-tetramethyl-N-trimethylenehexamethylenediammonium dibromide)]; 폴리(2-(디메틸아미노-에틸)메타크릴레이트)[Poly(2-(Dimethylamino-ethyl)methacrylate)]; 폴리(2-메타크릴로일옥시-에틸-트리메틸암모늄 클로라이드)[Poly(2-methacryloyloxy-ethyl-trimethylammonium chloride)]; 폴리(2-하이드록시-3-메타크릴옥시프로필-트리메틸암모늄 클로라이드)[Poly(2-hydroxy-3-methacryloxypropyl-trimethylammonium chloride)]; 폴리(3-클로로-2-하이드록시프로필-2-메타크릴옥시에틸-디메틸암모늄 클로라이드)[Poly(3-chloro-2-hydroxypropyl-2-methacryloxyethyl-dimethylammonium chloride), (PCHPMEDMAC)]; 폴리(N-[3-(디메틸아미노)-프로필 메타크릴아마이드]) {Poly(N-[3-(dimethylamino)-propyl methacrylamide])}; and 폴리([3-메타크릴옥시아미노-프로필]-트리메틸암모늄 클로라이드)[Poly([3-methacryloylamino-propyl]-trimethylammonium chloride)] 등을 들 수 있고, 상기 음이온성 고분자 전해질의 예로는, 폴리아크릴산[Poly(acrylic acid), (PAA)]; 폴리메타크릴산[Poly(methacrylic acid) (PMA)]; 폴리이타콘산[Poly(itaconic acid)]; 폴리(4-스티렌술폰산)[Poly(4-styrenesulfonic acid) (PSS)]; 폴리(비닐아인산)[Poly(vinylphosphonic acid)]; 폴리비닐술폰산[Poly(vinylsulphonic acid)]; 폴리아스파라틱산[Poly(aspartic acid)]; 폴리글루탐산[Poly(glutamic acid)]; 폴리(소듐 4-스티렌술포네이트)[Poly(sodium 4-styrenesulfonate) (NaPSS)]; 폴리-아네톨설폰산[Poly(anetholesulfonic acid)]; 폴리(3-술포프로필메타크릴레이트)[Poly(3-sulfopropyl methacrylate)]; 폴리(1,4-페닐렌 에터-설폰 설폰산)[Poly(1,4-phenylene ether-sulfone sulfonic acid)]; 또는 폴리(1,4-페닐렌 에터 케톤 설폰산)[Poly(1,4-phenylene ether ether ketone sulfonic acid)] 등을 들 수 있다.The polymer electrolyte includes both a cationic polymer electrolyte and an anionic polyelectrolyte. Examples of the cationic polymer electrolyte include poly (diallyldimethylammonium chloride) (PDADMA-Cl); poly (diallyldimethylammonium chloride); (N, N-dimethyl-3,5-dimethylene piperidinium chloride), poly (ethylenimine), (PEI Poly (vinylamine), (PVAH), poly (N-methyl vinylamine), poly (allylamine), (PAH Poly (4-vinyl-1-methylpyridinium bromide); poly (allylammonium fluoride); poly (dimethylamine- Poly (lysine)]; poly (N, N, N ', N' '- tetramethyl-N-trimethylenehexa (Dimethylamino-ethyl) methacrylate) [Poly (2- (Dimethylamino) ethyl methacrylate) [Poly (N, N, N'N'-tetramethyl-N-trimethylenehexamethylenediammonium dibromide) -ethyl) methacrylate); poly (2-methacryloyloxy-ethyl-trimethylammonium chloride) [Poly (2- methacryloyloxy-ethyl-trimethylammonium chloride), poly (2-hydroxy-3-methacryloxypropyl-trimethylammonium chloride) (Poly (3-chloro-2-hydroxypropyl-2-methacryloxyethyl-dimethylammonium chloride), (PCHPMEDMAC) ) -Propylmethacrylamide]) {Poly (N- [3- (dimethylamino) -propyl methacrylamide])}; and poly ([3-methacryloylamino-propyl] -trimethylammonium chloride)], and examples of the anionic polyelectrolyte include polyacrylic acid [Poly (acrylic acid), (PAA)]; Poly (methacrylic acid) (PMA)]; Poly (itaconic acid); Poly (4-styrenesulfonic acid) (PSS); Poly (vinylphosphonic acid); Poly (vinylsulphonic acid); Poly (aspartic acid); Polyglutamic acid [Poly (glutamic acid)]; Poly (sodium 4-styrenesulfonate) (NaPSS); poly (sodium 4-styrenesulfonate); Poly-anetholesulfonic acid]; Poly (3-sulfopropyl methacrylate)]; Poly (1,4-phenylene ether-sulfone sulfonic acid)]; Or poly (1,4-phenylene ether ether ketone sulfonic acid)].
상기 열변색성 미세 입자는 상전이 물질, 염료 및 현색제를 포함한 코어(core)부를 포함할 수 있다. 또한, 상기 열변색성 미세 입자는 고분자 수지를 포함한 쉘(shell)층을 포함할 수 있다. 즉, 상기 열변색성 미세 입자는 코어-쉘 구조를 가질 수 있으며, 고분자 수지 내부로 상전이 물질, 염료 및 현색제의 혼합물이 함침된 형태를 가질 수 있다.The thermochromic fine particles may include a core portion including a phase change material, a dye, and a color developing agent. In addition, the thermochromic fine particles may include a shell layer including a polymer resin. That is, the thermochromic fine particles may have a core-shell structure, and the polymer resin may have a form impregnated with a mixture of a phase transfer material, a dye, and a developer.
상기 고분자 수지의 예는 크게 제한되지 않으며, 비드 또는 마이크로 캡슐 제조분야에서 널리 사용되는 다양한 수지를 제한없이 사용할 수 있으나, 예를 들어, 멜라민 수지, 우레아 수지, 페놀 수지, 멜라민-우레아 공중합체, 멜라민-페놀 공중합체, 에폭시 수지 또는 이들의 2종 이상의 혼합물 등을 사용할 수 있다.Examples of the polymer resin include, but are not limited to, various resins widely used in the field of bead or microcapsule production, including but not limited to melamine resin, urea resin, phenol resin, melamine-urea copolymer, melamine Phenol copolymers, epoxy resins, or mixtures of two or more thereof.
상기 열변색성 미세 입자를 제조하는 방법의 예가 크게 한정되는 것은 아니나, 예를 들어, 공지의 경계면 중합법, 멜라민-포르말린계 등의 in Situ 중합법, 액중 경화 피복법, 수용액으로부터의 상분리법, 유기용매로부터의 상분리법, 융해 분산 냉각법, 기중 현탁 피복법, 분무건조(spray drying)법 등을 제한없이 사용할 수 있다.Examples of the method for producing the thermochromic fine particles include, but are not limited to, known boundary polymerization methods, in situ polymerization methods such as melamine-formalin type, liquid phase hardening coating methods, phase separation methods from an aqueous solution, A phase separation method from an organic solvent, a fusion dispersion cooling method, a suspension coating method, a spray drying method, and the like can be used without limitation.
한편, 발명의 또 다른 구현예에 따르면, 상기 다른 구현예의 열변색성 미세 입자를 포함하는 열변색성 잉크 조성물이 제공될 수 있다.On the other hand, according to another embodiment of the invention, a thermochromic ink composition containing the thermochromic fine particles of the another embodiment may be provided.
상기 열변색성 잉크 조성물은 상기 일 구현예에서 제조된 열변색성 미세 입자를 안료로 사용하고, 종래 잉크 조성물 제조 분야에서 널리 사용되는 용매, 수지, 기타 첨가제를 혼합하여 제조될 수 있다.The thermochromic ink composition may be prepared by using the thermochromic fine particles prepared in the above embodiment as a pigment and mixing solvents, resins and other additives widely used in the field of conventional ink composition.
상기 열변색성 미세 입자에 관한 내용은 상기 일 구현예에 관하여 상술한 내용을 포함한다. The content of the thermochromic fine particles includes the above-mentioned contents in relation to the above embodiment.
상기 용매의 예로는 물, 에탄올, 프로판올, 부탄올, 글리세린, 소르비톨, 트리에탄올아민, 디에탄올아민, 모노에탄올 아민, 에틸렌글리콜, 디에틸렌글리콜, 티오디 에틸렌글리콜, 폴리에틸렌 글리콜, 프로필렌 글리콜, 부틸렌 글리콜, 에틸렌글리콜모노 메틸에테르, 에틸렌글리콜모노 에틸에테르, 에틸렌글리콜모노 부틸 에테르, 디에틸렌글리콜모노 메틸에테르, 디에틸렌글리콜모노 에틸에테르, 디에틸렌글리콜모노 부틸 에테르, 프로필렌글리콜 모노 부틸 에테르, 에틸렌글리콜모노 메틸에테르 아세테이트, 설포란,2-피롤리돈, N-메틸-2-피롤리돈 등을 들 수 있다.Examples of the solvent include water, ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether Acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone and the like.
상기 수지의 예로는, 케톤 수지, 케톤 포르말알데히드 수지, 아미드 수지, 알키드 수지, 로진 변성 수지, 로진 변성 페놀수지, 페놀 수지, 크실렌 수지, 폴리비닐 피롤리돈, α- 및 β-피넨·페놀 중축합 수지, 폴리비닐 부티랄 수지, 아크릴 수지, 스티렌 말레인산 공중합물, 셀룰로오스 유도체, 폴리비닐 피롤리돈, 폴리비닐알코올, 덱스트린 등을 들 수 있다.Examples of the resin include ketone resins, ketone formaldehyde resins, amide resins, alkyd resins, rosin-modified resins, rosin-modified phenol resins, phenol resins, xylene resins, polyvinylpyrrolidone, Polycondensation resin, polyvinyl butyral resin, acrylic resin, styrene maleic acid copolymer, cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin and the like.
또한 기타 첨가제로는, 보습제, 증점제, 계면활성제, 방부제 또는 이들의 2 종 이상의 혼합물을 사용할 수 있다. As other additives, a moisturizing agent, a thickening agent, a surfactant, an antiseptic agent or a mixture of two or more thereof may be used.
상기 보습제의 예로는 요소, 글리세린, 비이온계 경계면 활성제, 환원 또는 비환원 전분 가수분해물, 트레할로스 등의 올리고당류, 자당, 사이클로덱스트린, 포도당, 덱스트린, 소르비트, 만나이트, 피로인산 나트륨 등을 들 수 있다.Examples of the moisturizing agent include urea, glycerin, a nonionic surface active agent, reduced or unmodified starch hydrolyzate, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin, sorbit, mannit, sodium pyrophosphate, .
상기 증점제(또는 전단감 점성 부여제)로서는, 잔탄검, 웰란검, 구성 단당이 글루코스와 갈락토스의 유기산 수식 헤테로다당체인숙시노글리칸(평균 분자량 약 100 내지 800만), 아르카감, 구아검, 로커스트빈검 및 그 유도체, 하이드록시 에틸셀룰로오스, 알긴산 알킬에스테르류, 메타크릴산의 알킬 에스테르를 주성분으로 하는 분자량 10만~15만의 중합체, 글루코만난, 한천이나 카라기난 등의 해조에서 추출되는 젤로 변하는 능력을 가지는 증점다당류, 벤질리덴소르비톨 및 벤질리덴 자일리톨 또는 이들의 유도체, 가교성 아크릴산 중합체, 무기질 미립자, 폴리글리세린 지방산 에스테르, 폴리옥시에틸렌소르비탄 지방산 에스테르, 폴리에틸렌 글리콜 지방산 에스테르, 폴리옥시에틸렌 피마자유, 폴리옥시에틸렌 lanolin·라놀린 알코올·밀랍 유도체, 폴리옥시에틸렌알킬 에테르·폴리옥시프로필렌알킬 에테르, 폴리옥시에틸렌알킬 페닐 에테르, 지방산 아미드 등의 HLB값이 8~12의 비이온계 경계면 활성제, 디알킬 또는 디알케닐 술포호박산의염류, N-알킬-2-피롤리돈과 음이온계 경계면 활성제의 혼합물, 폴리비닐알코올과 아크릴계 수지의 혼합물을 예시할수 있다.Examples of the thickening agent (or the shear viscosity imparting agent) include xanthan gum, welan gum, organosiloxane-modified polysaccharide of glucose and galactose, insulin syringoglycan (average molecular weight of about 100 to 800,000), arcacephan, guar gum, locust A thickener having a molecular weight of 100,000 to 150,000 and an alkylester of methacrylic acid as its main components, a thickener having a capability of changing into a gel extracted from seaweed such as glucan, or agar or carrageenan, Polysaccharides, benzylidene sorbitol and benzylidene xylitol or derivatives thereof, crosslinkable acrylic acid polymers, inorganic fine particles, polyglycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene lanolin · Lanolin Alcohol · Waxy Derivatives, Poly Nonionic surfactants having an HLB value of 8 to 12 such as ethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether and fatty acid amide, salts of dialkyl or dialkylsulfosuccinic acids, N-alkyl-2 A mixture of pyrrolidone and an anionic surface active agent, and a mixture of polyvinyl alcohol and acrylic resin.
또한, 상기 계면활성제의 예로는 올레인산 등의 고급 지방산, 장쇄알킬기를 가지는 비이온성경계면 활성제, 폴리에테르 변성 실리콘 오일, 티오 아인산 트리(알콕시카르보닐메틸 에스테르)나 티오 아인산 트리(알콕시카르보닐에틸 에스테르) 등의 티오 아인산 트리에스테르, 폴리옥시에틸렌알킬 에테르 또는 폴리옥시에틸렌알킬 아릴 에테르의 인산 모노에스테르, 폴리옥시에틸렌알킬 에테르 또는 폴리옥시에틸렌알킬 아릴 에테르의 인산 디에스테르 등을 들 수 있다.Examples of the surfactant include higher fatty acids such as oleic acid, nonionic surfactants having a long-chain alkyl group, polyether-modified silicone oil, thiophosphoric acid tri (alkoxycarbonylmethyl ester), thiophosphoric acid tri (alkoxycarbonylethyl ester ), Phosphoric acid monoester of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether, phosphoric acid diester of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether, and the like.
상기 방부제의 예로는 석탄산, 1,2-벤즈 티아졸린3-온의 나트륨염, 안식향산 나트륨, 디하이드로초산 나트륨, 소르빈산 칼륨, 파라옥시 안식향 산프로필, 2,3,5,6-테트라 클로로-4-(메틸술포닐) 피리딘 등을 들 수 있다.Examples of the preservative include phenolic acid, sodium salt of 1,2-benzthiazoline 3-one, sodium benzoate, sodium dihydroxyacetate, potassium sorbate, propyl p-hydroxybenzoate, 2,3,5,6-tetrachloro- - (methylsulfonyl) pyridine, and the like.
한편, 발명의 또 다른 구현예에 따르면, 상기 다른 구현예의 열변색성 잉크 조성물이 충전된 잉크저장용기를 포함하는 필기구가 제공될 수 있다. 상기 필기구의 예가 크게 한정되는 것은 아니나, 예를 들어, 하기 도5에 나타난 바와 같이 잉크저장용기(2)와 상기 잉크저장용기(2)의 선단에 설치되는 볼펜 팁(3)과 후단면에는 상기 열변색성 잉크 조성물(1)이 충전되고, 상기 열변색성 잉크 조성물(1)의 후단부에는 잉크와 같이 추종하는 추종체(4)로 이루어지는 잉크저장용기(2)를 포함하는 캡식 또는 녹크식 필기도구(7)에 사용할 수 있다.According to another embodiment of the present invention, a writing instrument including the ink storage container filled with the thermochromic ink composition of the another embodiment may be provided. 5, the
또한, 도 6에 나타난 바와 같이 잉크 흡장체에 상기 열변색성 잉크 조성물(1)을 저장하여 펜선으로 마킹하는 마킹펜이나, 도 7에 나타난 바와 같이 상기 열변색성 잉크 조성물(1)을 직접 잉크저장용기(2)에 저장하는 직액식 마킹펜의 필기구에도 사용할 수 있다.
As shown in Fig. 6, a marking pen for storing the thermochromic ink composition (1) in the ink occluding element and marking it with a pen line, or a marking pen for directly heating the thermochromic ink composition (1) And can also be used for writing instruments of a direct-acting marking pen stored in the
상기 열변색성 잉크 조성물은 상기 필기구의 잉크저장용기에 충전될 수 있고, 상기 필기구에 열변색성 잉크 조성물을 충전하는 방법의 예는 크게 한정되지 않으며, 잉크를 사용하는 필기구 제조 분야에서 널리 사용되는 다양한 방법을 제한없이 사용할 수 있다.The thermochromic ink composition can be filled in an ink reservoir of the writing implement and the method for filling the writing implement with the thermochromic ink composition is not limited to a wide range and is widely used in the field of writing instruments using ink Various methods can be used without limitation.
또한, 상기 필기구는 마찰체 또는 발열체를 더 포함할 수 있다. 상기 마찰체는 찰과 시에 적당한 마찰을 일으켜 마찰열을 발생시킬 수 있는 물체를 의미하며, 상기 필기구에 의해 형성된 필적을 소거시키기 위해서 사용될 수 있다. 상기 마찰체의 예가 크게 한정되는 것은 아니나, 예를 들어 엘라스토머, 플라스틱 발포체 등의 탄성체, 플라스틱 성형체 또는 금속을 사용할 수 있다. Further, the writing implement may further include a friction member or a heating element. The rubbing body refers to an object which can generate friction heat by causing appropriate friction at the time of rubbing, and can be used to erase the handwriting formed by the writing tool. Examples of the rubbing member are not limited to a great extent, but may be, for example, an elastomer such as an elastomer or a plastic foam, a plastic molding or a metal.
상기 마찰체의 재질로는 실리콘 수지 또는 SBS 수지(스티렌 부타디엔 스티렌 블록공중합체)를 들 수 있으며, 실리콘 수지는 찰과에 의해 소거한 부분에 수지가 부착하기 쉽고, 반복 필기했을 때에 필적이 튕겨지는 경향이 있기 때문에, SBS 수지가 보다 바람직하게 사용될 수 있다.As the material of the rubbing body, silicone resin or SBS resin (styrene-butadiene styrene block copolymer) can be mentioned. The silicone resin is liable to adhere to the part which is erased by scratching, The SBS resin can be more preferably used.
상기 발열체는 전지로부터 전원을 공급받아 열을 발생시키는 물체를 의미하며, 상기 필기구에 의해 형성된 필적을 소거시키기 위해서 사용될 수 있다. 상기 발열체의 예가 크게 한정되는 것은 아니며, 전기의 공급에 의해 발열할 수 있는 소재 예를 들어 니크롬선 등을 사용할 수 있다. The heating element refers to an object which generates heat by receiving power from a battery, and may be used to erase the handwriting formed by the writing instrument. Examples of the heating element are not limited, and a material capable of generating heat by the supply of electricity, such as a nichrome wire, may be used.
상기 발열체는 직접 사용될 수도 있지만, 덮개로 감싸인 형태로 사용될 수 있다. 상기 덮개의 예가 크게 한정되는 것은 아니나, 예를 들어, 고무나 내열성과 전기적 절연성을 갖춘 다양한 소재를 사용할 수 있다.The heating element may be directly used, but may be used in a form of being wrapped with a cover. Although the example of the cover is not limited to a wide range, various materials having rubber, heat resistance and electrical insulation can be used, for example.
상기 마찰체 또는 발열체는 필기구의 형상은 크게 한정되지 않으며, 상기 필기구에 결합된 상태로 위치할 수 있다. 상기 필기구에 결합함으로서 휴대성이 향상될 수 있다. 보다 구체적으로 하기 도 5에 나타난 바와 같이, 상기 마찰체 또는 발열체(5)는 상기 필기구의 캡(6) 선단부에 결합하거나 축통끝 단부에 결합될 수 있다.The shape of the writing instrument is not limited to a shape of the writing member, and may be positioned in a state of being coupled to the writing instrument. Portability can be improved by being coupled to the writing instrument. More specifically, as shown in FIG. 5, the rubbing body or the
한편, 발명의 또 다른 구현예에 따르면, 상기 일 구현예의 열변색성 미세 입자가 분산된 코팅층을 포함하는 스마트 윈도우가 제공될 수 있다. 이에 따라, 상기 스마트 윈도우는 유리 표면에 형성된 코팅층에 의해 외부 온도에 따라 색이 바뀌면서, 유리의 투명도 속성을 변화시켜 빛 또는 열의 흡수정도를 조절할 수 있다.Meanwhile, according to another embodiment of the present invention, a smart window may be provided in which the thermochromic fine particles of one embodiment include a coating layer dispersed therein. Accordingly, the color of the smart window is changed according to the external temperature by the coating layer formed on the glass surface, and the degree of absorption of light or heat can be controlled by changing the transparency property of the glass.
상기 열변색성 미세 입자에 관한 내용은 상기 일 구현예에 관하여 상술한 내용을 포함한다. The content of the thermochromic fine particles includes the above-mentioned contents in relation to the above embodiment.
상기 코팅층은 상기 열변색성 미세 입자를 분산시키면서 점착력을 통해 코팅층 형성을 용이하게 하기 위해 바인더 수지를 더 포함할 수 있다. 상기 바인더 수지의 예는 크게 한정되지 않으나, 예를 들면, 폴리비닐알코올계 수지, 폴리우레탄계 수지, 폴리에스테르계 수지 및 아크릴계 수지 등을 사용할 수 있다. 이외에도, 코팅층 제조분야에서 널리 사용되는 다양한 고분자 수지를 제한없이 사용할 수 있다.The coating layer may further include a binder resin to disperse the thermochromic fine particles and facilitate formation of a coating layer through adhesive force. Examples of the binder resin are not particularly limited, and for example, a polyvinyl alcohol resin, a polyurethane resin, a polyester resin and an acrylic resin can be used. In addition, various polymer resins widely used in the coating layer manufacturing field can be used without limitation.
상기 스마트 윈도우에 코팅층을 형성하는 방법의 예로는 상기 열변색성 미세 입자가 분산된 바인더 수지를 유리창 표면에 도포하는 방법을 들 수 있다.Examples of a method of forming a coating layer on the smart window include a method of applying a binder resin in which the thermochromic fine particles are dispersed to the surface of a glass window.
본 발명에 따르면, 높은 발색성 및 소색성을 안정적으로 구현할 수 있고, 소거성, 내열성 및 내화학성이 향상된 열변색성 잉크 조성물, 그리고 이를 이용한 입자, 잉크, 필기구 및 스마트 윈도우가 제공될 수 있다. According to the present invention, a thermochromic ink composition capable of stably realizing high coloring and decoloring properties and having improved smudge resistance, heat resistance and chemical resistance, and particles, inks, writing instruments and smart windows using the same can be provided.
도 1은 실시예의 열변색성 미세 입자에 대한 상전이 특성을 나타낸 것이다.
도 2는 실시예1에서 제조한 열변색성 미세 입자의 표면 SEM이미지를 나타낸 것이다.
도 3은 실시예1에서 제조한 열소거성 잉크용 입자의 DSC 특성을 나타낸 것이다.
도 4는 실시예의 열변색성 잉크 조성물의 열변색 특성을 나타낸 것이다.
도 5는 실시예의 열변색성 잉크 조성물이 포함된 캡식 또는 녹크식 필기구의 개략적인 구조를 나타낸 것이다.
도 6은 실시예의 열변색성 잉크 조성물이 포함된 흡장식 마킹펜의 개략적인 구조를 나타낸 것이다.
도 7은 실시예의 열변색성 잉크 조성물이 포함된 직액식 마킹펜의 개략적인 구조를 나타낸 것이다.1 shows the phase transition characteristics of the thermochromic fine particles of the example.
Fig. 2 shows a surface SEM image of the thermochromic fine particles prepared in Example 1. Fig.
Fig. 3 shows DSC characteristics of the thermosensitive ink particles prepared in Example 1. Fig.
4 shows the thermal discoloration characteristics of the thermochromic ink composition of the example.
Fig. 5 shows a schematic structure of a cap or knuckle writing instrument including the thermochromic ink composition of the embodiment.
Fig. 6 shows a schematic structure of a suction ornamental marking pen including the thermochromic ink composition of the embodiment.
7 shows a schematic structure of a direct-liquid marking pen including the thermochromic ink composition of the embodiment.
발명을 하기의 실시예에서 보다 상세하게 설명한다. 단, 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다. The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
<실시예 1 내지 2: 열변색성 미세 입자 및 잉크 조성물의 제조>≪ Examples 1 to 2: Preparation of thermochromic fine particles and ink composition >
실시예1Example 1
(1)열변색성 미세 입자의 제조(1) Production of thermochromic fine particles
상전이 물질 RT-9HC(Rubitherm사 파라핀 왁스)과 라우릴 알코올(Lauryl alcohol)을 용매로 하여, 현색제로서 비스페놀 A 3g, 락톤계 염료(Crystal violet lactone) 1g를 혼합하고, 벽막 재료로서 에폭시화합물을 8％ 폴리비닐알코올 수용액 중에서 미소 물방울이 되도록 유화 분산하고, 디에틸렌트리아민(Diethylenetriamine)을 첨가한 후, 70℃에서 약 5 시간 교반을 계속하여 현탁액을 얻었다. 이후, 상기 현탁액을 원심분리하여 열변색성 미세 입자를 얻었다.3 g of bisphenol A and 1 g of a crystal violet lactone as a color developing agent were mixed with the phase transition material RT-9HC (Rubitherm paraffin wax) and lauryl alcohol as a solvent, and an epoxy compound The mixture was emulsified and dispersed in an aqueous 8% polyvinyl alcohol solution so as to form small droplets, diethylenetriamine was added thereto, and stirring was continued at 70 캜 for about 5 hours to obtain a suspension. Thereafter, the suspension was centrifuged to obtain thermochromic fine particles.
(2)열변색성 잉크 조성물의 제조 (2) Preparation of thermochromic ink composition
상기 열변색성 미세입자 10중량%, 보습제로서 글리세린 10중량%, 증점제로서 Xanthan Gum 0.5중량%, 인산에스테르계 계면활성제(상품명:PHOSPHANOL RS-410, 일본국 토호케미칼인더스트리주식회사제) 1중량%, 물 65중량% 및 방부제로 Proxel XL-2 0.3중량%을 혼합하고, 용해 및 분산하여 열변색성 잉크 조성물을 얻었다.10 wt% of the thermochromic fine particles, 10 wt% of glycerin as a humectant, 0.5 wt% of Xanthan Gum as a thickener, 1 wt% of a phosphate ester surfactant (trade name: PHOSPHANOL RS-410, 65% by weight of water and 0.3% by weight of Proxel XL-2 as a preservative were mixed and dissolved and dispersed to obtain a thermochromic ink composition.
실시예2Example 2
(1)열변색성 미세 입자의 제조(1) Production of thermochromic fine particles
상전이 물질 ECOJOULE TS 1(파라핀 왁스) 10g 및 스테아릴알콜(Stearyl alcohol) 15g를 용매로 하여, 현색제로서 2,2-Bis(4-hydroxyphenyl)-hexafluoropropane 3g, 락톤계 염료(Crystal violet lactone) 1g를 혼합하고, 벽막 재료로서 KER 828(Epoxy resin, 금호피앤비화학제품)을 8％ 폴리비닐알코올 수용액 중에서 미소 물방울이 되도록 유화 분산하고, 경화제로서 A-053(국도화학사제)를 첨가한 후, 70℃에서 약 5 시간 교반을 계속하여 현탁액을 얻었다. 이후, 상기 현탁액을 원심분리하여 열변색성 미세 입자를 얻었다.3 g of 2,2-bis (4-hydroxyphenyl) -hexafluoropropane as a developer and 1 g of a crystal violet lactone as a solvent using 10 g of a phase change material ECOJOULE TS 1 (paraffin wax) and 15 g of stearyl alcohol as a solvent. And KER 828 (Epoxy resin, Kumho P & Chemicals) as a wall material was emulsified and dispersed in an aqueous 8% polyvinyl alcohol solution so as to form small droplets. A-053 (Kukdo Chemical Co., Ltd.) was added as a curing agent, Stirring was continued at 70 캜 for about 5 hours to obtain a suspension. Thereafter, the suspension was centrifuged to obtain thermochromic fine particles.
(2)열변색성 잉크 조성물의 제조(2) Preparation of thermochromic ink composition
상기 열변색성 미세입자 10중량%, 보습제로서 글리세린 10중량%, 증점제로서 Xanthan Gum 0.5중량%, 인산에스테르계 계면활성제(상품명:PHOSPHANOL RS-410, 일본국 토호케미칼인더스트리주식회사제) 1중량%, 물 65중량% 및 방부제로 Proxel XL-2 0.3중량%을 혼합하고, 용해 및 분산하여 열변색성 잉크 조성물을 얻었다.10 wt% of the thermochromic fine particles, 10 wt% of glycerin as a humectant, 0.5 wt% of Xanthan Gum as a thickener, 1 wt% of a phosphate ester surfactant (trade name: PHOSPHANOL RS-410, 65% by weight of water and 0.3% by weight of Proxel XL-2 as a preservative were mixed and dissolved and dispersed to obtain a thermochromic ink composition.
<비교예 1 내지 3: 열변색성 미세 입자 및 잉크 조성물의 제조>≪ Comparative Examples 1 to 3: Preparation of thermochromic fine particles and ink composition >
비교예1Comparative Example 1
(1)열변색성 미세 입자의 제조(1) Production of thermochromic fine particles
용매로 상전이 물질 없이 퍼푸릴알콜(Furfuryl alcohol)만을 사용한 점을 제외하고 상기 실시예1과 동일한 방법으로 열변색성 미세 입자를 얻었다.Thermochromic fine particles were obtained in the same manner as in Example 1 except that only furfuryl alcohol was used as a solvent without a phase transition material.
(2)열변색성 잉크 조성물의 제조 (2) Preparation of thermochromic ink composition
상기 실시예1과 동일한 방법으로 열변색성 잉크 조성물을 얻었다.A thermochromic ink composition was obtained in the same manner as in Example 1 above.
비교예2Comparative Example 2
(1)열변색성 미세 입자의 제조(1) Production of thermochromic fine particles
용매로 상전이 물질 없이 스테아릴 스테아레이트(Stearyl stearate)를 사용한 점을 제외하고 상기 실시예1과 동일한 방법으로 열변색성 미세 입자를 얻었다.Thermochromic fine particles were obtained in the same manner as in Example 1 except that stearyl stearate was used as a solvent without a phase transition material.
(2)열변색성 잉크 조성물의 제조 (2) Preparation of thermochromic ink composition
상기 실시예1과 동일한 방법으로 열변색성 잉크 조성물을 얻었다.A thermochromic ink composition was obtained in the same manner as in Example 1 above.
비교예3Comparative Example 3
(1)열변색성 미세 입자의 제조(1) Production of thermochromic fine particles
용매로 상전이 물질 없이 부틸 스테아레이트(Buthyl stearate)를 사용한 점을 제외하고 상기 실시예1과 동일한 방법으로 열변색성 미세 입자를 얻었다.Thermochromic fine particles were obtained in the same manner as in Example 1, except that butyl stearate was used as a solvent without a phase transition material.
(2)열변색성 잉크 조성물의 제조 (2) Preparation of thermochromic ink composition
상기 실시예1과 동일한 방법으로 열변색성 잉크 조성물을 얻었다.A thermochromic ink composition was obtained in the same manner as in Example 1 above.
<실험예><Experimental Example>
1. 결정화 온도 및 용융 온도1. Crystallization temperature and melting temperature
상기 실시예 및 비교예에서 얻어진 열변색성 미세 입자에 대하여, 시차주사 열량측정법(differential scanning calorimetry, DSC)을 이용하여, 하기 도3과 같은 곡선을 통해 결정화 온도 및 용융 온도를 측정하였으며, 그 결과를 하기 표1에 나타내었다.The crystallization temperature and the melting temperature were measured by the differential scanning calorimetry (DSC) of the thermochromic fine particles obtained in the above Examples and Comparative Examples through the curve shown in FIG. 3, Are shown in Table 1 below.
2. 상전이 특성2. Phase transition characteristics
상기 실시예 1 및 2에서 얻어진 열변색성 미세 입자에 대하여, 상전이 물질의 분율(Xpha)에 따른 상조성을 측정하였으며, 그 결과를 도1에 나타내었다.The composition of the thermochromic fine particles obtained in Examples 1 and 2 was measured according to the fraction (X pha ) of the phase transition material. The results are shown in FIG.
하기 도1에 나타난 바와 같이, 실시예의 열변색성 미세 입자는 -10℃ 와 -5℃ 사이에서 결정화 온도를 가지며, 50℃ 이상에서 녹는점을 갖는 특징을 나타냈다. 이에 따라, 50℃ 이상에서는 열변색성 미세 입자의 발색성이 사라져 무색을 띠는 것을 확인할 수 있다. 이러한 상전이 특성은 상기 열변색성 미세 입자에 포함된 상전이 물질에 의한 것으로서, 상전이 물질에 의해 염료의 변색온도범위가 조절되는 것을 확인할 수 있었다.As shown in FIG. 1, the thermochromic fine particles of the examples had a crystallization temperature between -10 ° C. and -5 ° C. and a melting point of 50 ° C. or higher. As a result, it can be confirmed that the color-forming property of the thermochromic fine particles disappears at 50 ° C or more and is colorless. It was confirmed that the phase transition property is attributed to the phase transition material contained in the thermochromic fine particles, and the temperature range of the color change of the dye was controlled by the phase transition material.
또한, 하기 도1의 그래프에서 곡선으로 표시된 경계면을 기준으로 고체와 액체로 이루어진 두개의 상이 공존하는 것을 확인하였고, 변곡점 분율(Xpha)에서 상전이 구간의 간격이 최대로 나타나 발색성과 소색성이 유지되는 효과가 높아진 것을 확인할 수 있었다.Also, it was confirmed that two phases of solid and liquid coexist on the basis of the curved line in the graph of FIG. 1, and the interval of the phase transition interval at the inflection point fraction (X pha ) was the maximum, The effect of the present invention can be confirmed.
3. 표면 형태3. Surface type
상기 실시예 1 에서 얻어진 열변색성 미세 입자에 대해 FE-SEM을 통해 표면 형태를 확인하였고, 그 결과를 하기 도2 에 나타내었다.The surface morphology of the thermochromic fine particles obtained in Example 1 was confirmed by FE-SEM, and the results are shown in Fig.
하기 도 2 에 나타난 바와 같이, 상기 실시예 1에서 얻어진 열변색성 미세 입자는 0.1 ㎛ 내지 10 ㎛의 직경을 갖는 구형의 입자 형태임을 확인할 수 있었다.As shown in FIG. 2, it was confirmed that the thermochromic fine particles obtained in Example 1 were spherical particles having a diameter of 0.1 to 10 μm.
4. 열변색성4. Thermal discoloration
상기 실시예 및 비교예에서 얻어진 열변색성 잉크 조성물을 이용하여, 하기 도4와 같이 상온에서 종이에 이미지를 그린 후에, 50℃ 온도로 가열하여 이미지의 변화를 관찰하였으며, 그 결과를 다음과 같은 기준하에 평가하여 하기 표1에 나타내었다.Using the thermochromic ink composition obtained in the above Examples and Comparative Examples, an image was drawn on paper at room temperature as shown in FIG. 4, and then the image was heated at a temperature of 50 DEG C to observe the change of the image. The results are shown in Table 1 below.
О: 50℃ 온도로 가열한 이후, 이미지가 완전히 소거됨 О: Image is completely erased after heating to 50 ° C
△: 50℃ 온도로 가열한 이후, 이미지가 일부 소거되지 않고 남아있음△: After heating to 50 ° C, the image remains partially erased
X : 50℃ 온도로 가열한 이후, 이미지가 소거되지 않음X: Image is not erased after heating to 50 ° C
상기 표1에 나타난 바와 같이, 상기 실시예에서 얻어진 열변색성 잉크 조성물을 이용해 상온에서 그렸던 이미지는 50℃ 온도로 가열한 이후, 완전히 소거되어 우수한 열변색성을 나타냄을 확인할 수 있었다. As shown in Table 1, it was confirmed that the image formed at room temperature using the thermochromic ink composition obtained in the above example was completely erased after heating to 50 ° C, and showed excellent discoloration.
반면, 상전이 물질이 사용되지 않은 비교예의 경우, 비교예1 및 3에서는 결정화 온도 또는 용융온도가 측정되지 않아 열변색성 자체가 구현되지 않았으며, 상기 비교예2에서는 변색온도 범위가 50℃ 미만으로 나타나, 충분한 열변색성이 구현되지 않음을 확인할 수 있었다.On the other hand, in the comparative example in which no phase transition material was used, the crystallization temperature or the melting temperature was not measured in Comparative Examples 1 and 3, and the thermochromic property itself was not realized. In Comparative Example 2, As a result, it was confirmed that sufficient heat discoloration was not realized.
이를 통해, 상기 실시예의 열변색성 잉크 조성물은 상온에서 우수한 발색성을 유지하면서, 상온과 50℃사이에서 변색이 발생하여 지우개에 의한 마찰열 등에 의한 신속하게 소거될 수 있음을 확인할 수 있다.It can be seen from the above that the thermochromic ink composition of the above example can be quickly erased by frictional heat caused by the eraser due to discoloration occurring between room temperature and 50 ° C while maintaining excellent coloring property at room temperature.
1: 열변색성 잉크 조성물
2: 잉크저장용기
3: 볼펜 팁 또는 펜선
4: 추종체
5: 마찰체 또는 발열체
6: 캡
7: 필기구 또는 도포구1: thermochromic ink composition
2: Ink storage container
3: Pen tip or pen line
4: follower
5: Friction body or heating element
6: Cap
7: Writing utensils or dispensers
Claims (20)
A core part comprising at least one chain-like hydrocarbon having at least 8 carbon atoms, a phase transition material including at least one selected from the group consisting of inorganic hydrated salts, alcohols having 5 or more carbon atoms, and polyalkylene glycols; And a shell layer comprising a polymeric resin.
하기 일반식 1로 정의되는 변색 온도 범위가 50 ℃ 이상인, 열변색성 미세 입자:
[일반식1]
변색온도범위(T) = 상전이 물질의 녹는점과 결정화 온도의 차이의 절대값.
The method according to claim 1,
A thermochromic fine particle having a discoloration temperature range defined by the following general formula (1)
[Formula 1]
Discoloration temperature range (T) = absolute value of the difference between the melting point of the phase transition material and the crystallization temperature.
상기 상전이 물질의 결정화 온도는 -20 ℃ 내지 0 ℃인, 열변색성 미세 입자.
3. The method of claim 2,
Wherein the phase transition material has a crystallization temperature of from -20 占 폚 to 0 占 폚.
상기 상전이 물질의 녹는점은 50 ℃ 이상인, 열변색성 미세 입자.
3. The method of claim 2,
Wherein the phase transition material has a melting point of 50 ° C or higher.
상기 탄소수 8이상의 사슬형 탄화수소는 탄소수 10 내지 50의 직쇄 포화탄화수소를 포함하는, 열변색성 미세 입자.
The method according to claim 1,
Wherein said chain-like hydrocarbon having at least 8 carbon atoms comprises a straight-chain saturated hydrocarbon having 10 to 50 carbon atoms.
상기 수화 무기염은 무기산 금속염의 수화물 또는 유기산 금속염의 수화물을 포함하는, 열변색성 미세 입자.
The method according to claim 1,
Wherein the hydrated inorganic salt comprises a hydrate of an inorganic acid metal salt or a hydrate of an organic acid metal salt.
상기 무기산 금속염은 금속의 황산염, 질산염, 탄산염, 인산염, 싸이오황산염 또는 할로겐화물을 포함하는, 열변색성 미세 입자.
The method according to claim 6,
Wherein said inorganic acid metal salt comprises a sulfate, nitrate, carbonate, phosphate, thiosulfate or halide of a metal.
상기 유기산 금속염은 금속의 아세트산염을 포함하는, 열변색성 미세 입자.
The method according to claim 6,
Wherein the organic acid metal salt comprises an acetate of a metal.
상기 탄소수 5 이상의 알코올은 탄소수 6 내지 50의 지방족 알코올 또는 탄소수 3 내지 20의 방향족 알코올을 포함하는, 열변색성 미세 입자.
The method according to claim 1,
Wherein the alcohol having 5 or more carbon atoms comprises an aliphatic alcohol having 6 to 50 carbon atoms or an aromatic alcohol having 3 to 20 carbon atoms.
상기 상전이 물질의 함량이 10 중량% 내지 70 중량%인, 열변색성 미세 입자.
The method according to claim 1,
Wherein the content of the phase transfer material is 10 wt% to 70 wt%.
상기 염료에 대한 현색제의 중량비율이 1 내지 10인, 열변색성 미세 입자.
The method according to claim 1,
Wherein the weight ratio of the color developer to the dye is 1 to 10.
상기 염료는 락톤계 염료인, 열변색성 미세 입자.
The method according to claim 1,
The dye is a lactone-based dye, a thermochromic fine particle.
상기 락톤계 염료는 프탈리드계 화합물 또는 플루오란계 화합물을 포함하는, 열변색성 미세 입자.
13. The method of claim 12,
Wherein the lactone-based dye comprises a phthalide-based compound or a fluororan-based compound.
상기 현색제는 페놀계 화합물을 포함하는, 열변색성 미세 입자.
The method according to claim 1,
Wherein the developer comprises a phenol-based compound.
상기 열변색성 미세 입자의 직경은 0.1 ㎛ 내지 10 ㎛인, 열변색성 미세 입자.
The method according to claim 1,
Wherein the thermochromic fine particles have a diameter of 0.1 占 퐉 to 10 占 퐉.
상기 고분자 수지는 멜라민 수지, 우레아 수지, 페놀 수지, 멜라민-우레아 공중합체, 멜라민-페놀 공중합체 및 에폭시 수지로 이루어진 군에서 선택된 1종 이상을 포함하는, 열변색성 미세 입자.
The method according to claim 1,
Wherein the polymer resin comprises at least one member selected from the group consisting of a melamine resin, a urea resin, a phenol resin, a melamine-urea copolymer, a melamine-phenol copolymer and an epoxy resin.
상기 열변색성 미세 입자에 포함된 코어부 또는 쉘층이 팽창제 또는 수축제를 더 포함하는, 열변색성 미세 입자.
The method according to claim 1,
Wherein the core or shell layer contained in the thermochromic fine particles further comprises a swelling agent or a shrinking agent.
A thermochromic ink composition comprising the thermochromic fine particles of claim 1.
18. A writing implement comprising an ink storage container filled with the thermochromic ink composition of claim 18.
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| ES16174734T ES2740828T3 (en) | 2015-06-26 | 2016-06-16 | Thermochromic microparticles and thermochromic ink composition, writing device or smart window that use them |
| EP16174734.0A EP3109286B1 (en) | 2015-06-26 | 2016-06-16 | Thermochromic micro particles and thermochromic ink composition, writing apparatus and smart window using the same |
| US15/190,090 US9879147B2 (en) | 2015-06-26 | 2016-06-22 | Thermochromic micro particles and thermochromic ink composition, writing apparatus and smart window using the same |
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