JPH1121464A - Molding resin composition with reversible thermal color changeability and molded form using the same - Google Patents
Molding resin composition with reversible thermal color changeability and molded form using the sameInfo
- Publication number
- JPH1121464A JPH1121464A JP20701497A JP20701497A JPH1121464A JP H1121464 A JPH1121464 A JP H1121464A JP 20701497 A JP20701497 A JP 20701497A JP 20701497 A JP20701497 A JP 20701497A JP H1121464 A JPH1121464 A JP H1121464A
- Authority
- JP
- Japan
- Prior art keywords
- reversible thermochromic
- molding
- electron
- resin composition
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は特別の電子受容性を
有する耐光性付与剤を存在させることにより発色時の耐
光性を向上させた可逆的熱変色性成形用樹脂組成物と成
形体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reversible thermochromic molding resin composition and a molded article having a light resistance imparting agent having a special electron-accepting property and having improved light resistance during color development.
【０００２】[0002]
【従来の技術】電子供与性化合物と電子受容性化合物を
組み合わせた熱変色性組成物は例えば米国特許第３，５
６０，２２９号明細書に示されるように公知である。こ
の組成物は組み合わせた両化合物の種類により変色温度
が定まるため、所望の温度で変色する組成物を得ること
が非常に困難であった。本発明者はこの問題を特定のア
ルコールやエステル、ケトンを変色温度調整剤として使
用し変色温度を所望の温度に調整する発明を提供した
（特公昭５１−４４７０６号、特公昭５１−４４７０８
号、特公昭５１−３５２１６号、特公昭５１−３７１８
０号）。2. Description of the Related Art Thermochromic compositions combining an electron-donating compound and an electron-accepting compound are disclosed, for example, in US Pat.
No. 60,229. Since the discoloration temperature of this composition is determined by the type of the two compounds combined, it has been very difficult to obtain a composition that discolors at a desired temperature. The inventor of the present invention has provided inventions which solve this problem by using a specific alcohol, ester or ketone as a discoloration temperature adjusting agent to adjust the discoloration temperature to a desired temperature (JP-B-51-44706, JP-B-51-44708).
No., JP-B-51-35216, JP-B-51-3718
No. 0).
【０００３】[0003]
【発明が解決しようとする課題】本発明者が前に提供し
た発明は同一の電子供与性化合物と電子受容性化合物の
組み合わせであっても変色温度を所望の温度に調節する
ことができる等の点で画期的な発明である。しかしなが
らこれ等の電子供与性化合物と電子受容性化合物を組み
合わせた発明は電子供与性化合物の耐光性が大きくない
ためこれを用いた熱変色性組成物も耐光性が大きくない
欠点がある。そのため変色した色が光により薄くなった
り甚だしいときは完全に脱色する場合もある。従来化合
物に耐光性を付与するために紫外線吸収剤を配合するこ
とが行われているが、電子供与性化合物と電子受容性化
合物からなる熱変色性組成物に紫外線吸収剤を配合する
と消色状態では耐光性が向上するが発色状態ではほとん
ど効果がなく、特に間接光に対しては全く効果がない。
また金属光沢顔料と紫外線吸収剤を併用して可視光線の
一部も遮断すると消色状態の耐光性は飛躍的に改良され
るが発色状態では効果は小さく、特に間接光に対しては
効果がない。この他ヒンダードアミン系、ヒンダードフ
ェノール系、イオウ系、ニッケル錯塩系等の光安定剤は
消色状態でも発色状態でもほとんど効果はない。本発明
者はこのような問題を解決するため、特別な耐光性付与
剤を用いて発色時の耐光性を向上する方法の発明を出願
した。（特願平７−３５４７１１） 本発明は発色時の耐光性を向上した可逆的熱変色性を有
する成形用樹脂組成物及びこれを用いた成形体を提供す
るものである。長期間の可逆的熱変色性を要求される成
形用樹脂組成物及びこれを用いた成形体には耐光性は非
常に重要な性能である。SUMMARY OF THE INVENTION The invention provided by the present inventor before can control the discoloration temperature to a desired temperature even with a combination of the same electron donating compound and electron accepting compound. This is a groundbreaking invention. However, the invention in which the electron donating compound and the electron accepting compound are combined does not have high light fastness of the electron donating compound, and therefore, the thermochromic composition using the compound has a disadvantage that the light fastness is not high. Therefore, when the discolored color becomes thin or severe due to light, it may be completely bleached. Conventionally, an ultraviolet absorber is blended to impart light resistance to the compound. However, when the ultraviolet absorber is blended in a thermochromic composition comprising an electron donating compound and an electron accepting compound, the decolored state is obtained. In this case, the light resistance is improved, but there is almost no effect in the color-developed state, and there is no effect particularly on indirect light.
In addition, when a part of visible light is blocked by using a metallic luster pigment and an ultraviolet absorber together, the light resistance in the decolored state is dramatically improved, but the effect is small in the colored state, and it is particularly effective for indirect light. Absent. In addition, hindered amine-based, hindered phenol-based, sulfur-based, nickel complex salt-based light stabilizers have almost no effect in a decolored state or a colored state. In order to solve such a problem, the present inventor has applied for an invention of a method for improving light fastness at the time of coloring by using a special light fastness imparting agent. (Japanese Patent Application No. 7-354711) The present invention provides a molding resin composition having reversible thermochromic property with improved light fastness at the time of color development, and a molded article using the same. Light resistance is a very important property for a molding resin composition that requires long-term reversible thermochromic properties and a molded article using the same.
【０００４】[0004]
【課題を解決した手段】本発明は、 「１． ａ．電子供与化合物と、 ｂ．電子受容化合物と、 ｃ．変色温度調整剤と、 ｄ．つぎの一般式Ｉで示され、ａ．の電子供与化合物
１．０重量部に対し０．３〜７０重量部の使用割合の電
子受容性を有する耐光性付与剤と一般式ＩThe present invention comprises: 1. a. An electron donating compound, b. An electron accepting compound, c. A discoloration temperature regulator, d. A lightfastness-imparting agent having an electron-accepting ratio of 0.3 to 70 parts by weight to 1.0 part by weight of an electron-donating compound;
【０００５】[0005]
【化２】 Embedded image
【０００６】｛式中、ｎ＝５〜１７（直鎖及び分岐）、
Ｘ＝Ｃ１〜Ｃ４（直鎖及び分岐）、ハロゲン、Ｙ＝Ｃ１
〜Ｃ４（直鎖及び分岐）、ハロゲン、ｐ＝０〜３、ｍ＝
０〜３である。｝ ｅ．成形用樹脂と、からなる、発色時の耐光性を向上し
た可逆的熱変色性を有する成形用樹脂組成物。 ２． ｄ．の電子受容性を有する耐光性付与剤を、 ｂ．の電子受容体に兼用した、１項に記載された発色時
の耐光性を向上した可逆的熱変色性を有する成形用樹脂
組成物。 ３． ａ．〜ｄ．成分をマイクロカプセルに内蔵した、
１項または２項に記載された発色時の耐光性を向上した
可逆的熱変色性を有する成形用樹脂組成物。 ４． ｅ．成分が熱可塑性樹脂である、１項ないし３項
のいずれか１項に記載された発色時の耐光性を向上した
可逆的熱変色性を有する成形用樹脂組成物。 ５． １項ないし４項のいずれか１項に記載された成形
用樹脂組成物を用いて成形した、発色時の耐光性を向上
した可逆的熱変色性を有する成形体。 ６． 前記成形体がフィラメントである、５項に記載さ
れた発色時の耐光性を向上した可逆的熱変色性を有する
成形体。 ７． 前記成形体がフイルムである、５項に記載された
発色時の耐光性を向上した可逆的熱変色性を有する成形
体。」に関する。Wherein n = 5 to 17 (linear and branched);
X = C 1 ~C 4 (linear and branched), halogen, Y = C 1
-C 4 (linear and branched), halogen, p = 0 to 3, m =
0 to 3. ｝ E. A resin composition for molding, comprising: a molding resin; and a reversible thermochromic property having improved light fastness during color development. 2. d. A light resistance imparting agent having an electron accepting property of b. 4. The molding resin composition having reversible thermochromic property and improved light fastness at the time of coloring described in 1 above, which is also used as the electron acceptor. 3. a. ~ D. Ingredients built in microcapsules,
4. A molding resin composition having reversible thermochromic properties as described in paragraph 1 or 2, which has improved light fastness during coloring. 4. e. Item 4. The resin composition for molding according to any one of Items 1 to 3, wherein the component is a thermoplastic resin and has reversible thermochromic properties with improved light fastness during color development. 5. A molded article molded using the molding resin composition according to any one of Items 1 to 4 and having reversible thermochromic properties with improved light fastness during color development. 6. 6. The molded article having reversible thermochromic properties as described in item 5, wherein the molded article is a filament and has improved light fastness during coloring. 7. 6. The molded article having reversible thermochromic properties as described in item 5, wherein the molded article is a film and has improved light fastness during color development. About.
【０００７】本発明は、電子供与性化合物と電子受容性
化合物と変色温度調整剤と成形用樹脂とからなる可逆的
熱変色性成形用樹脂組成物において、前述の一般式Ｉで
示される、耐光性付与剤を電子供与性化合物１．０重量
部に対して０．３〜７０重量部組成物中に存在させるこ
とにより発色時の耐光性を向上させた成形用樹脂組成物
である。耐光性付与剤の使用量は電子供与性化合物１．
０重量部に対し２．０〜７．０重量部が特に好ましい。
電子供与性化合物の代表としてロイコ染料があるが、電
子供与性化合物は電子を供与した状態つまりロイコ染料
で説明すると発色状態になるとイオン化されイオン状態
となる。このようにイオン化された状態になると耐光性
が低下し、光により電子供与性能が低下し可逆的熱変色
性が劣化することがわかった。この発色状態における耐
光性の低下は意外にも可視光線により発生するところが
大きい。特に間接光によって耐光性の低下は発生する。
消色状態はイオン化されてなく、無色の分子状態である
ため、可視光線の影響はほとんどない。The present invention relates to a reversible thermochromic molding resin composition comprising an electron-donating compound, an electron-accepting compound, a color-changing temperature regulator and a molding resin. A molding resin composition having improved light fastness at the time of color development by allowing a property imparting agent to be present in the composition in an amount of 0.3 to 70 parts by weight based on 1.0 part by weight of the electron donating compound. The amount of the light fastness-imparting agent to be used is as follows.
2.0 to 7.0 parts by weight to 0 parts by weight is particularly preferred.
A leuco dye is a representative example of the electron donating compound, and the electron donating compound is ionized and becomes an ionic state when it is in a state of donating electrons, that is, when it is described as a leuco dye, in a colored state. It has been found that when the ionized state is reached, the light resistance is reduced, the electron donating performance is reduced by light, and the reversible thermochromic property is deteriorated. Surprisingly, the decrease in light resistance in the color-developed state is largely caused by visible light. In particular, the light resistance is reduced by indirect light.
Since the decolored state is a non-ionized and colorless molecular state, there is almost no influence of visible light.
【０００８】耐光性を向上するために使用されている、
紫外線吸収剤、金属光沢顔料、酸化防止剤、老化防止剤
等はロイコ染料の消色状態の耐光性向上には効果がある
が、発色状態では効果が非常に小さい。従来使用されて
いるこのような耐光性配合剤は、分子状態にある物質の
耐光性を向上する作用はある。通常光を受ける可能性の
ある所で使用されている物質は分子状態にあるものがほ
とんどであって、イオン状態で使用されるものは稀であ
り、紫外線吸収剤等で充分効果があった。[0008] used to improve light fastness,
Ultraviolet absorbers, metallic luster pigments, antioxidants, antioxidants, etc. are effective in improving the light fastness of the decolorized state of the leuco dye, but are very small in the colored state. Such a light-fast compounding agent conventionally used has an effect of improving the light fastness of a substance in a molecular state. Most of the substances which are usually used in a place where there is a possibility of receiving light are in a molecular state, and those which are used in an ionic state are rare, and an ultraviolet absorber or the like is sufficiently effective.
【０００９】ところが、本発明の可逆的熱変色性を有す
る成形用樹脂組成物は特殊な技術に属し、電子を供与し
た物質はイオン状態となりこの状態で組成物は発色す
る。そして消色状態では分子状態となっており、分子状
態では無色で可視光線を吸収しないため、紫外線のカッ
トだけで、十分な耐光性向上効果がある。一方、イオン
状態では、着色しているため、紫外線のカットだけでは
不十分であり、更に可視光線のカットも必要である。However, the molding resin composition having a reversible thermochromic property of the present invention belongs to a special technique, and the electron donating substance becomes an ionic state, and the composition develops a color in this state. In the decolored state, it is in the molecular state, and in the molecular state, it is colorless and does not absorb visible light. Therefore, merely cutting off ultraviolet rays has a sufficient effect of improving light resistance. On the other hand, in the ionic state, since it is colored, it is not sufficient to cut only ultraviolet rays, and further, it is necessary to cut visible rays.
【００１０】本発明の可逆的熱変色性を有する成形用樹
脂組成物の発色状態と消色状態について説明する。本発
明での可逆的熱変色性を有する成形用樹脂組成物のａ．
成分、ｂ．成分、ｃ．成分は実際に取扱う状態ではイオ
ン化合物ではなく、全て分子状化合物である。これ等の
成分が均一に混合された可逆的熱変色性を有する成形用
樹脂組成物において、変色温度以下になるとａ．成分と
ｂ．成分がイオン化して結合し発色状態となる。逆に変
色温度以上になるとａ．成分とｂ，成分のイオン的結合
が消滅して、ａ．成分とｂ．成分は互いに独立して分子
状化合物になり消色する。ｂ．成分のフェノール性水酸
基はｃ．成分の変色温度調整剤に溶解することにより溶
媒和してｃ．成分との親和力が強くなる。また変色過渡
期においてはａ．成分とｂ．成分はイオン化状態と分子
状態の中間状態となり、ある程度イオン化された状態で
弱いイオン的結合をしていると考えられる。少しでもイ
オン化された状態となれば発色が生ずるので発色状態の
耐光性の問題が発生する。したがって、耐光性に関して
は遷移状態は発色状態とみなされる。したがって、通常
使用される紫外線吸収剤等の耐光性配合剤は消色状態の
組成物の耐光性の向上には有効であるが、発色状態にあ
る組成物の耐光性の向上にはあまり効果がない。この状
態のものは可視光線や間接光に対する耐光性は弱い。The color developing state and the color erasing state of the resin composition for molding having reversible thermochromic property of the present invention will be described. A. The resin composition for molding having reversible thermochromic properties in the present invention: a.
A component, b. A component, c. The components are not ionic compounds but actually molecular compounds when actually handled. In a molding resin composition having a reversible thermochromic property in which these components are uniformly mixed, when the temperature becomes lower than the color changing temperature, a. Ingredients and b. The components are ionized and combined to form a colored state. Conversely, if the temperature exceeds the discoloration temperature, a. The ionic bond between the component and b, component disappears, and a. Ingredients and b. The components become molecular compounds independently of each other and decolorize. b. The phenolic hydroxyl group of the component is c. Solvate by dissolving in the discoloring temperature controlling agent of the component; c. The affinity with the component is increased. In the discoloration transition period, a. Ingredients and b. It is considered that the component is in an intermediate state between the ionized state and the molecular state, and has a weak ionic bond in a state of being ionized to some extent. If a little ionized state occurs, a color is generated, so that a problem of light fastness in the colored state occurs. Therefore, regarding the light fastness, the transition state is regarded as a colored state. Therefore, a commonly used light-resistant compound such as an ultraviolet absorber is effective in improving the light resistance of a composition in a decolored state, but is not so effective in improving the light resistance of a composition in a colored state. Absent. In this state, light resistance to visible light and indirect light is weak.
【００１１】ところが本発明で使用する、一般式Ｉで示
される耐光性付与剤を発色時に存在させると耐光性が著
しく向上し、可視光や間接光でも老化しないことがわか
った。何故本発明の可逆的熱変色性を有する成形用樹脂
組成物が、発色状態にあると、可視光線や、間接光で老
化しないのか、消色状態にあるとこれ等の光で老化しな
いのか、その学問的解明は未だ充分ではないが、本発明
者は次のようにに考えている。一般式Ｉで示されるｄ．
耐光性付与剤は、電子受容性を有するため、ｃ．の変色
温度調整剤中で、ａ．電子供与性呈色性有機化合物と共
存した場合、変色温度以下では、ａ．電子供与性呈色性
有機化合物とイオン的に強く相互作用を行い、発色状態
を形成することができる。勿論、ａ．電子供与性呈色性
有機化合物は、通常のｂ．電子受容性化合物と、イオン
的に強く相互作用し、発色状態を形成するが、発色状態
となった時の、イオン的な相互作用に基づくイオン構造
が、ａ．とｂ．の場合と、ａ．とｄ．の場合で、光に対
する安定性が大きく異なっていると考えられる。However, it has been found that when the light-resistance imparting agent represented by the general formula I used in the present invention is present at the time of color formation, the light resistance is remarkably improved, and it does not age even with visible light or indirect light. Why the molding resin composition having reversible thermochromic properties of the present invention, when in the color-developed state, does not age with visible light or indirect light, or does not age with these lights when in the decolored state, Although the academic elucidation is not yet sufficient, the present inventor thinks as follows. D. Represented by the general formula I
Since the light resistance imparting agent has an electron accepting property, c. In the discoloration temperature regulator of a. When coexisting with an electron-donating color-forming organic compound, a. It interacts strongly with the electron-donating color-forming organic compound in an ionic manner to form a colored state. Of course, a. The electron-donating color-forming organic compound may be any of ordinary b. It interacts strongly with the electron-accepting compound to form a colored state. When the colored state is reached, the ionic structure based on the ionic interaction is a. And b. And a. And d. In this case, it is considered that the stability to light is greatly different.
【００１２】ｄ．耐光性付与剤は、長鎖アルキル基を有
しており、脂肪族雰囲気の強いｃ．変色温度調整剤への
溶解性が大きい。そのため、成形用樹脂組成物において
変色温度以下のｃ．変色温度調整剤が結晶化した固体中
においても、ａ．電子供与性呈色性有機化合物と強く相
互作用してイオン状態を形成したｄ．耐光性付与剤は、
ｃ．変色温度調整剤と弱く相互作用した状態で、長鎖ア
ルキル基の部分がｃ．変色温度調整剤が結晶化した固体
中で、安定化しており、その結果、イオン状態の構造全
体が光に対し安定化した状態になるのではないかと思わ
れる。従って、イオン状態にあるａ．電子供与性呈色性
有機化合物が、可視光線を吸収して光励起しても、光分
解あるいは光酸化されずに、そのエネルギーを放出して
基底状態に戻る安定したサイクルになる状態を、全体と
して形成しているのではないかと推察する。さらに、長
鎖アルキル基を有する構造は各種存在するが、その中で
も、一般式Ｉで示される構造が優れた耐光性向上効果を
示すのは、中心炭素の片方に水素、もう一方に長鎖アル
キル基となった分岐していない構造であるため、ｃ．変
色温度調整剤が結晶化した固体中における馴染み易さ、
すなわち安定性が特に優れているからではないかと思わ
れる。D. The light resistance imparting agent has a long-chain alkyl group and has a strong aliphatic atmosphere. High solubility in discoloration temperature regulator. Therefore, in the molding resin composition, c. Even in a solid in which the discoloration temperature regulator has crystallized, a. Strongly interacts with an electron-donating color-forming organic compound to form an ionic state d. The light resistance imparting agent is
c. When weakly interacting with the color change temperature regulator, the long-chain alkyl moiety is c. It is considered that the discoloration temperature regulator is stabilized in the crystallized solid, and as a result, the entire structure in an ionic state is stabilized against light. Therefore, a. Even if the electron-donating color-forming organic compound absorbs visible light and is photoexcited, it does not undergo photolysis or photo-oxidation, but releases its energy and returns to the ground state in a stable cycle. I guess it is forming. Further, there are various types of structures having a long-chain alkyl group. Among them, the structure represented by the general formula I shows an excellent effect of improving light resistance because one of the central carbon atoms has hydrogen and the other has a long-chain alkyl group. Because of the base unbranched structure, c. Ease of adaptation in the solid where the discoloration temperature regulator has crystallized,
That is, it is considered that the stability is particularly excellent.
【００１３】一方、通常のｂ．電子受容性化合物の場合
には、アルキル基が短く、変色温度以下のｃ．変色温度
調整剤が結晶化した固体中における馴染み易さが少な
く、安定性の悪い状態で、ａ．とｂ．のイオン状態の構
造が存在していると考えられる。従って、イオン状態に
あるａ．電子供与性呈色性有機化合物が、可視光線を吸
収して光励起すると、光分解あるいは光酸化する反応が
優先し、劣化がすすむのではないかと思われる。本発明
で使用するｄ．耐光性付与剤はそれ自体も電子受容性を
有しており電子供与性化合物１．０重量部に対し０．３
重量部以上発色状態で存在する必要がある。可逆的熱変
色性成形用樹脂組成物が発色した状態で耐光性付与剤が
電子供与性化合物１．０重量部に対し０．３重量部以下
の量が存在したのでは本発明の成形用樹脂組成物を用い
た成形体は充分な耐光性が得られない。On the other hand, the usual b. In the case of an electron-accepting compound, the alkyl group is short and has a color change temperature of c. In a state where the discoloration temperature adjusting agent is less easily compatible with the crystallized solid and has poor stability, a. And b. It is considered that the structure in the ionic state exists. Therefore, a. When the electron-donating color-forming organic compound absorbs visible light and is photo-excited, the reaction of photo-decomposition or photo-oxidation takes precedence, and it is thought that the deterioration proceeds. D. Used in the present invention; The light fastness imparting agent itself has an electron accepting property, and 0.3 part by weight of the electron donating compound is 1.0 part by weight.
It must be present in a color development state by weight part or more. When the amount of the lightfastness-imparting agent is 0.3 parts by weight or less based on 1.0 part by weight of the electron-donating compound in a state where the reversible thermochromic molding resin composition is colored, the molding resin of the present invention may be used. A molded article using the composition does not have sufficient light resistance.
【００１４】本発明で使用する一般式Ｉで示されるｄ．
耐光性付与剤は、一般式ＩThe d. Compound represented by the general formula I used in the present invention.
The lightfastness-imparting agent has the general formula I
【００１５】[0015]
【化３】 Embedded image
【００１６】｛式中、ｎ＝５〜１７（直鎖及び分岐）、
Ｘ＝Ｃ１〜Ｃ４（直鎖及び分岐）、ハロゲン、Ｙ＝Ｃ１
〜Ｃ４（直鎖及び分岐）、ハロゲン、ｐ＝０〜３、ｍ＝
０〜３である。｝で示されるアルキル基に水酸基を有す
るフェニル環が２つついたビスフェノール化合物或いは
ビス（ヒドロキシフェニル）化合物であるが、その特徴
はアルキル基が炭素数５〜１７であることであって、炭
素数が５未満であると、アルキル基が短いので脂肪族雰
囲気が強いｃ．変色温度調整剤への溶解性が不足し、変
色温度以下の固体雰囲気下で、十分な安定化構造が得ら
れない。また炭素数１７を越えると、アルキル基が長過
ぎるので脂肪族雰囲気が強いｃ．変色温度調整剤への溶
解性があり過ぎ、実用面を考えた場合、呈色力が弱くな
るとともに、変色感度が悪化するため、実用的ではな
い。アルキル基が直鎖アルキル基であることが最も好ま
しく、分岐を有する場合は分岐の短いものが好ましい。
フェニル環には直鎖または分岐アルキル基やハロゲンの
置換基がつく場合があるがフェニル環が付いているアル
キル基が前記のものであれば耐光性はほぼ同様に奏され
る。本発明で使用する耐光性付与剤はそれ自体も電子受
容性があるのでこれを用いることにより電子受容性化合
物の使用量を調整したり、場合によっては置き換えるこ
ともできる。Wherein n = 5 to 17 (linear and branched);
X = C 1 ~C 4 (linear and branched), halogen, Y = C 1
-C 4 (linear and branched), halogen, p = 0 to 3, m =
0 to 3. A bisphenol compound or a bis (hydroxyphenyl) compound in which two phenyl rings having a hydroxyl group are present in the alkyl group represented by つ つ is characterized in that the alkyl group has 5 to 17 carbon atoms and the number of carbon atoms is If it is less than 5, the aliphatic atmosphere is strong because the alkyl group is short. C. The solubility in the discoloration temperature regulator is insufficient, and a sufficient stabilized structure cannot be obtained in a solid atmosphere at or below the discoloration temperature. If the number of carbon atoms exceeds 17, the alkyl group is too long and the aliphatic atmosphere is strong. C. It has too much solubility in the discoloring temperature adjusting agent, and when considered from a practical point of view, it is not practical because the coloring power is weakened and the discoloring sensitivity is deteriorated. Most preferably, the alkyl group is a straight-chain alkyl group.
The phenyl ring may have a straight-chain or branched alkyl group or a halogen substituent, but if the alkyl group having the phenyl ring is as described above, the light resistance is almost the same. Since the light fastness imparting agent used in the present invention itself has an electron accepting property, the use thereof can be used to adjust the amount of the electron accepting compound to be used or to replace it in some cases.
【００１７】一般式Ｉで示されるｄ．耐光性付与剤を
ｂ．成分の電子受容性化合物に置き換える場合はこの化
合物が長鎖アルキル基を有しており、フェノール性水酸
基の当量が小さくなっているので、ａ．成分の電子供与
性化合物１．０重量部に対し０．３〜７．０重量部使用
する必要があり、特に２．０〜７．０重量部が好まし
い。成分ｂ．の電子受容性化合物としては、活性プロト
ンを有する化合物、偽酸性化合物群〔酸ではないが、組
成物中で酸として作用して成分ａ．を発色させる化合物
群〕、電子空孔を有する化合物群などがある。フェノー
ル性水酸基を有する化合物が最も有効な熱変色特性を発
現させることができるが、芳香族カルボン酸及び炭素数
２〜５の脂肪酸カルボン酸、カルボン酸金属塩、酸性リ
ン酸エステル及びそれらの金属塩、１、２、３−トリア
ゾール及びその誘導体、チオ尿素及びその誘導体、尿素
及びその誘導体、グアニジン及びその誘導体、芳香族及
び脂肪酸カルボン酸無水物、ホウ酸エステル類、ハロゲ
ン化アルコール類、オキサゾール類、チアゾール類、イ
ミダゾール類、ピラゾール類、ピロール類、芳香族スル
ホンアミド類、芳香族スルホンイミド類から選ばれる化
合物であってもよい。D. Represented by the general formula I B. A lightfastness-imparting agent; When the component is replaced with an electron-accepting compound, since this compound has a long-chain alkyl group and the equivalent weight of the phenolic hydroxyl group is small, a. It is necessary to use 0.3 to 7.0 parts by weight, preferably 2.0 to 7.0 parts by weight, based on 1.0 part by weight of the component electron donating compound. Component b. Examples of the electron-accepting compound include compounds having an active proton and a group of pseudo-acidic compounds [not an acid, but act as an acid in the composition to form a component a. And a group of compounds having electron vacancies. A compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties. However, aromatic carboxylic acids and fatty acid carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acid phosphates, and metal salts thereof 1,2,3-triazole and its derivatives, thiourea and its derivatives, urea and its derivatives, guanidine and its derivatives, aromatic and fatty acid carboxylic anhydrides, boric esters, halogenated alcohols, oxazoles, It may be a compound selected from thiazoles, imidazoles, pyrazoles, pyrroles, aromatic sulfonamides, and aromatic sulfonimides.
【００１８】本発明で使用する一般式Ｉで示される耐光
性付与剤はそれ自身が電子受容性を有する化合物であ
り、ｂ．成分の電子受容性化合物の量を調整することが
好ましい。またｂ．成分に代えて耐光性付与剤で兼用す
ることもできる。The light-fastness-imparting agent represented by the general formula I used in the present invention is a compound which itself has an electron-accepting property, and b. It is preferable to adjust the amount of the component electron accepting compound. B. Instead of the components, a lightfastness-imparting agent can also be used.
【００１９】本発明で使用されるａ．成分の電子供与性
呈色性化合物を表１と表２に例示する。A. Used in the present invention. Tables 1 and 2 show examples of the component electron-donating color-forming compounds.
【００２０】[0020]
【表１】 [Table 1]
【００２１】[0021]
【表２】 [Table 2]
【００２２】本発明で使用されるｂ．成分の電子受容性
化合物を表３ないし表５に例示する。B. Used in the present invention. Tables 3 to 5 show examples of the component electron accepting compounds.
【００２３】[0023]
【表３】 [Table 3]
【００２４】[0024]
【表４】 [Table 4]
【００２５】[0025]
【表５】 [Table 5]
【００２６】本発明で使用するｃ．成分の変色温度調整
剤を表６ないし表１２に示す。The c. Used in the present invention. Tables 6 to 12 show the discoloring temperature regulators of the components.
【００２７】[0027]
【表６】 [Table 6]
【００２８】[0028]
【表７】 [Table 7]
【００２９】[0029]
【表８】 [Table 8]
【００３０】[0030]
【表９】 [Table 9]
【００３１】[0031]
【表１０】 [Table 10]
【００３２】[0032]
【表１１】 [Table 11]
【００３３】[0033]
【表１２】 [Table 12]
【００３４】本発明で使用するｄ，成分の耐光性付与剤
を表１３と表１４に示す。Tables 13 and 14 show the light resistance imparting agents of component d used in the present invention.
【００３５】[0035]
【表１３】 [Table 13]
【００３６】[0036]
【表１４】 [Table 14]
【００３７】本発明で使用するｅ．成分の成形用樹脂を
表１５に示す。前記樹脂としては、熱可塑性樹脂あるい
は熱硬化性樹脂のいずれを用いることもできるが、成形
体を得るためには熱可塑性樹脂が好適に用いられる。E. Used in the present invention. Table 15 shows the molding resins of the components. As the resin, either a thermoplastic resin or a thermosetting resin can be used, but a thermoplastic resin is preferably used to obtain a molded article.
【００３８】[0038]
【表１５】 [Table 15]
【００３９】[0039]
【発明の実施の形態】本発明の可逆的熱変色性を有する
成形用樹脂組成物は通常ペレットの形状を有し、フイル
ム、シート、板、棒、パイプ、フィラメント等の成形に
用いられる。樹脂として熱可塑性樹脂を用いた場合は、
カレンダロールを用いてフイルムとすることができま
た、インフレーションによってもフイルムとすることが
できる。また押し出しによる板状体や棒状体、パイプあ
るいはフィラメントを成形することができる。この他射
出成形により種々な形状の成形体を成形することができ
る。たとえば射出成形により玩具のミニカー、人形、日
用品等を簡単に成形することができる。メルトスピニン
グ等により得たフィラメントは、織物や編物に用いられ
るだけでなく、植毛に用いることもできる。熱硬化性樹
脂を用いると、金型を用いることにより種々の成形体を
成形することができる。このような成形体は成形後も成
形用樹脂組成物と同様な可逆的熱変色性を示す。BEST MODE FOR CARRYING OUT THE INVENTION The molding resin composition having reversible thermochromic properties of the present invention usually has a pellet shape, and is used for molding films, sheets, plates, rods, pipes, filaments and the like. When using a thermoplastic resin as the resin,
The film can be formed by using a calendar roll, or can be formed by inflation. Further, a plate-like body, a rod-like body, a pipe or a filament can be formed by extrusion. In addition, molded articles of various shapes can be formed by injection molding. For example, toy minicars, dolls, daily necessities and the like can be easily formed by injection molding. The filament obtained by melt spinning or the like can be used not only for woven or knitted fabrics but also for flocking. When a thermosetting resin is used, various molded articles can be formed by using a mold. Such a molded article shows the same reversible thermochromic property as the resin composition for molding even after molding.
【００４０】[0040]
【実施例】次に実施例をあげて具体的に説明する。まず
熱変色性組成物の製造例を示す。 熱変色性組成物の製造例１ ３−（Ｎ−イソブチル−Ｎ−エチルアミノ）−７，８−
ベンゾフルオラン０．７重量部、１，１−ビス−（４−
ヒドロキシフェニル）−ｎ−デカン１０．０重量部、ラ
ウリン酸ステアリル３０，０重量部、カプリン酸ステア
リル２０．０重量部からなる４成分を１２０℃にて加温
溶解して均質相溶体となし、エポン８２８（油化シェル
エポキシ株式会社製、エポキシ樹脂）１０重量部の混合
溶液に混合した後、これを１０％ゼラチン水溶液１００
重量部中に滴下し、微小滴になるように撹拌する。別に
用意した５．０重量部の硬化剤エピキュアＵ（油化シェ
ルエポキシ株式会社製、エポキシ樹脂のアミン付加物）
を４５．０重量部の水に溶解させた溶液を前記撹拌中の
溶液中に徐々に添加し、液温を８０℃に保って５時間撹
拌を続け、マイクロカプセル原液を得た。前記原液を遠
心分離処理することにより、ピンクから無色に変化する
マイクロカプセルに内包した可逆的熱変色性組成物１を
得た。EXAMPLES Next, specific examples will be described. First, a production example of the thermochromic composition will be described. Production Example 1 of Thermochromic Composition 3- (N-isobutyl-N-ethylamino) -7,8-
0.7 parts by weight of benzofluoran, 1,1-bis- (4-
(Hydroxyphenyl) -n-decane 10.0 parts by weight, 30,0 parts by weight of stearyl laurate, 20.0 parts by weight of stearyl caprate were heated and dissolved at 120 ° C. to form a homogeneous compatible solution. Epon 828 (epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) was mixed with 10 parts by weight of a mixed solution, and then mixed with a 10% gelatin aqueous solution 100%.
The mixture is dropped into parts by weight and stirred to form fine droplets. Separately prepared 5.0 parts by weight of curing agent EpiCure U (manufactured by Yuka Shell Epoxy Co., Ltd., amine adduct of epoxy resin)
Was dissolved in 45.0 parts by weight of water, and the solution was gradually added to the stirring solution. Stirring was continued for 5 hours while maintaining the solution temperature at 80 ° C. to obtain a microcapsule stock solution. By centrifuging the stock solution, a reversible thermochromic composition 1 encapsulated in microcapsules that changed from pink to colorless was obtained.
【００４１】熱変色性組成物の製造例２〜１２ ａ．成分、ｂ．成分、ｃ．成分、ｄ．成分の組み合わせ
を変えて他は製造例１と同様にして可逆的熱変色性組成
物２〜１２を得た。１〜６はｄ．成分を含有する本発明
で用いる熱変色性組成物であり、７〜１２はｄ．成分を
含まない比較例で用いるものである。これ等の熱変色性
組成物の組成と色の変化を表１６及び表１７に示す。Production Examples 2 to 12 of Thermochromic Composition a. A component, b. A component, c. A component, d. The reversible thermochromic compositions 2 to 12 were obtained in the same manner as in Production Example 1 except that the combination of the components was changed. 1 to 6 are d. The thermochromic composition used in the present invention contains a component, and 7 to 12 are d. It is used in a comparative example containing no component. The composition and color change of these thermochromic compositions are shown in Tables 16 and 17.
【００４２】[0042]
【表１６】 [Table 16]
【００４３】[0043]
【表１７】 [Table 17]
【００４４】実施例１ 成形用樹脂組成物として、可逆的熱変色性組成物１のマ
イクロカプセル顔料４０．０重量部を低密度ポリエチレ
ン樹脂（メルトフローレート１．３）１０００．０重量
部、金属石鹸系滑剤０．５重量部中に配合しタンブラー
ミキサーで均一分散した後、押出成形機を用いてシリン
ダー温度１７０℃、先端ダイス温度１８０℃で成形し、
可逆的熱変色性ポリエチレン樹脂ペレットを得た。前記
成形用樹脂組成物を用いて、金魚型の金型を使用し、シ
リンダー部温度１６０℃でブロー成形により金魚形態の
可逆的熱変色性中空成形体を得た。なお、前記成形体
は、室温環境下ではピンク色を呈し、３４℃以上では無
色なる。Example 1 As a molding resin composition, 40.0 parts by weight of the microcapsule pigment of the reversible thermochromic composition 1 were mixed with 1000.0 parts by weight of a low-density polyethylene resin (melt flow rate 1.3), metal After mixing in 0.5 part by weight of a soap-based lubricant and uniformly dispersing with a tumbler mixer, using an extruder, molding was performed at a cylinder temperature of 170 ° C. and a tip die temperature of 180 ° C.,
A reversible thermochromic polyethylene resin pellet was obtained. Using the resin composition for molding, a reversible thermochromic hollow molded body in the form of a goldfish was obtained by blow molding using a goldfish mold at a cylinder temperature of 160 ° C. In addition, the said molded object shows pink color under room temperature environment, and becomes colorless above 34 degreeC.
【００４５】実施例２ 成形用樹脂組成物として、可逆的熱変色性組成物２のマ
イクロカプセル顔料３０．０重量部及び粉末蛍光顔料
（蛍光イエロー）７．０重量部をエチレン−酢酸ビニル
共重合樹脂（メルトフローレート１．４）１０００．０
重量部、金属石鹸系滑剤０．５重量部中に配合しタンブ
ラーミキサーで均一分散した後、押出成形機を用いて、
シリンダー温度１６０℃、先端ダイス温度１６０℃で成
形し、可逆的熱変色性エチレン−酢酸ビニル共重合樹脂
ペレットを得た。前記成形用樹脂組成物を用いて、人形
型の金型を使用し、シリンダー温度１５０℃でブロー成
形して人形形態の可逆的熱変色性中空成形体を得た。な
お、前記成形体は、室温環境下では緑色を呈し、３０℃
以上では蛍光黄色を呈する。Example 2 As a molding resin composition, 30.0 parts by weight of the microcapsule pigment and 7.0 parts by weight of a powdery fluorescent pigment (fluorescent yellow) of the reversible thermochromic composition 2 were subjected to ethylene-vinyl acetate copolymerization. Resin (melt flow rate 1.4) 1000.0
Parts by weight, blended in 0.5 parts by weight of a metal soap lubricant and uniformly dispersed with a tumbler mixer, using an extruder,
Molding was performed at a cylinder temperature of 160 ° C. and a tip die temperature of 160 ° C. to obtain a reversible thermochromic ethylene-vinyl acetate copolymer resin pellet. Using the resin composition for molding, a doll-shaped mold was blow-molded at a cylinder temperature of 150 ° C. to obtain a doll-shaped reversible thermochromic hollow molded article. In addition, the said molded object shows green at room temperature environment,
Above, it exhibits a fluorescent yellow color.
【００４６】実施例３ 成形用樹脂組成物として、可逆的熱変色性組成物３のマ
イクロカプセル顔料４０．０重量部及び粉末蛍光顔料
（蛍光ピンク）５．０重量部をポリプロピレン樹脂（メ
ルトフローレート３９．０）１０００．０重量部、金属
石鹸系滑剤０．５重量部中に配合し、タンブラーミキサ
ーで均一分散後、押出成形機を用いてシリンダー温度１
６０℃、先端ダイス温度１６０℃で成形し、可逆的熱変
色性ポリプロピレン樹脂ペレットを得た。前記成形用樹
脂組成物をシリンダー温度１７０℃、シリンダーヘッド
温度１７０℃で溶融紡糸を行い可逆的熱変色性フィラメ
ントを得た。前記フィラメントを用いて馬形態の玩具に
植毛を施し、たて髪と尻尾を形成した。なお、前記可逆
的熱変色性フィラメントは、室温環境下では紫色を呈
し、３４℃以上では蛍光ピンク色を呈する。Example 3 As a molding resin composition, 40.0 parts by weight of the microcapsule pigment and 5.0 parts by weight of the powdery fluorescent pigment (fluorescent pink) of the reversible thermochromic composition 3 were mixed with a polypropylene resin (melt flow rate). 39.0) 1000.0 parts by weight and 0.5 part by weight of a metal soap lubricant were uniformly mixed with a tumbler mixer, and then a cylinder temperature of 1 was obtained using an extruder.
Molding was performed at 60 ° C. and a die temperature of 160 ° C. to obtain a reversible thermochromic polypropylene resin pellet. The molding resin composition was melt-spun at a cylinder temperature of 170 ° C. and a cylinder head temperature of 170 ° C. to obtain a reversible thermochromic filament. The filament was used to implant hair into a horse-shaped toy to form a vertical hair and a tail. The reversible thermochromic filament exhibits a purple color in a room temperature environment and a fluorescent pink color at 34 ° C. or higher.
【００４７】実施例４ 成形用樹脂組成物として、可逆的熱変色性組成物４のマ
イクロカプセル顔料５０．０重量部及び粉末蛍光顔料
（黄色）０．１重量、粉末加工顔料（緑色）０．０１重
量部、粉末顔料（赤色）０．０４重量部を１２ナイロン
樹脂（融点１７８℃）１０００．０重量部、光安定剤
５．０重量部中に配合し、ヘンシルミキサーで均一分散
した後、押出成形機を用いてシリンダー温度１９０℃、
先端ダイス温度２００℃で成形し、可逆的熱変色性１２
ナイロン樹脂ペレットを得た。前記成形用樹脂組成物を
シリンダー温度１９０℃、ダイス温度２００℃で溶融紡
糸を行い可逆的熱変色性フィラメントを得た。前記フィ
ラメントを用いて人形の頭に植毛を施した。なお、前記
可逆的熱変色性フィラメントは室温環境下ではオレンジ
色を呈し、３４℃以上ではブロンド色を呈する。Example 4 As the resin composition for molding, 50.0 parts by weight of the microcapsule pigment of the reversible thermochromic composition 4, 0.1 part by weight of a powdery fluorescent pigment (yellow), and 0.1 part by weight of a powdered pigment (green). 01 parts by weight, 0.04 parts by weight of a powder pigment (red) were mixed in 1000.0 parts by weight of a 12 nylon resin (melting point: 178 ° C.) and 5.0 parts by weight of a light stabilizer, and then uniformly dispersed by a Hensyl mixer. A cylinder temperature of 190 ° C. using an extruder,
Molded at a tip die temperature of 200 ° C, reversible thermochromic 12
A nylon resin pellet was obtained. The molding resin composition was melt-spun at a cylinder temperature of 190 ° C. and a die temperature of 200 ° C. to obtain a reversible thermochromic filament. Hair was implanted on the head of the doll using the filament. The reversible thermochromic filament exhibits an orange color in a room temperature environment and a blond color at 34 ° C. or higher.
【００４８】実施例５ 成形用樹脂組成物として、可逆的熱変色性組成物５のマ
イクロカプセル顔料３０．０重量部及び粉末加工顔料
（白色）５．０重量部をスチレン−ブタジエン共重合樹
脂（メルトフローレート７．３）１０００．０重量部、
金属石鹸系滑剤０．５重量部中に配合し、タンブラーミ
キサーで均一分散した後、押出成形機を用いてシリンダ
ー温度１８０℃、先端ダイス温度１８０℃で成形し、可
逆的熱変色性スチレン−ブタジエン共重合樹脂ペレット
を得た。前記成形用樹脂組成物を用いて、イルカ型の金
型を使用し、シリンダー温度１８０℃、シリンダーヘッ
ド温度１８５℃で射出成形を行いイルカ形態の可逆的熱
変色性成形体を得た。なお、前記成形体は３０℃以上で
は白色を呈し、１３℃以下ではパステルブルー色を呈す
る。また、その間の温度域では任意に白色とパステルブ
ルー色を選択保持できる。Example 5 As a molding resin composition, 30.0 parts by weight of a microcapsule pigment and 5.0 parts by weight of a powder-processed pigment (white) of a reversible thermochromic composition 5 were mixed with a styrene-butadiene copolymer resin ( Melt flow rate 7.3) 1000.0 parts by weight,
After blending in 0.5 parts by weight of a metal soap lubricant and uniformly dispersing with a tumbler mixer, the mixture is molded using an extruder at a cylinder temperature of 180 ° C. and a tip die temperature of 180 ° C., and reversible thermochromic styrene-butadiene A copolymer resin pellet was obtained. Using the above resin composition for molding, injection molding was performed at a cylinder temperature of 180 ° C. and a cylinder head temperature of 185 ° C. using a dolphin mold, to obtain a dolphin-shaped reversible thermochromic molded body. In addition, the said molded object shows white above 30 degreeC, and shows pastel blue below 13 degreeC. Further, white and pastel blue colors can be arbitrarily selected and held in the temperature range between them.
【００４９】実施例６ 成形用樹脂組成物として、可逆的熱変色性組成物３のマ
イクロカプセル顔料３０．０重量部及び粉末加工顔料
（白色）５．０重量をＡＢＳ樹脂（メルトフローレート
６０．０）１０００．０重量部、金属石鹸系滑剤０．５
重量部中に配合し、タンブラーミキサーで均一分散した
後、押出成形機を用いてシリンダー温度２００℃、先端
ダイス温度２００℃で、可逆的熱変色性ＡＢＳ樹脂ペレ
ットを得た。前記成形用樹脂組成物を用いて、小型自動
車玩具成形用の金型を使用し、シリンダー温度２００
℃、シリンダーヘッドの温度２００℃で射出成形を行い
小型自動車形態の可逆的熱変色性成形体を得た。なお、
前記成形体は室温環境下ではパステルブルー色を呈し、
３４℃以上では白色を呈する。Example 6 As a resin composition for molding, 30.0 parts by weight of the microcapsule pigment and 5.0 parts by weight of a powder-processed pigment (white) of the reversible thermochromic composition 3 were mixed with an ABS resin (melt flow rate of 60%). 0) 1000.0 parts by weight, metal soap lubricant 0.5
After mixing in a weight part and uniformly dispersing with a tumbler mixer, reversible thermochromic ABS resin pellets were obtained at a cylinder temperature of 200 ° C. and a tip die temperature of 200 ° C. using an extruder. Using the resin composition for molding, a mold for molding a small car toy was used, and a cylinder temperature of 200
Injection molding was performed at 200 ° C. and a cylinder head temperature of 200 ° C. to obtain a reversible thermochromic molded article in the form of a small car. In addition,
The molded body has a pastel blue color under a room temperature environment,
Above 34 ° C. it is white.
【００５０】実施例７ 成形用樹脂組成物として、可逆的熱変色性組成物２のマ
イクロカプセル顔料３０．０重量部をポリエステルエラ
ストマー樹脂（メルトフローレート２０．０）１００
０．０重量部、金属石鹸系滑剤０．５重量部中に配合
し、タンブラーミキサーで均一分散した後、押出成形機
を用いてシリンダー温度１９０℃、先端ダイス温度１９
０℃で、可逆的熱変色性ポリエステルエラストマー樹脂
ペレットを得た。前記成形用樹脂組成物を用いて、ホッ
トカーラー型の金型を使用し、シリンダー温度１９０
℃、シリンダーヘッドの温度２００℃で射出成形を行い
ホットカーラー形態の可逆的熱変色性成形体を得た。な
お、前記成形体は室温環境下では青緑色を呈し、３０℃
以上では無色となる。Example 7 As a molding resin composition, 30.0 parts by weight of the microcapsule pigment of the reversible thermochromic composition 2 was mixed with 100 parts of a polyester elastomer resin (melt flow rate 20.0).
0.0 parts by weight and 0.5 part by weight of a metal soap lubricant were uniformly dispersed by a tumbler mixer, and then, using an extruder, a cylinder temperature of 190 ° C. and a tip die temperature of 19 were used.
At 0 ° C., reversible thermochromic polyester elastomer resin pellets were obtained. Using the molding resin composition, a hot curler type mold was used, and the cylinder temperature was set to 190.
Injection molding was performed at 200 ° C. and a cylinder head temperature of 200 ° C. to obtain a hot curler type reversible thermochromic molded body. In addition, the said molded object shows bluish green in a room temperature environment,
Above is colorless.
【００５１】実施例８ 成形用樹脂組成物として、可逆的熱変色性組成物４のマ
イクロカプセル顔料３０．０重量部をエチレン−エチル
アクリレート共重合樹脂（メルトフローレート５．０）
１０００．０重量部、金属石鹸系滑剤１．０重量部中に
配合し、タンブラーミキサーで均一分散した後、押出成
形機を用いてシリンダー温度１８０℃、先端ダイス温度
１８０℃で、可逆的熱変色性エチレン−エチルアクリレ
ート共重合樹脂ペレットを得た。前記成形用樹脂組成物
を用いて、シリンダー温度１８０℃でインフレーション
成形を行い、可逆的熱変色性エチレン−エチルアクリレ
ート共重合樹脂フイルムシートを得た。なお、前記フイ
ルムシートは室温環境下ではオレンジ色を呈し、３４℃
以上では無色となる。Example 8 As a molding resin composition, 30.0 parts by weight of the microcapsule pigment of the reversible thermochromic composition 4 was mixed with an ethylene-ethyl acrylate copolymer resin (melt flow rate 5.0).
1000.0 parts by weight, blended in 1.0 part by weight of a metal soap lubricant, uniformly dispersed by a tumbler mixer, and then, using an extruder, at a cylinder temperature of 180 ° C and a tip die temperature of 180 ° C, reversible thermal discoloration. An ethylene-ethyl acrylate copolymer resin pellet was obtained. Inflation molding was performed at a cylinder temperature of 180 ° C. using the molding resin composition to obtain a reversible thermochromic ethylene-ethyl acrylate copolymer resin film sheet. The film sheet has an orange color in a room temperature environment and has a temperature of 34 ° C.
Above is colorless.
【００５２】実施例９ 成形用樹脂組成物として、可逆的熱変色性組成物５のマ
イクロカプセル顔料１００．０重量部、粉末蛍光顔料
（ピンク色）５．０重量部をポリエーテルポリオール１
０００．０重量部中に均一分散した可逆的熱変色性ポリ
オールゾルを、イソシアネート化合物５００．０重量
部、触媒２０．０重量部、水５．０重量部中に混合分散
して反応させることにより可逆的熱変色性発泡ウレタン
フォームを得た。なお、前記成形用樹脂組成物は３３℃
以上では蛍光ピンク色を呈し、１４℃以下では紫色を呈
する。その間の温度域では任意にピンク色と紫色を選択
保持できる。Example 9 As a molding resin composition, 100.0 parts by weight of a microcapsule pigment and 5.0 parts by weight of a powdery fluorescent pigment (pink) of a reversible thermochromic composition 5 were mixed with a polyether polyol 1
The reversible thermochromic polyol sol uniformly dispersed in 000.0 parts by weight is mixed and dispersed in 500.0 parts by weight of an isocyanate compound, 20.0 parts by weight of a catalyst, and 5.0 parts by weight of water to react. A reversible thermochromic urethane foam was obtained. The molding resin composition is at 33 ° C.
Above, it exhibits a fluorescent pink color, and below 14 ° C., it exhibits a purple color. In the temperature range between them, pink and purple can be arbitrarily selected and held.
【００５３】実施例１０ 成形用樹脂組成物として、可逆的熱変色性組成物６のマ
イクロカプセル顔料５０．０重量部粉末顔料（青色）
０．３重量部をフタル酸ジオクチル４０重量部、塩化ビ
ニル樹脂６０．０重量部、塩化ビニル安定剤５．０重量
部からなる塩化ビニルペーストゾル中に均一分散し、可
逆的熱変色性塩化ビニルペースト樹脂ゾルを得た。前記
成形用樹脂組成物を用いて、スラッシュ成形を行い馬形
態の可逆的熱変色性スラッシュ成形体を得た。なお、前
記成形体は３３℃以上では青色を呈し、１４℃以下では
紫色を呈する。その間の温度域では任意に青色と紫色を
選択保持できる。Example 10 As a molding resin composition, 50.0 parts by weight of microcapsule pigment of reversible thermochromic composition 6 powder pigment (blue)
0.3 parts by weight are uniformly dispersed in a vinyl chloride paste sol consisting of 40 parts by weight of dioctyl phthalate, 60.0 parts by weight of a vinyl chloride resin, and 5.0 parts by weight of a vinyl chloride stabilizer to form a reversible thermochromic vinyl chloride. A paste resin sol was obtained. Slash molding was performed using the molding resin composition to obtain a horse-shaped reversible thermochromic slush molded article. Note that the molded body exhibits a blue color at 33 ° C. or higher and a purple color at 14 ° C. or lower. In the temperature range between them, blue and purple colors can be arbitrarily selected and held.
【００５４】実施例１１ 成形用樹脂組成物として、可逆的熱変色性組成物１のマ
イクロカプセル顔料１０．０重量部を付加反応型シリコ
ーンゴム１０００．０重量部中に均一分散し、可逆的熱
変色性硬化性シリコーン組成物を得た。前記成形用樹脂
組成物に硬化剤１０，０重量部を加えて分散、混合した
後、深さ５ｍｍの星形状の型枠に注入し１５０℃で３０
分間硬化させた後、室温で１日放置し星形状の可逆的熱
変色性シリコーン成形体を得た。なお、前記成形体は室
温環境下ではピンク色を呈し、３４℃以上では無色とな
る。Example 11 As a molding resin composition, 10.0 parts by weight of the microcapsule pigment of the reversible thermochromic composition 1 was uniformly dispersed in 1000.0 parts by weight of an addition reaction type silicone rubber. A discolorable curable silicone composition was obtained. 10.0 parts by weight of a curing agent was added to the resin composition for molding, dispersed and mixed, and then poured into a star-shaped mold having a depth of 5 mm.
After curing for 1 minute, the mixture was left at room temperature for 1 day to obtain a star-shaped reversible thermochromic silicone molding. In addition, the said molded object exhibits pink color in room temperature environment, and becomes colorless above 34 degreeC.
【００５５】実施例１２ 実施例１で得られた可逆的熱変色性ポリエチレン樹脂ペ
レットを用いて、シリンダー温度１６０℃でインフレー
ション成形を行い、可逆的熱変色性ポリエチレンフイル
ムを得た。なお、前記可逆的熱変色性フイルムは室温環
境下ではピンク色を呈し、３４℃以上では無色となる。Example 12 Using the reversible thermochromic polyethylene resin pellets obtained in Example 1, inflation molding was performed at a cylinder temperature of 160 ° C. to obtain a reversible thermochromic polyethylene film. The reversible thermochromic film exhibits a pink color at room temperature and becomes colorless at 34 ° C. or higher.
【００５６】比較例１ ｄ．成分を含まない可逆的熱変色性組成物７のマイクロ
カプセル顔料を用いて、実施例１と同様に可逆的熱変色
性ポリエチレン樹脂ペレットを得た。さらに、前記樹脂
ペレットを用いて金魚形態の中空成形体を得た。Comparative Example 1 d. Using the microcapsule pigment of the reversible thermochromic composition 7 containing no component, reversible thermochromic polyethylene resin pellets were obtained in the same manner as in Example 1. Furthermore, a goldfish-shaped hollow molded body was obtained using the resin pellet.
【００５７】比較例２ ｄ．成分を含まない可逆的熱変色性組成物８のマイクロ
カプセル顔料を用いて実施例２と同様に可逆的熱変色性
エチレン−酢酸ビニル共重合樹脂ペレットを得た。さら
に、前記樹脂ペレットを用いて人形形態の中空成形体を
得た。Comparative Example 2 d. A reversible thermochromic ethylene-vinyl acetate copolymer resin pellet was obtained in the same manner as in Example 2 using the microcapsule pigment of the reversible thermochromic composition 8 containing no component. Furthermore, a doll-shaped hollow molded body was obtained using the resin pellets.
【００５８】比較例３ ｄ．成分を含まない可逆的熱変色性組成物９のマイクロ
カプセル顔料を用いて、実施例３と同様に可逆的熱変色
性ポリプロピレン樹脂ペレットを得た。さらに、前記樹
脂ペレットを用いて形成した可逆的熱変色性フィラメン
トを、馬形態の玩具に植毛し、たて髪と尻尾を形成し
た。Comparative Example 3 d. A reversible thermochromic polypropylene resin pellet was obtained in the same manner as in Example 3 using the microcapsule pigment of the reversible thermochromic composition 9 containing no component. Further, the reversible thermochromic filaments formed using the resin pellets were implanted into horse-shaped toys to form vertical hairs and tails.
【００５９】比較例４ ｄ．成分を含まない可逆的熱変色性組成物１０のマイク
ロカプセル顔料を用いて、実施例４と同様に可逆的熱変
色性１２ナイロン樹脂ペレットを得た。前記、樹脂ペレ
ットを用いて形成した可逆的熱変色性フィラメントを、
人形の頭に植毛した。Comparative Example 4 d. A reversible thermochromic 12 nylon resin pellet was obtained in the same manner as in Example 4 using the microcapsule pigment of the reversible thermochromic composition 10 containing no component. The reversible thermochromic filament formed using the resin pellet,
I planted hair on the head of the doll.
【００６０】比較例５ ｄ．成分を含まない可逆的熱変色性組成物１１のマイク
ロカプセル顔料を用いて、実施例５と同様に可逆的熱変
色性スチレン−ブタジエン共重合樹脂ペレットを得た。
さらに、前記樹脂ペレットを用いてイルカ形態の成形体
を得た。Comparative Example 5 d. A reversible thermochromic styrene-butadiene copolymer resin pellet was obtained in the same manner as in Example 5 using the microcapsule pigment of the reversible thermochromic composition 11 containing no component.
Further, a dolphin-shaped molded body was obtained using the resin pellet.
【００６１】比較例６ ｄ．成分を含まない可逆的熱変色性組成物９のマイクロ
カプセル顔料を用いて、実施例６と同様に可逆的熱変色
性ＡＢＳ樹脂ペレットを得た。さらに、前記樹脂ペレッ
トを用いて小型自動車形態の成形体を得た。Comparative Example 6 d. Using the microcapsule pigment of the reversible thermochromic composition 9 containing no components, reversible thermochromic ABS resin pellets were obtained in the same manner as in Example 6. Further, a compact in the form of a small automobile was obtained using the resin pellet.
【００６２】比較例７ ｄ．成分を含まない可逆的熱変色性組成物８のマイクロ
カプセル顔料を用いて、実施例７と同様に可逆的熱変色
性ポリエステルエラストマー樹脂ペレットを得た。さら
に、前記樹脂ペレットを用いてホットカーラー形態の成
形体を得た。Comparative Example 7 d. A reversible thermochromic polyester elastomer resin pellet was obtained in the same manner as in Example 7 using the microcapsule pigment of the reversible thermochromic composition 8 containing no component. Furthermore, a molded product in a hot curler form was obtained using the resin pellet.
【００６３】比較例８ ｄ．成分を含まない可逆的熱変色性組成物１０のマイク
ロカプセル顔料を用いて、実施例８と同様に可逆的熱変
色性エチレン−エチルアクリレート共重合樹脂ペレット
を得た。さらに、前記樹脂ペレットを用いてフイルムシ
ートを得た。Comparative Example 8 d. A reversible thermochromic ethylene-ethyl acrylate copolymer resin pellet was obtained in the same manner as in Example 8, using the microcapsule pigment of the reversible thermochromic composition 10 containing no component. Further, a film sheet was obtained using the resin pellet.
【００６４】比較例９ ｄ．成分を含まない可逆的熱変色性組成物１１のマイク
ロカプセル顔料を用いて、実施例９と同様に可逆的熱変
色性発泡ウレタンフォームを得た。Comparative Example 9 d. Using the microcapsule pigment of the reversible thermochromic composition 11 containing no component, a reversible thermochromic urethane foam was obtained in the same manner as in Example 9.
【００６５】比較例１０ ｄ．成分を含まない可逆的熱変色性組成物１２のマイク
ロカプセル顔料を用いて、実施例１０と同様に可逆的熱
変色性塩化ビニルペーストゾルを得た。さらに、前記塩
化ビニルペーストゾルを用いて、馬形態のスラッシュ成
形体を得た。Comparative Example 10 d. A reversible thermochromic vinyl chloride paste sol was obtained in the same manner as in Example 10 using the microcapsule pigment of the reversible thermochromic composition 12 containing no component. Further, a slush molded article in the form of a horse was obtained using the above-mentioned vinyl chloride paste sol.
【００６６】比較例１１ ｄ．成分を含まない可逆的熱変色性組成物７のマイクロ
カプセル顔料を用いて、実施例１１と同様に可逆的熱変
色性硬化性シリコーン組成物を得た。さらに、前記シリ
コーン組成物を用いて星形状のシリコーン成形体を得
た。Comparative Example 11 d. Using the microcapsule pigment of the reversible thermochromic composition 7 containing no component, a reversible thermochromic curable silicone composition was obtained in the same manner as in Example 11. Further, a star-shaped silicone molded body was obtained using the silicone composition.
【００６７】次に実施例及び比較例の樹脂組成物の耐光
堅牢度を示す。 （１） 耐光堅牢度試験試料の調製 実施例１の可逆的熱変色性ポリエチレン樹脂ペレットを
用いて、成形樹脂温度１８０℃で射出成形を行い、４０
ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状の成形体を得
た。前記成形体を耐光性試験試料とする。実施例２の可
逆的熱変色性エチレン−酢酸ビニル共重合樹脂ペレット
を用いて、成形樹脂温度１７０℃で射出成形を行い、４
０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状の成形体を
得た。前記成形体を耐光性試験試料とする。実施例３の
可逆的熱変色性ポリプロピレン樹脂ペレットを用いて、
成形樹脂温度１７０℃で射出成形を行い、４０ｍｍ×６
０ｍｍ、厚み２ｍｍのプレート状の成形体を得た。前記
成形体を耐光性試験試料とする。実施例４の可逆的熱変
色性１２ナイロン樹脂ペレットを用いて、成形樹脂温度
２００℃で射出成形を行い、４０ｍｍ×６０ｍｍ、厚み
２ｍｍのプレート状の成形体を得た。前記成形体を耐光
性試験試料とする。実施例５の可逆的熱変色性スチレン
−ブタジエン共重合樹脂ペレットを用いて、成形樹脂温
度２００℃で射出成形を行い、４０ｍｍ×６０ｍｍ、厚
み２ｍｍのプレート状の成形体を得た。前記成形体を耐
光性試験試料とする。実施例６の可逆的熱変色性ＡＢＳ
樹脂ペレットを用いて、成形樹脂温度２００℃で射出成
形を行い、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート
状の成形体を得た。前記成形体を耐光性試験試料とす
る。実施例７の可逆的熱変色性ポリエステルエラストマ
ー樹脂ペレットを用いて、成形樹脂温度２００℃で射出
成形を行い、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレー
ト状の成形体を得た。前記成形体を耐光性試験試料とす
る。実施例８の可逆的熱変色性エチレン−エチルアクリ
レート共重合樹脂ペレットを用いて、成形樹脂温度１８
０℃で射出成形を行い、４０ｍｍ×６０ｍｍ、厚み２ｍ
ｍのプレート状の成形体を得た。前記成形体を耐光性試
験試料とする。実施例９の可逆的熱変色性発泡ウレタン
フォームを４０ｍｍ×６０ｍｍ、厚み１０ｍｍにスライ
スしたウレタンフォームを得た。前記ウレタンフォーム
を耐光性試験試料とする。実施例１０の可逆的熱変色性
塩化ビニルペーストゾルを４０ｍｍ×６０ｍｍ、厚み２
ｍｍのプレート状型枠に流し込んで成形体を得た。前記
成形体を耐光性試験試料とする。実施例１１の可逆的熱
変色性硬化性シリコーン組成物を４０ｍｍ×６０ｍｍ、
厚み２ｍｍのプレート状型枠に流し込んで成形体を得
た。前記成形体を耐光性試験試料とする。比較例１の可
逆的熱変色性ポリエチレン樹脂ペレットを用いて、成形
樹脂温度１８０℃で射出成形を行い、４０ｍｍ×６０ｍ
ｍ、厚み２ｍｍのプレート状の成形体を得た。前記成形
体を耐光性試験試料とする。比較例２の可逆的熱変色性
エチレン−酢酸ビニル共重合樹脂ペレットを用いて、成
形樹脂温度１７０℃で射出成形を行い、４０ｍｍ×６０
ｍｍ、厚み２ｍｍのプレート状の成形体を得た。前記成
形体を耐光性試験試料とする。比較例３の可逆的熱変色
性ポリプロピレン樹脂ペレットを用いて、成形樹脂温度
１７０℃で射出成形を行い、４０ｍｍ×６０ｍｍ、厚み
２ｍｍのプレート状の成形体を得た。前記成形体を耐光
性試験試料とする。比較例４の可逆的熱変色性１２ナイ
ロン樹脂ペレットを用いて、成形樹脂温度２００℃で射
出成形を行い、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレ
ート状の成形体を得た。前記成形体を耐光性試験試料と
する。比較例５の可逆的熱変色性スチレン−ブタジエン
共重合樹脂ペレットを用いて、成形樹脂温度２００℃で
射出成形を行い、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプ
レート状の成形体を得た。前記成形体を耐光性試験試料
とする。比較例６の可逆的熱変色性ＡＢＳ樹脂ペレット
を用いて、成形樹脂温度２００℃で射出成形を行い、４
０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状の成形体を
得た。前記成形体を耐光性試験試料とする。比較例７の
可逆的熱変色性ポリエステルエラストマー樹脂ペレット
を用いて、成形樹脂温度２００℃で射出成形を行い、４
０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状の成形体を
得た。前記成形体を耐光性試験試料とする。比較例８の
可逆的熱変色性エチレン−エチルアクリレート共重合樹
脂ペレットを用いて、成形樹脂温度１８０℃で射出成形
を行い、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状
の成形体を得た。前記成形体を耐光性試験試料とする。
比較例９の可逆的熱変色性発泡ウレタンフォームを４０
ｍｍ×６０ｍｍ、厚み１０ｍｍにスライスしたウレタン
フォームを得た。前記ウレタンフォームを耐光性試験試
料とする。比較例１０の可逆的熱変色性塩化ビニルペー
ストゾルを４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート
状型枠に流し込んで成形体を得た。前記成形体を耐光性
試験試料とする。比較例１１の可逆的熱変色性硬化性シ
リコーン組成物を４０ｍｍｘ６０ｍｍ、厚み２ｍｍのプ
レート状型枠に流し込んで成形体を得た。前記成形体を
耐光性試験試料とする。Next, the light fastness of the resin compositions of Examples and Comparative Examples will be shown. (1) Preparation of light fastness test sample Using the reversible thermochromic polyethylene resin pellets of Example 1, injection molding was carried out at a molding resin temperature of 180 ° C.
A plate-shaped molded body having a size of 60 mm × 60 mm and a thickness of 2 mm was obtained. The molded body is used as a light resistance test sample. Using the reversible thermochromic ethylene-vinyl acetate copolymer resin pellets of Example 2, injection molding was performed at a molding resin temperature of 170 ° C.
A plate-shaped molded body having a size of 0 mm × 60 mm and a thickness of 2 mm was obtained. The molded body is used as a light resistance test sample. Using the reversible thermochromic polypropylene resin pellets of Example 3,
Injection molding is performed at a molding resin temperature of 170 ° C, and 40 mm x 6
A plate-shaped molded body having a thickness of 0 mm and a thickness of 2 mm was obtained. The molded body is used as a light resistance test sample. Injection molding was performed at a molding resin temperature of 200 ° C. using the reversible thermochromic 12 nylon resin pellets of Example 4 to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm. The molded body is used as a light resistance test sample. Using the reversible thermochromic styrene-butadiene copolymer resin pellets of Example 5, injection molding was performed at a molding resin temperature of 200 ° C. to obtain a plate-like molded body having a size of 40 mm × 60 mm and a thickness of 2 mm. The molded body is used as a light resistance test sample. Reversible thermochromic ABS of Example 6
Using a resin pellet, injection molding was performed at a molding resin temperature of 200 ° C. to obtain a plate-like molded body having a size of 40 mm × 60 mm and a thickness of 2 mm. The molded body is used as a light resistance test sample. Using the reversible thermochromic polyester elastomer resin pellets of Example 7, injection molding was performed at a molding resin temperature of 200 ° C. to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm. The molded body is used as a light resistance test sample. Using the reversible thermochromic ethylene-ethyl acrylate copolymer resin pellets of Example 8, molding resin temperature 18
Injection molding at 0 ° C, 40mm x 60mm, thickness 2m
Thus, a plate-shaped molded product of m was obtained. The molded body is used as a light resistance test sample. A urethane foam obtained by slicing the reversible thermochromic urethane foam of Example 9 to a size of 40 mm × 60 mm and a thickness of 10 mm was obtained. The urethane foam is used as a light resistance test sample. 40 mm × 60 mm, thickness 2 of the reversible thermochromic vinyl chloride paste sol of Example 10
It was poured into a plate-shaped mold having a thickness of 2 mm to obtain a molded body. The molded body is used as a light resistance test sample. 40 mm × 60 mm of the reversible thermochromic curable silicone composition of Example 11,
It was poured into a plate-shaped mold having a thickness of 2 mm to obtain a molded body. The molded body is used as a light resistance test sample. Using the reversible thermochromic polyethylene resin pellets of Comparative Example 1, injection molding was performed at a molding resin temperature of 180 ° C. to obtain a 40 mm × 60 m
m, a plate-shaped molded body having a thickness of 2 mm was obtained. The molded body is used as a light resistance test sample. Using the reversible thermochromic ethylene-vinyl acetate copolymer resin pellets of Comparative Example 2, injection molding was performed at a molding resin temperature of 170 ° C., and 40 mm × 60.
Thus, a plate-shaped molded product having a thickness of 2 mm and a thickness of 2 mm was obtained. The molded body is used as a light resistance test sample. Using the reversible thermochromic polypropylene resin pellets of Comparative Example 3, injection molding was performed at a molding resin temperature of 170 ° C. to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm. The molded body is used as a light resistance test sample. Injection molding was performed at a molding resin temperature of 200 ° C. using the reversible thermochromic 12 nylon resin pellets of Comparative Example 4 to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm. The molded body is used as a light resistance test sample. Using the reversible thermochromic styrene-butadiene copolymer resin pellets of Comparative Example 5, injection molding was performed at a molding resin temperature of 200 ° C. to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm. The molded body is used as a light resistance test sample. Using the reversible thermochromic ABS resin pellet of Comparative Example 6, injection molding was performed at a molding resin temperature of 200 ° C.
A plate-shaped molded body having a size of 0 mm × 60 mm and a thickness of 2 mm was obtained. The molded body is used as a light resistance test sample. Using the reversible thermochromic polyester elastomer resin pellets of Comparative Example 7, injection molding was performed at a molding resin temperature of 200 ° C.
A plate-shaped molded body having a size of 0 mm × 60 mm and a thickness of 2 mm was obtained. The molded body is used as a light resistance test sample. Using the reversible thermochromic ethylene-ethyl acrylate copolymer resin pellets of Comparative Example 8, injection molding was performed at a molding resin temperature of 180 ° C. to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm. The molded body is used as a light resistance test sample.
40 g of the reversible thermochromic urethane foam of Comparative Example 9
A urethane foam sliced to a size of 60 mm x 60 mm and a thickness of 10 mm was obtained. The urethane foam is used as a light resistance test sample. The reversible thermochromic vinyl chloride paste sol of Comparative Example 10 was poured into a 40 mm × 60 mm, 2 mm thick plate-shaped mold to obtain a molded product. The molded body is used as a light resistance test sample. The reversible thermochromic curable silicone composition of Comparative Example 11 was poured into a 40 mm × 60 mm, 2 mm thick plate-shaped form to obtain a molded article. The molded body is used as a light resistance test sample.
【００６８】（２） 耐光堅牢度の試験方法 実施例１〜１１及び比較例１〜１１で得られた樹脂組成
物を用いた耐光性試験試料をキセノンアーク灯光試験機
（ヘラウス社製）を用いて耐光堅牢度試験を行い耐光堅
牢度を比較した。キセノンアーク灯耐光堅牢度試験は、
ＪＩＳ Ｌ−０８４３（キセノンアーク灯光に対する染
色堅牢度試験方法）の規格に準じて行った。キセノンア
ーク灯の照射時間は２０時間、４０時間、６０時間照射
の３ポイントにおいて測定した。(2) Test method for light fastness A light fastness test sample using the resin compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 11 was used using a xenon arc lamp light tester (manufactured by Heraus). A light fastness test was conducted to compare the light fastness. Xenon arc lamp light fastness test
The test was performed in accordance with the standard of JIS L-0843 (testing method for color fastness to xenon arc light). The irradiation time of the xenon arc lamp was measured at three points of irradiation for 20 hours, 40 hours, and 60 hours.
【００６９】（３） 耐光堅牢度試験結果 表１８〜表２１に、前記の耐光堅牢度試験による結果を
示す。(3) Results of light fastness test Tables 18 to 21 show the results of the light fastness test.
【００７０】[0070]
【表１８】 [Table 18]
【００７１】[0071]
【表１９】 [Table 19]
【００７２】[0072]
【表２０】 [Table 20]
【００７３】[0073]
【表２１】 [Table 21]
【００７４】前記耐光堅牢度試験結果の着色濃度保持率
について説明する。一定時間照射した各試料片と未照射
状態の試料片を、色差計（東京電色製）を用いて、試験
の着色状態での濃度刺激値（Ｘ値）を測定する。着色濃
度保持率は次の計算式から算出した。 着色濃度保持率（％）＝１００−照射後の刺激値（Ｘ）
／１００−照射前の刺激値（Ｘ）×１００The color density retention rate based on the light fastness test will be described. Using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd.), each of the sample pieces irradiated for a certain time and the sample pieces in the non-irradiated state are measured for the density stimulus value (X value) in the colored state of the test. The coloring density retention was calculated from the following formula. Color density retention rate (%) = 100−stimulus value (X) after irradiation
/ 100-stimulus value before irradiation (X) x 100
【００７５】[0075]
【発明の効果】本発明は従来耐光性の小さかった電子供
与受容反応による、可逆的熱変色性組成物の発色時の光
による老化を特別の化学構造を有する耐光性付与剤を用
いて防止し、前記可逆的熱変色性組成物を成形用樹脂中
に含有することにより、成形用樹脂組成物及びこれを用
いた成形体の耐光性を著しく向上させる優れた効果を奏
する。According to the present invention, the reversible thermochromic composition can be prevented from aging due to light during the color development due to the electron donating / accepting reaction, which was conventionally low in light resistance, by using a light resistance imparting agent having a special chemical structure. By including the reversible thermochromic composition in a molding resin, an excellent effect of remarkably improving the light resistance of the molding resin composition and a molded article using the same can be obtained.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０９Ｋ 3/00 Ｃ０９Ｋ 3/00 Ｙ Ｄ０１Ｆ 1/04 Ｄ０１Ｆ 1/04 Continued on the front page (51) Int.Cl. 6 Identification symbol FI C09K 3/00 C09K 3/00 Y D01F 1/04 D01F 1/04
Claims (7)
１．０重量部に対し０．３〜７０重量部の使用割合の電
子受容性を有する耐光性付与剤と一般式Ｉ 【化１】 ｛式中、ｎ＝５〜１７（直鎖及び分岐）、Ｘ＝Ｃ１〜Ｃ
（直鎖及び分岐）、ハロゲン、Ｙ＝Ｃ１〜Ｃ（直鎖及び
分岐）、ハロゲン、ｐ＝０〜３、ｍ＝０〜３である。｝ ｅ．成形用樹脂と、からなる、発色時の耐光性を向上し
た可逆的熱変色性を有する成形用樹脂組成物。1. A method comprising: a. An electron donating compound; b. An electron accepting compound; c. A discoloration temperature adjuster; d. Represented by the following general formula I, a. A light-fastness-imparting agent having an electron-accepting property in an amount of 0.3 to 70 parts by weight based on 1.0 part by weight of the electron-donating compound of formula (I) and a general formula I 中 wherein n = 5-17 (straight and branched), X = C 1 -C
(Linear and branched), halogen, Y = C 1 to C (linear and branched), halogen, p = 0 to 3, and m = 0 to 3. ｝ E. A resin composition for molding, comprising: a molding resin; and a reversible thermochromic property having improved light fastness during color development.
を、ｂ．の電子受容体に兼用した、請求項１に記載され
た発色時の耐光性を向上した可逆的熱変色性を有する成
形用樹脂組成物。2. d. A lightfastness imparting agent having an electron accepting property of b. The molding resin composition having reversible thermochromic properties and improved light fastness at the time of color development according to claim 1, which is also used as an electron acceptor.
蔵した、請求項１または２に記載された発色時の耐光性
を向上した可逆的熱変色性を有する成形用樹脂組成物。3. A method according to claim 1, wherein: a. ~ D. The resin composition for molding according to claim 1 or 2, wherein the component is incorporated in a microcapsule and has reversible thermochromic properties with improved light fastness during color development.
１ないし３のいずれか１項に記載された発色時の耐光性
を向上した可逆的熱変色性を有する成形用樹脂組成物。E. The resin composition for molding according to any one of claims 1 to 3, wherein the component is a thermoplastic resin, and has a reversible thermochromic property with improved light fastness during coloring.
された成形用樹脂組成物を用いて成形した、発色時の耐
光性を向上した可逆的熱変色性を有する成形体。5. A molded article having a reversible thermochromic property, which is formed by using the molding resin composition according to any one of claims 1 to 4 and has improved light fastness during color development.
項５に記載された発色時の耐光性を向上した可逆的熱変
色性を有する成形体。6. The molded article according to claim 5, wherein the molded article is a filament, wherein the molded article has reversible thermochromic properties with improved light fastness during color development.
に記載された発色時の耐光性を向上した可逆的熱変色性
を有する成形体。7. The molded article is a film.
A molded article having a reversible thermochromic property with improved light fastness at the time of coloring described in 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20701497A JPH1121464A (en) | 1997-06-27 | 1997-06-27 | Molding resin composition with reversible thermal color changeability and molded form using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20701497A JPH1121464A (en) | 1997-06-27 | 1997-06-27 | Molding resin composition with reversible thermal color changeability and molded form using the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005231774A Division JP2006037111A (en) | 2005-08-10 | 2005-08-10 | Molding resin composition having reversibly thermally color-changing property and molded article using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1121464A true JPH1121464A (en) | 1999-01-26 |
Family
ID=16532774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20701497A Pending JPH1121464A (en) | 1997-06-27 | 1997-06-27 | Molding resin composition with reversible thermal color changeability and molded form using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1121464A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006522179A (en) * | 2003-03-20 | 2006-09-28 | ストウ・ウッドワード・エフェ・ウント・エー・ゲー・エム・べー・ハー | Composition for preparation of thermosetting substance having thermochromic properties |
-
1997
- 1997-06-27 JP JP20701497A patent/JPH1121464A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006522179A (en) * | 2003-03-20 | 2006-09-28 | ストウ・ウッドワード・エフェ・ウント・エー・ゲー・エム・べー・ハー | Composition for preparation of thermosetting substance having thermochromic properties |
| JP4825941B2 (en) * | 2003-03-20 | 2011-11-30 | ストウ ウッドワード アーゲー | Composition for preparation of thermosetting substance having thermochromic properties |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3917269B2 (en) | Reversible thermochromic composition | |
| JP4567859B2 (en) | Reversible thermochromic composition with improved light resistance and products using the same | |
| EP1498447B1 (en) | Photochromic material | |
| JP4271401B2 (en) | Heat coloring type reversible thermochromic pigment | |
| DE3147146A1 (en) | THERMOCHROMIC MATERIAL | |
| US6602594B2 (en) | Irreversible heat-sensitive composition | |
| GB1353340A (en) | Thermoplastic moulding compositions and mouldings of polycarbonate | |
| CN109575664A (en) | Discoloration artistic oil painting stick steady in a long-term and preparation method thereof | |
| EP0781667B1 (en) | Reversible thermochromic composition | |
| JPH11166123A (en) | Molding resin composition having reversible thermal color change property and mold therefrom | |
| JPH1121464A (en) | Molding resin composition with reversible thermal color changeability and molded form using the same | |
| JPH08127768A (en) | Thermochromic composition | |
| KR100435856B1 (en) | A method for production of a light artificial clay hardening at room temperature | |
| JP4209518B2 (en) | Reversible thermochromic composition | |
| JP2006037111A (en) | Molding resin composition having reversibly thermally color-changing property and molded article using the same | |
| JP3984510B2 (en) | Reversible thermochromic molding resin composition and molded article using the same | |
| KR100466821B1 (en) | Ink composition including photochromic compounds and phosphorescent pigments, method of the composition and method for printing or coating by using thereof | |
| JP4510960B2 (en) | Microcapsule pigment containing reversible thermochromic composition | |
| JP4679085B2 (en) | Photochromic molding resin composition and molded article using the same | |
| JPH07186540A (en) | Reversible thermal discoloring composition | |
| JPH1121479A (en) | Liquid composition reversibly changing its color with heat | |
| JPH11131058A (en) | Coating liquid composition having reversible thermochromism and coating layer produced by applying light-protection layer on coating layer made of the composition | |
| JP2002129030A (en) | Reversibly thermally color-changeable resin composition for molding and molded product using the same | |
| JP2011162791A (en) | Reversible thermochromic coating material or ink composition | |
| JP2002294096A (en) | Reversibly thermally discolorable composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040507 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050126 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050208 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050405 |
|
| A02 | Decision of refusal |
Effective date: 20050614 Free format text: JAPANESE INTERMEDIATE CODE: A02 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20050713 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050810 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Effective date: 20050822 Free format text: JAPANESE INTERMEDIATE CODE: A911 |
|
| A912 | Removal of reconsideration by examiner before appeal (zenchi) |
Effective date: 20050930 Free format text: JAPANESE INTERMEDIATE CODE: A912 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7425 Effective date: 20060621 |