JPH11166123A - Molding resin composition having reversible thermal color change property and mold therefrom - Google Patents

Molding resin composition having reversible thermal color change property and mold therefrom

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Publication number
JPH11166123A
JPH11166123A JP24433098A JP24433098A JPH11166123A JP H11166123 A JPH11166123 A JP H11166123A JP 24433098 A JP24433098 A JP 24433098A JP 24433098 A JP24433098 A JP 24433098A JP H11166123 A JPH11166123 A JP H11166123A
Authority
JP
Japan
Prior art keywords
reversible thermochromic
weight
light
parts
molding
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
Application number
JP24433098A
Other languages
Japanese (ja)
Inventor
Katsuyuki Fujita
勝幸 藤田
Yoshiaki Ono
義明 小野
Yutaka Shibahashi
裕 柴橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pilot Ink Co Ltd
Original Assignee
Pilot Ink Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Pilot Ink Co Ltd filed Critical Pilot Ink Co Ltd
Priority to JP24433098A priority Critical patent/JPH11166123A/en
Publication of JPH11166123A publication Critical patent/JPH11166123A/en
Pending legal-status Critical Current

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  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a molding resin compsn. having reversible thermal color change property with improved photo-resistance at discoloration in non-colored state. SOLUTION: This compsn. comprises an electron donor compd. (a), an electron receptor compd. (b), a color change temperature moderator (c), 0.3-70 pts.wt. photo-resistance donor having electron receptor property (d) shown by the formula wherein n=5-17(linear or branched); X=1-4C(linear or branched) or halogen; Y=1-4C(linear or branched) or halogen; p=0-3, m=0-3} to 1.0 pts.wt. electron donor compd. mentioned as (a), a photo-stabilizer (e), and a molding resin (f).

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【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と光安定剤を存在させることにより
消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 resin composition having improved light fastness at the time of decolorization by the presence of a light fastness imparting agent having a special electron accepting property and a light stabilizer. And moldings.

【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が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。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
を用いて消色時の耐光性を向上する方法の発明を出願し
た。（特願平８−５３５８８） 本発明は消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 combining these electron-donating compounds and electron-accepting compounds has a drawback that the thermochromic composition using such an electron-donating compound does not have high light resistance because the electron-donating compound does not have high light resistance. Therefore, when the discolored color becomes thin or severe due to light, it may be completely bleached. 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 decoloring by using a special light fastness imparting agent. (Japanese Patent Application No. 8-53588) The present invention provides a molding resin composition having reversible thermochromic property with improved light resistance at the time of decoloring, 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．光安定剤と、 ｆ．成形用樹脂と、 からなる、消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項に記載された消色時の耐
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．〜ｅ．成分をマイクロカプセルに内蔵した、
１項または２項に記載された消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． ｆ．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項に記載された消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、消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
れた消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
消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。 ８． ５項ないし７項のいずれか１項に記載された成形
体の光にさらされる面に、光安定剤および／または光遮
蔽剤を含有する光保護層を１または複数層配置してな
る、消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 light stabilizer; f. A molding resin composition having reversible thermochromic property and improved light resistance at the time of decoloration, comprising: a molding resin. 2. d. A lightfastness 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 decoloring described in item 1, which is also used as the electron acceptor. 3. a. ~ E. Ingredients built in microcapsules,
A resin composition for molding having reversible thermochromic property and improved light fastness at the time of decoloring described in 1 or 2. 4. f. 4. The molding resin composition 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 at the time of decoloration. 5. A molded article formed by using the molding resin composition according to any one of Items 1 to 4 and having reversible thermochromic properties with improved light resistance during decoloration. 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 decoloration. 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 decoloring. 8. Item 9. A light-emitting device comprising: a molded article according to any one of Items 5 to 7 wherein one or more light-protecting layers containing a light stabilizer and / or a light-shielding agent are arranged on a surface exposed to light. A molded article having reversible thermochromic properties with improved light fastness when colored. About.

【０００７】[0007]

【発明の実施の形態】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重量部と光安定剤と
を組成物中に存在させることにより消色時の耐光性を向
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２．０〜５０
重量部が特に好ましい。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a reversible thermochromic molding resin composition comprising an electron-donating compound, an electron-accepting compound, a color change temperature regulator and a molding resin. The lightfastness at the time of decoloration is improved by adding 0.3 to 70 parts by weight of a lightfastness-imparting agent and 1.0 parts by weight of a light stabilizer to an electron-donating compound shown in the composition. Molding resin composition. The amount of the light fastness imparting agent to be used is 2.0 to 50 parts by weight based on 1.0 part by weight of the electron donating compound.
Part by weight is particularly preferred.

【０００８】電子供与性化合物の代表としてロイコ染料
があるが、ロイコ染料は耐光性が弱いのでこれを用いた
組成物は光により老化し変色性が劣化する。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可視光線、特に間接光によって大
きな影響を受け耐光性が低下し変色性が劣化する。一方
消色状態はイオン化されてなく、無色の分子状態である
ので、紫外線による影響が大きく変色性が著しく劣化す
る。熱変色組成物は発色、消色により表示を行うので消
色時の耐光性も必要である。しかしながら、消色状態で
も可視光線の影響は小さいとしても決して無視すること
は出来ず可視光線の照射量に応じて必ず影響は発生し、
可逆熱変色性は確実に劣化する。従来耐光性を向上する
ために使用されている紫外線吸収剤、金属光沢顔料等は
紫外線のカットには効果があるが可視光線に対しては効
果がない。[0008] Leuco dyes are typical electron-donating compounds. However, since leuco dyes have low light resistance, a composition using the compounds is aged by light and deteriorates in discoloration. When the electron-donating compound is in a state of donating electrons, that is, a color-forming state when described with a leuco dye, it is greatly affected by visible light, in particular, indirect light, so that light resistance is reduced and discoloration is deteriorated. On the other hand, since the decolored state is not ionized and is a colorless molecular state, the effect of ultraviolet rays is large and the discoloration is significantly deteriorated. Since the thermochromic composition performs display by coloring and decoloring, light resistance at the time of decoloring is also required. However, even in the decolored state, even if the influence of visible light is small, it can never be ignored and the effect always occurs according to the irradiation amount of visible light,
Reversible thermochromicity is definitely degraded. Ultraviolet absorbers, metallic luster pigments, and the like, which have been conventionally used to improve light resistance, are effective in cutting ultraviolet light but not in visible light.

【０００９】本発明は、消色状態において紫外線をカッ
トしても可逆熱変色性が低下するのは、従来影響がない
とされていた可視光線によると考え、研究の結果この事
実を明らかにしたのである。本発明は消色状態に大きな
影響を与える紫外線を光安定剤で防止し、可視光線の影
響を前述の一般式Ｉの化合物により防いで、耐光性を著
しく向上することに成功した。消色時の耐光性は光安定
剤と前述の一般式Ｉで示される耐光性付与剤の両者を併
用しなければ改善できないのである。この点が同じ熱変
色性組成物であっても発色時の耐光性の改善方法とは異
なる。According to the present invention, the fact that the reversible thermochromic property is reduced even when ultraviolet light is cut off in the decolored state is considered to be due to visible light, which has been considered to have no effect, and as a result of research, this fact was clarified. It is. The present invention has succeeded in remarkably improving the light fastness by preventing ultraviolet rays which greatly affect the decolored state with a light stabilizer and preventing the effects of visible light with the above-mentioned compound of the general formula I. The light resistance at the time of decoloring cannot be improved unless both the light stabilizer and the light resistance imparting agent represented by the above-mentioned general formula I are used in combination. This point is different from the method of improving the light fastness at the time of coloring even with the same thermochromic composition.

【００１０】本発明で用いる熱変色組成物の発色状態と
消色状態について説明する。本発明で用いる熱変色組成
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性熱変色性を有す
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。し
かしながら実際はａは単独分子ではなく、熱変色性を有
する成形用樹脂組成物中にｄ（ｂ）成分と共にｃ成分中
に溶解状態にあるため、ａ成分とｄ（ｂ）成分には消色
状態においては弱い相互作用がある。また、現実に消色
状態でもｂよりもｄは耐光性向上効果があることからも
少なくともｄ成分はａ成分と相互作用を有することがわ
かる。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。可逆熱変色組成物は消色状態と発色状態を繰り返し
て変色を行うので両状態の耐光性を向上させないと可逆
熱変色性は劣化するのである。したがって、紫外線をカ
ットしたり、一般式Ｉの耐光性付与剤を用いて可視光線
による老化を防止すると耐光性は向上するが、経時的に
は可逆熱変色性の劣化は進行する。本発明の特徴は前述
の一般式Ｉで示される耐光性付与剤と光安定剤を併用す
ることにより消色時の可視光線と紫外線の両方の影響を
除いたことである。The color-developed state and the decolored state of the thermochromic composition used in the present invention will be described. A. Thermochromic composition used 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. Ingredients and b. The ionic bonds of the components disappear, 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. However, actually, a is not a single molecule, but is in a dissolved state in the c component together with the d (b) component in the molding resin composition having thermochromic properties. There is a weak interaction in In addition, since d actually has an effect of improving light resistance more than b even in the decolored state, it can be seen that at least the d component has an interaction with the a component. 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. Since the reversible thermochromic composition changes its color by repeating the decoloring state and the color-developing state, the reversible thermochromic properties deteriorate unless the light resistance of both states is improved. Therefore, when ultraviolet rays are cut off or aging due to visible light is prevented by using a light-fastness imparting agent of the general formula I, the light fastness is improved, but the reversible thermochromic property deteriorates with time. A feature of the present invention is that the combined use of the lightfastness-imparting agent represented by the above-mentioned general formula I and the light stabilizer has eliminated the effects of both visible light and ultraviolet light at the time of decoloration.

【００１１】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重量部以上消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消色した状態で
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この様な成形用
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。The lightfastness imparting agent used in the present invention itself has an electron accepting property and must be present in a decolored state in an amount of 0.3 parts by weight or more based on 1.0 part by weight of the electron donating compound. . If the light-resistance imparting agent is present in an amount of 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 has been decolorized, such a molding may be used. A molded article using the resin composition does not have sufficient light resistance.

【００１２】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ＩA compound represented by the general formula I used in the present invention: d. The lightfastness-imparting agent has the general formula I

【００１３】[0013]

【化３】 Embedded image

【００１４】｛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
解性が大き過ぎ、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。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 is not practical because the solubility in the discoloring temperature adjusting agent is too large, and when considering the practical aspect, the coloring power is weakened and the discoloring sensitivity is deteriorated.

【００１５】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。Most preferably, the alkyl group is a straight-chain alkyl group, and when it has a branch, a group having a short branch is preferred. 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.

【００１６】本発明は前記ｄ．成分の耐光性付与剤であ
る一般式Ｉの化合物を電子供与性化合物１．０重量部に
対し０．３〜７０重量部使用する。０．３重量部以下で
は効果が充分でなく、７０重量部以上加えても効果は向
上しない。２．０〜５０重量部の使用が好ましい。この
耐光性付与剤はそれ自体も電子受容性を有しているの
で、これを用いることによりｂ．成分の電子受容性化合
物の量を調節したり、場合によっては全部置き換えるこ
ともできる。一般式Ｉで示される耐光性付与剤を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１．０〜６０重量部使用する必要
があり、特に２．０〜５０重量部が好ましい。The present invention provides the above d. The compound of the formula I, which is a component for imparting light resistance, is used in an amount of 0.3 to 70 parts by weight based on 1.0 part by weight of the electron donating compound. If the amount is less than 0.3 part by weight, the effect is not sufficient, and if the amount is more than 70 parts by weight, the effect is not improved. The use of 2.0 to 50 parts by weight is preferred. Since this lightfastness imparting agent itself has an electron accepting property, b. The amount of the component electron-accepting compound can be adjusted or, if necessary, entirely replaced. A lightfastness-imparting agent represented by the general formula I, b. 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 1.0 to 60 parts by weight, preferably 2.0 to 50 parts by weight, per 1.0 part by weight of the component electron donating compound.

【００１７】消色状態においてはａ．電子供与性呈色性
有機化合物はｃ．変色温度調整剤中に溶解状態にありな
がら、ｄ．耐光性付与剤とは弱い相互作用を保持してお
り、且つ、ｄ．耐光性付与剤は長鎖アルキル基により
ｃ．変色温度調整剤中に安定化している。光に対する安
定化の度合いは、ａ．電子供与性呈色性有機化合物と
ｄ．耐光性付与剤がイオン的な強い相互作用をしている
発色状態の場合のように大きくはないが、消色状態にお
いてもこの弱い相互作用が光によって引き起こされる光
酸化や光分解を抑止し、耐光性を向上させていると考え
られる。消色状態におけるａ．電子供与性呈色性有機化
合物とｄ．耐光性付与剤との弱い相互作用は、アミノ
基、カルボニル基等を有するａ．電子供与性呈色性有機
化合物とフェノール性水酸基を有するｄ．耐光性付与剤
のように極性の大きな置換基によって分極構造を有する
分子間に作用する静電的な力によるものと推定される。In the decolored state, a. The electron-donating color-forming organic compound is c. While being dissolved in the discoloration temperature regulator, d. Retains a weak interaction with the light resistance imparting agent, and d. The light resistance imparting agent is c. Stabilized in discoloration temperature regulator. The degree of stabilization to light can be determined by: a. An electron-donating color-forming organic compound and d. Although not as large as in the case of the color development state in which the light resistance imparting agent has a strong ionic interaction, this weak interaction suppresses photo-oxidation and photo-decomposition caused by light even in the decolored state, It is considered that the light resistance was improved. A. In the bleached state An electron-donating color-forming organic compound and d. The weak interaction with the light fastness-imparting agent is attributed to a. Having an electron-donating color-forming organic compound and a phenolic hydroxyl group d. It is presumed to be due to an electrostatic force acting between molecules having a polarized structure by a substituent having a large polarity such as a lightfastness-imparting agent.

【００１８】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、芳香族及び脂肪族カルボン酸無水物、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。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。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。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 aliphatic carboxylic anhydrides, boric esters, halogenated alcohols, oxazoles, thiazoles, imidazole , Pyrazoles, pyrroles, aromatic sulfonamides and aromatic sulfonimides. The lightfastness-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. A. Used in the present invention. Tables 1 and 2 show examples of the component electron-donating color-forming compounds.

【００１９】[0019]

【表１】 [Table 1]

【００２０】[0020]

【表２】 [Table 2]

【００２１】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.

【００２２】[0022]

【表３】 [Table 3]

【００２３】[0023]

【表４】 [Table 4]

【００２４】[0024]

【表５】 [Table 5]

【００２５】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に例示する。C. Used in the present invention. Tables 6 to 12 show examples of the discoloration temperature regulators of the components.

【００２６】[0026]

【表６】 [Table 6]

【００２７】[0027]

【表７】 [Table 7]

【００２８】[0028]

【表８】 [Table 8]

【００２９】[0029]

【表９】 [Table 9]

【００３０】[0030]

【表１０】 [Table 10]

【００３１】[0031]

【表１１】 [Table 11]

【００３２】[0032]

【表１２】 [Table 12]

【００３３】本発明で使用するｄ．成分の耐光性付与剤
を表１３と表１４に例示する。D. Used in the present invention. Tables 13 and 14 show examples of the components for imparting light resistance.

【００３４】[0034]

【表１３】 [Table 13]

【００３５】[0035]

【表１４】 [Table 14]

【００３６】本発明で使用するｅ．成分の光安定剤を表
１５ないし表１８に示す。E. Used in the present invention. The component light stabilizers are shown in Tables 15 to 18.

【００３７】[0037]

【表１５】 [Table 15]

【００３８】[0038]

【表１６】 [Table 16]

【００３９】[0039]

【表１７】 [Table 17]

【００４０】[0040]

【表１８】 [Table 18]

【００４１】赤外線吸収剤としては、７００〜２０００
ｎｍの近赤外領域に極大吸収を持ち、４００〜７００ｎ
ｍの可視領域にはあまり吸収を持たない性質を有する次
の一般式ＩＩ〜式Ｘで示される化合物が使用される。 式ＩＩAs the infrared absorbent, 700 to 2000
with a maximum absorption in the near infrared region of 400 nm
Compounds represented by the following general formulas II to X having the property of having little absorption in the visible region of m are used. Formula II

【００４２】[0042]

【化４】 Embedded image

【００４３】式中Ｒ１、Ｒ２、Ｒ３、Ｒ４はアルキル
基、ＭｅはＮｉ、Ｐｄ、Ｐｔのいずれかを示す。 式ＩＩＩIn the formula, R 1 , R 2 , R 3 and R 4 are alkyl groups, and Me is any of Ni, Pd and Pt. Formula III

【００４４】[0044]

【化５】 Embedded image

【００４５】式中Ｒ１、Ｒ２、Ｒ３、Ｒ４はアルキル
基、ＭｅはＮｉ，Ｐｄ、Ｐｔのいずれかを示す。 式ＩＶIn the formula, R 1 , R 2 , R 3 , and R 4 represent an alkyl group, and Me represents any of Ni, Pd, and Pt. Formula IV

【００４６】[0046]

【化６】 Embedded image

【００４７】式中Ｒ１、Ｒ２、Ｒ３、Ｒ４はアルキル
基、ＭｅはＮｉ、Ｐｄ、Ｐｔのいずれか、ＸはＣ、Ｏ、
Ｓのいずれかを示す。 式ＶIn the formula, R 1 , R 2 , R 3 and R 4 are alkyl groups, Me is any of Ni, Pd and Pt, X is C, O,
Indicates one of S. Equation V

【００４８】[0048]

【化７】 Embedded image

【００４９】式中Ｒ１、Ｒ２、Ｒ３、Ｒ４はアルキル
基、ＭｅはＮｉ、Ｐｄ、Ｐｔのいずれか、ＸはＣ、Ｏ、
Ｓのいずれかを示す。 式ＶＩIn the formula, R 1 , R 2 , R 3 and R 4 are an alkyl group, Me is any of Ni, Pd and Pt, X is C, O,
Indicates one of S. Formula VI

【００５０】[0050]

【化８】 Embedded image

【００５１】式中Ｒ１、Ｒ２、Ｒ３、Ｒ４はアルキル
基、ＭｅはＮｉ、Ｐｄ、Ｐｔのいずれか、Ｘはハロゲン
またはＨのいずれかを示す。 式ＶＩＩIn the formula, R 1 , R 2 , R 3 and R 4 are alkyl groups, Me is any of Ni, Pd and Pt, and X is any of halogen or H. Formula VII

【００５２】[0052]

【化９】 Embedded image

【００５３】式中ＲはＨ、アルキル基、フェニル基、ア
ルキルまたはアルコキシ置換フェニル基、チエニル基の
いずれか、ＭｅはＮｉ、Ｐｄ、Ｐｔのいずれかを示す。 式ＶＩＩＩIn the formula, R represents H, an alkyl group, a phenyl group, an alkyl- or alkoxy-substituted phenyl group, or a thienyl group, and Me represents any of Ni, Pd, and Pt. Formula VIII

【００５４】[0054]

【化１０】 Embedded image

【００５５】式中Ｒはアルキル基、Ｘは陰イオンとして
過塩素酸塩、フッ化ホウ素酸塩、トリクロロ酢酸塩、ト
リフルオロ酢酸塩、ピクリン酸塩、ヘキサフルオロ砒酸
塩、ヘキサクロロアンチモン酸塩、ヘキサフルオロアン
チモン酸塩、ベンゼンスルホン酸塩、アルキルスルホン
酸塩、リン酸塩、硫酸塩、塩化物、臭化物のいずれかを
示す。 式ＩＸIn the formula, R is an alkyl group, and X is an anion such as perchlorate, fluoroborate, trichloroacetate, trifluoroacetate, picrate, hexafluoroarsenate, hexachloroantimonate, hexachloride. Indicates any of fluoroantimonate, benzenesulfonate, alkylsulfonate, phosphate, sulfate, chloride, and bromide. Formula IX

【００５６】[0056]

【化１１】 Embedded image

【００５７】式中Ｒはアルキル基、Ｘは陰イオンとして
過塩素酸塩、フッ化ホウ素酸塩、トリクロロ酢酸塩、ト
リフルオロ酢酸塩、ピクリン酸塩、ヘキサフルオロ砒酸
塩、ヘキサクロロアンチモン酸塩、ヘキサフルオロアン
チモン酸塩、ベンゼンスルホン酸塩、アルキルスルホン
酸塩、リン酸塩、硫酸塩、塩化物、臭化物のいずれかを
示す。 式ＸIn the formula, R is an alkyl group, X is an anion, such as perchlorate, fluoroborate, trichloroacetate, trifluoroacetate, picrate, hexafluoroarsenate, hexachloroantimonate, hexachloride. Indicates any of fluoroantimonate, benzenesulfonate, alkylsulfonate, phosphate, sulfate, chloride, and bromide. Formula X

【００５８】[0058]

【化１２】 Embedded image

【００５９】式中Ｒはアルキル基、Ｘは陰イオンとして
過塩素酸塩、フッ化ホウ素酸塩、トリクロロ酢酸塩、ト
リフルオロ酢酸塩、ピクリン酸塩、ヘキサフルオロ砒酸
塩、ヘキサクロロアンチモン酸塩、ヘキサフルオロアン
チモン酸塩、ベンゼンスルホン酸塩、アルキルスルホン
酸塩、リン酸塩、硫酸塩、塩化物、臭化物のいずれかを
示す。これ等の主として紫外線を遮断するｅ．成分は、
組成物中にａ．成分１重量部に対し０．１〜４０重量部
を混合して使用することができる。また、ａ〜ｅ．成分
をマイクロカプセルに内蔵する場合は、前記カプセル外
に存在させることもできる。本発明で使用するｆ．成分
の成形用樹脂を表１９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。In the formula, R is an alkyl group, and X is an anion, such as perchlorate, fluoroborate, trichloroacetate, trifluoroacetate, picrate, hexafluoroarsenate, hexachloroantimonate, hexachloride. Indicates any of fluoroantimonate, benzenesulfonate, alkylsulfonate, phosphate, sulfate, chloride, and bromide. These mainly block ultraviolet rays e. The ingredients are
A. In the composition; 0.1 to 40 parts by weight can be mixed and used for 1 part by weight of the component. A to e. When the components are incorporated in microcapsules, they can be present outside the capsules. F. Used in the present invention; Table 19 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.

【００６０】[0060]

【表１９】 [Table 19]

【００６１】更に、前記ａ．〜ｆ．成分からなる成形用
樹脂組成物を用いて成形した成形体上に、前記光安定剤
および／または光遮蔽剤の層を積層することによって紫
外線の遮蔽を一層向上させることができ、著しい耐光性
向上効果が得られる。前記光安定剤および／または光遮
蔽剤の層として、具体的には、光安定剤を含む光安定剤
層、光遮蔽性顔料を含む光遮蔽層、あるいは、光安定剤
および光遮蔽性顔料を含む共存層が挙げられる。また、
前記した光安定剤層、光遮蔽層および共存層は、それぞ
れを積層して用いてもよく、例えば、共存層上に光安定
剤層を積層したり、光遮蔽層上に光安定剤層を積層する
構成などが挙げられ、前述の成形体上に光安定剤および
／または光遮蔽剤の単一層を設ける系よりも、更に著し
い耐光性効果が得られる。なお、前記光安定剤および／
または光遮蔽剤が層中に０．１〜４０重量％含まれる。Further, a. ~ F. By laminating a layer of the light stabilizer and / or the light shielding agent on a molded article molded using the molding resin composition comprising the components, ultraviolet light shielding can be further improved, and light resistance is remarkably improved. The effect is obtained. As the light stabilizer and / or light shielding layer, specifically, a light stabilizer layer containing a light stabilizer, a light shielding layer containing a light shielding pigment, or a light stabilizer and a light shielding pigment. Including coexisting layers. Also,
The light stabilizer layer, the light shielding layer and the coexisting layer may be used by laminating each.For example, a light stabilizer layer may be laminated on the coexisting layer, or a light stabilizer layer may be formed on the light shielding layer. There is a lamination structure and the like, and a more remarkable light resistance effect can be obtained than in a system in which a single layer of a light stabilizer and / or a light shielding agent is provided on the above-mentioned molded article. The light stabilizer and / or
Alternatively, a light shielding agent is contained in the layer in an amount of 0.1 to 40% by weight.

【００６２】前記光遮蔽性顔料は、金属光沢顔料、透明
二酸化チタン、透明酸化鉄、透明酸化セシウム、透明酸
化亜鉛等の顔料類である。金属光沢顔料は、天然雲母の
表面を酸化チタンで被覆した粒度が、５〜１００μｍの
金属光沢顔料であり、さらに具体的には、天然雲母の表
面を４１〜４４重量％の酸化チタンで被覆した粒度が５
〜６０μｍの金色光沢顔料、天然雲母の表面を１６〜３
９重量％の酸化チタンで被覆した粒度が５〜１００μｍ
の銀色金属光沢顔料、天然雲母の表面を４５〜５８重量
％の酸化チタンで被覆し、その上に４〜１０重量％の酸
化鉄で被覆したメタリック色金属光沢顔料、天然雲母の
表面を４５〜５８重量％の酸化チタンで被覆し、その上
に０．５〜１０重量％の非熱変色性有色染顔料を被覆し
たメタリック色金属光沢顔料等である。The light-shielding pigments are pigments such as metallic luster pigments, transparent titanium dioxide, transparent iron oxide, transparent cesium oxide, and transparent zinc oxide. The metallic luster pigment is a metallic luster pigment having a particle size of 5 to 100 μm in which the surface of natural mica is coated with titanium oxide. More specifically, the surface of natural mica is coated with 41 to 44% by weight of titanium oxide. Particle size is 5
~ 60μm golden luster pigment, natural mica surface of 16 ~ 3
Particle size coated with 9% by weight of titanium oxide is 5 to 100 μm
The metallic metallic luster pigment of the present invention is coated with 45 to 58% by weight of titanium oxide on the surface of natural mica and further coated with 4 to 10% by weight of iron oxide, and the surface of the natural mica is coated with 45 to 58% by weight of iron oxide. Metallic metallic luster pigments coated with 58% by weight of titanium oxide and further coated with 0.5 to 10% by weight of a non-thermochromic colored dye or pigment.

【００６３】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。The resin composition for molding having reversible thermochromic property of the present invention usually has a pellet shape, and is used for molding films, sheets, plates, rods, pipes, filaments and the like. When a thermoplastic resin is used 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.

【００６４】[0064]

【実施例】次に実施例と比較例をあげて本発明を具体的
に説明する。まず使用する熱変色性組成物の製造方法を
示す。Next, the present invention will be described in detail with reference to examples and comparative examples. First, a method for producing the thermochromic composition used will be described.

【００６５】熱変色性組成物の製造例１ １，２−ベンツ−６−（Ｎ−エチル−Ｎ−イソブチルア
ミノ）フルオラン０．７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重量部、
１，１−ビス−（４−ヒドロキシフェニル）−ｎ−デカ
ン８．０重量部、２−（３−ｔ−ブチル−５−メチル−
２−ヒドロキシフェニル）−５−クロロベンゾトリアゾ
ール５．０重量部、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〕１０．０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℃に保って約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、含水率約４０重量％のピンクから
無色に変化するマイクロカプセルに内包した可逆熱変色
性組成物１を得な。Preparation Example 1 of Thermochromic Composition 0.7 parts by weight of 1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane, 30.0 parts by weight of stearyl laurate, stearyl caprate 20 Parts by weight,
8.0 parts by weight of 1,1-bis- (4-hydroxyphenyl) -n-decane, 2- (3-t-butyl-5-methyl-
5.0 parts by weight of 2-hydroxyphenyl) -5-chlorobenzotriazole were heated and dissolved at 120 ° C. to form a homogeneous solution, and Epon 828 (Epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) 10.0 After mixing with the mixed solution in parts by weight, the mixture is dropped into 100 parts by weight of a 10% aqueous solution of gelatin, and the mixture is stirred so as to be fine droplets. 45. A separately prepared 5.0 parts by weight of a curing agent EpiCure U [available from Yuka Shell Epoxy Co., Ltd., amine adduct of epoxy resin].
A solution dissolved in 0 parts by weight of water was gradually added to the stirring solution, and stirring was continued for about 5 hours while maintaining the solution temperature at 80 ° C. to obtain a stock solution of microcapsules. By centrifuging the stock solution, a reversible thermochromic composition 1 encapsulated in microcapsules having a water content of about 40% by weight and changing from pink to colorless was not obtained.

【００６６】熱変色性組成物の製造例２〜１８ ａ．ｂ．ｃ．ｄ．ｅ．成分を表２０〜表２３に示したよ
うに変えて他は製造例１と同様にして製造した。Production Examples 2 to 18 of Thermochromic Compositions a. b. c. d. e. The components were produced in the same manner as in Production Example 1 except that the components were changed as shown in Tables 20 to 23.

【００６７】[0067]

【表２０】 [Table 20]

【００６８】[0068]

【表２１】 [Table 21]

【００６９】[0069]

【表２２】 [Table 22]

【００７０】[0070]

【表２３】 [Table 23]

【００７１】（註） 表中の配合量は重量部である。な
お製造例１〜９は本発明で使用する組成物であり、１０
〜１８はｄ．成分を含まない比較例で使用するものであ
る。(Note) The amounts in the table are parts by weight. Production Examples 1 to 9 are compositions used in the present invention,
-18 are d. It is used in a comparative example containing no component.

【００７２】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８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、紫外線吸収剤として、２−（３，５−ジ−ｔ−ア
ミル−２−ヒドロキシフェニル）ベンゾトリアゾール１
０．０重量部および酸化防止剤として、ビス（２，２，
６，６−テトラメチル−４−ピペリジル）セバケート
２．０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、１７℃未満ではピンク色を呈し、１７℃以
上では白色を呈する。更に、耐光性試験試料として前記
成形用樹脂組成物を用いて射出成形を行い、４０ｍｍ×
６０ｍｍ、厚み２ｍｍのプレート状の成形体を得た。Example 1 As a molding resin composition, 40.0 parts by weight of the microcapsule pigment of the reversible thermochromic composition 8 was mixed with 1000.0 parts by weight of a low-density polyethylene resin (melt flow rate: 1.3). 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole 1 as an ultraviolet absorber
0.0 parts by weight and bis (2,2,2) as an antioxidant
6,6-tetramethyl-4-piperidyl) sebacate (2.0 parts by weight) and a metal soap-based lubricant (0.5 parts by weight) were mixed and uniformly dispersed by a tumbler mixer. Tip die temperature 180 ℃
To obtain a reversible thermochromic polyethylene resin pellet. 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. The molded body exhibits a pink color below 17 ° C. and a white color at 17 ° C. or more. Furthermore, injection molding was carried out using the resin composition for molding as a light resistance test sample, and 40 mm ×
A plate-shaped molded body having a thickness of 60 mm and a thickness of 2 mm was obtained.

【００７３】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黄色顔
料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、紫外
線吸収剤として、２−ヒドロキシ−４−ｎ−オクチルオ
キシベンゾフェノン１０．０重量部と酸化防止剤とし
て、４−ベンゾイルオキシ−２，２，６，６−テトラメ
チルピペリジン２．０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。また、耐光性試験試
料として前記成形用樹脂組成物を用いて射出成形を行
い、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状の成
形体を得た。Example 2 As a molding resin composition, 30.0 parts by weight of the microcapsule pigment and 7.0 parts by weight of the powdery fluorescent yellow pigment of the reversible thermochromic composition 2 were mixed with an ethylene-vinyl acetate copolymer resin (melt). Flow rate: 1.4) 1000.0 parts by weight, 2-hydroxy-4-n-octyloxybenzophenone as an ultraviolet absorber 10.0 parts by weight, and 4-benzoyloxy-2,2,6, as an antioxidant , 6-tetramethylpiperidine (2.0 parts by weight) and a metal soap-based lubricant (0.5 parts by weight) and uniformly dispersed by a tumbler mixer.
Using an extruder, molding was performed at a cylinder temperature of 160 ° C and a tip die temperature of 160 ° C.
A vinyl acetate copolymer resin pellet was obtained. Using the resin composition for molding, a doll-shaped mold was used to obtain a doll-shaped reversible thermochromic hollow molded body at a cylinder temperature of 150 ° C. Note that the molded body exhibits a green color under a room temperature environment,
Above 30 ° C., it exhibits a fluorescent yellow color. In addition, injection molding was performed using the molding resin composition as a light resistance test sample to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【００７４】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、紫外
線吸収剤として、２−（２−ヒドロキシ−５−ｔ−オク
チルフェニル）ベンゾトリアゾール１０．０重量部、酸
化防止剤として、ビス（１，２，２，６，６−ペンタメ
チル−４−ピペリジル）セバケート３．０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℃、先端ダイス温度１
７０℃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。また、耐光性試験試
料として前記成形用樹脂組成物を用いて射出成形を行
い、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状の成
形体を得た。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, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole 10.0 parts by weight as an ultraviolet absorber, bis (1,2,2,2) as an antioxidant 6,6-pentamethyl-4-piperidyl) sebacate (3.0 parts by weight) and a metal soap-based lubricant (0.5 parts by weight) were mixed uniformly with a tumbler mixer, and then the cylinder temperature was adjusted to 1 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 heated at a cylinder temperature of 170 ° C. and a tip die temperature of 1
Melt spinning was performed at 70 ° 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 at room temperature, and
Above ° C, it exhibits a fluorescent pink color. In addition, injection molding was performed using the molding resin composition as a light resistance test sample to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【００７５】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重量部及び粉末加工黄色顔
料０．１重量部、粉末加工緑色顔料０．０１重量部、粉
末加工赤色顔料０．０４重量部を１２ナイロン樹脂（融
点１７８℃）１０００．０重量部、紫外線吸収剤とし
て、２−（３−ｔ−ブチル−５−オクチルオキシカルボ
ニルエチル−２−ヒドロキシフェニル）ベンゾトリアゾ
ール１０．０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１９
０℃、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。また、耐光性試験試料として前記成形用樹脂組成物
を用いて射出成形を行い、４０ｍｍ×６０ｍｍ、厚み２
ｍｍのプレート状の成形体を得た。Example 4 As the resin composition for molding, 50.0 parts by weight of the microcapsule pigment, 0.1 part by weight of the powder-processed yellow pigment, and 0.01 part by weight of the powder-processed green pigment of the reversible thermochromic composition 4 were used. 0.04 parts by weight of powder-processed red pigment, 1000.0 parts by weight of 12 nylon resin (melting point: 178 ° C.), and 2- (3-t-butyl-5-octyloxycarbonylethyl-2-hydroxyphenyl) as an ultraviolet absorber ) Compounded in 10.0 parts by weight of benzotriazole, uniformly dispersed with a Hensyl mixer, and then heated to a cylinder temperature of 19 using an extruder.
Molding was performed at 0 ° C. and a die temperature of 200 ° C. to obtain a reversible thermochromic 12 nylon resin pellet. 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. In addition, injection molding was performed using the above-mentioned resin composition for molding as a light resistance test sample to obtain a sample having a thickness of 40 mm × 60 mm and a thickness of 2 mm.
mm plate-shaped molded body was obtained.

【００７６】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７のマ
イクロカプセル顔料３０．０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）１００
０．０重量部、紫外線吸収剤として、２−（３−ｔ−ブ
チル−５−オクチルオキシカルボニルエチル−２−ヒド
ロキシフェニル）ベンゾトリアゾール１５．０重量部、
酸化防止剤として、２−（３，５−ジ−ｔ−ブチル−４
−ヒドロキシベンジル）−２−ｎ−ブチルマロン酸ビス
−（１，２，２，６，６−ペンタメチル−４−ピペリジ
ル）３．０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１
８０℃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
℃、先端ダイス温度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
１７℃以上では白色を呈し、１７℃未満では青色を呈す
る。また、耐光性試験試料として前記成形用樹脂組成物
を用いて射出成形を行い、４０ｍｍ×６０ｍｍ、厚み２
ｍｍのプレート状の成形体を得た。Example 5 As a molding resin composition, 30.0 parts by weight of the microcapsule pigment of the reversible thermochromic composition 7 was mixed with 100 parts of a styrene-butadiene copolymer resin (melt flow rate 7.3).
0.0 part by weight, 15.0 parts by weight of 2- (3-t-butyl-5-octyloxycarbonylethyl-2-hydroxyphenyl) benzotriazole as an ultraviolet absorber,
2- (3,5-di-tert-butyl-4) as an antioxidant
-Hydroxybenzyl) -2-n-butylmalonate bis- (1,2,2,6,6-pentamethyl-4-piperidyl) 3.0 parts by weight and metal soap-based lubricant 0.5 part by weight. After uniformly dispersing with a tumbler mixer, using an extruder, the cylinder temperature was 180 ° C and the tip die temperature was 1
Molding was performed at 80 ° C. to obtain a reversible thermochromic styrene-butadiene copolymer resin pellet. Using the above-mentioned resin composition for molding, a dolphin mold was used, and a cylinder temperature of 180 was used.
Injection molding was performed at 185 ° C. and a tip die temperature of 185 ° C. to obtain a dolphin-shaped reversible thermochromic molded body. In addition, the said molded object exhibits white above 17 degreeC, and exhibits blue below 17 degreeC. In addition, injection molding was performed using the above-mentioned resin composition for molding as a light resistance test sample to obtain a sample having a thickness of 40 mm × 60 mm and a thickness of 2 mm.
mm plate-shaped molded body was obtained.

【００７７】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重量部をＡＢＳ樹脂（メルトフローレー
ト６０．０）１０００．０重量部、紫外線吸収剤とし、
２−（３−ｔ−ブチル−５−オクチルオキシカルボニル
エチル−２−ヒドロキシフェニル）ベンゾトリアゾール
１５．０重量部、酸化防止剤として、２−（３，５−ジ
−ｔ−ブチル−４−ヒドロキシベンジル）−２−ｎ−ブ
チルマロン酸ビスー（１，２，２，６，６−ペンタメチ
ル−４−ピペリジル）３．０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℃、先端ダイスの温度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。また、耐光性試験試料と
して前記成形用樹脂組成物を用いて射出成形を行い、４
０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状の成形体を
得た。Example 6 As a molding resin composition, 30.0 parts by weight of the microcapsule pigment and 5.0 parts by weight of the powdered pigment (white) of the reversible thermochromic composition 3 were added to an ABS resin (melt flow rate 60). 0.0) 1000.0 parts by weight as an ultraviolet absorber,
15.0 parts by weight of 2- (3-tert-butyl-5-octyloxycarbonylethyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-4-hydroxy) as an antioxidant Benzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl) 3.0 parts by weight and a metal soap-based lubricant 0.5 part by weight were mixed in a tumbler mixer. After uniformly dispersing with a cylinder, the cylinder temperature was set to 200 using an extruder.
℃, reversible thermochromic ABS at tip temperature of 200 ℃
A resin pellet was obtained. Using the molding resin composition,
Injection molding was performed at a cylinder temperature of 200 ° C. and a tip die temperature of 200 ° C. using a mold for molding a small automobile toy to obtain a reversible thermochromic molded article in the form of a small automobile. In addition,
The molded body has a pastel blue color under a room temperature environment,
Above 34 ° C. it is white. In addition, injection molding was performed using the molding resin composition as a light resistance test sample, and 4
A plate-shaped molded body having a size of 0 mm × 60 mm and a thickness of 2 mm was obtained.

【００７８】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、紫外線吸収剤として、２，２’−ジヒド
ロキシ−４、４´−ジメトキシベンゾフェノン１０．０
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１９０℃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℃、先端ダ
イスの温度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℃以上では白色とな
る。また、耐光性試験試料として前記成形用樹脂組成物
を用いて射出成形を行い、４０ｍｍ×６０ｍｍ、厚み２
ｍｍのプレート状の成形体を得た。Example 7 As a molding resin composition, 30.0 parts by weight of the microcapsule pigment of the reversible thermochromic composition 2 was added to a polyester elastomer resin (melt flow rate 20.0) 100
0.0 parts by weight, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 10.0 as an ultraviolet absorber
Parts by weight, blended in 0.5 part by weight of a metal soap lubricant, and uniformly dispersed with a tumbler mixer, using an extruder at a cylinder temperature of 190 ° C. and a tip die temperature of 190 ° C.
A reversible thermochromic polyester elastomer resin pellet was obtained. Using the resin composition for molding, injection molding was performed at a cylinder temperature of 190 ° C. and a tip die temperature of 200 ° C. using a hot curler type mold to obtain a reversible thermochromic molded body in a hot curler form. . In addition, the said molded object shows bluish green in a room temperature environment, and becomes white at 30 degreeC or more. In addition, injection molding was performed using the above-mentioned resin composition for molding as a light resistance test sample to obtain a sample having a thickness of 40 mm × 60 mm and a thickness of 2 mm.
mm plate-shaped molded body was obtained.

【００７９】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９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、紫外線吸収剤とし、２−（３，５
−ジ−ｔ−アミル−２−ヒドロキシフェニル）ベンゾト
リアゾール１０．０重量部、酸化防止剤として、２−
（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）
−２−ｎ−ブチルマロン酸ビス−（１，２，２，６，６
−ペンタメチル−４−ピペリジル）３．０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１７℃未満で
はオレンジ色を呈し、１７℃以上では無色となる。ま
た、耐光性試験試料として前記成形用樹脂組成物を用い
て射出成形を行い、４０ｍｍ×６０ｍｍ、厚み２ｍｍの
プレート状の成形体を得た。Example 8 As a molding resin composition, 30.0 parts by weight of the microcapsule pigment of the reversible thermochromic composition 9 was mixed with an ethylene-ethyl acrylate copolymer resin (melt flow rate 5.0).
1000.0 parts by weight as an ultraviolet absorber, 2- (3,5
-Di-t-amyl-2-hydroxyphenyl) benzotriazole 10.0 parts by weight, as an antioxidant, 2-
(3,5-di-t-butyl-4-hydroxybenzyl)
Bis-n-butylmalonate- (1,2,2,6,6
-Pentamethyl-4-piperidyl) in 3.0 parts by weight of a metal soap-based lubricant and 1.0 part by weight of a metal soap-based lubricant, uniformly dispersed by a tumbler mixer, and then, using an extruder, a cylinder temperature of 180 ° C. and a tip die temperature of 180. C., a reversible thermochromic 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 is orange when the temperature is lower than 17 ° C. and colorless when the temperature is 17 ° C. or higher. In addition, injection molding was performed using the molding resin composition as a light resistance test sample to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【００８０】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２０．０重量部、粉末蛍光ピンク顔
料５．０重量部をポリエステルポリオール５０．０重量
部、紫外線吸収剤とし、２−（５−ｔ−ブチル−２−ヒ
ドロキシフェニル）ベンゾトリアゾール１．０重量部、
イソシアネート系硬化剤２０．０重量部からなるビヒク
ル中に撹拌混合して、可逆熱変色性ポリウレタンエラス
トマー樹脂溶液を得た。前記ポリウレタンエラストマー
樹脂溶液をハート型の注型金型に流し込み、１２０℃で
５分間硬化させ、ハート形状の可逆熱変色性ポリウレタ
ンエラストマー樹脂成形体を得た。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。また、耐光性試験試料と
して前記成形用樹脂組成物をプレート状型枠に流し込ん
だ後、硬化させ、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプ
レート状の成形体を得た。Example 9 As the molding resin composition, 20.0 parts by weight of the microcapsule pigment and 5.0 parts by weight of the powdered fluorescent pink pigment of the reversible thermochromic composition 5 were mixed with 50.0 parts by weight of a polyester polyol and ultraviolet rays. As an absorbent, 1.0 part by weight of 2- (5-t-butyl-2-hydroxyphenyl) benzotriazole,
The mixture was stirred and mixed in a vehicle comprising 20.0 parts by weight of an isocyanate-based curing agent to obtain a reversible thermochromic polyurethane elastomer resin solution. The polyurethane elastomer resin solution was poured into a heart-shaped casting mold and cured at 120 ° C. for 5 minutes to obtain a heart-shaped reversible thermochromic polyurethane elastomer resin molded product. In addition, the resin composition for molding exhibits a fluorescent pink color at 33 ° C. or higher, and a temperature of 14 ° C.
Below, it exhibits purple. In the temperature range between them, pink and purple can be arbitrarily selected and held. Further, the resin composition for molding was poured into a plate-shaped mold as a light resistance test sample, and then cured to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【００８１】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重量部および粉末青色顔料
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、紫外線吸収剤として、２−
（３−ｔ−ブチル−５−オクチルオキシカルボニルエチ
ル−２−ヒドロキシフェニル）ベンゾトリアゾール１
０．０重量部、酸化防止剤として、トリエチレングリコ
ールービス〔３−（３−ｔ−ブチル−５−メチル−４−
ヒドロキシフェニル）プロピオネート〕３．０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。また、耐光性
試験試料として前記成形用樹脂組成物をプレート状型枠
に流し込んだ後、硬化させ、４０ｍｍ×６０ｍｍ、厚み
２ｍｍのプレート状の成形体を得た。Example 10 As a molding resin composition, 50.0 parts by weight of the microcapsule pigment and 0.3 parts by weight of the powder blue pigment of the reversible thermochromic composition 6 were mixed with 40 parts by weight of dioctyl phthalate and vinyl chloride. 60.0 parts by weight of resin, 2-
(3-t-butyl-5-octyloxycarbonylethyl-2-hydroxyphenyl) benzotriazole 1
0.0 parts by weight, as an antioxidant, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-
Hydroxyphenyl) propionate] 3.0 parts by weight,
It was uniformly dispersed in a vinyl chloride paste sol consisting of 5.0 parts by weight of a vinyl chloride stabilizer to obtain a reversible thermochromic vinyl chloride paste sol. 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. Further, the resin composition for molding was poured into a plate-shaped mold as a light resistance test sample, and then cured to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【００８２】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２０．０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℃以上では白色とな
る。また、耐光性試験試料として前記成形用樹脂組成物
をプレート状型枠に流し込んだ後、前記の条件で硬化さ
せ、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状の成
形体を得た。Example 11 As a molding resin composition, 20.0 parts by weight of the microcapsule pigment of the reversible thermochromic composition 1 were uniformly dispersed in 1000.0 parts by weight of an addition-reaction type silicone rubber. A discolorable curable silicone composition was obtained. After adding and dispersing 10.0 parts by weight of a curing agent to the molding resin composition, the mixture was poured into a star-shaped mold having a depth of 5 mm, and the mixture was heated at 150 ° C.
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 shows pink color under room temperature environment, and becomes white above 34 degreeC. Further, after casting the resin composition for molding as a light resistance test sample into a plate-shaped mold, it was cured under the above conditions to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【００８３】実施例１２ 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１と同様に作製した金魚形態の可逆的熱変色
性中空成形体表面上に、紫外線吸収剤として、２−
（３，５−ジ−ｔ−アミル−２−ヒドロキシフェニル）
ベンゾトリアゾール３．０重量部および酸化防止剤とし
て、ビス−（２，２，６，６−テトラメチル−４−ピペ
リジル）セバケート１．０重量部を、アクリルポリオー
ル樹脂（固形分４０％）／キシレン溶液５０．０重量
部、キシレン６０．０重量部、イソシアネート系硬化剤
１０．０重量部中に均一に撹拌混合してなる表面コート
剤をスプレー塗装して、光安定剤層を設けた。なお、前
記光安定剤層を設けた成形体は、１７℃未満に冷却する
とピンク色を呈し、１７℃以上では白色を呈する。ま
た、耐光性試験試料として、実施例１と同様に作製した
プレート状の成形体表面上に、前記表面コート剤をスプ
レー塗装して光安定剤層を設けた。Example 12 Using the microcapsule pigment of the reversible thermochromic composition 8, a goldfish-shaped reversible thermochromic hollow molded article produced in the same manner as in Example 1 was used as an ultraviolet absorber. 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
3.0 parts by weight of benzotriazole and 1.0 part by weight of bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate as an antioxidant were added to an acrylic polyol resin (solid content 40%) / xylene A light stabilizer layer was provided by spray coating a surface coating agent obtained by uniformly stirring and mixing 50.0 parts by weight of a solution, 60.0 parts by weight of xylene, and 10.0 parts by weight of an isocyanate-based curing agent. The molded product provided with the light stabilizer layer exhibits a pink color when cooled to a temperature lower than 17 ° C., and exhibits a white color when the temperature is 17 ° C. or higher. Further, as a light resistance test sample, the surface coating agent was spray-coated on the surface of the plate-shaped molded body produced in the same manner as in Example 1 to provide a light stabilizer layer.

【００８４】実施例１３ 可逆的熱変色性組成物２のマイクロカプセル顔料を用い
て、実施例２と同様に作製した人形形態の可逆的熱変色
性中空成形体表面上に、紫外線吸収剤として、２−ヒド
ロキシ−４−ｎ−オクチルオキシベンゾフェノン３．０
重量部、酸化防止剤として、ビス（１，２，２，６，６
−ペンタメチル−４−ピペリジル）セバケート１．０重
量部、金属光沢顔料（商品名：イリオジン２３５、メル
クジャパン社製）５．０重量部を、アクリル樹脂（固形
分５０％）／キシレン溶液５０．０重量部、キシレン３
０．０重量部、メチルイソブチルケトン３０．０重量
部、イソシアネート系硬化剤１０．０重量部中に均一に
撹拌混合してなる表面コート剤をスプレー塗装して、光
安定剤および金属光沢顔料を含有する共存層を設けた。
なお、前記共存層を設けた成形体は室温環境下では金属
光沢調の緑色を呈し、３０℃以上では蛍光黄色を呈す
る。また、耐光性試験試料として、実施例２と同様に作
製したプレート状の成形体表面上に、前記表面コート剤
をスプレー塗装して共存層を設けた。Example 13 Using the microcapsule pigment of the reversible thermochromic composition 2, a doll-shaped reversible thermochromic hollow molded body produced in the same manner as in Example 2 was used as an ultraviolet absorber. 2-hydroxy-4-n-octyloxybenzophenone 3.0
Parts by weight, bis (1,2,2,6,6
-Pentamethyl-4-piperidyl) sebacate (1.0 part by weight) and 5.0 parts by weight of a metallic luster pigment (trade name: Iliodin 235, manufactured by Merck Japan Ltd.) in an acrylic resin (solid content: 50%) / xylene solution (50.0) Parts by weight, xylene 3
0.0 parts by weight, 30.0 parts by weight of methyl isobutyl ketone, and 10.0 parts by weight of an isocyanate-based curing agent are spray-coated with a surface coating agent which is uniformly stirred and mixed to form a light stabilizer and a metallic gloss pigment. A contained coexisting layer was provided.
The molded article provided with the coexisting layer exhibits a metallic glossy green color in a room temperature environment and a fluorescent yellow color at 30 ° C. or higher. Further, as a light resistance test sample, a coexistence layer was provided by spray-coating the surface coating agent on the surface of a plate-like molded product produced in the same manner as in Example 2.

【００８５】実施例１４ 可逆的熱変色性組成物３のマイクロカプセル顔料を用い
て、実施例３と同様に作製した可逆的熱変色性フィラメ
ントを、紫外線吸収剤として２−（２−ヒドロキシ−５
−ｔ−オクチルフェニル）ベンゾトリアゾール１．０重
量部、酸化防止剤として、ビス（１，２，２，６，６−
ペンタメチル−４−ピペリジル）セバケート０．５重量
部、ウレタン樹脂（固形分５０％）／キシレン溶液２０
重量部、トルエン８０重量部、ポリイソシアネート系硬
化剤５．０重量部を均一撹拌混合して得られたコーティ
ング溶液中に浸漬させた後、取り出して乾燥させ、光安
定剤層を設けた。なお、前記光安定剤層を設けたフィラ
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。また、耐光性試験試料として、
実施例３と同様に作製したプレート状の成形体を、前記
コーティング溶液中に浸漬させた後、乾燥させて、光安
定剤層を設けた。Example 14 A reversible thermochromic filament produced in the same manner as in Example 3 using the microcapsule pigment of the reversible thermochromic composition 3 was used as an ultraviolet absorber to obtain 2- (2-hydroxy-5).
-T-octylphenyl) benzotriazole 1.0 part by weight, bis (1,2,2,6,6-
0.5 parts by weight of pentamethyl-4-piperidyl) sebacate, urethane resin (solid content 50%) / xylene solution 20
Parts by weight, 80 parts by weight of toluene, and 5.0 parts by weight of a polyisocyanate-based curing agent were immersed in a coating solution obtained by uniformly stirring and mixing, then taken out and dried to provide a light stabilizer layer. The filament provided with the light stabilizer layer exhibits a purple color in a room temperature environment and a fluorescent pink color at 34 ° C. or higher. In addition, as a light resistance test sample,
The plate-shaped molded body produced in the same manner as in Example 3 was immersed in the coating solution and then dried to provide a light stabilizer layer.

【００８６】実施例１５ 可逆的熱変色性組成物４のマイクロカプセル顔料を用い
て、実施例４と同様に作製した可逆的熱変色性フィラメ
ントを、紫外線吸収剤として２−（３−ｔ−ブチル−５
−オクチルオキシカルボニルエチル−２−ヒドロキシフ
ェニル）ベンゾトリアゾール１．０重量部、酸化防止剤
として、ビス（１，２，２，６，６−ペンタメチル−４
−ピペリジル）セバケート０．５重量部、ウレタン樹脂
（固形分５０％）／キシレン溶液２０重量部、トルエン
８０重量部、ポリイソシアネート系硬化剤５．０重量部
を均一撹拌混合して得られたコーティング溶液中に浸漬
させた後、取り出して乾燥させ、光安定剤層を設けた。
前記光安定剤層を設けたフィラメントを用いて人形の頭
に植毛を施した。なお、前記光安定剤層を設けたフィラ
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。また、耐光性試験試料とし
て、実施例４と同様に作製したプレート状の成形体を、
前記コーティング溶液中に浸漬させた後、乾燥させて、
光安定剤層を設けた。Example 15 A reversible thermochromic filament prepared in the same manner as in Example 4 using the microcapsule pigment of the reversible thermochromic composition 4 was used as an ultraviolet absorber to obtain 2- (3-t-butyl). -5
-Octyloxycarbonylethyl-2-hydroxyphenyl) benzotriazole (1.0 part by weight) and bis (1,2,2,6,6-pentamethyl-4) as an antioxidant
A coating obtained by uniformly stirring and mixing 0.5 parts by weight of (piperidyl) sebacate, 20 parts by weight of a urethane resin (50% solids) / xylene solution, 80 parts by weight of toluene, and 5.0 parts by weight of a polyisocyanate-based curing agent. After being immersed in the solution, it was taken out and dried to provide a light stabilizer layer.
Hair was planted on the head of the doll using the filament provided with the light stabilizer layer. The filament provided with the light stabilizer layer has an orange color at room temperature and has a blond color at 34 ° C. or higher. Further, as a light resistance test sample, a plate-like molded body produced in the same manner as in Example 4 was used.
After immersion in the coating solution, dried,
A light stabilizer layer was provided.

【００８７】実施例１６ 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５と同様に作製したイルカ形態の可逆的熱変
色性成形体表面上に、金属光沢顔料（商品名：イリオジ
ン２２５、メルクジャパン社製）５．０重量部、アクリ
ル樹脂（固形分５０％）／キシレン溶液４０．０重量
部、キシレン３０．０重量部、メチルイソブチルケトン
３０．０重量部、ポリイソシアネート系硬化剤１０．０
重量部を均一撹拌混合して得られた金属光沢調表面コー
ト剤をスプレー塗装して光遮蔽層を設けた。なお、前記
光遮蔽層を設けた成形体は１７℃以上では白色を呈し、
１７℃未満では淡い金属光沢調の青色を呈する。また、
耐光性試験試料として、実施例５と同様に作製したプレ
ート状の成形体の表面上に、前記表面コート剤をスプレ
ー塗装して光遮蔽層を設けた。Example 16 Using the microcapsule pigment of the reversible thermochromic composition 7, a metallic luster pigment (trade name) was placed on the surface of a dolphin-shaped reversible thermochromic molded article produced in the same manner as in Example 5. : Iriodin 225, manufactured by Merck Japan Ltd.) 5.0 parts by weight, acrylic resin (solid content 50%) / xylene solution 40.0 parts by weight, xylene 30.0 parts by weight, methyl isobutyl ketone 30.0 parts by weight, polyisocyanate System curing agent 10.0
A metal glossy surface coating agent obtained by uniformly stirring and mixing parts by weight was spray-coated to provide a light shielding layer. In addition, the molded body provided with the light shielding layer exhibits a white color at 17 ° C. or higher,
When the temperature is lower than 17 ° C., a pale metallic glossy blue color is exhibited. Also,
As a light resistance test sample, a light shielding layer was provided by spray-coating the surface coating agent on the surface of a plate-like molded body produced in the same manner as in Example 5.

【００８８】実施例１７ 可逆的熱変色性組成物３のマイクロカプセル顔料を用い
て、実施例６と同様に作製した小型自動車形態の可逆的
熱変色性成形体表面上に、紫外線吸収剤として２−
（３，５−ジ−ｔ−アミル−２−ヒドロキシフェニル）
ベンゾトリアゾール３．０重量部、酸化防止剤として、
２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジ
ル）−２−ｎ−ブチルマロン酸ビス−（１，２，２，
６，６−ペンタメチル−４−ピペリジル）１．０重量
部、アクリルポリオール樹脂（固形分４０％）／キシレ
ン溶液５０．０重量部、キシレン６０．０重量部、ポリ
イソシアネート系硬化剤１０．０重量部を均一撹拌混合
して得られた表面コート剤をスプレー塗装して、光安定
剤層を設けた。なお、前記光安定剤層を設けた成形体は
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。また、耐光性試験試料として、実施例
６と同様に作製したプレート状の成形体表面上に、前記
表面コート剤をスプレー塗装して光安定剤層を設けた。Example 17 Using the microcapsule pigment of the reversible thermochromic composition 3 on the surface of a compact automobile-shaped reversible thermochromic molded article produced in the same manner as in Example 6, 2 as an ultraviolet absorber −
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole 3.0 parts by weight, as an antioxidant,
Bis- (1,2,2,2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate
6,6-pentamethyl-4-piperidyl) 1.0 part by weight, acrylic polyol resin (solid content 40%) / xylene solution 50.0 parts by weight, xylene 60.0 parts by weight, polyisocyanate-based curing agent 10.0 parts by weight The surface coating agent obtained by uniformly stirring and mixing the parts was spray-coated to form a light stabilizer layer. The molded article provided with the light stabilizer layer exhibits a pastel blue color in a room temperature environment and a white color at 34 ° C. or higher. Further, as a light resistance test sample, a light stabilizer layer was provided by spray-coating the surface coating agent on the surface of a plate-like molded product produced in the same manner as in Example 6.

【００８９】実施例１８ 可逆的熱変色性組成物２のマイクロカプセル顔料を用い
て、実施例７と同様に作製したホットカーラー形態の可
逆的熱変色性成形体表面上に、紫外線吸収剤として２，
２′−ジヒドロキシ−４、４′−ジメトキシベンゾフェ
ノン３．０重量部、アクリル樹脂（固形分５０％）／キ
シレン溶液４０．０重量部、キシレン３０．０重量部、
メチルイソブチルケトン３０．０重量部、ポリイソシア
ネート系硬化剤１０，０重量部を均一撹拌混合してなる
表面コート剤をスプレー塗装して光安定剤層を設けた。
なお、前記光安定剤層を設けた成形体は室温環境下では
青緑色を呈し、３０℃以上では白色となる。また、耐光
性試験試料として、実施例７と同様に作製したプレート
状の成形体表面上に、前記表面コート剤をスプレー塗装
して光安定剤層を設けた。Example 18 Using the microcapsule pigment of the reversible thermochromic composition 2, a hot curler-shaped reversible thermochromic molded article produced in the same manner as in Example 7 was coated with 2 ,
2′-dihydroxy-4,4′-dimethoxybenzophenone 3.0 parts by weight, acrylic resin (solid content 50%) / xylene solution 40.0 parts by weight, xylene 30.0 parts by weight,
A light stabilizer layer was formed by spray coating a surface coating agent obtained by uniformly stirring and mixing 30.0 parts by weight of methyl isobutyl ketone and 10.0 parts by weight of a polyisocyanate-based curing agent.
The molded product provided with the light stabilizer layer exhibits a bluish green color in a room temperature environment and becomes white at 30 ° C. or more. Further, as a light resistance test sample, a light stabilizer layer was provided on the surface of a plate-like molded body produced in the same manner as in Example 7 by spray-coating the surface coating agent.

【００９０】実施例１９ 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８と同様に作製した可逆的熱変色性エチレン
−エチルアクリレート樹脂フイルムシート表面上に、紫
外線吸収剤として２−（３，５−ジ−ｔ−アミル−２−
ヒドロキシフェニル）ベンゾトリアゾール３．０重量
部、酸化防止剤としてビス（２，２，６，６−テトラメ
チルピペリジル）セバケート１．０重量部、塩化ビニル
−酢酸ビニル共重合樹脂２５．０重量部、消泡剤０．５
重量部、キシレン３６．０重量部、シクロヘキサノン３
６．０重量部を均一撹拌混合して得られた表面コーティ
ング剤をドクターコーターにて塗工して、光安定剤層を
設けた。なお、前記光安定剤層を設けたフイルムシート
は１７℃未満ではオレンジ色を呈し、１７℃以上では無
色となる。また、耐光性試験試料として、実施例８と同
様に作製したプレート状の成形体表面上に、前記表面コ
ーティング剤をドクターコーターにて塗工し、光安定剤
層を設けた。Example 19 Using the microcapsule pigment of the reversible thermochromic composition 9, the surface of a reversible thermochromic ethylene-ethyl acrylate resin film sheet produced in the same manner as in Example 8 was used as an ultraviolet absorber. 2- (3,5-di-t-amyl-2-
(Hydroxyphenyl) benzotriazole 3.0 parts by weight, bis (2,2,6,6-tetramethylpiperidyl) sebacate as an antioxidant 1.0 part by weight, vinyl chloride-vinyl acetate copolymer resin 25.0 parts by weight, Antifoam 0.5
Parts by weight, 36.0 parts by weight of xylene, cyclohexanone 3
A surface coating agent obtained by uniformly stirring and mixing 6.0 parts by weight was applied by a doctor coater to provide a light stabilizer layer. The film sheet provided with the light stabilizer layer has an orange color below 17 ° C. and becomes colorless at 17 ° C. or higher. Further, as a light resistance test sample, the surface coating agent was applied by a doctor coater on the surface of a plate-like molded body produced in the same manner as in Example 8, and a light stabilizer layer was provided.

【００９１】実施例２０ 可逆的熱変色性組成物５のマイクロカプセル顔料を用い
て、実施例９と同様に作製したハート形状の可逆的熱変
色性ウレタンエラストマー樹脂成形体を、紫外線吸収剤
として２−（５−ｔ−ブチル−２−ヒドロキシフェニ
ル）ベンゾトリアゾール３．０重量部、金属光沢顔料
（商品名：イリオジン２２３、メルクジャパン社製）
５．０重量部、ポリエステルポリオール５０．０重量
部、酢酸エチル２５．０重量部、キシレン２５．０重量
部、イソシアネート系硬化剤１０．０重量部を均一撹拌
混合した金属光沢調表面コーティング溶液中に浸漬させ
た後、取り出して硬化させ、光安定剤および金属光沢調
顔料を含有する共存層を設けた。なお、前記共存層を設
けた成形体は、３３℃以上では蛍光ピンク色を呈し、１
４℃以下では金属光沢調の紫色を呈する。その間の温度
域では任意にピンク色と金属光沢調の紫色を選択保持で
きる。また、耐光性試験試料として、実施例９と同様に
作製したプレート状の成形体を、前記表面コーティング
溶液中に浸漬させた後、取り出して硬化させて共存層を
設けた。Example 20 Using a microcapsule pigment of the reversible thermochromic composition 5, a heart-shaped reversible thermochromic urethane elastomer resin molded article produced in the same manner as in Example 9 was used as an ultraviolet absorber. -(5-t-butyl-2-hydroxyphenyl) benzotriazole 3.0 parts by weight, metallic luster pigment (trade name: Iliodin 223, manufactured by Merck Japan Ltd.)
5.0 parts by weight of a polyester polyol, 50.0 parts by weight of a polyester polyol, 25.0 parts by weight of ethyl acetate, 25.0 parts by weight of xylene, and 10.0 parts by weight of an isocyanate-based curing agent are uniformly stirred and mixed in a metallic glossy surface coating solution. After being immersed in the substrate, the substrate was taken out and cured to provide a coexisting layer containing a light stabilizer and a metallic gloss pigment. The molded article provided with the coexistence layer exhibited a fluorescent pink color at 33 ° C. or higher,
At a temperature of 4 ° C. or lower, a metallic glossy purple color is exhibited. In the temperature range between them, pink and metallic glossy purple can be arbitrarily selected and held. Further, as a light resistance test sample, a plate-shaped molded body produced in the same manner as in Example 9 was immersed in the surface coating solution, taken out and cured to form a coexistence layer.

【００９２】実施例２１ 可逆的熱変色性組成物６のマイクロカプセル顔料を用い
て、実施例１０と同様に作製した馬形態の可逆的熱変色
性スラッシュ成形体表面上に、紫外線吸収剤として２−
（３，５−ジ−ｔ−アミル−２−ヒドロキシフェニル）
ベンゾトリアゾール３．０重量部、酸化防止剤として４
−ベンゾイルオキシ−２，２，６，６−テトラメチルピ
ペリジン１．０重量部、金属光沢顔料（商品名：イリオ
ジン２１９、メルクジャパン社製）５．０重量部、塩化
ビニル−酢酸ビニル共重合樹脂１０．０重量部、アクリ
ル樹脂（固形分５０％）／キシレン溶液４０．０重量
部、光安定剤３．０重量部、キシレン３０．０重量部、
メチルイソブチルケトン３０．０重量部を均一撹拌混合
して得られた金属光沢調表面コート剤をスプレー塗装し
て、光安定剤および金属光沢顔料を含有する共存層を設
けた。なお、前記共存層を設けた成形体は３３℃以上で
は淡い金属光沢調の青色を呈し、１４℃以下では金属光
沢調の紫色を呈する。その間の温度域では任意に淡い金
属光沢調の青色と金属光沢調の紫色を選択保持できる。
また、耐光性試験試料として、実施例１０と同様に作製
したプレート状の成形体表面上に、前記表面コート剤を
スプレー塗装して共存層を設けた。Example 21 Using the microcapsule pigment of the reversible thermochromic composition 6, a horse-shaped reversible thermochromic slush molded product prepared in the same manner as in Example 10 was coated with 2 −
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole 3.0 parts by weight, 4 as antioxidant
1.0 parts by weight of -benzoyloxy-2,2,6,6-tetramethylpiperidine, 5.0 parts by weight of a metallic luster pigment (trade name: Iliodin 219, manufactured by Merck Japan Ltd.), vinyl chloride-vinyl acetate copolymer resin 10.0 parts by weight, 40.0 parts by weight of an acrylic resin (50% solids) / xylene solution, 3.0 parts by weight of a light stabilizer, 30.0 parts by weight of xylene,
A metallic glossy surface coating agent obtained by uniformly stirring and mixing 30.0 parts by weight of methyl isobutyl ketone was spray-coated to form a coexisting layer containing a light stabilizer and a metallic glossy pigment. The molded body provided with the coexisting layer exhibits a pale metallic glossy blue color at 33 ° C. or higher and a metallic glossy purple color at 14 ° C. or less. In the temperature range between them, it is possible to arbitrarily select and maintain pale metallic glossy blue and metallic glossy purple.
Further, as a light resistance test sample, a coexistence layer was provided by spray-coating the surface coating agent on the surface of a plate-shaped molded body produced in the same manner as in Example 10.

【００９３】実施例２２ 可逆的熱変色性組成物１のマイクロカプセル顔料を用い
て、実施例１１と同様に作製した星形状の可逆的熱変色
性シリコーン成形体を、紫外線吸収剤として２−（５−
ｔ−ブチル−２−ヒドロキシフェニル）ベンゾトリアゾ
ール２．０重量部、付加反応型シリコーン溶液１００
０．０重量部、シリコーン硬化剤１０重量部を均一撹拌
混合して得られた表面コーティング溶液中に浸漬させた
後、取り出して硬化させ、光安定剤層を設けた。なお、
前記光安定剤層を設けた成形体は室温環境下ではピンク
色を呈し、３４℃以上では白色となる。また、耐光性試
験試料として、実施例１１と同様に作製したプレート状
の成形体を前記表面コーティング溶液中に浸漬し、硬化
させて光安定剤層を設けた。Example 22 Using the microcapsule pigment of the reversible thermochromic composition 1, a star-shaped reversible thermochromic silicone molded article produced in the same manner as in Example 11 was used as an ultraviolet absorber with 2- ( 5-
t-butyl-2-hydroxyphenyl) benzotriazole 2.0 parts by weight, addition reaction type silicone solution 100
0.0 parts by weight and 10 parts by weight of a silicone curing agent were immersed in a surface coating solution obtained by uniform stirring and mixing, then taken out and cured to provide a light stabilizer layer. In addition,
The molded article provided with the light stabilizer layer exhibits a pink color in a room temperature environment, and becomes white at 34 ° C. or more. Further, as a light resistance test sample, a plate-like molded body produced in the same manner as in Example 11 was immersed in the surface coating solution and cured to provide a light stabilizer layer.

【００９４】実施例２３ 実施例１３と同様に作製した、人形形態の可逆的熱変色
性中空成形体共存層上に、紫外線吸収剤として、２−
（３，５−ジ−ｔ−アミル−２−ヒドロキシフェニル）
ベンゾトリアゾール３．０重量部、酸化防止剤としてビ
ス（２，２，６，６−テトラメチル−４−ピペリジル）
セバケート１．０重量部、アクリルポリオール樹脂（固
形分４０％）／キシレン溶液５０．０重量部、キシレン
６０．０重量部、ポリイソシアネート系硬化剤１０．０
重量部を均一撹拌混合してなる表面コート剤をスプレー
塗装して、光安定剤層を設けた。なお、前記光安定剤層
を設けた成形体は、室温環境下では金属光沢調の緑色を
呈し、３０℃以上では蛍光黄色を呈する。また、耐光性
試験試料として、実施例１３と同様に作製したプレート
状の成形体の共存層上に、前記表面コート剤をスプレー
塗装して光安定剤層を設けた。Example 23 A doll-shaped reversible thermochromic hollow molded article coexisting layer produced in the same manner as in Example 13 was coated with 2-absorbent as an ultraviolet absorber.
(3,5-di-t-amyl-2-hydroxyphenyl)
3.0 parts by weight of benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidyl) as an antioxidant
1.0 part by weight of sebacate, 50.0 parts by weight of an acrylic polyol resin (solid content 40%) / xylene solution, 60.0 parts by weight of xylene, polyisocyanate-based curing agent 10.0
A surface coating agent formed by uniformly stirring and mixing parts by weight was spray-coated to provide a light stabilizer layer. The molded product provided with the light stabilizer layer exhibits a metallic glossy green color in a room temperature environment and a fluorescent yellow color at 30 ° C. or higher. Further, as a light resistance test sample, a light stabilizer layer was provided by spray-coating the surface coating agent on a coexisting layer of a plate-shaped molded body produced in the same manner as in Example 13.

【００９５】実施例２４ 実施例２０と同様に作製した、共存層を設けたハート形
状の可逆熱変色性ウレタンエラストマー樹脂成形体を、
紫外線吸収剤として２−（５−ｔ−ブチル−２−ヒドロ
キシフェニル）ベンゾトリアゾール３．０重量部、ポリ
エステルポリオール５０．０重量部、酢酸エチル２５．
０重量部、キシレン２５．０重量部、ポリイソシアネー
ト系硬化剤１０．０重量部を均一撹拌混合した表面コー
ティング溶液中に浸漬した後、取り出して硬化させ、光
安定剤層を設けた。なお、前記光安定剤層を設けた成形
体は３３℃以上では蛍光ピンク色を呈し、１４℃以下で
は金属光沢調の紫色を呈する。その間の温度域では任意
にピンク色と金属光沢調の紫色を選択保持できる。ま
た、耐光性試験試料として、実施例２０と同様に作製し
た共存層を設けたプレート状の成形体を、前記表面コー
ティング溶液中に浸漬した後、取り出して硬化させ、光
安定剤層を設けた。Example 24 A heart-shaped reversible thermochromic urethane elastomer resin molded article provided with a coexisting layer and produced in the same manner as in Example 20,
3.0 parts by weight of 2- (5-t-butyl-2-hydroxyphenyl) benzotriazole, 50.0 parts by weight of polyester polyol, 25.25 parts by weight of ethyl acetate as an ultraviolet absorber.
0 parts by weight, 25.0 parts by weight of xylene, and 10.0 parts by weight of a polyisocyanate-based curing agent were immersed in a surface coating solution obtained by uniformly stirring and mixing, then taken out and cured to provide a light stabilizer layer. The molded product provided with the light stabilizer layer exhibits a fluorescent pink color at 33 ° C. or higher, and exhibits a metallic glossy purple color at 14 ° C. or lower. In the temperature range between them, pink and metallic glossy purple can be arbitrarily selected and held. Further, as a light resistance test sample, a plate-shaped molded body provided with a coexistence layer prepared in the same manner as in Example 20 was immersed in the surface coating solution, taken out and cured to provide a light stabilizer layer. .

【００９６】実施例２５ 実施例２１と同様に作製した馬形態の可逆的熱変色性ス
ラッシュ成形体の共存層上に、紫外線吸収剤として２−
（３，５−ジ−ｔ−アミル−２−ヒドロキシフェニル）
ベンゾトリアゾール３．０重量部、酸化防止剤として４
−ベンゾイルオキシ−２，２，６，６−テトラメチルピ
ペリジン１．０重量部、塩化ビニル−酢酸ビニル共重合
樹脂１０．０重量部、アクリル樹脂（固形分５０％）／
キシレン溶液４０．０重量部、キシレン３０．０重量
部、メチルイソブチルケトン３０．０重量部を均一撹拌
混合して得られた表面コート剤をスプレー塗装し、光安
定剤層を設けた。なお、前記光安定剤層を設けた成形体
は３３℃以上では淡い金属光沢調の青色を呈し、１４℃
以下では金属光沢調の紫色を呈する。その間の温度域で
は任意に淡い金属光沢調の青色と金属光沢調の紫色を選
択保持できる。また、耐光性試験試料として、実施例２
１と同様に作製したプレート状の成形体の共存層上に、
前記表面コート剤をスプレー塗装して、光安定剤層を設
けた。Example 25 On the coexisting layer of a horse-shaped reversible thermochromic slush molded article produced in the same manner as in Example 21, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole 3.0 parts by weight, 4 as antioxidant
-Benzoyloxy-2,2,6,6-tetramethylpiperidine 1.0 part by weight, vinyl chloride-vinyl acetate copolymer resin 10.0 parts by weight, acrylic resin (solid content 50%) /
A surface coating agent obtained by uniformly stirring and mixing 40.0 parts by weight of a xylene solution, 30.0 parts by weight of xylene, and 30.0 parts by weight of methyl isobutyl ketone was spray-coated to provide a light stabilizer layer. The molded product provided with the light stabilizer layer exhibits a pale metallic glossy blue color at 33 ° C. or higher,
Below, it exhibits a metallic glossy purple color. In the temperature range between them, it is possible to arbitrarily select and maintain pale metallic glossy blue and metallic glossy purple. Further, as a light fastness test sample, Example 2 was used.
On the coexistence layer of the plate-shaped molded body produced in the same manner as in 1,
The light-stabilizing layer was provided by spray-coating the surface coating agent.

【００９７】比較例１ ｄ．成分を含まない可逆的熱変色性組成物１７のマイク
ロカプセル顔料を用いて、実施例１と同様にして可逆的
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。
前記中空成形体は、実施例１で得た可逆熱変色性中空成
形体と同様の色変化を呈する。また、耐光性試験試料と
して前記ペレットを用いて、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。Comparative Example 1 d. A reversible thermochromic polyethylene resin pellet was obtained in the same manner as in Example 1 using the microcapsule pigment of the reversible thermochromic composition 17 containing no component. Furthermore, a goldfish-shaped hollow molded body was obtained using the resin pellet.
The hollow molded article exhibits the same color change as the reversible thermochromic hollow molded article obtained in Example 1. In addition, injection molding was performed using the above-mentioned pellets as a light resistance test sample, and 40 mm
A plate-shaped molded body having a size of × 60 mm and a thickness of 2 mm was obtained.

【００９８】比較例２ 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２と同様にして可逆的熱
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。前記中空成形体は、実施例２で得た可逆
熱変色性中空成形体と同様の色変化を呈する。また、耐
光性試験試料として前記ペレットを用いて、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。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 11 containing no component. Furthermore, a doll-shaped hollow molded body was obtained using the resin pellets. The hollow molded article exhibits the same color change as the reversible thermochromic hollow molded article obtained in Example 2. In addition, injection molding was performed using the above pellets as a light resistance test sample to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【００９９】比較例３ 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３と同様にして可逆的
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。前記フィラメントは、実施例３で得た可逆熱変
色性フィラメントと同様の色変化を呈する。また、耐光
性試験試料として前記ペレットを用いて射出成形を行
い、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状の成
形体を得た。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 12 containing no component. further,
The reversible thermochromic filament formed using the resin pellet was implanted in a horse-shaped toy to form a vertical hair and a tail. The filament exhibits the same color change as the reversible thermochromic filament obtained in Example 3. In addition, injection molding was performed using the pellets as a light resistance test sample to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【０１００】比較例４ ｄ．成分を含まない可逆的熱変色性組成物１３のマイク
ロカプセル顔料を用いて、実施例４と同様にして可逆的
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。前記フィラメントは、実施例
４で得た可逆熱変色性フィラメントと同様の色変化を呈
する。また、耐光性試験試料として前記ペレットを用い
て射出成形を行い、４０ｍｍ×６０ｍｍ、厚み２ｍｍの
プレート状の成形体を得た。Comparative Example 4 d. Using a microcapsule pigment of the reversible thermochromic composition 13 containing no component, a reversible thermochromic 12 nylon resin pellet was obtained in the same manner as in Example 4. The reversible thermochromic filaments formed using the resin pellets were planted on the head of a doll. The filament exhibits the same color change as the reversible thermochromic filament obtained in Example 4. In addition, injection molding was performed using the pellets as a light resistance test sample to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【０１０１】比較例５ ｄ．成分を含まない可逆的熱変色性組成物１６のマイク
ロカプセル顔料を用いて、実施例５と同様にして可逆的
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。前記成形体は、実施例５で得た可逆熱変色
性成形体と同様の色変化を呈する。また、耐光性試験試
料として前記ペレットを用いて射出成形を行い、４０ｍ
ｍ×６０ｍｍ、厚み２ｍｍのプレート状の成形体を得
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 16 containing no component. Further, a dolphin-shaped molded body was obtained using the resin pellet. The molded product exhibits the same color change as the reversible thermochromic molded product obtained in Example 5. In addition, injection molding was carried out using the above-mentioned pellets as a light resistance test sample.
A plate-shaped molded body having a size of mx 60 mm and a thickness of 2 mm was obtained.

【０１０２】比較例６ 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６と同様にして可逆的
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。前記
成形体は、実施例６で得た可逆熱変色性成形体と同様の
色変化を呈する。また、耐光性試験試料として前記ペレ
ットを用いて射出成形を行い、４０ｍｍ×６０ｍｍ、厚
み２ｍｍのプレート状の成形体を得た。Comparative Example 6 d. A reversible thermochromic ABS resin pellet was obtained in the same manner as in Example 6 using the microcapsule pigment of the reversible thermochromic composition 12 containing no component. Further, a compact in the form of a small automobile was obtained using the resin pellet. The molded product exhibits the same color change as the reversible thermochromic molded product obtained in Example 6. In addition, injection molding was performed using the pellets as a light resistance test sample to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【０１０３】比較例７ 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７と同様にして可逆的
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。前記成形体は、実施例７で得た可
逆熱変色性成形体と同様の色変化を呈する。また、耐光
性試験試料として前記ペレットを用いて射出成形を行
い、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状の成
形体を得た。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 11 containing no component. Furthermore, a molded product in a hot curler form was obtained using the resin pellet. The molded product exhibits the same color change as the reversible thermochromic molded product obtained in Example 7. In addition, injection molding was performed using the pellets as a light resistance test sample to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【０１０４】比較例８ ｄ．成分を含まない可逆的熱変色性組成物１８のマイク
ロカプセル顔料を用いて、実施例８と同様にして可逆的
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インフ
レーション成形を行いフイルムシートを得た。前記シー
トは、実施例８で得たシートと同様の色変化を呈する。
また、耐光性試験試料として前記ペレットを用いて射出
成形を行い、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレー
ト状の成形体を得た。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 18 containing no component. Further, inflation molding was performed using the resin pellets to obtain a film sheet. The sheet exhibits the same color change as the sheet obtained in Example 8.
In addition, injection molding was performed using the pellets as a light resistance test sample to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【０１０５】比較例９ ｄ．成分を含まない可逆的熱変色性組成物１４のマイク
ロカプセル顔料を用いて、実施例９と同様にして可逆的
熱変色性ウレタンエラストマー樹脂溶液を得た。前記ウ
レタンエラストマー樹脂溶液をハート型の注型金型に流
し込み、１２０℃で５分間硬化させて、ハート型状のポ
リウレタンエラストマー樹脂成形体を得た。前記成形体
は、実施例９で得た可逆熱変色性成形体と同様の色変化
を呈する。また、耐光性試験試料として前記可逆熱変色
性ポリウレタンエラストマー樹脂溶液を型枠に流し込ん
で硬化させ、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレー
ト状の成形体を得た。Comparative Example 9 d. Using a microcapsule pigment of the reversible thermochromic composition 14 containing no component, a reversible thermochromic urethane elastomer resin solution was obtained in the same manner as in Example 9. The urethane elastomer resin solution was poured into a heart-shaped casting mold and cured at 120 ° C. for 5 minutes to obtain a heart-shaped polyurethane elastomer resin molded product. The molded product exhibits the same color change as the reversible thermochromic molded product obtained in Example 9. Further, as a light resistance test sample, the reversible thermochromic polyurethane elastomer resin solution was poured into a mold and cured to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【０１０６】比較例１０ ｄ．成分を含まない可逆的熱変色性組成物１５のマイク
ロカプセル顔料を用いて、実施例１０と同様にして可逆
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スラッシュ成形を行
い、馬形態のスラッシュ成形体を得た。前記成形体は、
実施例１０で得た成形体と同様の色変化を呈する。ま
た、耐光性試験試料として、前記可逆熱変色性塩化ビニ
ルペーストゾル樹脂溶液を型枠に流し込んで硬化させ、
４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状の成形体
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 15 containing no component. Further, slush molding was performed using the vinyl chloride paste sol to obtain a horse-shaped slush molded body. The molded body,
It exhibits the same color change as the molded article obtained in Example 10. Further, as a light resistance test sample, the reversible thermochromic vinyl chloride paste sol resin solution was poured into a mold and cured,
A 40 mm × 60 mm, 2 mm thick plate-like molded body was obtained.

【０１０７】比較例１１ 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１１と同様にして可逆
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型枠に注入し１５
０℃で３分間硬化させて星形状のシリコーン成形体を得
た。前記成形体は、実施例１１で得た成形体と同様の色
変化を呈する。また、耐光性試験試料として、前記可逆
熱変色性硬化性シリコーン組成物を型枠に流し込んで硬
化させ、４０ｍｍ×６０ｍｍ、厚み２ｍｍのプレート状
の成形体を得た。Comparative Example 11 d. A reversible thermochromic curable silicone composition was obtained in the same manner as in Example 11, using the microcapsule pigment of the reversible thermochromic composition 10 containing no component. Further, the silicone composition was injected into a star-shaped mold,
The mixture was cured at 0 ° C. for 3 minutes to obtain a star-shaped silicone molded body. The molded product exhibits the same color change as the molded product obtained in Example 11. In addition, as a light resistance test sample, the reversible thermochromic curable silicone composition was poured into a mold and cured to obtain a plate-shaped molded body having a size of 40 mm × 60 mm and a thickness of 2 mm.

【０１０８】比較例１２ ｄ．成分を含まない可逆的熱変色性組成物１７のマイク
ロカプセル顔料を用いて実施例１と同様の方法で作製し
た金魚形態の可逆的熱変色性中空成形体表面上に、実施
例１２と同じ表面コート剤をスプレー塗装して、光安定
層を設けた。前記光安定剤層を設けた中空成形体は、実
施例１２で得た中空成形体と同様の色変化を呈する。ま
た、耐光性試験試料として、実施例１２と同様に作製し
たプレート状の成形体の表面上に、前記表面コート剤を
スプレー塗装して光安定剤層を設けた。Comparative Example 12 d. A goldfish-shaped reversible thermochromic hollow molded body produced in the same manner as in Example 1 using the microcapsule pigment of the reversible thermochromic composition 17 containing no component has the same surface as in Example 12. A light stabilizer layer was provided by spray coating with a coating agent. The hollow molded article provided with the light stabilizer layer exhibits the same color change as the hollow molded article obtained in Example 12. Further, as a light resistance test sample, a light stabilizer layer was provided by spray-coating the surface coating agent on the surface of a plate-like molded body produced in the same manner as in Example 12.

【０１０９】比較例１３ 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２と同様の方法で作製
した人形形態の可逆的熱変色性中空成形体表面上に、実
施例１３と同様の表面コート剤をスプレー塗装して、共
存層を設けた。前記共存層を設けた中空成形体は、実施
例１３で得た中空成形体と同様の色変化を呈する。ま
た、耐光性試験試料として、実施例１３と同様に作製し
たプレート状の成形体表面上に、前記表面コート剤をス
プレー塗装して共存層を設けた。Comparative Example 13 d. Using the microcapsule pigment of the reversible thermochromic composition 11 containing no component, on the surface of a doll-shaped reversible thermochromic hollow molded body produced in the same manner as in Example 2, as in Example 13. Was applied by spray coating to form a coexisting layer. The hollow molded body provided with the coexistence layer exhibits the same color change as the hollow molded body obtained in Example 13. Further, as a light resistance test sample, a coexistence layer was provided by spray-coating the surface coating agent on the surface of a plate-like molded body produced in the same manner as in Example 13.

【０１１０】比較例１４ 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作製した可逆的熱変色性ポリプ
ロピレン樹脂ペレットを溶融紡糸した可逆的熱変色性フ
ィラメントを、実施例１４と同様にして得たコーティン
グ溶液中に浸漬させて光安定剤層を設けた。前記光安定
剤層を設けたフィラメントは、実施例１４で得たフィラ
メントと同様の色変化を呈する。また、耐光性試験試料
として、前記可逆的熱変色性ポリプロピレン樹脂ペレッ
トを用いて成形したプレート状の成形体を、前記コーテ
ィング溶液中に浸漬させて光安定剤層を設けた。Comparative Example 14 d. A reversible thermochromic filament obtained by melt-spinning a reversible thermochromic polypropylene resin pellet prepared using the microcapsule pigment of the reversible thermochromic composition 12 containing no component was obtained in the same manner as in Example 14. The light stabilizer layer was provided by dipping in the coating solution. The filament provided with the light stabilizer layer exhibits the same color change as the filament obtained in Example 14. Further, as a light resistance test sample, a plate-shaped molded product molded using the reversible thermochromic polypropylene resin pellets was immersed in the coating solution to provide a light stabilizer layer.

【０１１１】比較例１５ ｄ．成分を含まない可逆的熱変色性組成物１３のマイク
ロカプセル顔料を用いて作製した可逆的熱変色性１２ナ
イロン樹脂ペレットを溶融紡糸した可逆的熱変色性フィ
ラメントを、実施例１５で得たコーティング溶液中に浸
漬させて光安定剤層を設けた。前記光安定剤層を設けた
フィラメントは、実施例１５で得たフィラメントと同様
の色変化を呈する。また、耐光性試験試料として、前記
可逆的熱変色性１２ナイロン樹脂ペレットを用いて成形
したプレート状の成形体を、前記コーディング溶液中に
浸漬させて光安定剤層を設けた。Comparative Example 15 d. A reversible thermochromic filament obtained by melt-spinning a reversible thermochromic 12 nylon resin pellet prepared using the microcapsule pigment of the reversible thermochromic composition 13 containing no component was coated with the coating solution obtained in Example 15. The light stabilizer layer was provided by being immersed therein. The filament provided with the light stabilizer layer exhibits the same color change as the filament obtained in Example 15. Further, as a light resistance test sample, a plate-like molded body molded using the reversible thermochromic 12 nylon resin pellet was immersed in the coding solution to provide a light stabilizer layer.

【０１１２】比較例１６ ｄ．成分を含まない可逆的熱変色性組成物１６のマイク
ロカプセル顔料を用いて作製した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使用して成形した
イルカ形態の可逆的熱変色性成形体表面上に、実施例１
６で得た金属光沢調表面コート剤をスプレー塗装して光
遮蔽層を設けた。前記光遮蔽層を設けた可逆的熱変色性
成形体は、実施例１６で得た成形体と同様の色変化を呈
する。また、耐光性試験試料として前記可逆的熱変色性
スチレン−ブタジエン共重合樹脂ペレットを用いて成形
したプレート状の成形体に、前記金属光沢調表面コート
剤をスプレー塗装して光遮蔽層を設けた。Comparative Example 16 d. Surface of a dolphin-shaped reversible thermochromic molded article molded using reversible thermochromic styrene-butadiene copolymer resin pellets prepared using the microcapsule pigment of the reversible thermochromic composition 16 containing no component Above, Example 1
The light shielding layer was provided by spray-coating the metallic glossy surface coating agent obtained in 6 above. The reversible thermochromic molded article provided with the light shielding layer exhibits the same color change as the molded article obtained in Example 16. Further, a light shielding layer was formed by spray coating the metal glossy surface coating agent on a plate-like molded body molded using the reversible thermochromic styrene-butadiene copolymer resin pellets as a light resistance test sample. .

【０１１３】比較例１７ 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作製した可逆的熱変色性ＡＢＳ
樹脂ペレットを使用して作製した小型自動車形態の可逆
的熱変色性成形体表面上に、実施例１７で得た表面コー
ト剤をスプレー塗装して光安定剤層を設けた。前記光安
定剤層を設けた小型自動車形態の可逆的熱変色性成形体
は、実施例１７で得た成形体と同様の色変化を呈する。
また、耐光性試験試料として前記可逆的熱変色性ＡＢＳ
樹脂ペレットを用いて成形したプレート状の成形体に、
前記表面コート剤をスプレー塗装して光安定剤層を設け
た。Comparative Example 17 d. Thermochromic ABS prepared using microcapsule pigment of reversible thermochromic composition 12 containing no component
A light stabilizer layer was provided by spray-coating the surface coating agent obtained in Example 17 on the surface of a reversible thermochromic molded article in the form of a small automobile produced using resin pellets. The reversible thermochromic molded article in the form of a small automobile provided with the light stabilizer layer exhibits the same color change as the molded article obtained in Example 17.
The reversible thermochromic ABS was used as a light resistance test sample.
In a plate-shaped molded body molded using resin pellets,
The light stabilizer layer was provided by spray-coating the surface coating agent.

【０１１４】比較例１８ 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作製した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使用して成形したホ
ットカーラー形態の可逆的熱変色性成形体表面上に、実
施例１８で得た表面コート剤をスプレー塗装して光安定
剤層を設けた。前記光安定剤層を設けたホットカーラー
形態の可逆的熱変色性成形体は、実施例１８で得た成形
体と同様の色変化を呈する。また、耐光性試験試料とし
て前記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したプレート状の成形体に、前記表
面コート剤をスプレー塗装して光安定剤層を設けた。Comparative Example 18 d. On the surface of a hot curler type reversible thermochromic molded article molded using a reversible thermochromic polyester elastomer resin pellet prepared using the microcapsule pigment of the reversible thermochromic composition 11 containing no component. The light stabilizer layer was provided by spray coating the surface coating agent obtained in Example 18. The reversible thermochromic molded product in the form of a hot curler provided with the light stabilizer layer exhibits the same color change as the molded product obtained in Example 18. Further, a light stabilizer layer was provided by spray-coating the surface coating agent on a plate-like molded product molded using the reversible thermochromic polyester elastomer resin pellets as a light resistance test sample.

【０１１５】比較例１９ ｄ．成分を含まない可逆的熱変色性組成物１８のマイク
ロカプセル顔料を用いて作製した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使用して
作製した可逆的熱変色性エチレン−エチルアクリレート
樹脂フイルムシート表面上に、実施例１９で得た表面コ
ーティング剤を塗工して光安定剤層を設けた。前記光安
定剤層を設けた可逆的熱変色性エチレン−エチルアクリ
レート樹脂フイルムシートは、実施例１９で得たシート
と同様の色変化を呈する。また、耐光性試験試料として
前記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したプレート状の成形体
に、前記表面コーティング剤を塗工して光安定剤層を設
けた。Comparative Example 19 d. Reversible thermochromic ethylene-ethyl acrylate resin prepared using reversible thermochromic ethylene-ethyl acrylate copolymer resin pellets prepared using microcapsule pigment of reversible thermochromic composition 18 containing no component The light stabilizer layer was provided by applying the surface coating agent obtained in Example 19 on the surface of the film sheet. The reversible thermochromic ethylene-ethyl acrylate resin film sheet provided with the light stabilizer layer exhibits the same color change as the sheet obtained in Example 19. Further, as a light fastness test sample, the surface coating agent was applied to a plate-like molded body molded using the reversible thermochromic ethylene-ethyl acrylate copolymer resin pellets to provide a light stabilizer layer.

【０１１６】比較例２０ ｄ．成分を含まない可逆的熱変色性組成物１４のマイク
ロカプセル顔料を用いて作製した可逆的熱変色性ウレタ
ンエラストマー樹脂溶液を使用して作製したハート形状
のウレタンエラストマー樹脂成形体を、実施例２０で得
た表面コーティング剤中に浸漬させて共存層を設けた。
前記共存層を設けたハート形状の可逆的熱変色性ウレタ
ンエラストマー樹脂成形体は、実施例２０で得た成形体
と同様の色変化を呈する。また、耐光性試験試料とし
て、前記可逆熱変色性ウレタンエラストマー樹脂溶液を
用いて作製したプレート状の成形体を前記表面コーティ
ング剤中に浸漬させて光安定剤層を設けた。Comparative Example 20 d. A heart-shaped urethane elastomer resin molded article produced using a reversible thermochromic urethane elastomer resin solution produced using the microcapsule pigment of the reversible thermochromic composition 14 containing no component was prepared in Example 20. It was immersed in the obtained surface coating agent to form a coexisting layer.
The heart-shaped reversible thermochromic urethane elastomer resin molded article provided with the coexistence layer exhibits the same color change as the molded article obtained in Example 20. In addition, as a light resistance test sample, a plate-shaped molded body produced using the reversible thermochromic urethane elastomer resin solution was immersed in the surface coating agent to provide a light stabilizer layer.

【０１１７】比較例２１ ｄ．成分を含まない可逆的熱変色性組成物１５のマイク
ロカプセル顔料を用いて作製した可逆的熱変色性塩化ビ
ニルペーストゾルを使用して作製した馬形態の可逆的熱
変色性スラッシュ成形体表面上に、実施例２１で得た金
属光沢調表面コート剤をスプレー塗装して共存層を設け
た。前記共存層を設けた馬形態の可逆的熱変色性スラッ
シュ成形体は、実施例２１で得た成形体と同様の色変化
を呈する。また、耐光性試験試料として、前記可逆的熱
変色性塩化ビニルペーストゾルを用いて成形したプレー
ト状の成形体の表面上に、前記金属光沢調表面コート剤
をスプレー塗装して共存層を設けた。Comparative Example 21 d. On the surface of a horse-shaped reversible thermochromic slush molded body produced using a reversible thermochromic vinyl chloride paste sol produced using the microcapsule pigment of the reversible thermochromic composition 15 containing no component. The metallic glossy surface coating agent obtained in Example 21 was spray-coated to form a coexisting layer. The horse-shaped reversible thermochromic slash molded article provided with the coexistence layer exhibits the same color change as the molded article obtained in Example 21. Further, as a light fastness test sample, the metal glossy surface coating agent was spray-coated on the surface of a plate-shaped molded body molded using the reversible thermochromic vinyl chloride paste sol, to provide a coexistence layer. .

【０１１８】比較例２２ 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作製した可逆的熱変色性硬化性
シリコーン組成物を使用して作製した星形状の可逆的熱
変色性シリコーン成形体を、実施例２２で得た表面コー
ティング溶液に浸漬させて光安定剤層を設けた。前記光
安定剤層を設けた星形状の可逆的熱変色性シリコーン成
形体は、実施例２２で得た成形体と同様の色変化を呈す
る。また、耐光性試験試料として、前記可逆的熱変色性
硬化性シリコーン組成物を用いて作製したプレート状の
成形体を、前記表面コーティング溶液に浸漬させて光安
定剤層を設けた。Comparative Example 22 d. A star-shaped reversible thermochromic silicone molding produced using the reversible thermochromic curable silicone composition produced using the microcapsule pigment of the reversible thermochromic composition 10 containing no component, The light stabilizer layer was provided by dipping in the surface coating solution obtained in Example 22. The star-shaped reversible thermochromic silicone molded article provided with the light stabilizer layer exhibits the same color change as the molded article obtained in Example 22. In addition, as a light resistance test sample, a plate-like molded product produced using the reversible thermochromic curable silicone composition was immersed in the surface coating solution to provide a light stabilizer layer.

【０１１９】比較例２３ 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作製した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使用して作製した
人形形態の可逆的熱変色性中空成形体表面上に、実施例
１３と同様の表面コート剤をスプレー塗装して共存層を
設け、さらに前記共存層上に実施例２３で得た表面コー
ト剤をスプレー塗装して光安定剤層を設けた。前記共存
層および光安定剤層を設けた人形形態の可逆的熱変色性
中空成形体は、実施例２３で得た中空成形体と同様の色
変化を呈する。また、耐光性試験試料として前記可逆的
熱変色性エチレン−酢酸ビニル共重合樹脂ペレットを用
いて成形したプレート状の成形体上に、前記共存層を設
け、さらに共存層上に光安定剤層を設けた。Comparative Example 23 d. A doll-shaped reversible thermochromic hollow molding formed using reversible thermochromic ethylene-vinyl acetate copolymer resin pellets prepared using the microcapsule pigment of the reversible thermochromic composition 11 containing no component. On the body surface, the same surface coating agent as in Example 13 was spray-coated to provide a coexistence layer, and on the coexistence layer, the surface coating agent obtained in Example 23 was spray-coated to provide a light stabilizer layer. Was. The doll-shaped reversible thermochromic hollow molded article provided with the coexistence layer and the light stabilizer layer exhibits the same color change as the hollow molded article obtained in Example 23. Further, on a plate-shaped molded article molded using the reversible thermochromic ethylene-vinyl acetate copolymer resin pellets as a light resistance test sample, the coexistence layer is provided, and a light stabilizer layer is further formed on the coexistence layer. Provided.

【０１２０】比較例２４ ｄ．成分を含まない可逆的熱変色性組成物１４のマイク
ロカプセル顔料を用いて作製した可逆熱変色性ウレタン
エラストマー樹脂溶液を使用して作製したハート形状の
可逆熱変色性ウレタンエラストマー成形体を、実施例２
０で得た金属光沢調コーティング溶液に浸漬させて共存
層を設け、さらに、実施例２４で得た表面コーティング
溶液に浸漬させて光安定剤層を設けた。前記共存層およ
び光安定剤層を設けたハート形状の可逆熱変色性ウレタ
ンエラストマー樹脂成形体は、実施例２４で得た成形体
と同様の色変化を呈する。また、耐光性試験試料として
前記可逆熱変色性ウレタンエラストマー樹脂溶液を用い
て作製したプレート状の成形体に、前記共存層を設け、
さらに共存層上に光安定剤層を設けた。Comparative Example 24 d. A heart-shaped reversible thermochromic urethane elastomer molded article prepared using a reversible thermochromic urethane elastomer resin solution prepared using the microcapsule pigment of the reversible thermochromic composition 14 containing no component was prepared in Examples. 2
A coexistence layer was provided by dipping in the metallic glossy coating solution obtained in Example 0, and a light stabilizer layer was further provided by dipping in the surface coating solution obtained in Example 24. The heart-shaped reversible thermochromic urethane elastomer resin molded article provided with the coexistence layer and the light stabilizer layer exhibits the same color change as the molded article obtained in Example 24. Further, the coexistence layer is provided on a plate-shaped molded body produced using the reversible thermochromic urethane elastomer resin solution as a light resistance test sample,
Further, a light stabilizer layer was provided on the coexisting layer.

【０１２１】比較例２５ ｄ．成分を含まない可逆的熱変色性組成物１５のマイク
ロカプセル顔料を用いて作製した可逆的熱変色性塩化ビ
ニルペーストゾルを使用して作製した馬形態の可逆的熱
変色性スラッシュ成形体表面上に、実施例２１で得た金
属光沢調表面コート剤をスプレー塗装して共存層を設
け、さらに、実施例２５で得た表面コート剤をスプレー
塗装して光安定剤層を設けた。前記共存層および光安定
剤層を設けた馬形態の可逆的熱変色性スラッシュ成形体
は、実施例２５で得た成形体と同様の色変化を呈する。
また、耐光性試験試料として、前記可逆的熱変色性塩化
ビニルペーストゾルを用いて成形したプレート状の成形
体に、前記共存層を設け、さらに共存層上に光安定剤層
を設けた。Comparative Example 25 d. On the surface of a horse-shaped reversible thermochromic slush molded body produced using a reversible thermochromic vinyl chloride paste sol produced using the microcapsule pigment of the reversible thermochromic composition 15 containing no component. The metallic glossy surface coating agent obtained in Example 21 was spray-coated to provide a coexistence layer, and the surface coating agent obtained in Example 25 was spray-coated to provide a light stabilizer layer. The horse-shaped reversible thermochromic slush molded article provided with the coexistence layer and the light stabilizer layer exhibits the same color change as the molded article obtained in Example 25.
Further, as a light resistance test sample, the coexistence layer was provided on a plate-like molded product formed using the reversible thermochromic vinyl chloride paste sol, and a light stabilizer layer was further provided on the coexistence layer.

【０１２２】（１） 耐光堅牢度の試験方法 実施例１〜２５及び比較例１〜２５で得た耐光性試験試
料の耐光堅牢度を、カーボンアーク灯光試験機（スガ試
験機製）を用いて測定した。カーボンアーク灯耐光堅牢
度試験は、ＪＩＳ Ｌ−０８４２（カーボンアーク灯光
に対する染色堅牢度試験方法）の規格に準じて耐光性試
験を行った。カーボンアーク灯の照射時間は、実施例１
〜１１および比較例１〜１１は、２０時間、３０時間、
４０時間、５０時間、６０時間照射して、各ポイントで
耐光堅牢度を測定した。実施例１２〜２２および比較例
１２〜２２は、４０時間、６０時間、８０時間、１００
時間、１２０時間照射して、各ポイントで耐光堅牢度を
測定した。実施例２３〜２５および比較例２３〜２５
は、１００時間、１４０時間、１８０時間、２２０時
間、２６０時間照射して、各ポイントで耐光堅牢度を測
定した。(1) Light fastness test method The light fastness of the light fastness test samples obtained in Examples 1 to 25 and Comparative Examples 1 to 25 was measured using a carbon arc lamp light tester (manufactured by Suga Test Machine). did. In the light fastness test of carbon arc lamp, a light fastness test was performed in accordance with the standard of JIS L-0842 (testing method of dyeing fastness to carbon arc lamp light). The irradiation time of the carbon arc lamp was the same as in Example 1.
~ 11 and Comparative Examples 1 to 11 are 20 hours, 30 hours,
Irradiation was performed for 40 hours, 50 hours, and 60 hours, and light fastness was measured at each point. Examples 12 to 22 and Comparative Examples 12 to 22 were prepared for 40 hours, 60 hours, 80 hours, and 100 hours.
Irradiation was carried out for 120 hours, and light fastness was measured at each point. Examples 23 to 25 and Comparative Examples 23 to 25
Was irradiated for 100 hours, 140 hours, 180 hours, 220 hours, and 260 hours, and the light fastness was measured at each point.

【０１２３】（２） 耐光堅牢度試験結果 表２４〜表２９に、前記の耐光堅牢度試験による結果を
示す。(2) Light fastness test results Tables 24 to 29 show the results of the light fastness test.

【０１２４】[0124]

【表２４】 [Table 24]

【０１２５】[0125]

【表２５】 [Table 25]

【０１２６】[0126]

【表２６】 [Table 26]

【０１２７】[0127]

【表２７】 [Table 27]

【０１２８】[0128]

【表２８】 [Table 28]

【０１２９】[0129]

【表２９】 [Table 29]

【０１３０】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、試料
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 as a result of the light fastness test will be described. Using a color difference meter (manufactured by Tokyo Denshoku), the density stimulus value (X value) of the sample in the colored state is measured for each sample piece that has been irradiated for a certain period of time and the sample piece that has not been irradiated. 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

【０１３１】[0131]

【発明の効果】本発明は従来耐光性の小さかった、可逆
熱変色性組成物の消色時の光による老化を特別な耐光性
付与剤と光安定剤を併用することにより防止し、前記可
逆熱変色性組成物を成形用樹脂中に含有することによ
り、可逆熱変色性を有する成形用樹脂組成物およびそれ
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 aging of a reversible thermochromic composition, which was conventionally low in light resistance, due to light at the time of decolorization is prevented by using a special light resistance imparting agent and a light stabilizer in combination. When the thermochromic composition is contained in the molding resin, an excellent effect of remarkably improving the light resistance of the molding resin composition having reversible thermochromic properties and the molded article using the same is exhibited.

フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｄ０１Ｆ 1/04 Ｄ０１Ｆ 1/04 // Ｃ０７Ｄ 213/38 Ｃ０７Ｄ 213/38 213/65 213/65 215/14 215/14 307/88 307/88 401/10 ２３９ 401/10 ２３９ 405/04 ２０９ 405/04 ２０９ 405/14 ２０９ 405/14 ２０９ Continued on the front page (51) Int.Cl. 6 Identification code FI D01F 1/04 D01F 1/04 // C07D 213/38 C07D 213/38 213/65 213/65 215/14 215/14 307/88 307 / 88 401/10 239 401/10 239 405/04 209 405/04 209 405/14 209 405/14 209

Claims (8)

【特許請求の範囲】[Claims] 【請求項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Ｉ 【化１】 ｛式中、ｎ＝５〜１７（直鎖及び分岐）、Ｘ＝Ｃ１〜Ｃ
４（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．光安定剤と、 ｆ．成形用樹脂と、からなる、消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
4 (linear and branched), halogen, Y = C 1 -C 4 (linear and branched), halogen, p = 0 to 3, is m = 0 to 3. ｝ E. A light stabilizer; f. A resin composition for molding, comprising: a molding resin; and a reversible thermochromic property having improved light fastness during decoloring. 【請求項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、請求項１に記載され
た消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 decoloration according to claim 1, which is also used as an electron acceptor. 【請求項３】 ａ．〜ｅ．成分をマイクロカプセルに内
蔵した、請求項１または２に記載された消色時の耐光性
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. ~ E. 3. The molding resin composition having reversible thermochromic properties according to claim 1 or 2, wherein the components are incorporated in microcapsules. 【請求項４】 ｆ．成分が熱可塑性樹脂である、請求項
１ないし３のいずれか１項に記載された消色時の耐光性
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. The method according to claim 1, wherein f. 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 decoloration. 【請求項５】 請求項１ないし４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、消色時の耐
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 formed by using the resin composition for molding according to any one of claims 1 to 4 and having reversible thermochromic properties with improved light fastness at the time of decolorization. 【請求項６】 前記成形体がフィラメントである、請求
項５に記載された消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 having reversible thermochromic properties according to claim 5, wherein the molded article is a filament. 【請求項７】 前記成形体がフイルムである、請求項５
に記載された消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 having improved light fastness at the time of decoloration described in 1). 【請求項８】 請求項５ないし７のいずれか１項に記載
された成形体の光にさらされる面に、光安定剤および／
または光遮蔽剤を含有する光保護層を１または複数層配
置してなる、消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。8. A light stabilizer and / or a light stabilizer on a surface of the molded article according to claim 5 which is exposed to light.
Alternatively, a molded article having one or more light-protecting layers containing a light-shielding agent and having reversible thermochromic properties with improved light resistance during decoloring.
JP24433098A 1997-08-05 1998-07-28 Molding resin composition having reversible thermal color change property and mold therefrom Pending JPH11166123A (en)

Priority Applications (1)

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Application Number Priority Date Filing Date Title
JP9-241639 1997-08-05
JP24163997 1997-08-05
JP24433098A JPH11166123A (en) 1997-08-05 1998-07-28 Molding resin composition having reversible thermal color change property and mold therefrom

Publications (1)

Publication Number Publication Date
JPH11166123A true JPH11166123A (en) 1999-06-22

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Country Link
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