TW202246444A - Method for inhibiting color-changeable pressure-sensitive adhesive sheet from discoloring and laminated sheet - Google Patents
Method for inhibiting color-changeable pressure-sensitive adhesive sheet from discoloring and laminated sheet Download PDFInfo
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- TW202246444A TW202246444A TW111107968A TW111107968A TW202246444A TW 202246444 A TW202246444 A TW 202246444A TW 111107968 A TW111107968 A TW 111107968A TW 111107968 A TW111107968 A TW 111107968A TW 202246444 A TW202246444 A TW 202246444A
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- color
- adhesive sheet
- mentioned
- changing
- changing adhesive
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000002401 inhibitory effect Effects 0.000 title claims description 3
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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Abstract
Description
本發明係關於一種可變色黏著片材之變色抑制方法及積層片材。The present invention relates to a method for suppressing discoloration of a color-changing adhesive sheet and a laminated sheet.
已知有一種藉由特定波長之光照射而能夠使照射部位著色之透明黏著片材(可變色黏著片材)。可變色黏著片材含有因光照射而使該黏著片材著色之事後著色劑(成分或成分群)。A transparent adhesive sheet (color-changing adhesive sheet) capable of coloring an irradiated portion by irradiation with light of a specific wavelength is known. The color-changing adhesive sheet contains a subsequent coloring agent (ingredient or ingredient group) for coloring the adhesive sheet by light irradiation.
另一方面，有機EL(Electroluminescence，電致發光)面板等顯示面板具有包含像素面板及罩蓋構件等之積層構造。於此種顯示面板之製造過程中，為了使積層構造所包含之要素彼此貼合，例如使用可變色黏著片材。例如如下所述。On the other hand, a display panel such as an organic EL (Electroluminescence) panel has a laminated structure including a pixel panel, a cover member, and the like. In the manufacturing process of this kind of display panel, in order to make the elements contained in the laminated structure adhere to each other, for example, a color-changing adhesive sheet is used. For example as described below.
首先，將可變色黏著片材貼合於被黏著體(貼合步驟)。繼而，檢查被黏著體與可變色黏著片材之間有無異物及氣泡。於未通過檢查之情形時，將可變色黏著片材自第1被黏著體剝離，其後，使用另一可變色黏著片材重新進行貼合步驟。於通過檢查之情形時，為了對第1被黏著體上之可變色黏著片材之特定部位賦予設計性、遮蔽性、抗反射性等，藉由特定波長之光照射使該部位著色。即，於可變色黏著片材形成已著色區域。其後，經由該可變色黏著片材將第2被黏著體接合於第1被黏著體。例如，如此使用之可變色黏著片材例如記載於下述專利文獻1中。 [先前技術文獻] [專利文獻] First, a color-changing adhesive sheet is bonded to an adherend (bonding step). Then, check whether there are foreign objects and air bubbles between the adherend and the color-changing adhesive sheet. If the inspection fails, the color-changing adhesive sheet is peeled off from the first adherend, and thereafter, another color-changing adhesive sheet is used to perform the bonding step again. When passing the inspection, in order to impart designability, shielding properties, anti-reflection, etc. to a specific portion of the color-changing adhesive sheet on the first adherend, the portion is colored by irradiation with light of a specific wavelength. That is, a colored region is formed on the color-changing adhesive sheet. Thereafter, the second adherend is bonded to the first adherend via the color-changing adhesive sheet. For example, the color-variable adhesive sheet used in this way is described in the following patent document 1, for example. [Prior Art Literature] [Patent Document]
[專利文獻1]日本專利特開2020-152905號公報[Patent Document 1] Japanese Patent Laid-Open No. 2020-152905
[發明所欲解決之問題][Problem to be solved by the invention]
於可變色黏著片材中，為了實現良好之著色性，事後著色劑之調配量宜較多。然而，於形成已著色區域後之可變色黏著片材中，事後著色劑之調配量越多，則未形成已著色區域之區域(未著色區域)越容易經時變色。未著色區域之變色會導致已著色區域及未著色區域之功能劣化，從而不佳。In the color-changing adhesive sheet, in order to achieve good colorability, the amount of colorant should be more after the preparation. However, in the color-changing adhesive sheet after the colored region is formed, the more the amount of the coloring agent is added afterwards, the more likely the region where the colored region is not formed (uncolored region) to change color over time. The discoloration of the uncolored area degrades the function of the colored area and the uncolored area, which is not good.
本發明提供一種適於在藉由賦予外部刺激而能夠著色之可變色黏著片材中，既使已著色區域良好地著色又兼顧到抑制已著色區域形成後之未著色區域之經時性變色的方法及藉由該方法而獲得之積層片材。 [解決問題之技術手段] The present invention provides a color-changing adhesive sheet that is suitable for coloring a colored region while taking into account the suppression of time-dependent discoloration of an uncolored region after the colored region is formed in a color-changing adhesive sheet that can be colored by applying an external stimulus. Method and laminated sheet obtained by the method. [Technical means to solve the problem]
本發明[1]包含一種可變色黏著片材之變色抑制方法，其包括：第1步驟，其係準備可變色黏著片材，該可變色黏著片材具有因外部刺激而產生之著色性，且包含已著色區域及未著色區域；及第2步驟，其係令用以降低上述可變色黏著片材之上述著色性之著色性低下介質與上述可變色黏著片材接觸。The present invention [1] includes a method for suppressing discoloration of a color-changing adhesive sheet, which includes: a first step of preparing a color-changing adhesive sheet having coloring properties due to external stimuli, and It includes a colored area and an uncolored area; and a second step of contacting the color-changing adhesive sheet with a color-reducing medium for reducing the color-changing adhesive sheet.
於本方法中，在第2步驟中，令用以降低該黏著片材之著色性之著色性低下介質與包含已著色區域及未著色區域之可變色黏著片材接觸。此種構成適於在包含已著色區域及未著色區域之可變色黏著片材中，降低未著色區域之著色性，從而抑制未著色區域之經時性變色。又，於本方法中，預備後實施此種第2步驟之情況下，於第1步驟中，準備包含已著色區域及未著色區域之可變色黏著片材。此種構成適於將可變色黏著片材準備為因外部刺激而產生之著色性較高從而使已著色區域良好地著色之黏著片材。即便為著色性高至使已著色區域良好地著色之可變色黏著片材，亦於第2步驟中因與著色性低下介質接觸而使著色性降低，該第2步驟後，未著色區域之經時性變色得以抑制。如此，本方法適於在藉由賦予外部刺激而能夠著色之可變色黏著片材中，既使已著色區域良好地著色又兼顧到抑制已著色區域形成後之未著色區域之經時性變色。In this method, in the second step, the coloring property-reducing medium for reducing the coloring property of the adhesive sheet is brought into contact with the color-changing adhesive sheet including the colored area and the uncolored area. Such a configuration is suitable for reducing the colorability of the uncolored area in a color-changing adhesive sheet including the colored area and the uncolored area, thereby suppressing the time-dependent discoloration of the uncolored area. Moreover, in this method, when carrying out such a 2nd step after preparation, in the 1st step, the color changeable adhesive sheet containing the colored area|region and the non-colored area is prepared. Such a configuration is suitable for preparing the color-changing adhesive sheet as an adhesive sheet having high colorability due to external stimuli so that the colored regions are well colored. Even if the color-changing adhesive sheet is so high in coloring that the colored area is well colored, the coloring property is reduced due to contact with the medium with low coloring property in the second step, and the process of the uncolored area after the second step Seasonal discoloration is suppressed. In this way, this method is suitable for achieving satisfactory coloring of the colored region and suppressing time-dependent discoloration of the uncolored region after the formation of the colored region in a color-changing adhesive sheet that can be colored by application of external stimuli.
本發明[2]包含如上述[1]中所記載之可變色黏著片材之變色抑制方法，其中上述可變色黏著片材含有受外部刺激而發生第1反應之第1化合物及藉由與上述第1反應之產物之第2反應而顯色之第2化合物。The present invention [2] includes the method of suppressing discoloration of the color-changing adhesive sheet described in the above-mentioned [1], wherein the color-changing adhesive sheet contains a first compound that undergoes a first reaction to an external stimulus and is combined with the above-mentioned The second compound that develops color in the second reaction of the product of the first reaction.
根據此種構成，可於第1步驟中準備藉由第1化合物與第2化合物之協作而適當地著色之可變色黏著片材。According to such a configuration, a color-changing adhesive sheet appropriately colored by cooperation of the first compound and the second compound can be prepared in the first step.
本發明[3]包含如上述[2]中所記載之可變色黏著片材之變色抑制方法，其中上述第1化合物為光酸產生劑，且上述第2化合物為藉由與酸之反應而顯色之顯色性化合物。The present invention [3] includes the method for suppressing discoloration of a color-changing adhesive sheet as described in the above [2], wherein the first compound is a photoacid generator, and the second compound is produced by a reaction with an acid. Chromogenic compound of color.
根據此種構成，可於第1步驟中準備利用光照射作為上述外部刺激而著色之可變色黏著片材。藉由對可變色黏著片材照射特定波長之光，於該照射部位，由光酸產生劑產生酸，藉由與該酸之反應而使顯色性化合物顯色，從而可使該部位著色。According to such a configuration, a color-changing adhesive sheet that is colored by light irradiation as the above-mentioned external stimulus can be prepared in the first step. By irradiating the color-changing adhesive sheet with light of a specific wavelength, an acid is generated by a photoacid generator at the irradiated portion, and a color-developing compound is developed by reacting with the acid, whereby the portion can be colored.
本發明[4]包含如上述[2]或[3]中所記載之可變色黏著片材之變色抑制方法，其中於上述第2步驟中，將上述第1化合物自上述可變色黏著片材中提取至上述著色性低下介質中，或者上述著色性低下介質含有用以降低上述著色性之著色性低下成分，於上述第2步驟中，將上述著色性低下成分自上述著色性低下介質中導入至上述可變色黏著片材。The present invention [4] includes the discoloration suppression method of the color-changing adhesive sheet described in the above-mentioned [2] or [3], wherein in the above-mentioned second step, the above-mentioned first compound is extracted from the above-mentioned color-changing adhesive sheet extracted into the above-mentioned low-coloring medium, or the above-mentioned low-coloring medium contains the low-coloring component for reducing the above-mentioned coloring, and in the second step, the above-mentioned low-coloring component is introduced from the above-mentioned low-coloring medium into The above-mentioned color changeable adhesive sheet.
此種構成適於在第2步驟中降低可變色黏著片材之著色性。Such a constitution is suitable for reducing the colorability of the color-variable adhesive sheet in the second step.
本發明[5]包含如上述[4]中所記載之可變色黏著片材之變色抑制方法，其中第1系統中因上述外部刺激賦予所導致之透過率之降低ΔT1小於第2系統中因與上述外部刺激賦予相同之外部刺激賦予所導致之透過率之降低ΔT2，上述第1系統中共存有上述第1化合物、上述第2化合物及上述著色性低下成分，上述第2系統除不存在上述著色性低下成分以外與上述第1系統相同。The present invention [5] includes the method for suppressing discoloration of a color-changing adhesive sheet as described in the above [4], wherein in the first system, the decrease in transmittance ΔT1 caused by the application of the external stimulus is smaller than in the second system due to the combination with The decrease in transmittance ΔT2 caused by the application of the external stimulus is the same as that of the external stimulus. The above-mentioned first compound, the above-mentioned second compound, and the above-mentioned low-coloring component coexist in the above-mentioned first system, and the above-mentioned second system does not have the above-mentioned coloring. It is the same as the above-mentioned first system except for the low sex component.
此種構成適於在第2步驟中降低可變色黏著片材之著色性。Such a constitution is suitable for reducing the colorability of the color-variable adhesive sheet in the second step.
本發明[6]包含如上述[5]中所記載之可變色黏著片材之變色抑制方法，其中上述著色性低下成分包含選自由紫外線吸收劑、中和劑及自由基捕獲劑所組成之群中之至少一種。The present invention [6] includes the method for suppressing discoloration of a color-changing adhesive sheet as described in the above-mentioned [5], wherein the coloring-reducing component is selected from the group consisting of ultraviolet absorbers, neutralizers, and radical scavengers at least one of them.
此種構成適於在使用光酸產生劑作為上述第1成分之情形時，以第2步驟降低可變色黏著片材之著色性。Such a configuration is suitable for reducing the colorability of the color-variable adhesive sheet in the second step when a photoacid generator is used as the first component.
本發明[7]包含如上述[1]至[6]中任一項所記載之可變色黏著片材之變色抑制方法，其中上述著色性低下介質為著色性低下片材，且於上述第2步驟中，將上述著色性低下片材貼合於上述可變色黏著片材。The present invention [7] includes the method for suppressing discoloration of a color-changing adhesive sheet as described in any one of the above-mentioned [1] to [6], wherein the above-mentioned low-coloring medium is a low-coloring sheet, and in the above-mentioned second In the step, the above-mentioned low-colorability sheet is bonded to the above-mentioned color-changing adhesive sheet.
此種構成適於在使用可變色黏著片材之器件之製造過程中高效率地實施第2步驟。Such a configuration is suitable for efficiently implementing the second step in the manufacturing process of a device using a color-variable adhesive sheet.
本發明[8]包含如上述[7]中所記載之可變色黏著片材之變色抑制方法，其中於上述第2步驟中，於上述可變色黏著片材之上述已著色區域之至少一部分與上述著色性低下片材之間介存有遮罩材之狀態下，將上述著色性低下片材貼合於上述可變色黏著片材。The present invention [8] includes the discoloration suppression method of the color-changing adhesive sheet described in the above-mentioned [7], wherein in the second step, at least a part of the colored region of the color-changing adhesive sheet and the above-mentioned In the state where the mask material is interposed between the low-colorability sheets, the above-mentioned low-colorability sheet is bonded to the above-mentioned color-changing adhesive sheet.
此種構成適於在第2步驟中控制可變色黏著片材之著色性低下部位。Such a constitution is suitable for controlling the color-changing adhesive sheet in the second step where the colorability is reduced.
本發明[9]包含如上述[7]或[8]中所記載之可變色黏著片材之變色抑制方法，其中上述著色性低下片材包含含有極性基之聚合物。The present invention [9] includes the method for suppressing discoloration of a color-variable adhesive sheet as described in the above-mentioned [7] or [8], wherein the color-reducing sheet contains a polar group-containing polymer.
此種構成適於在第2步驟中將第1化合物自可變色黏著片材中提取至著色性低下片材。Such a configuration is suitable for extracting the first compound from the color-changing adhesive sheet to the sheet having low colorability in the second step.
本發明[10]包含如上述[7]至[9]中任一項所記載之可變色黏著片材之變色抑制方法，其中上述著色性低下片材為黏著片材。The present invention [10] includes the method of suppressing discoloration of a color-changing adhesive sheet according to any one of the above-mentioned [7] to [9], wherein the sheet having low colorability is an adhesive sheet.
此種構成適於在第2步驟中將著色性低下片材高度密接於可變色黏著片材。又，該構成適於使第2步驟中所獲得之積層片材(可變色黏著片材與著色性低下片材之積層體)作為雙面黏著片材發揮功能。Such a configuration is suitable for highly adhering the color-reducing sheet to the discoloration adhesive sheet in the second step. Moreover, this structure is suitable for making the laminated sheet obtained in the 2nd step (the laminated body of the color-variable adhesive sheet and the low coloring property sheet) function as a double-sided adhesive sheet.
本發明[11]包含如上述[1]至[6]中任一項所記載之變色抑制方法，其中上述著色性低下介質為著色性低下溶劑。The present invention [11] includes the discoloration suppression method described in any one of the above-mentioned [1] to [6], wherein the coloring property-reducing medium is a coloring property-reducing solvent.
此種構成有助於高效率地實施第2步驟。Such a configuration contributes to efficient implementation of the second step.
本發明[12]包含一種積層片材，其係藉由如上述[7]至[10]中任一項所記載之可變色黏著片材之變色抑制方法而獲得者，且具備：上述可變色黏著片材、及貼合於上述可變色黏著片材之上述著色性低下片材。The present invention [12] includes a laminated sheet obtained by the method for suppressing discoloration of a color-changing adhesive sheet described in any one of the above-mentioned [7] to [10], and comprising: the above-mentioned color-changing An adhesive sheet, and the aforementioned low-colorability sheet bonded to the aforementioned color-changing adhesive sheet.
此種積層片材適於組裝既使已著色區域良好地著色又兼顧到抑制未著色區域之變色的可變色黏著片材作為顯示面板等器件之構造構件。This kind of laminated sheet is suitable for assembling a color-changing adhesive sheet that not only makes the colored area well colored but also takes into account the suppression of discoloration of the uncolored area, as a structural member of devices such as display panels.
本發明之可變色黏著片材之變色抑制方法包含第1步驟及第2步驟。The method for suppressing discoloration of a color-changing adhesive sheet of the present invention includes a first step and a second step.
首先，於第1步驟中，如圖1所示，準備可變色黏著片材X。First, in the first step, as shown in FIG. 1 , a color-changing adhesive sheet X is prepared.
可變色黏著片材X具有特定厚度之片材形狀，且於與厚度方向正交之方向(面方向)上延伸。可變色黏著片材X由第1黏著性組合物形成。又，可變色黏著片材X係具有因外部刺激而產生之著色性之黏著片材，包含已著色之第1區域11(已著色區域)及未形成第1區域11之第2區域12(未著色區域)。第2區域12較佳為具有透明性(可見光透過性)。於本實施方式中，可變色黏著片材X含有基礎聚合物、受外部刺激而發生第1反應之第1化合物及藉由與第1反應之產物之第2反應而顯色之第2化合物。根據此種構成，可於第1步驟中準備藉由第1化合物與第2化合物之協作而適當地著色之可變色黏著片材X。The color-variable adhesive sheet X has a sheet shape with a specific thickness, and extends in a direction (plane direction) perpendicular to the thickness direction. The color-variable adhesive sheet X is formed from the first adhesive composition. In addition, the color-changing adhesive sheet X is an adhesive sheet having coloring properties caused by external stimuli, and includes a colored first region 11 (colored region) and a
作為外部刺激，根據可變色黏著片材X所含有之成分，例如可例舉光照射及加熱。作為光照射中之光之種類，例如可例舉紫外線、可見光及紅外線，就使用設備之多樣性之觀點而言，較佳為紫外線。於可變色黏著片材X中，較佳為第1化合物為光酸產生劑，且第2化合物為藉由與酸之反應而顯色之顯色性化合物。根據此種構成，可於第1步驟中準備利用光照射作為上述外部刺激而著色之可變色黏著片材X。藉由對可變色黏著片材X照射特定波長之光，於該照射部位，由光酸產生劑產生酸，藉由與該酸之反應而使顯色性化合物顯色，從而可使該部位著色。更具體而言，可變色黏著片材X之成分如下所述。As the external stimulus, depending on the components contained in the color-changing adhesive sheet X, for example, light irradiation and heating are mentioned. As the kind of light in light irradiation, ultraviolet rays, visible light, and infrared rays are mentioned, for example, and ultraviolet rays are preferable from a viewpoint of the variety of equipment used. In the color-variable adhesive sheet X, it is preferable that the first compound is a photoacid generator, and the second compound is a color-developing compound that develops color by reaction with an acid. According to such a structure, the color changeable adhesive sheet X colored by light irradiation as the said external stimulus can be prepared in a 1st step. When the color-changing adhesive sheet X is irradiated with light of a specific wavelength, an acid is generated from a photoacid generator at the irradiated portion, and a color-developing compound is developed by reacting with the acid, whereby the portion can be colored . More specifically, the components of the color-variable adhesive sheet X are as follows.
於第1步驟中，可變色黏著片材X可貼合於特定被黏著體。圖1例示性地示出可變色黏著片材X貼合於第1構件21之厚度方向T之一面之狀態。第1構件21例如為有機EL面板等顯示面板。第1構件21可為其他電子器件，亦可為光學器件。較佳為在可變色黏著片材X貼合於被黏著體之後，對可變色黏著片材X之特定部位賦予外部刺激，從而形成第1區域11。在將可變色黏著片材X貼合於第1構件21之後，較佳為於第1區域11形成前，檢查第1構件21與可變色黏著片材X之間有無異物及氣泡。In the first step, the color-changing adhesive sheet X can be attached to a specific adherend. FIG. 1 exemplarily shows the state where the color-changing adhesive sheet X is bonded to one surface in the thickness direction T of the
繼而，於第2步驟中，令用以降低可變色黏著片材X之著色性之著色性低下介質與此種可變色黏著片材X接觸。Then, in the second step, the color-changing adhesive sheet X is brought into contact with the color-changing adhesive sheet X with a color-changing property-lowering medium for reducing the coloring property of the color-changing adhesive sheet X.
作為著色性低下介質，可例舉失活用介質及提取用介質。所謂失活用介質係含有用以降低可變色黏著片材X之著色性之著色性低下成分，且用以將該成分導入至可變色黏著片材X之介質(失活用介質係用以作為可變色黏著片材X之功能之著色性之抑制、失活之介質)。於包含可變色黏著片材X及與該片材接觸之失活用介質之系統中，使著色性低下成分發生擴散，以便使系統內之著色性低下成分之濃度分佈之偏差變小。藉此，可將著色性低下成分自失活用介質中導入至可變色黏著片材X(導入功能)。另一方面，提取用介質係用以自可變色黏著片材X中提取上述第1化合物從而降低可變色黏著片材X之著色性之介質。於包含可變色黏著片材X及與該片材接觸之提取用介質之系統中，使第1化合物發生擴散，以便使系統內之第1化合物之濃度分佈之偏差變小。藉此，可將第1化合物自可變色黏著片材X中提取至提取用介質(提取功能)。上述失活用介質於兼具此種提取功能與上述導入功能之情形時，兼任提取用介質。如上之失活用介質及提取用介質適於在第2步驟中降低可變色黏著片材X之著色性。又，作為著色性低下介質，可例舉著色性低下片材及著色性低下溶劑。即，著色性低下介質中包含失活用片材、提取用片材、失活用溶劑及提取用溶劑。著色性低下片材於本實施方式中為黏著片材。Examples of the low-coloring medium include a deactivation medium and an extraction medium. The so-called deactivation medium is a medium that contains a coloring-reducing component to reduce the coloring property of the color-changing adhesive sheet X, and is used to introduce the component into the color-changing adhesive sheet X (the deactivation medium is used as a color-changing adhesive sheet X). Adhesive sheet X's function is inhibition of coloring, medium for inactivation). In the system including the color-changing adhesive sheet X and the inactivation medium in contact with the sheet, the coloring-reducing component is diffused so that the variation in the concentration distribution of the coloring-reducing component in the system is reduced. Thereby, the low-coloring component can be introduced into the color-changing adhesive sheet X from the inactivation medium (introduction function). On the other hand, the extraction medium is a medium for extracting the above-mentioned first compound from the color-variable adhesive sheet X to reduce the colorability of the color-variable adhesive sheet X. In the system including the color-variable adhesive sheet X and the extraction medium in contact with the sheet, the first compound is diffused so that the deviation of the concentration distribution of the first compound in the system is reduced. Thereby, the first compound can be extracted from the color-changing adhesive sheet X to the extraction medium (extraction function). In the case where the above-mentioned inactivation medium has both the above-mentioned extraction function and the above-mentioned introduction function, it also serves as the extraction medium. The above inactivation medium and extraction medium are suitable for reducing the colorability of the color-changing adhesive sheet X in the second step. Moreover, as a coloring-reducing medium, a coloring-reducing sheet|seat and a coloring-reducing solvent are mentioned. That is, the low-coloring medium includes a deactivation sheet, an extraction sheet, a deactivation solvent, and an extraction solvent. The color-reduced sheet|seat is an adhesive sheet in this embodiment.
圖2表示於第2步驟中使用作為著色性低下介質之著色性低下片材Y之情況。於該情形時，在第2步驟中，將著色性低下片材Y貼合於可變色黏著片材X之厚度方向T之一面。著色性低下片材Y具有特定厚度之片材形狀，且於與厚度方向正交之方向(面方向)上延伸。於本實施方式中，著色性低下片材Y係由第2黏著性組合物所形成之黏著片材。又，藉由本步驟，可獲得積層片材L。積層片材L具備可變色黏著片材X及貼合於可變色黏著片材X之著色性低下片材Y。Fig. 2 shows the case of using the color-reducing sheet Y as a color-reducing medium in the second step. In this case, in the second step, the color-reducing sheet Y is bonded to one surface of the color-changing adhesive sheet X in the thickness direction T. The low-coloring sheet Y has a sheet shape with a specific thickness, and extends in a direction (surface direction) perpendicular to the thickness direction. In the present embodiment, the low-coloring sheet Y is an adhesive sheet formed from the second adhesive composition. Moreover, the laminated sheet L can be obtained by this process. The laminated sheet L includes a color-changing adhesive sheet X and a color-changing adhesive sheet X bonded to the color-changing adhesive sheet X. The sheet Y having low colorability.
使著色性低下片材Y與可變色黏著片材X接觸之時間較佳為1分鐘以上，更佳為3分鐘以上，進而較佳為5分鐘以上。於事後自可變色黏著片材X剝離著色性低下片材Y之情形時，接觸時間較佳為72小時以下，更佳為48小時以下，進而較佳為24小時以下，特佳為12小時以下。The time for bringing the color-reducing sheet Y into contact with the color-changing adhesive sheet X is preferably at least 1 minute, more preferably at least 3 minutes, and still more preferably at least 5 minutes. When the color-changing adhesive sheet X is peeled off from the low-coloring sheet Y afterwards, the contact time is preferably 72 hours or less, more preferably 48 hours or less, further preferably 24 hours or less, particularly preferably 12 hours or less .
於第2步驟中使用著色性低下溶劑作為著色性低下介質之情形時，於第2步驟中，使著色性低下溶劑與可變色黏著片材X接觸。具體而言，著色性低下溶劑之成分如下所述。作為接觸方法，例如可例舉：將可變色黏著片材X浸漬於著色性低下溶劑及對可變色黏著片材X噴霧著色性低下溶劑。In the case of using the coloring property reducing solvent as the coloring property reducing medium in the second step, the coloring property reducing solvent is brought into contact with the color-changing adhesive sheet X in the second step. Specifically, the components of the low-coloring solvent are as follows. As a contact method, for example, immersing the color-changing adhesive sheet X in a color-reducing solvent and spraying the color-changing adhesive sheet X with a color-reducing solvent may, for example, be mentioned.
使著色性低下溶劑與可變色黏著片材X接觸之時間較佳為1分鐘以上，更佳為3分鐘以上，進而較佳為5分鐘以上。該接觸時間較佳為72小時以下，更佳為48小時以下，進而較佳為24小時以下，特佳為12小時以下。The time for bringing the color-reducing solvent into contact with the color-changing adhesive sheet X is preferably at least 1 minute, more preferably at least 3 minutes, and still more preferably at least 5 minutes. The contact time is preferably 72 hours or less, more preferably 48 hours or less, further preferably 24 hours or less, particularly preferably 12 hours or less.
於第2步驟中，較佳為對可變色黏著片材X及著色性低下介質(圖2中之著色性低下片材Y)進行加熱。於使用失活用介質作為著色性低下介質之情形時，藉由加熱，促進失活用介質中之著色性低下成分向可變色黏著片材X移動。於使用提取用介質作為著色性低下介質之情形時，藉由加熱，促進可變色黏著片材X中之第1成分向提取用介質移動。第2步驟中之加熱溫度較佳為30℃以上，更佳為50℃以上，又，較佳為150℃以下，更佳為100℃以下。In the second step, it is preferable to heat the color-changing adhesive sheet X and the low-coloring property medium (the low-coloring property sheet Y in FIG. 2 ). When the deactivation medium is used as the color-reducing medium, migration of the color-reducing component in the deactivation medium to the color-changing adhesive sheet X is promoted by heating. When the extraction medium is used as the low-coloring medium, the migration of the first component in the color-variable adhesive sheet X to the extraction medium is promoted by heating. The heating temperature in the second step is preferably at least 30°C, more preferably at least 50°C, and is preferably at most 150°C, more preferably at most 100°C.
於本方法中，如上所述，於第2步驟中，令用以降低該黏著片材之著色性之著色性低下介質與包含第1區域11(已著色區域)及第2區域12(未著色區域)之可變色黏著片材X接觸。此種構成適於在包含第1區域11及第2區域12之可變色黏著片材X中，降低第2區域12之著色性，從而抑制第2區域12之經時性變色。此外，該構成適於降低第1區域11之著色性從而抑制該第1區域11之經時性變色或抑制在第1區域11內顯色之第2化合物(著色成分)劣化，因此，亦適於確保第1區域11之著色穩定性(具體而言，例如如下述實施例7、8及比較例3所示)。即，本方法亦可作為具有已著色區域之可變色黏著片材X之著色穩定方法來實施。於在可變色黏著片材X整面形成有已著色區域之情形時，亦可享有該已著色區域之著色穩定效果。就確保與可變色黏著片材X之用途對應之已著色區域之功能(設計性、遮蔽性、抗反射性等)之觀點而言，較佳為穩定可變色黏著片材X之已著色區域之著色。In this method, as described above, in the second step, the coloring property-lowering medium used to reduce the coloring property of the adhesive sheet is mixed with the first area 11 (colored area) and the second area 12 (uncolored area). area) in contact with the color-changing adhesive sheet X. Such a configuration is suitable for reducing the coloring property of the
又，於本方法中，預備後實施此種第2步驟之情況下，在第1步驟中，準備包含第1區域11及第2區域12之可變色黏著片材X。此種構成適於將可變色黏著片材X準備為因外部刺激而產生之著色性較高從而使第1區域11良好地著色之黏著片材(可變色黏著片材X中之第1化合物及/或第2化合物之含量越多，則可變色黏著片材X之著色性越高)。即便為第1化合物及/或第2化合物之含量較多而著色性高至使第1區域11良好地著色之可變色黏著片材X，亦於第2步驟中因與著色性低下介質接觸而使著色性降低，此種第2步驟後，第2區域12之經時性變色得以抑制。Moreover, in this method, when carrying out such a 2nd step after preparation, in the 1st step, the color changeable adhesive sheet X containing the 1st area|
如上所述，本方法適於在藉由賦予外部刺激而能夠著色之可變色黏著片材X中，既使第1區域11良好地著色又兼顧到抑制第2區域12之經時性變色。如下述參考例1～4所示，在可變色黏著片材中，於自著色處理前便共存有起光酸產生劑(第1化合物)及顯色性化合物(第2化合物)與著色性低下成分之情形時，該可變色黏著片材之著色能力較低而不易著色。針對此種情況，事後使著色性低下成分浸透至使特定區域著色後之可變色黏著片材X，藉此，可使上述特定區域充分發揮其著色能力而良好地著色(第1區域11之形成)，並且使非著色區域(第2區域12)不易變色而抑制變色。As described above, this method is suitable for achieving satisfactory coloring of the
圖2所示之第2步驟後，例如，如圖3所示，第1構件21與第2構件22介隔積層片材L而接合。第2構件M2例如為透明罩蓋構件。作為透明罩蓋構件，例如可例舉透明塑膠膜及透明玻璃板。藉由本步驟，可獲得於厚度方向T上依序具備第1構件21、積層片材L(可變色黏著片材X及著色性低下片材Y)及第2構件22之積層體Z1。After the second step shown in FIG. 2 , for example, as shown in FIG. 3 , the
於第2步驟中使用著色性低下溶劑作為著色性低下介質之情形時，或者於圖2所示之第2步驟後自可變色黏著片材X剝離著色性低下片材Y之情形時，此種第2步驟後，例如，如圖4所示，第1構件21與第2構件22介隔可變色黏著片材X而接合。藉此，可獲得於厚度方向T上依序具備第1構件21、可變色黏著片材X及第2構件22之積層體Z2。In the case of using a coloring-reducing solvent in the second step as the coloring-reducing medium, or when peeling the color-reducing sheet Y from the color-changing adhesive sheet X after the second step shown in FIG. 2 , this After the second step, for example, as shown in FIG. 4 , the
於本實施方式中，形成可變色黏著片材X之第1黏著性組合物含有基礎聚合物、受外部刺激而發生第1反應之第1化合物及藉由與第1反應之產物之第2反應而顯色之第2化合物。In this embodiment, the first adhesive composition that forms the color-changing adhesive sheet X contains a base polymer, a first compound that undergoes a first reaction to external stimuli, and a second reaction with the product of the first reaction. And the second compound that develops color.
基礎聚合物係用以使可變色黏著片材X表現出黏著性之黏著成分。基礎聚合物於室溫範圍內顯示出橡膠彈性。作為基礎聚合物，例如可例舉：丙烯酸聚合物、橡膠聚合物、聚酯聚合物、胺基甲酸酯聚合物、聚醚聚合物、聚矽氧聚合物、聚醯胺聚合物及氟聚合物。就確保可變色黏著片材X中之良好之透明性及黏著性之觀點而言，基礎聚合物較佳為使用丙烯酸聚合物(第1丙烯酸聚合物)。The base polymer is an adhesive component used to make the color-changing adhesive sheet X exhibit adhesiveness. The base polymer exhibits rubber elasticity in the room temperature range. Examples of base polymers include acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluoropolymers. things. It is preferable to use an acrylic polymer (1st acrylic polymer) as a base polymer from a viewpoint of ensuring the favorable transparency and adhesiveness in the color-variable adhesive sheet X.
丙烯酸聚合物例如為以50質量%以上之比率包含(甲基)丙烯酸烷基酯之單體成分(第1單體成分)之共聚物。「(甲基)丙烯酸」意指丙烯酸及/或甲基丙烯酸。The acrylic polymer is, for example, a copolymer containing a monomer component (first monomer component) of an alkyl (meth)acrylate in a ratio of 50% by mass or more. "(Meth)acrylic acid" means acrylic acid and/or methacrylic acid.
作為(甲基)丙烯酸烷基酯，例如可例舉具有直鏈狀或支鏈狀之碳數1～20之烷基之(甲基)丙烯酸烷基酯。作為此種(甲基)丙烯酸烷基酯，例如可例舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸異十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸異十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸異十八烷基酯(丙烯酸異硬脂酯)、(甲基)丙烯酸十九烷基酯及(甲基)丙烯酸二十烷基酯。(甲基)丙烯酸烷基酯可單獨使用，亦可倂用兩種以上。(甲基)丙烯酸烷基酯較佳為使用具有碳數1～12之烷基之丙烯酸烷基酯，更佳為倂用甲基丙烯酸甲酯及具有碳數2～12之烷基之(甲基)丙烯酸烷基酯，進而較佳為倂用甲基丙烯酸甲酯及丙烯酸2-乙基己酯。As an alkyl (meth)acrylate, the alkyl (meth)acrylate which has a linear or branched C1-C20 alkyl group is mentioned, for example. Such alkyl (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, Isopropyl (meth)acrylate, Isobutyl (meth)acrylate, Second-butyl (meth)acrylate, Tertiary-butyl (meth)acrylate, Amyl (meth)acrylate, (Meth) Isoamyl acrylate, Neopentyl (meth)acrylate, Hexyl (meth)acrylate, Heptyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, Octyl (meth)acrylate, Isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate Alkyl esters, lauryl (meth)acrylate, isotridecyl (meth)acrylate, myristyl (meth)acrylate, isotetradecyl (meth)acrylate, Pentadecyl (meth)acrylate, Cetyl (meth)acrylate, Heptadecyl (meth)acrylate, Octadecyl (meth)acrylate, Iso(meth)acrylate Stearyl (isostearyl acrylate), nonadecyl (meth)acrylate and eicosyl (meth)acrylate. Alkyl (meth)acrylates may be used alone or in combination of two or more. Alkyl (meth)acrylate is preferably an alkyl acrylate having an alkyl group with 1 to 12 carbons, more preferably methyl methacrylate and an alkyl group with 2 to 12 carbons (methyl methacrylate) base) alkyl acrylate, and more preferably methyl methacrylate and 2-ethylhexyl acrylate.
就使可變色黏著片材X適當地表現出黏著性等基本特性之觀點而言，單體成分中之(甲基)丙烯酸烷基酯之比率較佳為50質量%以上，更佳為60質量%以上，進而較佳為70質量%以上。該比率例如為99質量%以下。From the viewpoint of making the color-changing adhesive sheet X appropriately express basic properties such as adhesiveness, the ratio of the alkyl (meth)acrylate in the monomer component is preferably at least 50% by mass, more preferably 60% by mass % or more, and more preferably 70% by mass or more. This ratio is, for example, 99% by mass or less.
第1單體成分可包含可與(甲基)丙烯酸烷基酯共聚之共聚性單體。作為共聚性單體，例如可例舉具有極性基之單體。作為含有極性基之單體，例如可例舉：含有羥基之單體、具有含有氮原子之環之單體及含有羧基之單體。含有極性基之單體有助於向丙烯酸聚合物導入交聯點、確保丙烯酸聚合物之凝聚力等丙烯酸聚合物之改質。The first monomer component may contain a copolymerizable monomer copolymerizable with an alkyl (meth)acrylate. As a copolymerizable monomer, the monomer which has a polar group is mentioned, for example. Examples of the polar group-containing monomer include a hydroxyl group-containing monomer, a nitrogen atom-containing ring monomer, and a carboxyl group-containing monomer. Monomers containing polar groups are helpful for the modification of acrylic polymers such as introducing crosslinking points into acrylic polymers and ensuring the cohesion of acrylic polymers.
共聚性單體較佳為包含選自由含有羥基之單體、具有含有氮原子之環之單體及含有羧基之單體所組成之群中之至少一種。共聚性單體更佳為包含含有羥基之單體及/或具有含有氮原子之環之單體。The copolymerizable monomer preferably contains at least one selected from the group consisting of hydroxyl group-containing monomers, nitrogen atom-containing ring monomers, and carboxyl group-containing monomers. The copolymerizable monomer is more preferably a monomer containing a hydroxyl group-containing monomer and/or a nitrogen atom-containing ring.
作為含有羥基之單體，例如可例舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯及(甲基)丙烯酸(4-羥基甲基環己基)甲酯。含有羥基之單體較佳為使用(甲基)丙烯酸2-羥基乙酯，更佳為使用丙烯酸2-羥基乙酯。Examples of hydroxyl-containing monomers include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylic acid 3-Hydroxypropyl, 4-Hydroxybutyl (meth)acrylate, 6-Hydroxyhexyl (meth)acrylate, 8-Hydroxyoctyl (meth)acrylate, 10-Hydroxydecyl (meth)acrylate, 12-Hydroxylauryl (meth)acrylate and (4-hydroxymethylcyclohexyl)methyl (meth)acrylate. As the hydroxyl group-containing monomer, it is preferable to use 2-hydroxyethyl (meth)acrylate, more preferably to use 2-hydroxyethyl acrylate.
就向丙烯酸聚合物導入交聯結構及確保可變色黏著片材X之凝聚力之觀點而言，第1單體成分中之含有羥基之單體之比率較佳為1質量%以上，更佳為3質量%以上，進而較佳為5質量%以上。就調整丙烯酸聚合物之極性之觀點而言，該比率較佳為30質量%以下，更佳為20質量%以下。丙烯酸聚合物之極性與可變色黏著片材X中之各種添加劑成分與丙烯酸聚合物之相容性有關。From the viewpoint of introducing a crosslinked structure into the acrylic polymer and ensuring the cohesion of the color-variable adhesive sheet X, the ratio of the hydroxyl group-containing monomer in the first monomer component is preferably at least 1% by mass, more preferably 3% by mass. mass % or more, and more preferably 5 mass % or more. From the viewpoint of adjusting the polarity of the acrylic polymer, the ratio is preferably at most 30% by mass, more preferably at most 20% by mass. The polarity of the acrylic polymer is related to the compatibility of various additives in the color-changing adhesive sheet X and the acrylic polymer.
作為具有含有氮原子之環之單體，例如可例舉：N-乙烯基-2-吡咯啶酮、N-甲基乙烯基吡咯啶酮、N-乙烯基吡啶、N-乙烯基哌啶酮、N-乙烯基嘧啶、N-乙烯基哌𠯤、N-乙烯基吡𠯤、N-乙烯基吡咯、N-乙烯基咪唑、N-乙烯基㗁唑、N-(甲基)丙烯醯基-2-吡咯啶酮、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯啶、N-乙烯基𠰌啉、N-乙烯基-3-𠰌啉酮、N-乙烯基-2-己內醯胺、N-乙烯基-1,3-㗁 𠯤-2-酮、N-乙烯基-3,5-𠰌啉二酮、N-乙烯基吡唑、N-乙烯基異㗁唑、N-乙烯基噻唑及N-乙烯基異噻唑。具有含有氮原子之環之單體較佳為使用N-乙烯基-2-吡咯啶酮。Examples of monomers having a nitrogen atom-containing ring include: N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone , N-vinylpyrimidine, N-vinylpiperazole, N-vinylpyrrole, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryl- 2-pyrrolidone, N-(meth)acrylpiperidine, N-(meth)acrylpyrrolidine, N-vinyl 𠰌line, N-vinyl-3-𠰌linone, N- Vinyl-2-caprolactam, N-vinyl-1,3-㗁𠯤-2-one, N-vinyl-3,5-𠰌linedione, N-vinylpyrazole, N-ethylene Isoxazole, N-vinylthiazole and N-vinylisothiazole. As a monomer having a nitrogen atom-containing ring, N-vinyl-2-pyrrolidone is preferably used.
就確保可變色黏著片材X中之凝聚力及確保可變色黏著片材X對被黏著體之密接力之觀點而言，第1單體成分中之具有含有氮原子之環之單體之比率較佳為1質量%以上，更佳為3質量%以上，進而較佳為5質量%以上。就調整丙烯酸聚合物之玻璃轉移溫度及調整丙烯酸聚合物之極性之觀點而言，該比率較佳為30質量%以下，更佳為20質量%以下。From the viewpoint of ensuring the cohesion in the color-changing adhesive sheet X and the adhesion of the color-changing adhesive sheet X to the adherend, the ratio of the monomer having a ring containing a nitrogen atom in the first monomer component is higher than that of the first monomer component. It is preferably at least 1% by mass, more preferably at least 3% by mass, and still more preferably at least 5% by mass. From the viewpoint of adjusting the glass transition temperature of the acrylic polymer and adjusting the polarity of the acrylic polymer, the ratio is preferably at most 30% by mass, more preferably at most 20% by mass.
作為含有羧基之單體，例如可例舉：丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、馬來酸、富馬酸、丁烯酸及異丁烯酸。Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and methacrylic acid.
就向丙烯酸聚合物導入交聯結構、確保可變色黏著片材X中之凝聚力及確保可變色黏著片材X對被黏著體之密接力之觀點而言，第1單體成分中之含有羧基之單體之比率較佳為1質量%以上，更佳為3質量%以上，進而較佳為5質量%以上。就調整丙烯酸聚合物之玻璃轉移溫度及避免因酸而腐蝕被黏著體之危險之觀點，該比率較佳為30質量%以下，更佳為20質量%以下。From the viewpoint of introducing a cross-linked structure into the acrylic polymer, securing the cohesion in the color-changing adhesive sheet X, and ensuring the adhesion of the color-changing adhesive sheet X to the adherend, the carboxyl group-containing substance in the first monomer component The ratio of the monomer is preferably at least 1% by mass, more preferably at least 3% by mass, and still more preferably at least 5% by mass. From the viewpoint of adjusting the glass transition temperature of the acrylic polymer and avoiding the risk of corrosion of the adherend due to acid, the ratio is preferably at most 30% by mass, more preferably at most 20% by mass.
第1單體成分可包含其他共聚性單體(下述第2單體成分亦相同)。作為其他共聚性單體，例如可例舉：酸酐單體、含有磺酸基之單體、含有磷酸基之單體、含有環氧基之單體、含有氰基之單體、含有烷氧基之單體及芳香族乙烯系化合物。The first monomer component may contain other copolymerizable monomers (the same applies to the second monomer component described below). Examples of other copolymerizable monomers include: acid anhydride monomers, monomers containing sulfonic acid groups, monomers containing phosphoric acid groups, monomers containing epoxy groups, monomers containing cyano groups, monomers containing alkoxy groups Monomers and aromatic vinyl compounds.
丙烯酸聚合物可藉由使上述第1單體成分聚合來形成。作為聚合方法，例如可例舉溶液聚合、塊狀聚合及乳化聚合，較佳為例舉溶液聚合。聚合起始劑例如使用熱聚合起始劑。相對於第1單體成分100質量份，聚合起始劑之使用量例如為0.05質量份以上，又，例如為1質量份以下。An acrylic polymer can be formed by polymerizing the above-mentioned first monomer component. As a polymerization method, for example, solution polymerization, block polymerization, and emulsion polymerization are mentioned, Preferably, solution polymerization is mentioned. As a polymerization initiator, for example, a thermal polymerization initiator is used. The usage-amount of a polymerization initiator is 0.05 mass part or more with respect to 100 mass parts of 1st monomer components, and is 1 mass part or less, for example.
作為熱聚合起始劑，例如可例舉：偶氮聚合起始劑及過氧化物聚合起始劑。作為偶氮聚合起始劑，例如可例舉：2,2'-偶氮二異丁腈、2,2'-偶氮雙-2-甲基丁腈、2,2'-偶氮雙(2-甲基丙酸)二甲酯、4,4'-偶氮雙-4-氰基戊酸、偶氮二異戊腈、2,2'-偶氮雙(2-脒基丙烷)二鹽酸鹽、2,2'-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2'-偶氮雙(2-甲基丙脒)二硫酸鹽及2,2'-偶氮雙(N,N'-二亞甲基異丁基脒)二鹽酸鹽。作為過氧化物聚合起始劑，例如可例舉：過氧化二苯甲醯、過氧化順丁烯二酸第三丁酯及過氧化月桂醯。As a thermal polymerization initiator, an azo polymerization initiator and a peroxide polymerization initiator are mentioned, for example. As an azo polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis( Dimethyl 2-methylpropionate, 4,4'-azobis-4-cyanopentanoic acid, azobisisovaleronitrile, 2,2'-azobis(2-amidinopropane)di Hydrochloride, 2,2'-Azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-Azobis(2-methyl propionamidine) disulfate and 2,2'-azobis(N,N'-dimethyleneisobutylamidine) dihydrochloride. As a peroxide polymerization initiator, dibenzoyl peroxide, t-butyl peroxymaleate, and lauryl peroxide may be mentioned, for example.
就確保可變色黏著片材X中之凝聚力之觀點而言，丙烯酸聚合物之重量平均分子量較佳為10萬以上，更佳為30萬以上，進而較佳為50萬以上。該重量平均分子量較佳為500萬以下，更佳為300萬以下，進而較佳為200萬以下。丙烯酸聚合物之重量平均分子量係藉由凝膠浸透層析法(GPC)進行測定並藉由聚苯乙烯換算而算出。From the viewpoint of securing the cohesive force in the color-changing adhesive sheet X, the weight average molecular weight of the acrylic polymer is preferably at least 100,000, more preferably at least 300,000, and still more preferably at least 500,000. The weight average molecular weight is preferably at most 5 million, more preferably at most 3 million, further preferably at most 2 million. The weight average molecular weight of the acrylic polymer was measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.
丙烯酸聚合物之玻璃轉移溫度(Tg)較佳為0℃以下，更佳為-10℃以下，進而較佳為-20℃以下。該玻璃轉移溫度例如為-80℃以上。The glass transition temperature (Tg) of the acrylic polymer is preferably at most 0°C, more preferably at most -10°C, further preferably at most -20°C. The glass transition temperature is, for example, -80°C or higher.
聚合物之玻璃轉移溫度(Tg)可使用基於下述Fox公式求出之玻璃轉移溫度(理論值)。Fox公式係聚合物之玻璃轉移溫度Tg與構成該聚合物之單體之均聚物之玻璃轉移溫度Tgi之關係式。於下述Fox公式中，Tg表示聚合物之玻璃轉移溫度(℃)，Wi表示構成該聚合物之單體i之重量分率，Tgi表示由單體i所形成之均聚物之玻璃轉移溫度(℃)。均聚物之玻璃轉移溫度可使用文獻值，例如於「聚合物手冊(Polymer Handbook)」(第4版，John Wiley & Sons, Inc.，1999年)及「新高分子文庫7 塗料用合成樹脂入門」(北岡協三著，高分子刊行會，1995年)中例舉了各種均聚物之玻璃轉移溫度。另一方面，單體之均聚物之玻璃轉移溫度亦可藉由日本專利特開2007-51271號公報中具體記載之方法求出。As the glass transition temperature (Tg) of the polymer, the glass transition temperature (theoretical value) obtained based on the following Fox formula can be used. The Fox formula is a relationship between the glass transition temperature Tg of a polymer and the glass transition temperature Tgi of a homopolymer of monomers constituting the polymer. In the following Fox formula, Tg represents the glass transition temperature (°C) of the polymer, Wi represents the weight fraction of monomer i constituting the polymer, and Tgi represents the glass transition temperature of the homopolymer formed by monomer i (℃). The glass transition temperature of homopolymers can use literature values, such as in "Polymer Handbook (Polymer Handbook)" (4th edition, John Wiley & Sons, Inc., 1999) and "New Polymer Library 7 Introduction to Synthetic Resins for Coatings "(Kyoko Kitaoka Sanzu, Polymer Press, 1995) exemplifies the glass transition temperature of various homopolymers. On the other hand, the glass transition temperature of the homopolymer of the monomer can also be obtained by the method specifically described in JP-A-2007-51271.
Fox公式 1/(273＋Tg)＝Σ[Wi/(273＋Tgi)]Fox formula 1/(273+Tg)=Σ[Wi/(273+Tgi)]
就向基礎聚合物導入交聯結構之觀點而言，第1黏著性組合物可含有交聯劑。作為交聯劑，例如可例舉：異氰酸酯交聯劑、環氧交聯劑、㗁唑啉交聯劑、氮丙啶交聯劑、碳二醯亞胺交聯劑及金屬螯合物交聯劑。交聯劑可單獨使用，亦可倂用兩種以上。From the viewpoint of introducing a crosslinked structure into the base polymer, the first adhesive composition may contain a crosslinking agent. Examples of crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, carbodiimide crosslinking agents, and metal chelate crosslinking agents. agent. The crosslinking agent may be used alone or in combination of two or more.
作為異氰酸酯交聯劑，例如可例舉：甲苯二異氰酸酯、六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、苯二甲基二異氰酸酯、氫化苯二甲基二異氰酸酯、二苯基甲烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、四甲基苯二甲基二異氰酸酯、萘二異氰酸酯、三苯基甲烷三異氰酸酯及聚亞甲基聚苯基異氰酸酯。又，作為異氰酸酯交聯劑，亦可例舉該等異氰酸酯之衍生物。作為該異氰酸酯衍生物，例如可例舉異氰尿酸酯改性體及多元醇改性體。作為異氰酸酯交聯劑之市售品，例如可例舉：Coronate L(甲苯二異氰酸酯之三羥甲基丙烷加成體，東曹公司製造)、Coronate HL(六亞甲基二異氰酸酯之三羥甲基丙烷加成體，東曹公司製造)、Coronate HX(六亞甲基二異氰酸酯之異氰尿酸酯體，東曹公司製造)及Takenate D110N(苯二甲基二異氰酸酯之三羥甲基丙烷加成體，三井化學公司製造)。As the isocyanate crosslinking agent, for example, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate , hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate and polymethylene polyphenylisocyanate. Moreover, as an isocyanate crosslinking agent, the derivative|guide_body of these isocyanate is also mentioned. As this isocyanate derivative, an isocyanurate modified body and a polyol modified body are mentioned, for example. Examples of commercially available isocyanate crosslinking agents include: Coronate L (trimethylolpropane adduct of toluene diisocyanate, manufactured by Tosoh Corporation), Coronate HL (trimethylol propane adduct of hexamethylene diisocyanate) propane adduct, manufactured by Tosoh Corporation), Coronate HX (isocyanurate body of hexamethylene diisocyanate, manufactured by Tosoh Corporation) and Takenate D110N (trimethylolpropane of xylylene diisocyanate Additive, manufactured by Mitsui Chemicals).
作為環氧交聯劑，可例舉：雙酚A、表氯醇型環氧樹脂、伸乙基縮水甘油醚、聚乙二醇二縮水甘油醚、甘油二縮水甘油醚、甘油三縮水甘油醚、1,6-己二醇縮水甘油醚、三羥甲基丙烷三縮水甘油醚、二縮水甘油基苯胺、二胺縮水甘油胺、N,N,N',N'-四縮水甘油基間苯二甲胺及1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷。Examples of the epoxy crosslinking agent include bisphenol A, epichlorohydrin type epoxy resin, ethylidene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether , 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N,N,N',N'-tetraglycidyl m-phenyl Dimethylamine and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane.
就確保可變色黏著片材X之凝聚力之觀點而言，相對於基礎聚合物100質量份，交聯劑之調配量較佳為0.01質量份以上，更佳為0.05質量份以上，進而較佳為0.07質量份以上。就確保可變色黏著片材X之良好之黏性之觀點而言，相對於基礎聚合物100質量份，交聯劑之調配量較佳為10質量份以下，更佳為5質量份以下，進而較佳為3質量份以下。From the viewpoint of ensuring the cohesion of the color-changing adhesive sheet X, the compounding amount of the crosslinking agent is preferably at least 0.01 parts by mass, more preferably at least 0.05 parts by mass, and still more preferably at least 0.05 parts by mass relative to 100 parts by mass of the base polymer. 0.07 parts by mass or more. From the viewpoint of ensuring good viscosity of the color-changing adhesive sheet X, the compounding amount of the crosslinking agent is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the base polymer. Preferably it is 3 parts by mass or less.
於向基礎聚合物導入交聯結構之情形時，為了有效進行交聯反應，可使用交聯觸媒。作為交聯觸媒，例如可例舉二月桂酸二丁基錫、鈦酸四正丁酯、鈦酸四異丙酯、三乙醯丙酮鐵及氧化丁基錫，較佳為使用二月桂酸二丁基錫。相對於基礎聚合物100質量份，交聯觸媒之使用量例如為0.0001質量份以上，又，例如為1質量份以下。In the case of introducing a crosslinked structure into the base polymer, a crosslinking catalyst can be used in order to efficiently advance the crosslinking reaction. Examples of the crosslinking catalyst include dibutyltin dilaurate, tetra-n-butyl titanate, tetraisopropyl titanate, iron triacetylacetonate, and butyltin oxide, and dibutyltin dilaurate is preferably used. The usage-amount of a crosslinking catalyst is 0.0001 mass part or more with respect to 100 mass parts of base polymers, and is 1 mass part or less, for example.
於使用交聯觸媒之情形時，可將可事後自第1黏著性組合物中去除之交聯抑制劑調配於第1黏著性組合物中。於使用二月桂酸二丁基錫作為交聯觸媒之情形時，交聯抑制劑較佳為使用乙醯丙酮。於該情形時，在第1黏著性組合物中，乙醯丙酮配位於二月桂酸二丁基錫，抑制交聯劑與基礎聚合物之交聯反應之進行。於可變色黏著片材X之下述製造過程中，向基材膜上塗佈第1黏著性組合物而形成塗膜後，藉由於所需時間進行加熱，可使乙醯丙酮揮發而自塗膜中去除。藉此，可進行交聯劑之交聯反應。In the case of using a crosslinking catalyst, a crosslinking inhibitor that can be removed from the first adhesive composition afterward can be formulated in the first adhesive composition. When dibutyltin dilaurate is used as the crosslinking catalyst, it is preferable to use acetylacetone as the crosslinking inhibitor. In this case, in the first adhesive composition, acetylacetone coordinates with dibutyltin dilaurate to suppress the progress of the crosslinking reaction between the crosslinking agent and the base polymer. In the following production process of the color-changing adhesive sheet X, after the first adhesive composition is applied to the base film to form a coating film, acetylacetone can be volatilized and self-coated by heating for a required period of time. removed from the film. Thereby, the crosslinking reaction of the crosslinking agent can proceed.
相對於交聯觸媒100質量份，交聯抑制劑之調配量較佳為100質量份以上，更佳為1000質量份以上。又，該調配量例如為5000質量份以下。The compounded amount of the crosslinking inhibitor is preferably at least 100 parts by mass, more preferably at least 1000 parts by mass, relative to 100 parts by mass of the crosslinking catalyst. Moreover, this compounding quantity is 5000 mass parts or less, for example.
作為第1化合物，例如可例舉酸產生劑。作為酸產生劑，例如可例舉光酸產生劑及熱酸產生劑。As a 1st compound, an acid generator is mentioned, for example. As an acid generator, a photoacid generator and a thermal acid generator are mentioned, for example.
光酸產生劑藉由照射特定波長或波長範圍之光而被激發，引起酸產生反應，產生酸。酸產生反應例如為光酸產生劑之分解反應。使酸產生反應高效率地發生之光之波長根據光酸產生劑之種類而不同。The photoacid generator is excited by irradiating light of a specific wavelength or wavelength range, causing an acid reaction to generate acid. The acid generation reaction is, for example, a decomposition reaction of a photoacid generator. The wavelength of light for efficiently generating an acid generation reaction differs depending on the type of photoacid generator.
作為光酸產生劑，例如可例舉藉由紫外線照射而產生酸之鎓化合物。鎓化合物例如可以鎓陽離子與陰離子之鎓鹽之形態提供。作為鎓陽離子，例如可例舉鋶及錪。作為陰離子，例如可例舉：Cl -、Br -、I -、ZnCl 3 -、HSO 3 -、BF 4 -、PF 6 -、AsF 6 -、SbF 6 -、CH 3SO 3 -、CF 3SO 3 -、C 4F 9HSO 3 -、(C 6F 5) 4B -及(C 4H 9) 4B -。光酸產生劑可單獨使用，亦可倂用兩種以上。光酸產生劑較佳為使用鋶與C 4F 9HSO 3 -之鎓鹽及/或錪鹽與C 4F 9HSO 3 -之鎓鹽。 As a photoacid generator, the onium compound which generate|occur|produces acid by ultraviolet-ray irradiation is mentioned, for example. The onium compound can be provided in the form of an onium salt of an onium cation and anion, for example. As the onium cation, for example, caldium and iodonium may be mentioned. Examples of anions include Cl - , Br - , I - , ZnCl 3 - , HSO 3 - , BF 4 - , PF 6 - , AsF 6 - , SbF 6 - , CH 3 SO 3 - , CF 3 SO 3 - , C 4 F 9 HSO 3 - , (C 6 F 5 ) 4 B - and (C 4 H 9 ) 4 B - . The photoacid generators may be used alone or in combination of two or more. The photoacid generator is preferably an onium salt of perium and C 4 F 9 HSO 3 - and/or an onium salt of odonium and C 4 F 9 HSO 3 - .
相對於基礎聚合物100質量份，光酸產生劑之調配量較佳為1質量份以上，更佳為2質量份以上，進而較佳為5質量份以上，特佳為7質量份以上。該調配量較佳為20質量份以下，更佳為15質量份以下，進而較佳為12質量份以下。The compounded amount of the photoacid generator is preferably at least 1 part by mass, more preferably at least 2 parts by mass, further preferably at least 5 parts by mass, particularly preferably at least 7 parts by mass, based on 100 parts by mass of the base polymer. The compounding amount is preferably at most 20 parts by mass, more preferably at most 15 parts by mass, further preferably at most 12 parts by mass.
又，相對於下述顯色性化合物100質量份，光酸產生劑之調配量較佳為100質量份以上，更佳為200質量份以上，進而較佳為300質量份以上，特佳為330質量份以上。該調配量較佳為1000質量份以下，更佳為700質量份以下，進而較佳為500質量份以下。In addition, the blending amount of the photoacid generator is preferably at least 100 parts by mass, more preferably at least 200 parts by mass, further preferably at least 300 parts by mass, particularly preferably at least 330 parts by mass, relative to 100 parts by mass of the following color-forming compound. parts by mass or more. The compounding amount is preferably at most 1000 parts by mass, more preferably at most 700 parts by mass, still more preferably at most 500 parts by mass.
作為第2化合物，例如可例舉藉由與酸之反應而顯色之顯色性化合物。作為該顯色性化合物，例如可例舉：隱色素、三芳基甲烷色素、二苯基甲烷色素、螢烷色素、螺哌喃色素及玫瑰紅色素。 顯色性化合物可單獨使用，亦可倂用兩種以上。 As a 2nd compound, the color-developing compound which develops a color by reaction with an acid is mentioned, for example. Examples of the color-forming compound include cryptochromes, triarylmethane dyes, diphenylmethane dyes, fluorane dyes, spiropyran dyes, and rose bengal. The color-forming compounds may be used alone or in combination of two or more.
作為隱色素，例如可例舉：2'-苯胺基-6'-(N-乙基-N-異戊基胺基)-3'-甲基螺[酞內酯-3,9'-[9H]𠮿
作為三芳基甲烷色素，例如可例舉p,p',p''-三-二甲基胺基三苯基甲烷。作為二苯基甲烷色素，例如可例舉4,4-雙-二甲基胺基苯基二苯甲基苄醚。作為螢烷色素，例如可例舉3-二乙基胺基-6-甲基-7-氯螢烷。作為螺哌喃色素，例如可例舉3-甲基螺二萘并哌喃。作為玫瑰紅色素，例如可例舉玫瑰紅-B-苯胺基內醯胺。As a triaryl methane dye, p,p',p''-tri-dimethylaminotriphenylmethane can be mentioned, for example. As a diphenylmethane dye, 4,4-bis- dimethylaminophenyl benzhydryl benzyl ether is mentioned, for example. As a fluorane dye, 3-diethylamino-6-methyl-7-chlorofluorane is mentioned, for example. As the spiropyran dye, 3-methylspirobinapyran may, for example, be mentioned. As rose bengal, rose bengal-B-anilinolactam is mentioned, for example.
就確保可變色黏著片材X中良好之著色性之觀點而言，顯色性化合物較佳為使用隱色素，更佳為使用2'-苯胺基-6'-(N-乙基-N-異戊基胺基)-3'-甲基螺[酞內酯-3,9'-[9H]𠮿
相對於基礎聚合物100質量份，顯色性化合物之調配量較佳為0.5質量份以上，更佳為1質量份以上。該調配量較佳為10質量份以下，更佳為7質量份以下。The compounded amount of the color-forming compound is preferably at least 0.5 parts by mass, more preferably at least 1 part by mass, relative to 100 parts by mass of the base polymer. The compounding amount is preferably at most 10 parts by mass, more preferably at most 7 parts by mass.
第1黏著性組合物亦可視需要含有其他成分。作為其他成分，例如可例舉：矽烷偶合劑、黏著性賦予劑、塑化劑、軟化劑、抗氧化劑、界面活性劑、增感劑及抗靜電劑。The 1st adhesive composition may contain other components as needed. As other components, a silane coupling agent, an adhesiveness imparting agent, a plasticizer, a softener, an antioxidant, a surfactant, a sensitizer, and an antistatic agent are mentioned, for example.
可變色黏著片材X例如可藉由如下方式製造：將上述第1黏著性組合物之清漆塗佈於基材膜上而形成塗膜後，使該塗膜乾燥。作為基材膜，例如可例舉具有可撓性之塑膠膜。作為該塑膠膜，例如可例舉：聚對苯二甲酸乙二酯膜、聚乙烯膜、聚丙烯膜及聚酯膜。基材膜之厚度例如為3 μm以上，又，例如為200 μm以下。基材膜之表面較佳為經離型處理。The color-variable adhesive sheet X can be produced, for example, by applying the varnish of the above-mentioned first adhesive composition on a base film to form a coating film, and then drying the coating film. As a base film, the plastic film which has flexibility is mentioned, for example. As this plastic film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and a polyester film are mentioned, for example. The thickness of the base film is, for example, 3 μm or more, and, for example, 200 μm or less. The surface of the base film is preferably subjected to release treatment.
於第1黏著性組合物包含交聯劑之情形時，與上述乾燥同時地進行交聯反應，或者藉由其後之老化進行交聯反應。老化條件可根據交聯劑之種類適當地設定。老化溫度例如為20℃～160℃。老化時間例如為1分鐘～7天。When the first adhesive composition contains a crosslinking agent, the crosslinking reaction proceeds simultaneously with the above-mentioned drying, or proceeds through subsequent aging. Aging conditions can be appropriately set according to the type of crosslinking agent. The aging temperature is, for example, 20°C to 160°C. The aging time is, for example, 1 minute to 7 days.
可於老化前或老化後，進一步於基材膜上之可變色黏著片材X上積層剝離膜(剝離襯墊)。剝離膜係實施過表面離型處理之可撓性塑膠膜。作為剝離膜，例如可例舉以上關於基材膜敍述之上述塑膠膜。A release film (release liner) may be further laminated on the color-changing adhesive sheet X on the base film before or after aging. The release film is a flexible plastic film with a surface release treatment. As the peeling film, for example, the above-mentioned plastic film described above with respect to the base film may be mentioned.
以如上方式，可製造藉由剝離膜被覆保護黏著面之可變色黏著片材X。在使用可變色黏著片材X時，各剝離膜視需要自可變色黏著片材X剝離。In this manner, the color-changing adhesive sheet X in which the adhesive surface is covered and protected with a release film can be produced. When using the color-changing adhesive sheet X, each peeling film is peeled from the color-changing adhesive sheet X as needed.
就確保對被黏著體之充分之黏著性之觀點而言，可變色黏著片材X之厚度較佳為10 μm以上，更佳為15 μm以上。就可變色黏著片材X之處理性之觀點而言，可變色黏著片材X之厚度較佳為300 μm以下，更佳為200 μm以下，進而較佳為100 μm以下，特佳為50 μm以下。From the viewpoint of securing sufficient adhesiveness to the adherend, the thickness of the color-changing adhesive sheet X is preferably at least 10 μm, more preferably at least 15 μm. From the viewpoint of the rationality of the color-changing adhesive sheet X, the thickness of the color-changing adhesive sheet X is preferably 300 μm or less, more preferably 200 μm or less, further preferably 100 μm or less, most preferably 50 μm the following.
可變色黏著片材X於波長400～700 nm下之平均透過率(外部刺激賦予前之平均透過率)較佳為80%以上，更佳為85%以上，進而較佳為90%以上，特佳為95%以上。此種構成適於在將可變色黏著片材X貼合於被黏著體之後檢查可變色黏著片材X與被黏著體之間有無異物及氣泡。波長400～700 nm下之平均透過率可藉由以下關於下述實施例敍述之方法來測定。The average transmittance of the color-changing adhesive sheet X at a wavelength of 400 to 700 nm (average transmittance before external stimulation is applied) is preferably at least 80%, more preferably at least 85%, still more preferably at least 90%, especially Better than 95%. Such a configuration is suitable for checking whether there are foreign substances and air bubbles between the color-changing adhesive sheet X and the adherend after the color-changing adhesive sheet X is attached to the adherend. The average transmittance at a wavelength of 400-700 nm can be measured by the method described in the following examples.
形成著色性低下片材Y之第2黏著性組合物含有基礎聚合物。作為基礎聚合物，可例舉以上關於第1黏著性組合物敍述之基礎聚合物，較佳為使用丙烯酸聚合物(第2丙烯酸聚合物)。The 2nd adhesive composition which forms the low coloring property sheet|seat Y contains a base polymer. The base polymer may, for example, be the base polymer described above for the first adhesive composition, and it is preferable to use an acrylic polymer (second acrylic polymer).
形成第2丙烯酸聚合物之單體成分(第2單體成分)包含(甲基)丙烯酸烷基酯。作為該(甲基)丙烯酸烷基酯，例如可例舉以上關於第1丙烯酸聚合物敍述之(甲基)丙烯酸烷基酯，較佳為使用具有碳數6～18之烷基之丙烯酸烷基酯，更佳為使用丙烯酸2-乙基己酯及/或丙烯酸異硬脂酯。The monomer component forming the second acrylic polymer (second monomer component) contains an alkyl (meth)acrylate. As the alkyl (meth)acrylate, for example, the alkyl (meth)acrylate described above for the first acrylic polymer can be mentioned, and it is preferable to use an alkyl acrylate having an alkyl group having 6 to 18 carbon atoms. ester, more preferably 2-ethylhexyl acrylate and/or isostearyl acrylate.
就使著色性低下片材Y適當地表現出黏著性等基本特性之觀點而言，第2單體成分中之(甲基)丙烯酸烷基酯之比率較佳為50質量%以上，更佳為60質量%以上，進而較佳為70質量%以上。該比率例如為99質量%以下。From the viewpoint of appropriately expressing basic properties such as adhesiveness of the poorly colored sheet Y, the ratio of the alkyl (meth)acrylate in the second monomer component is preferably at least 50% by mass, more preferably 60 mass % or more, and more preferably 70 mass % or more. This ratio is, for example, 99% by mass or less.
第2單體成分可包含可與(甲基)丙烯酸烷基酯共聚之共聚性單體。作為該共聚性單體，可例舉以上關於第1丙烯酸聚合物敍述之共聚性單體，較佳為使用含有極性基之單體，更佳為使用選自由含有羥基之單體、具有含有氮原子之環之單體及含有羧基之單體所組成之群中之至少一種。第2單體成分中之含有羥基之單體較佳為使用丙烯酸2-羥基乙酯及/或丙烯酸4-羥基丁酯。第2單體成分中之具有含有氮原子之環之單體較佳為使用N-乙烯基-2-吡咯啶酮。第2單體成分中之含有羧基之單體較佳為使用丙烯酸。作為包含含有極性基之單體之第2單體成分之共聚物的丙烯酸聚合物為含有極性基之聚合物。此種丙烯酸聚合物有助於自可變色黏著片材X中將上述光酸產生劑等第1化合物提取至著色性低下片材Y。The second monomer component may contain a copolymerizable monomer copolymerizable with an alkyl (meth)acrylate. As the copolymerizable monomer, the copolymerizable monomers described above for the first acrylic polymer can be mentioned, and it is preferable to use a monomer containing a polar group, and it is more preferable to use a monomer selected from monomers containing a hydroxyl At least one of the group consisting of monomers of ring atoms and monomers containing carboxyl groups. It is preferable to use 2-hydroxyethyl acrylate and/or 4-hydroxybutyl acrylate as the hydroxyl group-containing monomer in the second monomer component. It is preferable to use N-vinyl-2-pyrrolidone as a monomer having a nitrogen atom-containing ring in the second monomer component. It is preferable to use acrylic acid as the carboxyl group-containing monomer in the second monomer component. The acrylic polymer, which is a copolymer of the second monomer component containing a polar group-containing monomer, is a polar group-containing polymer. Such an acrylic polymer contributes to the extraction of the first compound such as the above-mentioned photoacid generator from the color-variable adhesive sheet X to the sheet Y having low colorability.
就確保丙烯酸聚合物之凝聚力之觀點及調整丙烯酸聚合物之極性之觀點而言，第2單體成分中之含有極性基之單體之比率較佳為1質量%以上，更佳為3質量%以上，進而較佳為5質量%以上，又，較佳為40質量%以下，更佳為30質量%以下。於著色性低下片材Y為提取用片材之情形時，就確保光酸產生劑自可變色黏著片材X向著色性低下片材Y轉移之容易性(提取性)之觀點而言，第2單體成分中之含有極性基之單體之比率較佳為5質量%以上，更佳為10質量%以上，進而較佳為15質量%以上，又，較佳為50質量%以下，更佳為35質量%以下。From the viewpoint of securing the cohesion of the acrylic polymer and adjusting the polarity of the acrylic polymer, the ratio of the polar group-containing monomer in the second monomer component is preferably at least 1% by mass, more preferably 3% by mass Above, more preferably at least 5% by mass, and preferably at most 40% by mass, more preferably at most 30% by mass. In the case where the low-coloring sheet Y is an extraction sheet, from the viewpoint of securing the ease of transfer of the photoacid generator from the color-changing adhesive sheet X to the low-coloring sheet Y (extractability), the second 2. The ratio of the polar group-containing monomer in the monomer component is preferably at least 5% by mass, more preferably at least 10% by mass, further preferably at least 15% by mass, and more preferably at most 50% by mass, and more preferably at least 50% by mass. Preferably, it is 35% by mass or less.
第2丙烯酸聚合物可藉由使上述第2單體成分聚合來形成。作為聚合方法，例如可例舉溶液聚合、塊狀聚合及乳化聚合，較佳為例舉溶液聚合。聚合起始劑例如使用上述熱聚合起始劑。相對於第2單體成分100質量份，聚合起始劑之使用量例如為0.05質量份以上，又，例如為1質量份以下。The second acrylic polymer can be formed by polymerizing the above-mentioned second monomer component. As a polymerization method, for example, solution polymerization, block polymerization, and emulsion polymerization are mentioned, Preferably, solution polymerization is mentioned. As the polymerization initiator, for example, the thermal polymerization initiator described above is used. The usage-amount of a polymerization initiator is 0.05 mass part or more with respect to 100 mass parts of 2nd monomer components, and is 1 mass part or less, for example.
就確保著色性低下片材Y之凝聚力之觀點而言，第2丙烯酸聚合物之重量平均分子量較佳為10萬以上，更佳為30萬以上，進而較佳為50萬以上。該重量平均分子量較佳為500萬以下，更佳為300萬以下，進而較佳為200萬以下。The weight average molecular weight of the second acrylic polymer is preferably at least 100,000, more preferably at least 300,000, and still more preferably at least 500,000, from the viewpoint of ensuring the cohesion of the low-coloring sheet Y. The weight average molecular weight is preferably at most 5 million, more preferably at most 3 million, further preferably at most 2 million.
第2丙烯酸聚合物之玻璃轉移溫度(Tg)較佳為0℃以下，更佳為-10℃以下，進而較佳為-20℃以下。該玻璃轉移溫度例如為-80℃以上。The glass transition temperature (Tg) of the second acrylic polymer is preferably at most 0°C, more preferably at most -10°C, further preferably at most -20°C. The glass transition temperature is, for example, -80°C or higher.
就向基礎聚合物導入交聯結構之觀點而言，第2黏著性組合物可含有交聯劑。作為交聯劑，例如可例舉：上述異氰酸酯交聯劑、上述環氧交聯劑、㗁唑啉交聯劑、氮丙啶交聯劑、碳二醯亞胺交聯劑及金屬螯合物交聯劑。交聯劑可單獨使用，亦可倂用兩種以上。就確保著色性低下片材Y之凝聚力之觀點而言，相對於基礎聚合物100質量份，交聯劑之調配量較佳為0.01質量份以上，更佳為0.05質量份以上，進而較佳為0.07質量份以上。就確保著色性低下片材Y之良好之黏性之觀點而言，相對於基礎聚合物100質量份，交聯劑之調配量較佳為10質量份以下，更佳為5質量份以下，進而較佳為3質量份以下。From the viewpoint of introducing a crosslinked structure into the base polymer, the second adhesive composition may contain a crosslinking agent. As the crosslinking agent, for example, the above-mentioned isocyanate crosslinking agent, the above-mentioned epoxy crosslinking agent, azoline crosslinking agent, aziridine crosslinking agent, carbodiimide crosslinking agent, and metal chelate crosslinking agent. The crosslinking agent may be used alone or in combination of two or more. From the viewpoint of securing the cohesive force of the poorly colored sheet Y, the amount of the crosslinking agent is preferably at least 0.01 parts by mass, more preferably at least 0.05 parts by mass, and still more preferably at least 0.05 parts by mass, based on 100 parts by mass of the base polymer. 0.07 parts by mass or more. From the viewpoint of ensuring good viscosity of the low-coloring sheet Y, the blending amount of the crosslinking agent is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the base polymer, and further Preferably it is 3 parts by mass or less.
於向基礎聚合物導入交聯結構之情形時，為了有效進行交聯反應，可使用交聯觸媒。作為該交聯觸媒，例如可例舉以上關於第1黏著性組合物敍述之交聯劑。相對於基礎聚合物100質量份，交聯觸媒之使用量例如為0.0001質量份以上，又，例如為1質量份以下。於使用交聯觸媒之情形時，可將可事後自第2黏著性組合物中去除之交聯抑制劑調配於第2黏著性組合物中。作為該交聯抑制劑，可例舉以上關於第1黏著性組合物敍述之交聯抑制劑。相對於交聯觸媒100質量份，交聯抑制劑之調配量較佳為100質量份以上，更佳為1000質量份以上。又，該調配量例如為5000質量份以下。In the case of introducing a crosslinked structure into the base polymer, a crosslinking catalyst can be used in order to efficiently advance the crosslinking reaction. As this crosslinking catalyst, the crosslinking agent mentioned above about the 1st adhesive composition is mentioned, for example. The usage-amount of a crosslinking catalyst is 0.0001 mass part or more with respect to 100 mass parts of base polymers, and is 1 mass part or less, for example. In the case of using a crosslinking catalyst, a crosslinking inhibitor that can be removed from the second adhesive composition afterward can be formulated in the second adhesive composition. As this crosslinking inhibitor, what was mentioned above about the 1st adhesive composition is mentioned. The compounded amount of the crosslinking inhibitor is preferably at least 100 parts by mass, more preferably at least 1000 parts by mass, relative to 100 parts by mass of the crosslinking catalyst. Moreover, this compounding quantity is 5000 mass parts or less, for example.
於著色性低下片材Y為失活用片材之情形時，第2黏著性組合物進而含有著色性低下成分。於可變色黏著片材X含有光酸產生劑作為上述第1成分之情形時，作為著色性低下成分，例如可例舉：紫外線吸收劑、中和劑及自由基捕獲劑。著色性低下成分較佳為包含選自由紫外線吸收劑、中和劑及自由基捕獲劑所組成之群中之至少一種。When the coloring-reducing sheet|seat Y is a sheet|seat for deactivation, a 2nd adhesive composition contains a coloring-reducing component further. When the color-variable adhesive sheet X contains a photoacid generator as the above-mentioned first component, as the coloring-reducing component, for example, an ultraviolet absorber, a neutralizer, and a radical scavenger may be mentioned. It is preferable that the coloring property reducing component contains at least 1 sort(s) chosen from the group which consists of an ultraviolet absorber, a neutralizer, and a radical scavenger.
紫外線吸收劑於在上述第2步驟中自著色性低下片材Y導入至可變色黏著片材X之後，吸收可變色黏著片材X所受之紫外線之一部分或全部。藉由該紫外線吸收，抑制光酸產生劑受到紫外線照射時所發生之酸產生反應，從而，抑制顯色性化合物之顯色。藉此，第2步驟後之可變色黏著片材X之著色性降低。The ultraviolet absorber absorbs part or all of the ultraviolet rays received by the color-changing adhesive sheet X after being introduced from the low-coloring sheet Y to the color-changing adhesive sheet X in the above-mentioned second step. This ultraviolet absorption suppresses the acid generation reaction that occurs when the photoacid generator is irradiated with ultraviolet rays, thereby suppressing the color development of the color-forming compound. Thereby, the colorability of the color-changing adhesive sheet X after a 2nd process falls.
作為紫外線吸收劑，例如可例舉：苯并***紫外線吸收劑、二苯甲酮紫外線吸收劑、氧基二苯甲酮紫外線吸收劑、羥基苯基三𠯤紫外線吸收劑、水楊酸酯紫外線吸收劑及氰基丙烯酸酯紫外線吸收劑。As the ultraviolet absorber, for example, benzotriazole ultraviolet absorber, benzophenone ultraviolet absorber, oxybenzophenone ultraviolet absorber, hydroxyphenyl trioxetine ultraviolet absorber, salicylate ultraviolet absorber, etc. Absorbers and cyanoacrylate UV absorbers.
中和劑於在上述第2步驟中自著色性低下片材Y導入至可變色黏著片材X之後，中和光酸產生劑所產生之酸之一部分或全部。藉由該中和作用，抑制光酸產生劑受到紫外線照射時所產生之酸與顯色性化合物之反應。藉此，第2步驟後之可變色黏著片材X之著色性降低。The neutralizing agent neutralizes part or all of the acid generated by the photoacid generator after being introduced from the low-coloring sheet Y to the color-changing adhesive sheet X in the second step above. This neutralization action suppresses the reaction between the acid generated when the photoacid generator is irradiated with ultraviolet rays and the color-forming compound. Thereby, the colorability of the color-changing adhesive sheet X after a 2nd process falls.
作為中和劑，例如可例舉：顯示出鹼性之一級胺、二級胺及三級胺。作為一級胺，例如可例舉：單乙胺及單乙醇胺。作為二級胺，例如可例舉：二乙胺及二乙醇胺。作為三級胺，例如可例舉：三乙胺、三乙醇胺、N,N,N'-三甲基乙二胺、N-甲基二乙醇胺及N,N-二乙基羥基胺。As a neutralizing agent, the primary amine which shows basicity, a secondary amine, and a tertiary amine are mentioned, for example. As a primary amine, monoethylamine and monoethanolamine are mentioned, for example. As a secondary amine, diethylamine and diethanolamine are mentioned, for example. As a tertiary amine, triethylamine, triethanolamine, N,N,N'-trimethylethylenediamine, N-methyldiethanolamine, and N,N-diethylhydroxylamine are mentioned, for example.
自由基捕獲劑於在上述第2步驟中自著色性低下片材Y導入至可變色黏著片材X之後，於在光酸產生劑之酸產生反應開始時產生自由基之情形時捕捉該自由基，從而抑制酸產生反應之進行。藉此，抑制顯色性化合物之顯色，第2步驟後之可變色黏著片材X之著色性降低。The free radical scavenger captures free radicals when they are generated at the start of the acid generation reaction of the photoacid generator after introducing from the low-coloring sheet Y to the color-changing adhesive sheet X in the second step above. , thereby inhibiting the progress of the acid generation reaction. Thereby, the color development of the color-forming compound is suppressed, and the colorability of the color-changing adhesive sheet X after the 2nd step falls.
作為自由基捕獲劑，例如可例舉受阻胺化合物、受阻酚化合物、N-烴氧基化合物、萘衍生物、硫醚化合物及偕腙肼化合物，較佳為使用受阻胺化合物。The radical scavengers include, for example, hindered amine compounds, hindered phenol compounds, N-oxyl compounds, naphthalene derivatives, thioether compounds, and hydrazone compounds, and hindered amine compounds are preferably used.
相對於基礎聚合物100質量份，第2黏著性組合物中之著色性低下成分之比率較佳為0.1質量份以上，更佳為1質量份以上，進而較佳為2質量份以上。相對於基礎聚合物100質量份，該比率較佳為20質量份以下，更佳為15質量份以下，進而較佳為10質量份以下。The ratio of the coloring property-lowering component in the second adhesive composition is preferably at least 0.1 parts by mass, more preferably at least 1 part by mass, and still more preferably at least 2 parts by mass, based on 100 parts by mass of the base polymer. The ratio is preferably at most 20 parts by mass, more preferably at most 15 parts by mass, and still more preferably at most 10 parts by mass, relative to 100 parts by mass of the base polymer.
於第1區域11(已著色區域)形成前之可變色黏著片材X中調配有著色性低下成分之情形時，阻礙藉由對可變色黏著片材X賦予外部刺激來形成第1區域11。於本發明之可變色黏著片材之變色抑制方法中，在使用失活用介質作為著色性低下介質之情形時，可在第1區域11形成後向可變色黏著片材X導入著色性低下成分，故而可避免此種缺陷。When the color-changing adhesive sheet X is blended with a color-changing adhesive sheet X before the first region 11 (colored region) is formed, the formation of the
於失活用介質中，第1系統中因外部刺激賦予所導致之透過率之降低ΔT1較佳為小於第2系統中因與外部刺激賦予相同之外部刺激賦予所導致之透過率之降低ΔT2，上述第1系統中共存有第1化合物、第2化合物及著色性低下成分，上述第2系統除不存在著色性低下成分以外與第1系統相同。ΔT2與ΔT1之差(ΔT2－ΔT1)較佳為5%以上，更佳為15%以上，進而較佳為30%以上，特佳為50%以上。透過率例如為波長400～700 nm下之平均透過率，可藉由以下關於下述實施例敍述之方法來測定。此種構成適於在第2步驟中降低可變色黏著片材X之著色性。In the inactivation medium, the decrease in transmittance ΔT1 due to the application of the external stimulus in the first system is preferably smaller than the decrease ΔT2 in the transmittance due to the same external stimulus as the application of the external stimulus in the second system. In the first system, the first compound, the second compound, and the coloring-reducing component coexist, and the above-mentioned second system is the same as the first system except that the coloring-reducing component does not exist. The difference between ΔT2 and ΔT1 (ΔT2 - ΔT1 ) is preferably at least 5%, more preferably at least 15%, further preferably at least 30%, and most preferably at least 50%. The transmittance is, for example, the average transmittance at a wavelength of 400 to 700 nm, and can be measured by the method described in the following examples. Such a constitution is suitable for reducing the colorability of the color-variable adhesive sheet X in the second step.
第2黏著性組合物亦可視需要含有其他成分。作為其他成分，例如可例舉：矽烷偶合劑、黏著性賦予劑、塑化劑、軟化劑、抗氧化劑、界面活性劑及抗靜電劑。The 2nd adhesive composition may contain other components as needed. As other components, a silane coupling agent, an adhesiveness imparting agent, a plasticizer, a softener, an antioxidant, a surfactant, and an antistatic agent are mentioned, for example.
形成著色性低下片材Y之第2黏著性組合物不含上述光酸產生劑等第1化合物及上述顯色性化合物等第2化合物。又，形成作為提取用片材之著色性低下片材Y之第2黏著性組合物不含紫外線吸收劑、中和劑及自由基捕獲劑等著色性低下成分。The 2nd adhesive composition which forms the low coloring property sheet|seat Y does not contain the 1st compound, such as the said photoacid generator, and the 2nd compound, such as the said color-developing compound. Moreover, the 2nd adhesive composition which forms the low coloring property sheet Y which is an extraction sheet does not contain coloring property low components, such as an ultraviolet absorber, a neutralizer, and a radical scavenger.
著色性低下片材Y例如可藉由如下方式製造：將上述第2黏著性組合物之清漆塗佈於基材膜上而形成塗膜後，使該塗膜乾燥。具體而言，與可變色黏著片材X之上述製造方法相同。The sheet Y having low colorability can be produced by, for example, applying the varnish of the above-mentioned second adhesive composition on a base film to form a coating film, and then drying the coating film. Specifically, it is the same as the above-mentioned manufacturing method of the color-variable adhesive sheet X.
就良好地表現出降低著色性之功能之觀點而言，著色性低下片材Y之厚度較佳為10 μm以上，更佳為20 μm以上。就著色性低下片材Y之處理性之觀點而言，著色性低下片材Y之厚度較佳為300 μm以下，更佳為200 μm以下。The thickness of the low-colorability sheet Y is preferably at least 10 μm, more preferably at least 20 μm, from the viewpoint of expressing the function of reducing colorability well. From the viewpoint of the rationality of the poorly colored sheet Y, the thickness of the poorly colored sheet Y is preferably 300 μm or less, more preferably 200 μm or less.
著色性低下片材Y於波長400～700 nm下之平均透過率高於可變色黏著片材X之第1區域11於波長400～700 nm下之平均透過率，例如為40%以上，又，例如為99%以下。例如，就調整積層片材L之面方向上之第2區域12(未著色區域)部分之透過率之觀點及提昇第2區域12部分與第1區域11(已著色區域)部分之對比度差之觀點而言，著色性低下片材Y於波長400～700 nm下之平均透過率較佳為45%以上，更佳為50%以上，進而較佳為60%以上。該平均透過率例如為100%以下。例如，就防止於積層片材L之面方向上之第2區域12(未著色區域)部分上之反射之觀點及調整第2區域12部分之外觀之觀點而言，著色性低下片材Y於波長400～700 nm下之平均透過率較佳為90%以下，更佳為80%以下，進而較佳為70%以下。該平均透過率例如為50%以上。The average transmittance of the poorly colored sheet Y at a wavelength of 400 to 700 nm is higher than the average transmittance of the
於第2步驟中，如圖5所示，可於可變色黏著片材X之第1區域11與著色性低下片材X之間介存有遮罩材M之狀態下，將著色性低下片材Y貼合於可變色黏著片材X。遮罩材M例如可於形成第1區域11之前配置於可變色黏著片材X上，亦可於形成第1區域11之後配置於可變色黏著片材X上。In the second step, as shown in FIG. 5 , the color-reducing sheet can be placed in the state where the mask material M is interposed between the
遮罩材M例如為透明塑膠膜。作為塑膠膜之材料，例如可例舉：聚烯烴、聚酯、聚醯胺、聚醯亞胺、聚氯乙烯、聚偏二氯乙烯、纖維素、聚苯乙烯及聚碳酸酯。作為聚烯烴，例如可例舉聚乙烯及聚丙烯。作為聚酯，例如可例舉：聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯及聚對苯二甲酸丁二酯。作為聚醯胺，例如可例舉：聚醯胺6、聚醯胺6,6及部分芳香族聚醯胺。The mask material M is, for example, a transparent plastic film. As the material of the plastic film, for example, polyolefin, polyester, polyamide, polyimide, polyvinyl chloride, polyvinylidene chloride, cellulose, polystyrene, and polycarbonate may be mentioned. As polyolefin, polyethylene and polypropylene are mentioned, for example. As polyester, polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate may be mentioned, for example. As the polyamide, for example, polyamide 6, polyamide 6,6, and partially aromatic polyamide may be mentioned.
於配置有遮罩材M之區域中，阻止成分在可變色黏著片材X與著色性低下片材Y之間移動。此種遮罩材M之使用適於在第2步驟中對第2區域12選擇性地且高效率地實施如下操作：藉由著色性低下片材Y向可變色黏著片材X導入著色性低下成分或藉由著色性低下片材Y自可變色黏著片材X中提取第1化合物。In the region where the masking material M is disposed, movement of components between the color-changing adhesive sheet X and the low-coloring property sheet Y is prevented. The use of such a masking material M is suitable for selectively and efficiently performing the following operation on the
作為著色性低下介質之著色性低下溶劑可包含極性溶劑作為主劑，亦可包含低極性溶劑(非極性溶劑)作為主劑。作為極性溶劑，例如可例舉水、醇及羧酸。作為極性溶劑，亦可例舉乙酸乙酯、丙酮、乙腈等中極性溶劑。作為醇，例如可例舉甲醇、乙醇、異丙醇及丁醇。作為羧酸，可例舉甲酸及乙酸。作為低極性溶劑，例如可例舉苯、甲苯及甲基異丁基酮。又，作為功能性液體之著色性低下溶劑亦可適宜地選用作為失活用溶劑或提取用溶劑顯示出充分之成分溶解性之液態單體。作為此種液態單體，例如可例舉各種丙烯酸酯單體。The coloring property reducing solvent used as the coloring property reducing medium may contain a polar solvent as a main ingredient, and may contain a low polarity solvent (non-polar solvent) as a main ingredient. As a polar solvent, water, alcohol, and a carboxylic acid are mentioned, for example. As the polar solvent, medium polar solvents such as ethyl acetate, acetone, and acetonitrile may also be mentioned. As alcohol, methanol, ethanol, isopropanol, and butanol are mentioned, for example. The carboxylic acid may, for example, be formic acid or acetic acid. As a low-polarity solvent, benzene, toluene, and methyl isobutyl ketone are mentioned, for example. In addition, as the low-coloring solvent of the functional liquid, a liquid monomer exhibiting sufficient component solubility as a deactivation solvent or an extraction solvent can be suitably selected. As such a liquid monomer, various acrylate monomers are mentioned, for example.
於著色性低下溶劑為失活用著色性低下溶劑之情形時，該著色性低下溶劑進而含有著色性低下成分。著色性低下成分較佳為包含選自由紫外線吸收劑、中和劑及自由基捕獲劑所組成之群中之至少一種。作為紫外線吸收劑、中和劑及自由基捕獲劑，可例舉著色性低下片材Y中敍述之紫外線吸收劑、中和劑及自由基捕獲劑，較佳為使用自由基捕獲劑。When the coloring property reducing solvent is the coloring property reducing solvent for deactivation, this coloring property reducing solvent further contains the coloring property reducing component. It is preferable that the coloring property reducing component contains at least 1 sort(s) chosen from the group which consists of an ultraviolet absorber, a neutralizer, and a radical scavenger. Examples of the ultraviolet absorber, neutralizer, and radical scavenger include the ultraviolet absorber, neutralizer, and radical scavenger described in the low-coloring sheet Y, and it is preferable to use a radical scavenger.
著色性低下溶劑中之著色性低下成分之比率較佳為1質量%以上，更佳為5質量%以上，又，較佳為60質量%以下，較佳為50質量%以下。 [實施例] The ratio of the coloring-reducing component in the coloring-reducing solvent is preferably at least 1% by mass, more preferably at least 5% by mass, and is preferably at most 60% by mass, more preferably at most 50% by mass. [Example]
以下，示出實施例對本發明進行具體說明，但本發明並不限定於實施例。又，以下所記載之調配量(含量)、物性值、參數等之具體數值可用上述「實施方式」中所記載之與該等對應之調配量(含量)、物性值、參數等之上限(定義為「以下」或「未達」之數值)或下限(定義為「以上」或「超過」之數值)來代替。Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited to an Example. In addition, the specific numerical values of the blending amount (content), physical property values, parameters, etc. described below can be defined by the upper limit (definition) of the blending amount (content), physical property values, parameters, etc. is a value that is "below" or "under") or a lower limit (defined as a value that is "above" or "exceeded").
＜丙烯酸聚合物P 1之製備＞ 於具備攪拌機、溫度計、回流冷凝器及氮氣導入管之反應容器內，將包含63質量份之丙烯酸2-乙基己酯(2EHA)、9質量份之甲基丙烯酸甲酯(MMA)、13質量份之丙烯酸2-羥基乙酯(HEA)、15質量份之N-乙烯基-2-吡咯啶酮(NVP)、0.2質量份之作為聚合起始劑之2,2'-偶氮二異丁腈(AIBN)及233質量份之作為溶劑之乙酸乙酯之混合物以60℃於氮氣氛圍下攪拌7小時(聚合反應)。藉此，獲得含有丙烯酸聚合物P 1之第1聚合物溶液。第1聚合物溶液中之丙烯酸聚合物P 1之重量平均分子量(Mw)為120萬。 <Preparation of Acrylic Polymer P 1 > In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, 63 parts by mass of 2-ethylhexyl acrylate (2EHA), 9 parts by mass of methyl Methyl acrylate (MMA), 13 parts by mass of 2-hydroxyethyl acrylate (HEA), 15 parts by mass of N-vinyl-2-pyrrolidone (NVP), 0.2 parts by mass of 2 , A mixture of 2'-azobisisobutyronitrile (AIBN) and 233 parts by mass of ethyl acetate as a solvent was stirred at 60° C. under a nitrogen atmosphere for 7 hours (polymerization reaction). Thereby, the 1st polymer solution containing acrylic acid polymer P1 was obtained. The weight average molecular weight (Mw) of the acrylic polymer P1 in the 1st polymer solution was 1.2 million.
＜丙烯酸聚合物P 2之製備＞ 於具備攪拌機、溫度計、回流冷凝器及氮氣導入管之反應容器內，將包含96質量份之丙烯酸2-乙基己酯(2EHA)、4質量份之丙烯酸2-羥基乙酯(HEA)、0.2質量份之作為聚合起始劑之2,2'-偶氮二異丁腈(AIBN)及233質量份之作為溶劑之乙酸乙酯之混合物以60℃於氮氣氛圍下攪拌7小時(聚合反應)。藉此，獲得含有丙烯酸聚合物P 2之第2聚合物溶液。第2聚合物溶液中之丙烯酸聚合物P 2之重量平均分子量(Mw)為60萬。 <Preparation of Acrylic Acid Polymer P 2 > In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, 96 parts by mass of 2-ethylhexyl acrylate (2EHA), 4 parts by mass of acrylic acid 2 -Hydroxyethyl ester (HEA), 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator and 233 parts by mass of ethyl acetate as a solvent were heated at 60°C under nitrogen Stirring was carried out under atmosphere for 7 hours (polymerization). Thereby, the 2nd polymer solution containing acrylic acid polymer P2 was obtained. The weight average molecular weight (Mw) of the acrylic acid polymer P2 in the 2nd polymer solution was 600,000.
＜丙烯酸聚合物P 3之製備＞ 於具備攪拌機、溫度計、回流冷凝器及氮氣導入管之反應容器內，將包含40質量份之丙烯酸2-乙基己酯(2EHA)、40質量份之丙烯酸異硬脂酯(iSTA)、2質量份之丙烯酸4-羥基丁酯(4HBA)、18質量份之N-乙烯基-2-吡咯啶酮(NVP)、0.2質量份之作為聚合起始劑之2,2'-偶氮二異丁腈(AIBN)及233質量份之作為溶劑之乙酸乙酯之混合物以60℃於氮氣氛圍下攪拌7小時(聚合反應)。藉此，獲得含有丙烯酸聚合物P 3之第3聚合物溶液。第3聚合物溶液中之丙烯酸聚合物P 3之重量平均分子量(Mw)為70萬。 <Preparation of acrylic acid polymer P3 > In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, 40 parts by mass of 2-ethylhexyl acrylate (2EHA), 40 parts by mass of isoacrylate Stearyl ester (iSTA), 2 parts by mass of 4-hydroxybutyl acrylate (4HBA), 18 parts by mass of N-vinyl-2-pyrrolidone (NVP), 0.2 parts by mass of 2 , A mixture of 2'-azobisisobutyronitrile (AIBN) and 233 parts by mass of ethyl acetate as a solvent was stirred at 60° C. under a nitrogen atmosphere for 7 hours (polymerization reaction). Thereby, the 3rd polymer solution containing acrylic polymer P3 was obtained. The weight average molecular weight (Mw) of the acrylic polymer P3 in the 3rd polymer solution was 700,000.
＜黏著性組合物C 1之製備＞ 向含有丙烯酸聚合物P 1之第1聚合物溶液中，添加相對於100質量份丙烯酸聚合物P 1為0.25質量份(固形物成分換算量)之作為交聯劑之異氰酸酯交聯劑(商品名為「Takenate D110N」，三井化學公司製造)、相對於100質量份丙烯酸聚合物P 1為0.01質量份(固形物成分換算量)之作為交聯觸媒之二月桂酸二丁基錫(商品名為「OL-1」，1質量%乙酸乙酯溶液，Tokyo Fine Chemical Co., Ltd.製造)、相對於100質量份丙烯酸聚合物P 1為3質量份之作為交聯抑制劑(針對交聯觸媒之配位基)之乙醯丙酮、相對於100質量份丙烯酸聚合物P 1為2質量份之作為顯色性化合物之隱色素(商品名為「S-205」，山田化學工業公司製造)及相對於100質量份丙烯酸聚合物P 1為7質量份之光酸產生劑(商品名為「SP-056」，ADEKA公司製造)並加以混合，從而製備黏著性組合物C 1。 <Preparation of Adhesive Composition C1 > To the first polymer solution containing acrylic polymer P1, 0.25 parts by mass (converted amount of solid content) of acrylic polymer P1 was added as an exchange The isocyanate crosslinking agent (trade name: "Takenate D110N", manufactured by Mitsui Chemicals Co., Ltd.) of the coupling agent is 0.01 parts by mass (converted amount of solid content) with respect to 100 parts by mass of acrylic polymer P1 as a crosslinking catalyst. Dibutyltin dilaurate (trade name "OL-1", 1% by mass ethyl acetate solution, manufactured by Tokyo Fine Chemical Co., Ltd.), 3 parts by mass per 100 parts by mass of acrylic polymer P1 Acetoacetone as a crosslinking inhibitor (ligand for the crosslinking catalyst), 2 parts by mass of cryptochrome (trade name "S- 205", manufactured by Yamada Chemical Industry Co., Ltd.) and 7 parts by mass of a photoacid generator (trade name "SP-056", manufactured by ADEKA Corporation) relative to 100 parts by mass of acrylic polymer P1 and mixed to prepare an adhesive Sexual composition C 1 .
＜黏著性組合物C 2之製備＞ 除進而添加4質量份之作為著色性低下成分之自由基捕獲劑(商品名為「Tinuvin 249」，BASF公司製造)以外，以與黏著性組合物C 1相同之方式，製備黏著性組合物C 2。 <Preparation of Adhesive Composition C2> In addition to adding 4 parts by mass of a free radical scavenger (trade name "Tinuvin 249", manufactured by BASF Co., Ltd.) In the same manner, adhesive composition C 2 was prepared.
＜黏著性組合物C 3之製備＞ 除進而添加8質量份之作為著色性低下成分之自由基捕獲劑(商品名為「Tinuvin 249」，BASF公司製造)以外，以與黏著性組合物C 1相同之方式，製備黏著性組合物C 3。 <Preparation of Adhesive Composition C 3 > In addition to adding 8 parts by mass of a free radical scavenger (trade name "Tinuvin 249", manufactured by BASF Corporation) as a coloring-reducing component, with the adhesive composition C 1 In the same manner, adhesive composition C 3 was prepared.
＜黏著性組合物C 4之製備＞ 向含有丙烯酸聚合物P 2之第2聚合物溶液中，添加相對於100質量份丙烯酸聚合物P 2為0.25質量份(固形物成分換算量)之作為交聯劑之異氰酸酯交聯劑(商品名為「Coronate HX」，六亞甲基二異氰酸酯之異氰尿酸酯體，東曹公司製造)、相對於100質量份丙烯酸聚合物P 2為0.01質量份(固形物成分換算量)之作為交聯觸媒之二月桂酸二丁基錫(商品名為「OL-1」，1質量%乙酸乙酯溶液，Tokyo Fine Chemical Co., Ltd.製造)、相對於100質量份丙烯酸聚合物P 2為3質量份之作為交聯抑制劑之乙醯丙酮及相對於100質量份丙烯酸聚合物P 2為4質量份之自由基捕獲劑(商品名為「Tinuvin 249」，BASF公司製造)並加以混合，從而製備黏著性組合物C 4。 <Preparation of Adhesive Composition C4 > To the second polymer solution containing acrylic polymer P2, 0.25 parts by mass (solid content conversion amount ) of acrylic polymer P2 was added as an exchange The isocyanate crosslinking agent of the linking agent (trade name "Coronate HX", isocyanurate body of hexamethylene diisocyanate, manufactured by Tosoh Corporation ) , 0.01 parts by mass relative to 100 parts by mass of acrylic polymer P2 Dibutyltin dilaurate (trade name "OL-1", 1% by mass ethyl acetate solution, manufactured by Tokyo Fine Chemical Co., Ltd.) as a crosslinking catalyst (in terms of solid content) compared to 100 parts by mass of acrylic polymer P2 is 3 parts by mass of acetylacetone as a crosslinking inhibitor and 4 parts by mass of a free radical scavenger (trade name "Tinuvin 249") relative to 100 parts by mass of acrylic polymer P2 , manufactured by BASF Corporation) and mixed to prepare an adhesive composition C 4 .
＜黏著性組合物C 5之製備＞ 除將自由基捕獲劑(商品名為「Tinuvin 249」，BASF公司製造)之調配量由4質量份變更為8質量份以外，以與黏著性組合物C 4相同之方式，製備黏著性組合物C 5。 <Preparation of Adhesive Composition C 5 > In addition to changing the compounding amount of the free radical scavenger (trade name "Tinuvin 249", manufactured by BASF Corporation) from 4 parts by mass to 8 parts by mass, with Adhesive Composition C 4 In the same manner, prepare the adhesive composition C 5 .
＜黏著性組合物C 6之製備＞ 向含有丙烯酸聚合物P 2之第2聚合物溶液中，添加相對於100質量份丙烯酸聚合物P 2為0.25質量份(固形物成分換算量)之作為交聯劑之異氰酸酯交聯劑(商品名為「Coronate HX」，東曹公司製造)、相對於100質量份丙烯酸聚合物P 2為0.01質量份(固形物成分換算量)之作為交聯觸媒之二月桂酸二丁基錫(商品名為「OL-1」，Tokyo Fine Chemical Co., Ltd.製造)及相對於100質量份丙烯酸聚合物P 2為3質量份之作為交聯抑制劑之乙醯丙酮並加以混合，從而製備黏著性組合物C 6。 <Preparation of Adhesive Composition C6 > To the second polymer solution containing acrylic polymer P2, 0.25 parts by mass (converted amount of solid content ) of acrylic polymer P2 was added as an exchange The isocyanate crosslinking agent of the coupling agent (trade name "Coronate HX", manufactured by Tosoh Corporation), 0.01 mass parts (solid content conversion amount ) with respect to 100 mass parts of acrylic polymer P2 as a crosslinking catalyst Dibutyltin dilaurate (trade name "OL-1", manufactured by Tokyo Fine Chemical Co., Ltd.) and 3 parts by mass of acetylacetone as a crosslinking inhibitor with respect to 100 parts by mass of acrylic polymer P2 and mixed to prepare an adhesive composition C 6 .
＜黏著性組合物C 7之製備＞ 除使用第3聚合物溶液來代替第2聚合物溶液以外，以與黏著性組合物C 6相同之方式，製備黏著性組合物C 7。 <Preparation of Adhesive Composition C 7 > An adhesive composition C 7 was prepared in the same manner as in the adhesive composition C 6 except that the third polymer solution was used instead of the second polymer solution.
＜黏著性組合物C 8之製備＞ 除進而添加4質量份之作為著色性低下成分之紫外線吸收劑(商品名為「Tinuvin 571」，BASF公司製造)以外，以與黏著性組合物C 1相同之方式，製備黏著性組合物C 8。 <Preparation of Adhesive Composition C8> It was the same as that of Adhesive Composition C1 , except that 4 parts by mass of a UV absorber (trade name "Tinuvin 571", manufactured by BASF Corporation) was added as a coloring-reducing component. In this way, the adhesive composition C 8 was prepared.
＜黏著性組合物C 9之製備＞ 除進而添加8質量份之作為著色性低下成分之紫外線吸收劑(商品名為「Tinuvin 571」，BASF公司製造)以外，以與黏著性組合物C 1相同之方式，製備黏著性組合物C 9。 <Preparation of Adhesive Composition C9 > It was the same as that of Adhesive Composition C1 , except that 8 parts by mass of an ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF Corporation) was further added as a coloring-reducing component. In this way, the adhesive composition C 9 was prepared.
＜黏著性組合物C 10之製備＞ 除使用4質量份之紫外線吸收劑(商品名為「Tinuvin 571」，BASF公司製造)來代替4質量份之自由基捕獲劑(Tinuvin 249)以外，以與黏著性組合物C 4相同之方式，製備黏著性組合物C 10。 <Preparation of Adhesive Composition C 10 > In addition to using 4 parts by mass of ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF Corporation) instead of 4 parts by mass of free radical scavenger (Tinuvin 249), with Adhesive composition C 10 was prepared in the same manner as adhesive composition C 4 .
＜黏著性組合物C 11之製備＞ 除使用8質量份之紫外線吸收劑(商品名為「Tinuvin 571」，BASF公司製造)來代替4質量份之自由基捕獲劑(Tinuvin 249)以外，以與黏著性組合物C 4相同之方式，製備黏著性組合物C 11。 <Preparation of Adhesive Composition C 11 > In addition to using 8 parts by mass of an ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF Corporation) instead of 4 parts by mass of a radical scavenger (Tinuvin 249), with Adhesive composition C 11 was prepared in the same manner as adhesive composition C 4 .
＜可變色黏著片材X 1之製作＞ 向單面經離型處理之厚度38 μm之基材膜(商品名為「MRF#38」，聚酯膜，三菱樹脂公司製造)之離型處理面上塗佈黏著性組合物C 1而形成塗膜。繼而，將該塗膜於132℃下加熱3分鐘，藉此使其乾燥。藉此，於基材膜上形成厚度25 μm之黏著劑層。繼而，將單面經離型處理之厚度38 μm之剝離膜(商品名為「MRE#38」，聚酯膜，三菱樹脂公司製造)之離型處理面貼合於基材膜上之黏著劑層。其後，於60℃下進行24小時之老化處理，進行黏著劑層中之交聯反應。以如上方式，製作附保護膜之可變色黏著片材X 1(厚度為25 μm)。將可變色黏著片材中之隱色素及光酸產生劑之相對調配量(質量份)示於表1～4。 <Preparation of color-changing adhesive sheet X 1 > To the release-treated side of a 38 μm-thick base film (trade name "MRF#38", polyester film, manufactured by Mitsubishi Plastics Corporation) that has been released on one side Adhesive composition C1 was applied to form a coating film. Next, this coating film was dried by heating at 132 degreeC for 3 minutes. Thereby, an adhesive layer with a thickness of 25 μm was formed on the base film. Next, attach the release-treated side of a release film with a thickness of 38 μm (trade name "MRE#38", polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) that has been released on one side to the adhesive on the base film Floor. Thereafter, aging treatment was carried out at 60° C. for 24 hours to carry out the cross-linking reaction in the adhesive layer. In the above manner, a color-changing adhesive sheet X 1 with a protective film (thickness 25 μm) was produced. The relative compounding quantities (parts by mass) of the cryptochrome and the photoacid generator in the color-variable adhesive sheet are shown in Tables 1-4.
＜可變色黏著片材R 1之製作＞ 除使用黏著性組合物C 2來代替黏著性組合物C 1以外，以與可變色黏著片材X 1相同之方式，製作附保護膜之可變色黏著片材R 1。 <Production of color-changing adhesive sheet R1> Except for using adhesive composition C2 instead of adhesive composition C1 , the color - changing adhesive sheet with protective film was produced in the same manner as color - changing adhesive sheet X1 Sheet R 1 .
＜可變色黏著片材R 2之製作＞ 除使用黏著性組合物C 3來代替黏著性組合物C 1以外，以與可變色黏著片材X 1相同之方式，製作附保護膜之可變色黏著片材R 2。 <Production of Color-changing Adhesive Sheet R 2 > Except for using Adhesive Composition C3 instead of Adhesive Composition C1 , a color-changing adhesive sheet with a protective film was produced in the same manner as Color - Changeable Adhesive Sheet X1 Sheet R2 .
＜可變色黏著片材R 3之製作＞ 除使用黏著性組合物C 8來代替黏著性組合物C 1以外，以與可變色黏著片材X 1相同之方式，製作附保護膜之可變色黏著片材R 3。 <Production of Color-changing Adhesive Sheet R 3 > Except for using Adhesive Composition C 8 instead of Adhesive Composition C 1 , a color-changing adhesive sheet with a protective film was produced in the same manner as Color-Changeable Adhesive Sheet X 1 Sheet R3 .
＜可變色黏著片材R 4之製作＞ 除使用黏著性組合物C 9來代替黏著性組合物C 1以外，以與可變色黏著片材X 1相同之方式，製作附保護膜之可變色黏著片材R 4。 <Production of Color - changing Adhesive Sheet R4> Except using Adhesive Composition C9 instead of Adhesive Composition C1 , in the same manner as Color-Changeable Adhesive Sheet X1, a color-changing adhesive with a protective film was produced Sheet R4 .
＜失活用黏著片材D 1之製作＞ 向單面經離型處理之厚度38 μm之基材膜(商品名為「MRF#38」，聚酯膜，三菱樹脂公司製造)之離型處理面上塗佈黏著性組合物C 4而形成塗膜。繼而，將該塗膜於室溫下放置10分鐘後，於80℃下加熱5分鐘，其後，於130℃下加熱1分鐘，藉此使其乾燥。藉此，於基材膜上形成厚度25 μm之黏著劑層。繼而，將單面經離型處理之厚度38 μm之剝離膜(商品名為「MRE#38」，聚酯膜，三菱樹脂公司製造)之離型處理面貼合於基材膜上之黏著劑層。其後，於60℃下進行24小時之老化處理，進行黏著劑層中之交聯反應。以如上方式，製作附保護膜之失活用黏著片材D 1(厚度為25 μm)。 ＜Preparation of adhesive sheet D1 for deactivation＞ To the release-treated surface of a 38 μm-thick substrate film (trade name: "MRF#38", polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) that has been released on one side Apply the adhesive composition C4 to form a coating film. Next, after leaving this coating film at room temperature for 10 minutes, it heated at 80 degreeC for 5 minutes, and dried it by heating at 130 degreeC for 1 minute after that. Thereby, an adhesive layer with a thickness of 25 μm was formed on the base film. Next, attach the release-treated side of a release film with a thickness of 38 μm (trade name "MRE#38", polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) that has been released on one side to the adhesive on the base film Floor. Thereafter, aging treatment was carried out at 60° C. for 24 hours to carry out the cross-linking reaction in the adhesive layer. In the above manner, the deactivation adhesive sheet D 1 with a protective film (thickness: 25 μm) was produced.
＜失活用黏著片材D 2之製作＞ 除使用黏著性組合物C 5來代替黏著性組合物C 4以外，以與失活用黏著片材D 1相同之方式，製作附保護膜之失活用黏著片材D 2。 <Preparation of the deactivation adhesive sheet D2 > Except for using the adhesive composition C5 instead of the adhesive composition C4 , in the same manner as the deactivation adhesive sheet D1, a deactivation adhesive with a protective film was produced. Sheet D2 .
＜失活用黏著片材D 3之製作＞ 除使用黏著性組合物C 10來代替黏著性組合物C 4以外，以與失活用黏著片材D 1相同之方式，製作附保護膜之失活用黏著片材D 3。 <Preparation of deactivation adhesive sheet D3 > Except for using adhesive composition C10 instead of adhesive composition C4 , in the same manner as deactivation adhesive sheet D1, a deactivation adhesive with a protective film was produced. Sheet D3 .
＜失活用黏著片材D 4之製作＞ 除使用黏著性組合物C 11來代替黏著性組合物C 4以外，以與失活用黏著片材D 1相同之方式，製作附保護膜之失活用黏著片材D 4。 <Preparation of deactivation adhesive sheet D4> Except for using adhesive composition C11 instead of adhesive composition C4 , in the same manner as deactivation adhesive sheet D1, a deactivation adhesive with a protective film was produced . Sheet D4 .
＜提取用黏著片材E 1之製作＞ 除使用黏著性組合物C 6來代替黏著性組合物C 4及將厚度由25 μm變更為100 μm以外，以與失活用黏著片材D 1相同之方式，製作附保護膜之提取用黏著片材E 1。 <Preparation of Adhesive Sheet E 1 for Extraction> Except that Adhesive Composition C 6 was used instead of Adhesive Composition C 4 and the thickness was changed from 25 μm to 100 μm, it was the same as that of Deactivation Adhesive Sheet D 1 In this way, an adhesive sheet E 1 for extraction with a protective film is produced.
＜提取用黏著片材E 2之製作＞ 除使用黏著性組合物C 7來代替黏著性組合物C 4及將厚度由25 μm變更為100 μm以外，以與失活用黏著片材D 1相同之方式，製作附保護膜之提取用黏著片材E 2。 <Preparation of Adhesive Sheet E 2 for Extraction> Except that Adhesive Composition C 7 was used instead of Adhesive Composition C 4 and the thickness was changed from 25 μm to 100 μm, it was the same as that of Deactivation Adhesive Sheet D 1 In this way, the extraction adhesive sheet E 2 with a protective film is produced.
[實施例1] 由可變色黏著片材X 1及失活用黏著片材D 1，以如下方式獲得積層體L 1。首先，準備可變色黏著片材X 1(第1步驟)。具體而言，將剝離膜自可變色黏著片材X 1剝離後，將該片材貼合於Eagle玻璃(厚度為0.55 mm，松浪硝子公司製造)。繼而，將基材膜自Eagle玻璃上之可變色黏著片材X 1剝離，並將剝離膜自失活用黏著片材D 1剝離後，將失活用黏著片材D 1貼合於可變色黏著片材X 1(第2步驟)。以如上方式，獲得實施例1之積層體L 1。積層體L 1依序具備Eagle玻璃、可變色黏著片材X 1(厚度為25 μm)、失活用黏著片材D 1(厚度為25 μm)及基材膜。積層體L 1包含可變色黏著片材X 1與失活用黏著片材D 1之積層片材。 [Example 1] A laminate L 1 was obtained from the color-variable adhesive sheet X 1 and the inactivation adhesive sheet D 1 in the following manner. First, color-changeable adhesive sheet X 1 is prepared (first step). Specifically, after the peeling film was peeled from the color - changing adhesive sheet X1, the sheet was bonded to Eagle glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, peel the substrate film from the color-changing adhesive sheet X 1 on the Eagle glass, peel the release film from the inactivation adhesive sheet D 1 , and attach the inactivation adhesive sheet D 1 to the color-changing adhesive sheet X 1 (step 2). In the above manner, the laminate L 1 of Example 1 was obtained. Laminate L 1 sequentially includes Eagle glass, color-changing adhesive sheet X 1 (thickness 25 μm), deactivation adhesive sheet D 1 (thickness 25 μm), and a base film. The laminate L1 includes a laminated sheet of the color - changing adhesive sheet X1 and the adhesive sheet D1 for deactivation.
[實施例2] 於第2步驟中，使用失活用黏著片材D 2來代替失活用黏著片材D 1，除此以外，實施與實施例1相同之各步驟，從而獲得實施例2之積層體L 2。積層體L 2依序具備Eagle玻璃、可變色黏著片材X 1、失活用黏著片材D 2及基材膜。積層體L 2包含可變色黏著片材X 1與失活用黏著片材D 2之積層片材。 [Example 2 ] In the second step, except that the inactivation adhesive sheet D2 was used instead of the inactivation adhesive sheet D1, the same steps as in Example 1 were carried out to obtain the laminate of Example 2 Body L 2 . The laminate L 2 includes Eagle glass, a color-changing adhesive sheet X 1 , an adhesive sheet D 2 for deactivation, and a base film in this order. The laminate L2 includes a laminated sheet of the color - changing adhesive sheet X1 and the adhesive sheet D2 for deactivation.
[實施例3] 於第2步驟中，使用失活用黏著片材D 3來代替失活用黏著片材D 1，除此以外，實施與實施例1相同之各步驟，從而獲得實施例3之積層體L 3。積層體L 3依序具備Eagle玻璃、可變色黏著片材X 1、失活用黏著片材D 3及基材膜。積層體L 3包含可變色黏著片材X 1與失活用黏著片材D 3之積層片材。 [Example 3] In the second step, except that the inactivation adhesive sheet D3 was used instead of the inactivation adhesive sheet D1, the same steps as in Example 1 were carried out to obtain the laminate of Example 3 Body L 3 . The laminate L 3 includes Eagle glass, a color-changing adhesive sheet X 1 , an adhesive sheet for deactivation D 3 , and a base film in this order. The laminate L3 is a laminated sheet including the color - changing adhesive sheet X1 and the adhesive sheet D3 for inactivation.
[實施例4] 於第2步驟中，使用失活用黏著片材D 4來代替失活用黏著片材D 1，除此以外，實施與實施例1相同之各步驟，從而獲得實施例4之積層體L 4。積層體L 4依序具備Eagle玻璃、可變色黏著片材X 1、失活用黏著片材D 3及基材膜。積層體L 4包含可變色黏著片材X 1與失活用黏著片材D 4之積層片材。 [Example 4 ] In the second step, except that the inactivation adhesive sheet D4 was used instead of the inactivation adhesive sheet D1, the same procedures as in Example 1 were carried out to obtain the laminate of Example 4 Body L 4 . The laminate L 4 includes Eagle glass, a color-changing adhesive sheet X 1 , an adhesive sheet for deactivation D 3 , and a base film in this order. The laminate L4 includes a laminated sheet of the color - changing adhesive sheet X1 and the adhesive sheet D4 for deactivation.
[比較例1] 實施與實施例1相同之第1步驟，從而獲得比較例1之積層體L 5。積層體L 5依序具備Eagle玻璃、可變色黏著片材X 1及基材膜(不具備失活用黏著片材)。 [Comparative Example 1] The same first step as in Example 1 was carried out to obtain a laminate L 5 of Comparative Example 1. Laminate L 5 sequentially includes Eagle glass, color-changing adhesive sheet X 1 , and base film (adhesive sheet for deactivation is not included).
[實施例5] 由可變色黏著片材X 1及失活用黏著片材D 1，以如下方式獲得積層體L 6。首先，準備實施例1之積層體L 1(Eagle玻璃/可變色黏著片材X 1/失活用黏著片材D 1/基材膜)。繼而，將基材膜自該積層體L 1中之失活用黏著片材D 1剝離。然後，將三乙醯纖維素(TAC)膜(商品名為「KC2UA」，厚度為28 μm，柯尼卡美能達公司製造)、具有紫外線吸收功能之黏著帶(商品名為「CS9934U」，日東電工公司製造)及聚對苯二甲酸乙二酯(PET)膜(商品名為「G981 E75」，厚度為75 μm，三菱化學公司製造)依序貼合併積層於該藉由剝離而露出之黏著片材面。以如上方式，獲得實施例5之積層體L 6。積層體L 6依序具備Eagle玻璃、可變色黏著片材X 1(厚度為25 μm)、失活用黏著片材D 1(厚度為25 μm)、TAC膜、紫外線吸收性黏著帶及PET膜(基材膜)。積層體L 6包含可變色黏著片材X 1與失活用黏著片材D 1之積層片材。 [Example 5 ] From the color - variable adhesive sheet X1 and the adhesive sheet D1 for inactivation, a laminate L6 was obtained as follows. First, the laminate L 1 of Example 1 (Eagle glass/color-changing adhesive sheet X 1 /inactivation adhesive sheet D 1 /substrate film) was prepared. Next, the base film was peeled off from the adhesive sheet D1 for deactivation in this laminated body L1. Then, a triacetyl cellulose (TAC) film (trade name "KC2UA", thickness 28 μm, manufactured by Konica Minolta Corporation), an adhesive tape with ultraviolet absorbing function (trade name "CS9934U", Nitto Denko Corporation) and polyethylene terephthalate (PET) film (trade name "G981 E75", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) were sequentially pasted and laminated on the adhesive surface exposed by peeling Sheet side. In the above manner, the laminate L 6 of Example 5 was obtained. The laminate L 6 is sequentially equipped with Eagle glass, color-changing adhesive sheet X 1 (thickness 25 μm), deactivation adhesive sheet D 1 (thickness 25 μm), TAC film, ultraviolet absorbing adhesive tape, and PET film ( base film). The laminate L 6 includes a laminated sheet of the color-changing adhesive sheet X 1 and the inactivation adhesive sheet D 1 .
[實施例6] 除使用實施例2之積層體L 2來代替實施例1之積層體L 1以外，實施與實施例5相同之各步驟，從而獲得實施例6之積層體L 7。積層體L 7依序具備Eagle玻璃、可變色黏著片材X 1(厚度為25 μm)、失活用黏著片材D 2(厚度為25 μm)、TAC膜、紫外線吸收性黏著帶及PET膜(基材膜)。積層體L 7包含可變色黏著片材X 1與失活用黏著片材D 2之積層片材。 [Example 6] Except that the laminate L 2 of Example 2 was used instead of the laminate L 1 of Example 1, the same steps as in Example 5 were carried out to obtain a laminate L 7 of Example 6. The laminate L 7 is sequentially equipped with Eagle glass, color-changing adhesive sheet X 1 (thickness 25 μm), deactivation adhesive sheet D 2 (thickness 25 μm), TAC film, ultraviolet absorbing adhesive tape, and PET film ( base film). Laminate L 7 includes a laminated sheet of color-changing adhesive sheet X 1 and inactivation adhesive sheet D 2 .
[比較例2] 除使用比較例1之積層體L 3來代替實施例1之積層體L 1以外，實施與實施例5相同之各步驟，從而獲得比較例2之積層體L 8。積層體L 8依序具備Eagle玻璃、可變色黏著片材X 1(厚度為25 μm)、TAC膜、紫外線吸收性黏著帶及PET膜(基材膜)(不具備失活用黏著片材)。 [Comparative Example 2] Except for using the laminated body L3 of Comparative Example 1 instead of the laminated body L1 of Example 1 , the same steps as in Example 5 were carried out to obtain a laminated body L8 of Comparative Example 2 . Laminate L 8 sequentially includes Eagle glass, color-changing adhesive sheet X 1 (thickness: 25 μm), TAC film, ultraviolet absorbing adhesive tape, and PET film (substrate film) (adhesive sheet for inactivation is not included).
[實施例7] 由可變色黏著片材X 1及失活用黏著片材D 3，以如下方式獲得積層體L 9。 [Example 7] A laminate L 9 was obtained from the color-variable adhesive sheet X 1 and the inactivation adhesive sheet D 3 in the following manner.
首先，準備可變色黏著片材X 1(第1步驟)。具體而言，將剝離膜自可變色黏著片材X 1剝離後，將該片材貼合於Eagle玻璃(厚度為0.55 mm，松浪硝子公司製造)。 First, color-changeable adhesive sheet X 1 is prepared (first step). Specifically, after the peeling film was peeled from the color - changing adhesive sheet X1, the sheet was bonded to Eagle glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.).
繼而，對Eagle玻璃上之可變色黏著片材X 1照射紫外線(UV)(第2步驟)。具體而言，於23℃及相對濕度50%之環境下，對於Eagle玻璃上之可變色黏著片材X 1自基材膜側(與Eagle玻璃相反之側)照射UV。藉此，於可變色黏著片材X 1中，由光酸產生劑產生酸，藉由該酸使隱色素顯色。於UV照射中，使用Quark Technology公司製造之UV-LED照射裝置(型號為「QEL-350-RU6W-CW-MY」)中之波長365 nm之UV-LED燈作為光源，將波長320～390 nm之範圍內之照射累計光量設為8000 mJ/cm 2。 Next, irradiate ultraviolet rays (UV) to the color-changing adhesive sheet X 1 on the Eagle glass (the second step). Specifically, in an environment of 23°C and a relative humidity of 50%, the color-changing adhesive sheet X1 on Eagle glass was irradiated with UV from the base film side (the side opposite to Eagle glass). Thereby, in the color-variable adhesive sheet X1, an acid is generated by the photoacid generator, and the leucochrome is developed by the acid. In UV irradiation, a UV-LED lamp with a wavelength of 365 nm in a UV-LED irradiation device manufactured by Quark Technology (model "QEL-350-RU6W-CW-MY") is used as a light source, and a wavelength of 320-390 nm The cumulative light intensity of irradiation within the range is set to 8000 mJ/cm 2 .
繼而，將基材膜自Eagle玻璃上之可變色黏著片材X 1剝離，並將剝離膜自失活用黏著片材D 3剝離後，將失活用黏著片材D 3貼合於可變色黏著片材X 1(第3步驟)。 Next, peel the substrate film from the color-changing adhesive sheet X 1 on the Eagle glass, peel the release film from the inactivation adhesive sheet D 3 , and attach the inactivation adhesive sheet D 3 to the color-changing adhesive sheet X 1 (step 3).
繼而，將基材膜自該失活用黏著片材D 3剝離後，將TAC膜(商品名為「KC2UA」，厚度為28 μm，柯尼卡美能達公司製造)、具有紫外線吸收功能之黏著帶(商品名為「CS9934U」，日東電工公司製造)及PET膜(商品名為「G981 E75」，厚度為75 μm，三菱化學公司製造)依序貼合併積層於該藉由剝離而露出之黏著片材面。 Next, after peeling the substrate film from the adhesive sheet D3 for inactivation, a TAC film (trade name "KC2UA", thickness 28 μm, manufactured by Konica Minolta Corporation), an adhesive tape having an ultraviolet absorbing function (trade name "CS9934U", manufactured by Nitto Denko Corporation) and PET film (trade name "G981 E75", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) were sequentially pasted and laminated on the adhesive sheet exposed by peeling Material surface.
以如上方式，獲得實施例7之積層體L 9。積層體L 9依序具備Eagle玻璃、經著色之可變色黏著片材X 1(厚度為25 μm)、失活用黏著片材D 3(厚度為25 μm)、TAC膜、紫外線吸收性黏著帶及PET膜(基材膜)。積層體L 9包含經著色之可變色黏著片材X 1與失活用黏著片材D 3之積層片材。 In the above manner, the laminate L 9 of Example 7 was obtained. The laminated body L 9 consists of Eagle glass, colored color-changing adhesive sheet X 1 (thickness 25 μm), deactivation adhesive sheet D 3 (thickness 25 μm), TAC film, ultraviolet absorbing adhesive tape and PET film (substrate film). The laminate L9 is a laminated sheet comprising the colored color - changing adhesive sheet X1 and the adhesive sheet D3 for deactivation.
[實施例8] 於第3步驟中，使用失活用黏著片材D 4來代替失活用黏著片材D 3，除此以外，實施與實施例7相同之各步驟，從而獲得實施例8之積層體L 10。積層體L 10依序具備Eagle玻璃、經著色之可變色黏著片材X 1(厚度為25 μm)、失活用黏著片材D 4(厚度為25 μm)、TAC膜、紫外線吸收性黏著帶及PET膜(基材膜)。積層體L 10包含經著色之可變色黏著片材X 1與失活用黏著片材D 4之積層片材。 [Example 8] In the third step, except that the inactivation adhesive sheet D4 was used instead of the inactivation adhesive sheet D3, the same steps as in Example 7 were carried out to obtain the laminate of Example 8 Body L 10 . The laminated body L 10 includes Eagle glass, colored color-changing adhesive sheet X 1 (thickness 25 μm), deactivation adhesive sheet D 4 (thickness 25 μm), TAC film, ultraviolet absorbing adhesive tape and PET film (substrate film). The laminate L10 is a laminated sheet comprising the colored color - changing adhesive sheet X1 and the adhesive sheet D4 for deactivation.
[比較例3] 除未實施第3步驟(失活用黏著片材D 3之貼合)以外，實施與實施例7相同之各步驟，從而獲得比較例3之積層體L 11。積層體L 11依序具備Eagle玻璃、經著色之可變色黏著片材X 1(厚度為25 μm)、TAC膜、紫外線吸收性黏著帶及PET膜(基材膜)(不具備失活用黏著片材)。 [Comparative Example 3] The same steps as in Example 7 were carried out except that the third step (lamination of the adhesive sheet D3 for deactivation) was not carried out, thereby obtaining a laminate L 11 of Comparative Example 3. Laminate L 11 is sequentially equipped with Eagle glass, colored color-changing adhesive sheet X 1 (thickness 25 μm), TAC film, ultraviolet absorbing adhesive tape, and PET film (base film) (adhesive sheet for deactivation is not provided) material).
[實施例9] 由可變色黏著片材X 1、失活用黏著片材D 1及遮罩膜，以如下方式獲得積層體L 12。首先，準備可變色黏著片材X 1(50 mm×100 mm)(第1步驟)。具體而言，將剝離膜自可變色黏著片材X 1剝離後，將該片材貼合於Eagle玻璃(厚度為0.55 mm，松浪硝子公司製造)。繼而，將基材膜自Eagle玻璃上之可變色黏著片材X 1剝離後，於該片材上積層厚度25 μm之遮罩膜(商品名為「Lumirror S10」，50 mm×50 mm，透明聚酯膜，東麗公司製造)。繼而，將剝離膜自失活用黏著片材D 1剝離後，將失活用黏著片材D 1(50 mm×100 mm)貼合於可變色黏著片材X 1(第2步驟)。以如上方式，獲得實施例9之積層體L 12。積層體L 12依序具備Eagle玻璃、可變色黏著片材X 1、部分遮蔽可變色黏著片材X 1之遮罩膜、失活用黏著片材D 1及基材膜。積層體L 12包含可變色黏著片材X 1、遮罩膜及失活用黏著片材D 1之積層片材。 [Example 9] From the color-variable adhesive sheet X 1 , the adhesive sheet for deactivation D 1 , and the mask film, a laminate L 12 was obtained as follows. First, a color-changeable adhesive sheet X 1 (50 mm×100 mm) was prepared (first step). Specifically, after the peeling film was peeled from the color - changing adhesive sheet X1, the sheet was bonded to Eagle glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Then, after peeling the base film from the color-changing adhesive sheet X 1 on the Eagle glass, a mask film (trade name "Lumirror S10", 50 mm x 50 mm, transparent) with a thickness of 25 μm was laminated on the sheet. polyester film, manufactured by Toray Corporation). Next, after peeling off the release film from the adhesive sheet D 1 for inactivation, the adhesive sheet D 1 for inactivation (50 mm×100 mm) was bonded to the color-changing adhesive sheet X 1 (second step). In the above manner, the laminate L 12 of Example 9 was obtained. The laminate L 12 sequentially includes Eagle glass, a color-changing adhesive sheet X 1 , a mask film that partially covers the color-changing adhesive sheet X 1 , an adhesive sheet D 1 for inactivation, and a base film. The laminate L12 is a laminated sheet including a color-changing adhesive sheet X1, a mask film, and an adhesive sheet D1 for inactivation.
[實施例10] 於第2步驟中，使用失活用黏著片材D 2(50 mm×100 mm)來代替失活用黏著片材D 1，除此以外，實施與實施例9相同之各步驟，從而獲得實施例10之積層體L 13。積層體L 13依序具備Eagle玻璃、可變色黏著片材X 1、部分遮蔽可變色黏著片材X 1之遮罩膜、失活用黏著片材D 2及基材膜。積層體L 13包含可變色黏著片材X 1、遮罩膜及失活用黏著片材D 2之積層片材。 [Example 10] In the second step, the same procedures as in Example 9 were carried out except that the inactivation adhesive sheet D 2 (50 mm×100 mm) was used instead of the inactivation adhesive sheet D 1 . Thus, the laminate L 13 of Example 10 was obtained. The laminate L 13 sequentially includes Eagle glass, a color-changing adhesive sheet X 1 , a mask film that partially covers the color-changing adhesive sheet X 1 , an adhesive sheet D 2 for inactivation, and a base film. The laminate L13 is a laminated sheet including a color-changing adhesive sheet X1, a mask film, and an adhesive sheet D2 for deactivation.
[比較例4] 於第2步驟中，使用厚度38 μm之基材膜(商品名為「MRF#38」，50 mm×100 mm，聚酯膜，三菱樹脂公司製造)來代替失活用黏著片材D 1，除此以外，實施與實施例9相同之各步驟，從而獲得比較例4之積層體L 14。積層體L 14依序具備Eagle玻璃、可變色黏著片材X 1、部分遮蔽可變色黏著片材X 1之遮罩膜及基材膜(不具備失活用黏著片材)。 [Comparative Example 4] In the second step, a substrate film with a thickness of 38 μm (trade name "MRF#38", 50 mm x 100 mm, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) was used instead of the deactivation adhesive sheet Except for the material D 1 , the same steps as in Example 9 were implemented to obtain a laminate L 14 of Comparative Example 4. The laminate L 14 sequentially includes Eagle glass, the color-changing adhesive sheet X 1 , a mask film that partially covers the color-changing adhesive sheet X 1 , and a base film (the deactivation adhesive sheet is not provided).
[實施例11] 於第2步驟中，使用提取用黏著片材E 1來代替失活用黏著片材D 1，除此以外，實施與實施例1相同之各步驟，從而而獲得實施例11之積層體L 15。積層體L 15依序具備Eagle玻璃、可變色黏著片材X 1、提取用黏著片材E 1及基材膜。積層體L 15包含可變色黏著片材X 1與提取用黏著片材E 1之積層片材。 [Example 11 ] In the second step, except that the adhesive sheet E1 for extraction was used instead of the adhesive sheet D1 for inactivation, the same steps as in Example 1 were carried out, thereby obtaining Example 11. Laminate L 15 . The laminate L 15 includes Eagle glass, a color-changing adhesive sheet X 1 , an extraction adhesive sheet E 1 , and a base film in this order. The laminate L15 is a laminated sheet including the color - changing adhesive sheet X1 and the adhesive sheet E1 for extraction.
[實施例12] 於第2步驟中，使用提取用黏著片材E 2來代替失活用黏著片材D 1，除此以外，實施與實施例1相同之各步驟，從而獲得實施例12之積層體L 16。積層體L 16依序具備Eagle玻璃、可變色黏著片材X 1、提取用黏著片材E 2及基材膜。積層體L 16包含可變色黏著片材X 1與提取用黏著片材E 2之積層片材。 [Example 12] In the second step, except that the adhesive sheet E2 for extraction was used instead of the adhesive sheet D1 for deactivation, the same steps as in Example 1 were carried out to obtain the laminate of Example 12 Body L 16 . The laminate L 16 includes Eagle glass, a color-changing adhesive sheet X 1 , an extraction adhesive sheet E 2 , and a base film in this order. The laminated body L16 includes a laminated sheet of the color-changing adhesive sheet X1 and the adhesive sheet E2 for extraction.
[實施例13] 以如下方式獲得實施例13之積層體L 17。首先，準備可變色黏著片材X 1。具體而言，將剝離膜自可變色黏著片材X 1剝離後，將該片材貼合於Eagle玻璃(厚度為0.55 mm，松浪硝子公司製造)。繼而，將基材膜自Eagle玻璃上之可變色黏著片材X 1剝離後，將該可變色黏著片材X 1與Eagle玻璃一同浸漬於乙醇中(作為著色性低下處理之浸漬處理)。浸漬時間設為2分鐘。繼而，將附Eagle玻璃之可變色黏著片材X 1自乙醇中取出，於132℃下加熱3分鐘，藉此使其乾燥。繼而，將厚度38 μm之基材膜(商品名為「MRF#38」，聚酯膜，三菱樹脂公司製造)貼合於Eagle玻璃上之可變色黏著片材X 1。以如上方式，獲得實施例13之積層體L 17。積層體L 17依序具備Eagle玻璃、經過乙醇浸漬之可變色黏著片材X 1及基材膜。 [Example 13] The laminate L 17 of Example 13 was obtained as follows. First, a color-changeable adhesive sheet X 1 is prepared. Specifically, after the peeling film was peeled from the color - changing adhesive sheet X1, the sheet was bonded to Eagle glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling the base film from the color - changing adhesive sheet X1 on the Eagle glass, the color-changing adhesive sheet X1 was immersed in ethanol together with the Eagle glass (dipping treatment as a coloring reduction treatment). The dipping time was set to 2 minutes. Next, the color - changing adhesive sheet X1 with Eagle glass was taken out from the ethanol, and dried by heating at 132°C for 3 minutes. Next, a base film with a thickness of 38 μm (trade name "MRF#38", polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) was bonded to the color-changing adhesive sheet X 1 on the Eagle glass. In the above manner, the laminate L 17 of Example 13 was obtained. Laminate L 17 is sequentially equipped with Eagle glass, ethanol-impregnated color-changing adhesive sheet X 1 and a base film.
[實施例14] 於著色性低下處理中，使用乙酸乙酯代替乙醇，除此以外，以與實施例13相同之方式，獲得實施例14之積層體L 18。積層體L 18依序具備Eagle玻璃、經過乙酸乙酯浸漬之可變色黏著片材X 1及基材膜。 [Example 14] A laminate L 18 of Example 14 was obtained in the same manner as in Example 13 except that ethyl acetate was used instead of ethanol in the coloring reduction treatment. The laminate L 18 is sequentially equipped with Eagle glass, a color-changing adhesive sheet X 1 impregnated with ethyl acetate, and a base film.
[實施例15] 以如下方式獲得實施例15之積層體L 19。首先，準備可變色黏著片材X 1(50 mm×100 mm)。具體而言，將剝離膜自可變色黏著片材X 1剝離後，將該片材貼合於Eagle玻璃(厚度為0.55 mm，松浪硝子公司製造)。繼而，將基材膜自Eagle玻璃上之可變色黏著片材X 1剝離後，向該片材上積層厚度25 μm之遮罩膜(商品名為「Lumirror S10」，50 mm×50 mm，透明聚酯膜，東麗公司製造)。繼而，將藉由該遮罩膜部分遮蔽表面(與Eagle玻璃側表面為相反側之表面)之可變色黏著片材X 1與Eagle玻璃一同浸漬於乙醇中(作為著色性低下處理之浸漬處理)。浸漬時間設為2分鐘。繼而，將附Eagle玻璃之可變色黏著片材X 1(表面藉由遮罩膜而被部分遮蔽)自乙醇中取出，於132℃下加熱3分鐘，藉此使其乾燥。繼而，將厚度38 μm之基材膜(商品名為「MRF#38」，聚酯膜，三菱樹脂公司製造)貼合於Eagle玻璃上之可變色黏著片材X 1中所露出之區域(未藉由遮罩膜遮蔽之區域)。以如上方式，獲得實施例15之積層體L 19。積層體L 19依序具備Eagle玻璃、經過乙醇浸漬之可變色黏著片材X 1及該片材上之遮罩膜及基材膜。積層體L 19包含經過乙醇浸漬之可變色黏著片材X 1與遮罩膜之積層片材。 [Example 15] The laminate L 19 of Example 15 was obtained as follows. First, color-changeable adhesive sheet X 1 (50 mm×100 mm) was prepared. Specifically, after the peeling film was peeled from the color - changing adhesive sheet X1, the sheet was bonded to Eagle glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling the base film from the color-changing adhesive sheet X 1 on the Eagle glass, a mask film (trade name "Lumirror S10", 50 mm x 50 mm, transparent) with a thickness of 25 μm was laminated on the sheet. polyester film, manufactured by Toray Corporation). Next, the color - changing adhesive sheet X1 whose surface (the surface opposite to the Eagle glass side surface) was partially covered by the mask film was dipped in ethanol together with the Eagle glass (dipping treatment as a coloring reduction treatment) . The dipping time was set to 2 minutes. Next, the color-changing adhesive sheet X 1 with Eagle glass (the surface is partially masked by a mask film) was taken out from the ethanol, and dried by heating at 132° C. for 3 minutes. Then, a substrate film with a thickness of 38 μm (trade name "MRF#38", polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) was attached to the exposed area of the color-changing adhesive sheet X 1 on the Eagle glass (not shown). Areas covered by masking film). In the above manner, the laminate L 19 of Example 15 was obtained. The laminated body L 19 is sequentially equipped with Eagle glass, a color-changing adhesive sheet X 1 impregnated with ethanol, and a mask film and a base film on the sheet. The laminated body L 19 comprises a laminated sheet of the color-changing adhesive sheet X 1 impregnated with ethanol and a masking film.
[參考例1] 除使用可變色黏著片材R 1來代替可變色黏著片材X 1以外，實施與實施例1之第1步驟相同之步驟，從而獲得參考例1之積層體L 21。積層體L 21依序具備Eagle玻璃、可變色黏著片材R 1及基材膜。 [Reference Example 1 ] Except for using the color-changing adhesive sheet R1 instead of the color-changing adhesive sheet X1, the same procedure as the first step of Example 1 was implemented to obtain the laminate L21 of Reference Example 1. The laminate L21 includes Eagle glass, a color-changing adhesive sheet R1, and a base film in this order.
[參考例2] 除使用可變色黏著片材R 2來代替可變色黏著片材X 1以外，實施與實施例1之第1步驟相同之步驟，從而獲得參考例2之積層體L 22。積層體L 22依序具備Eagle玻璃、可變色黏著片材R 2及基材膜。 [Reference Example 2 ] Except for using the color-changing adhesive sheet R2 instead of the color-changing adhesive sheet X1, the same procedure as the first step of Example 1 was implemented to obtain the laminate L22 of Reference Example 2 . The laminate L 22 includes Eagle glass, the color-changing adhesive sheet R 2 , and a base film in this order.
[參考例3] 除使用可變色黏著片材R 3來代替可變色黏著片材X 1以外，實施與實施例1之第1步驟相同之步驟，從而獲得參考例3之積層體L 23。積層體L 23依序具備Eagle玻璃、可變色黏著片材R 3及基材膜。 [Reference Example 3] Except for using the color-changing adhesive sheet R3 instead of the color-changing adhesive sheet X1, the same procedure as the first step of Example 1 was implemented to obtain the laminate L 23 of Reference Example 3. The laminate L 23 includes Eagle glass, the color-changing adhesive sheet R 3 , and a base film in this order.
[參考例4] 除使用可變色黏著片材R 4來代替可變色黏著片材X 1以外，實施與實施例1之第1步驟相同之步驟，從而獲得參考例4之積層體L 24。積層體L 24依序具備Eagle玻璃、可變色黏著片材R 4及基材膜。 [Reference Example 4 ] Except for using the color-changing adhesive sheet R4 instead of the color-changing adhesive sheet X1, the same procedure as the first step of Example 1 was implemented to obtain a laminate L24 of Reference Example 4. The laminate L 24 includes Eagle glass, a color-changing adhesive sheet R 4 , and a base film in this order.
＜初始透過率＞ 對於實施例1～10、13～15、比較例1～4及參考例1～4之各積層體，自製作起於25℃下經過24小時後，測定波長400～700 nm下之平均透過率(第1透過率測定)。該透過率測定使用透過率測定裝置(商品名為「U4150型分光光度計」，Hitachi High-Tech Science公司製造)。於裝置內，以積層體之Eagle玻璃位於光源側且該積層體之基材膜位於檢測器側之方式，配置積層體。又，於本測定中，使用僅對Eagle玻璃於相同條件下進行測定而獲得之透過率光譜作為基準線。所測得之平均透過率作為初始透過率T 0(%)示於表1～4、6、7。 <Initial transmittance> For each of the laminates of Examples 1-10, 13-15, Comparative Examples 1-4, and Reference Examples 1-4, after 24 hours at 25°C since the production, the measurement wavelength was 400-700 nm The average transmittance below (measurement of the first transmittance). For this transmittance measurement, a transmittance measuring device (trade name: "U4150 Spectrophotometer", manufactured by Hitachi High-Tech Science Co., Ltd.) was used. In the device, the laminate was arranged such that the Eagle glass of the laminate was on the light source side and the substrate film of the laminate was on the detector side. In addition, in this measurement, the transmittance spectrum obtained by measuring only Eagle glass under the same conditions was used as a reference line. The measured average transmittance is shown in Tables 1-4, 6, and 7 as initial transmittance T 0 (%).
＜積層體L 1～L 5、L 21～L 24之透過率變化＞ 對於經過第1透過率測定之實施例1～4、比較例1及參考例1～4之各積層體，以如下方式，研究因紫外線照射所導致之透過率變化。 <Change in transmittance of laminates L 1 to L 5 , L 21 to L 24 > The laminates of Examples 1 to 4, Comparative Example 1, and Reference Examples 1 to 4 subjected to the first transmittance measurement were performed as follows , to study the change of transmittance caused by ultraviolet radiation.
首先，對積層體照射紫外線(UV)(第1UV照射)。具體而言，於23℃及相對濕度50%之環境下，對於積層體中之可變色黏著片材自基材膜側照射UV。藉此，於可變色黏著片材中，由光酸產生劑產生酸，藉由該酸使隱色素顯色。於UV照射中，使用Quark Technology公司製造之UV-LED照射裝置(型號為「QEL-350-RU6W-CW-MY」)中之波長365 nm之UV-LED燈作為光源，將波長320～390 nm之範圍內之照射累計光量設為8000 mJ/cm 2。 First, ultraviolet rays (UV) are irradiated to the laminate (1st UV irradiation). Specifically, in an environment of 23° C. and a relative humidity of 50%, UV was irradiated to the color-changing adhesive sheet in the laminate from the base film side. Thereby, in the color-variable adhesive sheet, an acid is generated by the photoacid generator, and the leucochrome is developed by the acid. In UV irradiation, a UV-LED lamp with a wavelength of 365 nm in a UV-LED irradiation device manufactured by Quark Technology (model "QEL-350-RU6W-CW-MY") is used as a light source, and a wavelength of 320-390 nm The cumulative light intensity of irradiation within the range is set to 8000 mJ/cm 2 .
繼而，測定積層體於波長400～700 nm下之平均透過率(第2透過率測定)。本測定中之使用裝置及條件與第1透過率測定中之使用裝置及條件相同。將所測得之平均透過率於表1中表示為透過率T 1(%)。初始透過率T 0與透過率T 1之差ΔT(＝T 0－T 1)亦示於表1中。相較於比較例1之積層體L 5而言，實施例1～4之積層體L 1～L 4之ΔT明顯較小，顯示出良好之變色抑制性。又，比較例1之積層體L 5(未向可變色黏著片材內調配著色性低下成分)與參考例1～4之積層體L 21～L 24(向可變色黏著片材內調配了著色性低下成分)之透過率T 1之差表示著色性低下成分之著色性低下性能。即，於共存有光酸產生劑(第1化合物)及顯色性化合物(第2化合物)與著色性低下成分之積層體L 21～L 24之可變色黏著片材R 1～R 4(第1系統)中，著色性低下成分發揮著色性低下性能，故而該第1系統中因紫外線照射(外部刺激賦予)所導致之透過率之降低ΔT小於除不存在著色性低下成分以外與積層體L 21～L 24之可變色黏著片材R 1、R 2(第1系統)相同之積層體L 5之可變色黏著片材X 1(第2系統)中因紫外線照射(外部刺激賦予)所導致之透過率之降低ΔT'。如此可知，於可變色黏著片材中，自著色處理前便共存有光酸產生劑(第1化合物)及顯色性化合物(第2化合物)與著色性低下成分之情形時，該可變色黏著片材之著色能力較低而不易著色(參考例1～4)。針對此種情況，事後使著色性低下成分浸透至使特定區域著色後之可變色黏著片材，藉此，可使上述特定區域充分發揮其著色能力而良好地著色，並且使非著色區域(透明區域)不易變色而抑制變色(本發明)。 Next, the average transmittance of the laminate at a wavelength of 400 to 700 nm was measured (second transmittance measurement). The equipment and conditions used in this measurement are the same as those used in the first transmittance measurement. The measured average transmittance is expressed in Table 1 as transmittance T 1 (%). Table 1 also shows the difference ΔT (=T 0 −T 1 ) between the initial transmittance T 0 and the transmittance T 1 . Compared with the laminate L5 of Comparative Example 1, the ΔT of the laminates L 1 -L 4 of Examples 1-4 is significantly smaller, showing good discoloration suppression. In addition, the laminate L 5 of Comparative Example 1 (the color-changing adhesive sheet was not mixed with the color-changing adhesive sheet) and the laminates L 21 to L 24 of Reference Examples 1-4 (the color-changing adhesive sheet was mixed with the coloring The difference in the transmittance T1 of the low-coloring component) represents the low-coloring performance of the low-coloring component. That is, in the color-changing adhesive sheets R 1 to R 4 of the laminates L 21 to L 24 in which the photoacid generator (the first compound) and the color-developing compound (the second compound) and the coloring property-lowering component coexist In system 1), the coloring-reducing component exhibits coloring-reducing performance, so the decrease in transmittance ΔT due to ultraviolet irradiation (external stimulus application) in the first system is smaller than that of the laminate L except that there is no coloring-reducing component. 21 ~ L 24 color-changing adhesive sheet R 1 , R 2 (first system) same laminate L 5 color-changing adhesive sheet X 1 (second system) caused by ultraviolet radiation (external stimulus) The decrease in transmittance ΔT'. Thus, it can be seen that in the color-changing adhesive sheet, when the photoacid generator (the first compound) and the color-developing compound (the second compound) coexist with the low-coloring component before the coloring treatment, the color-changing adhesive sheet The coloring ability of the sheet is low and it is not easy to be colored (Reference Examples 1-4). In this case, the color-changing adhesive sheet after the color-reducing component is impregnated into the color-changing adhesive sheet after the coloring of the specific area can be made to fully exert its coloring ability in the above-mentioned specific area, and the non-coloring area (transparent area) can be colored well. region) is less prone to discoloration and suppresses discoloration (the present invention).
[表1]
＜積層體L 6～L 11之透過率變化＞ 對於經過第1透過率測定之實施例5～8及比較例2、3之各積層體，以如下方式，研究由耐候性試驗所得之透過率變化。 <Change in Transmittance of Laminates L 6 to L 11 > For each of the laminates of Examples 5 to 8 and Comparative Examples 2 and 3 that underwent the first transmittance measurement, the transmittance obtained from the weather resistance test was studied in the following manner Variety.
首先，於耐候試驗裝置(商品名為「Super Xenon Weather Meter SX75」，須賀試驗機公司製造)之腔室內配置積層體。具體而言，於腔室內，以積層體之基材膜位於光源(超級氙氣燈)側之方式，配置積層體。繼而，於55℃及相對濕度55%之環境下，藉由超級氙氣燈(波長為300～400 nm)對積層體中之可變色黏著片材進行24小時之光照射。First, the laminate was placed in a chamber of a weather resistance tester (trade name: "Super Xenon Weather Meter SX75", manufactured by Suga Testing Instrument Co., Ltd.). Specifically, the laminate was placed in the chamber so that the base film of the laminate was located on the light source (super xenon lamp) side. Then, under an environment of 55°C and a relative humidity of 55%, the color-changing adhesive sheet in the laminate was irradiated with light for 24 hours by a super xenon lamp (wavelength: 300-400 nm).
繼而，測定積層體於波長400～700 nm下之平均透過率(第3透過率測定)。將所測得之平均透過率於表2、3中表示為透過率T 2(%)。表2、3中亦示出初始透過率T 0與透過率T 2之差ΔT(＝T 0－T 2)。如表2所示，相較於比較例2之積層體L 8而言，實施例5、6之積層體L 6、L 7之ΔT明顯較小，顯示出良好之變色抑制性。如表3所示，相較於比較例3之積層體L 11而言，實施例7、8之積層體L 9、L 10之ΔT之絕對值明顯較小，顯示出良好之變色抑制性。 Next, the average transmittance of the laminate at a wavelength of 400 to 700 nm was measured (third transmittance measurement). The measured average transmittance is expressed in Tables 2 and 3 as transmittance T 2 (%). Tables 2 and 3 also show the difference ΔT (=T 0 −T 2 ) between the initial transmittance T 0 and the transmittance T 2 . As shown in Table 2, compared with the laminate L8 of Comparative Example 2, the ΔT of the laminates L 6 and L 7 of Examples 5 and 6 is significantly smaller, showing good discoloration suppression. As shown in Table 3, compared with the laminate L 11 of Comparative Example 3, the absolute value of ΔT of the laminates L 9 and L 10 of Examples 7 and 8 is significantly smaller, showing good discoloration inhibition.
[表2]
[表3]
＜積層體L 12～L 14之透過率變化＞ 對於經過第1透過率測定之實施例9、10及比較例4之各積層體，以如下方式，研究因紫外線照射所導致之透過率變化。 <Transmittance Changes of Laminates L 12 to L 14 > For each of the laminates of Examples 9 and 10 and Comparative Example 4 subjected to the first transmittance measurement, changes in transmittance due to ultraviolet irradiation were studied as follows.
首先，對積層體照射紫外線(UV)。UV照射之方法及條件與以上關於第1UV照射敍述之方法及條件相同。繼而，對於積層體中配置有遮罩膜之區域(遮蔽區域)及未配置遮罩膜之區域(非遮蔽區域)之各者，測定波長400～700 nm下之平均透過率。本測定中之使用裝置及條件與第1及第2透過率測定中之使用裝置及條件相同。將所測得之平均透過率於表4中表示為透過率T 1(%)。表4中亦示出遮蔽區域與非遮蔽區域之透過率T 1之差(區域間透過率差)。於比較例4之積層體L 14中，實質上並未產生區域間透過率差。即，於比較例4之積層體L 14中，非遮蔽區域與遮蔽區域相同，著色性實質上並未降低。相對於此，於實施例9、10之積層體L 12、L 13中，產生顯著之區域間透過率差。即，於實施例9、10之積層體L 12、L 13中，遮蔽區域之著色性實質上未降低且非遮蔽區域之著色性顯著降低(相較於比較例4之積層體L 14而言，實施例9、10之積層體L 12、L 13於非遮蔽區域顯示出良好之變色抑制性)。即，於實施例9、10之積層體L 12、L 13之可變色黏著片材中，可維持著色區域(遮蔽區域)之充分之著色性，並且抑制非著色區域(非遮蔽區域)之變色。 First, the laminate is irradiated with ultraviolet rays (UV). The method and conditions of UV irradiation are the same as those described above for the first UV irradiation. Next, the average transmittance at a wavelength of 400 to 700 nm was measured for each of the region where the mask film was arranged (shielded region) and the region where the mask film was not arranged (non-shielded region) in the laminate. The equipment and conditions used in this measurement are the same as those used in the first and second transmittance measurements. The measured average transmittance is expressed in Table 4 as transmittance T 1 (%). Table 4 also shows the difference in transmittance T1 between the shielded region and the non-shielded region (transmittance difference between regions). In the laminate L14 of Comparative Example 4 , there was substantially no difference in transmittance between regions. That is, in the laminate L14 of Comparative Example 4 , the non-shielded region was the same as the shielded region, and the colorability was not substantially lowered. In contrast, in the laminates L 12 and L 13 of Examples 9 and 10, a significant difference in transmittance between regions occurred. That is, in the laminates L 12 and L 13 of Examples 9 and 10, the coloring property of the masked area is not substantially reduced and the coloring property of the non-masking area is significantly reduced (compared to the laminated body L 14 of Comparative Example 4 , the laminates L 12 and L 13 of Examples 9 and 10 showed good discoloration suppression in the non-shielded area). That is, in the color-changing adhesive sheets of the laminates L12 and L13 of Examples 9 and 10, sufficient colorability of the colored region (masked region) can be maintained, and discoloration of the non-colored region (non-masked region) can be suppressed .
[表4]
＜積層體L 15、L 16、L 5之透過率變化＞ 對於實施例11、12及比較例1之各積層體，以如下方式，研究紫外線照射後之透過率之變化。 <Change in transmittance of laminates L 15 , L 16 , and L 5 > For each of the laminates in Examples 11 and 12 and Comparative Example 1, changes in transmittance after ultraviolet irradiation were studied as follows.
首先，對剛製作後之積層體照射紫外線(第2UV照射)，其後，測定該積層體於波長400～700 nm下之平均透過率(第4透過率測定)。對自製作起於25℃下經過48小時後之另一積層體照射紫外線(第3UV照射)，其後，測定該積層體於波長400～700 nm下之平均透過率(第5透過率測定)。對自第2步驟中之貼合起於85℃下經過48小時後之又一積層體照射紫外線(第4UV照射)，其後，測定該積層體於波長400～700 nm下之平均透過率(第6透過率測定)。第2～第4UV照射中之使用裝置及條件與第1UV照射中之使用裝置及條件相同。第4～第6透過率測定中之使用裝置及條件與第1透過率測定中之使用裝置及條件相同。將第4透過率測定中所測得之平均透過率於表5中表示為透過率T 3(%)，將第5透過率測定中所測得之平均透過率於表5中表示為透過率T 4(%)，將第6透過率測定中所測得之平均透過率於表5中表示為透過率T 5(%)。相較於比較例1之積層體L 5而言，實施例11、12之積層體L 15、L 16之透過率差T 4－T 3及透過率差T 5－T 3均明顯較大，顯示出顯著之著色性之降低(變色抑制性)。特別是，關於實施例11之積層體L 16，於更高溫下，可變色黏著片材之著色性降低之程度較高(即，透過率差T 5－T 3較大)，顯示出優異之變色抑制性。 First, the laminate immediately after production was irradiated with ultraviolet light (second UV irradiation), and thereafter, the average transmittance of the laminate at a wavelength of 400 to 700 nm was measured (fourth transmittance measurement). After 48 hours at 25°C from production, another laminate was irradiated with ultraviolet rays (3rd UV irradiation), and thereafter, the average transmittance of the laminate at a wavelength of 400 to 700 nm was measured (5th transmittance measurement) . UV rays were irradiated to another laminate after 48 hours at 85°C from bonding in the second step (4th UV irradiation), and then the average transmittance of the laminate at a wavelength of 400 to 700 nm was measured ( 6th transmittance measurement). The apparatus and conditions used in the second to fourth UV irradiations are the same as those used in the first UV irradiation. The equipment and conditions used in the fourth to sixth transmittance measurements are the same as those used in the first transmittance measurement. The average transmittance measured in the fourth transmittance measurement is expressed in Table 5 as transmittance T 3 (%), and the average transmittance measured in the fifth transmittance measurement is expressed in Table 5 as transmittance T 4 (%), the average transmittance measured in the sixth transmittance measurement is expressed in Table 5 as transmittance T 5 (%). Compared with the laminate L5 of Comparative Example 1, the transmittance difference T 4 -T 3 and the transmittance difference T 5 -T 3 of the laminates L 15 and L 16 of Examples 11 and 12 are significantly larger, Remarkable reduction in coloring property (discoloration inhibition property) was exhibited. In particular, regarding the laminate L 16 of Example 11, at a higher temperature, the degree of reduction in the coloring property of the color-changing adhesive sheet is higher (that is, the transmittance difference T 5 -T 3 is larger), showing excellent Discoloration inhibition.
[表5]
＜積層體L 17～L 19之透過率變化＞ 對於實施例13～15之各積層體，以如下方式，研究因著色性低下處理(浸漬處理)所導致之透過率之變化。 <Change in transmittance of laminates L 17 to L 19 > For each of the laminates in Examples 13 to 15, changes in transmittance due to coloring reduction treatment (dipping treatment) were studied as follows.
於積層體之製造過程之中途，對於將可變色黏著片材X 1(單面具有基材膜)貼合於Eagle玻璃而獲得之中間積層體，測定波長400～700 nm下之平均透過率(第7透過率測定)。又，對經過著色性低下處理(浸漬處理)而製作之積層體照射紫外線(第5UV照射)，其後，測定該積層體於波長400～700 nm下之平均透過率(第8透過率測定)。關於實施例15之積層體L 19，對於配置有遮罩膜之區域(遮蔽區域)及未配置遮罩膜之區域(非遮蔽區域)之各者，實施第8透過率測定。第5UV照射中之使用裝置及條件與第1UV照射中之使用裝置及條件相同。第7、第8透過率測定中之使用裝置及條件與第1透過率測定中之使用裝置及條件相同。將第7透過率測定中所測得之平均透過率於表6、7中表示為透過率T 6(%)，將第8透過率測定中所測得之平均透過率於表6、7中表示為透過率T 7(%)。表6中亦示出透過率T 6與透過率T 7之差ΔT(＝T 7－T 6)。又，為了進行比較，表6中亦示出表1中所示之比較例1之積層體L 5之透過率測定結果(T 0、T 1、T 0－T 1)。如表6所示，相較於比較例1之積層體L 5而言，實施例13、14之積層體L 17、L 18之ΔT明顯較小，顯示出良好之變色抑制性。另一方面，對於實施例15之積層體L 19，亦將遮蔽區域與非遮蔽區域之透過率T 7之差(區域間透過率差)示於表7。又，為了進行比較，表7中亦示出表4中所示之比較例4之積層體L 14之透過率測定結果(T 0、T 1、遮蔽區域與非遮蔽區域之透過率差)。於比較例4之積層體L 14中，實質上未產生區域間透過率差，相對於此，於實施例15之積層體L 19中，產生顯著之區域間透過率差。即，於實施例15之積層體L 19中，遮蔽區域之著色性實質上未降低且非遮蔽區域之著色性顯著降低(相較於比較例4之積層體L 14而言，實施例15之積層體L 19於非遮蔽區域顯示出良好之變色抑制性)。即，於實施例15之積層體L 19之可變色黏著片材中，可維持著色區域(遮蔽區域)之充分之著色性，並且抑制非著色區域(非遮蔽區域)之變色。 In the middle of the production process of the laminate, the average transmittance at a wavelength of 400-700 nm was measured for an intermediate laminate obtained by laminating the color-changing adhesive sheet X 1 (with a base film on one side) to Eagle glass ( 7th transmittance measurement). In addition, ultraviolet ray was irradiated to the laminate manufactured by the coloring reduction treatment (dipping treatment) (the 5th UV irradiation), and thereafter, the average transmittance of the laminate at a wavelength of 400 to 700 nm was measured (the 8th transmittance measurement) . Regarding the laminate L 19 in Example 15, the eighth transmittance measurement was carried out for each of the region where the mask film was arranged (shielding region) and the region where the mask film was not arranged (non-shielding region). The apparatus and conditions used in the 5th UV irradiation were the same as those used in the 1st UV irradiation. The equipment and conditions used in the seventh and eighth transmittance measurements are the same as those used in the first transmittance measurement. The average transmittance measured in the seventh transmittance measurement is expressed in Tables 6 and 7 as transmittance T 6 (%), and the average transmittance measured in the eighth transmittance measurement is shown in Tables 6 and 7 Expressed as transmittance T 7 (%). Table 6 also shows the difference ΔT (=T 7 −T 6 ) between the transmittance T 6 and the transmittance T 7 . Also, for comparison, Table 6 also shows the transmittance measurement results (T 0 , T 1 , T 0 -T 1 ) of the laminate L 5 of Comparative Example 1 shown in Table 1. As shown in Table 6, compared with the laminate L5 of Comparative Example 1, the ΔT of the laminates L 17 and L 18 of Examples 13 and 14 is significantly smaller, showing good discoloration suppression. On the other hand, for the laminate L 19 of Example 15, the difference in transmittance T 7 between the shielded region and the non-shielded region (transmittance difference between regions) is also shown in Table 7. Also, for comparison, Table 7 also shows the transmittance measurement results (T 0 , T 1 , transmittance difference between the shielded area and the non-shielded area) of the laminate L14 of Comparative Example 4 shown in Table 4. In the laminate L14 of Comparative Example 4 , substantially no difference in transmittance between regions occurred, whereas in the laminate L19 of Example 15, a significant difference in transmittance between regions occurred. That is, in the laminated body L19 of Example 15, the coloring property of the masked area was not substantially reduced and the coloring property of the non-masking area was significantly reduced (compared to the laminated body L14 of Comparative Example 4 , the coloring property of Example 15 The laminate L19 exhibited good discoloration inhibition in the non-shielding area). That is, in the color-changing adhesive sheet of the laminate L19 of Example 15, sufficient colorability of the colored region (masked region) was maintained, and discoloration of the non-colored region (non-masked region) was suppressed.
[表6]
[表7]
11:第1區域(已著色區域) 12:第2區域(未著色區域) 21:第1構件 22:第2構件 L:積層片材 M:遮罩材 T:厚度方向 X:可變色黏著片材 Y:著色性低下片材 Z1:積層體 Z2:積層體 11: Area 1 (shaded area) 12:Second area (uncolored area) 21: 1st component 22: 2nd component L: laminated sheet M: masking material T: Thickness direction X: Color changeable adhesive sheet Y: Sheet with low colorability Z1: laminated body Z2: laminated body
圖1表示本發明之可變色黏著片材之變色抑制方法之一實施方式中之第1步驟。 圖2表示本發明之可變色黏著片材之變色抑制方法之一實施方式中之第2步驟。 圖3表示圖2所示之第2步驟後，第1構件與第2構件介隔積層片材而接合之情況。 圖4表示於第2步驟中使用著色性低下溶劑作為著色性低下介質之情況、或於第2步驟後自可變色黏著片材剝離著色性低下片材之情形時該第2步驟後第1構件與第2構件介隔可變色黏著片材而接合之情況。 圖5表示本發明之可變色黏著片材之變色抑制方法之一變化例。於本變化例中，於可變色黏著片材之已著色區域與著色性低下片材之間介存有遮罩材之狀態下，將著色性低下片材貼合於可變色黏著片材。 Fig. 1 shows the first step in one embodiment of the discoloration suppression method of the discoloration adhesive sheet of the present invention. Fig. 2 shows the second step in one embodiment of the discoloration suppression method of the discoloration adhesive sheet of the present invention. Fig. 3 shows the state where the first member and the second member are bonded via the laminated sheet after the second step shown in Fig. 2 . Fig. 4 shows the first member after the second step when the coloring-reducing solvent is used as the coloring-reducing medium in the second step, or when the coloring-reducing sheet is peeled off from the color-changing adhesive sheet after the second step The case of joining with the second member via a color-changing adhesive sheet. Fig. 5 shows a modified example of the discoloration suppression method of the color-changing adhesive sheet of the present invention. In this variation example, the color-changing adhesive sheet is bonded to the color-changing adhesive sheet with the mask material interposed between the colored region of the color-changing adhesive sheet and the poorly-colorable sheet.
11:第1區域(已著色區域) 11: Area 1 (shaded area)
12:第2區域(未著色區域) 12:Second area (uncolored area)
21:第1構件 21: 1st component
T:厚度方向 T: Thickness direction
X:可變色黏著片材 X: Color changeable adhesive sheet
Claims (12)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-035205 | 2021-03-05 | ||
| JP2021035205 | 2021-03-05 | ||
| JP2022027086A JP2022135979A (en) | 2021-03-05 | 2022-02-24 | Discoloration prevention method of variable color adhesive sheet and laminate sheet |
| JP2022-027086 | 2022-02-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW202246444A true TW202246444A (en) | 2022-12-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW111107968A TW202246444A (en) | 2021-03-05 | 2022-03-04 | Method for inhibiting color-changeable pressure-sensitive adhesive sheet from discoloring and laminated sheet |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20230154822A (en) |
| TW (1) | TW202246444A (en) |
| WO (1) | WO2022186180A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62153377A (en) * | 1985-12-27 | 1987-07-08 | F S K Kk | Pressure-sensitive adhesive sheet |
| JP2753918B2 (en) * | 1992-05-26 | 1998-05-20 | 富士写真フイルム株式会社 | Image forming material |
| KR102484120B1 (en) | 2019-03-15 | 2023-01-04 | 닛토덴코 가부시키가이샤 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer and pressure-sensitive adhesive sheet |
| WO2020188985A1 (en) * | 2019-03-15 | 2020-09-24 | 日東電工株式会社 | Adhesive sheet, production method for adhesive sheet, production method for intermediate laminate, and intermediate laminate |
| WO2020189390A1 (en) * | 2019-03-15 | 2020-09-24 | 日東電工株式会社 | Adhesive agent composition, adhesive agent layer, and adhesive sheet |
-
2022
- 2022-03-01 WO PCT/JP2022/008527 patent/WO2022186180A1/en active Application Filing
- 2022-03-01 KR KR1020237029354A patent/KR20230154822A/en unknown
- 2022-03-04 TW TW111107968A patent/TW202246444A/en unknown
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| Publication number | Publication date |
|---|---|
| WO2022186180A1 (en) | 2022-09-09 |
| KR20230154822A (en) | 2023-11-09 |
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