TW202035618A - Colored adhesive sheet and display apparatus capable of improving the sense of design of a display apparatus - Google Patents
Colored adhesive sheet and display apparatus capable of improving the sense of design of a display apparatus Download PDFInfo
- Publication number
- TW202035618A TW202035618A TW108142904A TW108142904A TW202035618A TW 202035618 A TW202035618 A TW 202035618A TW 108142904 A TW108142904 A TW 108142904A TW 108142904 A TW108142904 A TW 108142904A TW 202035618 A TW202035618 A TW 202035618A
- Authority
- TW
- Taiwan
- Prior art keywords
- colored adhesive
- display device
- adhesive layer
- meth
- haze value
- Prior art date
Links
Images
Classifications
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- 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
-
- 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
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- 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
-
- 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
- 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]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
-
- 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
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Mounting And Adjusting Of Optical Elements (AREA)
- Liquid Crystal (AREA)
Abstract
Description
本發明是關於能夠用於黏合顯示設備構成構件的著色黏著片、以及使用該著色黏著片的顯示設備。The present invention relates to a colored adhesive sheet that can be used to bond constituent members of a display device, and a display device using the colored adhesive sheet.
近幾年的顯示設備(顯示器),例如汽車的儀表板、汽車導航系統、設置在控制台的各種儀表等的車載用顯示設備、一般用戶用的平板終端機等的顯示設備、商業用平板終端機或數位看板等的顯示設備、室外用數位看板等的顯示設備等,大多使用液晶顯示裝置。Display devices (displays) in recent years, such as automotive dashboards, car navigation systems, various meters installed in consoles, display devices such as in-vehicle display devices, display devices such as tablet terminals for general users, and commercial tablet terminals LCD devices are mostly used in display devices such as mobile phones and digital signage, and display devices such as outdoor digital signage.
在如上所述以車載用為首的顯示設備,要求在該顯示設備熄燈時,與該顯示設備的周邊構件,例如框材展現出一體感,而提升設計性。為此,可考慮將顯示設備著色,例如在專利文獻1~4,揭示關於顯示設備著色的發明。
[先前技術文獻]
[專利文獻]In the above-mentioned display devices, including in-vehicle use, it is required that when the display device is turned off, it is required to exhibit a sense of integration with the peripheral components of the display device, such as frame materials, so as to improve the design. For this reason, it can be considered to color the display device. For example,
[專利文獻1]日本特開2000-313871號公報 [專利文獻2]日本特開2009-188298號公報 [專利文獻3]日本特開2012-234028號公報 [專利文獻4]日本特開2017-57375號公報[Patent Document 1] Japanese Patent Application Publication No. 2000-313871 [Patent Document 2] JP 2009-188298 A [Patent Document 3] JP 2012-234028 A [Patent Document 4] JP 2017-57375 A
[發明所欲解決的課題][The problem to be solved by the invention]
但是,上述專利文獻1~4所揭示的技術,由於著色的目的均不同,並不能使顯示設備與周邊構件展現一體感,而提升設計性。However, the technologies disclosed in
本發明係有鑑於如上所述的緣由所完成,以提供可提升顯示設備的設計性的著色黏著片、及提升設計性的顯示設備為目標。 [用於解決課題的手段]The present invention is completed in view of the above-mentioned reasons, and aims to provide a colored adhesive sheet that can improve the design of a display device and a display device that can improve the design. [Means for solving problems]
為達成上述目標,第1,本發明提供一種著色黏著片,其特徵在於,其係具備用於黏合一顯示設備構成構件,與其他的顯示設備構成構件的含有著色劑的黏著劑所構成的著色黏著劑層的著色黏著片,上述著色黏著劑層在波長780nm的霧度值與在波長380nm的霧度值的平均值的平均霧度為1%以上且60%以下(發明1)。In order to achieve the above objectives, firstly, the present invention provides a colored adhesive sheet, which is characterized in that it is provided with a coloring agent composed of a coloring agent-containing adhesive for bonding a display device constituent member and other display device constituent members. In the colored adhesive sheet of the adhesive layer, the average haze of the haze value of the colored adhesive layer at a wavelength of 780 nm and the average haze value at a wavelength of 380 nm is 1% or more and 60% or less (Invention 1).
根據上述發明(發明1),將滿足上述物性的著色黏著劑層使用於顯示設備時,可提升將該顯示設備熄燈時該顯示設備的設計性,特別是外觀協調性。例如,可對該顯示設備,賦予與周邊構件(特別是黑色的框材等)的一體感。According to the above invention (Invention 1), when the colored adhesive layer that satisfies the above physical properties is used in a display device, the design of the display device when the display device is turned off can be improved, especially the appearance coordination. For example, the display device can be given a sense of unity with peripheral members (especially black frame materials, etc.).
在上述發明(發明1),其中上述著色黏著劑層,在波長780nm的霧度值與在波長380nm的霧度值的差值,以15百分點以下為佳(發明2).In the above invention (Invention 1), wherein the colored adhesive layer, the difference between the haze value at a wavelength of 780nm and the haze value at a wavelength of 380nm is preferably 15% or less (Invention 2).
在上述發明(發明1、2),其中在波長區域380nm~780nm的以5nm間距的各波長的上述著色黏著劑層的霧度值的標準差,以5以下為佳(發明3)。In the above inventions (
在上述發明(發明1~3),其中上述著色黏著劑層的全光線穿透率,以10%以上且小於95%,而上述著色黏著劑層的CIE1976L*a*b*表色系所規定的色度a*及色度b*,分別以-7~7為佳(發明4)。In the above inventions (
在上述發明(發明1~4),其中將上述著色劑,以醋酸乙酯稀釋1萬倍的液體,在波長780nm的霧度值與在波長380nm的霧度值的平均值的平均霧度,以1%以上且60%以下為佳(發明5)。In the above inventions (
在上述發明(發明1~5),其中將上述著色劑,以醋酸乙酯稀釋1萬倍的液體,在波長780nm的霧度值與在波長380nm的霧度值的差值,以30百分點以下為佳(發明6)。In the above invention (
在上述發明(發明1~6),其中上述著色劑以黑色的顏料為佳(發明7)。In the above inventions (
在上述發明(發明1~7),其中上述黏著劑以丙烯酸系黏著劑為佳(發明8)。In the above inventions (
在上述發明(發明1~8),其中上述黏著劑,以將含有(甲基)丙烯酸酯聚合物(A)、交聯劑(B)、及著色劑(C)的黏著性組合物交聯者為佳(發明9)。In the aforementioned inventions (
在上述發明(發明1~9),其具備:2片剝離片;及以接於上述2片剝離片的剝離面而被夾持在上述剝離片的上述著色黏著劑層為佳(發明10)。In the above inventions (
第2,本發明提供一種顯示設備,其特徵在於,其係具備:一顯示設備構成構件;其他的顯示設備構成構件;及將上述一顯示設備構成構件與上述其他的顯示設備構成構件互相黏合的著色黏著劑層的顯示設備,上述著色黏著劑層,係上述著色黏著片(發明1~10)的著色黏著劑層(發明11)。Second, the present invention provides a display device characterized in that it includes: a display device constituent member; other display device constituent members; and a display device constituent member and the other display device constituent members are bonded to each other In a display device with a colored adhesive layer, the colored adhesive layer is the colored adhesive layer of the colored adhesive sheet (
在上述發明(發明11),其中上述一顯示設備構成構件及上述其他的顯示設備構成構件的至少一方,以至少在以上述著色黏著劑層黏合側的面具有段差為佳(發明12)。In the above invention (Invention 11), it is preferable that at least one of the above-mentioned one display device constituent member and the above-mentioned other display device constituent members has a step at least on the surface where the colored adhesive layer is bonded (Invention 12).
在上述發明(發明11、12),其具有黑色框材為佳(發明13)。
[發明的效果]In the above inventions (
根據本發明的著色黏著片,可提升顯示設備的設計性。再者,關於本發明的顯示設備,可成為提升設計性的。According to the colored adhesive sheet of the present invention, the design of the display device can be improved. Furthermore, the display device of the present invention can be improved in design.
以下,說明關於本發明的實施形態。 [著色黏著片] 關於本發明的一實施形態的著色黏著片,具備為了黏合一顯示設備構成構件,與其他顯示設備構成構件的含有著色劑的黏著劑所構成的著色黏著劑層,較佳的是在該著色黏著劑層的一面或兩面層積剝離片而成。關於顯示設備及顯示設備構成構件將於後述。Hereinafter, embodiments of the present invention will be described. [Colored adhesive sheet] Regarding the colored adhesive sheet of one embodiment of the present invention, a colored adhesive layer composed of an adhesive containing a coloring agent for bonding a display device constituent member with other display device constituent members is preferably used in the colored adhesive It is formed by laminating release sheets on one or both sides of the agent layer. The display device and its components will be described later.
作為關於本實施形態的著色黏著片的一例,於圖1表示具體的構成。
如圖1所示,著色黏著片1是由2片剝離片12a、12b,及以接於該等2片剝離片12a、12b的剝離面,被該2片剝離片12a、12b夾持的黏著劑層11所構成。再者,在本說明書的剝離片的剝離面,是指在剝離片中具有剝離性的面,包含施以剝離處理的面及即使沒有施以剝離處理亦顯示剝離性的面之任一種。As an example of the colored adhesive sheet of this embodiment, the specific structure is shown in FIG.
As shown in Figure 1, the colored
1.各構件
1-1.著色黏著劑層
關於本實施形態的著色黏著片1的著色黏著劑層11在波長780nm的霧度值與在波長380nm的霧度值的平均值的平均霧度為1%以上且60%以下。再者,在本說明書的霧度值是遵照JIS K7136︰2000測定之值。1. Each component
1-1. Colored adhesive layer
With regard to the colored
將滿足上述物性的黏著劑層11,適用於顯示設備時,在將該顯示設備熄燈時,能夠提升該顯示設備的設計性。該設計性,作為一例可舉出在熄燈時的外觀協調性。此時,對於該顯示設備能夠賦予與周邊構件,例如與黑色框材的整體感,藉此,而展現出高級感。具體而言,藉由使上述平均霧度在1%以上,在顯示設備熄燈時,入射顯示設備的畫面的光被適度散射,而可使顯示部與其周邊構件的邊界難以察覺(無邊框化)。藉此,可提升顯示設備在熄燈時,顯示設備與周邊構件的整體感。另一方面,藉由使上述平均霧度在60%以下,在顯示設備的熄燈時,抑制顯示設備畫面的發白,而提升與周邊構件的整體感。即,藉由上述平均霧度,以1%以上且60%以下,能夠對顯示設備在熄燈時,賦予該顯示設備與周邊構件的整體感,而能夠呈現優良的外觀。根據關於本實施形態的著色黏著片1,能夠如此地提升顯示設備的設計性。When the
作為上述周邊構件,具體而言,可舉例如以CIE1976L*a*b*表色系所規定的明度L*為23.2,色度a*為-0.5,色度b*為-1.5的汽車儀表板。作為上述周邊構件的色調,以明度L*為5~90,色度a*以-40~40,色度b*以-40~40為佳,特別是以明度L*為10~80,色度a*以-30~30,色度b*以-30~30更佳,進一步以明度L*為15~70,色度以a*-20~20,色度b*以-20~20為佳。關於本實施形態的著色黏著片1,可良好地使用於具有上述色調的周邊構件的顯示設備。As the above-mentioned peripheral member, specifically, for example, an automobile instrument panel with a lightness L* of 23.2, a chromaticity a* of -0.5, and a chromaticity b* of -1.5 as specified by the CIE1976L*a*b* color system . As the hue of the above-mentioned peripheral components, lightness L* is 5~90, chroma a* is -40~40, and chroma b* is -40~40, especially lightness L* is 10~80. -30~30 for a*, -30~30 for chroma b*, 15~70 for lightness L*, a*-20~20 for chroma, -20~20 for chroma b* Better. Regarding the colored
上述平均霧度,從顯示設備在熄燈時,使顯示部與其周邊構件的邊界難以察覺的觀點而言,需要在1%以上,以1.5%以上為佳,特別是以1.8%以上為佳,進一步以2.2%以上為佳。另一方面,上述平均霧度,在顯示設備熄燈時,從抑制顯示設備的畫面發白的觀點而言,需要在60%以下,以45%以下為佳,以30是%以下為更佳,特別是以20%以下為佳,進一步以12%以下為佳。The above-mentioned average haze should be 1% or more, preferably 1.5% or more, especially 1.8% or more, from the viewpoint of making the boundary between the display portion and its surrounding members difficult to detect when the display device is turned off. More than 2.2% is preferred. On the other hand, the above-mentioned average haze needs to be 60% or less, preferably 45% or less, and more preferably 30% or less from the viewpoint of suppressing whitening of the screen of the display device when the display device is turned off. In particular, it is preferably 20% or less, and further preferably 12% or less.
在本實施形態的著色黏著劑層11,在波長780nm的霧度值,在波長380nm的霧度值的差值(絕對值),以15百分點以下為佳,特別是以10百分點以下為佳,進一步以7百分點以下為佳。藉此,將在本實施形態的著色黏著劑層11適用於顯示設備時,在該顯示設備的點燈時,不管觀測位置、角度等,不會改變畫面的色調平衡。結果,在顯示設備的點燈時,可提升從廣泛的角度觀看時的畫像‧影像視認性(廣角視認性),而提供良好的畫質。In the colored
上述霧度值的差的下限值,雖可為0百分點,惟從能夠容易將上述平均霧度調整為所期望之值的觀點而言,以1百分點以上為佳,以2百分點以上為更佳,特別是以3百分點以上為佳,進一步以4百分點以上為佳。The lower limit of the difference in the above-mentioned haze value may be 0%, but from the viewpoint that the above-mentioned average haze can be easily adjusted to a desired value, 1% or more is preferable, and 2% or more is more preferable. Preferably, it is particularly preferably 3% or more, and further preferably 4% or more.
在本實施形態的著色黏著劑層11的在波長780nm的霧度值,從容易將上述平均霧度、霧度值的差值及後述的霧度值的標準差調整為所期望之值的觀點而言,以0.1~50%為佳,0.5~30%為更佳,特別是以0.7~20%為佳,進一步以1~10%為佳。The haze value of the colored
此外,在本實施形態的著色黏著劑層11的在波長380nm的霧度值,從容易將上述平均霧度、霧度值的差值及後述的霧度值的標準差調整為所期望之值的觀點而言,以0.1~60%為佳,以1~40%為更佳,特別是以2~30%為佳,進一步以4~20%為佳,以5~15%最為佳。In addition, the haze value of the colored
在本實施形態的著色黏著劑層11的在波長區域380nm~780nm的5nm間距的各波長(即380nm、385nm、390nm、‧‧‧、775nm、780nm)的霧度值的標準差,以5以下為佳,特別是以3以下為佳,進一步以2以下為佳。藉此,將本實施形態的著色黏著劑層11適用於顯示設備時,在該顯示設備的點燈時,不管觀測位置、角度等,不會改變畫面的色調平衡。其結果,在顯示設備的點燈時,提升從廣泛的角度看的時候的畫像、影像的視認性(廣角視認性),能提供良好的畫質。In the colored
上述標準差的下限值,雖以0為最佳,通常,以0.1以上為佳,特別是以0.4以上為佳,進一步以0.8以上為佳。Although the lower limit of the aforementioned standard deviation is preferably 0, it is generally preferably 0.1 or more, particularly 0.4 or more, and more preferably 0.8 or more.
在本實施形態的著色黏著劑層11的全光線霧度值,從容易將上述平均霧度、霧度值的差值及後述的霧度值的標準差調整為所期望之值的觀點而言,以0.1~60%為佳,以0.5~40%為更佳,特別是以1~30%為佳,進一步以1.5~20%為佳,以2~15%最為佳。The total light haze value of the colored
在本實施形態的著色黏著劑層11的全光線穿透率(遵照JIS K7361-1:1997測定之值),以10%以上且小於95%為佳,該著色黏著劑層11的依照CIE1976L*a*b*表色系所規定的色度a*及色度b*,分別以-7~7為佳。再者,在本說明書的色度a*及色度b*的測定方法,是如後述的試驗例所示。In the present embodiment, the total light transmittance of the colored adhesive layer 11 (measured in accordance with JIS K7361-1:1997) is preferably 10% or more and less than 95%. The colored
藉由使著色黏著劑層11滿足上述光學物性,應用於顯示設備的時候,在該顯示設備的熄燈時,增加黑色調,可更加提升該顯示設備的設計性(作為一例,在熄燈時的外觀協調性)。具體而言,對於顯示設備,特別是車載顯示設備,能夠更加提升與周邊構件的整體感,例如與黑色框材的整體感。此外,藉由使全光線穿透率為10%以上,能夠良好地確保作為顯示設備的視認性(起因於畫面亮度的畫像‧影像視認性)。By making the colored
全光線穿透率的上限值,從容易將上述平均霧度、霧度值的差值及後述的霧度值的標準差調整為所期望之值的觀點而言,以小於95%為佳,以90%以下為更佳,特別是以85%以下為佳,進一步以80%以下為佳。此外,全光線穿透率的下限值,從顯示設備的視認性的觀點而言,以25%以上為佳,以40%以上為更佳,特別是以50%以上為佳,進一步以60%以上為佳。The upper limit of the total light transmittance is preferably less than 95% from the viewpoint that it is easy to adjust the average haze, the difference of the haze value, and the standard deviation of the haze value described later to the desired value. , 90% or less is more preferable, especially 85% or less, and more preferably 80% or less. In addition, from the viewpoint of the visibility of the display device, the lower limit of the total light transmittance is preferably 25% or more, more preferably 40% or more, particularly preferably 50% or more, and further preferably 60%. Above% is better.
上述色度a*,從上述顯示設備的設計性的觀點而言,以-7~7為佳,以-5~5為更佳,特別是以-3~3為佳,進一步以-1~1為佳。此外,上述色度b*,從上述顯示設備的設計性的觀點而言,以-7~7為佳,以-5~5為更佳,特別是以-3~3為佳,進一步以-1~1為佳。From the viewpoint of the design of the display device, the chromaticity a* is preferably -7~7, more preferably -5~5, particularly preferably -3~3, and further preferably -1~ 1 is better. In addition, the above-mentioned chromaticity b*, from the viewpoint of the design of the above-mentioned display device, is preferably -7~7, more preferably -5~5, particularly preferably -3~3, and further preferably- 1~1 is better.
另一方面,著色黏著劑層11之依照CIE1976L*a*b*表色系所規定的明度L*,從容易將上述平均霧度調整在1%以上,能夠使顯示設備與周邊構件的邊界難以察覺的觀點而言,以99以下為佳,以95以下為更佳,特別是以92以下為佳,進一步以91以下為佳。此外,該明度L*,從容易將上述平均霧度值調整在60%以下以抑制畫面的發白,或將上述霧度值的差值及標準差調整在所期望之值的觀點而言,以10以上為佳,以25以上為更佳,特別是以50以上為佳,進一步以70以上為佳,以80以上最為佳。On the other hand, the lightness L* specified by the CIE1976L*a*b* color system of the colored
以上的光學物性,可藉由適當地選擇構成著色黏著劑層11的黏著劑的著色劑的種類及含量而達成。The above optical properties can be achieved by appropriately selecting the type and content of the coloring agent constituting the adhesive of the
上述著色劑,以醋酸乙酯將該著色劑稀釋1萬倍的液體的在波長780nm的霧度值與在波長380nm的霧度值的平均值的平均霧度的下限值,以1%以上為佳,特別是以2%以上為佳,進一步以3%以上為佳。此外,上述著色劑,該平均霧度的上限值,以60%以下為佳,以40%以下為佳,特別是以30%以下為佳,進一步以25%以下為佳。藉由適量使用如此的著色劑,容易滿足上述著色黏著劑層11的平均霧度。The lower limit of the average haze value of the average value of the haze value at the wavelength of 780nm and the haze value at the wavelength of 380nm of the liquid obtained by diluting the colorant 10,000 times with ethyl acetate is 1% or more More preferably, it is more preferably 2% or more, and more preferably 3% or more. In addition, for the above-mentioned coloring agent, the upper limit of the average haze is preferably 60% or less, preferably 40% or less, particularly preferably 30% or less, and further preferably 25% or less. By using such a coloring agent in an appropriate amount, it is easy to satisfy the average haze of the colored
此外,上述著色劑,以醋酸乙酯將該著色劑稀釋1萬倍的液體的在波長780nm的霧度值與在波長380nm的霧度值的差值,以30百分點以下為佳,以25百分點以下為更佳,特別是以20百分點以下為佳,進一步以16百分點以下為佳。藉由適量使用如此的著色劑,容易滿足上述著色黏著劑層11的霧度值的差值。In addition, the above-mentioned colorant, the difference between the haze value at a wavelength of 780nm and the haze value at a wavelength of 380nm of a liquid in which the colorant is diluted 10,000 times with ethyl acetate, preferably 30% or less, 25% The following is more preferable, especially 20% or less is preferable, and 16% or less is more preferable. By using such a coloring agent in an appropriate amount, it is easy to satisfy the difference in the haze value of the colored
再者,上述霧度值的差的下限值,雖可為0百分點,惟從容易將上述的著色黏著劑層11的平均霧度調整為1%以上,或容易將上述著色黏著劑層11的霧度值的差值及標準差調整為所期望之值的觀點而言,以0.1百分點以上為佳,特別是以0.5百分點以上為佳,進一步以1百分點以上為佳。Furthermore, although the lower limit of the difference in the above-mentioned haze value may be 0%, it is easy to adjust the average haze of the above-mentioned colored
將上述著色劑以醋酸乙酯稀釋1萬倍的液體的在波長780nm的霧度值,以0.1~50%為佳,以0.5~40%為更佳,特別是以1~30%為佳,進一步以2~25%為佳。此外,將上述著色劑以醋酸乙酯稀釋1萬倍的液體的在波長380nm的霧度值,以1~60%為佳,以3~50%為更佳,特別是以6~40%為佳,進一步以10~30%為佳。藉此,容易滿足上述平均霧度、霧度值的差值及後述霧度值的標準差。The haze value of the above-mentioned colorant diluted 10,000 times with ethyl acetate at a wavelength of 780nm is preferably 0.1-50%, more preferably 0.5-40%, especially 1-30%. Further preferably 2-25%. In addition, the haze value at the wavelength of 380nm of the liquid diluted 10,000 times with ethyl acetate is preferably 1~60%, more preferably 3~50%, especially 6~40%. Better, further preferably 10~30%. Thereby, it is easy to satisfy the above-mentioned average haze, the difference of the haze value, and the standard deviation of the haze value mentioned later.
再者,將上述著色劑以醋酸乙酯稀釋1萬倍的液體的在波長區域380nm~780nm的以5nm間距的各波長(即380nm、385nm、390nm、‧‧‧、775nm、780nm)的霧度值的標準差,以10以下為佳,以8以下為更佳,特別是以6以下為佳,進一步以5以下為佳。上述標準差的下限值,雖以0最為佳,惟通常以0.1以上為佳,特別是以0.2以上為佳,進一步以0.3以上為佳。藉由,容易滿足上述著色黏著劑層11的霧度值的標準差。Furthermore, the haze of the liquid diluted 10,000 times with ethyl acetate in the wavelength range of 380nm~780nm at 5nm pitch (ie 380nm, 385nm, 390nm, ‧‧‧, 775nm, 780nm) The standard deviation of the value is preferably 10 or less, more preferably 8 or less, particularly preferably 6 or less, and further preferably 5 or less. Although the lower limit of the above standard deviation is preferably 0, it is usually 0.1 or more, especially 0.2 or more, and further 0.3 or more. As a result, it is easy to satisfy the standard deviation of the haze value of the colored
上述著色劑,可為顏料,亦可為染料。顏料,可為無機系顏料,亦可為有機系顏料。由所得黏著劑的耐久性的觀點而言,以無機系顏料為佳。著色劑的顏色,可配合所欲展現整體感的周邊構件的顏色適當選擇,惟一般以黑色、咖啡色、深藍色、紫色、藍色等的暗色或濃色為佳,特別是以黑色為佳。The above-mentioned colorant may be a pigment or a dye. The pigment may be an inorganic pigment or an organic pigment. From the viewpoint of durability of the obtained adhesive, inorganic pigments are preferred. The color of the coloring agent can be appropriately selected according to the color of the peripheral components that you want to show the overall feeling, but generally dark or strong colors such as black, coffee, dark blue, purple, and blue are preferred, and black is particularly preferred.
作為無機系顏料,可舉出例如,碳黑、鈷系色素、鐵系色素、鉻系色素、鈦系色素、釩系色素、鋯系色素、鉬系色素、釕系色素、鉑系色素、ITO(氧化銦錫)系色素、ATO(氧化銻錫)系色素等。Examples of inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (Indium tin oxide)-based dyes, ATO (antimony tin oxide)-based dyes, etc.
此外,作為有機系顏料及有機系染料,可舉出例如,胺鎓系色素、花青系色素、部花青素(merocyanine)系色素、克酮鎓(croconium)系色素、方酸鎓(squalium)系色素、甘菊環鎓(azulenium)系色素、聚甲炔(polymethine)系色素、萘醌(naphthoquinone)系色素、吡喃鎓系色素、酞青系色素、萘酞菁(naphthalocyanine)系色素、萘内醯胺(naphtholactam)系色素、偶氮基系色素、縮合偶氮基系色素、靛藍系色素、紫環酮(perinone)系色素、苝系色素、二噁嗪(dioxazine)系色素、喹吖酮(quinacridone)系色素、異吲哚啉酮(isoindolinone)系色素、喹酞酮(quinophthalone)系色素、吡咯系色素、硫靛藍(thioindigo)系色素、金屬錯合物系色素(金屬錯鹽染料)、二硫醇(dithiol)金屬錯合物系色素、吲哚酚(indole phenol)系色素、三烯丙基甲烷系色素、蒽醌系色素、二噁嗪系色素、萘酚(naphthol)色素、甲亞胺(azomethine)系色素、苯並咪唑酮(benzimidazolone)系色素、皮蒽酮(pyranthron)染料系色素及士林(threne)系色素等。In addition, as organic pigments and organic dyes, for example, amine-based pigments, cyanine-based pigments, merocyanine-based pigments, croconium-based pigments, and squalium ) Pigments, azulenium pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalene Naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacrine Quinacridone dyes, isoindolinone dyes, quinophthalone dyes, pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex salt dyes) ), dithiol metal complex dyes, indole phenol dyes, triallylmethane dyes, anthraquinone dyes, dioxazine dyes, naphthol dyes , Azomethine (azomethine) pigments, benzimidazolone (benzimidazolone) pigments, pyranthron (pyranthron) dyes and threne dyes, etc.
作為黑色顏料,可舉出例如碳黑、氧化銅、四氧化三鐵、二氧化錳、苯胺黑(aniline black)、活性炭等。此外,黑色染料,可舉出例如,高濃度的植物性染料或偶氮系染料等。Examples of black pigments include carbon black, copper oxide, triiron tetroxide, manganese dioxide, aniline black, activated carbon, and the like. In addition, black dyes include, for example, high-concentration vegetable dyes or azo dyes.
上述顏料或染料,為在著色黏著劑層11得到目標物性,可適當混合使用。The above-mentioned pigments or dyes can be appropriately mixed and used in order to obtain target physical properties in the colored
上述著色劑之中,由容易滿足上述物性,容易展現出與周邊構件的整體感的觀點而言,以碳黑、苯胺黑(nigrosine)系黑色染料及鉻酸鹽系黑色染料為佳。再者,碳黑,亦可對其表面施以既定的處理(例如親溶劑化處理),亦可不施行。Among the above-mentioned colorants, carbon black, nigrosine-based black dyes, and chromate-based black dyes are preferred from the viewpoint of easily satisfying the above-mentioned physical properties and easily exhibiting a sense of integration with peripheral members. Furthermore, carbon black may be subjected to a predetermined treatment (for example, a solvophilization treatment) on its surface, or not.
構成關於本實施形態的著色黏著片1的著色黏著劑層11的黏著劑種類,並無特別限定,可為例如,丙烯酸系黏著劑、聚酯系黏著劑、聚氨酯系黏著劑、橡膠系黏著劑、矽酮系黏著劑等的任一者。此外,該黏著劑,可為乳膠型、溶劑型或無溶劑型的任一者,可為交聯型或非交聯類型的任一者。該等之中,以黏著物性、光學特性等優良的丙烯酸系黏著劑為佳。The type of adhesive constituting the colored
此外,作為丙烯酸系黏著劑,可為活性能量線硬化性,亦可為活性能量線非硬化性。此外,作為丙烯酸系黏著劑,以交聯型為佳,進一步以熱交聯型為佳。In addition, as an acrylic adhesive, it may be active energy ray curable or active energy ray non-curable. In addition, as an acrylic adhesive, a cross-linked type is preferred, and a thermal cross-linked type is further preferred.
上述黏著劑,具體而言,以將含有(甲基)丙烯酸酯聚合物(A)、交聯劑(B)、及著色劑(C)的黏著性組合物(以下,有時稱為「黏著劑組合物P」。)交聯而成者為佳。此外,將上述黏著劑作成活性能量線硬化性的黏著劑時,黏著性組合物P,進一步含有活性能量線硬化性成分(D)為佳。The above-mentioned adhesive is specifically an adhesive composition containing (meth)acrylate polymer (A), crosslinking agent (B), and coloring agent (C) (hereinafter, sometimes referred to as "adhesive Agent composition P".) Cross-linked is preferred. In addition, when the aforementioned adhesive is used as an active energy ray-curable adhesive, the adhesive composition P preferably further contains an active energy ray-curable component (D).
黏著性組合物P所含有的著色劑(C)為上述著色劑。由該黏著性組合物P所得黏著劑,能夠發揮優良的光學特性、黏著力、耐久性(在高溫高濕條件下的段差追隨性)等。再者,在本說明書,所謂(甲基)丙烯酸是指丙烯酸及甲基丙烯酸的雙方。其他的類似用語亦相同。此外,在「聚合物」亦包含「共聚物」的概念。The coloring agent (C) contained in the adhesive composition P is the above-mentioned coloring agent. The adhesive obtained from the adhesive composition P can exhibit excellent optical properties, adhesive force, durability (step followability under high temperature and high humidity conditions) and the like. In addition, in this specification, (meth)acrylic acid means both acrylic acid and methacrylic acid. Other similar terms are also the same. In addition, "polymer" also includes the concept of "copolymer".
(1)黏著性組合物的成分 (1-1)(甲基)丙烯酸酯聚合物(A) 在本實施形態的(甲基)丙烯酸酯聚合物(A),作為構成該聚合物的單體單位,包含在分子內具有與交聯劑(B)反應的反應性基的含反應性基單體為佳。來自該含反應性基單體的反應性基與交聯劑(B)反應,形成交聯結構(三維網狀結構),得到具有所期望的凝聚力的黏著劑。(1) Ingredients of the adhesive composition (1-1) (Meth) acrylate polymer (A) In the (meth)acrylate polymer (A) of this embodiment, as a monomer unit constituting the polymer, a reactive group-containing monomer having a reactive group that reacts with the crosslinking agent (B) in the molecule is included Body is good. The reactive group derived from the reactive group-containing monomer reacts with the crosslinking agent (B) to form a crosslinked structure (three-dimensional network structure), and an adhesive having a desired cohesive force is obtained.
作為上述含反應性基單體,可良好地舉出在分子內具有羥基的單體(含羥基單體)、在分子內具有羧基的單體(含羧基單體)、在分子內具有胺基的單體(含胺基單體)等。該等之中,以與交聯劑(B)的反應性優良的含羥基單體或含羧基單體為佳,併用含羥基單體及含羧基單體亦佳。Examples of the above-mentioned reactive group-containing monomers include monomers having a hydroxyl group in the molecule (hydroxyl-containing monomers), monomers having a carboxyl group in the molecule (carboxyl group-containing monomers), and an amine group in the molecule. The monomers (amine-containing monomers) and so on. Among them, a hydroxyl group-containing monomer or a carboxyl group-containing monomer having excellent reactivity with the crosslinking agent (B) is preferred, and a combination of a hydroxyl group-containing monomer and a carboxyl group-containing monomer is also preferred.
作為含羥基單體,可舉出例如(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3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁基等的(甲基)丙烯酸羥基烷基酯等。其中,從所得到的(甲基)丙烯酸酯聚合物(A)的羥基與交聯劑(B)的反應性及與其他單體的共聚合性的觀點而言,以具有碳數為1~4的羥基烷基的(甲基)丙烯酸羥烷基酯為佳。具體而言,可良好地舉出例如,(甲基)丙烯酸2-羥基乙酯或(甲基)丙烯酸4-羥基丁酯等,特別是可良好地舉出丙烯酸2-羥基乙酯或丙烯酸4-羥基丁酯。該等可以單獨使用,亦可組合2種以上使用。Examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Hydroxyalkyl (meth)acrylates such as hydroxybutyl, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like. Among them, from the viewpoint of the reactivity of the hydroxyl group of the obtained (meth)acrylate polymer (A) with the crosslinking agent (B) and the copolymerizability with other monomers, it is assumed that it has a carbon number of 1 to The hydroxyalkyl (meth)acrylate of 4 hydroxyalkyl is preferred. Specifically, for example, 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, etc. can be mentioned well, especially 2-hydroxyethyl acrylate or
作為含羧基單體,可舉出例如丙烯酸、甲基丙烯酸、巴豆酸、馬來酸、依康酸、檸康酸等的乙烯性不飽和羧酸。其中,從所得到的(甲基)丙烯酸酯聚合物(A)的羧基與交聯劑(B)的反應性及與其他單體的共聚合性的觀點而言,以丙烯酸為佳。該等可以單獨使用,亦可組合2種以上使用。Examples of the carboxyl group-containing monomer include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Among them, from the viewpoint of the reactivity of the carboxyl group of the obtained (meth)acrylate polymer (A) with the crosslinking agent (B) and the copolymerizability with other monomers, acrylic acid is preferred. These can be used individually or in combination of 2 or more types.
作為含胺基單體,可舉出例如(甲基)丙烯酸胺基乙酯,(甲基)丙烯酸正丁基胺基乙酯等。該等可以單獨使用,亦可組合2種以上使用。Examples of the amine group-containing monomer include aminoethyl (meth)acrylate, n-butylaminoethyl (meth)acrylate, and the like. These can be used individually or in combination of 2 or more types.
(甲基)丙烯酸酯聚合物(A),作為構成該聚合物的單體單元,作為下限值以含有1質量%以上的含反應性基單體為佳,以含有5質量%以上為更佳,特別是以含有10質量%以上為佳。此外,從著色劑(C)在黏著劑中的分散性會變得更佳的傾向而言,以含有12質量%以上為更佳,以含有15質量%以上最為佳。另一方面,(甲基)丙烯酸酯聚合物(A),作為構成該聚合物的單體單元,作為上限值以含有35質量%以下的含反應性基單體為佳,以含有30質量%以下為更佳,特別是以含有20質量%以下為佳。此外,從著色劑(C)在黏著劑中的分散性會變得更佳的傾向而言,以含有18質量%以下為更佳。(甲基)丙烯酸酯聚合物(A),以上述的量含有含反應性基單體作為單體單元,則所得黏著劑可形成良好的交聯結構,能夠得到所期望的凝聚力。此外,著色劑(C)在黏著劑中的分散性有變得更佳的傾向,所得黏著劑的上述光學物性的再現性及均勻性良好,而顯示優良的設計性及視認性。再者,含反應性基單體為含羥基單體時,含量以15質量%以上為特佳。此時,會在黏著劑中殘留既定量的羥基。羥基為親水性基,而如此的親水性基以既定量存在於黏著劑中,則即使黏著劑被放置在高溫高濕條件下時,與在該高溫高濕條件下浸入黏著劑的水分的相溶性佳,結果,恢復到常溫常濕時可抑制黏著劑的白化(耐濕熱白化性優良)。The (meth)acrylate polymer (A), as the monomer unit constituting the polymer, the lower limit is preferably 1% by mass or more of reactive group-containing monomers, and more preferably 5% by mass or more. Preferably, it is particularly preferable to contain 10% by mass or more. In addition, from the tendency that the dispersibility of the colorant (C) in the adhesive becomes better, it is more preferable to contain 12% by mass or more, and 15% by mass or more is most preferable. On the other hand, the (meth)acrylate polymer (A), as the monomer unit constituting the polymer, preferably contains 35% by mass or less of reactive group-containing monomer as the upper limit, and preferably contains 30% by mass % Or less is more preferable, especially 20 mass% or less is preferable. In addition, in terms of the tendency that the dispersibility of the colorant (C) in the adhesive becomes better, the content of 18% by mass or less is more preferable. The (meth)acrylate polymer (A) contains a reactive group-containing monomer as a monomer unit in the above-mentioned amount, and the resulting adhesive can form a good crosslinked structure and can obtain a desired cohesive force. In addition, the dispersibility of the colorant (C) in the adhesive tends to become better, and the obtained adhesive has good reproducibility and uniformity of the above-mentioned optical physical properties, and exhibits excellent design and visibility. Furthermore, when the reactive group-containing monomer is a hydroxyl group-containing monomer, the content is particularly preferably 15% by mass or more. At this time, a predetermined amount of hydroxyl groups will remain in the adhesive. The hydroxyl group is a hydrophilic group, and such a hydrophilic group is present in the adhesive in a predetermined amount. Even when the adhesive is placed under high temperature and high humidity conditions, it will be the same as the moisture immersed in the adhesive under the high temperature and high humidity conditions. The solubility is good, and as a result, the whitening of the adhesive can be suppressed when returning to normal temperature and humidity (excellent heat and humid whitening resistance).
此外,(甲基)丙烯酸酯聚合物(A),作為構成該聚合物的單體單元,不含有含羧基單體亦佳。由於羧基為酸成分,故藉由不含有含羧基單體,可抑制黏著劑的黏附對象,因酸而發生不良,例如,存在錫摻雜氧化銦(ITO)等的透明導電膜、金屬膜等時,因酸發生該等不良(腐蝕、電阻值變化等)。惟,可容許以不發生該不良的程度,含有含羧基單體。具體而言,在(甲基)丙烯酸酯聚合物(A)中,作為單體單元,可容許含羧基單體以0.1質量%以下含有,較佳為0.01質量%以下,更佳的是0.001質量%以下。In addition, the (meth)acrylate polymer (A) preferably does not contain a carboxyl group-containing monomer as a monomer unit constituting the polymer. Since the carboxyl group is an acid component, by not containing the carboxyl group-containing monomer, the adhesion target of the adhesive can be suppressed, and the occurrence of defects due to acid, such as tin-doped indium oxide (ITO), etc. transparent conductive film, metal film, etc. At that time, such defects (corrosion, resistance value change, etc.) occur due to acid. However, it is acceptable to contain a carboxyl group-containing monomer to such an extent that this defect does not occur. Specifically, in the (meth)acrylate polymer (A), as a monomer unit, a carboxyl group-containing monomer may be allowed to be contained in 0.1% by mass or less, preferably 0.01% by mass or less, more preferably 0.001% by mass %the following.
(甲基)丙烯酸酯聚合物(A),含有(甲基)丙烯酸烷基酯作為構成該聚合物的單體單元為佳。藉此可顯現良好的黏著性。烷基可為直鏈狀,或亦可為分支鏈狀。The (meth)acrylate polymer (A) preferably contains an alkyl (meth)acrylate as a monomer unit constituting the polymer. This can show good adhesion. The alkyl group may be linear or branched.
(甲基)丙烯酸烷基酯,從黏著性及著色劑(C)的分散性的觀點而言,烷基的碳數為1~20的(甲基)丙烯酸烷基酯為佳。烷基的碳數為1~20的(甲基)丙烯酸烷基酯,可舉出例如(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)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸棕櫚酯、(甲基)丙烯酸硬脂酯等。其中以更加提升黏著性的觀點而言,以烷基的碳數為1~8的(甲基)丙烯酸酯為佳,以(甲基)丙烯酸甲酯、(甲基)丙烯酸正丁酯或(甲基)丙烯酸2-乙基己酯為特佳,以甲基丙烯酸甲酯、丙烯酸正丁酯、或丙烯酸2-乙基己酯為更佳。再者,該等可以單獨使用,亦可組合2種以上使用。The alkyl (meth)acrylate has an alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group from the viewpoint of adhesion and dispersibility of the coloring agent (C). (Meth) acrylate alkyl esters having 1 to 20 carbon atoms in the alkyl group include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth) ) N-butyl acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-hexyl (meth)acrylate Decyl ester, n-lauryl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, etc. Among them, from the viewpoint of improving the adhesiveness, (meth)acrylates with alkyl carbon numbers of 1 to 8 are preferred, and methyl (meth)acrylate, n-butyl (meth)acrylate or ( 2-ethylhexyl meth)acrylate is particularly preferred, and methyl methacrylate, n-butyl acrylate, or 2-ethylhexyl acrylate is more preferred. In addition, these can be used individually or in combination of 2 or more types.
(甲基)丙烯酸酯聚合物(A),作為構成該聚合物的單體單元含有50質量%以上的(甲基)丙烯酸烷基酯為佳,特別是以含有60質量%以上為佳,進一步以含有65質量%以上為佳。(甲基)丙烯酸烷基酯的含量的下限值為上述,則(甲基)丙烯酸酯聚合物(A)可發揮適當的黏著性。此外,著色劑(C)在黏著劑中的分散性有變良好的傾向,(甲基)丙烯酸酯聚合物(A)並不會損及所期望的黏著性。藉此,所得黏著劑,能夠發揮合適的黏著性的同時,上述光學物性的再現性及均勻性良好,而顯示優良的設計性及視認性。另一方面,(甲基)丙烯酸酯聚合物(A),以含有99質量%以下的(甲基)丙烯酸烷基酯作為構成該聚合物的單體單元為佳,以含有95質量%以下為更佳,特別是以含有90質量%以下為佳,進一步以含有85質量%以下為佳。(甲基)丙烯酸烷基酯的含量的上限值為上述,則可在(甲基)丙烯酸酯聚合物(A)中導入適當量的含反應性官能基單體等的其他單體成分。The (meth)acrylate polymer (A) preferably contains 50% by mass or more of alkyl (meth)acrylate as the monomer unit constituting the polymer, particularly preferably 60% by mass or more, and further It is preferable to contain 65% by mass or more. If the lower limit of the content of the alkyl (meth)acrylate is the above, the (meth)acrylate polymer (A) can exhibit appropriate adhesiveness. In addition, the dispersibility of the colorant (C) in the adhesive tends to become better, and the (meth)acrylate polymer (A) does not impair the desired adhesiveness. Thereby, the obtained adhesive can exhibit suitable adhesiveness, and at the same time, the reproducibility and uniformity of the above-mentioned optical physical properties are good, and it shows excellent design and visibility. On the other hand, the (meth)acrylate polymer (A) preferably contains 99% by mass or less of alkyl (meth)acrylate as the monomer unit constituting the polymer, and preferably contains 95% by mass or less. More preferably, the content is particularly preferably 90% by mass or less, and more preferably 85% by mass or less. The upper limit of the content of the alkyl (meth)acrylate is as described above, and an appropriate amount of other monomer components such as a reactive functional group-containing monomer can be introduced into the (meth)acrylate polymer (A).
上述(甲基)丙烯酸酯聚合物(A),含有在分子內具有脂環式結構的單體(含脂環式結構單體)作為構成該聚合物的單體單元亦佳。含脂環式結構單體由於體積大,藉由使其存在於聚合物中,可推測可擴大聚合物相互的間隔,而可使所得到的黏著劑的柔軟性優良。藉此可使黏著劑的段差追隨性優良。The (meth)acrylate polymer (A) may preferably contain a monomer having an alicyclic structure (alicyclic structure-containing monomer) in the molecule as a monomer unit constituting the polymer. Since the alicyclic structure-containing monomer has a large volume, by making it exist in the polymer, it can be estimated that the distance between the polymers can be enlarged, and the obtained adhesive can be made excellent in flexibility. This can make the adhesive's step followability excellent.
在含脂環式結構單體的脂環式結構的碳環,可為飽和結構,亦可為具有一部分不飽和鍵結。此外,脂環式結構,可為單環的脂環式結構,亦可為二環、三環等的多環的脂環式結構。在使所得(甲基)丙烯酸酯聚合物(A)相互具有適當的距離,賦予黏著劑更高的應力緩和性的觀點而言,上述脂環式結構,以多環的脂環式結構(多環結構)為佳。再者,考慮(甲基)丙烯酸酯聚合物(A)與其他的成分的相溶性,上述多環結構以二環至四環為特佳。此外,由與上述同樣賦予應力緩和性的觀點而言,脂環式結構的碳數(指所有形成環的部分的碳數,複數環獨立存在時是指其合計的碳數),通常以5以上為佳,以7以上特別佳。另一方面,脂環式結構的碳數的上限,並無特別限制,以與上述同樣的相溶性的觀點而言,以15以下為佳,以10以下特別佳。The carbocyclic ring of the alicyclic structure containing the alicyclic structure monomer may have a saturated structure or may have a partially unsaturated bond. In addition, the alicyclic structure may be a monocyclic alicyclic structure or a polycyclic alicyclic structure such as a bicyclic ring or a tricyclic ring. From the viewpoint of making the obtained (meth)acrylate polymer (A) have an appropriate distance from each other and imparting higher stress relaxation to the adhesive, the above-mentioned alicyclic structure is a polycyclic alicyclic structure (multiple Ring structure) is preferred. Furthermore, considering the compatibility of the (meth)acrylate polymer (A) with other components, the above-mentioned polycyclic structure is particularly preferably bicyclic to tetracyclic. In addition, from the viewpoint of imparting stress relaxation properties as described above, the number of carbons in the alicyclic structure (refers to the number of carbons in all parts forming the ring, and the total number of carbons when a plurality of rings exist independently) is usually 5 The above is preferable, and 7 or more is particularly preferable. On the other hand, the upper limit of the carbon number of the alicyclic structure is not particularly limited, and from the viewpoint of the same compatibility as described above, 15 or less is preferable, and 10 or less is particularly preferable.
作為上述含脂環式結構單體,具體而言,可舉出(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯等,其中,以可發揮更優良的段差追隨性之(甲基)丙烯酸二環戊酯(脂環式結構的碳數︰10)、(甲基)丙烯酸金剛烷酯(脂環式結構的碳數︰10)或(甲基)丙烯酸異莰酯(脂環式結構的碳數︰7)為佳,特別是以(甲基)丙烯酸異莰酯為佳,進一步以丙烯酸異莰為佳。該等,可以1種單獨使用,亦可以組合2種以上使用。As the aforementioned alicyclic structure-containing monomer, specifically, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid Isocampanate, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, etc., among them, dicyclopentyl (meth)acrylate which can exhibit better step followability Ester (the number of carbons in the alicyclic structure: 10), adamantyl (meth)acrylate (the number of carbons in the alicyclic structure: 10) or isocamyl (meth)acrylate (the number of carbons in the alicyclic structure: 7) Preferably, isocamyl (meth)acrylate is more preferable, and isobornyl acrylate is more preferable. These can be used individually by 1 type, and can also be used in combination of 2 or more types.
(甲基)丙烯酸酯聚合物(A),含有含脂環式結構單體作為構成該聚合物的單體單元時,含有1質量%以上該含脂環式結構單體為佳,特別是以含有4質量%以上為佳,進一步以含有8質量%以上為佳。此外,(甲基)丙烯酸酯聚合物(A),以含有30質量%以下的脂環式結構單體作為構成該聚合物的單體單元為佳,特別是以含有22質量%以下為佳,進一步以含有14質量%以下為佳。藉由使含脂環式結構單體的含量在上述範圍,能夠使所得黏著劑的段差追隨性更優良,同時對塑膠的黏著力更優良。When the (meth)acrylate polymer (A) contains an alicyclic structure-containing monomer as the monomer unit constituting the polymer, it is preferable to contain 1% by mass or more of the alicyclic structure-containing monomer, especially The content is preferably 4% by mass or more, and more preferably 8% by mass or more. In addition, the (meth)acrylate polymer (A) preferably contains 30% by mass or less of an alicyclic structural monomer as the monomer unit constituting the polymer, and particularly preferably contains 22% by mass or less. It is more preferable to contain 14% by mass or less. By making the content of the alicyclic structure-containing monomer within the above range, the resulting adhesive can have better step-following properties and better adhesion to plastics.
此外,上述(甲基)丙烯酸酯聚合物(A),含有含氮原子單體作為構成該聚合物的單體單元為佳。藉由使含氮原子單體作為構成單元存在於聚合物中,可賦予黏著劑既定的極性,而能夠對如玻璃般的具有某種程度的極性的被黏附體,親和性優良。在使(甲基)丙烯酸酯聚合物(A)具有適當的剛性的觀點而言,以具有含氮雜環的單體作為上述含氮原子單體為佳。此外,在構成黏著劑的高維結構中提高來自上述含氮原子單體部分的自由度的觀點而言,該含氮原子單體,以在用於形成(甲基)丙烯酸酯聚合物(A)的聚合的1個聚合性基以外,不含有反應性不飽和雙鍵鍵結基為佳。In addition, the (meth)acrylate polymer (A) described above preferably contains a nitrogen atom-containing monomer as a monomer unit constituting the polymer. The presence of a nitrogen atom-containing monomer as a structural unit in the polymer can impart a predetermined polarity to the adhesive, and can have a certain degree of polarity to an adherend like glass, and has excellent affinity. From the viewpoint of allowing the (meth)acrylate polymer (A) to have appropriate rigidity, a monomer having a nitrogen-containing heterocyclic ring is preferably used as the nitrogen atom-containing monomer. In addition, from the viewpoint of increasing the degree of freedom from the nitrogen atom-containing monomer portion in the high-dimensional structure constituting the adhesive, the nitrogen atom-containing monomer can be used to form the (meth)acrylate polymer (A) In addition to one polymerizable group in the polymerization of ), it is preferable that the reactive unsaturated double bond bonding group is not contained.
作為具有含氮雜環的單體,可舉出例如,N-(甲基)丙烯醯嗎福林(morpholine)、N-乙烯基-2-吡咯啶酮、N-(甲基)丙烯醯基吡咯啶酮、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯啶、N-(甲基)丙烯醯基氮丙啶、氮丙啶基乙基(甲基)丙烯酸酯、2-乙烯基吡啶、4-乙烯基吡啶、2-乙烯基吡嗪(pyrazine)、1-乙烯基咪唑、N-乙烯基咔唑、N-乙烯基鄰苯二甲醯亞胺等,以能夠發揮更優良的黏著力的N-(甲基)丙烯醯嗎福林為佳,特別是以N-丙烯醯嗎福林為佳。該等,可以1種單獨使用,亦可以組合2種以上使用。As the monomer having a nitrogen-containing heterocyclic ring, for example, N-(meth)acryloyl morpholine, N-vinyl-2-pyrrolidone, and N-(meth)acryloyl Pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-(meth)acryloylaziridine, aziridinylethyl (methyl) ) Acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-vinylpyrazine (pyrazine), 1-vinylimidazole, N-vinylcarbazole, N-vinylphthalimide Etc., N-(meth)acrylic methrin, which can exert better adhesive force, is preferable, especially N-acrylic methrin. These can be used individually by 1 type, and can also be used in combination of 2 or more types.
(甲基)丙烯酸酯聚合物(A),含有含氮原子單體作為構成該聚合物的單體單元時,以1質量%以上含有該含氮原子單體為佳,特別是以含有4質量%以上為佳,進一步以含有8質量%以上為佳。此外,(甲基)丙烯酸酯聚合物(A),作為構成該聚合物的單體單元含有20質量%以下的該含氮原子單體為佳,特別是以含有16質量%以下為佳,進一步以含有12質量%以下為佳。含氮原子單體的含量在上述的範圍內,則所得黏著劑能夠對玻璃充分發揮優良的黏著力。When the (meth)acrylate polymer (A) contains a nitrogen atom-containing monomer as the monomer unit constituting the polymer, it is preferable to contain the nitrogen atom-containing monomer at 1% by mass or more, especially 4 mass% % Or more is preferable, and it is more preferable to contain 8 mass% or more. In addition, the (meth)acrylate polymer (A) preferably contains 20% by mass or less of the nitrogen atom-containing monomer as the monomer unit constituting the polymer, particularly preferably 16% by mass or less, and further The content is preferably 12% by mass or less. If the content of the nitrogen atom-containing monomer is within the above range, the resulting adhesive can fully exhibit excellent adhesion to glass.
(甲基)丙烯酸酯聚合物(A),可根據所期望,含有其他的單體作為構成該聚合物的單體單元。作為其他的單體,以不阻礙含反應性官能基單體的上述的作用,以不含有反應性官能基的單體為佳。作為該單體,可舉出例如(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等的(甲基)丙烯酸烷氧基烷基酯、醋酸乙烯酯、苯乙烯等。該等可以單獨使用,亦可組合2種以上使用。The (meth)acrylate polymer (A) may contain other monomers as monomer units constituting the polymer as desired. As other monomers, it is preferable that the above-mentioned function of the reactive functional group-containing monomer is not hindered, and a monomer that does not contain a reactive functional group is preferable. Examples of the monomer include alkoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and other alkoxyalkyl (meth)acrylates, vinyl acetate, and styrene. Wait. These can be used individually or in combination of 2 or more types.
(甲基)丙烯酸酯聚合物(A),以直鏈狀的聚合物為佳。藉由以直鏈狀的聚合物,成為容易發生分子鏈的糾纏,而可期待凝聚力的提升,故容易使所得黏著劑的儲存彈性模數、凝膠分率及黏著力等變得合適,而在高溫高濕條件下的段差追隨性優良。The (meth)acrylate polymer (A) is preferably a linear polymer. By using a linear polymer, molecular chain entanglement is likely to occur, and the improvement of cohesive force can be expected, so it is easy to make the storage elastic modulus, gel fraction and adhesive force of the obtained adhesive suitable. It has excellent step followability under high temperature and high humidity conditions.
此外,(甲基)丙烯酸酯聚合物(A),以溶液聚合法所得的溶液聚合物為佳。藉由以溶液聚合物,容易得到高分子量的聚合物,而可期待凝聚力的提升,故容易使所得黏著劑的儲存彈性模數、凝膠分率及黏著力等變得合適,而在高溫高濕條件下的段差追隨性優良。In addition, the (meth)acrylate polymer (A) is preferably a solution polymer obtained by a solution polymerization method. By using solution polymer, it is easy to obtain high molecular weight polymer, and the improvement of cohesive force can be expected, so it is easy to make the storage elastic modulus, gel fraction and adhesive force of the obtained adhesive become suitable, and it is high at high temperature. It has excellent step followability under wet conditions.
(甲基)丙烯酸酯聚合物(A)的聚合態樣,可為隨機聚合物,亦可為嵌段聚合物。The polymerization state of the (meth)acrylate polymer (A) may be a random polymer or a block polymer.
(甲基)丙烯酸酯聚合物(A)的重量平均分子量,作為下限值以20萬以上為佳,特別是以30萬以上為佳,進一步以40萬以上為佳,從著色劑(C)的分散性的觀點而言,以50萬以上為佳,以70萬以上為特佳。藉由使(甲基)丙烯酸酯聚合物(A)的重量平均分子量的下限值在上述範圍內,容易使所得黏著劑的儲存彈性模數、凝膠分率及黏著力等變得合適,而在高溫高濕條件下的段差追隨性優良。此外,有使著色劑(C)的對黏著劑中的分散性良好的傾向,故所得的黏著劑成為上述光學物性的再現性及均勻性良好者,而顯示優良的設計性及視認性。The weight average molecular weight of the (meth)acrylate polymer (A) is preferably 200,000 or more as the lower limit, especially 300,000 or more, and further preferably 400,000 or more. From the colorant (C) From the viewpoint of dispersibility, 500,000 or more is preferable, and 700,000 or more is particularly preferable. By setting the lower limit of the weight average molecular weight of the (meth)acrylate polymer (A) within the above range, it is easy to make the storage elastic modulus, gel fraction, and adhesive force of the resulting adhesive suitable. And under the conditions of high temperature and humidity, the followability of the step difference is excellent. In addition, since the dispersibility of the colorant (C) in the adhesive tends to be good, the resulting adhesive has good reproducibility and uniformity of the above-mentioned optical properties, and exhibits excellent design and visibility.
此外,(甲基)丙烯酸酯聚合物(A)的重量平均分子量,作為上限值最以200萬以下為佳,特別是以150萬以下為佳,進一步以100萬以下為佳。藉由使(甲基)丙烯酸酯聚合物(A)的重量平均分子量的上限值在上述範圍內,容易使所得黏著劑的儲存彈性模數、凝膠分率及黏著力等變得合適,而初期的段差追隨性更優良。再者,在本說明書的重量平均分子量,是以凝膠滲透層析(GPC)法測定的標準聚苯乙烯換算值。In addition, the upper limit of the weight average molecular weight of the (meth)acrylate polymer (A) is preferably 2 million or less, particularly preferably 1.5 million or less, and further preferably 1 million or less. By making the upper limit of the weight average molecular weight of the (meth)acrylate polymer (A) within the above-mentioned range, it is easy to make the storage elastic modulus, gel fraction, and adhesive force of the obtained adhesive suitable. However, the initial stage difference followability is better. In addition, the weight average molecular weight in this specification is a standard polystyrene conversion value measured by a gel permeation chromatography (GPC) method.
在黏著性組合物P,(甲基)丙烯酸酯聚合物(A),可以1種單獨使用,亦可組合2種以上使用。In the adhesive composition P, the (meth)acrylate polymer (A) may be used alone or in combination of two or more.
(1-2)交聯劑(B) 交聯劑(B),是藉由黏著劑組合物P的加熱,使(甲基)丙烯酸酯聚合物(A)交聯,而可良好地形成三維網眼結構。藉此,能夠提升所得到的黏著劑的凝聚力,而在高溫高濕條件下的段差追隨性優良。(1-2) Crosslinking agent (B) The crosslinking agent (B) crosslinks the (meth)acrylate polymer (A) by heating the adhesive composition P, thereby forming a good three-dimensional network structure. Thereby, the cohesive force of the obtained adhesive can be increased, and the step followability under high temperature and high humidity conditions is excellent.
作為上述交聯劑(B),只要是可與(甲基)丙烯酸酯聚合物(A)所具有的反應性基反應者即可,可舉出例如,異氰酸酯系交聯劑、環氧系交聯劑、胺系交聯劑、三聚氰胺系交聯劑、氮丙啶系交聯劑、聯胺系交聯劑、醛系交聯劑、噁唑啉系交聯劑、金屬烷氧化合物系交聯劑、金屬螯合物系交聯劑、金屬鹽系交聯劑、銨鹽系交聯劑等。上述之中,(甲基)丙烯酸酯聚合物(A)所具的反應性基為羥基時,使用與羥基的反應性優良的異氰酸酯系交聯劑為佳,(甲基)丙烯酸酯聚合物(A)所具有的反應性基為羧基時,使用與羧基的反應性優良的環氧系交聯劑為佳。再者,交聯劑(B),可以1種單獨,或組合2種以上使用。As the above-mentioned crosslinking agent (B), any one that can react with the reactive group possessed by the (meth)acrylate polymer (A) may be used. For example, isocyanate-based crosslinking agents, epoxy-based crosslinking agents Linking agent, amine crosslinking agent, melamine crosslinking agent, aziridine crosslinking agent, amine crosslinking agent, aldehyde crosslinking agent, oxazoline crosslinking agent, metal alkoxy compound crosslinking agent Linking agents, metal chelate-based cross-linking agents, metal salt-based cross-linking agents, ammonium salt-based cross-linking agents, etc. Among the above, when the reactive group of the (meth)acrylate polymer (A) is a hydroxyl group, it is preferable to use an isocyanate-based crosslinking agent having excellent reactivity with the hydroxyl group, and the (meth)acrylate polymer ( A) When the reactive group possessed is a carboxyl group, it is better to use an epoxy-based crosslinking agent having excellent reactivity with the carboxyl group. In addition, the crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.
異氰酸酯系交聯劑,是至少含有聚異氰酸酯化合物者。聚異氰酸酯化合物,可舉出例如,甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、二甲苯撐基二異氰酸酯(xylylene diisocyanate)等的芳香族聚異氰酸酯;六亞甲基異氰酸酯等的脂肪族聚異氰酸酯;異佛爾酮二異氰酸酯、氫化二苯基甲烷二異氰酸酯等的脂環式聚異氰酸酯等,及該等的雙縮脲體、三聚異氰酸酯體、進一步與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等的含有低分子活性氫的化合物的反應物的加成物等。其中,與羥基的反應性的觀點而言,以三羥甲基丙烷改質的芳香族聚異氰酸酯為佳,以三羥甲基丙烷改質甲苯二異氰酸酯及三羥甲基丙烷改質二甲苯撐基二異氰酸酯特別佳。The isocyanate-based crosslinking agent contains at least a polyisocyanate compound. Examples of polyisocyanate compounds include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene isocyanate; isocyanate; Alicyclic polyisocyanates such as phorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc., and these biuret, trimeric isocyanate, and further with ethylene glycol, propylene glycol, neopentyl glycol, three Addition products of reactants of low-molecular-weight active hydrogen-containing compounds such as methylolpropane and castor oil. Among them, from the viewpoint of reactivity with hydroxyl groups, aromatic polyisocyanates modified with trimethylolpropane are preferred, toluene diisocyanate modified with trimethylolpropane and xylene diisocyanate modified with trimethylolpropane Base diisocyanate is particularly preferred.
作為環氧系交聯劑,可舉出例如1,3-雙(N,N-二環氧丙基胺甲基)環己烷、N,N,N′,N′-四環氧丙基間二甲苯二胺、乙二醇二環氧丙醚、1,6-己二醇二環氧丙醚、三羥甲基丙烷二環氧丙醚、二環氧丙基苯胺、二環氧丙基胺等。其中,與羧基的反應性的觀點而言,以1,3-雙(N,N-二環氧丙基胺甲基)環己烷為佳。Examples of epoxy-based crosslinking agents include 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N′,N′-tetraglycidyl M-xylene diamine, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl ether Base amine and so on. Among them, from the viewpoint of reactivity with a carboxyl group, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane is preferred.
在黏著性組合物P中的交聯劑(B)的含量,對(甲基)丙烯酸酯聚合物(A)100質量份,下限值以0.01質量份以上為佳,特別是以0.05質量份以上為佳,進一步以0.1質量份以上為佳。此外,該含量,以10質量份以下為佳,以5質量份以下更佳,特別是以1質量份以下為佳,進一步以0.4質量份以下為佳。藉由使交聯劑(B)的含量在上述範圍,所得黏著劑發揮良好的凝聚力,而容易滿足所期望的儲存彈性模數、凝膠分率及黏著力等,在高溫高濕條件下的段差追隨性優良。For the content of the crosslinking agent (B) in the adhesive composition P, with respect to 100 parts by mass of the (meth)acrylate polymer (A), the lower limit is preferably 0.01 parts by mass or more, especially 0.05 parts by mass The above is preferable, and more preferably 0.1 part by mass or more. In addition, the content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, particularly preferably 1 part by mass or less, and further preferably 0.4 parts by mass or less. By setting the content of the crosslinking agent (B) in the above range, the resulting adhesive exerts good cohesive force, and easily meets the desired storage elastic modulus, gel fraction and adhesive force, etc., under high temperature and high humidity conditions The level difference is good to follow.
(1-3)著色劑(C) 著色劑(C)是上述著色劑。具體的種類如上所述。(1-3) Coloring agent (C) The colorant (C) is the above-mentioned colorant. The specific types are as described above.
著色劑(C)對(甲基)丙烯酸酯聚合物(A)100質量份的含量,以0.01質量份以上為佳,以0.05質量份以上為更佳,特別是以0.1質量份以上為佳,進一步以0.2質量份以上為佳。此外,上述含量,以5質量份以下為佳,以3質量份以下為更佳,特別是以2質量份以下為佳,進一步以1質量份以下為佳。藉由使著色劑(C)的含量在上述範圍,容易滿足上述光學物性。The content of the colorant (C) to 100 parts by mass of the (meth)acrylate polymer (A) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and particularly preferably 0.1 parts by mass or more, More preferably, it is 0.2 parts by mass or more. In addition, the aforementioned content is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less, and further preferably 1 part by mass or less. By setting the content of the coloring agent (C) in the above range, it is easy to satisfy the above optical properties.
(1-4)活性能量線硬化性成分(D) 在將黏著性組合物P交聯而成的黏著劑,以活性能量線硬化之黏著劑,推測活性能量線硬化性成分(D)互相聚合,該聚合之活性能量線硬化性成分(D)與(甲基)丙烯酸酯聚合物(A)的交聯結構(三維網眼結構)纏繞。具有該高維結構的黏著劑,發揮非常優良的耐久性,而在在高溫高濕條件下的段差追隨性優良。(1-4) Active energy ray hardening component (D) In the adhesive formed by cross-linking the adhesive composition P, the active energy ray hardening component (D) is presumably polymerized with the active energy ray hardening component (D) and The crosslinked structure (three-dimensional mesh structure) of the (meth)acrylate polymer (A) is entangled. The adhesive with this high-dimensional structure exhibits very excellent durability, and has excellent step followability under high temperature and high humidity conditions.
活性能量線硬化性成分(D),只要是可藉由照射活性能量線而硬化,得到上述效果的成分,並無特別限制,可為單體、寡聚物或聚合物的任何一種,亦可為該等的混合物。其中,較佳的可舉出耐起泡性優良的多官能丙烯酸酯系單體。The active energy ray curable component (D) is not particularly limited as long as it is a component that can be cured by irradiation of active energy rays to obtain the above-mentioned effects, and it may be any of monomers, oligomers, or polymers, or It is a mixture of these. Among them, preferred are polyfunctional acrylate monomers having excellent foam resistance.
多官能丙烯酸酯系單體,可舉例如1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇己二酸二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、二環戊基二(甲基)丙烯酸酯、三環癸烷二甲醇(甲基)丙烯酸酯、己內酯改質二環戊烯基二(甲基)丙烯酸酯、環氧乙烷改質磷酸二(甲基)丙烯酸酯、二(丙烯醯氧基乙基)三聚異氰酸酯、烯丙基化環己基二(甲基)丙烯酸酯、乙氧基化雙酚A二丙烯酸酯,9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]茀等的2官能型;三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇三(甲基)丙烯酸酯、丙酸改質二新戊四醇三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、環氧丙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、三(丙烯醯氧基乙基)三聚異氰酸酯、ε-己內酯改質三(2-(甲基)丙烯醯氧基乙基)三聚異氰酸酯等的3官能型;二甘油四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯等的4官能型;丙酸改質二新戊四醇五(甲基)丙烯酸酯等的5官能型;二新戊四醇六(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯等的6官能型等。該等,可以1種單獨使用,亦可以組合2種以上使用。以與(甲基)丙烯酸酯聚合物(A)的相溶性的觀點而言,多官能丙烯酸酯系單體,分子量小於1000為佳。Multifunctional acrylate monomers, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth) Acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxytrimethyl acetate neopentyl glycol di(meth)acrylate, dicyclopentane Di(meth)acrylate, tricyclodecane dimethanol (meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified di(meth) phosphate Base) acrylate, bis(acryloxyethyl) trimer isocyanate, allylated cyclohexyl di(meth)acrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4 -(2-propenyloxyethoxy)phenyl] pyridine and other bifunctional types; trimethylolpropane tri(meth)acrylate, dineopentyl erythritol tri(meth)acrylate, propionic acid Modified dineopentaerythritol tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(acrylic acid) Ethylethyl) trimeric isocyanate, ε-caprolactone modified tris (2-(meth)acryloyloxyethyl) trimeric isocyanate and other trifunctional types; diglycerol tetra(meth)acrylate, new 4-functional type such as pentaerythritol tetra(meth)acrylate; 5-functional type such as dineopentaerythritol penta(meth)acrylate modified by propionic acid; dineopentaerythritol hexa(meth)acrylate , Caprolactone is used to modify the 6-functional type of dineopentaerythritol hexa(meth)acrylate, etc. These can be used individually by 1 type, and can also be used in combination of 2 or more types. From the viewpoint of compatibility with the (meth)acrylate polymer (A), the polyfunctional acrylate monomer preferably has a molecular weight of less than 1,000.
上述之中,從所得黏著劑的耐起泡性的觀點而言,以二(丙烯醯氧基乙基)三聚異氰酸酯、三(丙烯醯氧基乙基)三聚異氰酸酯、ε-己內酯改質三(2-(甲基)丙烯醯氧基乙基)三聚異氰酸酯等在分子內含有三聚異氰酸酯結構的多官能丙烯酸酯系單體、或三環癸烷二甲醇(甲基)丙烯酸酯等在分子內含有環狀結構(特別是環烷結構)的多官能丙烯酸酯系單體為佳,以3官能以上且在分子內含有三聚異氰酸酯結構的多官能丙烯酸酯系單體、或以2官能以上且在分子內含有多環結構(特別是環烷的多環結構)的多官能丙烯酸酯系單體為更佳,以ε-己內酯改質三(2-(甲基)丙烯醯氧基乙基)三聚異氰酸酯或三環癸烷二甲醇(甲基)丙烯酸酯為特佳,進一步以ε-己內酯改質三(2-丙烯醯氧基乙基)三聚異氰酸酯或三環癸烷二甲醇丙烯酸酯為佳,以ε-己內酯改質三(2-丙烯醯氧基乙基)三聚異氰酸酯最佳。Among the above, from the viewpoint of the foaming resistance of the resulting adhesive, di(acryloxyethyl) trimer isocyanate, tris(acryloxy ethyl) trimer isocyanate, and ε-caprolactone Modified tris (2-(meth)acryloyloxyethyl) trimer isocyanate and other multifunctional acrylate monomers containing trimer isocyanate structure in the molecule, or tricyclodecane dimethanol (meth)acrylic acid A polyfunctional acrylate monomer having a cyclic structure (especially a cycloalkane structure) in the molecule, such as an ester, is preferably a multifunctional acrylate monomer having trifunctional or higher and a trimeric isocyanate structure in the molecule, or It is more preferable to use a polyfunctional acrylate-based monomer having two or more functions and a polycyclic structure (especially a cycloalkane polycyclic structure) in the molecule, and ε-caprolactone is used to modify tris(2-(methyl) Acrylic oxyethyl) trimeric isocyanate or tricyclodecane dimethanol (meth) acrylate is particularly preferred, and ε-caprolactone is further used to modify tris(2-propylene oxyethyl) trimeric isocyanate Or tricyclodecane dimethanol acrylate is better, and ε-caprolactone is used to modify tris(2-propenyloxyethyl) trimeric isocyanate.
在黏著劑組合物P中的活性能量線硬化性成分(D)的含量,在使活性能量線硬化後的黏著劑在高溫高濕條件下的段差追隨性更優良的觀點而言,對(甲基)丙烯酸酯聚合物(A)100質量份,作為下限值以1質量份以上為佳,以3質量份以上為特佳,以4質量份以上為更佳。另一方面,上述含量,從活性能量線硬化後的黏著劑的黏著力的觀點而言,作為上限值以20質量份以下為佳,以12質量份以下為特佳,以8質量份以下為更佳。The content of the active energy ray curable component (D) in the adhesive composition P, from the viewpoint that the adhesive after curing the active energy ray has more excellent step followability under high temperature and high humidity conditions, it is suitable for (A The lower limit of 100 parts by mass of the base) acrylate polymer (A) is preferably 1 part by mass or more, particularly preferably 3 parts by mass or more, and more preferably 4 parts by mass or more. On the other hand, the above content, from the viewpoint of the adhesive force of the adhesive after curing by active energy rays, the upper limit is preferably 20 parts by mass or less, particularly preferably 12 parts by mass or less, and 8 parts by mass or less For better.
(1-5)光聚合起始劑(E) 使用紫外線作為使黏著性組合物P硬化的活性能量線時,黏著性組合物P,進一步含有光聚合起始劑(E)為佳。藉由含有如此的光聚合起始劑(E),可有效的使活性能量線硬化性成分(D)聚合,此外,能夠減少聚合硬化時間及活性能量線的照射量。(1-5) Photopolymerization initiator (E) When using ultraviolet rays as the active energy ray for curing the adhesive composition P, the adhesive composition P preferably further contains a photopolymerization initiator (E). By containing such a photopolymerization initiator (E), the active energy ray curable component (D) can be effectively polymerized, and the polymerization curing time and the irradiation amount of active energy ray can be reduced.
作為如此的光聚合起始劑(E),可舉出例如,安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香正丁醚、安息香異丁醚、苯乙酮、二甲胺基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、1-羥基環己基苯酮、2-甲基-1-[4-(甲基硫代)苯基]-2-嗎福林基-丙-1-酮、4-(2-羥基乙氧基)苯基-2-(羥基-2-丙基)酮、二苯基酮、對苯基二苯基酮、4,4-二乙基胺基二苯基酮、二氯二苯基酮、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌、2-甲基噻噸酮(2-methyl thioxanthone)、2-乙基噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、苄基二甲基縮酮、苯乙酮二甲基縮酮、對二甲基胺基安息香酸酯、寡聚[2-羥基-2-甲基-1[4-(1-甲基乙烯基)苯基]丙酮]、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦等。該等可以單獨使用,亦可組合2種以上使用。As such a photopolymerization initiator (E), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminobenzene Ethanone, 2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 1-hydroxycyclohexylphenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 4-( 2-Hydroxyethoxy) phenyl-2-(hydroxy-2-propyl) ketone, diphenyl ketone, p-phenyl diphenyl ketone, 4,4-diethylamino diphenyl ketone, two Chlorodiphenyl ketone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methyl thioxanthone (2-methyl thioxanthone), 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl Ketal, p-dimethylaminobenzoate, oligo[2-hydroxy-2-methyl-1[4-(1-methylvinyl)phenyl]acetone], 2,4,6- Trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, etc. These can be used individually or in combination of 2 or more types.
上述之中,以隔著含有紫外線吸收劑的塑膠板照射紫外線時,亦容易裂解,而容易使黏著劑確實硬化的氧化膦系的光聚合起始劑為佳。具體而言,以2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦等為佳。Among the above, when irradiated with ultraviolet rays through a plastic plate containing an ultraviolet absorber, a phosphine oxide-based photopolymerization initiator that is easy to be broken and is easy to harden the adhesive is preferred. Specifically, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, etc. are preferable.
在黏著劑組合物P中的光聚合起始劑(E)的含量,相對於活性能量線硬化性成分(D)100質量份,作為下限值以0.1質量份以上為佳,特別是以1質量份以上為佳,進一步以5質量份以上為佳。此外,作為上限值以30質量份以下為佳,特別是以20質量份以下為佳,進一步以12質量份以下為佳。The content of the photopolymerization initiator (E) in the adhesive composition P, relative to 100 parts by mass of the active energy ray curable component (D), is preferably 0.1 parts by mass or more as the lower limit, particularly 1 Part by mass or more is preferable, and more preferably 5 parts by mass or more. In addition, the upper limit is preferably 30 parts by mass or less, particularly 20 parts by mass or less, and further preferably 12 parts by mass or less.
光聚合起始劑(E)的量相對於著色劑(C)的量的質量比(光聚合起始劑(E)/著色劑(C))以0.01以上為佳,特別是以0.1以上為佳,進一步以0.2以上為佳。此外,該質量比以5以下為佳,特別是以3以下為佳,進一步以1以下為佳。藉由使光聚合起始劑(E)的量相對於著色劑(D)的量的比在上述範圍,可滿足上述光學物性,同時藉由活性能量線硬化容易得到具有合適的凝聚力或黏著性的黏著劑,而在高溫高濕條件下的段差追隨性容易變得更優良。The mass ratio of the amount of the photopolymerization initiator (E) to the amount of the colorant (C) (photopolymerization initiator (E)/colorant (C)) is preferably 0.01 or more, especially 0.1 or more Better, more preferably 0.2 or more. In addition, the mass ratio is preferably 5 or less, particularly 3 or less, and more preferably 1 or less. By setting the ratio of the amount of the photopolymerization initiator (E) to the amount of the coloring agent (D) in the above range, the above optical properties can be satisfied, and at the same time, it is easy to obtain a suitable cohesive force or adhesiveness by curing with active energy rays Adhesives, and the followability of the step under the conditions of high temperature and humidity is easy to become better.
(1-6)各種添加劑 黏著性組合物P,可根據期望添加通常使用於丙烯酸系黏著劑的各種添加劑,例如矽烷偶合劑、防銹劑、紫外線吸收劑、抗靜電劑、黏著賦予劑、抗氧化劑、光安定劑、軟化劑、折射率調整劑等。再者,後述的聚合溶劑及稀釋溶劑,設定為不包含於構成黏著性組合物P的添加劑。(1-6) Various additives Adhesive composition P can be added with various additives commonly used in acrylic adhesives as desired, such as silane coupling agents, rust inhibitors, ultraviolet absorbers, antistatic agents, adhesion imparting agents, antioxidants, light stabilizers, and softening agents. Agents, refractive index modifiers, etc. In addition, the polymerization solvent and the dilution solvent mentioned later are not included in the additive which comprises the adhesive composition P.
黏著性組合物P,在上述之中以含有矽烷偶合劑為佳。藉此,即使被黏附體為塑膠板,或即使是玻璃構件,亦可提升與該被黏附體的密著性,而在高溫高濕條件下的段差追隨性更優良。Among the above, the adhesive composition P preferably contains a silane coupling agent. As a result, even if the adherend is a plastic plate or even a glass member, the adhesion to the adherend can be improved, and the step followability under high temperature and high humidity conditions is better.
作為矽烷偶合劑,以在分子內至少具有1個烷氧基矽基的有機矽化合物,而與(甲基)丙烯酸酯聚合物(A)的相溶性佳,且具有光穿透性者為佳。As the silane coupling agent, an organosilicon compound having at least one alkoxysilyl group in the molecule, which has good compatibility with the (meth)acrylate polymer (A) and light penetration is preferred .
作為該矽烷偶合劑,可舉出例如,乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、甲基丙烯醯氧基丙基三甲氧基矽烷等的含聚合性不飽和基矽化合物、3-環氧丙氧丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等的具有環氧結構的矽化合物、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基二甲氧基甲基矽烷等的含巰基矽化合物、3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷等的含胺基矽化合物、3-氯丙基三甲氧基矽烷、3-異氰酸酯基丙基三乙氧基矽烷、或該等的至少1種,與甲基三乙氧基矽烷、乙基三乙氧基矽烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷等的含烷基矽化合物的縮合物等。該等,可以1種單獨使用,亦可組合2種以上使用。As the silane coupling agent, for example, vinyl trimethoxy silane, vinyl triethoxy silane, methacryloxy propyl trimethoxy silane and other polymerizable unsaturated group-containing silicon compounds, 3 -Glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and other silicon compounds having epoxy structure, 3-mercaptopropyltrimethoxysilane, Mercapto-containing silicon compounds such as 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl )-3-Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane and other amino-containing silicon compounds, 3-chloropropyl Trimethoxysilane, 3-isocyanatopropyltriethoxysilane, or at least one of these, with methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, ethyl Condensates of alkyl-containing silicon compounds such as trimethoxysilane. These can be used individually by 1 type, and can also be used in combination of 2 or more types.
在黏著性組合物P中的矽烷偶合劑的含量,對(甲基)丙烯酸酯聚合物(A)100質量份,以0.01質量份以上為佳,特別是以0.05質量份以上為佳,進一步以0.1質量份以上為佳。此外,該含量以1質量份以下為佳,特別是以0.5質量份以下為佳,進一步以0.3質量份以下為佳。The content of the silane coupling agent in the adhesive composition P is preferably 0.01 parts by mass or more based on 100 parts by mass of the (meth)acrylate polymer (A), particularly preferably 0.05 parts by mass or more, and further 0.1 part by mass or more is preferable. In addition, the content is preferably 1 part by mass or less, particularly preferably 0.5 parts by mass or less, and further preferably 0.3 parts by mass or less.
(2)黏著性組合物的調製 黏著性組合物P,可藉由製造(甲基)丙烯酸酯聚合物(A),將所得到的(甲基)丙烯酸酯聚合物(A),與交聯劑(B)、及著色劑(C)混合的同時,根據所期望加入活性能量線硬化性成分(D)、光聚合起始劑(E)、添加劑等而製造。(2) Preparation of adhesive composition The adhesive composition P can be produced by producing a (meth)acrylate polymer (A), and the resulting (meth)acrylate polymer (A) can be combined with a crosslinking agent (B) and a coloring agent ( C) It is produced by adding active energy ray curable component (D), photopolymerization initiator (E), additives, etc. as desired while mixing.
(甲基)丙烯酸酯聚合物(A),可藉由將構成聚合物的單體的混合物,以通常的自由基聚合法聚合而製造。(甲基)丙烯酸酯聚合物(A)的聚合,可根據所期望使用聚合起始劑,以溶液聚合法進行為佳。惟,本發明並非限定於此,亦可以無溶劑聚合。作為聚合溶劑,可舉出例如,醋酸乙酯、醋酸正丁酯、醋酸異丁酯、甲苯、丙酮、己烷、甲乙酮等,亦併用2種以上。The (meth)acrylate polymer (A) can be produced by polymerizing a mixture of monomers constituting the polymer by a normal radical polymerization method. The polymerization of the (meth)acrylate polymer (A) can be carried out by a solution polymerization method using a polymerization initiator as desired. However, the present invention is not limited to this, and solventless polymerization is also possible. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone, etc., and two or more of them are also used in combination.
作為聚合起始劑,可舉出偶氮系化合物、有機過氧化物等,亦可併用2種以上。偶氮系化合物,例如,2,2′-偶氮雙異丁腈、2,2′-偶氮雙(2-甲基丁腈)、1,1′-偶氮雙(環己烷-1-甲腈)、2,2′-偶氮雙(2,4-二甲基戊腈)、2,2′-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基-2,2′-偶氮雙(2-甲基丙酸酯)、4,4′-偶氮雙(4-氰戊酸)( 4,4′-azobis(4-cyanovaleric acid))、2,2′-偶氮雙(2-羥甲基丙腈)、2,2′-偶氮雙[2-(2-咪唑啉-2-基)丙烷]等。Examples of the polymerization initiator include azo compounds, organic peroxides, and the like, and two or more types may be used in combination. Azo compounds, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1 -Carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) , Dimethyl-2,2′-azobis(2-methylpropionate), 4,4′-azobis(4-cyanovaleric acid) (4,4′-azobis(4-cyanovaleric acid )), 2,2'-azobis(2-hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], etc.
作為有機過氧化物,可舉出例如,過氧化苯甲醯、過氧化苯甲酸第三丁酯、氫過氧化異丙苯、過氧化二碳酸二異丙酯、過氧化二碳酸二正丙酯、過氧化二碳酸二(2-乙氧基乙酯)、過氧化新癸酸第三丁酯、過氧化異丁酸第三丁酯、 (3,5,5-三甲基己醯基) 過氧化物、過氧化二丙醯、過氧化二乙醯等。Examples of organic peroxides include benzyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, and di-n-propyl peroxydicarbonate. , Peroxydicarbonate bis(2-ethoxyethyl), t-butyl peroxyneodecanoate, t-butyl peroxyisobutyrate, (3,5,5-trimethylhexyl) Peroxide, dipropylene peroxide, diacetyl peroxide, etc.
再者,在上述聚合步驟,藉由調配2-巰基乙醇等的鏈轉移劑,可調節所得聚合物的重量平均分子量。Furthermore, in the above-mentioned polymerization step, by formulating a chain transfer agent such as 2-mercaptoethanol, the weight average molecular weight of the obtained polymer can be adjusted.
得到(甲基)丙烯酸酯聚合物(A),則對(甲基)丙烯酸酯聚合物(A)的溶液,添加交聯劑(B)、著色劑(C)、以及根據所期望的稀釋溶劑、活性能量線硬化性成分(D)、光聚合起始劑(E)、添加劑等,藉由充分混合,得到以溶劑稀釋的黏著性組合物P(塗佈溶液)。再者,在上述各成分的任一者,使用固體狀的情形時,或以沒有稀釋的狀態與其他的成分混合時會產生析出時,亦可將該成份預先單獨以稀釋溶劑溶解或稀釋,再與其他的成份混合。To obtain the (meth)acrylate polymer (A), to the solution of the (meth)acrylate polymer (A), add a crosslinking agent (B), a colorant (C), and a diluting solvent as desired , Active energy ray curable component (D), photopolymerization initiator (E), additives, etc., are thoroughly mixed to obtain an adhesive composition P (coating solution) diluted with a solvent. Furthermore, when any of the above-mentioned components is used in a solid state, or when precipitation occurs when mixed with other components in an undiluted state, the component may be separately dissolved or diluted with a diluting solvent in advance. Mix with other ingredients.
作為上述稀釋溶劑,可舉出例如,己烷、庚烷、環己烷等的脂肪烴,甲苯、二甲苯等的芳香烴、二氯甲烷、氯乙烯等的鹵化烴,甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等的醇,丙酮、甲乙酮、2-戊酮、異佛爾酮、環己酮等的酮,醋酸乙酯、醋酸丁酯等的酯,乙基賽珞蘇等的賽珞蘇系溶劑等。As the above-mentioned dilution solvent, for example, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and vinyl chloride, methanol, ethanol, and propanol Alcohols such as, butanol, 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone, etc., esters such as ethyl acetate and butyl acetate, Serosu series solvents such as ethyl Serosu.
如此調製的塗佈溶液的濃度、黏度,只要在可塗佈的範圍即可,並無特別限制,能夠按照狀況適當選定。例如,將黏著性組合物P稀釋成濃度10~60質量%。再者,得到塗佈溶液時,稀釋溶劑等的添加並非必要條件,只要黏著性組合物P在可塗佈的黏度,亦可不添加稀釋溶劑。此時,黏著性組合物P,成為將(甲基)丙烯酸酯聚合物(A)的聚合溶劑直接作為稀釋溶劑的塗佈溶液。The concentration and viscosity of the coating solution prepared in this manner are not particularly limited as long as they are in the coatable range, and can be appropriately selected according to the situation. For example, the adhesive composition P is diluted to a concentration of 10 to 60% by mass. In addition, when obtaining a coating solution, the addition of a dilution solvent etc. is not an essential condition, as long as the adhesive composition P has the viscosity which can apply|coat, the dilution solvent may not be added. At this time, the adhesive composition P becomes a coating solution in which the polymerization solvent of the (meth)acrylate polymer (A) is directly used as the dilution solvent.
(3)著色黏著劑層的形成
本實施形態的著色黏著劑層11,較佳為由黏著性組合物P(的塗佈層)所交聯的黏著劑構成。黏著性組合物P的交聯,通常可藉由加熱處理而進行。再者,該加熱處理,可兼做使稀釋溶劑等從塗佈在所期望對象物的黏著性組合物P的塗佈層揮發時的乾燥處理。(3) Formation of colored adhesive layer
The colored
加熱處理的加熱溫度,以50~150℃為佳,特別是以70~120℃為佳。此外,加熱時間,以10秒~10分鐘為佳,特別是以50秒~2分鐘為佳。The heating temperature of the heat treatment is preferably 50~150℃, especially 70~120℃. In addition, the heating time is preferably 10 seconds to 10 minutes, especially 50 seconds to 2 minutes.
加熱處理之後,可視需要,亦可設置以常溫(例如23℃、50%RH)1~2週左右的熟化期間。需要該熟化期間時,在經過熟化期間之後,無需熟化期間時,在加熱處理結束之後,形成黏著劑。After the heat treatment, if necessary, an aging period of about 1 to 2 weeks at room temperature (for example, 23° C., 50% RH) can also be set. When the aging period is required, after the aging period has passed, and when the aging period is not required, the adhesive is formed after the heat treatment is completed.
藉由上述的加熱處理(及熟化),經由交聯劑(B)使(甲基)丙烯酸酯聚合物(A)充分交聯。如此所得黏著劑,容易滿足所期望的儲存彈性模數、凝膠分率及黏著力等,在高溫高濕條件下的段差追隨性優良。By the above-mentioned heat treatment (and aging), the (meth)acrylate polymer (A) is sufficiently crosslinked via the crosslinking agent (B). The adhesive obtained in this way easily meets the desired storage elastic modulus, gel fraction and adhesive force, etc., and has excellent step followability under high temperature and high humidity conditions.
(4)黏著劑的物性 在本實施形態的黏著劑,具有以下物性為佳。 (4-1)凝膠分率 在本實施形態的黏著劑的凝膠分率,作為下限值以20%以上為佳,以40%以上為更佳,以50%以上為特佳,進一步以60%以上為佳。黏著劑的凝膠分率的下限值為上述,則黏著劑的凝聚力會變高,而在高溫高濕條件下的段差追隨性更優良。此外,關於本實施形態的黏著劑的凝膠分率,作為上限值以100%以下為佳,以90%以下為更佳,以80%以下為特佳,進一步以70%以下為佳。黏著劑的凝膠分率的上限值為上述,則黏著劑不會過度硬化,而在初期的段差追隨性及高溫高濕條件下的段差追隨性均優良。此外,可顯現良好的黏著力,與被黏附體的黏著性更優良。(4) Physical properties of adhesive The adhesive of this embodiment preferably has the following physical properties. (4-1) Gel fraction The gel fraction of the adhesive of this embodiment is preferably 20% or more as the lower limit, more preferably 40% or more, particularly preferably 50% or more, and further preferably 60% or more. When the lower limit of the gel fraction of the adhesive is the above, the cohesive force of the adhesive becomes higher, and the step followability under high temperature and high humidity conditions is better. In addition, as for the gel fraction of the adhesive of the present embodiment, the upper limit is preferably 100% or less, more preferably 90% or less, particularly preferably 80% or less, and more preferably 70% or less. The upper limit of the gel fraction of the adhesive is as described above, so that the adhesive does not harden excessively, and is excellent in the initial step followability and the step followability under high temperature and high humidity conditions. In addition, good adhesion can be displayed, and the adhesion to the adherend is better.
在此,黏著劑的凝膠分率的測定方法,是如後述的試驗例所示。此外,在活性能量線硬化性的黏著劑的情形,設定為活性能量線硬化後的黏著劑的凝膠分率。再者,在活性能量線硬化性的黏著劑的情形的活性能量線硬化前的黏著劑的凝膠分率,從可使初期段差追隨性良好的觀點而言,以20~70%為佳,以30~60%為特佳,以40~55%更佳。Here, the method of measuring the gel fraction of the adhesive is as shown in the test example described later. In addition, in the case of an active energy ray-curable adhesive, it is set as the gel fraction of the adhesive after the active energy ray has been cured. Furthermore, in the case of an active energy ray-curable adhesive, the gel fraction of the adhesive before curing of the active energy ray is preferably 20 to 70% from the viewpoint of good initial step followability. 30~60% is particularly preferred, and 40~55% is more preferred.
(4-2)儲存彈性模數 關於本實施形態的黏著劑在23℃的儲存彈性模數,作為下限值,以0.001MPa以上為佳,以0.01MPa以上更為佳,特別是以0.05MPa以上為佳,進一步以0.1MPa以上為佳。藉由使上述儲存彈性模數的下限值為上述,在高溫高濕條件下的段差追隨性優良。此外,上述儲存彈性模數,作為上限值,以2MPa以下為佳,以1MPa以下更為佳,特別是以0.8MPa以下為佳,進一步以0.4MPa以下為佳,以0.2MPa以下最為佳。藉由使上述儲存彈性模數的上限值在上述範圍內,在初期段差追隨性及高溫高濕條件下的段差追隨性優良。(4-2) Storage elastic modulus Regarding the storage elastic modulus of the adhesive of this embodiment at 23°C, as the lower limit, it is preferably 0.001 MPa or more, more preferably 0.01 MPa or more, especially 0.05 MPa or more, and further 0.1 MPa or more Better. By setting the lower limit of the storage elastic modulus to the above, the step followability under high temperature and high humidity conditions is excellent. In addition, the upper limit of the storage elastic modulus is preferably 2 MPa or less, more preferably 1 MPa or less, especially 0.8 MPa or less, further preferably 0.4 MPa or less, and most preferably 0.2 MPa or less. By setting the upper limit of the storage elastic modulus within the above range, the initial step followability and the step followability under high temperature and high humidity conditions are excellent.
在此,在本說明書的儲存彈性模數,是遵照JIS K7244-6,以測定頻率1Hz,以扭轉剪力法測定之值。具體而言,是如後述試驗例所示。此外,在活性能量線硬化性的黏著劑的情形,設定為活性能量線硬化後的黏著劑的儲存彈性模數。再者,在活性能量線硬化性的黏著劑的情形的活性能量線硬化前的黏著劑的儲存彈性模數,從可使初期的段差追隨性良好的觀點而言,以0.01~1MPa為佳,以0.02~0.5MPa為特佳,以0.04~0.1MPa更為佳。Here, the storage modulus of elasticity in this specification is a value measured by the torsional shear method in compliance with JIS K7244-6 with a measurement frequency of 1 Hz. Specifically, it is as shown in the test example mentioned later. In addition, in the case of an active energy ray-curable adhesive, it is set as the storage elastic modulus of the adhesive after the active energy ray has been cured. Furthermore, in the case of an active energy ray curable adhesive, the storage elastic modulus of the adhesive before curing of the active energy ray is preferably 0.01 to 1 MPa from the viewpoint that the initial step followability is good. 0.02~0.5MPa is particularly preferred, and 0.04~0.1MPa is more preferred.
(5)著色黏著劑層的厚度
著色黏著劑層11的厚度,作為下限值,以1μm以上為佳,以2μm以上為更佳,特別是以4μm以上為佳。藉由使著色黏著劑層11的厚度的下限值在上述範圍內,則在與著色劑(C)含量的關係,容易滿足上述光學物性,同時容易發揮所期望的黏著力。此外,從容易發揮優良的段差追隨性的觀點而言,作為下限值,以10μm以上為佳,以20μm以上為更佳,以50μm以上為特佳,以80μm以上進一步為佳。(5) The thickness of the colored adhesive layer
The lower limit of the thickness of the colored
另一方面,著色黏著劑層11的厚度,作為上限值,以500μm以下為佳,以300μm以下為更佳,特別是以200μm以下為佳,進一步以150μm以下為佳。著色黏著劑層11的厚度的上限值在上述範圍內,則加工性良好,此外,不容易發生因按壓痕跡的外觀不良。再者,在與著色劑(C)含量的關係,容易滿足上述光學物性。再者,著色黏著劑層11,能夠以單層形成,亦可層積複數層而形成。On the other hand, the upper limit of the thickness of the colored
1-2.剝離片
剝離片12a、12b,是用於保護著色黏著劑層11到使用著色黏著片1時,在使用著色黏著片1(著色黏著劑層11)時會剝離。在關於本實施形態的著色黏著片1,剝離片12a、12b的一方或雙方,並非必要。1-2. Peeling sheet
The
作為剝離片12a、12b,可使用例如聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對苯二甲酸乙二醇酯薄膜、聚萘二甲酸乙二醇酯薄膜、聚對苯二甲酸丁二醇酯薄膜、聚氨酯薄膜、乙烯-醋酸乙烯酯薄膜、離聚物樹脂薄膜、乙烯‧(甲基)丙烯酸共聚物薄膜、乙烯‧(甲基)丙烯酸酯共聚合物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜、氟化樹脂薄膜等。此外,可使用該等的交聯薄膜。進一步,亦可為該等的層積薄膜。As the
上述剝離片12a,12b的剝離面(特別是接於著色黏著劑層11的面)以施加剝離處理為佳。作為使用於剝離處理的剝離劑,可舉出例如,醇酸系、矽酮系、氟系、不飽和聚酯系、聚烯烴系、蠟系的剝離劑。再者,剝離片12a、12b之中,使一方的剝離片作成剝離力大的重剝離型剝離片,使另一方的剝離片作成剝離力小的輕剝離型剝離片為佳。The peeling surface of the
關於剝離片12a、12b的厚度,並無特別限制,通常為20~150μm左右。The thickness of the
2.物性(黏著力)
關於本實施形態的著色黏著片1對鈉鈣玻璃的黏著力,作為下限值以1N/25mm以上為佳,以2N/25mm以上為更佳,以4N/25mm以上為特佳,以8N/25mm以上進一步為佳。黏著力的下限值在上述範圍內,則在高溫高濕條件下的段差追隨性更優良。此外,關於本實施形態的著色黏著片1的對於鈉鈣玻璃的黏著力,作為上限值,以80N/25mm以下為佳,以50N/25mm以下為更佳,以30N/25mm以下為特佳。黏著力的上限值在上述範圍內,則可得良好的再加工性,當發生黏合失誤時,可再利用顯示設備構成構件,特別是高價的顯示設備構成構件。2. Physical properties (adhesion)
Regarding the adhesion of the colored
在此,在本說明書的黏著力,基本上是指遵照JIS Z0237:2009之180∘拉剝法所測定的黏著力,惟測定樣品為寬25mm、長100mm,將該測定樣品黏貼在被黏附體,以0.5MPa,50℃加壓20分鐘之後,以常壓,23℃,50%RH的條件下放置24小時之後,以剝離速度300mm/min測定。此外,在活性能量線硬化性的黏著劑的情形,是關於在黏貼於被黏附體後,以活性能量線硬化的著色黏著劑層的黏著力。再者,在活性能量線硬化性的黏著劑的情形時的活性能量線硬化前的黏著劑的黏著力,從與被黏附體的密著性及再加工性的觀點而言,以1~80N/25mm為佳,以2~50N/25mm為特佳,以4~30N/25mm進一為佳。Here, the adhesive force in this specification basically refers to the adhesive force measured in compliance with the 180∘ peeling method of JIS Z0237:2009, but the measured sample is 25mm wide and 100mm long, and the measured sample is pasted on the adherend , After pressurizing at 0.5MPa, 50℃ for 20 minutes, after leaving it under normal pressure, 23℃, 50%RH conditions for 24 hours, measuring at a peeling speed of 300mm/min. In addition, in the case of an active energy ray-curable adhesive, it is about the adhesive force of the colored adhesive layer hardened by the active energy ray after being adhered to the adherend. Furthermore, in the case of an active energy ray-curable adhesive, the adhesive force of the adhesive before curing of the active energy ray is 1 to 80 N from the viewpoint of adhesion to the adherend and reworkability /25mm is better, 2~50N/25mm is particularly preferred, and 4~30N/25mm is better.
3.著色黏著片的製造
作為著色黏著片1的一製造例,在一方的剝離片12a(或12b)的剝離面,塗佈上述黏著性組合物P的塗佈液,進行加熱處理使黏著性組合物P熱交聯,形成塗佈層之後,使另一面的剝離片12b(或12a)的剝離面與該塗佈層疊合。需要熟化期間時給予熟化期間,無需熟化期間,則上述塗佈層直接成為著色黏著劑層11。藉此,可得上述著色黏著片1。關於加熱處理及熟化的條件,依如上所述。3. Manufacturing of colored adhesive sheets
As an example of the production of the colored
作為著色黏著片1之其他的製造例,是在一方的剝離片12a的剝離面,塗佈上述黏著性組合物P的塗佈液,進行加熱處理使黏著性組合物P熱交聯,形成塗佈層,得到附有塗佈層的剝離片12a。此外,在另一方的剝離片12b的剝離面,塗佈上述黏著性組合物P的塗佈液,進行加熱處理使黏著性組合物P熱交聯,形成塗佈層,得到附有塗佈層的剝離片12b。然後,使附有塗佈層的剝離片12a與附有塗佈層的剝離片12b,以兩塗佈層互相接觸地黏貼。在此,亦可製作複數附有塗佈層的剝離片,將該塗佈層僅以所期望的數量黏貼。需要熟化期間時給予熟化期間,無須熟化期間,則上述塗佈層直接成為著色黏著劑層11。藉此,可得上述著色黏著片1。根據該製造例,即使著色黏著劑層11較厚時,亦可以穩定地製造。As another example of the production of the colored
作為塗佈上述黏著性組合物P的塗佈液的方法,可利用例如,棒塗佈法、刮刀塗佈法、輥塗法、刮板塗佈法、模具塗佈法、凹版塗佈法等。As a method of applying the coating liquid of the adhesive composition P, for example, bar coating method, knife coating method, roll coating method, blade coating method, die coating method, gravure coating method, etc. can be used. .
[顯示設備] 作為關於本實施形態的顯示設備(顯示器)的種類,可舉出例如汽車的儀表板、汽車導航系統、設在控制台的各種儀表等的車載用的顯示設備,一般用戶用平板終端機等的顯示設備、商業用平板終端機或數位看板等的顯示設備、室外用數位看板等的顯示設備。該等顯示設備,有時被要求與周邊構件的外觀協調性、或高級感等。惟關於本發明的顯示設備,不應限定於該等。[display screen] The types of display devices (displays) related to this embodiment include, for example, automobile dashboards, car navigation systems, various meters installed in consoles, and other vehicle-mounted display devices, and general user-use tablet terminals. Display devices, display devices such as commercial tablet terminals or digital signage, and display devices such as outdoor digital signage. Such display devices are sometimes required to have an appearance coordination with peripheral components, or a sense of luxury. However, the display device of the present invention should not be limited to these.
如圖2所示,關於本實施形態的顯示設備2,其構成具備:第1顯示設備構成構件21(一顯示設備構成構件);第2顯示設備構成構件22(其他的顯示設備構成構件);及著色黏著劑層11,其位於該等之間,互相黏貼第1顯示設備構成構件21及第2的顯示設備構成構件22。As shown in FIG. 2, regarding the
第1顯示設備構成構件21及第2顯示設備構成構件22的至少一方,至少在藉由著色黏著劑層11黏貼之側的面,亦可具有段差。在圖2所示本實施形態,第1顯示設備構成構件21,在著色著色黏著劑層11側的面,具有印刷層3等的段差。At least one of the first display device
在上述顯示設備2的著色黏著劑層11,是上述著色黏著片1的著色黏著劑層11。The colored
作為顯示設備2,可舉出例如液晶(LCD)顯示器、發光二極體(LED)顯示器、有機電致發光(有機EL)顯示器、電子紙等,亦可為觸控面板。As the
第1顯示設備構成構件21,以玻璃板、塑膠板等之外,以含有該等的層積體等所構成的保護板為佳。此時,印刷層3一般在第1顯示設備構成構件21的著色黏著劑層11側形成畫框狀。The first display device
作為上述玻璃板,並無特別限定,可舉出例如,化學強化玻璃、無鹼玻璃、石英玻璃、鈉鈣玻璃、含有鋇鍶的玻璃、鋁矽酸玻璃、鉛玻璃、硼矽酸玻璃、鋇硼矽酸玻璃等。玻璃板的厚度,並無特別限定,通常為0.1~5mm,以0.2~2mm為佳。The glass plate is not particularly limited, and examples include chemically strengthened glass, alkali-free glass, quartz glass, soda lime glass, barium-strontium-containing glass, aluminosilicate glass, lead glass, borosilicate glass, barium Borosilicate glass, etc. The thickness of the glass plate is not particularly limited, but is usually 0.1 to 5 mm, preferably 0.2 to 2 mm.
作為塑膠板,並無特別限定,可舉出例如壓克力板、聚碳酸酯板等。塑膠板的厚度,並無特別限定,通常為0.2~5mm,較佳的是0.4~3mm。The plastic plate is not particularly limited, and examples include acrylic plates and polycarbonate plates. The thickness of the plastic plate is not particularly limited, and is usually 0.2 to 5 mm, preferably 0.4 to 3 mm.
再者,在上述玻璃板、塑膠板的一面或兩面,亦可設置各種功能層(透明導電膜、金屬層、二氧化矽層、硬塗層、防眩層等),亦可層積光學構件。此外,透明導電膜及金屬層,亦可圖案化。Furthermore, various functional layers (transparent conductive film, metal layer, silicon dioxide layer, hard coating, anti-glare layer, etc.) can also be provided on one or both sides of the glass plate and plastic plate, and optical components can also be laminated . In addition, the transparent conductive film and the metal layer can also be patterned.
第2顯示設備構成構件22,以應該被貼在第1顯示設備構成構件21的光學構件、顯示體模組(例如,液晶(LCD)模組、發光二極體(LED)模組、有機電致發光(有機EL)模組等)、作為顯示體模組的一部分的光學構件、或包含顯示體模組的層積體為佳。The second display device
作為上述光學構件,可舉出例如,飛散防止薄膜、偏光板(偏光薄膜)、偏光片、相位差板(相位差薄膜)、視野角補償薄膜、亮度提升薄膜、對比提升薄膜、液晶聚合物薄膜、擴散薄膜、半穿透反射薄膜、透明導電性薄膜等。作為飛散防止薄膜,可例示在基材薄膜的一面形成硬塗層而成的硬塗層薄膜等。Examples of the above-mentioned optical members include anti-scattering films, polarizers (polarizing films), polarizers, retardation films (retardation films), viewing angle compensation films, brightness enhancement films, contrast enhancement films, and liquid crystal polymer films , Diffusion film, transflective film, transparent conductive film, etc. As the anti-scattering film, a hard coat film formed by forming a hard coat layer on one side of a base film, etc. can be exemplified.
構成印刷層3的材料,無特別限定,能夠使用印刷用的習知材料。印刷層3的厚度,即段差的高度的下限值,以3μm以上為佳,以5μm以上為更佳,以7μm以上為特佳,以10μm以上最佳。藉由使下限值在上述以上,能夠充分確保從視認者側無法看到電路配路等的隱蔽性。此外,上限值以50μm以下為佳,以35μm以下為更佳,以25μm以下為特佳,進一步以20μm以下為佳。藉由使上限值在上述以下,可防止著色黏著劑層11對該印刷層3的段差追隨性的惡化。The material constituting the printed
作為製造上述顯示設備2的一個例子,將著色黏著片1的一側的剝離片12a剝離,將著色黏著片1的露出的著色黏著劑層11,與第1顯示設備構成構件21的存在有印刷層3側的面黏貼。As an example of manufacturing the
之後,從著色黏著片1的著色黏著劑層11,將另一方的剝離片12b剝離,將著色黏著片1的露出的著色黏著劑層11與第2顯示設備構成構件22黏合。此外,作為其他的例子,亦可將第1顯示設備構成構件21及第2顯示設備構成構件22的黏合順序交替。After that, from the colored
著色黏著劑層11為活性能量線硬化性的情形,如上所述經由著色黏著劑層11將第1顯示設備構成構件21與第2顯示設備構成構件22黏合之後,對著色黏著劑層11照射活性能量線。藉此,使著色黏著劑層11中的能量線硬化性成分(D)聚合,而著色黏著劑層11硬化。對著色黏著劑層11的能量線照射,通常,隔著第1顯示設備構成構件21或第2顯示設備構成構件22的任一方進行,較佳為隔著作為保護面板的第1顯示設備構成構件21進行。When the colored
所謂活性能量線,是指在電磁波或帶電粒子線之中具有能量子,具體而言,可舉出紫外線或電子射線等。活性能量線之中,以容易操作的紫外線特別佳。The term "active energy ray" means that there are energy ions in electromagnetic waves or charged particle rays, and specific examples include ultraviolet rays, electron beams, and the like. Among the active energy rays, ultraviolet rays that are easy to operate are particularly preferred.
紫外線的照射,可藉由高壓水銀燈、Fusion H燈、氙氣燈等進行,紫外線的照射量,以照度50~1000mW/cm2 的程度為佳,以100~500mW/cm2 的程度為佳。此外,光量以50~10000mJ/cm2 為佳,以200~7000mJ/cm2 為更佳,以500~3000mJ/cm2 為特佳。另一方面,電子射線的照射,可藉由電子射線加速器等進行,電子射線的照射量,以10~1000krad的程度為佳。Ultraviolet rays can be irradiated by high-pressure mercury lamps, Fusion H lamps, xenon lamps, etc. The amount of ultraviolet radiation is preferably 50~1000mW/cm 2 and 100~500mW/cm 2 . Further, the light amount to 50 ~ 10000mJ / cm 2 preferably, to 200 ~ 7000mJ / cm 2 is more preferably to 500 ~ 3000mJ / cm 2 is particularly preferred. On the other hand, the irradiation of electron beams can be carried out by an electron beam accelerator, etc. The irradiation dose of electron beams is preferably about 10 to 1000 krad.
如圖3所示,關於本實施形態的顯示設備2,在該顯示設備2的周緣部具有框材4為佳。該框材4以黑色為佳。此外,作為框材4的色調,以CIE1976L*a*b*表色系所規定的明度L*、色度a*及色度b*的較佳的範圍,是如先前所述的作為周邊構件的色調。框材4,藉由具有該色調,容易被人眼辨識為視覺上具有高級感的框材。此外,在本實施形態的著色黏著劑層11,藉由框材4具有上述色調,增加與該框材4的整體感,而使外觀協調性更好。As shown in FIG. 3, regarding the
在上述顯示設備2,藉由上述著色黏著劑層11的物性,抑制顯示設備熄燈時的發白,而提高設計性。藉此,例如,賦予與黑色框材4的整體感,而具有優良的外觀協調性。此外,上述顯示設備2,確保了作為顯示設備的視認性。In the
再者,在上述顯示設備2,著色黏著劑層11是由黏著性組合物P形成時,由於該著色黏著劑層11在高溫高濕條件下的段差追隨性優良,故即使顯示設備2,被放置在例如高溫高濕條件下(例如85℃、85%RH)時,亦可抑制段差附近發生浮起、剝落等。Furthermore, in the above-mentioned
上述的段差追隨性,能夠以段差追隨率(%)作為指標而判斷。
著色黏著劑層11,以下述式所示的段差追隨率(%),作為下限值,以10%以上為佳,以20%以上為更佳,特別是以40%以上為佳,進一步以60%以上為佳。此外,作為段差追隨率的上限值,並無特別限定,通常,以80%以下為佳,特別是以70%以下為佳。
段差追隨率(%)={(既定耐久試驗後,維持沒有氣泡、浮起、剝落等而填埋的狀態的段差高度(μm))/(著色黏著劑層的厚度)}×100
再者,段差追隨率的試驗方法,是如後述的試驗例所示。The above-mentioned level difference followability can be judged using the level difference follow-up rate (%) as an indicator.
For the colored
以上所說明的實施形態,是為了容易理解本發明所記載,而並非用於限定本發明而記載。因此,揭示於上述實施形態的各要素,是含有屬於本發明的技術範圍的全部設計變更或均等物在內的主旨。The embodiments described above are described for easy understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above-mentioned embodiment includes all design changes or equivalents belonging to the technical scope of the present invention.
例如,在著色黏著片1的剝離片12a、12b的任一方或雙方可以省略,此外,亦可取代剝離片12a及/或12b層積所期望的光學構件。此外,第1顯示設備構成構件21,亦可沒有段差。再者,不只是第1顯示設備構成構件21,第2顯示設備構成構件22,亦可是在著色黏著劑層11側具有段差。
[實施例]For example, one or both of the
以下,將本發明以實施例等更具體地說明,惟本發明的範圍並非限定於該等實施例等。Hereinafter, the present invention will be explained more specifically with examples and the like, but the scope of the present invention is not limited to these examples and the like.
[實施例1] 1.(甲基)丙烯酸酯聚合物的調製 使70質量份丙烯酸2-乙基己酯、15質量份甲基丙烯酸甲酯、及15質量份丙烯酸2-羥基乙酯,藉由溶液聚合法使之共聚合,調製(甲基)丙烯酸酯聚合物(A)。將該(甲基)丙烯酸酯聚合物(A)的分子量,以後述方法測定,結果重量平均分子量(Mw)為80萬。[Example 1] 1. Preparation of (meth)acrylate polymer Copolymerize 70 parts by mass of 2-ethylhexyl acrylate, 15 parts by mass of methyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate by solution polymerization to prepare (meth)acrylate polymerization物(A). The molecular weight of the (meth)acrylate polymer (A) was measured by the method described later, and as a result, the weight average molecular weight (Mw) was 800,000.
2.黏著性組合物的調製
將100質量份(以固體含量換算值;以下相同),以上述步驟1所得的(甲基)丙烯酸酯聚合物(A)、0.2質量份作為交聯劑(B)的三羥甲基丙烷改質甲苯二異氰酸酯(TOYO CHEM公司製,產品名「BHS8515」)、0.4質量份作為著色劑(C)的碳黑系黑色顏料(C1)、0.2質量份作為矽烷偶合劑的3-環氧丙醚氧丙基三甲氧基矽烷混合,充分攪拌,藉由以甲乙酮稀釋,得到黏著性組合物的塗佈溶液。2. Preparation of adhesive composition
Change 100 parts by mass (based on solid content conversion value; the same below), using the (meth)acrylate polymer (A) obtained in
在此,將以(甲基)丙烯酸酯聚合物(A)為100質量份(固體含量換算值)時的黏著性組合物的各調配量(固體含量換算值)示於表1。再者,表1所記載的簡稱的詳細表示如下。 [(甲基)丙烯酸酯聚合物(A)] 2EHA:丙烯酸2-乙基己酯 MMA︰甲基丙烯酸甲酯 HEA︰丙烯酸2-羥基乙酯 IBXA︰丙烯酸異莰酯 ACMO︰N-丙烯醯嗎福林 BA︰丙烯酸正丁酯 AA︰丙烯酸 [著色劑(C)] C1~C6:具有表2所示物性的碳黑系黑色顏料Here, each blending amount (solid content conversion value) of the adhesive composition when the (meth)acrylate polymer (A) is 100 parts by mass (solid content conversion value) is shown in Table 1. In addition, the details of the abbreviations described in Table 1 are as follows. [(Meth)acrylate polymer (A)] 2EHA: 2-ethylhexyl acrylate MMA: methyl methacrylate HEA: 2-hydroxyethyl acrylate IBXA: Isobornyl acrylate ACMO: N-Acrylic Folin BA: n-butyl acrylate AA: Acrylic [Colorant (C)] C1~C6: Carbon black black pigments with physical properties shown in Table 2
3.著色黏著片的製造
將上述步驟2所得黏著性組合物的塗佈溶液,以刮刀塗佈機塗佈在,以矽酮系剝離劑對聚對苯二甲酸乙二醇酯薄膜的一面進行剝離處理的重剝離型剝離片(LINTEC公司製,產品名「SP-PET752150」)的剝離處理面之後,以90℃加熱處理1分鐘形成塗佈層(厚度︰50μm)。此外,將同樣以上述步驟2所得黏著性組合物的塗佈溶液,以刮刀塗佈機塗佈在,以矽酮系剝離劑對聚對苯二甲酸乙二醇酯薄膜的一面進行剝離處理的輕剝離型剝離片(LINTEC公司製,產品名「SP-PET381130」)的剝離處理面之後,以90℃加熱處理1分鐘形成塗佈層(厚度︰50μm)。3. Manufacturing of colored adhesive sheets
The coating solution of the adhesive composition obtained in the
接著,將上述所得附有塗佈層的重剝離型剝離片,與上述所得的附有塗佈層的輕剝離型剝離片,以兩塗佈層互相接觸地黏貼,以23℃、50%RH的條件下熟化7天,製作由重剝離型剝離片/著色黏著劑層(厚度︰100μm)/輕剝離型剝離片的構成所構成的著色黏著片。Next, the above-obtained heavy release release sheet with a coating layer and the light release release sheet with a coating layer obtained above are pasted with the two coating layers in contact with each other, at 23°C, 50%RH It was aged for 7 days under the conditions of, and a colored adhesive sheet composed of a heavy peeling type release sheet/colored adhesive layer (thickness: 100 μm)/light peeling type peeling sheet was produced.
再者,上述黏著劑層的厚度,是遵照JIS K7130,使用定壓厚度測定器(TECLOCK公司製,產品名「PG-02」)測定之值。In addition, the thickness of the said adhesive layer is the value measured using the constant pressure thickness measuring device (The product name "PG-02" made by TECLOCK) in compliance with JIS K7130.
[實施例2~8、比較例1~2] 將構成(甲基)丙烯酸酯聚合物(A)的各單體的種類及比例,(甲基)丙烯酸酯聚合物(A)的重量平均分子量(Mw),著色劑(C)的種類及調配量,矽烷偶合劑的調配量,以及著色黏著劑層的厚度,變更為表1所示以外,以與實施例1同樣地製造著色黏著片。惟在實施例5,進一步添加5.0質量份作為活性能量線硬化性成分(D)的ε-己內酯改質三(2-丙烯醯氧基乙基)三聚異氰酸酯(新中村化學公司製,產品名「NK ESTER A-9300-CL」)及0.5質量份作為光聚合起始劑(E)的2,4,6-三甲基苯甲醯基二苯基氧化膦,得到活性能量線硬化性的黏著劑。在比較例1,雖沒有使用著色劑(C),但權宜上,使用著色黏著劑層、著色黏著片的字眼。[Examples 2 to 8, Comparative Examples 1 to 2] The type and ratio of each monomer constituting the (meth)acrylate polymer (A), the weight average molecular weight (Mw) of the (meth)acrylate polymer (A), the type and blending of the colorant (C) Except that the amount, the blending amount of the silane coupling agent, and the thickness of the colored adhesive layer were changed to those shown in Table 1, the colored adhesive sheet was produced in the same manner as in Example 1. However, in Example 5, 5.0 parts by mass of ε-caprolactone was further added as the active energy ray curable component (D) to modify tris(2-propenoxyethyl) triisocyanate (manufactured by Shinnakamura Chemical Co., Ltd., Product name "NK ESTER A-9300-CL") and 0.5 parts by mass of 2,4,6-trimethylbenzyldiphenylphosphine oxide as a photopolymerization initiator (E) to obtain active energy ray hardening Sexual adhesive. In Comparative Example 1, although the coloring agent (C) was not used, the terms colored adhesive layer and colored adhesive sheet were used expediently.
再者,關於實施例3~8及比較例1~2的著色黏著片,是如下製造。將以與實施例1同樣地調製的黏著性組合物的塗佈溶液,以刮刀塗佈機塗佈在,以矽酮系剝離劑對聚對苯二甲酸乙二醇酯薄膜的一面進行剝離處理的重剝離型剝離片(LINTEC公司製,產品名「SP-PET752150」)的剝離處理面之後,以90℃加熱處理1分鐘形成塗佈層。使所得附有塗佈層的重剝離型剝離片的塗佈層側的面,與以矽酮系剝離劑對聚對苯二甲酸乙二醇酯薄膜的一面進行剝離處理的輕剝離型剝離片(LINTEC公司製,產品名「SP-PET381130」)的剝離處理面黏合,以23℃、50%RH的條件下熟化7天,製作由重剝離型剝離片/著色黏著劑層/輕剝離型剝離片的構成所構成的著色黏著片In addition, the colored adhesive sheets of Examples 3 to 8 and Comparative Examples 1 to 2 were manufactured as follows. The coating solution of the adhesive composition prepared in the same manner as in Example 1 was applied with a knife coater, and one side of the polyethylene terephthalate film was peeled off with a silicone-based release agent After the peeling treatment surface of the heavy peeling type peeling sheet (manufactured by LINTEC, product name "SP-PET752150"), the coating layer was formed by heat treatment at 90°C for 1 minute. A light-peelable release sheet in which the coated layer side surface of the obtained heavy-peelable release sheet with a coating layer and one side of the polyethylene terephthalate film are peeled off with a silicone-based release agent (Product name "SP-PET381130" made by LINTEC) is bonded on the peel-off treated surface and cured at 23°C and 50%RH for 7 days to produce a heavy peeling type peeling sheet/coloring adhesive layer/light peeling type peeling Colored adhesive sheet
上述重量平均分子量(Mw)是使用凝膠滲透層析(GPC),以如下條件測定(GPC測定)之聚苯乙烯換算的重量平均分子量。 >測定條件> ‧GPC測定裝置︰TOSOH公司製,HLC-8020 ‧GPC管柱(依以下順序通過):TOSOH公司製 TSK guard column HXL-H TSK ge1 GMHXL (×2) TSK ge1 G2000HXL ‧測定溶劑︰四氫呋喃 ‧測定溫度︰40℃The above-mentioned weight average molecular weight (Mw) is a weight average molecular weight in terms of polystyrene measured (GPC measurement) using gel permeation chromatography (GPC) under the following conditions. >Measurement conditions> ‧GPC measuring device: made by TOSOH, HLC-8020 ‧GPC column (pass in the following order): made by TOSOH TSK guard column HXL-H TSK ge1 GMHXL (×2) TSK ge1 G2000HXL ‧Measuring solvent: Tetrahydrofuran ‧Measuring temperature: 40℃
[試驗例1](著色劑稀釋液的霧度值的測定) 將C1~C6的著色劑以醋酸乙酯稀釋1萬倍的液體,遵照JIS K7136︰2000,使用霧度計(日本電色工業公司製,產品名「SH-7000」,光路長10mm)測定霧度值(%)。從該測定值,算出在波長780nm的霧度值與在波長380nm的霧度值的差;在波長780nm的霧度值與在波長380nm的霧度值的平均值的平均霧度;在波長區域380nm~780nm的5nm間距的各波長的霧度值的標準差。將各個結果示於表2。[Test Example 1] (Measurement of Haze Value of Colorant Diluent) Dilute C1~C6 colorants with ethyl acetate 10,000 times as a liquid, comply with JIS K7136:2000, and measure the haze using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "SH-7000", optical path length 10mm) Degree value (%). From the measured value, calculate the difference between the haze value at the wavelength of 780nm and the haze value at the wavelength of 380nm; the average haze of the average value of the haze value at the wavelength of 780nm and the haze value at the wavelength of 380nm; in the wavelength region The standard deviation of the haze value of each wavelength at a 5nm pitch from 380nm to 780nm. The respective results are shown in Table 2.
[試驗例2](凝膠分率的測定) 將實施例及比較例所得的著色黏著片,裁切成80mm×80mm的尺寸,將該黏著劑層裝在聚酯製網(網目尺寸200),將其質量以精密天平秤量,扣除上述網單獨的質量,算出只有黏著劑的質量。此時的質量為M1。[Test Example 2] (Measurement of Gel Fraction) The colored adhesive sheets obtained in the examples and comparative examples were cut into a size of 80mm×80mm, the adhesive layer was placed on a polyester mesh (mesh size 200), and the mass was weighed with a precision balance, and the net alone was deducted Calculate the quality of only the adhesive. The mass at this time is M1.
接著,將裝在上述聚酯製網的黏著劑,以室溫下(23℃)浸漬在醋酸乙酯24小時。之後,取出黏著劑,在溫度23℃,相對濕度50%的環境下,風乾24小時,進一步在80℃的烘箱中乾燥12小時。乾燥之後,以精密天平秤量其質量,扣除上述網子單獨的質量,算出只有黏著劑的質量。此時的質量為M2。凝膠分率(%),是以(M2/M1)×100表示。將結果示於表3。Next, the adhesive attached to the above-mentioned polyester mesh was immersed in ethyl acetate at room temperature (23°C) for 24 hours. After that, the adhesive was taken out and dried in air for 24 hours at a temperature of 23°C and a relative humidity of 50%, and further dried in an oven at 80°C for 12 hours. After drying, weigh the mass with a precision balance and deduct the mass of the net alone to calculate the mass of only the adhesive. The mass at this time is M2. The gel fraction (%) is expressed as (M2/M1)×100. The results are shown in Table 3.
再者,關於實施例5的著色黏著片,是在輕剝離型剝離片上,疊置在聚碳酸酯樹脂(PC)板層積聚甲基丙烯酸甲酯樹脂(PMMA)層的塑膠板(三菱氣體化學公司製,產品名「Iupilon sheet MR58U」,厚度︰0.7mm,含有紫外線吸收劑),隔著該塑膠板,以下述條件照射活性能量線,使著色黏著劑層硬化。關於該硬化後的著色黏著劑層的黏著劑,亦與上述同樣地導出凝膠分率(UV後)。Furthermore, regarding the colored adhesive sheet of Example 5, a plastic sheet (Mitsubishi Gas Chemical Co., Ltd.) is laminated on a polycarbonate resin (PC) sheet and a layer of methyl methacrylate resin (PMMA) on a lightly peelable release sheet. Made by the company, product name "Iupilon sheet MR58U", thickness: 0.7mm, containing UV absorber), through the plastic sheet, irradiated with active energy rays under the following conditions to harden the colored adhesive layer. Regarding the adhesive of the colored adhesive layer after curing, the gel fraction (after UV) is derived in the same manner as described above.
>活性能量線照射條件> ‧使用高壓汞燈 ‧照度200mW/cm2 、光量2000mJ/cm2 ‧UV照度‧光量計使用EYE GRAPHICS公司製「UVPF-A1」>Active energy ray irradiation conditions> ‧Using a high-pressure mercury lamp ‧Illuminance 200mW/cm 2 , light intensity 2000mJ/cm 2 ‧UV illuminance ‧Light meter uses EYE GRAPHICS company "UVPF-A1"
[試驗例3](儲存彈性模數的測定)
從實施例及比較例所得到的著色黏著片剝離剝離片,將著色黏著劑層以厚度成為3mm層積複數層。從所得到的著色黏著劑層的層積體,沖出直徑8mm的圓柱體(高度3mm),將此作為樣品。[Test Example 3] (Measurement of Storage Elastic Modulus)
The release sheet was peeled off from the colored adhesive sheets obtained in the examples and comparative examples, and a plurality of colored adhesive layers were laminated with a thickness of 3 mm. From the obtained laminated body of the colored adhesive layer, a cylinder with a diameter of 8 mm (
關於上述樣品,遵照JIS K7244-6,使用黏彈性測定裝置(Physica公司製,產品名「MCR300」),以扭轉剪力法,在如下條件測定儲存彈性模數(MPa)。將結果示於表3。 測定頻率︰1Hz 測定溫度︰23℃Regarding the above sample, in compliance with JIS K7244-6, using a viscoelasticity measuring device (manufactured by Physica, product name "MCR300"), the storage elastic modulus (MPa) was measured under the following conditions by the torsional shear method. The results are shown in Table 3. Measuring frequency: 1Hz Measuring temperature: 23℃
再者,對實施例5的著色黏著片,以與試驗例2同樣地照射活性能量線,使著色黏著劑層硬化,對該硬化後的著色黏著劑層,亦如上所述地測定儲存彈性模數(UV後)。Furthermore, the colored adhesive sheet of Example 5 was irradiated with active energy rays in the same manner as in Test Example 2 to harden the colored adhesive layer, and the cured colored adhesive layer was also measured for storage elastic modulus as described above. Number (after UV).
[試驗例4](霧度值的測定) 對實施例及比較例所得的著色黏著片的著色黏著劑層,遵照JIS K7136︰2000,使用霧度計(日本電色工業公司製,產品名「SH-7000」)測定霧度值(%)。將所得全光線霧度值(%)示於表3。此外,從測定值算出在波長780nm的霧度值與在波長380nm的霧度值的平均值的平均霧度;在波長780nm的霧度值與在波長380nm的霧度值的差;在波長區域380nm~780nm的5nm間距的各波長的霧度值的標準差。[Test Example 4] (Measurement of Haze Value) For the colored adhesive layer of the colored adhesive sheets obtained in the Examples and Comparative Examples, the haze value (%) was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "SH-7000") in accordance with JIS K7136: 2000 . The obtained total light haze value (%) is shown in Table 3. In addition, the average haze value of the average value of the haze value at the wavelength of 780nm and the haze value at the wavelength of 380nm is calculated from the measured value; the difference between the haze value at the wavelength of 780nm and the haze value at the wavelength of 380nm; in the wavelength range The standard deviation of the haze value of each wavelength at a 5nm pitch from 380nm to 780nm.
再者,對實施例5的著色黏著片,以與試驗例2同樣地照射活性能量線,使著色黏著劑層硬化,對該硬化後的著色黏著劑層,亦如上所述測定全光線霧度值(UV後)。然後,從測定值算出在波長780nm的霧度值與在波長380nm的霧度值的平均霧度(UV後);在波長780nm的霧度值與在波長380nm的霧度值的差(UV後);在波長區域380nm~780nm的5nm間距的各波長的霧度值的標準差(UV後)。將各個結果示於表3。Furthermore, the colored adhesive sheet of Example 5 was irradiated with active energy rays in the same manner as in Test Example 2 to harden the colored adhesive layer, and the total light haze of the cured colored adhesive layer was also measured as described above Value (after UV). Then, calculate the average haze between the haze value at the wavelength of 780nm and the haze value at the wavelength of 380nm (after UV) from the measured values; the difference between the haze value at the wavelength of 780nm and the haze value at the wavelength of 380nm (after UV) ); The standard deviation of the haze value of each wavelength (after UV) at the 5nm pitch in the wavelength region of 380nm~780nm. The respective results are shown in Table 3.
[試驗例5](全光線穿透率的測定) 將實施例及比較例所得到的著色黏著片的著色黏著劑層與玻璃黏合,將此作為測定樣品。以玻璃進行背景測定,對上述測定樣品,遵照JIS K7361-1:1997,使用霧度計(日本電色工業公司製,產品名「SH-7000」)測定全光線穿透率(%)。再者,對實施例5的著色黏著片,以與試驗例2同樣地照射活性能量線使著色黏著劑層硬化,對該硬化後的著色黏著劑層,亦如上所述測定全光線穿透率(UV後)。將結果示於表3。[Test Example 5] (Measurement of total light transmittance) The colored adhesive layer of the colored adhesive sheets obtained in the Examples and Comparative Examples were bonded to glass, and this was used as a measurement sample. The background measurement was performed on glass, and the total light transmittance (%) was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "SH-7000") for the above-mentioned measurement sample in compliance with JIS K7361-1:1997. Furthermore, the colored adhesive sheet of Example 5 was irradiated with active energy rays in the same manner as in Test Example 2 to harden the colored adhesive layer, and the cured colored adhesive layer was also measured for total light transmittance as described above (After UV). The results are shown in Table 3.
[試驗例6](L*a*b*測定) 對實施例及比較例所得到的著色黏著片的著色黏著劑層,使用同時測光分光式色度計(日本電色工業公司製,產品名「SQ2000」),測定CIE1976L*a*b*表色系所規定的明度L*、色度a*及色度b*。再者,對實施例5的著色黏著片,以與試驗例2同樣地照射活性能量線使著色黏著劑層硬化,對該硬化後的著色黏著劑層,亦如上所述測定明度L*(UV後)、色度a*(UV後)及色度b*(UV後)。將結果示於表3。[Test Example 6] (L*a*b* measurement) For the colored adhesive layer of the colored adhesive sheets obtained in the Examples and Comparative Examples, the CIE1976L*a*b* color was measured using a simultaneous photometric spectrophotometer (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "SQ2000") It is the specified lightness L*, chroma a*, and chroma b*. Furthermore, the colored adhesive sheet of Example 5 was irradiated with active energy rays in the same manner as in Test Example 2 to harden the colored adhesive layer, and the lightness L*(UV) of the colored adhesive layer after curing was also measured as described above. After), chromaticity a* (after UV) and chromaticity b* (after UV). The results are shown in Table 3.
[試驗例7](黏著力的測定) 從實施例及比較例所得到的著色黏著片剝離輕剝離型剝離片,將露出的著色黏著劑層,黏貼於具有易接著層的聚對苯二甲酸乙二醇酯(PET)薄膜(東洋紡公司製,產品名「PET A4300」,厚度︰100μm)的易接著層,得到剝離片/著色黏著劑層/PET薄膜的層積體。將所得層積體裁切成寬25mm,長100mm,將此作為樣品。[Test Example 7] (Measurement of Adhesion) The light-peelable release sheet was peeled from the colored adhesive sheets obtained in the Examples and Comparative Examples, and the exposed colored adhesive layer was pasted on a polyethylene terephthalate (PET) film with an easy-adhesion layer (Toyobo Co., Ltd. Product name "PET A4300", thickness: 100μm) easy-to-adhesive layer to obtain a laminate of release sheet/colored adhesive layer/PET film. The obtained laminate was cut into a width of 25 mm and a length of 100 mm, and this was used as a sample.
在23℃,50%RH的環境下,從上述樣品剝離重剝離型剝離片,將露出的黏著劑層黏貼在鈉鈣玻璃(日本板硝子公司製)之後,以栗原製造所公司製高壓釜,以0.5MPa,50℃,加壓20分鐘。之後,在23℃、50%RH的條件下放置24小時之後,使用拉伸試驗機(Orientec公司製,產品名「Tensilon」),以剝離速度300mm/min,剝離角度180度的條件,測定黏著力(N/25mm)。在此所記載以外的條件,遵照JIS Z0237:2009,進行測定。將結果示於表3。In an environment of 23°C and 50% RH, the heavy-peelable release sheet was peeled from the above sample, and the exposed adhesive layer was pasted on soda lime glass (manufactured by Nippon Sheet Glass Co., Ltd.), and then an autoclave made by Kurihara Manufacturing Co., Ltd. 0.5MPa, 50℃, pressurized for 20 minutes. Then, after leaving for 24 hours under the conditions of 23°C and 50%RH, the adhesion was measured using a tensile tester (manufactured by Orientec, product name "Tensilon") at a peeling speed of 300 mm/min and a peeling angle of 180 degrees. Force (N/25mm). Conditions other than those described here were measured in compliance with JIS Z0237:2009. The results are shown in Table 3.
再者,對實施例5的著色黏著片,與上述同樣地將著色黏著劑層黏貼在鈉鈣玻璃,以高壓釜處理之後,在23℃、50%RH的條件下放置24小時之後,以與試驗例2同樣地照射活性能量線,使著色黏著劑層硬化。對該硬化後的著色黏著劑層,亦與上述同樣地測定黏著力(UV後)。In addition, for the colored adhesive sheet of Example 5, the colored adhesive layer was adhered to soda lime glass in the same manner as above, and after autoclave treatment, it was left for 24 hours under the conditions of 23°C and 50%RH, and then In Test Example 2, active energy rays were irradiated in the same manner to harden the colored adhesive layer. The adhesive force (after UV) of the colored adhesive layer after curing was also measured in the same manner as above.
[試驗例8](段差追隨率的測定) 在玻璃板(NSG精密公司製,產品名「康寧玻璃 EAGLE XG」,長90mm×寬50mm×厚度0.5mm)的表面,將紫外線硬化型墨水(Teikoku Printing Inks Mfg公司製,產品名「POS-911 BLACK」),網版印刷成畫框狀(外形:縱90mm×橫50mm,寬5mm)。接著,照射紫外線(80W/cm2,金屬鹵素燈2盞,燈泡高度15cm,輸送帶速度10~15m/分),使印刷的上述紫外線硬化型墨水硬化,製作具有因印刷的段差(段差的高度︰5μm、10μm、15μm、20μm、25μm、50μm、60μm及70μm的任一個)的附有段差的玻璃板。[Test Example 8] (Measurement of the following rate of step difference) On the surface of a glass plate (product name "Corning Glass EAGLE XG" manufactured by NSG Precision Co., Ltd., length 90mm×width 50mm×thickness 0.5mm), UV curable ink (manufactured by Teikoku Printing Inks Mfg, product name "POS-911 BLACK”), screen printing into a frame shape (outer shape: vertical 90mm × horizontal 50mm, width 5mm). Then, irradiate ultraviolet rays (80W/cm2, 2 metal halide lamps, 15cm height of bulb, 10~15m/min of conveyor belt speed) to harden the above-mentioned ultraviolet curable ink for printing, and produce a step with printing (the height of the step: 5μm, 10μm, 15μm, 20μm, 25μm, 50μm, 60μm and 70μm) glass plate with stepped.
從實施例及比較例所得的著色黏著片所得的黏著片,剝離輕剝離型剝離片,將露出的著色黏著劑層,黏貼於具有易接著層的聚對苯二甲酸乙二醇酯薄膜(東洋紡公司製,產品名「PET A4300」,厚度︰100μm)的易接著層。接著,將重剝離型剝離片剝下,使著色黏著劑層露出。然後,使用貼合機(FUJIPLA公司製,產品名「LPD3214」),使著色黏著劑層覆蓋畫框狀的印刷全面,以上述層積體層壓在附有段差的玻璃板,將此作為評價樣品。In the adhesive sheet obtained from the colored adhesive sheets obtained in the Examples and Comparative Examples, the light-peelable release sheet was peeled off, and the exposed colored adhesive layer was adhered to a polyethylene terephthalate film with an easy-adhesive layer (Toyobo The easy-adhesive layer made by the company, product name "PET A4300", thickness: 100μm). Next, the heavy peeling type release sheet is peeled off to expose the colored adhesive layer. Then, using a laminating machine (manufactured by FUJIPLA, product name "LPD3214"), the colored adhesive layer was used to cover the frame-like printed surface, and the laminate was laminated on a glass plate with steps, and this was used as an evaluation sample .
將所得評價樣品,以50℃、0.5MPa的條件下高壓釜處理30分鐘之後,在常壓、23℃、50%RH的條件下放置24小時。接著,以85℃、85%RH的高溫高濕條件下保管72小時(耐久試驗),之後,評價段差追隨性。段差追隨性,是以印刷段差是否完全被著色黏著劑層填埋而判斷,在印刷段差與著色黏著劑層的界面,觀察到氣泡、浮起、剝落等時,判斷為無法追隨印刷段差。在此,段差追隨性,是以下述式所示段差追隨率(%)評價。將結果示於表3。 段差追隨率(%)={(耐久試驗後,維持沒有氣泡、浮起、剝落等的被填埋的狀態的段差高度(μm))/(著色黏著劑層的厚度)}×100The obtained evaluation sample was subjected to autoclave treatment under the conditions of 50° C. and 0.5 MPa for 30 minutes, and then left for 24 hours under the conditions of normal pressure, 23° C., and 50% RH. Next, it was stored under high temperature and high humidity conditions of 85° C. and 85% RH for 72 hours (endurance test), and after that, the step followability was evaluated. The step followability is judged based on whether the printing step is completely buried by the colored adhesive layer. When bubbles, floating, peeling, etc. are observed at the interface between the printing step and the colored adhesive layer, it is judged that the printing step cannot be followed. Here, the level difference followability is evaluated by the level difference followability rate (%) shown by the following formula. The results are shown in Table 3. Level difference follow-up rate (%)={(After the durability test, the level difference height (μm) to maintain the state of being buried without bubbles, floating, peeling, etc.)/(the thickness of the colored adhesive layer)}×100
再者,關於實施例5的著色黏著片,製作厚度為25μm的著色黏著劑層,以與上述同樣地將所得評價樣品,做高壓釜處理之後,以23℃、50%RH的條件下放置24小時之後,以與試驗例2同樣地照射活性能量線,使著色黏著劑層硬化。對該硬化後的著色黏著劑層,以與上述同樣地測定段差追隨率(UV後)。Furthermore, with regard to the colored adhesive sheet of Example 5, a colored adhesive layer with a thickness of 25 μm was prepared, and the resulting evaluation sample was subjected to autoclave treatment in the same manner as above, and then it was left at 23°C and 50% RH for 24 After hours, the active energy ray was irradiated in the same manner as in Test Example 2 to harden the colored adhesive layer. For the colored adhesive layer after curing, the step following rate (after UV) was measured in the same manner as described above.
[試驗例9](設計性的評價) 將實施例及比較例所得的著色黏著片裁成長70mm×寬70mm,將該著色黏著片的著色黏著劑層,以被2片鈉鈣玻璃(日本平板玻璃公司製,長70mm×寬70mm×厚度1.1mm)夾持的方式黏合,將此作為樣品。再者,對實施例5的著色黏著片,以與試驗例2同樣地照射活性能量線,使著色黏著劑層硬化,將此作為樣品。[Test Example 9] (Design evaluation) The colored adhesive sheets obtained in the Examples and Comparative Examples were cut to a length of 70 mm × width 70 mm, and the colored adhesive layer of the colored adhesive sheet was covered with 2 sheets of soda lime glass (manufactured by Japan Plate Glass Co., Ltd., length 70 mm × width 70 mm × thickness 1.1mm) Glue in a clamping manner, and use this as a sample. In addition, the colored adhesive sheet of Example 5 was irradiated with active energy rays in the same manner as in Test Example 2 to harden the colored adhesive layer, and this was used as a sample.
將所得的樣品,設置在熄燈狀態的顯示器(富士通公司製,產品名「LITEBOOK A574/H」,尺寸15.6英寸,解析度1366×768)的正前方。此時,使樣品的周緣部與顯示器的框材鄰接地設置該樣品。然後,在3波長日光燈下(從日光燈的距離︰200cm),以目視判斷樣品的色調(黑的程度‧發白),以如下基準評價關於畫面色調的設計性。將結果示於表3。 ◎︰即使在日光燈的反射下亦有很深的黑色調。 ○:若沒有日光燈的反射,則有很深的黑色調。 ╳:全體看起來發白。The obtained sample was set directly in front of a display (manufactured by Fujitsu Corporation, product name "LITEBOOK A574/H", size 15.6 inches, resolution 1366×768) in a light-off state. At this time, the sample is set so that the peripheral edge of the sample is adjacent to the frame material of the display. Then, under a 3-wavelength fluorescent lamp (distance from the fluorescent lamp: 200cm), the color tone of the sample (the degree of black and whiteness) was visually judged, and the design of the color tone of the screen was evaluated based on the following criteria. The results are shown in Table 3. ◎: There is a deep black tone even under the reflection of fluorescent lamps. ○: If there is no reflection from the fluorescent lamp, there is a deep black tone. ╳: The whole looks pale.
此外,以目視判斷樣品部分,與上述顯示器的框材的邊界的觀感,以如下基準評價關於無邊框化性的設計性。將結果示於表3。 ◎:無法視認邊界。 ○:能夠些微視認邊界但並不明顯。 ╳:能夠清楚視認邊界。In addition, the appearance of the boundary between the sample portion and the frame material of the above-mentioned display was judged visually, and the design of framelessness was evaluated based on the following criteria. The results are shown in Table 3. ◎: The boundary cannot be seen. ○: The boundary can be slightly visualized but is not obvious. ╳: Can clearly see the boundary.
再者,上述顯示器框材的色調(CIE1976L*a*b*表色系),是使用分光測色計(BYK公司製,產品名「SPECRO GUIDE」)測定,結果是L*:19.7,a*:-0.3,b*:-1.5。Furthermore, the hue of the display frame material (CIE1976L*a*b* color system) was measured using a spectrophotometer (manufactured by BYK, product name "SPECRO GUIDE"). The result was L*: 19.7, a* : -0.3, b*: -1.5.
[試驗例10](視認性的評價) 以與試驗例9同樣地製作樣品,設置在點燈狀態的顯示器(富士通公司製,產品名「LITEBOOK A574/H」,尺寸15.6英寸,解析度1366×768)的正前方。此時,在顯示器,顯示ARIB多格式彩條。然後,在3波長日光燈下(從日光燈的距離︰200cm),對樣品從正面及斜面(45∘的角度),以目視判斷隔著樣品的顯示器的觀感,以如下基準評價視認性(廣角視認性)。將結果示於表3。 ◎:從正面的觀感與從斜向的觀感沒有變化。 ○:與正面的觀感相比,從斜向的觀感會變暗,但色調不變。 ╳:從正面的觀感與從斜向的觀感,色調會變化。[Test Example 10] (Evaluation of visibility) A sample was produced in the same manner as in Test Example 9, and it was installed in front of a display (manufactured by Fujitsu Corporation, product name "LITEBOOK A574/H", size 15.6-inch, resolution 1366×768) in a lighting state. At this time, on the display, ARIB multi-format color bars are displayed. Then, under a three-wavelength fluorescent lamp (distance from the fluorescent lamp: 200cm), the sample was visually judged from the front and inclined surface (45∘ angle), and the look and feel of the display across the sample was evaluated by the following criteria (wide-angle visibility) ). The results are shown in Table 3. ◎: There is no change between the frontal look and the oblique look. ○: Compared with the frontal look, the oblique look becomes darker, but the color tone does not change. ╳: The color tone will change from the frontal look and the oblique look.
再者,在任一例子,從正面觀看時的畫面明亮,故起因於畫面明亮度的畫像視認性良好。Furthermore, in either example, the screen when viewed from the front is bright, so the visibility of the image due to the brightness of the screen is good.
[表1]
[表2]
[表3]
由表3可知,使用實施例所得著色黏著片的,設計性(特別是關於畫面的色調的設計性)及視認性(特別是廣角視認性及起因於畫面的明亮度的視認性)優良。此外,以實施例所得的著色黏著片,段差追隨性亦優良。 [產業上的可利性]It can be seen from Table 3 that the use of the colored adhesive sheets obtained in the examples has excellent design properties (especially design properties regarding the hue of the screen) and visibility (especially wide-angle visibility and visibility due to the brightness of the screen). In addition, the colored adhesive sheets obtained in the examples have excellent step followability. [Industrial Profitability]
本發明的著色黏著片,可良好地使用在例如在具有黑色框材的顯示設備的顯示設備構成構件的相互黏合,特別是具有段差的保護板與所期望的顯示設備構成構件的黏合等。The colored adhesive sheet of the present invention can be suitably used for, for example, bonding of display device constituent members of a display device with a black frame material, particularly bonding of a protective plate with a step and a desired display device constituent member, etc.
1:著色黏著片
11:著色黏著劑層
12a,12b:剝離片
2:顯示設備
21:第1顯示設備構成構件
22:第2顯示設備構成構件
3:印刷層
4:框材1: Colored adhesive sheet
11: Colored
[圖1]係關於本發明的一實施形態的著色黏著片的剖面圖。 [圖2]係關於本發明的一實施形態的顯示設備的剖面圖。 [圖3]係關於本發明的一實施形態的具有框材的顯示設備的平面圖。Fig. 1 is a cross-sectional view of a colored adhesive sheet according to an embodiment of the present invention. Fig. 2 is a cross-sectional view of a display device related to an embodiment of the present invention. Fig. 3 is a plan view of a display device having a frame material related to an embodiment of the present invention.
1:著色黏著片 1: Colored adhesive sheet
11:黏著劑層 11: Adhesive layer
12a,12b:剝離片 12a, 12b: peeling sheet
Claims (13)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019068290A JP6792662B2 (en) | 2019-03-29 | 2019-03-29 | Colored adhesive sheet and display |
JP2019-068290 | 2019-03-29 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW202035618A true TW202035618A (en) | 2020-10-01 |
TWI834763B TWI834763B (en) | 2024-03-11 |
Family
ID=72672912
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW108142904A TWI834763B (en) | 2019-03-29 | 2019-11-26 | Colored adhesive sheets and display equipment |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6792662B2 (en) |
KR (1) | KR20200115066A (en) |
CN (1) | CN111748289A (en) |
TW (1) | TWI834763B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7341033B2 (en) | 2019-11-11 | 2023-09-08 | キヤノン株式会社 | Parallax detection device, imaging device, parallax detection method, and program |
WO2021106743A1 (en) * | 2019-11-28 | 2021-06-03 | 日東電工株式会社 | Optical laminate and image display device |
CN114761840A (en) * | 2019-11-28 | 2022-07-15 | 日东电工株式会社 | Optical laminate, optical device, and image display device |
JP6945091B1 (en) | 2020-08-31 | 2021-10-06 | 日東電工株式会社 | Adhesive sheet, display device, structure and adhesive sheet with light transmissive member |
KR20230024749A (en) * | 2021-08-12 | 2023-02-21 | (주)이녹스첨단소재 | Adhesive sheet for display and preparing method of the same |
JP7289008B1 (en) | 2022-03-25 | 2023-06-08 | 日東電工株式会社 | ADHESIVE LAYER, LAMINATED SHEET, ADHESIVE COMPOSITION, AND OPTICAL SEMICONDUCTOR DEVICE |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000265133A (en) * | 1999-03-11 | 2000-09-26 | Tomoegawa Paper Co Ltd | Application film for electronic display |
JP2000313871A (en) * | 1999-04-30 | 2000-11-14 | Nitto Denko Corp | Pressure-sensitive adhesive composition for attaching functional film and image display device |
JP2009188298A (en) * | 2008-02-08 | 2009-08-20 | Dainippon Printing Co Ltd | Method of manufacturing electromagnetic wave blocking composite filter |
JP2012234028A (en) * | 2011-04-28 | 2012-11-29 | Asahi Glass Co Ltd | Optical filter and display device |
JP5924507B2 (en) | 2014-09-25 | 2016-05-25 | 三菱マテリアル株式会社 | Surface coated cutting tool with excellent chipping resistance due to hard coating layer |
JP6774806B2 (en) * | 2015-09-18 | 2020-10-28 | 日東電工株式会社 | Adhesive sheet |
-
2019
- 2019-03-29 JP JP2019068290A patent/JP6792662B2/en active Active
- 2019-11-26 TW TW108142904A patent/TWI834763B/en active
- 2019-12-17 CN CN201911301433.XA patent/CN111748289A/en active Pending
-
2020
- 2020-01-23 KR KR1020200009388A patent/KR20200115066A/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
TWI834763B (en) | 2024-03-11 |
CN111748289A (en) | 2020-10-09 |
JP6792662B2 (en) | 2020-11-25 |
KR20200115066A (en) | 2020-10-07 |
JP2020164702A (en) | 2020-10-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI834851B (en) | Adhesive sheets and displays | |
TWI834763B (en) | Colored adhesive sheets and display equipment | |
JP7198009B2 (en) | Display body manufacturing method | |
JP6937338B2 (en) | Display and adhesive sheet | |
TWI835640B (en) | Adhesive sheet, display body and display body manufacturing method | |
TWI741057B (en) | Adhesive composition, adhesive, adhesive sheet and display body | |
TW201802206A (en) | Double-surface adhesion sheet, display member and manufacturing method of display member | |
KR20200001462A (en) | Adhesive sheet and optical laminate | |
JP7273887B2 (en) | colored adhesive sheet | |
TW202138844A (en) | Scattering-resistant adhesive sheet and display device wherein the scattering-resistant adhesive sheet is disposed on a surface side of a protection panel of a display device and includes a base material and a coloring adhesive layer | |
JP2021014591A (en) | Colored adhesive sheet and display body | |
JP7256856B2 (en) | colored adhesive sheet | |
JP7233405B2 (en) | PSA SHEET, DISPLAY, AND METHOD FOR MANUFACTURING DISPLAY | |
JP7426539B2 (en) | Method of manufacturing the construct | |
CN111748300B (en) | Colored adhesive sheet and display |