TW202128937A - Pressure sensitive adhesive composition, pressure sensitive adhesive layer, pressure sensitive adhesive sheet, and optical laminate - Google Patents

Pressure sensitive adhesive composition, pressure sensitive adhesive layer, pressure sensitive adhesive sheet, and optical laminate Download PDF

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TW202128937A
TW202128937A TW109140549A TW109140549A TW202128937A TW 202128937 A TW202128937 A TW 202128937A TW 109140549 A TW109140549 A TW 109140549A TW 109140549 A TW109140549 A TW 109140549A TW 202128937 A TW202128937 A TW 202128937A
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film
resin
adhesive layer
layer
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久門浩司
佐瀬光敬
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日商住友化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special 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
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention provides a pressure sensitive adhesive composition for forming a pressure-sensitive adhesive layer which allows release films provided on both sides of the pressure-sensitive adhesive layer to be satisfactorily peeled off, a pressure-sensitive adhesive layer and a pressure-sensitive adhesive sheet including the same, and an optical laminate including the pressure-sensitive adhesive layer.
The pressure-sensitive adhesive composition contains a resin, a cross-linking agent, a leveling agent and a silane compound, wherein the leveling agent including a fluorine compound.

Description

黏著劑組成物、黏著劑層、黏著劑片及光學積層體 Adhesive composition, adhesive layer, adhesive sheet and optical laminate

本發明係有關黏著劑組成物、使用該黏著劑組成物之黏著劑層及黏著劑片、含有黏著劑層之光學積層體。 The present invention relates to an adhesive composition, an adhesive layer and an adhesive sheet using the adhesive composition, and an optical laminate containing the adhesive layer.

液晶顯示裝置或有機EL顯示裝置等圖像顯示裝置一般係具備將偏光板或相位差膜等光學構件隔著黏著劑層而貼合於含有顯示元件等顯示單元之構成。如此之圖像顯示裝置可藉由例如下述方式製造，該方式為：從具有以可剝離的形式設置於黏著劑層的雙面的剝離膜之黏著劑片中，將其中一側的剝離膜剝離而將露出的黏著劑層貼合於光學構件，然後將另一側的剝離膜剝離而將露出的黏著劑層貼合於顯示元件。 An image display device such as a liquid crystal display device or an organic EL display device generally has a configuration in which an optical member such as a polarizing plate or a retardation film is bonded to a display unit including a display element through an adhesive layer. Such an image display device can be manufactured by, for example, the following method: from an adhesive sheet having a double-sided release film provided on the adhesive layer in a peelable form, the release film on one side After peeling and bonding the exposed adhesive layer to the optical member, the peeling film on the other side is peeled off, and the exposed adhesive layer is bonded to the display element.

[先前技術文獻] [Prior Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1] 日本特開2018-104655號公報 [Patent Document 1] Japanese Patent Application Publication No. 2018-104655

於黏著劑片的黏著劑層的雙面所設置之剝離膜具有相同的離型處理層時，黏著劑層與剝離膜的離型處理層側之剝離力會成為相同。因此，有時會發生黏著劑層的某部分會與其中一側的剝離膜一起被剝離，黏著劑層的其他部分則與另一側的剝離膜一起被剝離，而黏著劑層被部分分離之不良情形。如此之不良情形有時稱為黏著劑分離，但產生黏著劑分離時，難以於光學構件與顯示元件之間形成均勻的黏著劑層，變得難以確保光學構件與顯示元件之良好的接著性。 When the release film provided on both sides of the adhesive layer of the adhesive sheet has the same release treatment layer, the release force of the release treatment layer side of the adhesive layer and the release film will be the same. Therefore, it sometimes happens that a part of the adhesive layer is peeled off together with the release film on one side, and the other part of the adhesive layer is peeled off together with the release film on the other side, and the adhesive layer is partially separated. Bad situation. Such a problem is sometimes called adhesive separation, but when adhesive separation occurs, it is difficult to form a uniform adhesive layer between the optical member and the display element, and it becomes difficult to ensure good adhesion between the optical member and the display element.

本發明之目的係提供一種用以形成黏著劑層的黏著劑組成物、使用該黏著劑組成物之黏著劑層及黏著劑片、及包含該黏著劑層之光學積層體，其中，可將設置於該黏著劑層之雙面的剝離膜良好地剝離。 The object of the present invention is to provide an adhesive composition for forming an adhesive layer, an adhesive layer and an adhesive sheet using the adhesive composition, and an optical laminate containing the adhesive layer, wherein The release film on both sides of the adhesive layer peeled off well.

本發明係提供以下的黏著劑組成物、黏著劑層、黏著劑片、及光學積層體。 The present invention provides the following adhesive composition, adhesive layer, adhesive sheet, and optical laminate.

[1]一種黏著劑組成物，係含有樹脂、交聯劑、調平劑及矽烷化合物；其中， [1] An adhesive composition containing resin, crosslinking agent, leveling agent and silane compound; wherein,

前述調平劑係包含氟系化合物。 The aforementioned leveling agent contains a fluorine-based compound.

[2]如[1]所述之黏著劑組成物，其中，前述矽烷化合物的含量(質量份)小於前述氟系化合物之含量(質量份)。 [2] The adhesive composition according to [1], wherein the content (parts by mass) of the silane compound is less than the content (parts by mass) of the fluorine-based compound.

[3]如[1]或[2]所述之黏著劑組成物，其中，前述氟系化合物為具有全氟烷基及全氟伸烷基中之至少一者的化合物。 [3] The adhesive composition according to [1] or [2], wherein the fluorine-based compound is a compound having at least one of a perfluoroalkyl group and a perfluoroalkylene group.

[4]如[1]至[3]中任一項所述之黏著劑組成物，其中，前述矽烷化合物與前述氟系化合物的質量比(矽烷化合物的質量/氟系化合物的質量)為0.8以下。 [4] The adhesive composition according to any one of [1] to [3], wherein the mass ratio of the silane compound to the fluorine compound (mass of the silane compound/mass of the fluorine compound) is 0.8 the following.

[5]如[1]至[4]中任一項所述之黏著劑組成物，其中，前述樹脂含有(甲基)丙烯酸系樹脂。 [5] The adhesive composition according to any one of [1] to [4], wherein the resin contains a (meth)acrylic resin.

[6]一種黏著劑層，係使用[1]至[5]中任一項所述之黏著劑組成物。 [6] An adhesive layer using the adhesive composition described in any one of [1] to [5].

[7]一種黏著劑片，係在[6]所述之黏著劑層的雙面設置有相同的剝離膜，而且 [7] An adhesive sheet provided with the same release film on both sides of the adhesive layer described in [6], and

將前述黏著劑層的其中一面與前述剝離膜之間的剝離力作為第1剝離力，且將前述黏著劑層之與前述一面為相反側之另一面、與前述剝離膜之間的剝離力作為第2剝離力時，前述第1剝離力與前述第2剝離力彼此相異。 The peeling force between one side of the adhesive layer and the peeling film is taken as the first peeling force, and the peeling force between the other surface of the adhesive layer on the opposite side to the one surface and the peeling film is taken as In the case of the second peeling force, the first peeling force and the second peeling force are different from each other.

[8]一種光學積層體，係含有光學層及黏著劑層；其中， [8] An optical laminate comprising an optical layer and an adhesive layer; wherein,

前述黏著劑層為[6]所述之黏著劑層。 The aforementioned adhesive layer is the adhesive layer described in [6].

[9]如[8]所述之光學積層體，其中，前述光學層含有偏光板。 [9] The optical layered body according to [8], wherein the optical layer contains a polarizing plate.

依據本發明，可提供用以形成黏著劑層的黏著劑組成物、使用該黏著劑組成物之黏著劑層及黏著劑片、及包含該黏著劑層之光學積層體，可將設置於該黏著劑層之雙面的剝離膜良好地剝離。 According to the present invention, an adhesive composition for forming an adhesive layer, an adhesive layer and an adhesive sheet using the adhesive composition, and an optical laminate including the adhesive layer can be provided, which can be placed on the adhesive The release film on both sides of the agent layer peeled off well.

1:光學積層體 1: Optical laminate

2:偏光片 2: Polarizer

3:第1樹脂膜 3: The first resin film

4:第2樹脂膜 4: The second resin film

5,6,7,8:光學積層體 5, 6, 7, 8: optical laminate

10:光學層 10: Optical layer

10a:單面保護偏光板 10a: Single-sided protection polarizing plate

10b:雙面保護偏光板 10b: Double-sided protective polarizing plate

20:黏著劑層 20: Adhesive layer

30:導電層 30: conductive layer

40:基板 40: substrate

50:樹脂層 50: Resin layer

圖1係顯示本發明之光學積層體的一例之概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing an example of the optical laminate of the present invention.

圖2係顯示本發明之光學積層體所具有的光學層的一例之概略剖面圖。 Fig. 2 is a schematic cross-sectional view showing an example of the optical layer included in the optical laminate of the present invention.

圖3係顯示本發明之光學積層體所具有的光學層的另一例之概略剖面圖。 3 is a schematic cross-sectional view showing another example of the optical layer included in the optical laminate of the present invention.

圖4係顯示本發明之光學積層體的層構成的另一例之概略剖面圖。 4 is a schematic cross-sectional view showing another example of the layer structure of the optical laminate of the present invention.

圖5係顯示本發明之光學積層體的層構成的另一例之概略剖面圖。 Fig. 5 is a schematic cross-sectional view showing another example of the layer structure of the optical laminate of the present invention.

圖6係顯示本發明之光學積層體的層構成的另一例之概略剖面圖。 Fig. 6 is a schematic cross-sectional view showing another example of the layer structure of the optical laminate of the present invention.

圖7係顯示本發明之光學積層體的層構成的另一例之概略剖面圖。 Fig. 7 is a schematic cross-sectional view showing another example of the layer structure of the optical laminate of the present invention.

圖8係顯示本發明之光學積層體的層構成的另一例之概略剖面圖。 Fig. 8 is a schematic cross-sectional view showing another example of the layer structure of the optical laminate of the present invention.

<黏著劑組成物> <Adhesive composition>

本發明之黏著劑組成物(Pressure sensitive adhesive composition，又稱壓敏性接著劑組成物)係含有樹脂、交聯劑、至少含有氟系化合物之調平劑及矽烷化合物。以下有時將上述樹脂稱為「樹脂(A)」、上述交聯劑稱為「交聯劑(B)」、上述調平劑稱為「調平劑(C)」、上述矽烷化合物稱為「矽烷化合物(D)」。 The adhesive composition (Pressure sensitive adhesive composition, also known as pressure sensitive adhesive composition) of the present invention contains a resin, a cross-linking agent, a leveling agent containing at least a fluorine-based compound, and a silane compound. Hereinafter, the above-mentioned resin is sometimes referred to as "resin (A)", the above-mentioned cross-linking agent is referred to as "cross-linking agent (B)", the above-mentioned leveling agent is referred to as "leveling agent (C)", and the above-mentioned silane compound is referred to as "Silane compound (D)".

黏著劑組成物例如可列舉(甲基)丙烯酸系黏著劑組成物、胺酯(urethane)系黏著劑組成物、聚矽氧系黏著劑組成物、聚酯系黏著劑組成物、聚醯胺系黏著劑組成物、聚醚系黏著劑組成物、氟系黏著劑組成物、橡膠系黏著劑組成物等。上述黏著劑組成物當中，從透明性、黏著力、可靠性、重 工性等的觀點來看，較佳可使用(甲基)丙烯酸系黏著劑組成物。本說明書中，所謂「(甲基)丙烯酸」係表示選自由丙烯酸及甲基丙烯酸所組成的群組之至少一種。有關「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等的標記亦同。 The adhesive composition includes, for example, a (meth)acrylic adhesive composition, a urethane adhesive composition, a silicone adhesive composition, a polyester adhesive composition, and a polyamide-based adhesive composition. Adhesive composition, polyether adhesive composition, fluorine adhesive composition, rubber adhesive composition, etc. Among the above adhesive compositions, from transparency, adhesion, reliability, weight From the viewpoint of workability and the like, it is preferable to use a (meth)acrylic adhesive composition. In this specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The same applies to the markings of "(meth)acryloyl" and "(meth)acrylate".

(樹脂(A)) (Resin (A))

黏著劑組成物含有樹脂(A)。樹脂(A)可列舉(甲基)丙烯酸系樹脂、胺酯系樹脂、聚矽氧系樹脂、聚酯系樹脂、聚醯胺系樹脂、聚醚系樹脂、氟系樹脂、天然橡膠、合成橡膠等。此等之中，從透明性、黏著力、可靠性、重工性等的觀點來看，樹脂(A)較佳係以(甲基)丙烯酸系樹脂作為主成分(含有50質量%以上)。 The adhesive composition contains resin (A). The resin (A) includes (meth)acrylic resins, urethane resins, silicone resins, polyester resins, polyamide resins, polyether resins, fluorine resins, natural rubber, and synthetic rubber. Wait. Among these, from the viewpoints of transparency, adhesion, reliability, reworkability, etc., the resin (A) preferably has a (meth)acrylic resin as a main component (containing 50% by mass or more).

((甲基)丙烯酸系樹脂) ((Meth) acrylic resin)

可適合作為黏著劑組成物的樹脂(A)使用之(甲基)丙烯酸系樹脂的具體例為以源自下述式(I)所示之(甲基)丙烯酸酯的結構單元作為主成分(含有50質量%以上)的聚合物(以下有時將該聚合物稱為「(甲基)丙烯酸系樹脂(a1)」)。 A specific example of the (meth)acrylic resin suitable for use as the resin (A) of the adhesive composition is a structural unit derived from the (meth)acrylate represented by the following formula (I) as the main component ( Containing 50% by mass or more) of the polymer (hereinafter, this polymer may be referred to as "(meth)acrylic resin (a1)").

Figure 109140549-A0202-12-0005-1
Figure 109140549-A0202-12-0005-1

於上述式(I)中，R1表示氫原子或甲基，R2表示可經碳數1至10的烷氧基取代之碳數1至14的烷基、或可經碳數1至10的烷氧基取代之碳數7至21的芳烷基。R2較佳為可經碳數1至10的烷氧基取代之碳數1至14的烷基。 In the above formula (I), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 1 to 14 carbons which may be substituted by an alkoxy group having 1 to 10 carbons, or may be substituted by an alkoxy group having 1 to 10 carbons. The alkoxy substituted aralkyl group having 7 to 21 carbons. R 2 is preferably an alkyl group having 1 to 14 carbons which may be substituted by an alkoxy group having 1 to 10 carbons.

式(I)所示之(甲基)丙烯酸酯的具體例係包含如(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)丙烯酸正辛酯、(甲基)丙烯酸十二烷酯等直鏈狀的(甲基)丙烯酸烷酯；如(甲基)丙烯酸異丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯等分支狀的(甲基)丙烯酸烷酯。(甲基)丙烯酸烷酯中之烷基部分的碳數較佳為1至8，更佳為1至6。 Specific examples of the (meth)acrylate represented by formula (I) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. Ester, n-octyl (meth)acrylate, dodecyl (meth)acrylate and other linear alkyl (meth)acrylates; such as isobutyl (meth)acrylate, 2-(meth)acrylate Branched alkyl (meth)acrylates such as ethylhexyl and isooctyl (meth)acrylate. The carbon number of the alkyl moiety in the alkyl (meth)acrylate is preferably from 1 to 8, more preferably from 1 to 6.

R2為經烷氧基取代之烷基時，亦即R2為烷氧基烷基時之式(I)所示之(甲基)丙烯酸酯的具體例係包含(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸乙氧基甲酯等。R2為碳數7至21的芳烷基時之式(I)所示之(甲基)丙烯酸酯的具體例係包含(甲基)丙烯酸苯甲酯等。 When R 2 is an alkyl group substituted with an alkoxy group, that is, when R 2 is an alkoxyalkyl group, specific examples of the (meth)acrylate represented by formula (I) include (meth)acrylic acid 2- Methoxyethyl, (meth)acrylate ethoxymethyl and the like. Specific examples of the (meth)acrylate represented by formula (I) when R 2 is an aralkyl group having 7 to 21 carbon atoms include benzyl (meth)acrylate and the like.

式(I)所示之(甲基)丙烯酸酯可只單獨使用1種，亦可併用2種以上。其中，(甲基)丙烯酸酯較佳係包含(甲基)丙烯酸烷酯，更佳係包含(甲基)丙烯酸正丁酯。在構成(甲基)丙烯酸系樹脂(a1)的全單體中，(甲基)丙烯酸系樹脂(a1)較佳係含有50質量%以上的丙烯酸正丁酯。當然，除了丙烯酸正丁酯以外，亦可併用除此以外之式(I)所示之(甲基)丙烯酸酯。 The (meth)acrylate represented by the formula (I) may be used alone or in combination of two or more. Among them, the (meth)acrylate preferably includes alkyl (meth)acrylate, and more preferably includes n-butyl (meth)acrylate. Among all the monomers constituting the (meth)acrylic resin (a1), the (meth)acrylic resin (a1) preferably contains 50% by mass or more of n-butyl acrylate. Of course, in addition to n-butyl acrylate, other (meth)acrylates represented by formula (I) may also be used in combination.

(甲基)丙烯酸系樹脂(a1)通常係上述式(I)的(甲基)丙烯酸酯、與以具有極性官能基的單體為代表之至少一種其他單體之共聚物。具有極性官能基的單體較佳為具有極性官能基的(甲基)丙烯酸系化合物。極性官能基可列舉游離羧基、羥基、胺基、以環氧基為首的雜環基等。 The (meth)acrylic resin (a1) is usually a copolymer of the (meth)acrylate of the above formula (I) and at least one other monomer represented by a monomer having a polar functional group. The monomer having a polar functional group is preferably a (meth)acrylic compound having a polar functional group. Examples of polar functional groups include free carboxyl groups, hydroxyl groups, amino groups, and heterocyclic groups including epoxy groups.

具有極性官能基的單體之具體例係包含：如(甲基)丙烯酸、(甲基)丙烯酸β-羧基乙酯等具有游離羧基的單體；如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-(2-羥 基乙氧基)乙酯、(甲基)丙烯酸2-(或3-)氯-2-羥基丙酯、二乙二醇單(甲基)丙烯酸酯等具有羥基的單體；如(甲基)丙烯醯基嗎啉、乙烯基己內醯胺、N-乙烯基-2-吡咯啶酮、乙烯基吡啶、(甲基)丙烯酸四氫呋喃甲酯、己內酯改性(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸縮水甘油酯、2,5-二氫呋喃等具有雜環基的單體；如(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸二甲基胺基丙酯等具有不同於雜環的胺基之單體等。具有極性官能基的單體可只單獨使用1種，亦可併用2種以上。 Specific examples of monomers with polar functional groups include monomers with free carboxyl groups such as (meth)acrylic acid, β-carboxyethyl (meth)acrylate, etc.; such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-(2-hydroxyl (meth)acrylate Ethyl ethoxy) ethyl ester, 2-(or 3-) chloro-2-hydroxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate and other monomers with hydroxyl groups; such as (methyl) )Acrylic morpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, methyl tetrahydrofuran (meth)acrylate, caprolactone modified methyl tetrahydrofuran (meth)acrylate Monomers with heterocyclic groups such as esters, 3,4-epoxycyclohexyl methyl (meth)acrylate, glycidyl (meth)acrylate, 2,5-dihydrofuran, etc.; such as amine (meth)acrylate Ethyl ethyl, N,N-dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and other monomers having an amine group different from a heterocyclic ring. The monomer having a polar functional group may be used alone or in combination of two or more kinds.

上述之中，從(甲基)丙烯酸系樹脂(a1)的反應性之觀點來看，就構成(甲基)丙烯酸系樹脂(a1)的含極性官能基的單體之一而言，較佳係使用具有羥基的單體。除了具有羥基的單體以外，還併用其他具有極性官能基的單體例如具有游離羧基的單體者亦為有效。 Among the above, from the viewpoint of the reactivity of the (meth)acrylic resin (a1), one of the polar functional group-containing monomers constituting the (meth)acrylic resin (a1) is preferable A monomer having a hydroxyl group is used. In addition to the monomer having a hydroxyl group, it is also effective to use a monomer having a polar functional group in combination, for example, a monomer having a free carboxyl group.

(甲基)丙烯酸系樹脂(a1)可更含有下述結構單元，該結構單元係源自於分子內具有1個烯烴性雙鍵及至少1個芳香環的單體(但是排除符合上述式(I)所示之單體及上述具有極性官能基的單體者)。合適例可列舉具有芳香環的(甲基)丙烯酸系化合物。具有芳香環的(甲基)丙烯酸系化合物之合適例為如下述式(II)所示之含苯氧基乙基的(甲基)丙烯酸酯等具有芳氧基烷基之(甲基)丙烯酸酯： The (meth)acrylic resin (a1) may further contain the following structural unit, which is derived from a monomer having one olefinic double bond and at least one aromatic ring in the molecule (except that the above formula ( I) the monomers shown and the above-mentioned monomers with polar functional groups). Suitable examples include (meth)acrylic compounds having an aromatic ring. Suitable examples of the (meth)acrylic compound having an aromatic ring are (meth)acrylic acid having aryloxyalkyl groups such as (meth)acrylic acid esters containing phenoxyethyl groups as shown in the following formula (II) ester:

Figure 109140549-A0202-12-0007-2
Figure 109140549-A0202-12-0007-2

於上述式(II)中，R3表示氫原子或甲基，n表示1至8的整數， R4表示氫原子、烷基、芳烷基或芳基。R4為烷基時，其碳數可為1至9左右，R4為芳烷基時，其碳數可為7至11左右，R4為芳基時，其碳數可為6至10左右。 In the above formula (II), R 3 represents a hydrogen atom or a methyl group, n represents an integer of 1 to 8, and R 4 represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group. When R 4 is an alkyl group, its carbon number can be about 1 to 9; when R 4 is an aralkyl group, its carbon number can be about 7 to 11; when R 4 is an aryl group, its carbon number can be about 6 to 10. about.

式(II)中之構成R4之碳數1至9的烷基可列舉甲基、丁基、壬基等，碳數7至11的芳烷基可列舉苯甲基、苯乙基、萘基甲基等，碳數6至10的芳基可列舉苯基、甲苯基、萘基等。 In formula (II), the alkyl group having 1 to 9 carbon atoms constituting R 4 includes methyl, butyl, nonyl, etc., and the aralkyl group having 7 to 11 carbon atoms includes benzyl, phenethyl, and naphthalene. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, naphthyl and the like.

式(II)所示之含苯氧基乙基的(甲基)丙烯酸酯的具體例係包含(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸2-(2-苯氧基乙氧基)乙酯、環氧乙烷改性壬基酚的(甲基)丙烯酸酯、(甲基)丙烯酸2-(鄰苯基苯氧基)乙酯等。含苯氧基乙基的(甲基)丙烯酸酯可只單獨使用1種，亦可併用2種以上。其中，含苯氧基乙基的(甲基)丙烯酸酯較佳係包含(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸2-(鄰苯基苯氧基)乙酯及/或(甲基)丙烯酸2-(2-苯氧基乙氧基)乙酯。 Specific examples of the phenoxyethyl-containing (meth)acrylate represented by the formula (II) include 2-phenoxyethyl (meth)acrylate and 2-(2-phenoxy) (meth)acrylate (Meth)acrylate of ethylene oxide-modified nonylphenol, 2-(o-phenylphenoxy)ethyl (meth)acrylate, etc. The phenoxyethyl group-containing (meth)acrylate may be used individually by 1 type, and may use 2 or more types together. Among them, the phenoxyethyl-containing (meth)acrylate preferably includes 2-phenoxyethyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, and /Or 2-(2-phenoxyethoxy)ethyl (meth)acrylate.

(甲基)丙烯酸系樹脂(a1)係以其固形分整體量為基準計，可以含有較佳為60至99.9質量%(更佳為80至99.6質量%)的比率之源自上述式(I)所示之(甲基)丙烯酸酯的結構單元，含有較佳為0.1至20質量%(更佳為0.4至10質量%)的比率之源自具有極性官能基的單體之結構單元，含有較佳為0至40質量%(更佳為6至12質量%)的比率之源自於分子內具有1個烯烴性雙鍵及至少1個芳香環的單體之結構單元。 The (meth)acrylic resin (a1) is based on its total solid content, and may contain preferably 60 to 99.9% by mass (more preferably 80 to 99.6% by mass) derived from the above formula (I The structural unit of the (meth)acrylate shown in) contains the structural unit derived from a monomer having a polar functional group in a ratio of preferably 0.1 to 20% by mass (more preferably 0.4 to 10% by mass), and contains Preferably, the ratio of 0 to 40% by mass (more preferably 6 to 12% by mass) is derived from a structural unit of a monomer having one olefinic double bond and at least one aromatic ring in the molecule.

(甲基)丙烯酸系樹脂(a1)亦可含有下述結構單元，該結構單元為源自式(I)所示之(甲基)丙烯酸酯、具有極性官能基的單體、及於分子內具有1個烯烴性雙鍵及至少1個芳香環的單體以外的單體(以下亦稱為「其他 單體」)者。其他單體的具體例係包含源自於分子內具有脂環式結構的(甲基)丙烯酸酯之結構單元、源自苯乙烯系單體的結構單元、源自乙烯基系單體的結構單元、源自於分子內具有複數個(甲基)丙烯醯基的單體之結構單元、源自(甲基)丙烯醯胺單體之結構單元等。其他單體可只單獨使用1種，亦可併用2種以上。 The (meth)acrylic resin (a1) may also contain the following structural unit, which is derived from the (meth)acrylate represented by formula (I), a monomer having a polar functional group, and in the molecule Monomers other than monomers having one olefinic double bond and at least one aromatic ring (hereinafter also referred to as "other "Single"). Specific examples of other monomers include structural units derived from (meth)acrylates having an alicyclic structure in the molecule, structural units derived from styrene monomers, and structural units derived from vinyl monomers , Structural units derived from monomers having multiple (meth)acrylic acid groups in the molecule, structural units derived from (meth)acrylic amide monomers, etc. The other monomers may be used alone or in combination of two or more.

脂環式結構的碳數通常為5以上，較佳為5至7左右。具有脂環式結構的(甲基)丙烯酸酯之具體例係包含(甲基)丙烯酸異莰酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸環十二烷基酯、(甲基)丙烯酸甲基環己酯、(甲基)丙烯酸三甲基環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸環己基苯酯、α-乙氧基(甲基)丙烯酸環己酯等。 The carbon number of the alicyclic structure is usually 5 or more, preferably about 5 to 7. Specific examples of (meth)acrylates having an alicyclic structure include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, and (meth)acrylic acid Cyclododecyl ester, methylcyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate Phenyl ester, α-ethoxy (meth) acrylate cyclohexyl ester, etc.

苯乙烯系單體的具體例係包含：苯乙烯；如甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、三乙基苯乙烯、丙基苯乙烯、丁基苯乙烯、己基苯乙烯、庚基苯乙烯、辛基苯乙烯等烷基苯乙烯；如氟苯乙烯、氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯等鹵化苯乙烯；硝基苯乙烯、乙醯基苯乙烯、甲氧基苯乙烯、二乙烯基苯等。 Specific examples of styrene monomers include: styrene; such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, acrylic Alkyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, etc.; such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene, etc. Halogenated styrene; nitrostyrene, acetoxystyrene, methoxystyrene, divinylbenzene, etc.

乙烯基系單體的具體例係包含：如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、十二烷酸乙烯酯之脂肪酸乙烯酯；如氯乙烯、溴乙烯之鹵乙烯；如偏二氯乙烯之偏二鹵乙烯；如乙烯基吡啶、乙烯基吡咯啶酮、乙烯基咔唑之含氮的芳香族乙烯基；如丁二烯、異戊二烯、氯丁二烯之共軛二烯單體；丙烯腈、甲基丙烯腈等。 Specific examples of vinyl monomers include: fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl dodecanoate; such as vinyl chloride, Vinyl halide of vinyl bromide; such as vinylidene chloride; vinylidene halide; such as vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, nitrogen-containing aromatic vinyl; such as butadiene, isoprene , Conjugated diene monomer of chloroprene; acrylonitrile, methacrylonitrile, etc.

於分子內具有複數個(甲基)丙烯醯基的單體之具體例係包含：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、1,9-壬二醇 二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯之分子內具有2個(甲基)丙烯醯基的單體；如三羥甲基丙烷三(甲基)丙烯酸酯之分子內具有3個(甲基)丙烯醯基的單體等。 Specific examples of monomers having multiple (meth)acrylic groups in the molecule include: 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(methyl) Acrylate, 1,9-nonanediol Di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth) Monomers with two (meth)acrylic groups in the molecule of acrylate; for example, monomers with three (meth)acrylic groups in the molecule of trimethylolpropane tri(meth)acrylate.

(甲基)丙烯醯胺化合物的具體例係包含：N-羥甲基(甲基)丙烯醯胺、N-(2-羥基乙基)(甲基)丙烯醯胺、N-(3-羥基丙基)(甲基)丙烯醯胺、N-(4-羥基丁基)(甲基)丙烯醯胺、N-(5-羥基戊基)(甲基)丙烯醯胺、N-(6-羥基己基)(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-(3-二甲基胺基丙基)(甲基)丙烯醯胺、N-(1,1-二甲基-3-側氧基丁基)(甲基)丙烯醯胺、N-[2-(2-側氧基-1-咪唑啶基)乙基](甲基)丙烯醯胺、2-丙烯醯基胺基-2-甲基-1-丙烷磺酸、N-(甲氧基甲基)丙烯醯胺、N-(乙氧基甲基)(甲基)丙烯醯胺、N-(丙氧基甲基)(甲基)丙烯醯胺、N-(1-甲基乙氧基甲基)(甲基)丙烯醯胺、N-(1-甲基丙氧基甲基)(甲基)丙烯醯胺、N-(2-甲基丙氧基甲基)(甲基)丙烯醯胺[別名：N-(異丙氧基甲基)(甲基)丙烯醯胺]、N-(丁氧基甲基)(甲基)丙烯醯胺、N-(1,1-二甲基乙氧基甲基)(甲基)丙烯醯胺、N-(2-甲氧基乙基)(甲基)丙烯醯胺、N-(2-乙氧基乙基)(甲基)丙烯醯胺、N-(2-丙氧基乙基)(甲基)丙烯醯胺、N-[2-(1-甲基乙氧基)乙基](甲基)丙烯醯胺、N-[2-(1-甲基丙氧基)乙基](甲基)丙烯醯胺、N-[2-(2-甲基丙氧基)乙基](甲基)丙烯醯胺[別名：N-(2-異丁氧基乙基)(甲基)丙烯醯胺]、N-(2-丁氧基乙基)(甲基)丙烯醯胺、N-[2-(1,1-二甲基乙氧基)乙基](甲基)丙烯醯胺等。 Specific examples of (meth)acrylamide compounds include: N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(3-hydroxyl Propyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, N-(5-hydroxypentyl)(meth)acrylamide, N-(6- Hydroxyhexyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(methyl) Acrylamide, N-(3-dimethylaminopropyl)(meth)acrylamide, N-(1,1-dimethyl-3-oxobutyl)(meth)acrylamide Amine, N-[2-(2-Pendant oxy-1-imidazolidinyl)ethyl](meth)acrylamide, 2-propenylamino-2-methyl-1-propanesulfonic acid, N-(Methoxymethyl)acrylamide, N-(ethoxymethyl)(meth)acrylamide, N-(propoxymethyl)(meth)acrylamide, N-( 1-Methylethoxymethyl)(meth)acrylamide, N-(1-methylpropoxymethyl)(meth)acrylamide, N-(2-methylpropoxymethyl) Yl)(meth)acrylamide [alias: N-(isopropoxymethyl)(meth)acrylamide], N-(butoxymethyl)(meth)acrylamide, N- (1,1-Dimethylethoxymethyl)(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N-(2-ethoxyethyl) Yl)(meth)acrylamide, N-(2-propoxyethyl)(meth)acrylamide, N-[2-(1-methylethoxy)ethyl](methyl) Allylamide, N-[2-(1-methylpropoxy)ethyl](meth)acrylamide, N-[2-(2-methylpropoxy)ethyl](methyl) Allylamide [alias: N-(2-isobutoxyethyl)(meth)acrylamide], N-(2-butoxyethyl)(meth)acrylamide, N-[2 -(1,1-Dimethylethoxy)ethyl](meth)acrylamide and the like.

(甲基)丙烯酸系樹脂(a1)係以其固形分整體的量為基準計，含有通常為0至20質量%(較佳為0至10質量%)的比率之其他單體。 The (meth)acrylic resin (a1) is based on the total solid content and contains other monomers in a ratio of usually 0 to 20% by mass (preferably 0 to 10% by mass).

從黏著劑層與光學構件的密著性之觀點來看，(甲基)丙烯酸系樹脂(a1)之藉由凝膠滲透層析(GPC)所測得之標準聚苯乙烯換算的重量平均分子量(Mw)較佳為50萬以上，更佳為60萬以上。(甲基)丙烯酸系樹脂(a1)的Mw通常為170萬以下。 From the viewpoint of the adhesion between the adhesive layer and the optical member, the weight average molecular weight of the (meth)acrylic resin (a1) measured by gel permeation chromatography (GPC) in terms of standard polystyrene (Mw) is preferably 500,000 or more, more preferably 600,000 or more. The Mw of the (meth)acrylic resin (a1) is usually 1.7 million or less.

(甲基)丙烯酸系黏著劑組成物的樹脂(A)可含有2種以上之(甲基)丙烯酸系樹脂(a1)。又，樹脂(A)除了(甲基)丙烯酸系樹脂(a1)以外，還可含有不同於該(甲基)丙烯酸系樹脂(a1)的(甲基)丙烯酸系樹脂，例如具有源自式(I)的(甲基)丙烯酸酯的結構單元且不具有極性官能基之(甲基)丙烯酸系樹脂(a2)、或以源自上述式(I)所示之(甲基)丙烯酸酯的結構單元作為主成分且Mw在0.5萬至12萬的範圍之(甲基)丙烯酸系樹脂(a3)等。 The resin (A) of the (meth)acrylic adhesive composition may contain two or more (meth)acrylic resins (a1). In addition, the resin (A) may contain (meth)acrylic resins other than the (meth)acrylic resin (a1) in addition to the (meth)acrylic resin (a1), and has, for example, a (meth)acrylic resin derived from the formula ( I) (meth)acrylic resin (a2) which is a structural unit of (meth)acrylate and does not have a polar functional group, or a structure derived from the (meth)acrylate represented by the above formula (I) (Meth)acrylic resin (a3) etc. whose unit is the main component and Mw is in the range of 5,000 to 120,000.

(交聯劑(B)) (Crosslinking agent (B))

黏著劑組成物含有交聯劑(B)。藉由使黏著劑組成物含有交聯劑(B)，於黏著劑組成物中所含之樹脂(A)形成交聯結構，可對使用黏著劑組成物所形成的黏著劑層賦予良好的耐久性或重工性。 The adhesive composition contains a crosslinking agent (B). By including the crosslinking agent (B) in the adhesive composition, the resin (A) contained in the adhesive composition forms a crosslinked structure, which can impart good durability to the adhesive layer formed using the adhesive composition Sexuality or reworkability.

交聯劑(B)係與樹脂(A)中之尤其是源自含極性官能基的單體的結構單元反應，而使如(甲基)丙烯酸系樹脂(a1)之樹脂(A)交聯之化合物。具體而言，可列舉異氰酸酯系化合物、環氧系化合物、氮丙啶(aziridine)系化合物、金屬螯合物系化合物等。此等之中，異氰酸酯系化合物、環氧系化合物及氮丙啶系化合物係於分子內具有至少2個可與樹脂(A)中之極性官能基反應的官能基。交聯劑(B)可只單獨使用1種，亦可併用2種以上。 The crosslinking agent (B) reacts with the structural unit of the resin (A), especially derived from the monomer containing a polar functional group, to crosslink the resin (A) such as the (meth)acrylic resin (a1) The compound. Specifically, isocyanate-based compounds, epoxy-based compounds, aziridine-based compounds, metal chelate-based compounds, and the like can be cited. Among these, isocyanate-based compounds, epoxy-based compounds, and aziridine-based compounds have at least two functional groups in the molecule that can react with the polar functional groups in the resin (A). A crosslinking agent (B) may be used individually by 1 type, and may use 2 or more types together.

異氰酸酯系化合物為於分子內具有至少2個異氰酸基(-NCO)之化合物。異氰酸酯系化合物的具體例係包含甲苯二異氰酸酯、六亞甲基二 異氰酸酯、異佛酮二異氰酸酯、苯二甲基二異氰酸酯、氫化苯二甲基二異氰酸酯、二苯基甲烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、萘二異氰酸酯、三苯基甲烷三異氰酸酯等。又，使該等異氰酸酯化合物與甘油或三羥甲基丙烷等多元醇反應而成的加成物，或使異氰酸酯化合物形成二聚物、三聚物等而成者，亦可作為交聯劑(B)。 The isocyanate compound is a compound having at least two isocyanate groups (-NCO) in the molecule. Specific examples of isocyanate compounds include toluene diisocyanate, hexamethylene diisocyanate Isocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc. In addition, adducts obtained by reacting these isocyanate compounds with polyols such as glycerin or trimethylolpropane, or those obtained by forming isocyanate compounds into dimers, trimers, etc., can also be used as crosslinking agents ( B).

環氧系化合物為於分子內具有至少2個環氧基之化合物。環氧系化合物的具體例係包含雙酚A型的環氧樹脂、乙二醇二縮水甘油基醚、聚乙二醇二縮水甘油基醚、甘油二縮水甘油基醚、甘油三縮水甘油基醚、1,6-己二醇二縮水甘油基醚、三羥甲基丙烷三縮水甘油基醚、N,N-二縮水甘油基苯胺、N,N,N’,N’-四縮水甘油基-間苯二甲胺、1,3-雙(N,N’-二縮水甘油基胺基甲基)環己烷等。 The epoxy compound is a compound having at least two epoxy groups in the molecule. Specific examples of epoxy compounds include bisphenol A type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidyl ether , 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N,N-diglycidyl aniline, N,N,N',N'-tetraglycidyl- M-xylylenediamine, 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, etc.

氮丙啶系化合物為於分子內具有至少2個由1個氮原子及2個碳原子所構成之3員環(亦被稱為伸乙亞胺(ethylene imine))的骨架之化合物。氮丙啶系化合物的具體例係包含二苯基甲烷-4,4’-雙(1-氮丙啶甲醯胺)、甲苯-2,4-雙(1-氮丙啶甲醯胺)、三伸乙基三聚氰胺、間苯二甲醯基雙-1-(2-甲基氮丙啶)、參-1-氮丙啶基氧化膦、六亞甲基-1,6-雙(1-氮丙啶甲醯胺)、三羥甲基丙烷-參-β-氮丙啶基丙酸酯、四羥甲基甲烷-參-β-氮丙啶基丙酸酯等。 The aziridine-based compound is a compound having a skeleton of at least two 3-membered rings (also called ethylene imine) composed of one nitrogen atom and two carbon atoms in the molecule. Specific examples of aziridine compounds include diphenylmethane-4,4'-bis(1-aziridine carboxamide), toluene-2,4-bis(1-aziridine carboxamide), Triethylene melamine, m-phthaloyl bis-1-(2-methylaziridine), ginseng-1-aziridinyl phosphine oxide, hexamethylene-1,6-bis(1- Aziridine methamide), trimethylolpropane-ginseng-β-aziridinyl propionate, tetramethylolmethane-ginseng-β-aziridinyl propionate and the like.

金屬螯合物化合物的具體例係包含：於鋁、鐵、銅、鋅、錫、鈦、鎳、銻、鎂、釩、鉻及鋯等多價金屬配位有乙醯丙酮或乙醯乙酸乙酯之化合物等。 Specific examples of metal chelate compounds include: acetone or ethyl acetone coordinated with polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium Ester compounds, etc.

相對於樹脂(A)(使用2種以上時為該等的合計)的固形分100質量份，通常含有0.05質量份以上5質量份以下(較佳為0.1質量份以上5 質量份以下)的比率之交聯劑(B)。交聯劑(B)的含量為0.05質量份以上時，有黏著劑層的耐久性提升之傾向。 With respect to 100 parts by mass of the solid content of the resin (A) (when two or more types are used, the sum of these), it usually contains 0.05 parts by mass or more and 5 parts by mass or less (preferably 0.1 parts by mass or more and 5 parts by mass). Parts by mass or less) of the crosslinking agent (B). When the content of the crosslinking agent (B) is 0.05 parts by mass or more, the durability of the adhesive layer tends to improve.

(調平劑(C)) (Leveling agent (C))

黏著劑組成物含有調平劑(C)。調平劑(C)可用於提升使用黏著劑組成物所得之黏著劑層表面的平滑性，或抑制塗裝黏著劑組成物時之塗裝不均。調平劑(C)只要至少含有氟系化合物即可，除了氟系化合物，亦可含有氟系化合物以外的調平劑，例如，可包含丙烯酸系化合物、聚矽氧系化合物、聚酯系化合物等1種或2種以上。調平劑(C)可包含1種或2種以上的氟系化合物。 The adhesive composition contains a leveling agent (C). The leveling agent (C) can be used to improve the smoothness of the surface of the adhesive layer obtained by using the adhesive composition, or to prevent uneven coating when the adhesive composition is applied. The leveling agent (C) only needs to contain at least a fluorine-based compound. In addition to the fluorine-based compound, it may also contain a leveling agent other than the fluorine-based compound. For example, it may contain an acrylic compound, a silicone compound, and a polyester compound. Etc. 1 or 2 or more types. The leveling agent (C) may contain one type or two or more types of fluorine-based compounds.

作為調平劑(C)的氟系化合物可使用具有全氟烷基及全氟伸烷基中之至少一者的化合物。前述全氟烷基及全氟伸烷基可包含氧伸乙基鏈(-O-CH2-)等氧基伸烷基鏈(-O-R’-：R’表示烷二基)等。 As the fluorine-based compound of the leveling agent (C), a compound having at least one of a perfluoroalkyl group and a perfluoroalkylene group can be used. The aforementioned perfluoroalkyl group and perfluoroalkylene group may include an oxyalkylene chain (-O-CH 2 -) such as an oxyalkylene chain (-O-R'-: R'represents an alkanediyl group) and the like.

從黏著劑層表面的平滑性及黏著劑層的耐熱性、黏著劑組成物的塗佈性的觀點來看，相對於黏著劑組成物的樹脂(A)的固形分100質量份，氟系化合物通常為0.01質量份以上，較佳為0.1質量份以上，更佳為0.5質量份以上，亦可為1質量份以上，此外，通常為10質量份以下，較佳為7質量份以下，更佳為5質量份以下，亦可為4質量份以下。 From the viewpoint of the smoothness of the adhesive layer surface, the heat resistance of the adhesive layer, and the coatability of the adhesive composition, relative to 100 parts by mass of the solid content of the resin (A) of the adhesive composition, the fluorine-based compound Usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, or 1 part by mass or more, in addition, usually 10 parts by mass or less, preferably 7 parts by mass or less, more preferably It is 5 parts by mass or less, and may be 4 parts by mass or less.

於黏著劑組成物中，氟系化合物的含量(質量份)較佳為大於後述矽烷化合物的含量(質量份)。更具體而言，於黏著劑組成物中，氟系化合物和矽烷化合物(D)之質量比(矽烷化合物之質量/氟系化合物之質量)較佳為0.8以下，更佳為0.6以下，再更佳為0.5以下，通常為0.01以上，較佳為0.05以上。 In the adhesive composition, the content (parts by mass) of the fluorine-based compound is preferably greater than the content (parts by mass) of the silane compound described later. More specifically, in the adhesive composition, the mass ratio of the fluorine compound to the silane compound (D) (the mass of the silane compound/the mass of the fluorine compound) is preferably 0.8 or less, more preferably 0.6 or less, and still more It is preferably 0.5 or less, usually 0.01 or more, and preferably 0.05 or more.

黏著劑組成物藉由包含作為調平劑(C)的氟系化合物，讓使黏 著劑組成物形成的黏著劑層的兩面對剝離膜的密著力彼此不同，即便在黏著劑層的兩面設有相同的剝離膜時，亦可使用以將剝離膜剝離的剝離力有所不同。特別是藉由使氟系化合物的含量(質量份)大於矽烷化合物(D)的含量(質量份)，可使黏著劑層的兩面對剝離膜的密著力的差變大，即便在黏著劑層的兩面設有相同的剝離膜時，亦可增大用以將剝離膜剝離的剝離力差。藉此，即便為在黏著劑層的兩面設有相同的剝離膜的黏著劑片，在剝離剝離膜時，可以抑制屬於黏著劑層的一部分同時被剝往向一個剝離膜，黏著劑層的其他部分被剝往向另一個剝離膜，使黏著劑層被部分的分離的不良情形。其結果，於後述的黏著劑片中，可使得剝離膜變得容易剝離。 The adhesive composition contains a fluorine-based compound as a leveling agent (C) to make the adhesive The adhesive layer formed by the adhesive composition has different adhesion forces on both sides of the peeling film. Even when the same peeling film is provided on both sides of the adhesive layer, it can be used to peel off the peeling film. The peeling force is different. . In particular, by making the content (parts by mass) of the fluorine-based compound greater than the content (parts by mass) of the silane compound (D), the difference in adhesion of the peeling film on both sides of the adhesive layer can be increased, even in the adhesive When the same release film is provided on both sides of the layer, the difference in peeling force for peeling the release film can also be increased. As a result, even if it is an adhesive sheet with the same release film provided on both sides of the adhesive layer, when the release film is peeled off, it is possible to prevent a part of the adhesive layer from being peeled toward one release film and other adhesive layers. Part of the peeling film is peeled toward the other, so that the adhesive layer is partially separated. As a result, in the pressure-sensitive adhesive sheet described later, the release film can be easily peeled.

(矽烷化合物(D)) (Silane compound (D))

黏著劑組成物係含有矽烷化合物(D)。藉由使黏著劑組成物含有矽烷化合物(D)，可提升黏著劑層的耐熱性，此外，在要將黏著劑層貼合於玻璃基板或導電層等時，容易使黏著劑層與玻璃基板或導電層等的密著性提升，而可提升耐剝離性等。 The adhesive composition system contains a silane compound (D). By including the silane compound (D) in the adhesive composition, the heat resistance of the adhesive layer can be improved. In addition, when the adhesive layer is attached to the glass substrate or conductive layer, it is easy to make the adhesive layer and the glass substrate Or the adhesion of the conductive layer etc. improves, and the peeling resistance etc. can be improved.

矽烷化合物(D)較佳為於矽原子鍵結有任意官能基的化合物。這樣的官能基例如可列舉烷氧基等水解性基，具有乙烯基、胺基、環氧基、鹵烷基、(甲基)丙烯醯基、巰基等反應性官能基的有機基等。矽烷化合物(D)可組合1種或2種以上使用。 The silane compound (D) is preferably a compound having an arbitrary functional group bonded to a silicon atom. Examples of such functional groups include hydrolyzable groups such as alkoxy groups, organic groups having reactive functional groups such as vinyl groups, amino groups, epoxy groups, haloalkyl groups, (meth)acrylic groups, and mercapto groups. The silane compound (D) can be used in combination of one type or two or more types.

矽烷化合物(D)例如可列舉乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基 二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基二甲氧基甲基矽烷、3-縮水甘油氧基丙基乙氧基二甲基矽烷等。 Examples of the silane compound (D) include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, and N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-condensation Glyceroxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxy propyl dimethoxymethyl silane, 3-glycidoxy propyl ethoxy dimethyl silane, etc.

矽烷化合物(D)亦可為聚矽氧低聚物型者。若以(單體)低聚物的形式表示聚矽氧低聚物，則例如可列舉如下述者。 The silane compound (D) may also be a polysiloxane oligomer type. If the polysiloxane oligomer is expressed in the form of (monomer) oligomer, for example, the following can be mentioned.

3-巰基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、 3-mercaptopropyl trimethoxysilane-tetramethoxysilane copolymer,

3-巰基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer,

3-巰基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、 3-mercaptopropyl triethoxysilane-tetramethoxysilane copolymer,

3-巰基丙基三乙氧基矽烷-四乙氧基矽烷共聚物等含巰基丙基的共聚物； 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer and other mercaptopropyl-containing copolymers;

巰基甲基三甲氧基矽烷-四甲氧基矽烷共聚物、 Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer,

巰基甲基三甲氧基矽烷-四乙氧基矽烷共聚物、 Mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer,

巰基甲基三乙氧基矽烷-四甲氧基矽烷共聚物、 Mercaptomethyltriethoxysilane-tetramethoxysilane copolymer,

巰基甲基三乙氧基矽烷-四乙氧基矽烷共聚物等含巰基甲基的共聚物； Mercaptomethyl-containing copolymers such as mercaptomethyltriethoxysilane-tetraethoxysilane copolymer;

3-縮水甘油氧基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer,

3-縮水甘油氧基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer,

3-縮水甘油氧基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、 3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer,

3-縮水甘油氧基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer,

3-縮水甘油氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-縮水甘油氧基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-縮水甘油氧基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、 3-glycidoxypropylmethyl diethoxysilane-tetramethoxysilane copolymer,

3-縮水甘油氧基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物等含3-縮水甘油氧基丙基的共聚物； 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer and other copolymers containing 3-glycidoxypropyl;

3-甲基丙烯醯氧基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane copolymer,

3-甲基丙烯醯氧基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane copolymer,

3-甲基丙烯醯氧基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、 3-methacryloxypropyltriethoxysilane-tetramethoxysilane copolymer,

3-甲基丙烯醯氧基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、 3-methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer,

3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,

3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物等含甲基丙烯醯氧基丙基的共聚物； 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer and other methacryloxypropyl-containing copolymers;

3-丙烯醯氧基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、 3-propenyloxypropyltrimethoxysilane-tetramethoxysilane copolymer,

3-丙烯醯氧基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、 3-propenyloxypropyltrimethoxysilane-tetraethoxysilane copolymer,

3-丙烯醯氧基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、 3-propylene oxypropyl triethoxysilane-tetramethoxysilane copolymer,

3-丙烯醯氧基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、 3-propylene oxypropyl triethoxysilane-tetraethoxysilane copolymer,

3-丙烯醯氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、 3-propenyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-丙烯醯氧基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、 3-propenyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-丙烯醯氧基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、 3-propylene oxypropyl methyl diethoxy silane-tetramethoxy silane copolymer,

3-丙烯醯氧基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物等含丙烯醯氧基丙基的共聚物； 3-propylene oxy propyl methyl diethoxy silane-tetraethoxy silane copolymer and other propylene oxy propyl-containing copolymers;

乙烯基三甲氧基矽烷-四甲氧基矽烷共聚物、 Vinyl trimethoxysilane-tetramethoxysilane copolymer,

乙烯基三甲氧基矽烷-四乙氧基矽烷共聚物、 Vinyl trimethoxysilane-tetraethoxysilane copolymer,

乙烯基三乙氧基矽烷-四甲氧基矽烷共聚物、 Vinyl triethoxysilane-tetramethoxysilane copolymer,

乙烯基三乙氧基矽烷-四乙氧基矽烷共聚物、 Vinyl triethoxysilane-tetraethoxysilane copolymer,

乙烯基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、 Vinyl methyl dimethoxysilane-tetramethoxysilane copolymer,

乙烯基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、 Vinyl methyl dimethoxy silane-tetraethoxy silane copolymer,

乙烯基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、 Vinyl methyl diethoxy silane-tetramethoxy silane copolymer,

乙烯基甲基二乙氧基矽烷-四乙氧基矽烷共聚物等含乙烯基的共聚物； Vinyl-containing copolymers such as vinyl methyl diethoxy silane-tetraethoxy silane copolymer;

3-胺基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer,

3-胺基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer,

3-胺基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer,

3-胺基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、 3-Aminopropyltriethoxysilane-tetraethoxysilane copolymer,

3-胺基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、 3-Aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-胺基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、 3-Aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-胺基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、 3-aminopropylmethyl diethoxysilane-tetramethoxysilane copolymer,

3-胺基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物等含胺基的共聚物等。 Amine group-containing copolymers, such as 3-aminopropylmethyl diethoxysilane-tetraethoxysilane copolymer, etc.

矽烷化合物(D)較佳為含環氧基之矽烷化合物，含烯基之矽烷化合物或含巰基之矽烷化合物。此外，從與交聯劑的反應性的觀點，更佳為含環氧基之矽烷化合物或含巰基之矽烷化合物，再更佳為含環氧基之矽烷化合物或含巰基之聚矽氧低聚物。 The silane compound (D) is preferably an epoxy group-containing silane compound, an alkenyl group-containing silane compound or a mercapto group-containing silane compound. In addition, from the viewpoint of reactivity with the crosslinking agent, epoxy-containing silane compounds or mercapto-containing silane compounds are more preferred, and epoxy-containing silane compounds or mercapto-containing polysiloxane oligomers are more preferred. Things.

相對於黏著劑組成物的樹脂(A)之固形分100質量份，通常含有0.01質量份以上的矽烷化合物(D)，較佳為0.05質量份以上，更佳為0.1質量份以上，此外，通常為10質量份以下、較佳為5質量份以下，更佳為3質量份以下。矽烷化合物(D)的含量為0.01質量份以上時，容易提升使用黏著劑組成物而形成的黏著劑層之耐熱性，而且容易提升黏著劑層與玻璃基板等的密著性。矽烷化合物(D)的含量為10質量份以下時，可抑制矽烷化合物(D)從黏著劑層滲出的情形。 With respect to 100 parts by mass of the solid content of the resin (A) of the adhesive composition, it usually contains 0.01 parts by mass or more of the silane compound (D), preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more. In addition, usually It is 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. When the content of the silane compound (D) is 0.01 parts by mass or more, the heat resistance of the adhesive layer formed using the adhesive composition is easily improved, and the adhesion between the adhesive layer and the glass substrate and the like is easily improved. When the content of the silane compound (D) is 10 parts by mass or less, it is possible to suppress the exudation of the silane compound (D) from the adhesive layer.

如上所述，黏著劑組成物中，矽烷化合物(D)的含量(質量份)較佳為小於作為調平劑(C)的氟系化合物的含量(質量份)。更具體而言，與作為調平劑(C)的氟系化合物的質量比(矽烷化合物之質量/氟系化合物之質量)較佳為如上述般為0.01以上0.8以下。藉此，即便在使用黏著劑組成物所成的黏著劑層的兩面設置相同的剝離膜時，亦可增大用以剝離剝離膜的剝離力差，於後述黏著劑片中，可使得剝離膜變得容易剝離。 As described above, in the adhesive composition, the content (parts by mass) of the silane compound (D) is preferably less than the content (parts by mass) of the fluorine-based compound as the leveling agent (C). More specifically, the mass ratio (mass of the silane compound/mass of the fluorine compound) to the fluorine-based compound as the leveling agent (C) is preferably 0.01 or more and 0.8 or less as described above. Thereby, even when the same peeling film is provided on both sides of the adhesive layer formed by using the adhesive composition, the difference in peeling force for peeling the peeling film can be increased. In the adhesive sheet described later, the peeling film can be made It becomes easy to peel off.

(其他成分) (Other ingredients)

黏著劑組成物可含有樹脂(A)、交聯劑(B)、調平劑(C)、及矽烷化合物(D)以外的其他成分。其他成分可包含1種或2種以上之交聯觸媒、紫外線吸收劑、耐候穩定劑、增黏劑(tackifier)、塑化劑、軟化劑、染料、顏料、無機填料、光散射性微粒、賦黏劑等添加劑。 The adhesive composition may contain components other than resin (A), crosslinking agent (B), leveling agent (C), and silane compound (D). Other ingredients may include one or more types of crosslinking catalysts, ultraviolet absorbers, weathering stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, light scattering particles, Additives such as tackifiers.

黏著劑組成物通常係藉由含有有機溶劑而調製成溶解或分散有調配成分之黏著劑液。有機溶劑較佳係因應樹脂(A)的種類來選擇。有機溶劑的具體例係包含：如甲苯、二甲苯等芳香族系烴；如己烷、庚烷、戊烷等脂肪族系烴；如甲基乙基酮、甲基異丁基酮等酮類；如乙酸乙酯、乙酸丁酯 之酯類。黏著劑液中之樹脂(A)的濃度通常為3至20質量%。 The adhesive composition is usually prepared by containing an organic solvent into an adhesive liquid in which the compounding ingredients are dissolved or dispersed. The organic solvent is preferably selected according to the type of resin (A). Specific examples of organic solvents include: aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, and pentane; and ketones such as methyl ethyl ketone and methyl isobutyl ketone ; Such as ethyl acetate, butyl acetate The esters. The concentration of the resin (A) in the adhesive liquid is usually 3 to 20% by mass.

<黏著劑層> <Adhesive layer>

本發明之黏著劑層係含有上述本發明之黏著劑組成物，典型者係由本發明之黏著劑組成物所構成。黏著劑層例如可藉由將構成黏著劑組成物的各成分溶解或分散於溶劑而形成黏著劑液，將該黏著劑液塗布於光學層或剝離膜的表面並乾燥而得到。 The adhesive layer of the present invention contains the above-mentioned adhesive composition of the present invention, and is typically composed of the adhesive composition of the present invention. The adhesive layer can be obtained, for example, by dissolving or dispersing each component constituting the adhesive composition in a solvent to form an adhesive liquid, coating the adhesive liquid on the surface of the optical layer or the release film, and drying.

本發明之黏著劑層，由於係藉由上述樹脂組成物所形成者，故在兩面設有剝離膜的情況，亦能夠良好地剝離剝離膜。 Since the adhesive layer of the present invention is formed by the above-mentioned resin composition, the release film can be peeled off well even when a release film is provided on both sides.

此外，上述黏著劑層，可使其雙面之對於剝離膜的密著力彼此為不同。因此，即使是後述之於黏著劑層的雙面設置有相同的剝離膜之黏著劑片，在將剝離膜剝離時，亦可抑制下述不良情形：黏著劑層的某部分與其中一側的剝離膜一起被剝離，黏著劑層的其他部分與另一側的剝離膜一起被剝離，而黏著劑層部分地分離。藉此，可將均勻的黏著劑層形成於光學層或玻璃基板等被接著構件。 In addition, the adhesive layer can be made to have different adhesion to the release film on both sides. Therefore, even if it is an adhesive sheet having the same release film provided on both sides of the adhesive layer described later, when the release film is peeled off, the following disadvantages can be suppressed: The peeling film is peeled off together, the other part of the adhesive layer is peeled off together with the peeling film on the other side, and the adhesive layer is partially separated. Thereby, a uniform adhesive layer can be formed on the member to be bonded such as the optical layer or the glass substrate.

<黏著劑片> <Adhesive Tablets>

本發明之黏著劑片係於上述本發明之黏著劑層的雙面設置具有相同的離型處理層之剝離膜而成者。剝離膜具有基材膜及設置於基材膜的至少一面之離型處理層，且使離型處理層側貼合於黏著劑層。具有相同的離型處理層之剝離膜係指將藉由相同的離型處理在相同的基材上設置離型處理層而成的剝離膜之離型處理層側貼合於黏著劑層的同一面時，剝離力彼此為相同之離型膜。 The adhesive sheet of the present invention is formed by arranging release films with the same release treatment layer on both sides of the adhesive layer of the present invention. The release film has a base film and a release treatment layer provided on at least one surface of the base film, and the release treatment layer side is attached to the adhesive layer. The release film with the same release treatment layer refers to the same release film that is formed by setting the release treatment layer on the same substrate by the same release treatment and the release treatment layer side is attached to the same adhesive layer. When facing, the peeling force is the same as the release film.

此外，本發明之黏著劑片中，當將黏著劑層的其中一面與剝 離膜的離型處理層側之間的剝離力設為第1剝離力，將黏著劑層之與前述一面為相反側之另一面與剝離膜的離型處理層側之間的黏著力設為第2剝離力時，第1剝離力與第2剝離力不為相同，而是彼此不同。上述黏著劑層的雙面對於剝離膜的密著力係彼此不同。因此，即使未準備具有不同的離型處理層之剝離膜，仍可藉由使用具有相同的離型處理層之剝離膜，而得到第1剝離力與第2剝離力為不同的黏著劑片。藉此，從黏著劑片將剝離膜剝離時，可抑制黏著劑層被部分地分離之不良情形。第1剝離力及第2剝離力可依據實施例記載的方法來測定。 In addition, in the adhesive sheet of the present invention, when one side of the adhesive layer is peeled off The peeling force between the release treatment layer side of the release film is set as the first release force, and the adhesive force between the other side of the adhesive layer opposite to the aforementioned side and the release treatment layer side of the release film is set as In the case of the second peeling force, the first peeling force and the second peeling force are not the same, but are different from each other. The adhesive force of the both sides of the adhesive layer to the release film is different from each other. Therefore, even if release films with different release treatment layers are not prepared, by using release films with the same release treatment layer, an adhesive sheet with different first and second release forces can be obtained. Thereby, when the release film is peeled from the adhesive sheet, it is possible to suppress the problem that the adhesive layer is partially separated. The first peeling force and the second peeling force can be measured according to the method described in the examples.

例如可藉由在剝離膜的離型處理面側塗布/乾燥上述黏著劑液而形成黏著劑層，並在黏著劑層之與剝離膜為相反側之表面上積層剝離膜的離型處理面側，而得到黏著劑片。此時，積層於黏著劑層上之剝離膜與黏著劑層之間的剝離力係有比塗布有黏著劑液的剝離膜與黏著劑層之間的剝離力更大的傾向。 For example, the adhesive layer can be formed by applying/drying the above-mentioned adhesive liquid on the release treatment surface side of the release film, and the release treatment surface side of the release film can be laminated on the surface of the adhesive layer opposite to the release film. , And get the adhesive sheet. At this time, the peeling force between the peeling film laminated on the adhesive layer and the adhesive layer tends to be greater than the peeling force between the peeling film coated with the adhesive liquid and the adhesive layer.

第1剝離力及第2剝離力分別較佳為0.010N/50mm以上，更佳為0.020N/50mm以上，又更佳為0.030N/50mm以上，亦可為0.040N/50mm以上，此外，較佳為0.15N/50mm以下，更佳為0.12N/50mm以下，亦可為0.10N/50mm以下。第1剝離力與第2剝離力之差的絶對值可為0.010N/50mm以上，較佳為0.015N/50mm以上，更佳為0.020N/50mm以上，亦可為0.023N/50mm以上，此外，較佳為0.09N/50mm以下，亦可為0.07N/50mm以下或0.05N/50mm以下。 The first peeling force and the second peeling force are preferably 0.010N/50mm or more, more preferably 0.020N/50mm or more, still more preferably 0.030N/50mm or more, and may also be 0.040N/50mm or more. It is preferably 0.15N/50mm or less, more preferably 0.12N/50mm or less, and may also be 0.10N/50mm or less. The absolute value of the difference between the first peeling force and the second peeling force can be 0.010N/50mm or more, preferably 0.015N/50mm or more, more preferably 0.020N/50mm or more, and can also be 0.023N/50mm or more. , Preferably 0.09N/50mm or less, and may also be 0.07N/50mm or less or 0.05N/50mm or less.

用於黏著劑片的剝離膜可列舉在使用樹脂而形成的基材膜施予離型處理而成之膜。構成基材膜的樹脂並無特別限定，例如可列舉聚對苯 二甲酸乙二酯、聚對苯二甲酸丁二酯、聚碳酸酯、聚芳酯等。又，施予基材膜的離型處理只要進行公知的離型處理即可，較佳係將氟化合物或聚矽氧化合物等離型劑塗布於基材膜之方法。 Examples of the release film used for the adhesive sheet include a base film formed using a resin and subjected to a release treatment. The resin constituting the base film is not particularly limited, for example, poly-p-phenylene Ethylene dicarboxylate, polybutylene terephthalate, polycarbonate, polyarylate, etc. In addition, the release treatment to be applied to the base film only needs to perform a known release treatment, and a method of applying a release agent such as a fluorine compound or a polysiloxane compound to the base film is preferred.

<光學積層體> <Optical Laminate>

圖1為顯示本發明之光學積層體的一例之概略剖面圖。圖2及圖3為顯示本發明之光學積層體所具有的光學層之一例的概略剖面圖。圖4至圖8為顯示本發明之光學積層體的層構成之另一例的概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing an example of the optical laminate of the present invention. 2 and 3 are schematic cross-sectional views showing an example of the optical layer included in the optical laminate of the present invention. 4 to 8 are schematic cross-sectional views showing another example of the layer structure of the optical laminate of the present invention.

本發明之光學積層體係含有光學層、及上述本發明之黏著劑層。由於黏著劑層如上述般耐熱性優異，故在光學積層體中亦可顯示良好的耐熱性。 The optical laminated system of the present invention includes an optical layer and the above-mentioned adhesive layer of the present invention. Since the adhesive layer is excellent in heat resistance as described above, it can also exhibit good heat resistance in an optical laminate.

例如，如圖1所示，光學積層體1係於光學層10的至少一面含有黏著劑層20，亦可於光學層10的雙面具有黏著劑層20。將黏著劑層20設置於光學層10的表面時，以於光學層10的貼合面及/或黏著劑層20的貼合面形成底塗層或施予表面活化處理例如電漿處理、電暈處理等為較佳，更佳係施予電暈處理。 For example, as shown in FIG. 1, the optical laminate 1 includes an adhesive layer 20 on at least one surface of the optical layer 10, and may have an adhesive layer 20 on both sides of the optical layer 10. When the adhesive layer 20 is disposed on the surface of the optical layer 10, a primer layer is formed on the bonding surface of the optical layer 10 and/or the bonding surface of the adhesive layer 20, or a surface activation treatment such as plasma treatment, electric Corona treatment is preferable, and it is more preferable to apply corona treatment.

光學層10可為於偏光片的單面或雙面具有樹脂膜之偏光板。亦即，如圖2所示，光學層10可為於偏光片2的單面具有第1樹脂膜3之單面保護偏光板10a，或如圖3所示，光學層10亦可為於偏光片2的其中一面具有第1樹脂膜3而於另一面具有第2樹脂膜4之雙面保護偏光板10b。圖2所示之單面保護偏光板10a中，黏著劑層20通常係積層於偏光片表面，亦即積層於偏光片2之與第1樹脂膜3為相反側之面。黏著劑層20較佳係直接積層於偏光片2。圖3所示之雙面保護偏光板10b中，黏著劑層20可 積層於第1樹脂膜3及第2樹脂膜4中之任一者的外表面，亦可積層於兩者的外表面。 The optical layer 10 may be a polarizer with a resin film on one side or both sides of the polarizer. That is, as shown in FIG. 2, the optical layer 10 may be a single-sided protective polarizer 10a having a first resin film 3 on one side of the polarizer 2, or as shown in FIG. 3, the optical layer 10 may also be a polarizer. The sheet 2 has a double-sided protective polarizing plate 10b having a first resin film 3 on one side and a second resin film 4 on the other side. In the single-sided protective polarizing plate 10a shown in FIG. 2, the adhesive layer 20 is usually laminated on the surface of the polarizer, that is, laminated on the surface of the polarizer 2 on the opposite side to the first resin film 3. The adhesive layer 20 is preferably directly laminated on the polarizer 2. In the double-sided protective polarizing plate 10b shown in FIG. 3, the adhesive layer 20 can be It is laminated on the outer surface of any one of the first resin film 3 and the second resin film 4, or may be laminated on the outer surface of both.

圖1所示之光學積層體1可含有積層於黏著劑層20的外表面之分隔片(剝離膜)。該分隔片通常係在使用黏著劑層20時(例如積層於導電層或玻璃基板等被接著構件時)被剝離除去。分隔片可使用與上述剝離膜相同者，而且可為黏著劑片所具有的2片剝離膜中之一者。 The optical laminate 1 shown in FIG. 1 may include a separator (release film) laminated on the outer surface of the adhesive layer 20. This separator is usually peeled and removed when the adhesive layer 20 is used (for example, when it is laminated on a conductive layer or a glass substrate or other adhered member). The separator may be the same as the above-mentioned release film, and may be one of the two release films of the adhesive sheet.

光學積層體1可藉由於光學層10的表面塗布/乾燥上述黏著劑液(使構成黏著劑組成物的各成分溶解或分散於溶劑而成者)來形成黏著劑層20而得到。又，光學積層體1亦可藉由於剝離膜的離型處理面以與上述同樣的方式形成黏著劑層20，並將該黏著劑層20積層(轉印)於光學層10的表面而得到。 The optical layered body 1 can be obtained by forming the adhesive layer 20 by applying/drying the above-mentioned adhesive liquid (which is obtained by dissolving or dispersing each component constituting the adhesive composition in a solvent) on the surface of the optical layer 10. In addition, the optical layered body 1 can also be obtained by forming the adhesive layer 20 on the release treatment surface of the release film in the same manner as described above, and laminating (transferring) the adhesive layer 20 on the surface of the optical layer 10.

又，圖4及圖5所示之光學積層體5、6係依序具有光學層10(單面保護偏光板10a、雙面保護偏光板10b)、黏著劑層20及導電層30。圖4所示之光學積層體5係使用圖2所示之單面保護偏光板10a作為光學層10之例，圖5所示之光學積層體6係使用圖3所示之雙面保護偏光板10b作為光學層10之例。圖4及圖5所示之光學積層體5、6的黏著劑層20係以直接與導電層30相接的方式積層於導電層30上。光學積層體5、6亦可在導電層30的與黏著劑層20為相反側處具有基板40。如後所述，基板40例如為玻璃基板或樹脂膜。 In addition, the optical laminates 5 and 6 shown in FIGS. 4 and 5 have an optical layer 10 (single-sided protective polarizing plate 10a, double-sided protective polarizing plate 10b), an adhesive layer 20, and a conductive layer 30 in this order. The optical laminate 5 shown in Fig. 4 uses the single-sided protective polarizer 10a shown in Fig. 2 as an example of the optical layer 10, and the optical laminate 6 shown in Fig. 5 uses the double-sided protective polarizer shown in Fig. 3 10b is an example of the optical layer 10. The adhesive layer 20 of the optical laminates 5 and 6 shown in FIGS. 4 and 5 is laminated on the conductive layer 30 so as to directly contact the conductive layer 30. The optical layered bodies 5 and 6 may have the substrate 40 on the side opposite to the adhesive layer 20 of the conductive layer 30. As described later, the substrate 40 is, for example, a glass substrate or a resin film.

圖6所示之光學積層體7係將圖1所示之光學積層體1隔著樹脂層50而積層於導電層30者。黏著劑層20係直接與樹脂層50相接。光學積層體7可於導電層30的與黏著劑層20為相反側處具有基板40。 The optical layered body 7 shown in FIG. 6 is a layer in which the optical layered body 1 shown in FIG. 1 is laminated on the conductive layer 30 with the resin layer 50 interposed therebetween. The adhesive layer 20 is directly connected to the resin layer 50. The optical laminate 7 may have a substrate 40 on the opposite side of the conductive layer 30 to the adhesive layer 20.

圖7所示之光學積層體8除了不具有樹脂層50及導電層30以外，其餘係與圖6所示之光學積層體7為同樣。此時，黏著劑層20係積層於基板40。 The optical laminate 8 shown in FIG. 7 is the same as the optical laminate 7 shown in FIG. 6 except that it does not have the resin layer 50 and the conductive layer 30. At this time, the adhesive layer 20 is laminated on the substrate 40.

圖8所示之光學積層體除了使導電層30圖案化成既定的形狀以外，其餘係與圖6所示之光學積層體7為同樣。圖8所示之光學積層體的導電層30例如可作為觸控輸入式液晶顯示裝置所具有的觸控輸入元件的金屬配線層(亦即電極層)使用。於圖8所示之光學積層體中，可省略樹脂層50。於經圖案化的導電層30上積層黏著劑層20時，黏著劑層20可具有未與導電層30接觸的部分。 The optical laminate shown in FIG. 8 is the same as the optical laminate 7 shown in FIG. 6 except that the conductive layer 30 is patterned into a predetermined shape. The conductive layer 30 of the optical laminate shown in FIG. 8 can be used, for example, as a metal wiring layer (that is, an electrode layer) of a touch input element included in a touch input type liquid crystal display device. In the optical laminate shown in FIG. 8, the resin layer 50 can be omitted. When the adhesive layer 20 is laminated on the patterned conductive layer 30, the adhesive layer 20 may have a portion that is not in contact with the conductive layer 30.

上述光學積層體可使用於液晶顯示裝置或有機電致發光(EL)顯示裝置等圖像顯示裝置。液晶顯示裝置或有機EL顯示裝置可以是具有觸控面板機能的觸控輸入式之顯示裝置。 The above-mentioned optical laminate can be used in image display devices such as a liquid crystal display device or an organic electroluminescence (EL) display device. The liquid crystal display device or the organic EL display device may be a touch input type display device with a touch panel function.

(光學層) (Optical layer)

光學層可以是能夠被組裝於液晶顯示裝置等圖像顯示裝置中之各種光學膜(具有光學特性的膜)。光學層例如可列舉偏光片、偏光板、相位差膜、增亮膜、防眩膜、抗反射膜、擴散膜、集光膜等。光學層可為單層結構，亦可為多層結構。 The optical layer may be various optical films (films having optical characteristics) that can be incorporated in image display devices such as liquid crystal display devices. Examples of the optical layer include a polarizer, a polarizing plate, a retardation film, a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, and a light collection film. The optical layer can be a single-layer structure or a multilayer structure.

(偏光片) (Polarizer)

偏光片為具有從自然光向某一方向的直線偏光選擇性穿透的機能之層或膜。偏光片例如可列舉使聚乙烯醇系樹脂膜吸附/配向二色性色素而成的膜。二色性色素可列舉碘、二色性有機染料等。又，偏光片可以是將溶致液晶狀態的二色性染料塗布於基材膜並配向/固定化而成的塗布型偏光膜。該 等偏光片由於會從自然光向某一方向的直線偏光選擇性穿透，並將另一方向的直線偏光吸收，故被稱為吸收型偏光片。 The polarizer is a layer or film with the function of selectively penetrating linearly polarized light from natural light to a certain direction. Examples of the polarizer include a film obtained by adsorbing and aligning a dichroic dye on a polyvinyl alcohol-based resin film. Examples of dichroic dyes include iodine and dichroic organic dyes. In addition, the polarizer may be a coating type polarizing film obtained by applying a dichroic dye in a lyotropic liquid crystal state to a base film and aligning/fixing it. Should Equal-polarizers are called absorption polarizers because they selectively penetrate linearly polarized light in one direction from natural light and absorb linearly polarized light in the other direction.

偏光片並不限定於吸收型偏光片，亦可為從自然光向某一方向的直線偏光選擇性穿透並將另一方向的直線偏光反射之反射型偏光片，或將另一方向的直線偏光散射之散射型偏光片，但從視認性優異之點來看，較佳為吸收型偏光片。其中，更佳為由聚乙烯醇系樹脂膜所構成之聚乙烯醇系偏光膜，又更佳為使聚乙烯醇系樹脂膜吸附/配向碘或二色性染料等二色性色素而成的聚乙烯醇系偏光膜，特佳為使聚乙烯醇系樹脂膜吸附/配向碘而成的聚乙烯醇系偏光膜。 Polarizers are not limited to absorbing polarizers, but can also be reflective polarizers that selectively penetrate linearly polarized light in one direction from natural light and reflect linearly polarized light in the other direction, or linearly polarized light in another direction. The scattering type polarizer is a scattering type, but from the viewpoint of excellent visibility, an absorption type polarizer is preferable. Among them, a polyvinyl alcohol-based polarizing film composed of a polyvinyl alcohol-based resin film is more preferable, and a polyvinyl alcohol-based resin film is more preferably formed by adsorbing/aligning dichroic pigments such as iodine or dichroic dyes. The polyvinyl alcohol-based polarizing film is particularly preferably a polyvinyl alcohol-based polarizing film obtained by adsorbing and aligning iodine with a polyvinyl alcohol-based resin film.

聚乙烯醇系樹脂可使用將聚乙酸乙烯酯系樹脂皂化者。聚乙酸乙烯酯系樹脂可列舉屬於乙酸乙烯酯的均聚物之聚乙酸乙烯酯，以及乙酸乙烯酯和可與該乙酸乙烯酯共聚的其他單體之共聚物等。可與乙酸乙烯酯共聚的其他單體可列舉不飽和羧酸類、烯烴類、乙烯基醚類、不飽和磺酸類、及具有銨基的(甲基)丙烯醯胺類等。 As the polyvinyl alcohol-based resin, a polyvinyl acetate-based resin saponified can be used. Examples of the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable with the vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth)acrylamides having an ammonium group.

聚乙烯醇系樹脂的皂化度通常為85莫耳%以上100莫耳%以下，較佳為98莫耳%以上。聚乙烯醇系樹脂可經改性，例如可使用經醛類改性之聚乙烯甲醛或聚乙烯縮醛等。聚乙烯醇系樹脂的平均聚合度通常為1000以上10000以下，較佳為1500以上5000以下。聚乙烯醇系樹脂的平均聚合度可依據JIS K 6726：1994而求出。 The degree of saponification of the polyvinyl alcohol-based resin is usually 85 mol% or more and 100 mol% or less, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, for example, polyvinyl formaldehyde or polyvinyl acetal modified with aldehydes can be used. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 or more and 10,000 or less, preferably 1,500 or more and 5,000 or less. The average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726:1994.

如此之聚乙烯醇系樹脂經製膜而成者，可作為由聚乙烯醇系樹脂膜所構成之偏光膜的胚膜使用。將聚乙烯醇系樹脂予以製膜之方法並無特別限定，可採用公知的方法。聚乙烯醇系胚膜的厚度例如為150μm以下， 較佳為100μm以下(例如50μm以下)且為5μm以上。 Such a polyvinyl alcohol-based resin formed by forming a film can be used as an embryo film of a polarizing film composed of a polyvinyl alcohol-based resin film. The method of forming a polyvinyl alcohol-based resin into a film is not particularly limited, and a known method can be adopted. The thickness of the polyvinyl alcohol-based embryonic membrane is, for example, 150 μm or less, It is preferably 100 μm or less (for example, 50 μm or less) and 5 μm or more.

由聚乙烯醇系樹脂膜所構成之偏光膜可藉由公知的方法而製造。具體而言，可藉由包含下列步驟的方法製造：對聚乙烯醇系樹脂膜進行一軸延伸之步驟；藉由將聚乙烯醇系樹脂膜以二色性色素染色而使其吸附二色性色素之步驟；將已吸附二色性色素的聚乙烯醇系樹脂膜以硼酸水溶液進行處理(交聯處理)之步驟；以及在藉由硼酸水溶液處理後進行水洗之步驟。 The polarizing film composed of a polyvinyl alcohol-based resin film can be produced by a known method. Specifically, it can be manufactured by a method including the following steps: a step of uniaxially stretching a polyvinyl alcohol-based resin film; by dyeing the polyvinyl alcohol-based resin film with a dichroic pigment to adsorb the dichroic pigment The step; the step of treating the polyvinyl alcohol resin film on which the dichroic pigment has been adsorbed with a boric acid aqueous solution (crosslinking treatment); and the step of washing with water after being treated with the boric acid aqueous solution.

偏光片的厚度可設為40μm以下，較佳為30μm以下(例如20μm以下，更佳為15μm以下，又更佳為10μm以下或8μm以下)。若依據日本特開2000-338329號公報或日本特開2012-159778號公報所記載的方法，則可更容易製造薄膜的偏光片，更容易將偏光片的厚度設為例如20μm以下，較佳為15μm以下，又更佳為10μm以下或8μm以下。偏光片的厚度通常為2μm以上。使偏光片的厚度小係有利於使含有偏光板的光學積層體、及含有該光學積層體之圖像顯示裝置薄型化。 The thickness of the polarizer may be 40 μm or less, preferably 30 μm or less (for example, 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less or 8 μm or less). According to the method described in Japanese Patent Application Publication No. 2000-338329 or Japanese Patent Application Publication No. 2012-159778, it is easier to manufacture a thin film polarizer, and it is easier to set the thickness of the polarizer to, for example, 20 μm or less. 15 μm or less, more preferably 10 μm or less or 8 μm or less. The thickness of the polarizer is usually 2 μm or more. Making the thickness of the polarizer small is advantageous in reducing the thickness of the optical layered body including the polarizing plate and the image display device including the optical layered body.

(第1樹脂膜、第2樹脂膜) (The first resin film, the second resin film)

第1樹脂膜3及第2樹脂膜4係設置於偏光片2上，例如可為用以保護偏光片2之保護膜，或後述相位差膜等兼具光學機能的保護膜。第1樹脂膜3及第2樹脂膜4分別可為由具有透光性(較佳為光學上為透明)的熱塑性樹脂所構成之膜，該熱塑性樹脂例如為：鏈狀聚烯烴系樹脂(聚丙烯系樹脂等)、環狀聚烯烴系樹脂(降莰烯系樹脂等)等聚烯烴系樹脂；三乙酸纖維素、二乙酸纖維素等纖維素酯系樹脂；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯等聚酯系樹脂；聚碳酸酯系樹脂；(甲基)丙烯酸系樹脂；聚苯乙烯系樹脂；或此等的混合物、共聚物等。 The first resin film 3 and the second resin film 4 are provided on the polarizer 2, and may be, for example, a protective film for protecting the polarizer 2, or a protective film with optical functions such as a retardation film described later. Each of the first resin film 3 and the second resin film 4 may be a film made of a thermoplastic resin having translucency (preferably optically transparent), the thermoplastic resin being, for example, a chain polyolefin resin (poly Polyolefin resins such as propylene resins, etc.), cyclic polyolefin resins (norbornene resins, etc.); cellulose ester resins such as cellulose triacetate and cellulose diacetate; polyethylene terephthalate , Polyester resins such as polyethylene naphthalate and polybutylene terephthalate; polycarbonate resins; (meth)acrylic resins; polystyrene resins; or mixtures or copolymers of these Things and so on.

第1樹脂膜3及第2樹脂膜4分別可為未經延伸的膜、或經一軸或二軸延伸的膜之任一者。二軸延伸可為同時在2個延伸方向進行延伸之同時二軸延伸，亦可為在第1方向進行延伸後在不同於該第1方向的第2方向進行延伸之逐次二軸延伸。 The first resin film 3 and the second resin film 4 may be either unstretched films or films stretched uniaxially or biaxially. The biaxial extension may be simultaneous biaxial extension while extending in two extension directions, or it may be sequential biaxial extension in which extension is performed in a first direction and then is extended in a second direction different from the first direction.

鏈狀聚烯烴系樹脂可列舉聚乙烯樹脂、聚丙烯樹脂等鏈狀烯烴的均聚物、以及由2種以上的鏈狀烯烴所構成之共聚物。 Examples of the chain polyolefin resin include homopolymers of chain olefins such as polyethylene resins and polypropylene resins, and copolymers composed of two or more chain olefins.

環狀聚烯烴系樹脂係含有以降莰烯、四環十二烯(別名：二甲橋八氫萘)或此等的衍生物為代表例之環狀烯烴作為聚合單元之樹脂的總稱。環狀聚烯烴系樹脂可列舉環狀烯烴的開環(共)聚合物及其氫化物，環狀烯烴的加成聚合物，環狀烯烴與乙烯、丙烯等鏈狀烯烴或具有乙烯基的芳香族化合物之共聚物，以及將此等以不飽和羧酸或其衍生物改性後之改性(共)聚合物等。其中，環狀烯烴較佳係利用降莰烯系樹脂，該降莰烯系樹脂係使用了降莰烯或多環降莰烯系單體等降莰烯系單體。 Cyclic polyolefin-based resins are a general term for resins containing cyclic olefins as representative examples of norbornene, tetracyclododecene (alias: dimethyl octahydronaphthalene) or these derivatives as polymerized units. Cyclic polyolefin resins include ring-opening (co)polymers of cyclic olefins and their hydrogenated products, addition polymers of cyclic olefins, cyclic olefins and chain olefins such as ethylene and propylene, or aromatics with vinyl groups. Copolymers of group compounds, and modified (co)polymers modified with unsaturated carboxylic acids or their derivatives. Among them, the cyclic olefin preferably uses a norbornene-based resin, and the norbornene-based resin uses a norbornene-based monomer such as a norbornene or a polycyclic norbornene-based monomer.

纖維素酯系樹脂為纖維素中之至少一部分的羥基經乙酸酯化之樹脂，亦可為一部分經乙酸酯化而一部分經其他酸酯化之混合酯。纖維素酯系樹脂較佳為乙酸纖維素系樹脂。乙酸纖維素系樹脂可列舉三乙酸纖維素、二乙酸纖維素、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等。 The cellulose ester resin is a resin in which at least a part of the hydroxyl groups in cellulose is esterified with acetic acid, and may also be a mixed ester in which a part is esterified with acetic acid and a part is esterified with other esters. The cellulose ester resin is preferably a cellulose acetate resin. Examples of the cellulose acetate resin include cellulose triacetate, cellulose diacetate, cellulose acetate propionate, and cellulose acetate butyrate.

聚酯系樹脂為具有酯鍵之上述纖維素酯系樹脂以外的樹脂，一般係由多元羧酸或其衍生物與多元醇之聚縮物所構成者。聚酯系樹脂可列舉：聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、聚對苯二甲酸丙二酯、聚萘二甲酸丙二酯、聚對苯二甲酸環己烷二甲酯、聚萘二甲酸環己烷二甲酯等。其中，從機械性質、耐溶劑性、 抗刮性、成本等的觀點來看，較佳係使用聚對苯二甲酸乙二酯。所謂聚對苯二甲酸乙二酯係指重複單元的80莫耳%以上係由對苯二甲酸乙二酯所構成之樹脂，且亦可含有源自其他共聚成分(間苯二甲酸等二羧酸成分；丙二醇等二醇成分等)的構成單元。 The polyester resin is a resin other than the above-mentioned cellulose ester resin having an ester bond, and is generally composed of a polycondensation product of a polycarboxylic acid or its derivative and a polyhydric alcohol. Polyester resins include: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, Polypropylene naphthalate, polycyclohexane dimethyl terephthalate, polycyclohexane dimethyl naphthalate, etc. Among them, from the mechanical properties, solvent resistance, From the viewpoints of scratch resistance and cost, it is preferable to use polyethylene terephthalate. The so-called polyethylene terephthalate refers to a resin in which more than 80 mol% of the repeating unit is composed of ethylene terephthalate, and may also contain other copolymerized components (dicarboxylic acid such as isophthalic acid). Acid component; diol component such as propylene glycol, etc.) structural unit.

聚碳酸酯系樹脂為由碳酸及二醇或雙酚所形成之聚酯。其中，從耐熱性、耐候性及耐酸性的觀點來看，較佳係使用於分子鏈具有二苯基烷烴之芳香族聚碳酸酯。聚碳酸酯可列舉由2,2-雙(4-羥基苯基)丙烷(別名雙酚A)、2,2-雙(4-羥基苯基)丁烷、1,1-雙(4-羥基苯基)環己烷、1,1-雙(4-羥基苯基)異丁烷、1,1-雙(4-羥基苯基)乙烷等雙酚衍生之聚碳酸酯。 The polycarbonate resin is a polyester formed from carbonic acid and glycol or bisphenol. Among them, from the viewpoints of heat resistance, weather resistance, and acid resistance, it is preferable to use aromatic polycarbonates having diphenylalkanes in the molecular chain. Polycarbonates include 2,2-bis(4-hydroxyphenyl)propane (alias bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl) Phenyl) cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutane, 1,1-bis(4-hydroxyphenyl)ethane and other bisphenol-derived polycarbonates.

(甲基)丙烯酸系樹脂為含有源自(甲基)丙烯酸系單體的構成單元之聚合物，(甲基)丙烯酸系單體可列舉甲基丙烯酸酯及丙烯酸酯。 The (meth)acrylic resin is a polymer containing a structural unit derived from a (meth)acrylic monomer, and examples of the (meth)acrylic monomer include methacrylate and acrylate.

甲基丙烯酸酯可列舉甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸環己酯、甲基丙烯酸苯酯、甲基丙烯酸苯甲酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸2-羥基乙酯等。 Methacrylates include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and methacrylic acid. Phenyl ester, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, etc.

丙烯酸酯可列舉丙烯酸乙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第三丁酯、丙烯酸環己酯、丙烯酸苯酯、丙烯酸苯甲酯、丙烯酸2-乙基己酯、丙烯酸2-羥基乙酯等。 Acrylic esters include ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxy acrylate Ethyl and so on.

(甲基)丙烯酸系樹脂可為只由源自(甲基)丙烯酸單體的構成單元所構成之聚合物，亦可含有其他構成單元。 The (meth)acrylic resin may be a polymer composed only of structural units derived from (meth)acrylic monomers, or may contain other structural units.

在較佳實施形態之一中，(甲基)丙烯酸系樹脂係含有甲基丙烯酸甲酯作為共聚成分，或含有甲基丙烯酸甲酯與丙烯酸甲酯作為共聚成分。 在較佳實施形態之一中，(甲基)丙烯酸系樹脂可以是以甲基丙烯酸酯作為主要單體(含有50質量%以上)之聚合物，較佳為共聚有甲基丙烯酸酯與其他共聚成分之共聚物。 In one of the preferred embodiments, the (meth)acrylic resin system contains methyl methacrylate as a copolymerization component, or contains methyl methacrylate and methyl acrylate as a copolymerization component. In one of the preferred embodiments, the (meth)acrylic resin may be a polymer with methacrylate as the main monomer (containing 50% by mass or more), preferably copolymerized with methacrylate and other copolymers. Copolymer of ingredients.

(甲基)丙烯酸系樹脂的玻璃轉移溫度較佳為80℃以上160℃以下。玻璃轉移溫度可藉由調整甲基丙烯酸酯系單體與丙烯酸酯系單體之聚合比、各別的酯基之碳鏈長及此等所具有的官能基種類、以及多官能單體相對於單體整體之聚合比來控制。 The glass transition temperature of the (meth)acrylic resin is preferably 80°C or more and 160°C or less. The glass transition temperature can be adjusted by adjusting the polymerization ratio of methacrylate-based monomers and acrylate-based monomers, the carbon chain lengths of individual ester groups, and the types of functional groups possessed by these, as well as the relative ratio of polyfunctional monomers to polyfunctional monomers. The polymerization ratio of the whole monomer is controlled.

就用以提高(甲基)丙烯酸系樹脂的玻璃轉移溫度之手段而言，將環結構導入於高分子的主鏈亦為有效。環結構較佳為環狀酸酐結構、環狀醯亞胺結構及內酯結構等雜環結構。具體而言，可列舉：戊二酸酐結構、丁二酸酐結構等環狀酸酐結構；戊二醯亞胺結構、丁二醯亞胺結構等環狀醯亞胺結構；丁內酯、戊內酯等內酯環結構。主鏈中之環結構的含量愈大，會有愈可使(甲基)丙烯酸系樹脂的玻璃轉移溫度變高之傾向。環狀酸酐結構、環狀醯亞胺結構可藉由下述方法導入，該方法為：藉由使順丁烯二酸酐、順丁烯二醯亞胺等具有環狀結構的單體共聚而導入之方法；聚合後藉由脫水/脫甲醇縮合反應而導入環狀酸酐結構之方法；使胺基化合物反應而導入環狀醯亞胺結構之方法等。具有內酯環結構的樹脂(聚合物)可藉由下述方法而得到，該方法為：將於高分子鏈具有羥基及酯基的聚合物調製後，使所得之聚合物中之羥基及酯基藉由加熱並視需要在有機磷化合物等觸媒的存在下進行環化縮合而形成內酯環結構。 As a means for increasing the glass transition temperature of the (meth)acrylic resin, it is also effective to introduce a ring structure into the main chain of the polymer. The ring structure is preferably a heterocyclic structure such as a cyclic anhydride structure, a cyclic imine structure, and a lactone structure. Specifically, examples include: cyclic anhydride structures such as glutaric anhydride structure and succinic anhydride structure; cyclic imine structures such as glutaric anhydride structure and succinimide structure; butyrolactone, valerolactone And other lactone ring structure. The larger the content of the ring structure in the main chain, the higher the glass transition temperature of the (meth)acrylic resin tends to be. The cyclic anhydride structure and the cyclic imine structure can be introduced by the following method: by copolymerizing a monomer having a cyclic structure such as maleic anhydride, maleimide, etc. The method; the method of introducing the cyclic acid anhydride structure by dehydration/demethanol condensation reaction after polymerization; the method of introducing the cyclic imine structure by reacting the amine-based compound, etc. A resin (polymer) having a lactone ring structure can be obtained by the following method: after preparing a polymer having a hydroxyl group and an ester group in the polymer chain, the hydroxyl group and the ester group in the polymer The group is heated and optionally undergoes cyclization condensation in the presence of a catalyst such as an organophosphorus compound to form a lactone ring structure.

(甲基)丙烯酸系樹脂及由該(甲基)丙烯酸系樹脂形成之熱塑性樹脂膜可視需要而含有添加劑。添加劑例如可列舉潤滑劑、抗結塊劑、熱 穩定劑、抗氧化劑、抗靜電劑、耐光劑、耐衝撃性改良劑、界面活性劑等。該等添加劑在使用(甲基)丙烯酸系樹脂以外之其他熱塑性樹脂作為構成熱塑性樹脂膜的熱塑性樹脂時亦可使用。 The (meth)acrylic resin and the thermoplastic resin film formed of the (meth)acrylic resin may contain additives as necessary. Examples of additives include lubricants, anti-caking agents, heat Stabilizers, antioxidants, antistatic agents, lightfastness agents, impact resistance modifiers, surfactants, etc. These additives can also be used when using thermoplastic resins other than (meth)acrylic resins as the thermoplastic resin constituting the thermoplastic resin film.

從對膜的製膜性或膜的耐衝撃性等的觀點來看，(甲基)丙烯酸系樹脂可含有屬於衝撃性改良劑之丙烯酸系橡膠粒子。所謂丙烯酸系橡膠粒子為以主體為丙烯酸酯的彈性聚合物作為必須成分之粒子，可列舉實質上只由該彈性聚合物所構成之單層結構者，或以該彈性聚合物作為其中1層之多層結構者。 The (meth)acrylic resin may contain acrylic rubber particles, which are impact modifiers, from the viewpoints of film-forming properties and impact resistance of the film. The so-called acrylic rubber particles are particles whose main component is an elastic polymer of acrylate as an essential component. Examples include those having a single-layer structure consisting essentially of only the elastic polymer, or those with one layer of the elastic polymer. Multi-layer structure.

上述彈性聚合物之例可列舉交聯彈性共聚物，該交聯彈性共聚物係以丙烯酸烷酯為主成分且為丙烯酸烷酯和可與該丙烯酸烷酯共聚之其他乙烯基系單體及交聯性單體共聚而成者。彈性聚合物的主成分之丙烯酸烷酯例如可列舉丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等烷基的碳數為1以上8以下左右者，較佳係使用具有碳數為4以上的烷基之丙烯酸烷酯。 Examples of the above-mentioned elastic polymers include cross-linked elastic copolymers, which are mainly composed of alkyl acrylate and are alkyl acrylate and other vinyl monomers copolymerizable with the alkyl acrylate and cross-linked elastic copolymers. Co-polymerized monomers. The alkyl acrylate as the main component of the elastic polymer includes, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and other alkyl groups whose carbon number is about 1 or more and about 8 or less. It is preferably used An alkyl acrylate having an alkyl group with 4 or more carbon atoms.

可與上述丙烯酸烷酯共聚之其他乙烯基系單體可列舉於分子內具有1個聚合性碳-碳雙鍵之化合物，更具體而言，可列舉：甲基丙烯酸甲酯等甲基丙烯酸酯；苯乙烯等芳香族乙烯基化合物；丙烯腈等氰乙烯化合物等。 Other vinyl monomers that can be copolymerized with the above-mentioned alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, include methacrylates such as methyl methacrylate ; Aromatic vinyl compounds such as styrene; vinyl cyanide compounds such as acrylonitrile.

上述交聯性單體可列舉於分子內具有至少2個聚合性碳-碳雙鍵之交聯性的化合物，更具體而言，可列舉：乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯等多元醇的(甲基)丙烯酸酯類；(甲基)丙烯酸烯丙酯等(甲基)丙烯酸烯酯；二乙烯基苯等。 The above-mentioned crosslinkable monomer may be a compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, it may include ethylene glycol di(meth)acrylate, butane (Meth)acrylates of polyhydric alcohols such as alcohol di(meth)acrylate; allyl (meth)acrylate and other alkenyl (meth)acrylates; divinylbenzene, etc.

亦可將由不含橡膠粒子的(甲基)丙烯酸系樹脂所構成之膜、及由含有橡膠粒子的(甲基)丙烯酸系樹脂所構成之膜之積層體，作為貼合於光學層10之熱塑性樹脂膜。又，亦可將於由不同於(甲基)丙烯酸樹脂的樹脂所構成之相位差顯現層的單面或雙面形成(甲基)丙烯酸系樹脂層而顯現相位差者，作為貼合於光學層10之熱塑性樹脂膜。 A laminate of a film composed of a (meth)acrylic resin containing no rubber particles and a film composed of a (meth)acrylic resin containing rubber particles may be used as the thermoplastic bonded to the optical layer 10 Resin film. In addition, a (meth)acrylic resin layer may be formed on one side or both sides of a phase difference expressing layer composed of a resin other than (meth)acrylic resin to express the retardation, as a bonded optical Layer 10 thermoplastic resin film.

第1樹脂膜3及第2樹脂膜4分別較佳為含有選自由纖維素酯系樹脂、聚酯系樹脂、(甲基)丙烯酸系樹脂及環狀聚烯烴系樹脂所組成的群組之1種以上的熱塑性樹脂之膜，更佳為纖維素酯系樹脂膜、聚酯系樹脂膜、(甲基)丙烯酸系樹脂膜、或環狀聚烯烴系樹脂膜。 The first resin film 3 and the second resin film 4 each preferably contain 1 selected from the group consisting of cellulose ester resin, polyester resin, (meth)acrylic resin, and cyclic polyolefin resin. The film of more than one type of thermoplastic resin is more preferably a cellulose ester resin film, a polyester resin film, a (meth)acrylic resin film, or a cyclic polyolefin resin film.

第1樹脂膜3及/或第2樹脂膜4可含有紫外線吸收劑、紅外線吸收劑、有機系染料、顏料、無機色素、抗氧化劑、抗靜電劑、界面活性劑、潤滑劑、分散劑、熱穩定劑等。將光學積層體應用於圖像顯示裝置時，藉由將含有紫外線吸收劑的熱塑性樹脂膜配置於圖像顯示元件(例如液晶單元或有機EL顯示元件等)的視認側，可抑制圖像顯示元件因紫外線造成之劣化。紫外線吸收劑可列舉水楊酸酯系化合物、二苯基甲酮系化合物、苯并***系化合物、氰基丙烯酸酯系化合物、鎳錯鹽系化合物等。 The first resin film 3 and/or the second resin film 4 may contain ultraviolet absorbers, infrared absorbers, organic dyes, pigments, inorganic pigments, antioxidants, antistatic agents, surfactants, lubricants, dispersants, heat Stabilizers, etc. When the optical laminate is applied to an image display device, by arranging a thermoplastic resin film containing an ultraviolet absorber on the visible side of an image display element (for example, a liquid crystal cell or an organic EL display element, etc.), the image display element can be suppressed Deterioration caused by ultraviolet rays. Examples of the ultraviolet absorber include salicylate-based compounds, benzophenone-based compounds, benzotriazole-based compounds, cyanoacrylate-based compounds, and nickel complex salt-based compounds.

第1樹脂膜3及第2樹脂膜4可為由相同的熱塑性樹脂所構成之膜，亦可為由彼此不同的熱塑性樹脂所構成之膜。第1樹脂膜3及第2樹脂膜4的厚度、有無添加劑及其種類、相位差特性等可為相同或不同。 The first resin film 3 and the second resin film 4 may be films composed of the same thermoplastic resin, or may be films composed of different thermoplastic resins. The thickness of the first resin film 3 and the second resin film 4, the presence or absence of additives and their types, retardation characteristics, etc. may be the same or different.

於第1樹脂膜3及/或第2樹脂膜4的外表面(與光學層10為相反側的表面)可具備硬塗層、防眩層、抗反射層、光擴散層、抗靜電層、防污層、導電層等表面處理層(塗布層)、防護膜(protect film)。防護膜係以保護 偏光板等光學層10的表面避免受到刮傷或污染為目的而使用之膜，通常係在將圖1所示之光學積層體1例如貼合於導電層或玻璃基板上之後被剝離除去。 The outer surface of the first resin film 3 and/or the second resin film 4 (the surface opposite to the optical layer 10) may be provided with a hard coat layer, an anti-glare layer, an anti-reflection layer, a light diffusion layer, an antistatic layer, Surface treatment layers (coating layers) such as antifouling layers and conductive layers, and protective films. Protective film to protect A film used for the purpose of avoiding scratches or contamination on the surface of the optical layer 10 such as a polarizing plate is usually peeled off after bonding the optical laminate 1 shown in FIG. 1 to a conductive layer or a glass substrate, for example.

防護膜通常係由基材膜、及積層於該基材膜上之黏著劑層所構成。基材膜可由熱塑性樹脂所構成，該熱塑性樹脂例如為：聚乙烯系樹脂、聚丙烯系樹脂等聚烯烴系樹脂；聚對苯二甲酸乙二酯或聚萘二甲酸乙二酯等聚酯系樹脂；聚碳酸酯系樹脂；(甲基)丙烯酸系樹脂等。 The protective film is usually composed of a base film and an adhesive layer laminated on the base film. The base film may be composed of a thermoplastic resin, such as polyolefin resins such as polyethylene resins and polypropylene resins; polyester resins such as polyethylene terephthalate or polyethylene naphthalate. Resins; polycarbonate resins; (meth)acrylic resins, etc.

第1樹脂膜3及第2樹脂膜4的厚度分別通常為5μm以上200μm以下，較佳為10μm以上120μm以下，更佳為10μm以上85μm以下，又更佳為15μm以上65μm以下。第1樹脂膜3及第2樹脂膜4的厚度分別可為50μm以下，亦可為40μm以下。使第1樹脂膜3及第2樹脂膜4的厚度變小係有利於使光學積層體(偏光板)、及含有該光學積層體的圖像顯示裝置薄型化。 The thickness of the first resin film 3 and the second resin film 4 is generally 5 μm or more and 200 μm or less, preferably 10 μm or more and 120 μm or less, more preferably 10 μm or more and 85 μm or less, and still more preferably 15 μm or more and 65 μm or less. The thickness of the first resin film 3 and the second resin film 4 may be 50 μm or less, or 40 μm or less. Reducing the thickness of the first resin film 3 and the second resin film 4 is advantageous in reducing the thickness of the optical laminate (polarizing plate) and the image display device containing the optical laminate.

第1樹脂膜3及第2樹脂膜4可隔著接著劑層或黏著劑層而貼合於偏光片2。形成接著劑層的接著劑可使用水系接著劑或活性能量線硬化性接著劑。 The first resin film 3 and the second resin film 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer. As the adhesive for forming the adhesive layer, a water-based adhesive or an active energy ray curable adhesive can be used.

水系接著劑可列舉慣用的水系接著劑(例如由聚乙烯醇系樹脂水溶液所構成之接著劑、水系二液型胺酯系乳液接著劑、醛化合物、環氧化合物、三聚氰胺系化合物、羥甲基化合物、異氰酸酯化合物、胺化合物、多價金屬鹽等的交聯劑等)。此等之中，可適合使用由聚乙烯醇系樹脂水溶液所構成之水系接著劑。此外，使用水系接著劑時，在將偏光片2與第1樹脂膜3及/或第2樹脂膜4貼合後，為了將水系接著劑中所含之水除去，較佳係 實施乾燥的步驟。乾燥步驟後，可設置例如在20至45℃左右的溫度進行熟化之熟化步驟。 Examples of water-based adhesives include commonly used water-based adhesives (e.g., adhesives composed of polyvinyl alcohol-based resin aqueous solutions, water-based two-component urethane emulsion adhesives, aldehyde compounds, epoxy compounds, melamine-based compounds, methylol Compounds, isocyanate compounds, amine compounds, crosslinking agents such as polyvalent metal salts, etc.). Among these, an aqueous adhesive composed of a polyvinyl alcohol-based resin aqueous solution can be suitably used. In addition, when a water-based adhesive is used, after the polarizer 2 is bonded to the first resin film 3 and/or the second resin film 4, in order to remove the water contained in the water-based adhesive, it is preferable to Implement the drying step. After the drying step, a aging step for aging at a temperature of about 20 to 45°C can be set.

活性能量線硬化性接著劑係指會因照射紫外線或電子束等活性能量線而硬化之接著劑，例如可列舉含有聚合性化合物及光聚合起始劑的硬化性組成物、含有光反應性樹脂的硬化性組成物、含有黏合劑樹脂及光反應***聯劑的硬化性組成物等，較佳為紫外線硬化性接著劑。 Active energy ray curable adhesive refers to an adhesive that is cured by irradiating active energy rays such as ultraviolet rays or electron beams. Examples include curable compositions containing polymerizable compounds and photopolymerization initiators, and photoreactive resins. The curable composition, the curable composition containing a binder resin and a photoreactive crosslinking agent, etc., are preferably ultraviolet curable adhesives.

使用活性能量線硬化性接著劑時，在將偏光片2與第1樹脂膜3及/或第2樹脂膜4貼合後，視需要進行乾燥步驟，然後照射活性能量線，藉此進行使活性能量線硬化性接著劑硬化之硬化步驟。活性能量線的光源並無特別限定，較佳為於波長400nm以下具有發光分布之紫外線。 When using an active energy ray curable adhesive, after bonding the polarizer 2 to the first resin film 3 and/or the second resin film 4, a drying step is performed as necessary, and then the active energy ray is irradiated to activate the The hardening step of the hardening of the energy ray hardening adhesive. The light source of the active energy ray is not particularly limited, but is preferably ultraviolet light having a luminescence distribution at a wavelength of 400 nm or less.

將偏光片2與第1樹脂膜3及/或第2樹脂膜4貼合之方法，可列舉於此等中至少任一者的貼合面施予皂化處理、電暈處理、電漿處理等表面活性化處理之方法等。於偏光片2的雙面貼合樹脂膜時，用以將該等樹脂膜貼合之接著劑可為同種類的接著劑或不同種類的接著劑。 The method of bonding the polarizer 2 to the first resin film 3 and/or the second resin film 4 includes applying saponification treatment, corona treatment, plasma treatment, etc. to the bonding surface of at least any one of these Surface activation methods, etc. When the resin film is attached to both sides of the polarizer 2, the adhesive used to attach the resin film may be the same type of adhesive or different types of adhesives.

(相位差膜) (Retardation film)

相位差膜可列舉對具有透光性的熱塑性樹脂進行一軸延伸或二軸延伸後之延伸膜；配向固定有盤狀液晶或向列型液晶等液晶性化合物之膜；於基材膜上形成有上述液晶層者等。又，於本說明書中，無遲滯膜亦包含在相位差膜之內。基材膜通常為由熱塑性樹脂所構成之膜，熱塑性樹脂之一例為三乙酸纖維素等纖維素酯系樹脂。具有透光性的熱塑性樹脂可列舉上述構成第1樹脂膜3或第2樹脂膜4之樹脂等。 The retardation film includes a stretched film obtained by uniaxially or biaxially stretched with a translucent thermoplastic resin; a film in which liquid crystal compounds such as discotic liquid crystal or nematic liquid crystal are fixed in alignment; and a film formed on a base film The above-mentioned liquid crystal layer, etc. In addition, in this specification, the retardation film is also included in the retardation film. The base film is usually a film made of a thermoplastic resin, and an example of the thermoplastic resin is a cellulose ester resin such as cellulose triacetate. Examples of the translucent thermoplastic resin include the resins constituting the first resin film 3 or the second resin film 4 described above.

所謂無遲滯膜係指面內相位差值Re及厚度方向相位差值Rth 均為-15至15nm之膜。該相位差膜適合使用於IPS模式的液晶顯示裝置。面內相位差值Re及厚度方向相位差值Rth較佳係均為-10至10nm，更佳係均為-5至5nm。在此所稱之面內相位差值Re及厚度方向相位差值Rth為於波長590nm之值。 The so-called non-hysteresis film refers to the in-plane retardation value Re and the thickness direction retardation value Rth All are -15 to 15nm film. This retardation film is suitable for use in an IPS mode liquid crystal display device. The in-plane retardation value Re and the thickness direction retardation value Rth are preferably both -10 to 10 nm, and more preferably both are -5 to 5 nm. The in-plane retardation value Re and the thickness direction retardation value Rth referred to herein are values at a wavelength of 590 nm.

面內相位差值Re及厚度方向相位差值Rth分別由下述式所定義： The in-plane retardation value Re and the thickness direction retardation value Rth are respectively defined by the following equations:

Re=(nx-ny)×d Re=(n x -n y )×d

Rth=[(nx+ny)/2-nz]×d Rth=[(n x +n y )/2-n z ]×d

式中，nx為膜面內的慢軸方向(x軸方向)之折射率，ny為膜面內的快軸方向(在面內與x軸正交的y軸方向)之折射率，nz為膜厚度方向(與膜面垂直的z軸方向)之折射率，d為膜的厚度。 Where n x is the refractive index in the slow axis direction (x-axis direction) in the film plane, n y is the refractive index in the fast axis direction (y-axis direction orthogonal to the x-axis in the plane) in the film plane, n z is the refractive index in the film thickness direction (the z-axis direction perpendicular to the film surface), and d is the film thickness.

無遲滯膜例如可使用由下述者所構成之樹脂膜：纖維素系樹脂、鏈狀聚烯烴系樹脂及環狀聚烯烴系樹脂等聚烯烴系樹脂、聚對苯二甲酸乙二酯系樹脂或(甲基)丙烯酸系樹脂。尤其從容易控制相位差值且亦容易取得來看，較佳係使用纖維素系樹脂、聚烯烴系樹脂或(甲基)丙烯酸系樹脂。 For the non-hysteresis film, for example, resin films composed of cellulose resins, polyolefin resins such as chain polyolefin resins and cyclic polyolefin resins, and polyethylene terephthalate resins can be used. Or (meth)acrylic resin. In particular, it is preferable to use a cellulose resin, a polyolefin resin, or a (meth)acrylic resin from the viewpoint of easy control of the retardation value and easy acquisition.

藉由塗布/配向液晶性化合物而顯現光學異向性之膜可列舉下述者， The following can be listed as a film that exhibits optical anisotropy by coating/aligning a liquid crystal compound.

第一形態：棒狀液晶化合物在與支撐基材水平的方向配向而成的相位差膜； The first form: a retardation film formed by a rod-shaped liquid crystal compound aligned in a horizontal direction with the support substrate;

第二形態：棒狀液晶化合物在與支撐基材垂直的方向配向而成的相位差膜； The second form: a retardation film formed by aligning rod-shaped liquid crystal compounds in a direction perpendicular to the supporting substrate;

第三形態：棒狀液晶化合物的配向方向在面內呈螺旋狀地改變之相位差膜； The third form: the phase difference film in which the alignment direction of the rod-shaped liquid crystal compound changes spirally in the plane;

第四形態：圓盤狀液晶化合物傾斜配向之相位差膜； Fourth form: a retardation film with a discotic liquid crystal compound in oblique alignment;

第五形態：圓盤狀液晶化合物在與支撐基材垂直的方向配向而成的二軸性相 位差膜。 Fifth aspect: a biaxial phase in which a discotic liquid crystal compound is aligned in a direction perpendicular to the supporting substrate Position difference film.

例如使用於有機電致發光顯示器之光學層適合使用第一形態、第二形態、第五形態。或者，亦可將此等積層而使用。 For example, the first form, the second form, and the fifth form are suitable for the optical layer used in the organic electroluminescence display. Alternatively, these may be stacked and used.

相位差膜為由聚合性液晶化合物的配向狀態之聚合物所構成之層(以下有時稱為「光學異向性層」)時，相位差膜較佳係具有逆波長分散性。所謂逆波長分散性為在短波長的液晶配向面內相位差值小於在長波長的液晶配向面內相位差值之光學特性，較佳係相位差膜滿足下述式(1)及式(2)。此外，Re(λ)表示對於波長λnm的光之面內相位差值。 When the retardation film is a layer composed of a polymer in an aligned state of a polymerizable liquid crystal compound (hereinafter sometimes referred to as an "optically anisotropic layer"), the retardation film preferably has reverse wavelength dispersibility. The so-called inverse wavelength dispersion is an optical characteristic in which the retardation value in the alignment plane of the short-wavelength liquid crystal is smaller than the retardation value in the alignment plane of the long-wavelength liquid crystal. It is preferable that the retardation film satisfies the following equations (1) and (2) ). In addition, Re(λ) represents the value of the in-plane phase difference with respect to the light of the wavelength λnm.

Re(450)/Re(550)≦1 (1) Re(450)/Re(550)≦1 (1)

1≦Re(630)/Re(550) (2) 1≦Re(630)/Re(550) (2)

相位差膜為第一形態且具有逆波長分散性時，會減少在顯示裝置之黑顯示時的著色，因而較佳，於式(1)中，若為0.82≦Re(450)/Re(550)≦0.93則更佳。又更佳為120≦Re(550)≦150。 When the retardation film is in the first form and has reverse wavelength dispersion, it will reduce the coloration during black display of the display device, so it is better. In the formula (1), if 0.82≦Re(450)/Re(550) )≦0.93 is better. More preferably, 120≦Re(550)≦150.

就相位差膜為具有光學異向性層的膜時之聚合性液晶化合物而言，可列舉液晶手冊(液晶手冊編集委員會編，丸善(股)2000年10月30日發行)的「3.8.6網狀(完全交聯型)」、「6.5.1液晶材料b.聚合性向列型液晶材料」所記載之化合物中具有聚合性基的化合物、以及日本特開2010-31223號公報、日本特開2010-270108號公報、日本特開2011-6360號公報、日本特開2011-207765號公報、日本特開2016-81035號公報、及國際公開第2017/043438號所記載的聚合性液晶化合物。 Regarding the polymerizable liquid crystal compound when the retardation film is a film with an optically anisotropic layer, the "3.8.6" of the Liquid Crystal Handbook (Edited by the Liquid Crystal Handbook Compilation Committee, issued by Maruzen Co., Ltd. on October 30, 2000) Net-like (fully cross-linked type)", "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material", among the compounds having a polymerizable group, as well as JP 2010-31223 A and JP The polymerizable liquid crystal compounds described in 2010-270108, Japanese Patent Application Publication No. 2011-6360, Japanese Patent Application Publication No. 2011-207765, Japanese Patent Application Publication No. 2016-81035, and International Publication No. 2017/043438.

由聚合性液晶化合物的配向狀態之聚合物製造相位差膜的方法，例如可列舉日本特開2010-31223號公報所記載的方法。 As a method of producing a retardation film from a polymer in an aligned state of a polymerizable liquid crystal compound, for example, the method described in JP 2010-31223 A can be cited.

為第二形態時，面內相位差值Re(550)只要調整為0至10nm的範圍(較佳為0至5nm的範圍)即可，厚度方向的相位差值Rth只要調整為-10至-300nm的範圍(較佳為-20至-200nm的範圍)即可。意指厚度方向的折射率異向性之厚度方向的相位差值Rth可由以面內的快軸作為傾斜軸使其傾斜50度而測定之相位差值R50及面內相位差值Re算出。亦即，厚度方向的相位差值Rth可從面內的相位差值Re、以快軸作為傾斜軸使其傾斜50度而測定得到的相位差值R50、相位差膜的厚度d及相位差膜的平均折射率n0，藉由下述式(4)至(6)求出nx、ny及nz，並將此等代入式(3)而算出。 In the second aspect, the in-plane retardation value Re(550) only needs to be adjusted to the range of 0 to 10 nm (preferably the range of 0 to 5 nm), and the thickness direction retardation value Rth only needs to be adjusted to -10 to- The range of 300 nm (preferably the range of -20 to -200 nm) is sufficient. The thickness direction retardation value Rth, which means the refractive index anisotropy in the thickness direction, can be calculated from the retardation value R50 and the in-plane retardation value Re measured by tilting the fast axis in the plane as the tilt axis by 50 degrees. That is, the retardation value Rth in the thickness direction can be measured from the in-plane retardation value Re, the retardation value R50, the thickness d of the retardation film, and the retardation film measured by tilting the fast axis as the tilt axis by 50 degrees. The average refractive index n 0 of is calculated by calculating n x , n y, and n z from the following formulas (4) to (6), and substituting these into formula (3).

Rth=[(nx+ny)/2-nz]×d (3) Rth=[(n x +n y )/2-n z ]×d (3)

Re=(nx-ny)×d (4) Re=(n x -n y )×d (4)

Figure 109140549-A0202-12-0035-4
Figure 109140549-A0202-12-0035-4

(nx+ny+nz)/3=n0 (6) (n x +n y +n z )/3=n 0 (6)

其中， in,

Figure 109140549-A0202-12-0035-3
Figure 109140549-A0202-12-0035-3

相位差膜可為具有二層以上的層之多層膜。例如可列舉於相位差膜的單面或雙面積層有保護膜者，或將二層以上的相位差膜隔著黏著劑或接著劑積層而成者。 The retardation film may be a multilayer film having two or more layers. For example, one having a protective film on one side or two-area layer of the retardation film, or one having two or more retardation films laminated with an adhesive or adhesive interposed therebetween can be cited.

(導電層) (Conductive layer)

導電層30例如可列舉透明電極層或金屬層等。透明電極層可列舉由氧化銦錫、氧化錫、氧化銦、氧化鋅、氧化鈦、氧化鎵、氧化鋁、氧化銦鋅、 氧化鎵鋅、氧化鋁鋅、及此等的混合物所構成之層。從導電性及可見光穿透率的點來看，較佳為ITO。金屬層可列舉含有選自金屬單質及合金之至少一種中之至少一者的層等，該金屬單質係選自由鋁、銅、銀、鐵、錫、鋅、鎳、鉬、鉻、鎢、鉛所組成的群組之一種，該合金係含有選自該等群組之2種以上金屬元素。此等之中，從導電性的觀點來看，較佳為含有選自鋁、銅、銀及金之至少一種金屬單質的金屬層，更佳為含有選自鋁、銅及銀之至少一種金屬單質的層。 As the conductive layer 30, for example, a transparent electrode layer, a metal layer, or the like can be cited. The transparent electrode layer can include indium tin oxide, tin oxide, indium oxide, zinc oxide, titanium oxide, gallium oxide, aluminum oxide, indium zinc oxide, A layer composed of gallium zinc oxide, aluminum oxide zinc, and a mixture of these. From the viewpoint of conductivity and visible light transmittance, ITO is preferred. The metal layer may be a layer containing at least one selected from the group consisting of simple metal and alloy, and the simple metal is selected from aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, and lead. One of the group consisting of, the alloy contains two or more metal elements selected from these groups. Among these, from the viewpoint of conductivity, a metal layer containing at least one simple metal selected from aluminum, copper, silver, and gold is preferred, and at least one metal selected from aluminum, copper, and silver is more preferred. Simple layer.

導電層30可為已將細線的金屬配線層配置於基板上之金屬網，或已將金屬奈米粒子、金屬奈米線材添加於黏合劑中之層。 The conductive layer 30 can be a metal mesh in which a thin wire metal wiring layer has been arranged on a substrate, or a layer in which metal nanoparticles and metal nanowires have been added to an adhesive.

導電層30的調製方法並無特別限定，可由真空蒸鍍法、濺鍍法、離子鍍法、噴墨印刷法、凹版印刷法形成。導電層30較佳係透明電極層及藉由濺鍍法、噴墨印刷法或凹版印刷法所形成之金屬層，更佳係透明電極層及藉由濺鍍法所形成之金屬層。導電層30的厚度並無特別限定，通常為3μm以下，較佳為1μm以下，更佳為0.8μm以下，通常為0.01μm以上。此外，導電層30為金屬配線層(例如金屬網)時，該金屬配線的線寬通常為10μm以下，較佳為5μm以下，更佳為3μm以下，通常為0.5μm以上。 The preparation method of the conductive layer 30 is not particularly limited, and it can be formed by a vacuum vapor deposition method, a sputtering method, an ion plating method, an inkjet printing method, or a gravure printing method. The conductive layer 30 is preferably a transparent electrode layer and a metal layer formed by a sputtering method, an inkjet printing method or a gravure printing method, and more preferably a transparent electrode layer and a metal layer formed by a sputtering method. The thickness of the conductive layer 30 is not particularly limited, and is usually 3 μm or less, preferably 1 μm or less, more preferably 0.8 μm or less, and usually 0.01 μm or more. In addition, when the conductive layer 30 is a metal wiring layer (for example, a metal mesh), the line width of the metal wiring is usually 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, and usually 0.5 μm or more.

(基板) (Substrate)

基板40可為觸控輸入元件中所含之透明基板，較佳為玻璃基板或樹脂膜。該玻璃基板的材料可使用鈉鈣玻璃、低鹼玻璃、無鹼玻璃等。構成樹脂膜的樹脂例如可列舉上述構成第1樹脂膜3或第2樹脂膜4的樹脂等。 The substrate 40 may be a transparent substrate included in the touch input device, and is preferably a glass substrate or a resin film. As the material of the glass substrate, soda lime glass, low-alkali glass, non-alkali glass, etc. can be used. Examples of the resin constituting the resin film include the above-mentioned resin constituting the first resin film 3 or the second resin film 4, and the like.

(樹脂層) (Resin layer)

形成樹脂層50的樹脂例如可列舉上述構成第1樹脂膜或第2樹脂膜的樹脂等。又，樹脂層50可為硬化性樹脂的硬化物層。可形成樹脂層50之硬化性樹脂可使用公知者，例如可列舉日本特開2009-217037號公報所記載者。 Examples of the resin forming the resin layer 50 include the above-mentioned resins constituting the first resin film or the second resin film. In addition, the resin layer 50 may be a cured product layer of curable resin. As the curable resin capable of forming the resin layer 50, known ones can be used, and examples thereof include those described in Japanese Patent Application Laid-Open No. 2009-217037.

(實施例) (Example)

以下列舉實施例來更具體地說明本發明，但本發明並不限定於該等例子。實施例及比較例中之「%」及「份」只要沒有特別註明，均表示質量%及質量份。 Examples are given below to explain the present invention more specifically, but the present invention is not limited to these examples. Unless otherwise specified, "%" and "parts" in the examples and comparative examples indicate mass% and mass parts.

[剝離狀態的確認及剝離力的測定] [Confirmation of peeling state and measurement of peeling force]

使用實施例及比較例所得之黏著劑片，依下列順序進行剝離狀態的確認及剝離力的測定。 Using the adhesive sheets obtained in the Examples and Comparative Examples, the confirmation of the peeling state and the measurement of the peeling force were performed in the following order.

(試驗片的準備) (Preparation of test piece)

將實施例及比較例所得之黏著劑片在溫度23℃、濕度55%RH的條件下熟化1星期。使用超級切割機從熟化後的黏著劑片切割出寬度5cm×長度12cm的尺寸之試驗片。 The adhesive sheets obtained in the Examples and Comparative Examples were cured for 1 week under the conditions of a temperature of 23° C. and a humidity of 55% RH. A super cutter was used to cut a test piece with a width of 5 cm × a length of 12 cm from the cured adhesive sheet.

(黏著劑層與第1剝離膜的離型處理層側之間的第1剝離力的測定) (Measurement of the first peeling force between the adhesive layer and the release treatment layer side of the first peeling film)

於玻璃基板(EAGLE XG，Corning公司製)的單面整面平行於長邊方向貼附寬度25mm×長度22cm的雙面膠帶(NICETACK(商品名)，Nichiban(股)公司製)，並貼合上述所準備的試驗片的第2剝離膜(以將已塗布形成於第1剝離膜上之黏著劑層被覆之方式設置的剝離膜)之與黏著劑層為相反側處，而將該雙面膠帶與玻璃基板貼合。在此狀態下，使用萬能試驗機(AGS- 50NX，島津製作所製)，將第1剝離膜(製作黏著劑片時在黏著劑組成物的塗布側之剝離膜)的長度方向之一端(寬5cm的一邊)挾持，並在溫度23℃、濕度55%RH的條件下以剝離速度300mm/min將其往180°方向拉扯而從黏著劑層剝離，將此時的剝離力紀錄於圖表。由於測定剛開始後及測定要結束前的數據並不穩定，故將測定開始後20%的數據及測定結束後20%的數據移除，只由相較穩定之中間部分60%的範圍算出平均值，將該平均值作為第1剝離力[N/50mm]。 A double-sided tape (NICETACK (trade name), manufactured by Nichiban Co., Ltd.) (NICETACK (trade name), manufactured by Nichiban Co., Ltd.) was attached to the glass substrate (EAGLE XG, manufactured by Corning Corporation) on one side of the entire surface parallel to the longitudinal direction. The second release film of the test piece prepared above (the release film provided so as to coat the adhesive layer formed on the first release film) and the adhesive layer are on the opposite side, and the double-sided The tape is attached to the glass substrate. In this state, use the universal testing machine (AGS- 50NX, manufactured by Shimadzu Corporation), the first release film (the release film on the coating side of the adhesive composition when making the adhesive sheet) is pinched at one end (the side with a width of 5 cm) in the longitudinal direction, and the temperature is 23°C and humidity Under the condition of 55%RH, it was pulled in the direction of 180° at a peeling speed of 300mm/min and peeled off from the adhesive layer. The peeling force at this time was recorded on the graph. Since the data just after the start of the measurement and before the end of the measurement is not stable, the 20% of the data after the start of the measurement and the 20% of the data after the end of the measurement are removed, and the average is calculated only from the 60% range of the stable middle part Value, the average value is regarded as the first peeling force [N/50mm].

(黏著劑層與第2剝離膜的離型處理層側之間的第2剝離力的測定) (Measurement of the second peeling force between the adhesive layer and the release treatment layer side of the second peeling film)

從上述所準備的試驗片將第1剝離膜剝離，將露出的黏著劑層與玻璃基板(EAGLE XG，Corning公司製)貼合。除了在此狀態下將第2剝離膜剝離以外，其餘以與上述第1剝離力的測定同樣的順序將剝離力紀錄於圖表，並根據所得之數據算出第2剝離力[N/50mm]。 The first release film was peeled off from the test piece prepared above, and the exposed adhesive layer was bonded to a glass substrate (EAGLE XG, manufactured by Corning Corporation). Except that the second peeling film was peeled in this state, the peeling force was recorded on the graph in the same order as the measurement of the first peeling force described above, and the second peeling force [N/50mm] was calculated based on the obtained data.

(剝離力差的算出) (Calculation of the difference in peeling force)

將上述所得之第1剝離力與第2剝離力之差的絶對值作為剝離力差[N/50mm]。 The absolute value of the difference between the first peeling force and the second peeling force obtained above was taken as the peeling force difference [N/50mm].

(剝離狀態的確認(剝離試驗)) (Confirmation of peeling state (peeling test))

剝離力測定時，以目視進行剝離狀態的確認。將「可在不會使黏著劑層部分分離的狀態下將剝離膜剝離之情形」評價為A，將「因剝離膜的剝離而使黏著劑層分離之情形」評價為B。 At the time of the peeling force measurement, the peeling state was confirmed visually. The "case where the release film can be peeled without partially separating the adhesive layer" was evaluated as A, and the "case where the adhesive layer was separated due to peeling of the release film" was evaluated as B.

<製造例1及2：(甲基)丙烯酸系樹脂的製造> <Production Examples 1 and 2: Production of (meth)acrylic resin>

於具有冷卻管、氮導入管、溫度計及攪拌機之反應容器中，添加已將表1所示之組成(表1的數值為質量份)的單體與乙酸乙酯81.8份混合而得之溶液。將反應容器內的空氣以氮氣取代後，將內溫設為60℃。然後添加已使偶氮雙異丁腈0.12份溶解於乙酸乙酯10份中而成的溶液。在添加偶氮雙異丁腈後直到經過12小時為止將內溫保持在54至56℃後，添加乙酸乙酯而將聚合物的濃度調整成20%，得到(甲基)丙烯酸系樹脂的乙酸乙酯溶液。 In a reaction vessel with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, a solution obtained by mixing a monomer having the composition shown in Table 1 (the value in Table 1 is parts by mass) and 81.8 parts of ethyl acetate was added. After replacing the air in the reaction vessel with nitrogen, the internal temperature was set to 60°C. Then, a solution prepared by dissolving 0.12 parts of azobisisobutyronitrile in 10 parts of ethyl acetate was added. After adding azobisisobutyronitrile and keeping the internal temperature at 54 to 56°C until 12 hours passed, ethyl acetate was added to adjust the polymer concentration to 20% to obtain acetic acid of (meth)acrylic resin Ethyl acetate solution.

對製造例1所得之(甲基)丙烯酸系樹脂(A1)及製造例2所得之(甲基)丙烯酸系樹脂(A2)測定重量平均分子量Mw及數量平均分子量Mn。有關重量平均分子量Mw及數量平均分子量Mn，係在GPC裝置中將4條Tosoh(股)製的「TSKgel XL」及1條昭和電工(股)製的「Shodex GPC KF-802」共計5條以串聯的方式連接配置作為管柱，並使用四氫呋喃作為洗提液，在試料濃度5mg/mL、試料導入量100μL、溫度40℃、流速1mL/分鐘的條件下經標準聚苯乙烯換算而測定。 The weight average molecular weight Mw and the number average molecular weight Mn of the (meth)acrylic resin (A1) obtained in Production Example 1 and the (meth)acrylic resin (A2) obtained in Production Example 2 were measured. Regarding the weight average molecular weight Mw and the number average molecular weight Mn, a total of 5 "TSKgel XL" manufactured by Tosoh and 1 "Shodex GPC KF-802" manufactured by Showa Denko Co., Ltd. are used in the GPC device. The column is connected in series, and tetrahydrofuran is used as the eluent. The measurement is performed by standard polystyrene conversion under the conditions of a sample concentration of 5 mg/mL, a sample introduction amount of 100 μL, a temperature of 40°C, and a flow rate of 1 mL/min.

[表1]

Figure 109140549-A0202-12-0039-5
[Table 1]
Figure 109140549-A0202-12-0039-5

表1的「單體組成」欄中之簡稱意指下述單體。 The abbreviations in the "monomer composition" column of Table 1 mean the following monomers.

BA：丙烯酸正丁酯 BA: n-butyl acrylate

MA：丙烯酸甲酯 MA: methyl acrylate

HEA：丙烯酸2-羥基乙酯 HEA: 2-hydroxyethyl acrylate

AA：丙烯酸 AA: Acrylic

BMAA：丁氧基甲基丙烯醯胺 BMAA: Butoxy methacrylamide

PEA：丙烯酸2-苯氧基乙酯 PEA: 2-phenoxyethyl acrylate

[比較例1、實施例1至3] [Comparative Example 1, Examples 1 to 3]

(1)黏著劑組成物的調製 (1) Preparation of adhesive composition

在上述製造例所得之(甲基)丙烯酸系樹脂的乙酸乙酯溶液(樹脂濃度：20%)中，相對於該溶液的固形分100份，分別將表2所示之交聯劑(B)、調平劑(C)、矽烷化合物(D)及其他成分依表2所示之量(質量份)混合，並且以使固形分濃度成為14%之方式添加乙酸乙酯而得到黏著劑組成物。在所使用的商品含有溶劑等時，表2所示之各調配成分的調配量為其中所含之有效成分的質量份數。 In the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above production example, the crosslinking agent (B) shown in Table 2 was added to 100 parts of the solid content of the solution. , Leveling agent (C), silane compound (D) and other ingredients are mixed in the amount (parts by mass) shown in Table 2, and ethyl acetate is added so that the solid content concentration becomes 14% to obtain an adhesive composition . When the product used contains a solvent, etc., the blending amount of each blending ingredient shown in Table 2 is the mass part of the active ingredient contained therein.

[表2]

Figure 109140549-A0202-12-0040-6
[Table 2]
Figure 109140549-A0202-12-0040-6

表2中以簡稱表示之各調配成分的詳細內容如下所述。 The details of each compounding component represented by abbreviations in Table 2 are as follows.

(交聯劑(B)) (Crosslinking agent (B))

B：Coronate L(甲苯二異氰酸酯的三羥甲基丙烷加成物之乙酸乙酯溶液：固形分濃度75質量%，Tosoh(股)公司製) B: Coronaate L (Ethyl acetate solution of trimethylolpropane adduct of toluene diisocyanate: solid content 75% by mass, manufactured by Tosoh Co., Ltd.)

(調平劑(C)) (Leveling agent (C))

C1：氟系化合物，從DIC股份有限公司取得之商品名「F-554」(具有全氟烷基之調平劑) C1: Fluorine compound, trade name "F-554" (leveling agent with perfluoroalkyl group) obtained from DIC Co., Ltd.

(矽烷化合物(D)) (Silane compound (D))

D1：3-縮水甘油氧基丙基三甲氧基矽烷，從信越化學工業(股)取得之商品名「KBM403」(黏度：4.2mPa．s) D1: 3-glycidoxypropyltrimethoxysilane, the trade name "KBM403" obtained from Shin-Etsu Chemical Co., Ltd. (Viscosity: 4.2mPa·s)

(其他成分) (Other ingredients)

e1：從新中村化學工業(股)取得之M-130G e1: M-130G obtained from Shinnakamura Chemical Industry Co., Ltd.

e2：N-己基-4-甲基吡啶鎓六氟磷(60%甲苯溶液) e2: N-hexyl-4-methylpyridinium hexafluorophosphorus (60% toluene solution)

(2)黏著劑片的製作 (2) Production of adhesive sheet

將上述(1)所調製之各黏著劑組成物使用塗敷器以使乾燥後的厚度成為20μm的方式塗布於已施予離型處理之由聚對苯二甲酸乙二酯膜所構成之離型膜[從Lintec(股)取得之商品名「PLR-382051」](作為上述第1剝離膜)的離型處理面，在100℃乾燥1分鐘而製作黏著劑層。在該黏著劑層的與離型膜為相反側處積層與上述相同的離型膜(作為上述第2剝離膜)之離型處理面側，而得到黏著劑片。使用所得之黏著劑片進行剝離狀態的確認及剝離力的測定。將其結果呈示於表3。 Each adhesive composition prepared in (1) above was applied to a release process composed of polyethylene terephthalate film using an applicator so that the thickness after drying became 20 μm. The release treatment surface of the molded film [trade name "PLR-382051" obtained from Lintec Co., Ltd.) (as the first release film) was dried at 100°C for 1 minute to prepare an adhesive layer. On the side of the adhesive layer opposite to the release film, the release treatment surface side of the same release film (as the second release film) described above was laminated to obtain an adhesive sheet. Using the obtained adhesive sheet, the confirmation of the peeling state and the measurement of the peeling force were performed. The results are shown in Table 3.

[表3]

Figure 109140549-A0202-12-0042-7
[table 3]
Figure 109140549-A0202-12-0042-7

[實施例4至16] [Examples 4 to 16]

(1)黏著劑組成物的調製 (1) Preparation of adhesive composition

在上述製造例所得之(甲基)丙烯酸系樹脂的乙酸乙酯溶液(樹脂濃度：20%)中，相對於該溶液的固形分100份，分別將表4所示之交聯劑(B)、調平劑(C)、矽烷化合物(D)、及其他成分依表4所示之量(質量份)混合，並且以使固形分濃度成為14%之方式添加乙酸乙酯而得到黏著劑組成物。在所使用的商品含有溶劑等時，表4所示之各調配成分的調配量為其中所含之有效成分的質量份數。 In the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above production example, the crosslinking agent (B) shown in Table 4 was added to 100 parts of the solid content of the solution. , Leveling agent (C), silane compound (D), and other ingredients are mixed in the amounts (parts by mass) shown in Table 4, and ethyl acetate is added so that the solid content concentration becomes 14% to obtain the adhesive composition Things. When the product used contains a solvent, etc., the blending amount of each blending ingredient shown in Table 4 is the mass parts of the active ingredient contained therein.

[表4]

Figure 109140549-A0202-12-0043-8
[Table 4]
Figure 109140549-A0202-12-0043-8

表4中以簡稱表示之各調配成分的詳細內容如下所述。 The details of each compounding component represented by abbreviations in Table 4 are as follows.

((甲基)丙烯酸系樹脂(A)) ((Meth) acrylic resin (A))

A2：製造例2所合成之(甲基)丙烯酸系樹脂(A2) A2: The (meth)acrylic resin (A2) synthesized in Production Example 2

(交聯劑(B)) (Crosslinking agent (B))

B：Coronate L(甲苯二異氰酸酯的三羥甲基丙烷加成物之乙酸乙酯溶液：固形分濃度75質量%，Tosoh(股)公司製) B: Coronaate L (Ethyl acetate solution of trimethylolpropane adduct of toluene diisocyanate: solid content 75% by mass, manufactured by Tosoh Co., Ltd.)

(調平劑(C)) (Leveling agent (C))

C1：氟系化合物、從DIC股份有限公司取得之商品名「F-554」(具有全氟烷基之調平劑) C1: Fluorine compound, trade name "F-554" (leveling agent with perfluoroalkyl group) obtained from DIC Co., Ltd.

C2：氟系化合物、從DIC股份有限公司取得之商品名「F-444」(含有氧 伸乙基鏈之具有全氟烷基之調平劑) C2: Fluorine-based compound, the trade name "F-444" obtained from DIC Co., Ltd. (containing oxygen Leveling agent with perfluoroalkyl group of ethylene chain)

C3：氟系化合物、從DIC股份有限公司取得之商品名「F-563」(具有全氟伸烷基之調平劑) C3: Fluorine-based compound, trade name "F-563" (leveling agent with perfluoroalkylene) obtained from DIC Co., Ltd.

(矽烷化合物(D)) (Silane compound (D))

D1：3-縮水甘油氧基丙基三甲氧基矽烷，從信越化學工業(股)取得之商品名「KBM403」(黏度：4.2mPa．s) D1: 3-glycidoxypropyltrimethoxysilane, the trade name "KBM403" obtained from Shin-Etsu Chemical Co., Ltd. (Viscosity: 4.2mPa·s)

D2：含有驗基之聚矽氧低聚物「KR-519」(巰基當量450g/mol)、信越化學工業(股)製 D2: Polysilicone oligomer "KR-519" (mercapto equivalent 450g/mol) containing a test base, manufactured by Shin-Etsu Chemical Co., Ltd.

D3：乙烯三甲氧基矽烷、從信越化學工業(股)取得之商品名「KBM1003」 D3: Ethylene trimethoxysilane, the trade name "KBM1003" obtained from Shin-Etsu Chemical Co., Ltd.

(2)黏著劑片的製作 (2) Production of adhesive sheet

將上述(1)所調製之各黏著劑組成物使用塗敷器以使乾燥後的厚度成為20μm的方式塗布於已施予離型處理之由聚對苯二甲酸乙二酯膜所構成之離型膜[從Lintec(股)取得之商品名「PLR-382051」](作為上述第1剝離膜)的離型處理面，在100℃乾燥1分鐘而製作黏著劑層。在該黏著劑層的與離型膜為相反側處積層與上述相同的離型膜(作為上述第2剝離膜)之離型處理面側，而得到黏著劑片。使用所得之黏著劑片進行剝離狀態的確認及剝離力的測定。將其結果呈示於表5。表5中亦呈示比較例1的結果。 Each adhesive composition prepared in (1) above was applied to a release process composed of polyethylene terephthalate film using an applicator so that the thickness after drying became 20 μm. The release treatment surface of the molded film [trade name "PLR-382051" obtained from Lintec Co., Ltd.) (as the first release film) was dried at 100°C for 1 minute to prepare an adhesive layer. On the side of the adhesive layer opposite to the release film, the release treatment surface side of the same release film (as the second release film) described above was laminated to obtain an adhesive sheet. Using the obtained adhesive sheet, the confirmation of the peeling state and the measurement of the peeling force were performed. The results are shown in Table 5. Table 5 also shows the results of Comparative Example 1.

[耐久性的評估(耐久性試驗)] [Evaluation of durability (durability test)]

準備具有厚度40μm的三乙酸纖維素樹脂膜/水系接著劑層/厚度23μm聚乙烯醇系偏光片/水系接著劑層/厚度23μm的環烯烴樹脂膜的積層構造的偏光板。 A polarizing plate having a laminated structure of a cellulose triacetate resin film with a thickness of 40 μm/aqueous adhesive layer/a polyvinyl alcohol-based polarizer with a thickness of 23 μm/aqueous adhesive layer/a cycloolefin resin film with a thickness of 23 μm was prepared.

在前述偏光板的環烯烴樹脂膜面施以電暈處理。 Corona treatment is applied to the cycloolefin resin film surface of the aforementioned polarizing plate.

從上述(2)所製作的黏著劑片，將形成黏著劑層時塗布有黏著劑組成物之離型膜(作為上述第1剝離膜的離型膜)剝離後，將該黏著劑層面黏貼於前述偏光板的環烯烴樹脂膜的電暈處理面，得到附黏著劑層偏光板。從所得的附黏著劑層偏光板剝離離型膜(上述第2剝離膜)，將該黏著劑層面黏貼於無鹼玻璃基板[Corning公司製的「Eagle XG」]，製作評估用樣品。一面對該評估用樣品施以壓力(0.49MPa)，一面在溫度50℃的環境下靜置20分鐘。之後，將評估用樣品進行在溫度80℃的乾燥條件下保持250小時的耐久性試驗，以及在溫度80℃的乾燥條件下保持500小時的耐久性試驗。 From the adhesive sheet produced in (2) above, the release film (as the release film of the first release film) coated with the adhesive composition when the adhesive layer is formed is peeled off, and then the adhesive layer is pasted on The corona-treated surface of the cycloolefin resin film of the aforementioned polarizing plate obtained a polarizing plate with an adhesive layer. The release film (the second release film mentioned above) was peeled from the obtained polarizing plate with an adhesive layer, and the adhesive layer was stuck on an alkali-free glass substrate ["Eagle XG" manufactured by Corning Corporation] to prepare an evaluation sample. While applying pressure (0.49 MPa) to the sample for evaluation, it was allowed to stand for 20 minutes in an environment with a temperature of 50°C. After that, the sample for evaluation was subjected to a durability test that was maintained under dry conditions at a temperature of 80°C for 250 hours, and a durability test that was maintained under dry conditions at a temperature of 80°C for 500 hours.

對於耐久性試驗後的評估用樣品，以目視觀察在黏著劑層與玻璃基板的界面有無浮起及剝離，依照下述評估基準評估耐久性。對於使用比較例1之(2)黏著劑片時也與上述相同地製作評估用樣品，進行耐久性試驗。結果呈示於表5。 For the evaluation sample after the durability test, the presence or absence of floating and peeling at the interface between the adhesive layer and the glass substrate was visually observed, and the durability was evaluated according to the following evaluation criteria. In the case of using (2) the adhesive sheet of Comparative Example 1, samples for evaluation were produced in the same manner as described above, and a durability test was performed. The results are shown in Table 5.

<關於剝離> <About peeling>

A：沒有剝離。 A: No peeling.

B：產生未達0.5mm的剝離。 B: Peeling of less than 0.5 mm occurred.

C：產生0.5至未達1mm的剝離。 C: Peeling of 0.5 to less than 1 mm occurs.

D：產生1mm以上的剝離。 D: Peeling of 1 mm or more occurred.

<關於氣泡> <About bubbles>

A：沒有氣泡。 A: No bubbles.

B：未達0.3mm的尺寸的氣泡產生不到10個。 B: Less than 10 bubbles with a size of less than 0.3 mm are generated.

C：未達0.3mm的尺寸的氣泡產生10個以上。 C: 10 or more bubbles with a size of less than 0.3 mm are generated.

D：0.3mm以上的尺寸的氣泡大量產生。 D: A large number of bubbles having a size of 0.3 mm or more are generated.

[表5]

Figure 109140549-A0202-12-0046-9
[table 5]
Figure 109140549-A0202-12-0046-9

1:光學積層體 1: Optical laminate

10:光學層 10: Optical layer

20:黏著劑層 20: Adhesive layer

Claims (9)

一種黏著劑組成物，係含有樹脂、交聯劑、調平劑及矽烷化合物；其中， An adhesive composition containing resin, crosslinking agent, leveling agent and silane compound; wherein, 前述調平劑係包含氟系化合物。 The aforementioned leveling agent contains a fluorine-based compound. 如請求項1所述之黏著劑組成物，其中，前述矽烷化合物的含量(質量份)小於前述氟系化合物之含量(質量份)。 The adhesive composition according to claim 1, wherein the content (parts by mass) of the silane compound is less than the content (parts by mass) of the fluorine-based compound. 如請求項1或2所述之黏著劑組成物，其中，前述氟系化合物為具有全氟烷基及全氟伸烷基中之至少一者的化合物。 The adhesive composition according to claim 1 or 2, wherein the fluorine-based compound is a compound having at least one of a perfluoroalkyl group and a perfluoroalkylene group. 如請求項1至3中任一項所述之黏著劑組成物，其中，前述矽烷化合物與前述氟系化合物的質量比(矽烷化合物的質量/氟系化合物的質量)為0.8以下。 The adhesive composition according to any one of claims 1 to 3, wherein the mass ratio of the silane compound to the fluorine compound (mass of the silane compound/mass of the fluorine compound) is 0.8 or less. 如請求項1至4中任一項所述之黏著劑組成物，其中，前述樹脂含有(甲基)丙烯酸系樹脂。 The adhesive composition according to any one of claims 1 to 4, wherein the resin contains a (meth)acrylic resin. 一種黏著劑層，係使用請求項1至5中任一項所述之黏著劑組成物。 An adhesive layer using the adhesive composition described in any one of claims 1 to 5. 一種黏著劑片，係在請求項6所述之黏著劑層的雙面設置有相同的剝離膜，而且 An adhesive sheet provided with the same release film on both sides of the adhesive layer described in claim 6, and 將前述黏著劑層的其中一面與前述剝離膜之間的剝離力作為第1剝離力，且將前述黏著劑層之與前述一面為相反側之另一面、與前述剝離膜之間的剝離力作為第2剝離力時，前述第1剝離力與前述第2剝離力彼此相異。 The peeling force between one side of the adhesive layer and the peeling film is taken as the first peeling force, and the peeling force between the other surface of the adhesive layer on the opposite side to the one surface and the peeling film is taken as In the case of the second peeling force, the first peeling force and the second peeling force are different from each other. 一種光學積層體，係含有光學層及黏著劑層；其中， An optical laminated body containing an optical layer and an adhesive layer; wherein, 前述黏著劑層為請求項6所述之黏著劑層。 The aforementioned adhesive layer is the adhesive layer described in claim 6. 如請求項8所述之光學積層體，其中，前述光學層含有偏光板。 The optical laminate according to claim 8, wherein the optical layer contains a polarizing plate.
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