TWI688794B - Optical film with adhesive layer - Google Patents

Optical film with adhesive layer Download PDF

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TWI688794B
TWI688794B TW105106263A TW105106263A TWI688794B TW I688794 B TWI688794 B TW I688794B TW 105106263 A TW105106263 A TW 105106263A TW 105106263 A TW105106263 A TW 105106263A TW I688794 B TWI688794 B TW I688794B
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adhesive layer
adhesive
meth
layer
acrylate
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TW105106263A
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TW201643480A (en
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又野仁
荒井隆行
竹厚流
淺津悠司
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日商琳得科股份有限公司
日商住友化學股份有限公司
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    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Liquid Crystal (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

本發明提供一種即使在使用經薄膜化之光學薄膜時，亦係耐久性優異、顯示面板不易翹曲、且不易產生熱不均之附有黏著劑層之光學薄膜。 The present invention provides an optical film with an adhesive layer, which is excellent in durability, hard to warp a display panel, and hardly generates thermal unevenness even when an optical film that has been thinned is used.

一種附有黏著劑層之光學薄膜(1A)，其具備：第1相位差板(11)；積層於第1相位差板(11)的一面之第1黏著劑層(21)；積層於第1相位差板(11)之與第1黏著劑層(21)側的面相反的一面側之第2黏著劑層(22)；及積層於第2黏著劑層(22)之與第1相位差板(11)側的面相反的一面側之第2相位差板(12)，該附有黏著劑層之光學薄膜(1A)中，第1相位差板(11)之與第1黏著劑層(21)相接的面由丙烯酸系樹脂構成，構成第1黏著劑層(21)之黏著劑的凝膠分率為55~90%，第1黏著劑層(21)的85℃下之儲存彈性模數(G’)為0.03~0.25MPa，構成第2黏著劑層(22)之黏著劑的凝膠分率為80~100%，第2黏著劑層(22)的85℃下之儲存彈性模數(G’)為0.15~3.00MPa。 An optical film (1A) with an adhesive layer, comprising: a first phase difference plate (11); a first adhesive layer (21) layered on one side of the first phase difference plate (11); layered on the first 1 the second adhesive layer (22) on the side opposite to the side of the first adhesive layer (21) of the phase difference plate (11); and the first phase deposited on the second adhesive layer (22) The second retardation plate (12) on the opposite side of the side of the difference plate (11), in the optical film (1A) with an adhesive layer, the first retardation plate (11) and the first adhesive The surface where the layer (21) is in contact is composed of acrylic resin, the gel fraction of the adhesive constituting the first adhesive layer (21) is 55 to 90%, and that of the first adhesive layer (21) at 85°C The storage elastic modulus (G') is 0.03 to 0.25 MPa, the gel fraction of the adhesive constituting the second adhesive layer (22) is 80 to 100%, and that of the second adhesive layer (22) at 85℃ The storage elastic modulus (G') is 0.15~3.00MPa.

Description

附有黏著劑層之光學薄膜 Optical film with adhesive layer

本發明係關於附有黏著劑層之光學薄膜者，尤其係關於在液晶單元等上貼合複合偏光板等光學薄膜時使用之附有黏著劑層之光學薄膜。 The present invention relates to an optical film with an adhesive layer, and particularly to an optical film with an adhesive layer used when an optical film such as a composite polarizer is attached to a liquid crystal cell or the like.

近年來、作為各種電子設備之顯示面板，廣泛使用兼作顯示裝置和輸入機構之觸控面板。觸控面板的種類主要有電阻膜式、電容式、光學式及超音波式，電阻膜式有類比電阻膜式及矩陣電阻膜式；電容式有表面型及投影型。 In recent years, as display panels of various electronic devices, touch panels that double as display devices and input mechanisms are widely used. The types of touch panels are mainly resistive film type, capacitive type, optical type and ultrasonic type. Resistive film type has analog resistive film type and matrix resistive film type; capacitive type has surface type and projection type.

最近備受矚目的智慧型手機或平板電腦等行動電子裝置之觸控面板中廣泛使用投影型電容式者。作為相關行動電子裝置之投影型電容式的觸控面板，提出例如從下方依次積層了液晶顯示裝置(LCD)、黏著劑層、透明導電膜(錫摻雜氧化銦：ITO)、玻璃基板、透明導電膜(ITO)以及強化玻璃等之保護板者。 Recently, projection-type capacitors are widely used in touch panels of mobile electronic devices such as smart phones or tablet computers. As a projection type capacitive touch panel of a related mobile electronic device, for example, a liquid crystal display device (LCD), an adhesive layer, a transparent conductive film (tin-doped indium oxide: ITO), a glass substrate, and a transparent layer are sequentially deposited from below Protective plates such as conductive film (ITO) and tempered glass.

作為構成上述液晶顯示裝置之光學組件，一般使用液晶單元。液晶單元係通常配置成將形成配向層的兩片透明電極基板之配向層作為內側並藉由間隔物形成既定間隔，且密封其周圍並在兩片透明電極基板之間夾持液晶材料者。通常在液晶單元中之兩片透明電極基板的外側分別藉由黏著劑接著 有具有偏光板或相位差板之複合偏光板。 As an optical component constituting the liquid crystal display device, a liquid crystal cell is generally used. The liquid crystal cell is generally configured such that the alignment layers of the two transparent electrode substrates forming the alignment layer are inside and a predetermined interval is formed by a spacer, and the surroundings are sealed and the liquid crystal material is sandwiched between the two transparent electrode substrates. Usually, the two transparent electrode substrates in the liquid crystal cell are respectively adhered by an adhesive There are composite polarizing plates with polarizing plates or phase difference plates.

作為光學用之黏著劑，已知有例如專利文獻1所示者。該黏著劑含有(甲基)丙烯酸系聚合物、以及相對於(甲基)丙烯酸系聚合物100質量份含有作為交聯劑之過氧化物0.02~2質量份及環氧系交聯劑0.005~5質量份，前述(甲基)丙烯酸系聚合物係作為單體單元，相對於具有碳原子數為4~14的烷基之烷基(甲基)丙烯酸酯100質量份，含有含羧基單體0.2~20質量份作為共聚合成分而構成。 As an adhesive for optics, for example, those shown in Patent Document 1 are known. The adhesive contains a (meth)acrylic polymer, and contains 0.02 to 2 parts by mass of peroxide as a crosslinking agent and 0.005 to an epoxy crosslinking agent with respect to 100 parts by mass of the (meth)acrylic polymer. 5 parts by mass of the (meth)acrylic polymer system as a monomer unit, containing 100 parts by mass of an alkyl (meth)acrylate having an alkyl group having 4 to 14 carbon atoms, containing a carboxyl group-containing monomer 0.2 to 20 parts by mass is constituted as a copolymerization component.

【先前技術文獻】 【Prior Technical Literature】 【專利文獻】 【Patent Literature】

專利文獻1：日本特開2009-242786號公報 Patent Document 1: Japanese Patent Laid-Open No. 2009-242786

在此，隨著近年來對行動電子裝置的薄型化之要求，對偏光板等光學薄膜亦要求薄膜化。但是，薄膜之偏光板之由熱等引起的收縮率較高，在專利文獻1等習知之黏著劑中，顯示面板會產生翹曲，或者在高溫條件下或濕熱條件下會發生翹起或表面剝離。還指出由於光學薄膜熱收縮時的應力，會發生藉由光學薄膜的光學軸偏離所引起的漏光(即所謂熱不均)之問題。 Here, with the recent demand for thinner mobile electronic devices, thinner films such as polarizing plates are also required. However, the film polarizer has a high shrinkage rate due to heat, etc. In conventional adhesives such as Patent Document 1, the display panel may warp, or the surface may warp or have a surface under high temperature or humid heat. Peel off. It is also pointed out that due to the stress during the thermal contraction of the optical film, the problem of light leakage (so-called thermal unevenness) caused by the deviation of the optical axis of the optical film occurs.

本發明係鑑於這種實際情況而完成者，其目的為提供一種即使在使用經薄膜化之光學薄膜時，亦係耐久性優異、顯示面板不易翹曲、且不易產生熱不均之附有黏著劑層之光學薄膜。 The present invention has been completed in view of this actual situation, and its object is to provide an adhesion with adhesion that is excellent in durability, hard to warp in a display panel, and hard to generate thermal unevenness even when an optical film that has been thinned is used The optical film of the agent layer.

為了實現上述目的，首先，本發明提供一種附有黏著劑層之光學薄膜，其具備：第1相位差板；積層於前述第1相位差板的一面之第1黏著劑層；積層於前述第1相位差板之與前述第1黏著劑層側的面相反的一面側之第2黏著劑層；及積層於前述第2黏著劑層之與前述第1相位差板側的面相反的一面側之第2相位差板，前述附有黏著劑層之光學薄膜中，前述第1相位差板之與前述第1黏著劑層相接的面由丙烯酸系樹脂構成，構成前述第1黏著劑層之黏著劑的凝膠分率為55~90%，前述第1黏著劑層的85℃下之儲存彈性模數(G’)為0.03~0.25MPa，構成前述第2黏著劑層之黏著劑的凝膠分率為80~100%，前述第2黏著劑層的85℃下之儲存彈性模數(G’)為0.15~3.00MPa(發明1)。 In order to achieve the above object, first, the present invention provides an optical film with an adhesive layer, comprising: a first phase difference plate; a first adhesive layer laminated on one side of the first phase difference plate; and a layer laminated on the first 1 a second adhesive layer on the side opposite to the first adhesive layer side surface of the phase difference plate; and a side layer on the opposite side of the first phase difference plate side layer deposited on the second adhesive layer The second phase difference plate, in the optical film with an adhesive layer, the surface of the first phase difference plate that is in contact with the first adhesive layer is made of acrylic resin, and constitutes the first adhesive layer The gel fraction of the adhesive is 55 to 90%, and the storage elastic modulus (G') at 85°C of the first adhesive layer is 0.03 to 0.25 MPa, which constitutes the condensation of the adhesive of the second adhesive layer The gel fraction is 80 to 100%, and the storage elastic modulus (G') of the second adhesive layer at 85°C is 0.15 to 3.00 MPa (Invention 1).

依上述發明(發明1)，與光學薄膜的黏著劑層相接的面由丙烯酸系樹脂構成，而且該光學薄膜已進行了薄膜化之情況下，亦可藉由第1黏著劑層及第2黏著劑層滿足上述物性，從而在使用於顯示面板時，耐久性優異，並且顯示面板不易翹曲，還不易產生熱不均。 According to the above invention (Invention 1), the surface in contact with the adhesive layer of the optical film is made of acrylic resin, and when the optical film has been thinned, the first adhesive layer and the second The adhesive layer satisfies the above physical properties, so that when used in a display panel, the durability is excellent, and the display panel is less likely to be warped and thermal unevenness is less likely to occur.

上述發明(發明1)中，前述第1相位差板之與前述第1黏著劑層相接之最外層由經由擠出成形而形成之丙烯酸系樹脂層構成為較佳(發明2)。 In the above invention (Invention 1), it is preferable that the outermost layer of the first phase difference plate that is in contact with the first adhesive layer is composed of an acrylic resin layer formed by extrusion molding (Invention 2).

上述發明(發明2)中，前述第1相位差板係具備前述丙烯酸系樹脂層、第2丙烯酸系樹脂層、以及位於前述丙烯酸系樹脂層與前述第2丙烯酸系樹脂層之間之相位差表現層 者為較佳(發明3)。 In the above invention (Invention 2), the first retardation plate includes the acrylic resin layer, the second acrylic resin layer, and the phase difference expression between the acrylic resin layer and the second acrylic resin layer Floor Which is better (Invention 3).

在上述發明(發明3)中，前述相位差表現層由苯乙烯系樹脂構成為較佳(發明4)。 In the above invention (Invention 3), it is preferable that the phase difference expression layer is made of styrene resin (Invention 4).

在上述發明(1~4)中，前述第2相位差板由環式烯烴系樹脂構成為較佳(發明5)。 In the above inventions (1 to 4), it is preferable that the second phase difference plate is made of a cycloolefin-based resin (Invention 5).

在上述發明(1~5)中，前述第1黏著劑層由從黏著性組成物得到的黏著劑所構成，前述黏著性組成物含有：(甲基)丙烯酸酯共聚物(A)含有含脂環式結構單體(a1)及含芳香環單體(a2)；以及交聯劑(B)作為構成聚合物的單體單元(發明6)。 In the above inventions (1 to 5), the first adhesive layer is composed of an adhesive obtained from an adhesive composition, and the adhesive composition contains: (meth)acrylate copolymer (A) contains a fat The ring structure monomer (a1) and the aromatic ring-containing monomer (a2); and the crosslinking agent (B) as monomer units constituting the polymer (Invention 6).

在上述發明(發明1~6)中，在前述第2相位差板之與前述第2黏著劑層側的面相反的一面側還積層有偏光板為較佳(發明7)。 In the above inventions (Inventions 1 to 6), it is preferable that a polarizing plate is further laminated on the side of the second retardation plate opposite to the surface on the side of the second adhesive layer (Invention 7).

依本發明之附有黏著劑層之光學薄膜，即使在光學薄膜已進行薄膜化之情況下，亦會耐久性優異、顯示面板不易翹曲、還不易產生熱不均。 According to the optical film with an adhesive layer of the present invention, even when the optical film has been thinned, the durability is excellent, the display panel is less likely to warp, and thermal unevenness is also less likely to occur.

1A、1B‧‧‧附有黏著劑層之光學薄膜 1A, 1B‧‧‧Optical film with adhesive layer

11‧‧‧第1相位差板 11‧‧‧First phase difference plate

111‧‧‧第1丙烯酸系樹脂層 111‧‧‧The first acrylic resin layer

112‧‧‧相位差表現層 112‧‧‧Phase difference layer

113‧‧‧第2丙烯酸系樹脂層 113‧‧‧The second acrylic resin layer

12‧‧‧第2相位差板 12‧‧‧The second phase difference plate

21‧‧‧第1黏著劑層 21‧‧‧1st adhesive layer

22‧‧‧第2黏著劑層 22‧‧‧ 2nd adhesive layer

3‧‧‧偏光板 3‧‧‧ Polarizer

31‧‧‧偏光子 31‧‧‧ Polaron

32‧‧‧保護層 32‧‧‧Protection layer

圖1係本發明的一實施形態之附有黏著劑層之光學薄膜的剖面圖。 1 is a cross-sectional view of an optical film with an adhesive layer according to an embodiment of the present invention.

圖2係表示相位差板的構成例的剖面圖。 FIG. 2 is a cross-sectional view showing a configuration example of a phase difference plate.

圖3係本發明的另一實施形態之附有黏著劑層之光學薄膜的剖面圖。 3 is a cross-sectional view of an optical film with an adhesive layer according to another embodiment of the present invention.

圖4係表示附有黏著劑層之光學薄膜之耐熱不均勻性試驗(肉眼觀察)的評價基準的圖(彩色)。 FIG. 4 is a diagram (color) showing the evaluation criteria of the heat resistance unevenness test (visual observation) of the optical film with an adhesive layer.

以下，對本發明的實施形態進行說明。 Hereinafter, embodiments of the present invention will be described.

〔第1實施形態之附有黏著劑層之光學薄膜〕 [Optical film with adhesive layer according to the first embodiment]

如圖1所示，本發明的第1實施形態之附有黏著劑層之光學薄膜1A構成為具備：第1相位差板11；積層於第1相位差板11的一面(圖1中為下面)之第1黏著劑層21；積層於第1相位差板11之與第1黏著劑層21側的面相反的一面側(圖1中為上面側)之第2黏著劑層22；及積層於第2黏著劑層22之與第1相位差板11側的面相反的一面側(圖1中為上面側)之第2相位差板12。上述第1相位差板11之與第1黏著劑層21相接的面由丙烯酸系樹脂構成。並且，構成上述第1黏著劑層21之黏著劑的凝膠分率為55~90%，上述第1黏著劑層21的85℃下之儲存彈性模數(G’)為0.03~0.25MPa。另外，構成上述第2黏著劑層22之黏著劑的凝膠分率為80~100%，上述第2黏著劑層22的85℃下之儲存彈性模數(G’)為0.15~3.00MPa。 As shown in FIG. 1, the optical film 1A with an adhesive layer according to the first embodiment of the present invention is configured to include: a first retardation plate 11; and a layer deposited on one side of the first retardation plate 11 (in FIG. 1 is the following ) Of the first adhesive layer 21; the second adhesive layer 22 laminated on the side (the upper side in FIG. 1) of the first phase difference plate 11 opposite to the surface of the first adhesive layer 21; The second retardation plate 12 is on the side of the second adhesive layer 22 opposite to the surface on the first retardation plate 11 side (the upper side in FIG. 1 ). The surface of the first phase difference plate 11 that is in contact with the first adhesive layer 21 is made of acrylic resin. In addition, the gel fraction of the adhesive constituting the first adhesive layer 21 is 55 to 90%, and the storage elastic modulus (G') of the first adhesive layer 21 at 85°C is 0.03 to 0.25 MPa. The gel fraction of the adhesive constituting the second adhesive layer 22 is 80 to 100%, and the storage elastic modulus (G') of the second adhesive layer 22 at 85°C is 0.15 to 3.00 MPa.

關於上述附有黏著劑層之光學薄膜1A，即使在所使用之光學薄膜(第1相位差板11、第2黏著劑層22及第2相位差板12的積層體)與習知產品相比已進行了薄膜化之情況下，亦會在使用於顯示面板時，耐久性優異，在高溫條件下、濕熱條件下或熱衝擊下，亦可抑制翹起或表面剝離的產生。另外，上述顯示面板在高溫條件下亦不易翹曲，還不易產生熱不 均。該效果主要藉由第1黏著劑層21及第2黏著劑層22分別由滿足上述物性之黏著劑構成之條件，以及將由滿足上述物性之黏著劑構成之第1黏著劑層21和、與該第1黏著劑層21相接的面由丙烯酸系樹脂構成之第1相位差板11進行組合來實現。 Regarding the above-mentioned optical film 1A with an adhesive layer, even if the optical film used (the laminated body of the first retardation plate 11, the second adhesive layer 22, and the second retardation plate 12) is compared with conventional products In the case where the film has been thinned, it is also excellent in durability when used in a display panel. It can also suppress the occurrence of warpage or surface peeling under high temperature conditions, humid heat conditions or thermal shock. In addition, the above display panel is not easy to warp under high temperature conditions, and it is not easy to generate heat. all. This effect is mainly due to the condition that the first adhesive layer 21 and the second adhesive layer 22 are respectively composed of an adhesive satisfying the above physical properties, and the first adhesive layer 21 composed of an adhesive satisfying the above physical properties and the The surface where the first adhesive layer 21 contacts is realized by combining the first retardation plate 11 made of acrylic resin.

並且，如上所述，藉由具有第1相位差板11及第2相位差板12，從而在液晶顯示裝置，尤其在IPS(In-Place-Switching)模式液晶顯示裝置中，可發揮優異的視角補償性能。 Moreover, as described above, by having the first retardation plate 11 and the second retardation plate 12, it is possible to exert an excellent viewing angle in a liquid crystal display device, especially in an IPS (In-Place-Switching) mode liquid crystal display device Compensation performance.

構成第1黏著劑層21之黏著劑的凝膠分率如上述為55~90%，較佳為65~85%，特佳為73~78%。上述凝膠分率未滿55%時，所得到之顯示面板的耐久性降低，而超過90%時，在高溫條件下顯示面板容易翹曲，亦容易產生熱不均。 The gel fraction of the adhesive constituting the first adhesive layer 21 is 55 to 90% as described above, preferably 65 to 85%, and particularly preferably 73 to 78%. When the above gel fraction is less than 55%, the durability of the resulting display panel is reduced, and when it exceeds 90%, the display panel is easily warped under high temperature conditions, and thermal unevenness is also likely to occur.

構成第2黏著劑層22之黏著劑的凝膠分率如上述為80~100%，較佳為85~99%，特佳為90~97%。上述凝膠分率未滿80%時，所得到之顯示面板的耐久性容易降低。 The gel fraction of the adhesive constituting the second adhesive layer 22 is 80 to 100% as described above, preferably 85 to 99%, and particularly preferably 90 to 97%. When the gel fraction is less than 80%, the durability of the resulting display panel is likely to be reduced.

在此，黏著劑的凝膠分率的測定方法如後述之試驗例所示。 Here, the method of measuring the gel fraction of the adhesive is as shown in the test example described later.

構成第1黏著劑層21之黏著劑的85℃下之儲存彈性模數(G’)如上述為0.03~0.25MPa，較佳為0.06~0.15MPa，特佳為0.08~0.10MPa。上述儲存彈性模數(G’)未滿0.03MPa時，所得到之顯示面板的耐久性降低，而超過0.25MPa時，在高溫條件下顯示面板容易翹曲，亦容易產生熱不均。 The storage elastic modulus (G') at 85°C of the adhesive constituting the first adhesive layer 21 is 0.03 to 0.25 MPa as described above, preferably 0.06 to 0.15 MPa, and particularly preferably 0.08 to 0.10 MPa. When the storage elastic modulus (G') is less than 0.03 MPa, the durability of the obtained display panel is reduced, and when it exceeds 0.25 MPa, the display panel is likely to warp under high temperature conditions, and thermal unevenness is also likely to occur.

構成第2黏著劑層22之黏著劑的85℃下之儲存彈 性模數(G’)如上述為0.15~3.00MPa，較佳為0.20~1.00MPa，特佳為0.25~0.50MPa。上述儲存彈性模數(G’)未滿0.15MPa時，將第2黏著劑層22進行了薄膜化時的密接性變得不充分，而超過3.00MPa時，第2黏著劑層22的黏著力不足，結果任何情況都容易使耐久性惡化。 The storage bomb at 85°C that constitutes the adhesive of the second adhesive layer 22 As described above, the sexual modulus (G') is 0.15 to 3.00 MPa, preferably 0.20 to 1.00 MPa, and particularly preferably 0.25 to 0.50 MPa. When the storage elastic modulus (G') is less than 0.15 MPa, the adhesiveness when the second adhesive layer 22 is thinned becomes insufficient, and when it exceeds 3.00 MPa, the adhesive force of the second adhesive layer 22 Insufficient, as a result, the durability is easily deteriorated in any case.

在此，黏著劑的儲存彈性模數(G’)的測定方法如後述之試驗例所示。 Here, the method of measuring the storage elastic modulus (G') of the adhesive is as shown in the test example described later.

另外，雖未圖示，但亦可在第1黏著劑層21之與第1相位差板11側相反一側的面(圖1中為下面)上積層剝離片，直至附有黏著劑層之光學薄膜1A被使用。 In addition, although not shown, a release sheet may be laminated on the surface of the first adhesive layer 21 on the side opposite to the first retardation plate 11 side (the lower surface in FIG. 1) until the adhesive layer is attached The optical film 1A is used.

1.第1相位差板 1. The first phase difference plate

第1相位差板11可由表現相位差之單層構成，亦可由包含相位差表現層之複數層構成。第1相位差板11之與第1黏著劑層21相接的面由丙烯酸系樹脂構成。藉由在第1相位差板11的相應部位使用丙烯酸系樹脂，能夠不損失既定的光學性能而進行第1相位差板11的薄膜化。第1相位差板11由單層構成時，該第1相位差板11由丙烯酸系樹脂單層構成。第1相位差板11由複數層構成時，與第1黏著劑層21相接之最外層由經由擠出成形而形成之丙烯酸系樹脂層構成為較佳。該丙烯酸系樹脂與以往公知的黏著劑層密接性較低且耐久性亦較低，但依本實施形態之第1黏著劑層21，即使是對於丙烯酸系樹脂接著力亦高，而且應力緩和性亦優異。因此，在高溫條件下、濕熱條件下、熱衝擊下等，耐久性亦優異。另外，「經由擠出成形而形成之丙烯酸系樹脂層」中亦包含擠出成形之後進 行延伸處理而得到之丙烯酸系樹脂層。 The first phase difference plate 11 may be composed of a single layer expressing the phase difference, or may be composed of a plurality of layers including the phase difference expressing layer. The surface of the first retardation plate 11 that is in contact with the first adhesive layer 21 is made of acrylic resin. By using an acrylic resin in the corresponding part of the first retardation film 11, the first retardation film 11 can be thinned without losing a predetermined optical performance. When the first retardation plate 11 is composed of a single layer, the first retardation plate 11 is composed of a single layer of acrylic resin. When the first retardation plate 11 is composed of a plurality of layers, the outermost layer in contact with the first adhesive layer 21 is preferably composed of an acrylic resin layer formed by extrusion molding. This acrylic resin has a low adhesion and a low durability to the conventionally known adhesive layer, but according to the first adhesive layer 21 of the present embodiment, the adhesive force to the acrylic resin is high, and the stress relaxation property Also excellent. Therefore, the durability is also excellent under high temperature conditions, humid heat conditions, thermal shock, etc. In addition, "acrylic resin layer formed by extrusion molding" also includes The acrylic resin layer obtained by the stretching process.

本實施形態之第1相位差板11係至少具有丙烯酸系樹脂層及相位差表現層者為較佳，尤其如圖2所示，構成為具備以下者為較佳：相位差表現層112；積層於相位差表現層112的一面(圖2中為下側的面)之第1丙烯酸系樹脂層111；及積層於相位差表現層112的另一面(圖2中為上側的面)之第2丙烯酸系樹脂層113。從固有雙折射率為負且容易薄膜化之觀點來看，相位差表現層112由苯乙烯系樹脂構成為較佳。這樣，具有第1相位差板11之附有黏著劑層之光學薄膜1A在液晶顯示裝置，尤其在IPS(In-Place-Switching)模式液晶顯示裝置中視角補償的性能優異，前述第1相位差板11構成為具備：第1丙烯酸系樹脂層111、由苯乙烯系樹脂構成之相位差表現層112及第2丙烯酸系樹脂層113。另外，由於相位差表現層112受到存在於其兩面之第1丙烯酸系樹脂層111及第2丙烯酸系樹脂層113的保護，因此附有黏著劑層之光學薄膜1A無需降低相位差表現層112的性能就可成為機械強度和耐藥品性優異者。 The first phase difference plate 11 of the present embodiment preferably has at least an acrylic resin layer and a phase difference expression layer, and as shown in FIG. 2 in particular, it is preferable to have the following structure: phase difference expression layer 112; build-up The first acrylic resin layer 111 on one side of the phase difference expression layer 112 (the lower side in FIG. 2); and the second on the other side of the phase difference expression layer 112 (the upper side in FIG. 2) Acrylic resin layer 113. From the viewpoint that the intrinsic birefringence is negative and it is easy to make the film thin, it is preferable that the phase difference expression layer 112 is composed of a styrene resin. In this way, the adhesive film-attached optical film 1A having the first phase difference plate 11 is excellent in viewing angle compensation performance in liquid crystal display devices, especially in IPS (In-Place-Switching) mode liquid crystal display devices, and the aforementioned first phase difference The plate 11 is configured to include a first acrylic resin layer 111, a phase difference expression layer 112 made of styrene resin, and a second acrylic resin layer 113. In addition, since the phase difference expression layer 112 is protected by the first acrylic resin layer 111 and the second acrylic resin layer 113 existing on both sides thereof, the optical film 1A with the adhesive layer does not need to reduce the phase difference expression layer 112. Performance can become those with excellent mechanical strength and chemical resistance.

另外，第1相位差板11中，與第1黏著劑層21相接之層為第1丙烯酸系樹脂層111時，第1丙烯酸系樹脂層111對於該第1相位差板11之接著力提高。因此，該附有黏著劑層之光學薄膜1A在高溫條件下、濕熱條件下、熱衝擊下等亦可成為耐久性優異者。 In addition, in the first phase difference plate 11, when the layer that is in contact with the first adhesive layer 21 is the first acrylic resin layer 111, the adhesion of the first acrylic resin layer 111 to the first phase difference plate 11 is improved . Therefore, the optical film 1A with an adhesive layer can also be excellent in durability under high temperature conditions, wet heat conditions, and thermal shock.

而且，第1相位差板11為藉由延伸被賦予面內相位差者為較佳。藉此，成為視角補償性能更加優異者。 Moreover, it is preferable that the first retardation plate 11 is given an in-plane retardation by extension. By this, the viewing angle compensation performance becomes more excellent.

構成相位差表現層112的苯乙烯系樹脂可為苯乙烯或其衍生物的均聚物，亦可為苯乙烯或其衍生物與其他共聚合性單體之二元或二元以上的共聚物。苯乙烯衍生物是指苯乙烯上鍵結有其他的基團之化合物，例如可舉出，如鄰-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、2,4-二甲基苯乙烯、鄰-乙基苯乙烯、對-乙基苯乙烯等烷基苯乙烯、或如羥基苯乙烯、第三丁氧基苯乙烯、乙烯基苯甲酸、鄰-氯苯乙烯、對-氯苯乙烯等苯乙烯的苯核上導入有羥基、烷氧基、羧基、鹵等而成的取代苯乙烯等。 The styrene-based resin constituting the phase difference expression layer 112 may be a homopolymer of styrene or its derivatives, or may be a binary or more binary copolymer of styrene or its derivatives and other copolymerizable monomers . Styrene derivatives refer to compounds with other groups bonded to styrene, for example, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4- Dimethylstyrene, o-ethylstyrene, p-ethylstyrene and other alkylstyrene, or such as hydroxystyrene, third butoxystyrene, vinyl benzoic acid, o-chlorostyrene, Hydroxy, alkoxy, carboxyl, halogen, etc. are introduced into the benzene core of styrene such as p-chlorostyrene.

作為苯乙烯系樹脂亦可使用如日本特開2003-50316號公報或日本特開2003-207640號公報所揭示之三元共聚物。 As the styrene-based resin, a terpolymer as disclosed in Japanese Patent Application Publication No. 2003-50316 or Japanese Patent Application Publication No. 2003-207640 can also be used.

構成相位差表現層112的苯乙烯系樹脂為苯乙烯或苯乙烯衍生物與選自丙烯腈、馬來酸酐、甲基丙烯酸甲酯以及丁二烯中之至少一種單體的共聚物為較佳。 The styrene-based resin constituting the phase difference expression layer 112 is preferably a copolymer of styrene or a styrene derivative and at least one monomer selected from acrylonitrile, maleic anhydride, methyl methacrylate, and butadiene. .

另外，作為構成相位差表現層112的苯乙烯系樹脂，具有耐熱性的苯乙烯系樹脂為較佳。苯乙烯系樹脂的玻璃轉移溫度(Tg)一般為100℃以上，但玻璃轉移溫度(Tg)為120℃以上的苯乙烯系樹脂為較佳。 In addition, as the styrene-based resin constituting the phase difference expression layer 112, a styrene-based resin having heat resistance is preferable. The glass transition temperature (Tg) of the styrene-based resin is generally 100°C or higher, but a styrene resin having a glass transition temperature (Tg) of 120°C or higher is preferred.

相位差表現層112的厚度為10~100μm為較佳。藉由使相位差表現層112的厚度為10μm以上，可藉由延伸表現充分的延遲值。另一方面，相位差表現層112的厚度為100μm以下時，衝擊強度高，另外，基於外部應力之延遲變化小，適用於液晶顯示裝置時，很難產生熱不均等。 The thickness of the phase difference expression layer 112 is preferably 10 to 100 μm. By setting the thickness of the phase difference expression layer 112 to 10 μm or more, a sufficient retardation value can be expressed by extension. On the other hand, when the thickness of the phase difference expression layer 112 is 100 μm or less, the impact strength is high, and the change in delay due to external stress is small, and when applied to a liquid crystal display device, it is difficult to cause thermal unevenness.

第1丙烯酸系樹脂層111以及第2丙烯酸系樹脂層113由在(甲基)丙烯酸系樹脂中配合橡膠粒子之(甲基)丙烯酸系樹脂組成物構成為較佳。藉由配合橡膠粒子，可提高丙烯酸系樹脂層的耐衝擊性。 The first acrylic resin layer 111 and the second acrylic resin layer 113 are preferably composed of a (meth)acrylic resin composition in which rubber particles are mixed with a (meth)acrylic resin. By blending rubber particles, the impact resistance of the acrylic resin layer can be improved.

作為(甲基)丙烯酸系樹脂，例如可舉出甲基丙烯酸烷基酯或丙烯酸烷基酯之均聚物、或甲基丙烯酸烷基酯與丙烯酸烷基酯之共聚物等。作為甲基丙烯酸烷基酯，可舉出甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯等。另外，作為丙烯酸烷基酯，可舉出丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯等。這樣的(甲基)丙烯酸系樹脂，可使用作為泛用之(甲基)丙烯酸系樹脂而市售者。而且，(甲基)丙烯酸系樹脂中亦包含：被稱為耐衝擊(甲基)丙烯酸系樹脂者、或主鏈中具有戊二酸酐結構或內酯環結構之被稱為高耐熱(甲基)丙烯酸系樹脂者。 Examples of (meth)acrylic resins include homopolymers of alkyl methacrylates or alkyl acrylates, and copolymers of alkyl methacrylates and alkyl acrylates. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, and propyl methacrylate. In addition, examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, and propyl acrylate. Such (meth)acrylic resins can be used as commercially available (meth)acrylic resins. In addition, (meth)acrylic resins include those called impact-resistant (meth)acrylic resins, or those with glutaric anhydride structure or lactone ring structure in the main chain are called high heat resistance (methyl ) Acrylic resin.

配合在(甲基)丙烯酸系樹脂中之橡膠粒子為丙烯酸系者為較佳。丙烯酸系橡膠粒子是指，以如丙烯酸丁酯或丙烯酸2-乙基己酯等丙烯酸烷基酯為主成分，且在多官能單體的存在下進行聚合而得到的具有橡膠彈性的粒子。 The rubber particles blended in the (meth)acrylic resin are preferably acrylic. Acrylic rubber particles refer to particles having rubber elasticity obtained by polymerizing in the presence of a polyfunctional monomer mainly composed of an alkyl acrylate such as butyl acrylate or 2-ethylhexyl acrylate.

橡膠粒子可為將具有橡膠彈性之材料製成均質的粒子狀而成者，亦可為具有至少一層橡膠彈性層的多層結構體。作為多層結構之丙烯酸系橡膠粒子，可舉出：將如上述具有橡膠彈性之粒子作為核，並將其周圍用硬質的甲基丙烯酸烷基酯系聚合物覆蓋者；將硬質的甲基丙烯酸烷基酯系聚合物作為核，並將其周圍用如上述具有橡膠彈性之丙烯酸系聚合物覆 蓋者；又，將硬質的核的周圍用具有橡膠彈性之丙烯酸系聚合物覆蓋，且進一步將其周圍用硬質的甲基丙烯酸烷基酯系聚合物覆蓋者等。 The rubber particles may be made of a material having rubber elasticity into homogeneous particles, or may be a multilayer structure having at least one rubber elastic layer. Examples of the acrylic rubber particles with a multi-layer structure include those having rubber elasticity as described above as the core, and the periphery thereof is covered with a hard alkyl methacrylate polymer; and the hard alkyl methacrylate The ester-based polymer is used as the core, and its periphery is covered with an acrylic polymer having rubber elasticity as described above In addition, the periphery of the hard core is covered with an acrylic polymer having rubber elasticity, and the periphery is further covered with a hard alkyl methacrylate polymer.

橡膠粒子的平均直徑為50~400nm左右為較佳。橡膠粒子的平均直徑可藉由雷射繞射散射法進行測定。 The average diameter of the rubber particles is preferably about 50 to 400 nm. The average diameter of the rubber particles can be measured by laser diffraction scattering method.

構成第1丙烯酸系樹脂層111以及第2丙烯酸系樹脂層113之(甲基)丙烯酸系樹脂組成物中上述橡膠粒子的含量係在每100質量份(甲基)丙烯酸系樹脂中，為5~50質量份左右為較佳。 The content of the rubber particles in the (meth)acrylic resin composition constituting the first acrylic resin layer 111 and the second acrylic resin layer 113 is 5 to 100 parts by mass of (meth)acrylic resin. About 50 parts by mass is preferred.

作為構成第1丙烯酸系樹脂層111以及第2丙烯酸系樹脂層113之(甲基)丙烯酸系樹脂組成物，可使用以(甲基)丙烯酸系樹脂與丙烯酸系橡膠粒子混合之狀態市售者。作為配合有丙烯酸系橡膠粒子的(甲基)丙烯酸系樹脂((甲基)丙烯酸系樹脂組成物)的市售品的例子，分別以商品名可舉出：Sumitomo Chemical Co.,Ltd.所販售之“HT55X”或“TechnolloyS001”等。 As the (meth)acrylic resin composition constituting the first acrylic resin layer 111 and the second acrylic resin layer 113, a commercially available product in a state in which the (meth)acrylic resin and the acrylic rubber particles are mixed can be used. As examples of commercially available products of (meth)acrylic resin ((meth)acrylic resin composition) blended with acrylic rubber particles, trade names include: Sumitomo Chemical Co., Ltd. Sold "HT55X" or "TechnolloyS001" and so on.

(甲基)丙烯酸系樹脂組成物的玻璃轉移溫度(Tg)一般為160℃以下，但玻璃轉移溫度(Tg)為120℃以下的(甲基)丙烯酸系樹脂組成物為較佳，特佳為110℃以下的(甲基)丙烯酸系樹脂組成物。亦即，相位差表現層112的玻璃轉移溫度(Tg)與第1丙烯酸系樹脂111以及第2丙烯酸系樹脂層113的玻璃轉移溫度(Tg)不重疊為較佳，相位差表現層112具有比第1丙烯酸系樹脂層111以及第2丙烯酸系樹脂層113更高的玻璃轉移溫度(Tg)為較佳。 The glass transition temperature (Tg) of the (meth)acrylic resin composition is generally 160°C or lower, but the (meth)acrylic resin composition having a glass transition temperature (Tg) of 120°C or lower is preferred, and particularly preferred is (Meth)acrylic resin composition below 110°C. That is, it is preferable that the glass transition temperature (Tg) of the phase difference expression layer 112 and the glass transition temperature (Tg) of the first acrylic resin 111 and the second acrylic resin layer 113 do not overlap, and the phase difference expression layer 112 has a ratio It is preferable that the first acrylic resin layer 111 and the second acrylic resin layer 113 have a higher glass transition temperature (Tg).

第1丙烯酸系樹脂層111與第2丙烯酸系樹脂層113的材料可相同，亦可不同。 The materials of the first acrylic resin layer 111 and the second acrylic resin layer 113 may be the same or different.

第1丙烯酸系樹脂層111以及第2丙烯酸系樹脂層113的厚度分別為10~100μm為較佳。若厚度為10μm以上，則能夠容易地進行製膜，若厚度為100μm以下，則可以忽略第1丙烯酸系樹脂層111以及第2丙烯酸系樹脂層113的延遲。另外，第1丙烯酸系樹脂層111的厚度與第2丙烯酸系樹脂層113的厚度係大致相同為較佳。 The thicknesses of the first acrylic resin layer 111 and the second acrylic resin layer 113 are preferably 10 to 100 μm, respectively. If the thickness is 10 μm or more, film formation can be easily performed, and if the thickness is 100 μm or less, the retardation of the first acrylic resin layer 111 and the second acrylic resin layer 113 can be ignored. In addition, it is preferable that the thickness of the first acrylic resin layer 111 is substantially the same as the thickness of the second acrylic resin layer 113.

於第1相位差板11之第2黏著劑層22側的面，亦可實施電暈處理等表面處理。 The surface of the first retardation film 11 on the second adhesive layer 22 side may be subjected to surface treatment such as corona treatment.

製造第1相位差板11時，例如將苯乙烯系樹脂和配合有橡膠粒子之(甲基)丙烯酸系樹脂組成物共擠出之後進行延伸即可。可藉由縱向單軸延伸、拉幅機橫向單軸延伸、同時雙軸延伸或逐次雙軸延伸等進行延伸，只要延伸至能夠得到所希望的延遲值即可。除了上述方法之外，亦可在分別製作單層薄膜(相位差表現層112、第1丙烯酸系樹脂層111以及第2丙烯酸系樹脂層113)之後，藉由熱層壓使該等熱熔接後，將其積層體延伸。 When manufacturing the first retardation film 11, for example, the styrene-based resin and the (meth)acrylic resin composition blended with rubber particles may be coextruded and then stretched. It can be extended by longitudinal uniaxial extension, tenter horizontal uniaxial extension, simultaneous biaxial extension or successive biaxial extension, etc., as long as the extension can be obtained to a desired retardation value. In addition to the above method, after the single-layer films (the phase difference expression layer 112, the first acrylic resin layer 111, and the second acrylic resin layer 113) are separately formed, these thermal fusion bonds may be performed by thermal lamination To extend its laminate.

另外，延伸後的第1相位差板11的總厚度，從維持充分的性能且應對行動通訊用途中的薄型化要求的觀點來看，係5~100μm為較佳，10~50μm為更佳，15~30μm為特佳。 In addition, the total thickness of the first retardation film 11 after extension is preferably 5 to 100 μm, and more preferably 10 to 50 μm from the viewpoint of maintaining sufficient performance and meeting the thinning requirements in mobile communication applications. 15~30μm is particularly good.

2.第1黏著劑層 2. The first adhesive layer

第1黏著劑層21只要由具有前述物性之黏著劑構成即可， 較佳為由丙烯酸系黏著劑構成，特佳為由從黏著性組成物(以下有時稱「黏著性組成物P」。)得到之黏著劑構成，前述黏著性組成物含有：含有含脂環式結構單體(a1)及含芳香環單體(a2)作為構成聚合物之單體單元的(甲基)丙烯酸酯共聚物(A)；以及交聯劑(B)。另外，在本說明書中，(甲基)丙烯酸酯表示丙烯酸酯及甲基丙烯酸酯這兩者。其他類似術語亦相同。 The first adhesive layer 21 only needs to be composed of an adhesive having the aforementioned physical properties, It is preferably composed of an acrylic adhesive, and particularly preferably composed of an adhesive obtained from an adhesive composition (hereinafter sometimes referred to as "adhesive composition P"). The foregoing adhesive composition contains: contains an alicyclic ring The (meth)acrylate copolymer (A) in which the structural monomer (a1) and the aromatic ring-containing monomer (a2) are monomer units constituting the polymer; and the crosslinking agent (B). In addition, in this specification, (meth)acrylate means both acrylate and methacrylate. Other similar terms are also the same.

藉由含有該含脂環式結構單體(a1)以及含芳香環單體(a2)所得到的黏著劑能夠兼備適當的內聚力與應力緩和性，並且對於光學薄膜或透明導電膜之密接性提高，因此，當使用於顯示面板時，能夠發揮優異的耐久性、翹曲抑制性以及耐熱不均勻性。 The adhesive obtained by containing the alicyclic structure-containing monomer (a1) and the aromatic ring-containing monomer (a2) can have appropriate cohesion and stress relaxation, and improve the adhesion of the optical film or transparent conductive film Therefore, when used in a display panel, it can exhibit excellent durability, warpage suppression properties, and heat resistance unevenness.

(1)(甲基)丙烯酸酯共聚物(A) (1) (Meth)acrylate copolymer (A)

(甲基)丙烯酸酯共聚物(A)，除了上述的含脂環式結構單體(a1)以及含芳香環單體(a2)之外，還含有含羥基單體(a3)作為構成該共聚物的單體單元為較佳，進而含有烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯為特佳。另外，亦可根據需要含有其他單體。 The (meth)acrylate copolymer (A), in addition to the above-mentioned alicyclic structure-containing monomer (a1) and aromatic ring-containing monomer (a2), also contains a hydroxyl-containing monomer (a3) as a constituent of the copolymerization The monomer unit of the compound is preferable, and the alkyl (meth)acrylate having 1 to 20 carbon atoms containing an alkyl group is particularly preferable. In addition, other monomers may be contained as needed.

在此，(甲基)丙烯酸酯共聚物(A)的羥值為5~20mgKOH/g為較佳，特佳為8~18mgKOH/g，進一步較佳為10~16mgKOH/g。(甲基)丙烯酸酯共聚物(A)的羥值為5mgKOH/g以上時，能夠確保交聯點而維持較高的內聚力，容易將所得到之黏著劑的儲存彈性模數及凝膠分率設計於前述下限值以上的範圍內。另外，(甲基)丙烯酸酯共聚物(A)的 羥值為20mgKOH/g以下時，可防止交聯點變得過多，所得到之黏著劑成為柔軟者，容易將儲存彈性模數及凝膠分率設計於前述上限值以下的範圍內。 Here, the (meth)acrylate copolymer (A) has a hydroxyl value of preferably 5 to 20 mgKOH/g, particularly preferably 8 to 18 mgKOH/g, and further preferably 10 to 16 mgKOH/g. When the (meth)acrylate copolymer (A) has a hydroxyl value of 5 mgKOH/g or more, it can ensure the crosslinking point and maintain a high cohesive force, and it is easy to adjust the storage elastic modulus and gel fraction of the obtained adhesive The design is within the range above the aforementioned lower limit. In addition, (meth)acrylate copolymer (A) When the hydroxyl value is 20 mgKOH/g or less, it is possible to prevent the crosslinking point from becoming excessive, and the obtained adhesive to become soft, and it is easy to design the storage elastic modulus and gel fraction within the range below the upper limit.

另外，(甲基)丙烯酸酯共聚物(A)的酸值為5mgKOH/g以下為較佳，特佳為2mgKOH/g以下，進一步較佳為1mgKOH/g以下。(甲基)丙烯酸酯共聚物(A)的酸值為5mgKOH/g以下時，即使黏著劑的貼附對象是因酸而會產生不良狀況者，例如為錫摻雜氧化銦(ITO)等透明導電膜或金屬膜等時，亦能夠抑制因酸產生之該等的不良狀況。尤其，當貼附對象為透明導電膜時，能夠抑制該透明導電膜的腐蝕或該透明導電膜的電阻值的改變。另外，由於(甲基)丙烯酸酯共聚物(A)的酸值的下限值越小越佳，係0mgKOH/g為特佳。 In addition, the acid value of the (meth)acrylate copolymer (A) is preferably 5 mgKOH/g or less, particularly preferably 2 mgKOH/g or less, and still more preferably 1 mgKOH/g or less. When the acid value of the (meth)acrylate copolymer (A) is 5 mgKOH/g or less, even if the adhesive is applied to an object that will cause defects due to acid, such as tin-doped indium oxide (ITO) and other transparent In the case of a conductive film, a metal film, etc., it is also possible to suppress such defects caused by acid. In particular, when the object to be attached is a transparent conductive film, the corrosion of the transparent conductive film or the change in the resistance value of the transparent conductive film can be suppressed. In addition, the smaller the lower limit value of the acid value of the (meth)acrylate copolymer (A), the better, and the range of 0 mgKOH/g is particularly preferable.

在此，本說明書中之羥值及酸值基本上設為從(甲基)丙烯酸酯共聚物(A)的配合比例導出之理論值，當無法導出該理論值時，設為基於JIS K0070測定的值。 Here, the hydroxyl value and the acid value in this specification are basically set to the theoretical value derived from the blending ratio of the (meth)acrylate copolymer (A). When the theoretical value cannot be derived, the measurement is based on JIS K0070. Value.

(甲基)丙烯酸酯共聚物(A)含有烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯作為構成該共聚物的單體單元，藉此能夠表現較佳的黏著性。作為烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，例如可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十八烷基酯等。 其中，從進一步提高黏著性的觀點來看，烷基的碳原子數為1~8的(甲基)丙烯酸酯為較佳，(甲基)丙烯酸正丁酯或(甲基)丙烯酸2-乙基己酯為特佳，並且能够提升所得到之(甲基)丙烯酸酯共聚物(A)的玻璃轉移溫度(Tg)的觀點來看，(甲基)丙烯酸正丁酯為特佳。另外，該等可以單獨使用，亦可以組合兩種以上使用。 The (meth)acrylate copolymer (A) contains an alkyl (meth)acrylate having 1 to 20 carbon atoms as the monomer unit constituting the copolymer, thereby showing better adhesion . Examples of the alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, ( N-butyl meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (meth) N-decyl acrylate, n-dodecyl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, octadecyl (meth)acrylate, etc. . Among them, from the viewpoint of further improving adhesion, (meth)acrylates having 1 to 8 carbon atoms in the alkyl group are preferred, and n-butyl (meth)acrylate or 2-ethyl (meth)acrylate Hexyl hexyl ester is particularly preferred, and n-butyl (meth)acrylate is particularly preferred from the viewpoint that the glass transition temperature (Tg) of the obtained (meth)acrylate copolymer (A) can be increased. In addition, these can be used alone or in combination of two or more.

(甲基)丙烯酸酯共聚物(A)以含有40~97.5質量%之烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯作為構成該共聚物的單體單元為較佳，特佳為含有55~94質量%，進一步較佳為含有65~83質量%。若含有40質量%以上的(甲基)丙烯酸烷基酯，則能夠賦予(甲基)丙烯酸酯共聚物(A)適宜的黏著性。另外，藉由將(甲基)丙烯酸烷基酯設為97.5質量%以下，能夠對(甲基)丙烯酸酯共聚物(A)中導入所需量的其他單體成分。 (Meth) acrylate copolymer (A) It is preferable to use a (meth)acrylate alkyl ester having 1 to 20 carbon atoms containing 40 to 97.5% by mass of an alkyl group as the monomer unit constituting the copolymer In particular, it is preferably 55 to 94% by mass, more preferably 65 to 83% by mass. If 40% by mass or more of (meth)acrylic acid alkyl ester is contained, (meth)acrylic acid ester copolymer (A) can be given suitable adhesiveness. In addition, by setting the alkyl (meth)acrylate to 97.5% by mass or less, it is possible to introduce a required amount of other monomer components into the (meth)acrylate copolymer (A).

含脂環式結構單體(a1)之脂環式結構的碳環可以是飽和結構者，亦可以是局部具有不飽和鍵者。另外，脂環式結構可以是單環的脂環式結構，亦可以是二環、三環等多環的脂環式結構。從將所得到之(甲基)丙烯酸酯共聚物(A)的相互之間的距離設為適當，並賦予黏著劑應力緩和性，並且藉由提升所得到之(甲基)丙烯酸酯共聚物(A)的玻璃轉移溫度(Tg)來提高與丙烯酸系樹脂的密接性的觀點來看，上述脂環式結構為多環的脂環式結構(多環結構)為較佳。進一步考慮到(甲基)丙烯酸酯共聚物(A)與其他成分的相容性，則上述多環結構為二環至四環為特佳。另外，從與上述相同地 賦予應力緩和性，並且提升所得到之(甲基)丙烯酸酯共聚物(A)的玻璃轉移溫度(Tg)的觀點來看，脂環式結構的碳原子數(是指形成環之部分的所有碳原子數，複數個環獨立存在時，指其合計的碳原子數)通常為5以上為較佳，7以上為特佳。另一方面，脂環式結構的碳原子數的上限並沒有特別限制，但與上述相同地，從相容性的觀點來看，15以下為較佳，10以下為特佳。 The carbocyclic ring of the alicyclic structure containing the alicyclic structure monomer (a1) may be a saturated structure or a partially unsaturated bond. In addition, the alicyclic structure may be a monocyclic alicyclic structure or a polycyclic alicyclic structure such as bicyclic and tricyclic. The distance between each of the obtained (meth)acrylate copolymers (A) is set as appropriate, and the adhesive is given stress relaxation, and by improving the obtained (meth)acrylate copolymer ( A) The glass transition temperature (Tg) improves the adhesiveness with an acrylic resin, and the alicyclic structure is preferably a polycyclic alicyclic structure (polycyclic structure). Further considering the compatibility of the (meth)acrylate copolymer (A) with other components, it is particularly preferable that the above polycyclic structure is bicyclic to tetracyclic. In addition, from the same as above From the viewpoint of imparting stress relaxation and increasing the glass transition temperature (Tg) of the obtained (meth)acrylate copolymer (A), the number of carbon atoms in the alicyclic structure (refers to all The number of carbon atoms, when a plurality of rings independently exist, refers to the total number of carbon atoms) is usually 5 or more, preferably 7 or more. On the other hand, the upper limit of the number of carbon atoms in the alicyclic structure is not particularly limited, but as described above, from the viewpoint of compatibility, 15 or less is preferable, and 10 or less is particularly preferable.

作為脂環式結構，例如可舉出包含如下骨架者，環己基骨架、二環戊二烯骨架、金剛烷骨架、異冰片骨架、環烷骨架(環庚烷骨架、環辛烷骨架、環壬烷骨架、環癸烷骨架、環十一烷骨架、環十二烷骨架等)、環烯骨架(環庚烯骨架、環辛烯骨架等)、降冰片烯骨架、降冰片二烯骨架、立方烷骨架、籃烷骨架、房烷骨架、螺環骨架等，其中，包含可發揮更加優異的耐久性之二環戊二烯骨架(脂環式結構的碳原子數：10)、金剛烷骨架(脂環式結構的碳原子數：10)或異冰片骨架(脂環式結構的碳原子數：7)者為較佳，特佳為包含異冰片骨架者。 Examples of the alicyclic structure include those containing the following skeletons, cyclohexyl skeleton, dicyclopentadiene skeleton, adamantane skeleton, isobornyl skeleton, naphthene skeleton (cycloheptane skeleton, cyclooctane skeleton, cyclonon Alkane skeleton, cyclodecane skeleton, cycloundecane skeleton, cyclododecane skeleton, etc.), cycloene skeleton (cycloheptene skeleton, cyclooctene skeleton, etc.), norbornene skeleton, norbornene diene skeleton, cubic The alkane skeleton, basket skeleton, aorane skeleton, spiro ring skeleton, etc., including dicyclopentadiene skeleton (alicyclic structure carbon number: 10) and adamantane skeleton ( The number of carbon atoms of the alicyclic structure: 10) or the isobornyl skeleton (number of carbon atoms of the alicyclic structure: 7) is preferred, and those containing an isobornyl skeleton are particularly preferred.

作為上述含脂環式結構單體(a1)，包含上述骨架之(甲基)丙烯酸酯單體為較佳，具體而言，可舉出(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯等，其中，可發揮比較優異的耐久性之(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷酯或(甲基)丙烯酸異冰片酯為較佳，特佳為(甲基)丙烯酸 異冰片酯，該等可以單獨使用，亦可以組合兩種以上使用。 As the above alicyclic structure-containing monomer (a1), (meth)acrylate monomers containing the above skeleton are preferred, and specific examples thereof include cyclohexyl (meth)acrylate and (meth)acrylic acid. Dicyclopentyl ester, adamantyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc., of which , Dicyclopentyl (meth) acrylate, adamantyl (meth) acrylate or isobornyl (meth) acrylate, which can exert relatively excellent durability, is preferably (meth) acrylic acid Isobornyl esters can be used alone or in combination of two or more.

從所得到的黏著劑發揮優異的耐久性、翹曲抑制性以及耐熱不均勻性的觀點來看，(甲基)丙烯酸酯共聚物(A)以含有1~20質量%的含脂環式結構單體(a1)作為構成該共聚物的單體單元為較佳。除上述觀點之外，還從所得到的黏著劑發揮良好的再處理性的觀點來看，尤其是含有2~15質量%的含脂環式結構單體(a1)為更佳，含有3~9質量%為特佳。 The (meth)acrylate copolymer (A) contains an alicyclic structure containing 1 to 20% by mass from the viewpoint of the obtained adhesive exhibiting excellent durability, warpage suppression properties, and heat resistance unevenness. The monomer (a1) is preferred as a monomer unit constituting the copolymer. In addition to the above points, from the viewpoint that the obtained adhesive exhibits good reprocessing properties, it is particularly preferable to contain 2 to 15% by mass of the alicyclic structure-containing monomer (a1), and to contain 3 to 9% by mass is particularly good.

作為含芳香環單體(a2)，具有芳香環之(甲基)丙烯酸酯為較佳。作為芳香環，可以舉出苯環、萘環、蒽環、聯苯環、茀環等，其中苯環為較佳。 The aromatic ring-containing monomer (a2) is preferably a (meth)acrylate having an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring, and a stilbene ring. Among them, a benzene ring is preferred.

作為含芳香環單體(a2)，例如可舉出(甲基)丙烯酸苯酯、(甲基)丙烯酸2-苯基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基丁酯、乙氧基化鄰苯基苯酚丙烯酸酯、苯氧基二乙二醇(甲基)丙烯酸酯、環氧乙烷改質甲酚(甲基)丙烯酸酯、環氧乙烷(EO)改質壬基苯酚(甲基)丙烯酸酯等，其中，從提高內聚力的觀點來看，(甲基)丙烯酸2-苯基乙基為較佳。該等可以單獨使用，亦可以組合兩種以上使用。 Examples of the aromatic ring-containing monomer (a2) include phenyl (meth)acrylate, 2-phenylethyl (meth)acrylate, benzyl (meth)acrylate, naphthyl (meth)acrylate, Phenoxyethyl (meth)acrylate, phenoxybutyl (meth)acrylate, ethoxylated o-phenylphenol acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide Alkane-modified cresol (meth)acrylate, ethylene oxide (EO)-modified nonylphenol (meth)acrylate, etc. Among them, from the viewpoint of improving cohesion, 2-(meth)acrylic acid 2-benzene Ethyl ethyl is preferred. These can be used alone or in combination of two or more.

(甲基)丙烯酸酯共聚物(A)以含有1~30質量%的含芳香環單體(a2)作為構成該共聚物的單體單元為較佳，特佳為含有3~25質量%，進一步較佳為含有12~22質量%。藉由將含芳香環單體(a2)的含量設在上述範圍內、能夠使所得到的黏著劑發揮優異的耐久性、翹曲抑制性以及耐熱不均勻性。 The (meth)acrylate copolymer (A) preferably contains 1 to 30% by mass of an aromatic ring-containing monomer (a2) as a monomer unit constituting the copolymer, and particularly preferably contains 3 to 25% by mass. It is more preferably 12 to 22% by mass. By setting the content of the aromatic ring-containing monomer (a2) within the above range, the resulting adhesive can exhibit excellent durability, warpage suppression properties, and heat resistance unevenness.

(甲基)丙烯酸酯共聚物(A)中含有含羥基單體(a3)作為構成該共聚物之單體單元為較佳。羥基顯示出與交聯劑(B)的良好的反應性，藉由它們的反應，(甲基)丙烯酸酯共聚物(A)藉由交聯劑(B)交聯。由於該交聯結構，所得到之黏著劑容易滿足前述儲存彈性模數及凝膠分率。 It is preferable that the (meth)acrylate copolymer (A) contains a hydroxyl group-containing monomer (a3) as a monomer unit constituting the copolymer. The hydroxyl group shows good reactivity with the crosslinking agent (B), and by their reaction, the (meth)acrylate copolymer (A) is crosslinked by the crosslinking agent (B). Due to the cross-linked structure, the obtained adhesive easily satisfies the aforementioned storage elastic modulus and gel fraction.

作為含羥基單體(a3)，例如可舉出(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯等，其中，從與交聯劑(B)的反應性的觀點來看，(甲基)丙烯酸2-羥基乙酯或(甲基)丙烯酸4-羥基丁酯為較佳，特佳為(甲基)丙烯酸2-羥基乙酯。該等可以單獨使用，亦可以組合兩種以上使用。 Examples of the hydroxyl group-containing monomer (a3) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (methyl) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxyalkyl (meth)acrylate, etc. From the viewpoint of reactivity, 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate is preferred, and 2-hydroxyethyl (meth)acrylate is particularly preferred. These can be used alone or in combination of two or more.

(甲基)丙烯酸酯共聚物(A)以含有0.5~10質量%的含羥基單體(a3)作為構成該共聚物的單體單元為較佳，特佳為含有1~5質量%，進一步較佳為含有2~4質量%。藉由將含羥基單體(a3)的含量設在上述範圍內，能夠容易使(甲基)丙烯酸酯共聚物(A)的羥值落入前述範圍內，並容易滿足前述儲存彈性模數及凝膠分率。 The (meth)acrylate copolymer (A) preferably contains 0.5 to 10% by mass of a hydroxyl group-containing monomer (a3) as a monomer unit constituting the copolymer, and particularly preferably contains 1 to 5% by mass, further Preferably, it contains 2 to 4% by mass. By setting the content of the hydroxyl group-containing monomer (a3) within the above range, the hydroxyl value of the (meth)acrylate copolymer (A) can easily fall within the aforementioned range, and it is easy to satisfy the aforementioned storage elastic modulus and Gel fraction.

為了使酸值在前述範圍內，(甲基)丙烯酸酯共聚物(A)中以不含有含羧基單體作為構成該共聚物的單體單元為較佳，即使含有含羧基單體，亦含有0.5質量%以下的含量為較佳，特佳為含有0.1質量%以下的含量。 In order to make the acid value within the aforementioned range, it is preferable that the (meth)acrylate copolymer (A) does not contain a carboxyl group-containing monomer as a monomer unit constituting the copolymer, even if it contains a carboxyl group-containing monomer, The content of 0.5 mass% or less is preferable, and the content of 0.1 mass% or less is particularly preferable.

(甲基)丙烯酸酯共聚物(A)亦可含有前述單體 以外的其他單體作為構成該共聚物的單體單元。為了不妨礙上述含羥基單體(a3)的羥基與交聯劑(B)的反應，以不含有與交聯劑(B)具有反應性之官能基的單體作為該其他單體為較佳。 (Meth)acrylate copolymer (A) may also contain the aforementioned monomers Other monomers than these are used as monomer units constituting the copolymer. In order not to hinder the reaction of the hydroxyl group of the above-mentioned hydroxyl group-containing monomer (a3) with the cross-linking agent (B), it is preferable to use a monomer that does not contain a functional group reactive with the cross-linking agent (B) as the other monomer .

作為該其他單體，例如可舉出：(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯；丙烯醯胺、甲基丙烯醯胺等非交聯性的丙烯醯胺；(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基丙酯等具有非交聯性3級胺基的(甲基)丙烯酸酯；乙酸乙烯酯等。該等可以單獨使用，亦可以組合兩種以上使用。 Examples of such other monomers include methoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; acrylamide and methyl Non-crosslinkable acrylamide such as acrylamide; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, etc. Cross-linkable tertiary amine (meth)acrylate; vinyl acetate, etc. These can be used alone or in combination of two or more.

(甲基)丙烯酸酯共聚物(A)的聚合樣態可為無規共聚物，亦可為嵌段共聚物。 The polymerized form of the (meth)acrylate copolymer (A) may be a random copolymer or a block copolymer.

(甲基)丙烯酸酯共聚物(A)的重量平均分子量為130萬~300萬為較佳，特佳為150萬~250萬，進一步較佳為160萬~190萬。(甲基)丙烯酸酯共聚物(A)的重量平均分子量為130萬以上時，容易將所得到之黏著劑的儲存彈性模數及凝膠分率設計為前述下限值以上，並能夠良好地確保耐久性。另外，(甲基)丙烯酸酯共聚物(A)的重量平均分子量為300萬以下時，容易將所得到之黏著劑的儲存彈性模數及凝膠分率設計為前述上限值以下，能夠良好地確保應力緩和性，並能夠有效地發揮翹曲抑制性及耐熱不均勻性。 The weight average molecular weight of the (meth)acrylate copolymer (A) is preferably 1.3 million to 3 million, particularly preferably 1.5 million to 2.5 million, and further preferably 1.6 million to 1.9 million. When the weight average molecular weight of the (meth)acrylate copolymer (A) is 1.3 million or more, it is easy to design the storage elastic modulus and gel fraction of the obtained adhesive to be not less than the above-mentioned lower limit, and to be good Ensure durability. In addition, when the weight average molecular weight of the (meth)acrylate copolymer (A) is 3 million or less, it is easy to design the storage elastic modulus and gel fraction of the obtained adhesive to be below the above upper limit, which can be good To ensure stress relaxation, and can effectively exert warpage suppression and heat resistance unevenness.

在此，本說明書中之重量平均分子量為利用凝膠滲透層析(GPC)法測定的標準聚苯乙烯換算值。 Here, the weight average molecular weight in this specification is the standard polystyrene conversion value measured by the gel permeation chromatography (GPC) method.

(甲基)丙烯酸酯共聚物(A)的聚合樣態可為無規共聚物，亦可為嵌段共聚物。 The polymerized form of the (meth)acrylate copolymer (A) may be a random copolymer or a block copolymer.

黏著性組成物P中，(甲基)丙烯酸酯共聚物(A)可以單獨使用一種，亦可以組合兩種以上使用。另外，黏著性組成物P還可含有如下(甲基)丙烯酸酯聚合物，其中該(甲基)丙烯酸酯聚合物不含有含脂環式結構單體(a1)或含芳香環單體(a2)作為構成單體單元。 In the adhesive composition P, (meth)acrylate copolymer (A) may be used alone or in combination of two or more. In addition, the adhesive composition P may further contain the following (meth)acrylate polymer, wherein the (meth)acrylate polymer does not contain an alicyclic structure-containing monomer (a1) or an aromatic ring-containing monomer (a2 ) As a constituent monomer unit.

(2)交聯劑(B) (2) Crosslinking agent (B)

交聯劑(B)只要是可與(甲基)丙烯酸酯共聚物(A)所具有的官能基發生反應者即可，例如可舉出異氰酸酯系交聯劑、環氧系交聯劑、胺系交聯劑、三聚氰胺系交聯劑、氮丙啶系交聯劑、肼系交聯劑、醛系交聯劑、噁唑啉系交聯劑、金屬烷氧系交聯劑、金屬螯合物系交聯劑、金屬鹽系交聯劑、銨鹽系交聯劑等。 The crosslinking agent (B) may be any one that can react with the functional group of the (meth)acrylate copolymer (A), and examples thereof include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and amines. Based crosslinking agent, melamine based crosslinking agent, aziridine based crosslinking agent, hydrazine based crosslinking agent, aldehyde based crosslinking agent, oxazoline based crosslinking agent, metal alkoxy crosslinking agent, metal chelate Material-based crosslinking agent, metal salt-based crosslinking agent, ammonium salt-based crosslinking agent, etc.

當(甲基)丙烯酸酯共聚物(A)中作為構成該共聚物的單體單元含有含羥基單體(a3)時，使用與來自該含羥基單體(a3)的羥基之反應性優異的異氰酸酯系交聯劑為較佳。而且，交聯劑(B)可以單獨使用一種，亦可以組合兩種以上使用。 When the (meth)acrylate copolymer (A) contains a hydroxyl group-containing monomer (a3) as a monomer unit constituting the copolymer, use of the hydroxyl group-containing monomer (a3) with excellent reactivity Isocyanate-based crosslinking agents are preferred. Moreover, the crosslinking agent (B) may be used alone or in combination of two or more.

異氰酸酯系交聯劑係至少含有聚異氰酸酯化合物者。作為聚異氰酸酯化合物，例如可舉出：甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、亞二甲苯基二異氰酸酯等芳香族聚異氰酸酯；六亞甲基二異氰酸酯等脂肪族聚異氰酸酯；異氟爾酮二異氰酸酯、加氫二苯基甲烷二異氰酸酯等脂環式聚異氰酸 酯，除此之外，還有該等之縮二脲體、異氰脲酸酯體、進一步與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等含低分子活性氫化合物之反應物的加成體(以上有時統稱為「改質體」。)等。該等之中，從所得到的黏著劑的耐久性的觀點來看，具有芳香環的化合物，即芳香族聚異氰酸酯或其改質體為較佳，具有經由有機基(例如，可舉出較佳為亞烷基鏈，可舉出特佳為碳原子數1~4的亞烷基鏈)與芳香環鍵結之異氰酸酯基的聚異氰酸酯或其改質體為特佳。具體而言，亞二甲苯基二異氰酸酯或其改質體為進一步較佳，三羥甲基丙烷改質亞二甲苯基二異氰酸酯為最佳。上述異氰酸酯系交聯劑可以單獨使用一種，亦可以組合兩種以上使用。 The isocyanate-based crosslinking agent contains at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; and isophorone diisocyanate Alicyclic polyisocyanates such as isocyanate and hydrogenated diphenylmethane diisocyanate Esters, in addition to these biuret bodies, isocyanurate bodies, and further with ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. containing low molecular activity Adducts of reactants of hydrogen compounds (sometimes referred to collectively as "modified bodies" above), etc. Among these, from the viewpoint of the durability of the obtained adhesive, a compound having an aromatic ring, that is, an aromatic polyisocyanate or a modified body thereof is preferred, and has an organic group (e.g. An alkylene chain is preferred, and polyisocyanates or modified versions of isocyanate groups in which an alkylene chain having 1 to 4 carbon atoms) and an aromatic ring are particularly preferred are preferred. Specifically, xylylene diisocyanate or its modified body is more preferable, and trimethylolpropane modified xylylene diisocyanate is most preferable. The isocyanate-based crosslinking agent may be used alone or in combination of two or more.

黏著性組成物P中之交聯劑(B)的含量相對於(甲基)丙烯酸酯共聚物(A)100質量份，較佳為0.01~10質量份，特佳為0.05~5質量份，進一步較佳為0.1~0.4質量份。藉由將交聯劑(B)的含量設在上述範圍內，容易將所得到之黏著劑的儲存彈性模數及凝膠分率設計為前述範圍內。 The content of the crosslinking agent (B) in the adhesive composition P is preferably 0.01 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the (meth)acrylate copolymer (A). It is further preferably 0.1 to 0.4 parts by mass. By setting the content of the crosslinking agent (B) within the above range, it is easy to design the storage elastic modulus and gel fraction of the obtained adhesive within the aforementioned range.

(3)矽烷偶合劑(C) (3) Silane coupling agent (C)

黏著性組成物P中，除了上述(甲基)丙烯酸酯共聚物(A)以及交聯劑(B)之外，還含有矽烷偶合劑(C)為較佳，從賦予所得到的黏著劑優異的耐久性的觀點來看，特佳為含有含環氧基矽烷偶合劑(C1)及/或含巰基矽烷偶合劑(C2)，進一步較佳為含有含環氧基矽烷偶合劑(C1)以及含巰基矽烷偶合劑(C2)這兩者。 In the adhesive composition P, it is preferable to contain a silane coupling agent (C) in addition to the (meth)acrylate copolymer (A) and the cross-linking agent (B), and the adhesive obtained is excellent From the viewpoint of durability, it is particularly preferable to contain an epoxy group-containing silane coupling agent (C1) and/or a mercapto group-containing silane coupling agent (C2), and it is more preferable to contain an epoxy group-containing silane coupling agent (C1) and Mercaptosilane-containing coupling agent (C2) both.

作為含環氧基矽烷偶合劑(C1)適宜者係，分子 內具有至少一個環氧基(含環氧基的有機基)及至少一個烷氧基矽烷基之有機矽化合物，並且與黏著劑成分的相容性佳且具有透光性者，例如實質上透明者。 Suitable as an epoxy-containing silane coupling agent (C1), molecular Organosilicon compound with at least one epoxy group (organic group containing epoxy group) and at least one alkoxy silane group, and having good compatibility with adhesive components and having light transmittance, such as substantially transparent By.

作為含環氧基矽烷偶合劑(C1)的具體例，可舉出：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等3-縮水甘油氧基丙基三烷氧基矽烷；3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷等3-縮水甘油氧基丙基烷基二烷氧基矽烷；甲基三(縮水甘油基)矽烷；2-(3,4-環氧基環己基)乙基三甲氧基矽烷、2-(3,4-環氧基環己基)乙基三乙氧基矽烷等2-(3,4-環氧基環己基)乙基三烷氧基矽烷等。其中，從更加提高耐久性的觀點來看，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-縮水甘油氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷為較佳，特佳為3-縮水甘油氧基丙基三甲氧基矽烷。該等可以單獨使用一種，亦可以組合兩種以上使用。 Specific examples of the epoxy group-containing silane coupling agent (C1) include 3-glycidol such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane. Oxypropyltrialkoxysilane; 3-glycidoxypropylmethyl diethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and other 3-glycidoxypropyl groups Alkyldialkoxysilane; methyltri(glycidyl)silane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl) ) 2-(3,4-epoxycyclohexyl) ethyl trialkoxysilane, etc. Among them, from the viewpoint of further improving durability, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldi Ethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferred, and 3-glycidoxypropyltrimethoxysilane is particularly preferred. These can be used alone or in combination of two or more.

作為含巰基矽烷偶合劑(C2)適宜者係，分子內具有至少一個巰基(含巰基的有機基)及至少一個烷氧基矽烷基之有機矽化合物，並且與黏著劑成分的相容性佳且具有透光性者，例如實質上透明者。 Suitable as a mercapto group-containing silane coupling agent (C2), an organosilicon compound having at least one mercapto group (mercapto group-containing organic group) and at least one alkoxysilane group in the molecule, and has good compatibility with the adhesive component and Those with light transmission, such as those that are substantially transparent.

作為含巰基矽烷偶合劑(C2)的具體例，可舉出：3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基二甲氧基甲基矽烷等含巰基低分子型矽烷偶合劑；以及含巰基矽烷化合物(例如3-巰基丙基三甲氧基矽烷、3-巰基丙基 三乙氧基矽烷、3-巰基丙基二甲氧基甲基矽烷等)與含烷基矽烷化合物(例如甲基三乙氧基矽烷、乙基三乙氧基矽烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷等)之共縮合物等含巰基寡聚物型矽烷偶合劑等。其中，從兼顧耐久性與再處理性的觀點來看，含巰基寡聚物型矽烷偶合劑為較佳，特佳為含巰基矽烷化合物與含烷基矽烷化合物之共縮合物，進一步較佳為3-巰基丙基三甲氧基矽烷與甲基三乙氧基矽烷之共縮合物。該等可以單獨使用一種，亦可以組合兩種以上使用。 Specific examples of the mercapto group-containing silane coupling agent (C2) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane Mercapto-containing low molecular silane coupling agent; and mercapto-containing silane compounds (such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Triethoxysilane, 3-mercaptopropyldimethoxymethylsilane, etc.) and alkyl-containing silane compounds (such as methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane , Ethyl trimethoxy silane, etc.) co-condensate, thiol-containing oligomer type silane coupling agent, etc. Among them, from the viewpoint of taking into consideration both durability and reprocessing properties, a mercapto group-containing oligomer-type silane coupling agent is preferred, and particularly preferred is a co-condensate of a mercapto group-containing silane compound and an alkyl group-containing silane compound, further preferably Co-condensate of 3-mercaptopropyltrimethoxysilane and methyltriethoxysilane. These can be used alone or in combination of two or more.

作為矽烷偶合劑(C)，除了上述含環氧基矽烷偶合劑(C1)以及含巰基矽烷偶合劑(C2)之外，還可以根據需要並用例如，丙烯醯系矽烷偶合劑、羥基系矽烷偶合劑、羧基系矽烷偶合劑、胺基系矽烷偶合劑、醯胺基系矽烷偶合劑、異氰酸酯基系矽烷偶合劑等。 As the silane coupling agent (C), in addition to the above-mentioned epoxy group-containing silane coupling agent (C1) and mercapto group-containing silane coupling agent (C2), for example, an acrylic silane coupling agent and a hydroxy silane coupling agent can be used in combination as needed. Mixture, carboxyl-based silane coupling agent, amine-based silane coupling agent, amide-based silane coupling agent, isocyanate-based silane coupling agent, etc.

黏著性組成物P中之矽烷偶合劑(C)的合計含量相對於(甲基)丙烯酸酯共聚物(A)100質量份，較佳為0.01~5質量份，特佳為0.1~2質量份，進一步較佳為0.2~1質量份。 The total content of the silane coupling agent (C) in the adhesive composition P is preferably 0.01 to 5 parts by mass, and particularly preferably 0.1 to 2 parts by mass relative to 100 parts by mass of the (meth)acrylate copolymer (A). It is further preferably 0.2 to 1 part by mass.

另外，黏著性組成物P中之含環氧基矽烷偶合劑(C1)的含量相對於(甲基)丙烯酸酯共聚物(A)100質量份，較佳為0.005~2.5質量份，特佳為0.05~1質量份，進一步較佳為0.1~0.5質量份。另一方面，黏著性組成物P中之含巰基矽烷偶合劑(C2)的含量相對於(甲基)丙烯酸酯共聚物(A)100質量份，較佳為0.005~2.5質量份，特佳為0.05~1質量份，進一步較佳為0.1~0.5質量份。 In addition, the content of the epoxy group-containing silane coupling agent (C1) in the adhesive composition P is preferably 0.005 to 2.5 parts by mass relative to 100 parts by mass of the (meth)acrylate copolymer (A), particularly preferably 0.05 to 1 part by mass, more preferably 0.1 to 0.5 part by mass. On the other hand, the content of the mercapto group-containing silane coupling agent (C2) in the adhesive composition P is preferably 0.005 to 2.5 parts by mass relative to 100 parts by mass of the (meth)acrylate copolymer (A), particularly preferably 0.05 to 1 part by mass, more preferably 0.1 to 0.5 part by mass.

(4)抗靜電劑(D) (4) Antistatic agent (D)

黏著性組成物P進一步含有抗靜電劑(D)為較佳。積層於第1黏著劑層21之光學薄膜(第1相位差板11)或剝離片通常由塑膠材料構成，因此電絕緣性高，如在剝離剝離片時易產生靜電。殘留有這樣產生的靜電的狀態下，將光學薄膜貼合於液晶單元時，液晶分子的配向可能產生紊亂，另外，靜電的存在會引發吸引飛塵或塵垢等問題。因此，藉由黏著性組成物P含有抗靜電劑(D)，所得到的黏著劑(第1黏著劑層21)能夠發揮抗靜電性，從而消除如上述之問題。 It is preferable that the adhesive composition P further contains an antistatic agent (D). The optical film (the first retardation film 11) or the release sheet deposited on the first adhesive layer 21 is usually made of a plastic material, and therefore has high electrical insulation. For example, static electricity is easily generated when the release sheet is peeled off. When the static electricity generated in this way is left, when the optical film is bonded to the liquid crystal cell, the alignment of the liquid crystal molecules may be disturbed. In addition, the presence of static electricity may cause problems such as attracting flying dust or dirt. Therefore, by containing the antistatic agent (D) in the adhesive composition P, the obtained adhesive (the first adhesive layer 21) can exhibit antistatic properties, thereby eliminating the problems described above.

作為抗靜電劑(D)，只要是能夠賦予所得到的黏著劑抗靜電性者即可，例如可舉出離子性化合物、非離子性化合物等，其中，離子性化合物為較佳。離子性化合物在室溫下可以是液體，亦可以是固體，但從即使曝露於耐久條件下亦容易表現出安定的抗靜電性的觀點來看，在室溫下是固體者為較佳。在此，本說明書中之離子性化合物是指，以陽離子與陰離子為主且藉由靜電引力結合之化合物。 The antistatic agent (D) may be any one that can impart antistatic properties to the obtained adhesive, and examples thereof include ionic compounds and nonionic compounds. Among them, ionic compounds are preferred. The ionic compound may be liquid or solid at room temperature, but from the viewpoint of easily exhibiting stable antistatic properties even when exposed to durable conditions, it is preferably solid at room temperature. Here, the ionic compound in this specification refers to a compound mainly composed of cations and anions and bonded by electrostatic attraction.

作為離子性化合物，含氮鎓鹽、含硫鎓鹽、含磷鎓鹽、鹼金屬鹽以及鹼土類金屬鹽為較佳，從所得到的黏著劑的耐久性優異的觀點來看，特佳為含氮鎓鹽。含氮鎓鹽係由含氮雜環陽離子及其抗衡陰離子構成之離子性化合物為較佳，特佳為由含氮雜環陽離子及鹵化磷酸陰離子構成之離子性化合物，進一步較佳為在室溫下是固體且由含氮雜環陽離子及鹵化磷酸陰離子構成之離子性化合物。根據在室溫下是固體且由含氮雜環陽離子及鹵化磷酸陰離子構成之離子性化合物，能夠兼 顧抗靜電性與耐久性。 As the ionic compound, a nitrogen-containing onium salt, a sulfur-containing onium salt, a phosphorus-containing onium salt, an alkali metal salt, and an alkaline earth metal salt are preferred, and from the viewpoint of excellent durability of the obtained adhesive, particularly preferred is Nitrogen-containing onium salts. The nitrogen-containing onium salt is preferably an ionic compound composed of a nitrogen-containing heterocyclic cation and its counter anion, particularly preferably an ionic compound composed of a nitrogen-containing heterocyclic cation and a halogenated phosphate anion, further preferably at room temperature The following are solid ionic compounds composed of nitrogen-containing heterocyclic cations and halogenated phosphate anions. According to ionic compounds that are solid at room temperature and composed of nitrogen-containing heterocyclic cations and halogenated phosphoric acid anions, both Take into account antistatic properties and durability.

作為含氮雜環陽離子的含氮雜環骨架，吡啶環、嘧啶環、咪唑環、吲哚環等為較佳，其中，吡啶環為較佳。另外，作為鹵化磷酸陰離子的鹵素，氟、氯、溴等為較佳，其中，氟為較佳。 As the nitrogen-containing heterocyclic skeleton of the nitrogen-containing heterocyclic cation, a pyridine ring, a pyrimidine ring, an imidazole ring, an indole ring and the like are preferred, and among them, a pyridine ring is preferred. In addition, as the halogen of the halogenated phosphoric acid anion, fluorine, chlorine, bromine and the like are preferred, and among them, fluorine is preferred.

作為上述抗靜電劑(D)的具體例，可舉出N-丁基-4-甲基吡啶鎓六氟磷酸鹽、N-己基-4-甲基吡啶鎓六氟磷酸鹽、N-辛基吡啶鎓六氟磷酸鹽、N-辛基-4-甲基吡啶鎓六氟磷酸鹽、N-十二烷基吡啶鎓六氟磷酸鹽、N-十四烷基吡啶鎓六氟磷酸鹽、N-十六烷基吡啶鎓六氟磷酸鹽、N-十二烷基-4-甲基吡啶鎓六氟磷酸鹽、N-十四烷基-4-甲基吡啶鎓六氟磷酸鹽、N-十六烷基-4-甲基吡啶鎓六氟磷酸鹽等。該等之中，從與(甲基)丙烯酸酯共聚物(A)的相容性的觀點來看，N-丁基-4-甲基吡啶鎓六氟磷酸鹽、N-己基-4-甲基吡啶鎓六氟磷酸鹽以及N-辛基-4-甲基吡啶鎓六氟磷酸鹽為較佳。以上的抗靜電劑(D)可以單獨使用一種，亦可以組合兩種以上使用。 Specific examples of the antistatic agent (D) include N-butyl-4-methylpyridinium hexafluorophosphate, N-hexyl-4-methylpyridinium hexafluorophosphate, and N-octyl Pyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, N-dodecylpyridinium hexafluorophosphate, N-tetradecylpyridinium hexafluorophosphate, N -Hexadecylpyridinium hexafluorophosphate, N-dodecyl-4-methylpyridinium hexafluorophosphate, N-tetradecyl-4-methylpyridinium hexafluorophosphate, N- Cetyl-4-methylpyridinium hexafluorophosphate, etc. Among these, from the viewpoint of compatibility with (meth)acrylate copolymer (A), N-butyl-4-methylpyridinium hexafluorophosphate, N-hexyl-4-methyl Pyridinium hexafluorophosphate and N-octyl-4-methylpyridinium hexafluorophosphate are preferred. The above antistatic agent (D) may be used alone or in combination of two or more.

黏著性組成物P中之抗靜電劑(D)的含量相對於(甲基)丙烯酸酯共聚物(A)100質量份，較佳為0.1~15質量份，特佳為0.5~10質量份，進一步較佳為1~5質量份。藉由將抗靜電劑(D)的含量設在上述範圍內，能夠有效地發揮抗靜電性，並且能夠防止光學特性或耐久性等物性的下降。 The content of the antistatic agent (D) in the adhesive composition P is preferably 0.1 to 15 parts by mass, and particularly preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the (meth)acrylate copolymer (A). It is further preferably 1 to 5 parts by mass. By setting the content of the antistatic agent (D) within the above range, the antistatic property can be effectively exhibited, and the decrease in physical properties such as optical characteristics and durability can be prevented.

(5)各種添加劑 (5) Various additives

在黏著性組成物P中可根據需要添加通常使用於丙烯酸系黏著劑之各種添加劑，例如可添加分散劑(例如，亞烷基二醇 二烷基醚)、增黏劑、抗氧化劑、紫外線吸收劑、光安定劑、軟化劑、填充劑、折射率調整劑等。另外，黏著性組成物P係表示在黏著劑層中保持原樣或以進行了反應之狀態殘留之各種成分的混合物者，且在乾燥製程等中被去除之成分、例如後述之聚合溶劑或稀釋溶劑並不包含於黏著性組成物P中。 Various additives commonly used in acrylic adhesives can be added to the adhesive composition P as needed, for example, a dispersant (for example, alkylene glycol can be added Dialkyl ether), tackifier, antioxidant, ultraviolet absorber, light stabilizer, softener, filler, refractive index adjuster, etc. In addition, the adhesive composition P means a component of a mixture of various components remaining in the adhesive layer as it is or in a state of being reacted, and is removed during the drying process, such as a polymerization solvent or a dilution solvent described later It is not included in the adhesive composition P.

(6)黏著性組成物的製造方法 (6) Manufacturing method of adhesive composition

黏著性組成物P可藉由以下方法製造：製造(甲基)丙烯酸酯共聚物(A)，將所得到的(甲基)丙烯酸酯共聚物(A)與交聯劑(B)、根據需要添加之矽烷偶合劑(C)、抗靜電劑(D)及添加劑等進行混合來製造。 The adhesive composition P can be manufactured by the following method: manufacturing a (meth)acrylate copolymer (A), combining the obtained (meth)acrylate copolymer (A) with a crosslinking agent (B), if necessary The added silane coupling agent (C), antistatic agent (D) and additives are mixed and manufactured.

(甲基)丙烯酸酯共聚物(A)可藉由用通常的自由基聚合法將構成聚合物的單體單元的混合物聚合來製造。(甲基)丙烯酸酯共聚物(A)的聚合可根據需要使用聚合起始劑且利用溶液聚合法等來進行。作為聚合溶劑，例如可舉出乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲苯、丙酮、己烷、甲基乙基酮等，亦可並用兩種類以上。 The (meth)acrylate copolymer (A) can be produced by polymerizing a mixture of monomer units constituting the polymer by a general radical polymerization method. The polymerization of the (meth)acrylate copolymer (A) can be carried out by a solution polymerization method using a polymerization initiator as needed. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, and methyl ethyl ketone. Two or more types may be used in combination.

作為聚合起始劑，可舉出偶氮系化合物、有機過氧化物等，亦可並用兩種以上。作為偶氮系化合物，例如可舉出2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丁腈)、1,1'-偶氮雙(環己烷1-腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基2,2'-偶氮雙(2-甲基丙酸酯)、4,4'-偶氮雙(4-氰戊酸)、2,2'-偶氮雙(2-羥基甲基丙腈)、2,2'-偶氮雙〔2-(2-咪唑啉-2-基)丙烷〕等。 Examples of the polymerization initiator include azo compounds and organic peroxides, and two or more of them may be used in combination. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis(cyclohexyl) Alkane 1-nitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile ), dimethyl 2,2'-azobis (2-methyl propionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2- Hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], etc.

作為有機過氧化物，例如可舉出過氧化苯甲醯、 過苯甲酸第三丁酯、氫過氧化異丙苯、過氧化二碳酸二異丙酯、過氧化二碳酸二正丙酯、-過氧化二碳酸二-(2-乙氧基乙基)酯、過氧新癸第三丁酯、過氧化新戊酸第三丁酯、(3,5,5-三甲基己醯基)過氧化物、二丙醯基過氧化物、二乙醯基過氧化物等。 Examples of organic peroxides include benzoyl peroxide, Third butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxide dicarbonate, di-n-propyl peroxide dicarbonate, di-(2-ethoxyethyl) peroxydicarbonate , Tertiary butyl peroxyneodecoxide, tertiary butyl peroxypivalate, (3,5,5-trimethylhexyl) peroxide, dipropylamide peroxide, diethylamide Peroxide, etc.

另外，在上述聚合製程中，藉由配合2-巰基乙醇等鏈轉移劑，能夠調節所得到的聚合物的重量平均分子量。 In addition, in the above polymerization process, by blending a chain transfer agent such as 2-mercaptoethanol, the weight average molecular weight of the obtained polymer can be adjusted.

得到(甲基)丙烯酸酯共聚物(A)之後，向(甲基)丙烯酸酯共聚物(A)的溶液中添加交聯劑(B)、以及根據需要添加矽烷偶合劑(C)、抗靜電劑(D)、添加劑、稀釋溶劑等並充分混合，藉此得到經溶劑稀釋後的黏著性組成物P(塗佈溶液)。 After obtaining the (meth)acrylate copolymer (A), add the crosslinking agent (B) to the solution of the (meth)acrylate copolymer (A), and if necessary, add the silane coupling agent (C), antistatic The agent (D), additives, diluting solvent, etc. are mixed well, thereby obtaining the adhesive composition P (coating solution) diluted by the solvent.

作為用於稀釋黏著性組成物P來作為塗佈溶液之稀釋溶劑，例如可以使用：己烷、庚烷、環己烷等脂肪族烴；甲苯、二甲苯等芳香族烴；二氯甲烷、氯化乙烯等鹵化烴；甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等醇；丙酮、甲基乙基酮、2-戊酮、異佛爾酮、環己酮等酮；乙酸乙酯、乙酸丁酯等酯；乙基溶纖劑等溶纖劑系溶劑等。 As a dilution solvent for diluting the adhesive composition P as a coating solution, for example, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; dichloromethane, and chlorine Halogenated hydrocarbons such as ethylene; methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol and other alcohols; acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone Other ketones; ethyl acetate, butyl acetate and other esters; ethyl cellosolve and other cellosolve-based solvents.

作為這樣製備之塗佈溶液的濃度和黏度，只要在可塗佈範圍內，則並無特別限制，可根據情況適宜地進行選擇。例如，將黏著性組成物P的濃度稀釋成10~40質量%。另外，在獲取塗佈溶液時，稀釋溶劑等的添加並非必要條件，只要黏著性組成物P的黏度為能夠進行塗佈的黏度等，亦可以不添加稀釋溶劑。該情況下，黏著性組成物P成為將(甲基)丙烯酸 酯共聚物(A)的聚合溶劑直接作為稀釋溶劑之塗佈溶液。 The concentration and viscosity of the coating solution prepared in this way are not particularly limited as long as they are within the coating range, and can be appropriately selected according to circumstances. For example, the concentration of the adhesive composition P is diluted to 10 to 40% by mass. In addition, when obtaining a coating solution, the addition of a dilution solvent or the like is not a necessary condition. As long as the viscosity of the adhesive composition P is a viscosity that can be applied, the dilution solvent may not be added. In this case, the adhesive composition P becomes (meth)acrylic acid The polymerization solvent of the ester copolymer (A) is directly used as the coating solution of the dilution solvent.

(7)黏著劑 (7) Adhesive

本實施形態中構成第1黏著劑層21之黏著劑係由以上說明之黏著性組成物P得到者。具體而言係將黏著性組成物P進行交聯而成者。黏著性組成物P的交聯可藉由加熱處理來進行。另外，亦可利用將黏著性組成物P的稀釋溶劑等進行揮發時的乾燥處理兼作該加熱處理。 In this embodiment, the adhesive constituting the first adhesive layer 21 is obtained from the adhesive composition P described above. Specifically, it is a product obtained by crosslinking the adhesive composition P. The crosslinking of the adhesive composition P can be performed by heat treatment. In addition, the drying treatment when volatilizing the diluent solvent of the adhesive composition P or the like may be used as the heat treatment.

進行加熱處理時，加熱溫度較佳為50~150℃，特佳為70~120℃。另外，加熱時間較佳為30秒~10分鐘，特佳為50秒~2分鐘。加熱處理後，亦可根據需要設定常溫(例如，23℃、50%RH)下1~2周左右的養護期。需要該養護期時，在經過養護期後形成具備既定物性之黏著劑層，而不需要養護期時，則在加熱處理結束後形成前述黏著劑層。 When performing heat treatment, the heating temperature is preferably 50 to 150°C, particularly preferably 70 to 120°C. In addition, the heating time is preferably 30 seconds to 10 minutes, particularly preferably 50 seconds to 2 minutes. After the heat treatment, a curing period of about 1 to 2 weeks at normal temperature (for example, 23°C, 50%RH) can also be set as needed. When the curing period is required, an adhesive layer having predetermined physical properties is formed after the curing period, and when the curing period is not required, the aforementioned adhesive layer is formed after the heat treatment is completed.

依上述加熱處理(及養護)，(甲基)丙烯酸酯共聚物(A)藉由交聯劑(B)交聯而形成三維網狀結構。這樣交聯而得到之黏著劑的交聯的程度，亦即凝膠分率在如前述範圍內。 According to the above heat treatment (and curing), the (meth)acrylate copolymer (A) is cross-linked by the cross-linking agent (B) to form a three-dimensional network structure. The degree of crosslinking of the adhesive obtained by such crosslinking, that is, the gel fraction is within the aforementioned range.

(8)第1黏著劑層的物性 (8) Physical properties of the first adhesive layer

第1黏著劑層21的厚度為5~100μm為較佳，10~60μm為更佳，10~50μm為特佳，15~30μm為進一步較佳。藉由第1黏著劑層21的厚度在上述範圍內，可有效地發揮基於構成該第1黏著劑層21之黏著劑的凝膠分率及儲存彈性模數之效果，亦即優異的耐久性、翹曲抑制性及耐熱不均勻性。 The thickness of the first adhesive layer 21 is preferably from 5 to 100 μm, more preferably from 10 to 60 μm, particularly preferably from 10 to 50 μm, and further preferably from 15 to 30 μm. When the thickness of the first adhesive layer 21 is within the above range, the effects of the gel fraction and storage elastic modulus based on the adhesive constituting the first adhesive layer 21 can be effectively exerted, that is, excellent durability , Warpage inhibition and heat resistance unevenness.

第1黏著劑層21的霧度值(依照JIS K7136：2000 測定的值)較佳為2%以下，特佳為1%以下。霧度值為2%以下時，透明性非常高，係適宜作為光學用途者。 Haze value of the first adhesive layer 21 (in accordance with JIS K7136: 2000 The measured value) is preferably 2% or less, and particularly preferably 1% or less. When the haze value is 2% or less, the transparency is very high, which is suitable for optical applications.

3.第2黏著劑層 3. The second adhesive layer

關於第2黏著劑層22，只要由具有前述物性之黏著劑構成即可，可為硬化性黏著劑，亦可為非硬化性黏著劑，但為了將儲存彈性模數及凝膠分率設在前述範圍內，還是使用活性能量射線硬化性黏著劑為較佳。 The second adhesive layer 22 may be formed of an adhesive having the aforementioned physical properties, and may be a curable adhesive or a non-curable adhesive. However, in order to set the storage elastic modulus and gel fraction at Within the aforementioned range, it is preferable to use an active energy ray-curable adhesive.

活性能量射線硬化性黏著劑可為以具有活性能量射線硬化性之聚合物作為主成分者，亦可為以不具有活性能量射線硬化性之聚合物與活性能量射線硬化性之多官能單體及/或寡聚物的混合物作為主成分者。另外，可為具有活性能量射線硬化性之聚合物與不具有活性能量射線硬化性之聚合物的混合物，亦可為具有活性能量射線硬化性之聚合物與活性能量射線硬化性之多官能單體及/或寡聚物的混合物，還可為該等三種的混合物。 The active energy ray-curable adhesive may be a polymer having active energy ray-curable polymer as a main component, or a multifunctional monomer and a polymer having no active energy ray-curable polymer and active energy ray-curable and And/or a mixture of oligomers as the main component. In addition, it may be a mixture of an active energy ray-curable polymer and an active energy ray-curable polymer, or it may be an active energy ray-curable polymer and an active energy ray-curable multifunctional monomer. And/or the mixture of oligomers may also be a mixture of these three.

在上述中，從容易得到維持黏著性且發揮內聚力的黏著劑的觀點來看，以不具有活性能量射線硬化性之聚合物與活性能量射線硬化性之多官能單體及/或寡聚物的混合物作為主成分者為較佳，特佳為以不具有活性能量射線硬化性之聚合物與活性能量射線硬化性之多官能單體的混合物作為主成分者。 In the above, from the viewpoint of easily obtaining an adhesive that maintains adhesion and exerts cohesive force, a polymer having no active energy ray-curable polymer and an active energy ray-curable polyfunctional monomer and/or oligomer The mixture is preferably used as a main component, and particularly preferably a mixture of a polymer having no active energy ray-curable polymer and an active energy ray-curable polyfunctional monomer as a main component.

作為不具有活性能量射線硬化性之聚合物，不具有活性能量射線硬化性基的(甲基)丙烯酸酯聚合物(以下有稱為「(甲基)丙烯酸酯聚合物(X)」)為較佳。(甲基)丙烯酸 酯聚合物(X)以含有烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯作為構成該聚合物的單體為較佳。藉此，所得到的黏著劑能夠表現較佳的黏著性。另外，(甲基)丙烯酸酯聚合物(X)係，烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯、具有反應性官能基的單體(含反應性官能基單體)、以及根據需要所使用的其他單體的共聚物為特佳。藉由使(甲基)丙烯酸酯聚合物(X)含有含反應性官能基單體作為構成該聚合物的單體，能夠改善與液晶單元等之玻璃表面的密接性，另外，亦可藉由與後述交聯劑(Z)進行反應而形成交聯結構。 As a polymer that does not have active energy ray-curable properties, a (meth)acrylate polymer that does not have an active energy ray-curable group (hereinafter referred to as "(meth)acrylate polymer (X)") is preferred good. (Methacrylate The ester polymer (X) is preferably an alkyl (meth)acrylate having an alkyl group and having 1 to 20 carbon atoms as a monomer constituting the polymer. Thereby, the obtained adhesive can exhibit better adhesiveness. In addition, (meth)acrylate polymer (X) series, alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group, monomers with reactive functional groups (including reactive functional group monomers) Copolymer), and copolymers of other monomers used as needed are particularly preferred. By making the (meth)acrylate polymer (X) contain a reactive functional group-containing monomer as the monomer constituting the polymer, the adhesion to the glass surface of the liquid crystal cell or the like can be improved. It reacts with a crosslinking agent (Z) described later to form a crosslinked structure.

作為烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，例如可舉出：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十八烷基酯等。其中，從進一步提高黏著性的觀點來看，烷基的碳原子數為1~8的(甲基)丙烯酸酯為較佳，(甲基)丙烯酸正丁酯為特佳。另外，該等可以單獨使用，亦可以組合兩種以上使用。 Examples of the alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, N-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (methyl ) N-decyl acrylate, n-dodecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, octadecyl (meth) acrylate Wait. Among them, from the viewpoint of further improving adhesiveness, (meth)acrylates having 1 to 8 carbon atoms in the alkyl group are preferred, and n-butyl (meth)acrylate is particularly preferred. In addition, these can be used alone or in combination of two or more.

(甲基)丙烯酸酯聚合物(X)以含有50~99質量%之烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯作為構成該聚合物的單體單元為較佳，特佳為含有60~99質量%，進一步較佳為含有70~98質量%。 (Meth)acrylate polymer (X) It is preferable to use a (meth)acrylic acid alkyl ester having 1 to 20 carbon atoms containing 50 to 99% by mass of an alkyl group as the monomer unit constituting the polymer In particular, it is preferably 60 to 99% by mass, more preferably 70 to 98% by mass.

作為上述含反應性官能基單體，可較佳地舉出分子 內具有羥基的單體(含羥基單體)、分子內具有羧基的單體(含羧基單體)、分子內具有胺基的單體(含胺基單體)等。該等含反應性官能基單體可以單獨使用一種，亦可以組合兩種以上使用。 As the reactive functional group-containing monomer, a molecule is preferably mentioned Monomers with hydroxyl groups (hydroxyl-containing monomers), monomers with carboxyl groups in the molecule (carboxyl-containing monomers), monomers with amine groups in the molecule (amine-containing monomers), etc. These reactive functional group-containing monomers may be used alone or in combination of two or more.

作為含羥基單體，例如可舉出(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯等。 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-(meth)acrylic acid. Hydroxybutyl (meth)acrylate such as hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like.

作為含羧基單體，例如可舉出：丙烯酸、甲基丙烯酸、巴豆酸、馬來酸、衣康酸、檸康酸等乙烯性不飽和羧酸。其中，從所得到的(甲基)丙烯酸酯聚合物(X)之羧基與交聯劑(Z)的反應性以及與其他單體的共聚合性這一點來看，丙烯酸為較佳。該等可以單獨使用，亦可以組合兩種以上使用。 Examples of carboxyl group-containing monomers include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Among them, acrylic acid is preferred from the viewpoint of the reactivity of the carboxyl group of the obtained (meth)acrylate polymer (X) with the crosslinking agent (Z) and the copolymerizability with other monomers. These can be used alone or in combination of two or more.

作為含胺基單體，例如可舉出(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸正丁基胺基乙酯等。該等可以單獨使用，亦可以組合兩種以上使用。 Examples of the amine group-containing monomer include aminoethyl (meth)acrylate and n-butylaminoethyl (meth)acrylate. These can be used alone or in combination of two or more.

(甲基)丙烯酸酯聚合物(X)以含有1~25質量%的含反應性官能基單體作為構成該聚合物的單體單元為較佳，特佳為含有1~20質量%，進一步較佳為含有2~5質量%。 The (meth)acrylate polymer (X) preferably contains 1 to 25% by mass of a reactive functional group-containing monomer as the monomer unit constituting the polymer, and particularly preferably contains 1 to 20% by mass. Preferably, it contains 2 to 5% by mass.

(甲基)丙烯酸酯聚合物(X)的聚合樣態可為無規共聚物，亦可為嵌段共聚物。 The polymerization state of the (meth)acrylate polymer (X) may be a random copolymer or a block copolymer.

(甲基)丙烯酸酯聚合物(X)的重量平均分子量為30萬~300萬為較佳，特佳為100萬~250萬，進一步較佳 為160萬~220萬。 The weight average molecular weight of the (meth)acrylate polymer (X) is preferably 300,000 to 3 million, particularly preferably 1 million to 2.5 million, further preferably From 1.6 million to 2.2 million.

另外，(甲基)丙烯酸酯聚合物(X)可以單獨使用一種，亦可以組合兩種以上使用。 In addition, (meth)acrylate polymer (X) may be used alone or in combination of two or more.

作為活性能量射線硬化性之多官能單體，與(甲基)丙烯酸酯聚合物(X)等的相容性優異的分子量1000以下的多官能丙烯酸酯系單體為較佳。 As the active energy ray-curable polyfunctional monomer, a polyfunctional acrylate monomer having a molecular weight of 1,000 or less excellent in compatibility with (meth)acrylate polymer (X) or the like is preferred.

作為分子量1000以下的多官能丙烯酸酯系單體，例如可舉出：1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇己二酸酯二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、二環戊基二(甲基)丙烯酸酯、己內酯改質二環戊烯基二(甲基)丙烯酸酯、環氧乙烷改質磷酸二(甲基)丙烯酸酯、二(丙烯醯氧基乙基)異氰脲酸酯、烯丙基化環己基二(甲基)丙烯酸酯等2官能型；三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、丙酸改質二季戊四醇三(甲基)丙烯酸酯、季戊四醇三-(甲基)丙烯酸酯、環氧丙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、三(丙烯醯氧基乙基)異氰脲酸酯、ε-己內酯改質三(2-(甲基)丙烯醯氧基乙基)異氰脲酸酯等3官能型；二甘油四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等4官能型；丙酸改質二季戊四醇五(甲基)丙烯酸酯等5官能型；二季戊四醇六(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯等6官能型等。該等可以單獨使用一種，亦可以組合兩種以上使用。 Examples of polyfunctional acrylate monomers with a molecular weight of 1000 or less include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl Glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxytrimethyl acetate neopentyl glycol di(meth) Group) acrylate, dicyclopentyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified di(meth)acrylate, 2-functional types such as di(acryloyloxyethyl)isocyanurate, allylated cyclohexyl di(meth)acrylate; trimethylolpropane tri(meth)acrylate, dipentaerythritol tri( Methacrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri-(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tri(meth)acrylate 3-functional types such as acryloyloxyethyl) isocyanurate and ε-caprolactone modified tris(2-(meth)acryloyloxyethyl) isocyanurate; diglycerol Base) acrylate, pentaerythritol tetra(meth)acrylate and other 4 functional types; propionic acid modified dipentaerythritol penta(meth)acrylate and other 5 functional types; dipentaerythritol hexa(meth)acrylate and caprolactone modified 6 functional types such as qualitative dipentaerythritol hexa(meth)acrylate etc. These can be used alone or in combination of two or more.

活性能量射線硬化性化合物(Y)的含量相對於(甲基)丙烯酸酯聚合物(X)100質量份，為1~50質量份為較佳，特佳為5~30質量份，進一步較佳為10~20質量份。 The content of the active energy ray-curable compound (Y) is preferably 1 to 50 parts by mass relative to 100 parts by mass of the (meth)acrylate polymer (X), particularly preferably 5 to 30 parts by mass, further preferably It is 10-20 parts by mass.

上述活性能量射線硬化性黏著劑含有交聯劑(Z)為較佳。黏著劑含有包含含反應性官能基單體的(甲基)丙烯酸酯聚合物(X)以及交聯劑(Z)作為構成聚合物的單體單元時，如果將該黏著劑進行加熱等，則交聯劑(Z)與構成(甲基)丙烯酸酯聚合物(X)的含反應性官能基單體的反應性官能基進行反應。藉此，形成(甲基)丙烯酸酯聚合物(X)藉由交聯劑(Z)交聯之結構，所得到的黏著劑的內聚力提高，並且所得到之黏著劑容易滿足前述儲存彈性模數及凝膠分率。 It is preferable that the active energy ray-curable adhesive contains a crosslinking agent (Z). When the adhesive contains a (meth)acrylate polymer (X) containing a reactive functional group-containing monomer and a crosslinking agent (Z) as monomer units constituting the polymer, if the adhesive is heated, etc., then The crosslinking agent (Z) reacts with the reactive functional group of the reactive functional group-containing monomer constituting the (meth)acrylate polymer (X). Thereby, a structure in which the (meth)acrylate polymer (X) is cross-linked by the cross-linking agent (Z) is formed, the cohesive force of the obtained adhesive agent is improved, and the obtained adhesive agent easily meets the aforementioned storage elastic modulus And gel fraction.

作為交聯劑(Z)，係與(甲基)丙烯酸酯聚合物(X)所具有的反應性官能基反應者即可，例如可舉出異氰酸酯系交聯劑、環氧系交聯劑、胺系交聯劑、三聚氰胺系交聯劑、氮丙啶系交聯劑、肼系交聯劑、醛系交聯劑、噁唑啉系交聯劑、金屬醇鹽系交聯劑、金屬螯合物系交聯劑、金屬鹽系交聯劑、銨鹽系交聯劑等。作為異氰酸酯系交聯劑，可使用與前述交聯劑(B)相同者。另外，交聯劑(Z)可以單獨使用一種，亦可以組合兩種以上使用。 The crosslinking agent (Z) may be any one that reacts with the reactive functional group possessed by the (meth)acrylate polymer (X), and examples thereof include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, Amine-based crosslinking agent, melamine-based crosslinking agent, aziridine-based crosslinking agent, hydrazine-based crosslinking agent, aldehyde-based crosslinking agent, oxazoline-based crosslinking agent, metal alkoxide-based crosslinking agent, metal chelate Compound-based cross-linking agent, metal salt-based cross-linking agent, ammonium salt-based cross-linking agent, etc. As the isocyanate-based crosslinking agent, the same as the aforementioned crosslinking agent (B) can be used. In addition, the crosslinking agent (Z) may be used alone or in combination of two or more.

交聯劑(Z)的含量，相對於(甲基)丙烯酸酯聚合物(X)100質量份，為0.01~10質量份為較佳，特佳為0.05~5質量份尤為佳，進一步較佳為0.1~1質量份。 The content of the crosslinking agent (Z) is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the (meth)acrylate polymer (X), particularly preferably 0.05 to 5 parts by mass, further preferably 0.1 to 1 part by mass.

上述活性能量射線硬化性黏著劑根據需要亦可含有各種添加劑，例如：光聚合起始劑、矽烷偶合劑、折射率調 整劑、抗靜電劑、增黏劑、抗氧化劑、紫外線吸收劑、光安定劑、軟化劑、填充劑等。 The above active energy ray-curable adhesive may contain various additives as needed, for example: photopolymerization initiator, silane coupling agent, refractive index adjustment Finishing agent, antistatic agent, tackifier, antioxidant, ultraviolet absorber, light stabilizer, softener, filler, etc.

使用紫外線作為使上述活性能量射線硬化性黏著劑硬化之活性能量射線時，上述活性能量射線硬化性黏著劑含有光聚合起始劑為較佳。 When ultraviolet light is used as the active energy ray for curing the active energy ray-curable adhesive, the active energy ray-curable adhesive preferably contains a photopolymerization initiator.

作為光聚合起始劑，例如，可舉出：安息香、安息香甲醚、安息香***、安息香異丙醚、安息香正丁醚、安息香異丁醚、苯乙酮、二甲基胺基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、1-羥基環己基苯基酮、2-甲基-1-〔4-(甲硫基)苯基〕-2-嗎啉基-丙-1-酮、4-(2-羥基乙氧基)苯基-2-(羥基-2-丙基)酮、二苯甲酮、對-苯基二苯甲酮、4,4’-二乙基胺基二苯甲酮、二氯二苯甲酮、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌、2-甲基噻噸酮、2-乙基噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、苄基二甲基縮酮、苯乙酮二甲基縮酮、對-二甲基胺基苯甲酸酯、低聚〔2-羥基-2-甲基-1〔4-(1-甲基乙烯基)苯基〕丙酮〕、2,4,6-三甲基苯甲醯基-二苯基-氧化膦等。該等可以單獨使用，亦可以組合兩種以上使用。 Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1 -Ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 4-(2-hydroxyethyl Oxy)phenyl-2-(hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorodi Benzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-third-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethyl Aminoaminobenzoate, oligomeric [2-hydroxy-2-methyl-1[4-(1-methylvinyl)phenyl]acetone], 2,4,6-trimethylbenzoyl -Diphenyl-phosphine oxide and so on. These can be used alone or in combination of two or more.

光聚合起始劑相對於上述活性能量射線硬化性黏著劑中的活性能量射線硬化性化合物(Y)100質量份，以0.1~20質量份的範圍的量使用為較佳、特佳為1~12質量份。 The photopolymerization initiator is preferably used in an amount ranging from 0.1 to 20 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (Y) in the active energy ray-curable adhesive, preferably 1 to 1 to 12 parts by mass.

另外，從改善所得到的黏著劑對薄膜的密接性的觀點來看，上述活性能量射線硬化性黏著劑含有矽烷偶合劑為較 佳。作為矽烷偶合劑，係在分子內具有至少一個烷氧基矽烷基的有機矽化合物，且與黏著成分的相容性佳並具有透光性者為佳。 In addition, from the viewpoint of improving the adhesiveness of the obtained adhesive to the film, the active energy ray-curable adhesive contains a silane coupling agent. good. As a silane coupling agent, it is an organosilicon compound having at least one alkoxysilane group in the molecule, and it is preferably compatible with the adhesive component and having light transmittance.

作為該矽烷偶合劑，例如，除了前述含環氧基矽烷偶合劑(C1)以及含巰基矽烷偶合劑(C2)之外，還可舉出含聚合性不飽和基矽化合物(例如乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、甲基丙烯醯氧基丙基三甲氧基矽烷等)、含胺基矽化合物(例如3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷等)、3-氯丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、或該等之中的至少一個、與含烷基矽化合物(例如甲基三乙氧基矽烷、乙基三乙氧基矽烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷等)之縮合物等。該等可以單獨使用一種，亦可以組合兩種以上使用。 As the silane coupling agent, for example, in addition to the epoxy group-containing silane coupling agent (C1) and the mercapto group-containing silane coupling agent (C2), a polymerizable unsaturated group-containing silicon compound (such as vinyl trimethoxy) Silane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, etc.), amine-containing silicon compounds (such as 3-aminopropyltrimethoxysilane, N-(2-amine Ethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, etc.), 3-chloropropyltrimethoxysilane Silane, 3-isocyanate propyltriethoxysilane, or at least one of these, and alkyl-containing silicon compounds (such as methyltriethoxysilane, ethyltriethoxysilane, methyltrimethyl Condensate of oxysilane, ethyl trimethoxysilane, etc.). These can be used alone or in combination of two or more.

矽烷偶合劑的含量相對於(甲基)丙烯酸酯聚合物(X)100質量份，為0.01~10質量份為較佳，特佳為0.05~5質量份，進一步較佳為0.1~1質量份。 The content of the silane coupling agent is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the (meth)acrylate polymer (X), particularly preferably 0.05 to 5 parts by mass, further preferably 0.1 to 1 part by mass .

另外，具有上述活性能量射線硬化性之聚合物係，側鏈上導入有具有活性能量射線硬化性的官能基(活性能量射線硬化性基)的(甲基)丙烯酸酯(共)聚合物為較佳。 In addition, the polymer system having the above-mentioned active energy ray-curing property, a (meth)acrylate (co)polymer having a functional group (active energy ray-curing group) having active energy ray hardening introduced into the side chain is preferred good.

第2黏著劑層22的厚度為1~50μm為較佳，1~20μm為更佳，2~7μm為特佳。藉由構成第2黏著劑層22之黏著劑具有前述儲存彈性模數及凝膠分率，即使將第2黏著劑層22的厚度薄膜化至上述範圍內的情況下，亦能夠確保充分 的密接性。再者，藉由將第2黏著劑層22如上述般進行薄膜化，從而能夠使在第2黏著劑層22的光學特性的損失最小化。 The thickness of the second adhesive layer 22 is preferably 1-50 μm, more preferably 1-20 μm, and particularly preferably 2-7 μm. Since the adhesive constituting the second adhesive layer 22 has the aforementioned storage elastic modulus and gel fraction, even if the thickness of the second adhesive layer 22 is thinned to the above range, it can ensure sufficient Of tightness. Furthermore, by thinning the second adhesive layer 22 as described above, it is possible to minimize the loss of optical characteristics in the second adhesive layer 22.

4.第2相位差板 4. Second phase difference plate

第2相位差板12由烯烴系樹脂構成為較佳。烯烴系樹脂是指由從乙烯以及丙烯等鏈狀脂肪族烯烴、或者降冰片烯或其取代物(以下，亦將該等統稱為降冰片烯系單體)等脂環式烯烴衍生的結構單元所構成之樹脂。烯烴系樹脂亦可為使用兩種以上的單體之共聚物。 The second retardation plate 12 is preferably made of olefin resin. The olefin-based resin refers to a structural unit derived from an alicyclic olefin such as a chain aliphatic olefin such as ethylene and propylene, or norbornene or a substitution thereof (hereinafter, also referred to collectively as norbornene-based monomers) The resin made up. The olefin resin may be a copolymer using two or more monomers.

其中，作為烯烴系樹脂，可較佳地使用係主要含有從脂環式烯烴衍生之結構單元之樹脂，亦即環狀烯烴系樹脂。藉由第2相位差板12由環狀烯烴系樹脂構成，能夠將耐久條件下之第2相位差板12的光學特性變化抑制為較小。 Among them, as the olefin-based resin, a resin mainly containing a structural unit derived from an alicyclic olefin, that is, a cyclic olefin-based resin can be preferably used. Since the second retardation plate 12 is composed of a cyclic olefin-based resin, it is possible to suppress changes in the optical characteristics of the second retardation plate 12 under durable conditions to be small.

作為構成環狀烯烴系樹脂的脂環式烯烴的典型例可舉出降冰片烯系單體等。降冰片烯是指降冰片烷的一個碳-碳鍵成為雙鍵之化合物，依IUPAC命名法係命名為雙環〔2,2,1〕庚-2-烯者。作為降冰片烯的取代物的例子，將降冰片烯的雙鍵位置設為1,2-位時，可舉出3-取代物、4-取代物、4,5-二取代物等，此外，亦可將二環戊二烯或二甲橋八氫萘等作為構成環狀烯烴系樹脂的單體。 Typical examples of the alicyclic olefin constituting the cyclic olefin-based resin include norbornene-based monomers. Norbornene refers to a compound in which a carbon-carbon bond of norbornane becomes a double bond, and is named bicyclo[2,2,1]hept-2-ene according to the IUPAC nomenclature system. As an example of the norbornene substitute, when the double bond position of norbornene is set to the 1,2-position, a 3-substituted, 4-substituted, 4,5-disubstituted, etc. may be mentioned. Alternatively, dicyclopentadiene, dimethyl octahydronaphthalene, or the like may be used as the monomer constituting the cyclic olefin resin.

環狀烯烴系樹脂在其結構單元可具有降冰片烷環，亦可不具有。作為形成結構單元不具有降冰片烷環的環狀烯烴系樹脂之降冰片烯系單體，例如可舉出藉由開環成為5員環者，代表性者可舉出降冰片烯、二環戊二烯、1-或4-甲基降冰片烯、4-苯基降冰片烯等。環狀烯烴系樹脂為共聚物時，其 分子的排列狀態無特別限定，可為無規共聚物，可為嵌段共聚物，亦可為接枝共聚物。 The cyclic olefin-based resin may or may not have a norbornane ring in its structural unit. Examples of norbornene-based monomers that form a cyclic olefin-based resin that does not have a norbornene ring include, for example, those having a 5-membered ring by ring opening, and representative examples include norbornene and bicyclic Pentadiene, 1- or 4-methyl norbornene, 4-phenyl norbornene, etc. When the cyclic olefin resin is a copolymer, its The arrangement state of the molecules is not particularly limited, and may be a random copolymer, a block copolymer, or a graft copolymer.

作為環狀烯烴系樹脂的更具體的例子，例如可舉出降冰片烯系單體的開環聚合物、降冰片烯系單體與其他單體的開環共聚物、對該等進行馬來酸加成或環戊二烯加成等而成的聚合物改質物、以及將該等氫化而成的聚合物或共聚物、降冰片烯系單體的加成聚合物、降冰片烯系單體與其他單體的加成共聚物等。作為共聚物時的其他單體，可舉出α-烯烴類、環烯烴類、非共軛二烯類等。另外，環狀烯烴系樹脂亦可為使用了一種或兩種以上的降冰片烯系單體以及其他脂環式烯烴的共聚物。 As a more specific example of the cyclic olefin-based resin, for example, a ring-opening polymer of a norbornene-based monomer, a ring-opening copolymer of a norbornene-based monomer and other monomers, or a male Modified products of polymers such as acid addition or cyclopentadiene addition, hydrogenated polymers or copolymers, addition polymers of norbornene monomers, norbornene monomers Addition copolymers of polymer and other monomers, etc. Examples of other monomers in the copolymer include α-olefins, cycloolefins, and non-conjugated dienes. In addition, the cyclic olefin-based resin may be a copolymer using one or two or more norbornene-based monomers and other alicyclic olefins.

在上述具體例中，作為環狀烯烴系樹脂，可較佳地使用將使用降冰片烯系單體之開環聚合物予以氫化而成的樹脂。這樣的環狀烯烴系樹脂除了可對其實施延伸處理而製成相位差板，亦可藉由延伸以及將具有既定收縮率之收縮性薄膜貼合並實施加熱收縮處理，而作為均勻性高且具有大的相位差值的相位差板。 In the above specific example, as the cyclic olefin-based resin, a resin obtained by hydrogenating a ring-opening polymer using a norbornene-based monomer can be preferably used. Such a cyclic olefin resin can be stretched to form a retardation plate, and it can also be stretched and a shrinkable film with a predetermined shrinkage ratio can be attached and subjected to heat shrinkage treatment, which has high uniformity and has A phase difference plate with a large phase difference value.

作為使用了降冰片烯系單體的環狀烯烴系樹脂的市售品(皆以商品名)有，Zeon Corporation所販售之“ZEONEX”以及“ZEONOR”、JSR CORPORATION所販售之“ARTON”等。該等環狀烯烴系樹脂的薄膜或其延伸薄膜都可由市售品得到，例如(皆以商品名)有，Zeon Corporation所販售之“ZEONOR薄膜”、JSR CORPORATION所販售之“ARTON薄膜”、SEKISUI CHEMICAL CO.,LTD.所販售之“ESSINA”等。 There are "ZEONEX" and "ZEONOR" sold by Zeon Corporation and "ARTON" sold by JSR CORPORATION as commercially available products (all trade names) of cyclic olefin resins using norbornene monomers. Wait. These cyclic olefin-based resin films or their stretched films can be obtained from commercially available products, for example (both under the trade name) "ZEONOR Film" sold by Zeon Corporation and "ARTON Film" sold by JSR CORPORATION , "ESSINA" sold by SEKISUI CHEMICAL CO., LTD. etc.

另外，第2相位差板12亦可使用，由含有兩種以上烯烴系樹脂的混合樹脂構成的薄膜、或由烯烴系樹脂與其他熱可塑性樹脂的混合樹脂構成的薄膜。例如，作為含有兩種以上烯烴系樹脂的混合樹脂，可舉出如上述的環狀烯烴系樹脂與鏈狀脂肪族烯烴系樹脂的混合物。使用烯烴系樹脂與其他熱可塑性樹脂的混合樹脂時，其他熱可塑性樹脂可根據目的適宜地選擇適當者。作為具體例，可舉出：聚氯乙烯系樹脂、纖維素系樹脂、聚苯乙烯系樹脂、丙烯腈/丁二烯/苯乙烯共聚合樹脂、丙烯腈/苯乙烯共聚合樹脂、(甲基)丙烯酸系樹脂、聚乙酸乙烯酯系樹脂、聚偏二氯乙烯系樹脂、聚醯胺系樹脂、聚縮醛系樹脂、聚碳酸酯系樹脂、改質聚苯醚系樹脂、聚對苯二甲酸丁二酯系樹脂、聚對苯二甲酸乙二酯系樹脂、聚苯硫醚系樹脂、聚碸系樹脂、聚醚碸系樹脂、聚醚醚酮系樹脂、聚芳酯系樹脂、液晶性樹脂、聚醯胺醯亞胺系樹脂、聚醯亞胺系樹脂、聚四氟乙烯系樹脂等。熱可塑性樹脂可僅單獨使用一種，或組合兩種以上使用。另外，上述熱可塑性樹脂亦可在進行任意適當的聚合物改質後使用。作為聚合物改質的例子，可舉出：共聚合、交聯、分子末端改質、賦予立體規則性等。 In addition, the second retardation film 12 may also be a film composed of a mixed resin containing two or more olefin resins, or a film composed of a mixed resin of an olefin resin and another thermoplastic resin. For example, as a mixed resin containing two or more kinds of olefin resins, a mixture of the above-mentioned cyclic olefin resin and chain aliphatic olefin resin can be mentioned. When a mixed resin of an olefin-based resin and other thermoplastic resins is used, other thermoplastic resins can be appropriately selected according to the purpose. Specific examples include polyvinyl chloride resin, cellulose resin, polystyrene resin, acrylonitrile/butadiene/styrene copolymer resin, acrylonitrile/styrene copolymer resin, (methyl )Acrylic resins, polyvinyl acetate resins, polyvinylidene chloride resins, polyamide resins, polyacetal resins, polycarbonate resins, modified polyphenylene ether resins, polyphenylene terephthalate Butyl formate resin, polyethylene terephthalate resin, polyphenylene sulfide resin, poly lanthanide resin, polyether lanthanide resin, polyether ether ketone resin, polyarylate resin, liquid crystal Resin, polyimide amide imide resin, polyimide resin, polytetrafluoroethylene resin, etc. The thermoplastic resin may be used alone or in combination of two or more. In addition, the above thermoplastic resin can also be used after any appropriate polymer modification. Examples of polymer modification include copolymerization, cross-linking, molecular terminal modification, and stereoregularity.

使用烯烴系樹脂與其他熱可塑性樹脂的混合樹脂時，其他熱可塑性樹脂的含量相對於所有樹脂，通常為50質量%左右以下，40質量%左右以下為較佳。藉由將其他熱可塑性樹脂的含量設在該範圍內，能夠得到光彈性係數的絕對值小、顯示良好的波長分散特性，並且耐久性、機械強度以及透明性優異的相位差板。 When a mixed resin of an olefin-based resin and another thermoplastic resin is used, the content of the other thermoplastic resin is generally about 50% by mass or less, and preferably about 40% by mass or less with respect to all resins. By setting the content of other thermoplastic resins within this range, a retardation plate having a small absolute value of photoelastic coefficient, exhibiting good wavelength dispersion characteristics, and having excellent durability, mechanical strength, and transparency can be obtained.

烯烴系樹脂可藉由溶液的澆鑄法或熔融擠出法等進行製膜。使用兩種以上的混合樹脂進行製膜時，對其製膜方法並無特別限定，例如可採用：使用將樹脂成分以既定比例與溶劑一同攪拌混合而得到的均勻溶液並藉由澆鑄法製造薄膜之方法；將樹脂成分以既定比例進行熔融混合並藉由熔融擠出法製造薄膜之方法等。 The olefin resin can be formed into a film by a solution casting method or a melt extrusion method. When two or more mixed resins are used for film formation, the film formation method is not particularly limited. For example, a film can be produced by a casting method using a uniform solution obtained by stirring and mixing a resin component with a solvent at a predetermined ratio. The method of melting the resin components at a predetermined ratio and producing a film by the melt extrusion method.

由上述烯烴系樹脂構成的薄膜亦可含有殘留溶劑、安定劑、可塑劑、抗老化劑、抗靜電劑以及紫外線吸收劑等，根據需要亦可含有其他成分。另外，亦可含有調平劑以減小表面粗糙度。 The film composed of the olefin-based resin may contain residual solvents, stabilizers, plasticizers, anti-aging agents, antistatic agents, ultraviolet absorbers, and the like, and may contain other components as necessary. In addition, it may also contain leveling agents to reduce surface roughness.

第2相位差板12之第2黏著劑層22側的面亦可實施電暈處理等表面處理。 The surface of the second retardation film 12 on the second adhesive layer 22 side may be subjected to surface treatment such as corona treatment.

第2相位差板12具有滿足下述條件之折射率各向異性為較佳，該條件係，當將面內慢軸方向、面內快軸方向以及厚度方向的折射率分別設為nx、ny以及nz，且將薄膜的厚度設為d時，由下述式(1)：Re=(nx-ny)×d (1)所定義之波長為590nm時的面內延遲值Re為30~150nm，且由下述式(2)：Nz係數=(nx-nz)/(nx-ny) (2)所定義之Nz係數超過1、未滿2。 It is preferable that the second retardation plate 12 has a refractive index anisotropy that satisfies the following conditions: when the in-plane slow axis direction, the in-plane fast axis direction, and the thickness direction are respectively set to n x , n y and n z, and the thickness of the film is set to d, the following formula (1): R e = ( n x -n y) × d (1) is defined as the wavelength of 590nm when the in-plane retardation R e is a value of 30 ~ 150nm, and represented by the following formula (2): Nz coefficient = (n x -n z) / (n x -n y) (2) Nz coefficient defined exceeds 1, less than 2.

具有如上述折射率各向異性的第2相位差板12，可藉由對由上述烯烴系樹脂構成的薄膜的縱向單軸延伸、拉幅機橫向單軸延伸、同時雙軸延伸或逐次雙軸延伸等而得到，並 能夠藉由適當地調整延伸倍率與延伸速度、或適宜地選擇延伸時的預熱溫度、延伸溫度、熱固溫度、冷卻溫度等的各種溫度及其模式，來得到所希望的折射率各向異性。 The second retardation plate 12 having the refractive index anisotropy as described above can be obtained by longitudinal uniaxial stretching of the film composed of the olefin-based resin, transverse uniaxial stretching of the tenter, simultaneous biaxial stretching, or successive biaxial stretching Obtained by extension, and The desired refractive index anisotropy can be obtained by appropriately adjusting the stretching ratio and stretching speed, or appropriately selecting various temperatures and modes such as preheating temperature, stretching temperature, thermosetting temperature, cooling temperature, etc. during stretching .

第2相位差板12，其厚度在5~80μm的範圍內為較佳，在10~80μm的範圍內為更佳，在10~30μm的範圍內為特佳。 The thickness of the second phase difference plate 12 is preferably in the range of 5 to 80 μm, more preferably in the range of 10 to 80 μm, and particularly preferably in the range of 10 to 30 μm.

5.附有黏著劑層之光學薄膜的製造方法 5. Manufacturing method of optical film with adhesive layer

對附有黏著劑層之光學薄膜1A的製造方法的較佳例進行說明。 A preferred example of the method for manufacturing the optical film 1A with the adhesive layer attached will be described.

(1)相位差板積層體的製造 (1) Manufacturing of phase difference plate laminate

首先，製造由第1相位差板11、第2黏著劑層22及第2相位差板12構成之相位差板積層體。關於該相位差板積層體的製造，可以利用通常的方法進行。 First, a phase difference plate laminate composed of the first phase difference plate 11, the second adhesive layer 22, and the second phase difference plate 12 is manufactured. The manufacturing of this phase difference plate laminate can be performed by a usual method.

例如，於剝離片的剝離面形成構成第2黏著劑層22的黏著劑的塗膜。具體而言，將構成第2黏著劑層22的黏著劑的塗佈液塗佈於剝離片的剝離面，並進行乾燥。剝離片的說明後述。 For example, an adhesive coating film constituting the second adhesive layer 22 is formed on the peeling surface of the peeling sheet. Specifically, the adhesive coating liquid constituting the second adhesive layer 22 is applied to the peeling surface of the peeling sheet and dried. The description of the release sheet will be described later.

作為塗佈上述塗佈溶液之方法，可使用例如棒塗法、刮刀塗佈法、輥塗法、刮板塗佈法、模塗法、凹版塗佈法等。 As a method of applying the coating solution, for example, a bar coating method, a blade coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.

藉由加熱處理進行上述乾燥時，加熱溫度較佳為50~150℃，特佳為70~120℃。另外，加熱時間較佳為30秒~10分鐘，特佳為50秒~2分鐘。 When the above drying is performed by heat treatment, the heating temperature is preferably 50 to 150°C, particularly preferably 70 to 120°C. In addition, the heating time is preferably 30 seconds to 10 minutes, particularly preferably 50 seconds to 2 minutes.

接著，於第2相位差板12，貼合構成上述剝離片 上的第2黏著劑層22的黏著劑的塗膜。然後，透過上述剝離片照射活性能量射線並使上述黏著劑的塗膜硬化，將該塗膜作為第2黏著劑層22。 Next, the second phase difference plate 12 is bonded to constitute the above-mentioned peeling sheet The coating film of the adhesive on the second adhesive layer 22 above. Then, the active energy rays are irradiated through the release sheet to harden the coating film of the adhesive, and this coating film is used as the second adhesive layer 22.

其中，活性能量射線是指於電磁波或帶電粒子束中具有能量量子者，具體而言，可舉出紫外線或電子束等。活性能量射線之中，易於操作的紫外線為特佳。 Among them, the active energy ray refers to those having energy quanta in electromagnetic waves or charged particle beams, and specific examples include ultraviolet rays and electron beams. Among the active energy rays, ultraviolet rays that are easy to handle are particularly preferred.

紫外線的照射，可藉由高壓水銀燈、金屬鹵化物燈、熔融H燈、氙氣燈等來進行，紫外線的照射量係照度為50~1000mW/cm2左右為較佳。另外，光量為50~10000mJ/cm2為較佳，為80~5000mJ/cm2為更佳，特佳為100~1000mJ/cm2。另一方面，電子束的照射可藉由電子束加速器等來進行，電子束的照射量為10~1000krad左右為較佳。 The irradiation of ultraviolet rays can be performed by a high-pressure mercury lamp, a metal halide lamp, a molten H lamp, a xenon lamp, etc. The irradiation amount of ultraviolet rays is preferably about 50 to 1000 mW/cm 2 . In addition, the light amount is preferably 50 to 10000 mJ/cm 2 , more preferably 80 to 5000 mJ/cm 2 , and particularly preferably 100 to 1000 mJ/cm 2 . On the other hand, the irradiation of the electron beam can be performed by an electron beam accelerator or the like, and the irradiation amount of the electron beam is preferably about 10 to 1000 krad.

之後，從藉由上述所形成的第2黏著劑層22將剝離片剝離，將第1相位差板11之第2丙烯酸系樹脂層113側的面貼合於被露出的第2黏著劑層22。藉此，得到由第2相位差板12、第2黏著劑層22以及第1相位差板11積層而成的相位差板積層體(光學薄膜)。 After that, the release sheet is peeled off from the second adhesive layer 22 formed as described above, and the surface of the first phase difference plate 11 on the second acrylic resin layer 113 side is bonded to the exposed second adhesive layer 22 . By this, a phase difference plate laminate (optical film) formed by laminating the second phase difference plate 12, the second adhesive layer 22, and the first phase difference plate 11 is obtained.

另外，相位差板積層體的總厚度15~200μm為較佳，25~150μm為更佳，30~65μm為特佳。 In addition, the total thickness of the phase difference plate laminate is preferably 15 to 200 μm, more preferably 25 to 150 μm, and particularly preferably 30 to 65 μm.

(2)第1黏著劑層之黏著片的製造 (2) Manufacture of the adhesive sheet of the first adhesive layer

製造於由黏著性組成物P形成的黏著劑層的一面或兩面之上積層剝離片而成之黏著片。在此，以製造於黏著劑層的兩面之上積層剝離片而成之黏著片者作為一例。 An adhesive sheet manufactured by laminating a release sheet on one side or both sides of an adhesive layer formed of an adhesive composition P. Here, an example of an adhesive sheet manufactured by stacking peeling sheets on both sides of the adhesive layer is described.

作為剝離片，可使用例如聚乙烯薄膜、聚丙烯薄膜、 聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對苯二甲酸乙二酯薄膜、聚萘二甲酸乙二酯薄膜、聚對苯二甲酸丁二酯薄膜、聚胺基甲酸酯薄膜、乙烯乙酸乙烯酯薄膜、離子聚合物樹脂薄膜、乙烯-(甲基)丙烯酸共聚物薄膜、乙烯-(甲基)丙烯酸酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜、氟樹脂薄膜等。另外，亦可使用該等之交聯薄膜。還可以是該等之積層薄膜。 As the release sheet, for example, polyethylene film, polypropylene film, Polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, parylene Butyl phthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene-(meth)acrylic copolymer film, ethylene-(meth)acrylate copolymer film , Polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. In addition, such cross-linked films can also be used. It may also be such a laminated film.

在上述剝離片的至少一面(尤其是與黏著劑層相接的剝離面)實施剝離處理為較佳。作為剝離處理中所使用的剝離劑，例如可舉出醇酸系、矽酮系、氟系、不飽和聚酯系、聚烯烴系、蠟系的剝離劑。另外，本說明書中的剝離片的剝離面是指剝離片上具有剝離性的面，亦包含實施剝離處理後的面以及未實施剝離處理而仍顯示出剝離性的面中的任意者。 It is preferable to perform peeling treatment on at least one surface of the peeling sheet (particularly the peeling surface in contact with the adhesive layer). Examples of the release agent used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents. In addition, the peeling surface of the peeling sheet in this specification means the surface which has peelability on a peeling sheet, and also includes any one of the surface after peeling processing and the surface which shows peeling without performing peeling processing.

於黏著劑層的兩面之上積層剝離片時，將一側的剝離片作為剝離力大的重剝離型剝離片，並將另一側的剝離片作為剝離力小的輕剝離型剝離片為較佳。 When stacking release sheets on both sides of the adhesive layer, use one release sheet as the heavy peel release sheet with high peel force, and the other release sheet as the light release peel sheet with low release force. good.

對於剝離片的厚度並沒有特別限制，但通常為20~150μm左右。 The thickness of the release sheet is not particularly limited, but it is usually about 20 to 150 μm.

作為上述黏著片的製造方法的一例，在剝離片的剝離面上塗佈黏著性組成物P的塗佈溶液，進行加熱處理而形成塗膜之後，根據需要，在該塗膜上積層其他剝離片(以剝離面與塗膜相接的方式)或基材。上述塗膜在不需要養護期時，直接形成第1黏著劑層21，而在需要養護期時，在經過養護期後形成第1黏著劑層21。關於加熱處理以及養護的條件如 前述。 As an example of the method for manufacturing the above-mentioned adhesive sheet, after applying a coating solution of the adhesive composition P on the peeling surface of the peeling sheet and performing a heat treatment to form a coating film, if necessary, another peeling sheet is laminated on the coating film (In such a way that the peeling surface is in contact with the coating film) or the substrate. The above coating film directly forms the first adhesive layer 21 when the curing period is not required, and forms the first adhesive layer 21 after the curing period when the curing period is required. Conditions regarding heat treatment and maintenance such as Aforementioned.

作為塗佈上述塗佈溶液之方法，可使用例如棒塗法、刮刀塗佈法、輥塗法、刮板塗佈法、模塗法、凹版塗佈法等。 As a method of applying the coating solution, for example, a bar coating method, a blade coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.

(3)附有黏著劑層之光學薄膜的製造 (3) Manufacture of optical film with adhesive layer

從如上述般得到之黏著片剝離一側的剝離片(輕剝離型剝離片)。然後，將相位差板積層體之第1相位差板11的第1丙烯酸系樹脂層111重疊於所露出之黏著劑層，並壓著黏著片與相位差板積層體。藉此，得到上述附有黏著劑層之光學薄膜1A(附有剝離片)。 The peeling sheet (light peeling type peeling sheet) peeled from the adhesive sheet obtained as described above. Then, the first acrylic resin layer 111 of the first phase difference plate 11 of the phase difference plate laminate is overlaid on the exposed adhesive layer, and the pressure-sensitive adhesive sheet and the phase difference plate laminate are pressed. Thereby, the above-mentioned optical film 1A with an adhesive layer (with a release sheet attached) was obtained.

作為附有黏著劑層之光學薄膜1A的製造方法的另一例，於剝離片的剝離面塗佈含有前述黏著性組成物P之溶液(塗佈溶液)，進行加熱處理而形成塗膜之後，將相位差板積層體之第1相位差板11的第1丙烯酸系樹脂層111重疊於該塗膜。上述塗膜在需要養護期時，藉由間隔養護期而形成第1黏著劑層21，而在不需要養護期時，直接形成第1黏著劑層21。藉此，得到上述附有黏著劑層之光學薄膜1A(附有剝離片)。 As another example of the manufacturing method of the optical film 1A with an adhesive layer, a solution (coating solution) containing the aforementioned adhesive composition P is applied to the release surface of the release sheet, and heat treatment is performed to form a coating film. The first acrylic resin layer 111 of the first phase difference plate 11 of the phase difference plate laminate is superimposed on the coating film. When the above-mentioned coating film requires a curing period, the first adhesive layer 21 is formed by the interval of the curing period, and when the curing period is not required, the first adhesive layer 21 is directly formed. Thereby, the above-mentioned optical film 1A with an adhesive layer (with a release sheet attached) was obtained.

6.附有黏著劑層之光學薄膜的物性 6. Physical properties of optical film with adhesive layer

本實施形態之附有黏著劑層之光學薄膜1A的黏著力對於無鹼玻璃的黏著力，為0.5~20N/25mm為較佳，特佳為1~10N/25mm。藉此，附有黏著劑層之光學薄膜1A成為耐久性優異者。進而從再處理性亦優異者的觀點來看，上述黏著力為2~7N/25mm為較佳。另外，這裡所說的黏著力是指基本上依據JIS Z0237：2009並藉由180°剝離法而測定的黏著力，設定為 如下者：設定測定樣品為寬25mm、長100mm，將該測定樣品於0.5MPa、50℃下加壓20分鐘並貼附於被著體後，於常壓、23℃、50%RH的條件下放置24小時，然後以300mm/min的剝離速度進行測定而得到者。藉由使黏著力在上述範圍內，貼附於液晶單元時，可防止翹起或表面剝離等。 The adhesion of the optical film 1A with an adhesive layer of this embodiment to an alkali-free glass is preferably 0.5 to 20 N/25 mm, and particularly preferably 1 to 10 N/25 mm. With this, the optical film 1A with the adhesive layer becomes excellent in durability. Furthermore, from the viewpoint of those who are also excellent in reprocessing properties, the above-mentioned adhesive force is preferably 2 to 7 N/25 mm. In addition, the adhesive force mentioned here refers to the adhesive force measured by the 180° peel method basically according to JIS Z0237:2009, and is set to The following: set the measurement sample to 25 mm wide and 100 mm long, pressurize the measurement sample at 0.5 MPa, 50° C. for 20 minutes and attach it to the subject, under normal pressure, 23° C., and 50% RH After standing for 24 hours, the product was measured at a peeling speed of 300 mm/min. By making the adhesive force within the above range, when sticking to the liquid crystal cell, it is possible to prevent lifting and peeling of the surface.

另外，本實施形態之附有黏著劑層之光學薄膜1A，自貼合於上述被著體後，進一步在23℃、50%RH的條件下放置14天後的黏著力(貼附14天後的黏著力)為1~20N/25mm為佳，特佳為3~9N/25mm。如此抑制隨時間經過之黏著力的提高，藉此，本實施形態之附有黏著劑層之光學薄膜1A的再處理性亦優異，貼附於液晶單元後，亦能夠容易重新貼附。 In addition, the adhesive layer-attached optical film 1A of the present embodiment has an adhesive force after being attached to the above-mentioned object, and then placed at 23°C and 50% RH for 14 days (after 14 days of attachment) The adhesive force) is preferably 1~20N/25mm, especially 3~9N/25mm. In this way, it is possible to suppress the increase in the adhesive force with time, whereby the adhesive film-attached optical film 1A of the present embodiment is also excellent in reprocessing properties, and can be easily re-attached after being attached to the liquid crystal cell.

另外，本實施形態之附有黏著劑層之光學薄膜1A，自貼合於上述被著體後，在50℃、50%RH的條件下放置2天後的黏著力(50℃下貼附2天後的黏著力)從耐久性的觀點來看，為1~20N/25mm為較佳，進一步考慮再處理性的觀點時，為6~12N/25mm為特佳。 In addition, the adhesive film-attached optical film 1A of the present embodiment has an adhesive force after being attached to the above-mentioned object under the conditions of 50°C and 50% RH for 2 days (sticking 2 at 50°C) From the viewpoint of durability, 1-20N/25mm is preferable from the viewpoint of durability, and 6-12N/25mm is particularly preferable when the reprocessing property is further considered.

本實施形態之附有黏著劑層之光學薄膜1A之第1黏著劑層21的表面電阻率為1.0×1012Ω/sq以下為較佳，特佳為5.0×1011Ω/sq以下，進一步較佳為7.0×1010Ω/sq以下。藉由使表面電阻率為上述值以下，可於顯示面板發揮充分的抗靜電性。該表面電阻率能夠藉由使黏著性組成物P含有前述抗靜電劑(D)來實現。另外，第1黏著劑層21表面電阻率的測定係依據JIS K6911來進行者，具體如後述試驗例所示。另外，上述表面電阻率的下限值並無特別限制，但從不會不利地影響耐 久性和耐熱不均勻性的觀點來看，為5.0×108Ω/sq左右。 The surface resistivity of the first adhesive layer 21 of the optical film 1A with an adhesive layer according to this embodiment is preferably 1.0×10 12 Ω/sq or less, particularly preferably 5.0×10 11 Ω/sq or less, and further It is preferably 7.0×10 10 Ω/sq or less. By making the surface resistivity equal to or lower than the above value, it is possible to exert sufficient antistatic properties in the display panel. This surface resistivity can be achieved by making the adhesive composition P contain the antistatic agent (D). In addition, the measurement of the surface resistivity of the first adhesive layer 21 is performed in accordance with JIS K6911, and specifics are shown in the test examples described later. In addition, the lower limit value of the surface resistivity is not particularly limited, but it is about 5.0×10 8 Ω/sq from the viewpoint of not adversely affecting durability and heat resistance unevenness.

7．附有黏著劑層之光學薄膜的使用 7. Use of optical film with adhesive layer

本實施形態之附有黏著劑層之光學薄膜1A係如後述之附有黏著劑層之光學薄膜1B，藉由在第2相位差板12上積層偏光板，能夠作為附有黏著劑層之複合偏光板而使用。藉由使用該附有黏著劑層複合偏光板，例如能夠製造具備液晶單元和複合偏光板之液晶顯示裝置。詳細內容於後述之附有黏著劑層之光學薄膜1B的段落中進行說明。 The optical film 1A with an adhesive layer of this embodiment is an optical film 1B with an adhesive layer as described later. By laminating a polarizing plate on the second retardation plate 12, it can be used as a compound with an adhesive layer Use polarizing plate. By using this adhesive layer-composite polarizing plate, for example, a liquid crystal display device including a liquid crystal cell and a composite polarizing plate can be manufactured. The details are described in the paragraph of the optical film 1B with an adhesive layer to be described later.

〔第2實施形態之附有黏著劑層之光學薄膜〕 [The second embodiment of the optical film with an adhesive layer]

如圖3所示，本發明的第2實施形態之附有黏著劑層之光學薄膜1B構成為具備：第1相位差板11；積層於第1相位差板11的一面(圖3中為下面)之第1黏著劑層21；積層於第1相位差板11之與第1黏著劑層21側的面相反的一面側(圖3中為上面側)之第2黏著劑層22；積層於第2黏著劑層22之與第1相位差板11側的面相反的一面側(圖3中為上面側)之第2相位差板12；及積層於第2相位差板12之與第2黏著劑層22側的面相反的一面側(圖3中為上面側)之偏光板3。亦即，第2實施形態之附有黏著劑層之光學薄膜1B係於前述第1實施形態之附有黏著劑層之光學薄膜1A上積層偏光板3而成者。藉此能夠提供具有非常優異的視角補償性能之附有黏著劑層之複合偏光板。另外，本實施形態之複合偏光板構成為具備：第1相位差板11、第2黏著劑層22、第2相位差板12及偏光板3。 As shown in FIG. 3, the optical film 1B with an adhesive layer according to the second embodiment of the present invention is configured to include: a first retardation plate 11; and a layer laminated on one side of the first retardation plate 11 (in FIG. 3 is the following ) Of the first adhesive layer 21; the second adhesive layer 22 laminated on the side opposite to the surface of the first adhesive layer 21 side of the first phase difference plate 11 (the upper side in FIG. 3); The second phase difference plate 12 on the side opposite to the side of the first phase difference plate 11 (the upper side in FIG. 3) of the second adhesive layer 22; and the second phase difference plate 12 laminated on the second phase difference plate 12 and the second The polarizing plate 3 on the opposite side (upper side in FIG. 3) of the adhesive layer 22 side. That is, the optical film 1B with an adhesive layer of the second embodiment is formed by laminating the polarizing plate 3 on the optical film 1A with an adhesive layer of the first embodiment. Thereby, it is possible to provide a composite polarizing plate with an adhesive layer having very excellent viewing angle compensation performance. In addition, the composite polarizing plate of the present embodiment is configured to include the first retardation plate 11, the second adhesive layer 22, the second retardation plate 12, and the polarizing plate 3.

第2實施形態之附有黏著劑層之光學薄膜1B之第 1相位差板11、第1黏著劑層21、第2黏著劑層22及第2相位差板12分別具有與第1實施形態之附有黏著劑層之光學薄膜1A之第1相位差板11、第1黏著劑層21、第2黏著劑層22及第2相位差板12相同的結構。另外，雖未圖示，亦可於第1黏著劑層21之與第1相位差板11側相反一側的面(圖3中為下面)上積層剝離片，直至附有黏著劑層之光學薄膜1B被使用。 The second embodiment of the optical film with an adhesive layer 1B 1 The phase difference plate 11, the first adhesive layer 21, the second adhesive layer 22, and the second phase difference plate 12 respectively have the first phase difference plate 11 of the optical film 1A with the adhesive layer attached to the first embodiment 1. The first adhesive layer 21, the second adhesive layer 22, and the second retardation plate 12 have the same structure. In addition, although not shown, a release sheet may be laminated on the surface of the first adhesive layer 21 opposite to the first retardation plate 11 side (the lower surface in FIG. 3) until the optical layer with the adhesive layer attached The film 1B is used.

關於上述附有黏著劑層之光學薄膜1B，即使所使用的光學薄膜(複合偏光板)與習知產品相比已進行了薄膜化之情況下，亦會在使用於顯示面板時，耐久性優異，在高溫條件下、濕熱條件下或熱衝擊下亦可抑制翹起或表面剝離的產生。另外，上述顯示面板在高溫條件下亦不易翹曲，還不易產生熱不均。 Regarding the above-mentioned optical film 1B with an adhesive layer, even if the optical film (composite polarizing plate) used has been thinned compared to conventional products, it will be excellent in durability when used in a display panel It can also suppress the occurrence of warping or surface peeling under high temperature conditions, humid heat conditions or thermal shock. In addition, the above display panel is also less likely to warp under high temperature conditions, and is also less prone to thermal unevenness.

1.偏光板 1. Polarizer

本實施形態之偏光板3構成為具備：位於第2相位差板12側之偏光子31及位於與第2相位差板12相反一側之保護層32。另外，雖未圖示，亦可於偏光子31與保護層32之間及/或偏光子31與第2相位差板12之間夾持接著劑層。 The polarizing plate 3 of this embodiment is configured to include a polarizer 31 located on the side of the second retardation plate 12 and a protective layer 32 located on the side opposite to the second retardation plate 12. Although not shown, the adhesive layer may be sandwiched between the polarizer 31 and the protective layer 32 and/or between the polarizer 31 and the second retardation plate 12.

(1)偏光子 (1) Polarizer

偏光子31由二色性色素吸附配向之聚乙烯醇系樹脂薄膜構成為較佳。 The polarizer 31 is preferably composed of a polyvinyl alcohol resin film with a dichroic dye adsorption orientation.

構成偏光子31之聚乙烯醇系樹脂可藉由對聚乙酸乙烯酯系樹脂進行皂化而得到。作為聚乙酸乙烯酯系樹脂，除了乙酸乙烯酯的均聚物即聚乙酸乙烯酯之外，還例示出乙酸乙 烯酯以及可與其共聚合之其他單體共聚物等。作為可與乙酸乙烯酯共聚合之其他單體，例如可舉出不飽和羧酸類、烯烴類、乙烯基醚類、不飽和磺酸類等。 The polyvinyl alcohol-based resin constituting the polarizer 31 can be obtained by saponifying the polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, ethyl acetate is also exemplified. Allyl esters and other monomer copolymers copolymerizable therewith. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids.

聚乙烯醇系樹脂的皂化度通常為85~100莫耳%、較佳為98~100莫耳%的範圍內。聚乙烯醇系樹脂亦可進一步改質。例如，亦可使用被醛類改質之聚乙烯醇縮甲醛或聚乙烯醇縮醛等。聚乙烯醇系樹脂的聚合度通常為1,000~10,000，較佳為1,500~5,000的範圍內。 The saponification degree of the polyvinyl alcohol-based resin is usually in the range of 85 to 100 mol%, preferably 98 to 100 mol%. The polyvinyl alcohol-based resin can be further modified. For example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 to 10,000, preferably 1,500 to 5,000.

藉由經以下製程來較佳地製造出如上述之偏光子31，前述製程有：對聚乙烯醇系樹脂薄膜進行單軸延伸；用二色性色素對聚乙烯醇系樹脂薄膜進行染色並吸附該二色性色素；以及用硼酸水溶液對二色性色素被吸附之聚乙烯醇系樹脂薄膜進行處理。 The polarizer 31 as described above is preferably manufactured by the following process, which includes: uniaxial stretching of the polyvinyl alcohol-based resin film; dyeing and adsorption of the polyvinyl alcohol-based resin film with a dichroic dye The dichroic dye; and the polyvinyl alcohol resin film on which the dichroic dye is adsorbed is treated with an aqueous solution of boric acid.

單軸延伸可在用二色性色素染色之前進行，亦可與用二色性色素染色之過程同時進行，還可在用二色性色素染色之後進行。在用二色性色素染色之後進行單軸延伸時，該單軸延伸可在硼酸處理之前進行，亦可在硼酸處理過程中進行。當然，亦能夠在該等複數個階段進行單軸延伸。進行單軸延伸時，可在圓周速度不同的輥之間向單軸延伸，亦可使用熱輥向單軸延伸。另外，可以是在大氣中進行延伸之乾式延伸，亦可為在經溶劑膨潤之狀態下進行延伸之濕式延伸。延伸倍率通常為4~8倍左右。 Uniaxial stretching can be performed before dyeing with dichroic pigments, or simultaneously with the process of dyeing with dichroic pigments, or after dyeing with dichroic pigments. When uniaxial stretching is performed after dyeing with a dichroic pigment, the uniaxial stretching may be performed before boric acid treatment or may be performed during boric acid treatment. Of course, it is also possible to perform uniaxial extension in these plural stages. When uniaxial stretching is performed, it can be uniaxially extended between rollers with different peripheral speeds, or it can be uniaxially extended using a hot roller. In addition, it may be dry stretching in the atmosphere, or wet stretching in the state of being swollen with a solvent. The stretch magnification is usually about 4 to 8 times.

用二色性色素對聚乙烯醇系樹脂薄膜進行染色時，例如，將聚乙烯醇系樹脂薄膜浸漬於含有二色性色素之水溶液 中即可。具體可使用碘或二色性有機染料作為二色性色素。 When dyeing a polyvinyl alcohol-based resin film with a dichroic dye, for example, the polyvinyl alcohol-based resin film is immersed in an aqueous solution containing a dichroic dye It’s ok. Specifically, iodine or a dichroic organic dye can be used as a dichroic pigment.

使用碘作為二色性色素時，通常採用將聚乙烯醇系樹脂薄膜浸漬於含有碘以及碘化鉀的水溶液中而進行染色的方法。該水溶液中碘的含量相對於每100質量份水，通常為0.01~0.5質量份左右，碘化鉀的含量相對於每100質量份水，通常為0.5~10質量份左右。該水溶液的溫度通常為20~40℃左右，另外，於該水溶液中之浸漬時間(染色時間)通常為30~300秒左右。 When iodine is used as a dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide and dyeing is generally used. The content of iodine in the aqueous solution is usually about 0.01 to 0.5 parts by mass per 100 parts by mass of water, and the content of potassium iodide is usually about 0.5 to 10 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution is usually about 20 to 40°C, and the immersion time (dyeing time) in the aqueous solution is usually about 30 to 300 seconds.

用二色性色素染色之後的硼酸處理藉由將經染色的聚乙烯醇系樹脂薄膜浸漬於硼酸水溶液來進行。硼酸水溶液中的硼酸的含量相對於每100質量份水，通常為2~15質量份左右，較佳為5~12質量份左右。使用碘作為二色性色素時，該硼酸水溶液中含有碘化鉀為較佳。硼酸水溶液中的碘化鉀的含量相對於每100質量份水，通常為2~20質量份左右，較佳為5~15質量份。於硼酸水溶液中之浸漬時間通常為100~1,200秒左右，較佳為150~600秒左右，進一步較佳為200~400秒左右。硼酸水溶液的溫度通常為50℃以上，較佳為50~85℃。 The boric acid treatment after dyeing with a dichroic pigment is performed by immersing the dyed polyvinyl alcohol-based resin film in an aqueous solution of boric acid. The content of boric acid in the aqueous solution of boric acid is generally about 2 to 15 parts by mass, preferably about 5 to 12 parts by mass, per 100 parts by mass of water. When iodine is used as the dichroic dye, it is preferable that the boric acid aqueous solution contains potassium iodide. The content of potassium iodide in the aqueous solution of boric acid per 100 parts by mass of water is usually about 2 to 20 parts by mass, preferably 5 to 15 parts by mass. The immersion time in the boric acid aqueous solution is usually about 100 to 1,200 seconds, preferably about 150 to 600 seconds, and more preferably about 200 to 400 seconds. The temperature of the boric acid aqueous solution is usually 50°C or higher, preferably 50 to 85°C.

硼酸處理之後的聚乙烯醇系樹脂薄膜通常被水洗處理。水洗處理藉由例如將經硼酸處理的聚乙烯醇系樹脂薄膜浸漬於水中來進行。水洗後進行乾燥處理，從而得到偏光子31。水洗處理中的水溫通常為5~40℃左右，浸漬時間通常為2~120秒左右。其後進行的乾燥處理通常使用熱風乾燥機或遠紅外線加熱器來進行。乾燥溫度通常為40~100℃。另外，乾燥 處理時間通常為120~600秒左右。 The polyvinyl alcohol-based resin film after boric acid treatment is usually washed with water. The water washing treatment is performed by, for example, immersing the boric acid-treated polyvinyl alcohol-based resin film in water. After washing with water, a drying process is performed to obtain polarizer 31. The water temperature in the washing process is usually about 5 to 40°C, and the dipping time is usually about 2 to 120 seconds. The subsequent drying treatment is usually performed using a hot air dryer or a far-infrared heater. The drying temperature is usually 40~100℃. In addition, dry The processing time is usually about 120 to 600 seconds.

偏光子31的厚度為3~50μm左右為較佳，尤其被要求薄膜化時，3~15μm左右為較佳。 The thickness of the polarizer 31 is preferably about 3 to 50 μm, and particularly when thinning is required, about 3 to 15 μm is preferable.

(2)保護層 (2) Protective layer

保護層32由透明樹脂薄膜構成為較佳。構成保護層32的透明樹脂薄膜可以是未經延伸之薄膜、或被單軸或者雙軸延伸之薄膜中的任一者。 The protective layer 32 is preferably made of a transparent resin film. The transparent resin film constituting the protective layer 32 may be either an unstretched film or a uniaxially or biaxially stretched film.

構成保護層32的透明樹脂薄膜的主成分較佳為選自由聚酯系樹脂、聚碳酸酯系樹脂、丙烯酸系樹脂、非晶性聚烯烴系樹脂以及纖維素系樹脂構成的組群之至少一種樹脂。上述之中，保護層32由纖維素系樹脂構成為較佳。 The main component of the transparent resin film constituting the protective layer 32 is preferably at least one selected from the group consisting of polyester resins, polycarbonate resins, acrylic resins, amorphous polyolefin resins, and cellulose resins Resin. Among the above, the protective layer 32 is preferably composed of cellulose-based resin.

作為纖維素系樹脂，係纖維素中的羥基的至少一部分被乙酸酯化的樹脂，亦可以是一部分被乙酸酯化且一部分被其他酸酯化的混合酯。纖維素系樹脂較佳為纖維素酯系樹脂，更佳為乙醯纖維素系樹脂。作為乙醯纖維素系樹脂的具體例，可舉出三乙醯纖維素、二乙醯纖維素、乙酸丙酸纖維素、乙酸丁酸纖維素等。作為由這樣的乙醯纖維素系樹脂構成的薄膜的市售品，例如可舉出：FUJIFILM Corporation製造的“Fujitac TD80”、“Fujitac TD80UF”以及“Fujitac TD80UZ”；Konica Minolta Opto Products Co.,Ltd.製造的“KC8UX2M”、“KC2UA”以及“KC8UY”等。 As the cellulose-based resin, a resin in which at least a part of hydroxyl groups in the cellulose is esterified with acetate may be a mixed ester in which a part of the hydroxyl group is esterified with acetate and a part of the hydroxyl group is esterified with another. The cellulose-based resin is preferably a cellulose ester-based resin, and more preferably an acetyl cellulose-based resin. Specific examples of the acetyl cellulose-based resin include triacetyl cellulose, diethyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate. Examples of commercially available films made of such acetyl cellulose-based resins include "Fujitac TD80", "Fujitac TD80UF", and "Fujitac TD80UZ" manufactured by FUJIFILM Corporation; Konica Minolta Opto Products Co., Ltd. .Manufactured "KC8UX2M", "KC2UA" and "KC8UY" etc.

亦可使用被賦予光學補償功能的纖維素系樹脂薄膜作為保護層32。作為該光學補償薄膜，例如可舉出：在纖維素系樹脂中含有具有相位差調整功能的化合物之薄膜；在纖維 素系樹脂的表面上塗佈有具有相位差調整功能的化合物者；以及將纖維素系樹脂單軸或者雙軸延伸而得到的薄膜等。市售中的纖維素系樹脂的光學補償薄膜的例子可舉出：FUJIFILM Corporation製造的“Wide View Film WV BZ 438”以及“Wide View Film WV EA”、Konica Minolta Opto Products Co.,Ltd.製造的“KC4FR-1”以及“KC4HR-1”等。 As the protective layer 32, a cellulose resin film provided with an optical compensation function may be used. As the optical compensation film, for example, a film containing a compound having a phase difference adjustment function in a cellulose-based resin; A compound having a phase difference adjustment function coated on the surface of the element-based resin; a film obtained by uniaxially or biaxially stretching the cellulose-based resin. Examples of commercially available cellulose-based resin optical compensation films include “Wide View Film WV BZ 438” manufactured by FUJIFILM Corporation and “Wide View Film WV EA”, manufactured by Konica Minolta Opto Products Co., Ltd. "KC4FR-1" and "KC4HR-1" etc.

在上述纖維素系樹脂之中，保護層32由纖維素酯系樹脂構成為較佳，由乙醯纖維素系樹脂構成為特佳，由三乙醯纖維素構成為進一步較佳。 Among the above-mentioned cellulose-based resins, the protective layer 32 is preferably composed of a cellulose ester-based resin, particularly preferably composed of an acetyl cellulose-based resin, and further preferably composed of tri-acetyl cellulose.

保護層32亦可含有紫外線吸收劑。這是因為，藉由將含有紫外線吸收劑的保護層配置於液晶單元的視認側，能夠保護液晶單元不因紫外線劣化。 The protective layer 32 may also contain an ultraviolet absorber. This is because, by arranging a protective layer containing an ultraviolet absorber on the viewing side of the liquid crystal cell, the liquid crystal cell can be protected from deterioration by ultraviolet light.

保護層32在貼合於偏光子31之前，可對貼合面實施皂化處理、電暈處理、底漆處理、錨塗層處理等的易接著處理。另外，保護層32之與偏光子31的貼合面相反一側的表面可具有硬塗層、抗反射層、防眩層等各種處理層。 Before the protective layer 32 is bonded to the polarizer 31, the bonding surface may be subjected to easy adhesion treatment such as saponification treatment, corona treatment, primer treatment, anchor coating treatment, and the like. In addition, the surface of the protective layer 32 opposite to the bonding surface of the polarizer 31 may have various treatment layers such as a hard coat layer, an anti-reflection layer, and an anti-glare layer.

保護層32的厚度通常為5~200μm左右的範圍，較佳為10~120μm，特佳為10~85μm，進一步較佳為10~30μm。 The thickness of the protective layer 32 is usually in the range of about 5 to 200 μm, preferably 10 to 120 μm, particularly preferably 10 to 85 μm, and further preferably 10 to 30 μm.

(3)接著劑層 (3) Adhesive layer

作為構成亦可夾持於偏光子31與保護層32之間及/或偏光子31與第2相位差板12之間的接著劑層之接著劑，可根據被著體的種類和目的而適宜地使用適當者。例如可舉出溶劑型接著劑、乳液型接著劑、水系接著劑、感壓性接著劑、再濕性接 著劑、縮聚型接著劑、無溶劑型接著劑、薄膜狀接著劑、熱熔型接著劑等。 As a configuration, the adhesive of the adhesive layer that may be sandwiched between the polarizer 31 and the protective layer 32 and/or between the polarizer 31 and the second retardation plate 12 may be suitable according to the type and purpose of the object Use the appropriate one. Examples include solvent-based adhesives, emulsion-based adhesives, water-based adhesives, pressure-sensitive adhesives, and rewet adhesives. Adhesives, polycondensation adhesives, solventless adhesives, film adhesives, hot melt adhesives, etc.

構成上述接著劑的一較佳的接著劑為水系接著劑，其代表例係以聚乙烯醇系樹脂為主成分者。作為可以是水系接著劑即市售的聚乙烯醇系樹脂，例如有KURARAY CO.,LTD製造的“KL-318”等。 A preferred adhesive constituting the above adhesive is an aqueous adhesive, and a representative example thereof is a polyvinyl alcohol resin as a main component. Examples of commercially available polyvinyl alcohol-based resins that can be water-based adhesives include “KL-318” manufactured by KURARAY CO., LTD.

上述水系接著劑可含有交聯劑。作為交聯劑，胺化合物、醛化合物、羥甲基化合物、環氧基化合物、異氰酸酯化合物、多價金屬鹽等為較佳，特佳為環氧基化合物。作為交聯劑的市售品，例如有乙二醛或、Sumika Chemtex Company,Limited販售的水溶性環氧基化合物的水溶液之“Sumirez Resin650(30)”等。 The water-based adhesive may contain a cross-linking agent. As the crosslinking agent, amine compounds, aldehyde compounds, methylol compounds, epoxy compounds, isocyanate compounds, polyvalent metal salts and the like are preferred, and epoxy compounds are particularly preferred. As a commercially available product of the crosslinking agent, for example, there are "Sumirez Resin 650 (30)" of glyoxal or an aqueous solution of a water-soluble epoxy compound sold by Sumika Chemtex Company, Limited.

作為其他較佳的接著劑，可舉出由含有藉由活性能量射線的照射或加熱而硬化的環氧樹脂之環氧系樹脂組成物構成的接著劑。使用該接著劑時，薄膜間的接著可藉由對夾持於薄膜間的接著劑層照射活性能量射線或加熱，使接著劑所含的硬化性環氧樹脂硬化來進行。基於活性能量射線的照射或加熱之環氧樹脂的硬化，以藉由環氧樹脂的陽離子聚合來進行為較佳，另外，本說明書中的環氧樹脂是指在分子內具有兩個以上的環氧基的化合物。 Examples of other preferable adhesives include adhesives composed of an epoxy resin composition containing an epoxy resin hardened by irradiation or heating of active energy rays. When using this adhesive, the bonding between the films can be performed by irradiating the adhesive layer sandwiched between the films with active energy rays or heating to harden the curable epoxy resin contained in the adhesive. The curing of the epoxy resin by irradiation of active energy rays or heating is preferably carried out by cationic polymerization of the epoxy resin. In addition, the epoxy resin in this specification refers to having two or more rings in the molecule. Oxygen compounds.

從耐候性、折射率、陽離子聚合性的觀點來看，接著劑，即硬化性環氧樹脂組成物中所含的環氧樹脂為分子內不含芳香環的環氧樹脂為較佳。作為這樣的環氧樹脂，可例示氫化環氧樹脂、脂環式環氧樹脂、脂肪族環氧樹脂等。 From the viewpoint of weather resistance, refractive index, and cationic polymerizability, it is preferable that the epoxy resin contained in the adhesive agent, that is, the curable epoxy resin composition is an epoxy resin that does not contain an aromatic ring in the molecule. Examples of such epoxy resins include hydrogenated epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

2.附有黏著劑層之光學薄膜的製造方法 2. Manufacturing method of optical film with adhesive layer

對附有黏著劑層之光學薄膜1B的製造方法的較佳例進行說明。 A preferred example of the method for manufacturing the optical film 1B with the adhesive layer attached will be described.

(1)複合偏光板的製造 (1) Manufacture of composite polarizer

複合偏光板的製造可藉由通常的方法進行。以下，作為一例，對使用水系接著劑作為上述接著劑時的製造方法進行說明。 The production of the composite polarizing plate can be carried out by a usual method. In the following, as an example, a manufacturing method when an aqueous adhesive is used as the adhesive will be described.

首先，於剝離片的剝離面形成構成第2黏著劑層22之黏著劑的塗膜。具體而言，將構成第2黏著劑層22之黏著劑的塗佈溶液塗佈於剝離片的剝離面後進行乾燥。 First, a coating film of the adhesive constituting the second adhesive layer 22 is formed on the peeling surface of the peeling sheet. Specifically, the coating solution of the adhesive constituting the second adhesive layer 22 is applied to the peeling surface of the peeling sheet, and then dried.

另一方面，於偏光子31的貼合面或第2相位差板12以及保護層32的貼合面形成接著劑層。接著劑層的形成可利用例如棒塗法、刮刀塗佈法、輥塗佈法、刮板塗佈法、模具塗佈法、凹版塗佈法等。另外，亦能夠採用以使兩者的貼合面成為內側的方式連續供給偏光子31與保護層32，同時於其之間使接著劑流延之方式。塗佈接著劑後，根據需要實施加熱處理而使水分蒸發，從而乾燥接著劑層。 On the other hand, an adhesive layer is formed on the bonding surface of the polarizer 31 or the bonding surface of the second retardation plate 12 and the protective layer 32. For the formation of the adhesive layer, for example, a bar coating method, a blade coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used. In addition, a method of continuously supplying the polarizer 31 and the protective layer 32 such that the bonding surface of the two is the inner side while casting the adhesive between them is also possible. After the adhesive is applied, heat treatment is performed as necessary to evaporate water to dry the adhesive layer.

接著劑層的膜厚可根據偏光板3的特性設計來任意設定，但從降低接著劑材料成本的觀點來看，較小者為較佳，從抑制貼合時的氣泡或異物等缺點的觀點來看，較大者為較佳，從密接性、耐久性的觀點來看，在按每個被著體與接著劑的組合所確定的最佳範圍內實施為較佳。一般為0.005~10μm、較佳為0.01~5μm、進一步較佳為0.03~1μm。 The thickness of the adhesive layer can be arbitrarily set according to the characteristic design of the polarizing plate 3, but from the viewpoint of reducing the material cost of the adhesive, the smaller one is preferable, and from the viewpoint of suppressing defects such as bubbles or foreign substances during bonding In view of this, the larger one is better, and from the viewpoint of adhesion and durability, it is preferably implemented within the optimum range determined for each combination of the object and the adhesive. It is generally 0.005 to 10 μm, preferably 0.01 to 5 μm, and more preferably 0.03 to 1 μm.

在接著第2相位差板12及偏光子31，或接著偏光 子31及保護層32時，亦可在兩者的貼合面中的一方或雙方，於形成接著劑的塗佈層之前，實施如電暈放電處理、電漿處理、火焰處理、底漆處理、錨塗層處理之易接著處理。 After the second phase difference plate 12 and the polarizer 31, or after the polarized light For the sub-31 and the protective layer 32, one or both of the bonding surfaces of the two may be subjected to corona discharge treatment, plasma treatment, flame treatment, primer treatment before forming the coating layer of the adhesive , Easy to deal with anchor coating.

如上述般形成接著劑層之後，隔著該接著劑層將保護層32貼合於偏光子31的一面，並且將第2相位差板12貼合於偏光子31的另一面，從而獲得由保護層32、偏光子31及第2相位差板12構成之積層體。 After the adhesive layer is formed as described above, the protective layer 32 is bonded to one side of the polarizer 31 via the adhesive layer, and the second retardation plate 12 is bonded to the other side of the polarizer 31 to obtain protection. The layered body composed of the layer 32, the polarizer 31, and the second retardation plate 12.

之後，於所得到之積層體的第2相位差板12側的面上貼合構成上述剝離片上的第2黏著劑層22之黏著劑的塗膜。並且，隔著上述剝離片照射活性能量射線而使上述黏著劑的塗膜硬化，將該塗膜設為第2黏著劑層22。活性能量射線的照射條件等與前述附有黏著劑層之光學薄膜1A的製造方法相同。 After that, a coating film of an adhesive that constitutes the second adhesive layer 22 on the release sheet is bonded to the surface of the obtained laminated body on the second retardation plate 12 side. In addition, active energy rays are irradiated through the release sheet to harden the coating film of the adhesive, and this coating film is used as the second adhesive layer 22. The irradiation conditions of the active energy rays and the like are the same as the method of manufacturing the optical film 1A with the adhesive layer.

最後，從藉由上述所形成的第2黏著劑層22將剝離片剝離，將第1相位差板11之第2丙烯酸系樹脂層113側的面貼合於被露出的第2黏著劑層22。藉此，得到由保護層32、偏光子31、第2相位差板12、第2黏著劑層22以及第1相位差板11積層而成的複合偏光板2B。 Finally, the peeling sheet is peeled off from the second adhesive layer 22 formed as described above, and the surface of the first retardation film 11 on the second acrylic resin layer 113 side is bonded to the exposed second adhesive layer 22 . Thereby, a composite polarizing plate 2B obtained by stacking the protective layer 32, the polarizer 31, the second retardation plate 12, the second adhesive layer 22, and the first retardation plate 11 is obtained.

另外，複合偏光板2B的總厚度為20~300μm為較佳，30~150μm為更佳，50~100μm為特佳。 In addition, the total thickness of the composite polarizing plate 2B is preferably 20 to 300 μm, more preferably 30 to 150 μm, and particularly preferably 50 to 100 μm.

(2)第1黏著劑層之黏著片的製造 (2) Manufacture of the adhesive sheet of the first adhesive layer

另一方面，製造於由黏著性組成物P形成的第1黏著劑層21面或兩面之上積層剝離片而成之黏著片。在此，以製造於第1黏著劑層21兩面之上積層剝離片而成之黏著片者作為一例。 該黏著片可藉由於附有黏著劑層之光學薄膜1A的製造方法中所說明之方法進行製造。 On the other hand, an adhesive sheet manufactured by laminating a release sheet on the 21 side or both sides of the first adhesive layer formed of the adhesive composition P is manufactured. Here, as an example, an adhesive sheet manufactured by stacking peeling sheets on both sides of the first adhesive layer 21 is laminated. This adhesive sheet can be manufactured by the method described in the manufacturing method of the optical film 1A with an adhesive layer attached.

(3)附有黏著劑層之光學薄膜的製造 (3) Manufacture of optical film with adhesive layer

從如上述般得到的黏著片中剝離一側的剝離片(輕剝離型剝離片)。然後，將複合偏光板的第1相位差板11重疊於露出之第1黏著劑層21，壓著黏著片與複合偏光板。藉此，得到附有上述黏著劑層之光學薄膜1B(附有剝離片)。 One side release sheet (light release type release sheet) was peeled from the adhesive sheet obtained as described above. Then, the first phase difference plate 11 of the composite polarizing plate is overlaid on the exposed first adhesive layer 21, and the adhesive sheet and the composite polarizing plate are pressed. Thereby, the optical film 1B (with the release sheet attached) with the above-mentioned adhesive layer is obtained.

作為附有黏著劑層之光學薄膜1B的製造方法的其他例，在剝離片的剝離面上塗佈含前述黏著性組成物P之溶液，進行加熱處理而形成塗膜之後，將複合偏光板的第1相位差板11重疊於該塗膜。上述塗膜在需要養護期時，間隔養護期而形成黏著劑層，而在不需要養護期時，直接形成第1黏著劑層21。藉此，得到附有上述黏著劑層之光學薄膜1B(附有剝離片)。 As another example of the method for manufacturing the optical film 1B with an adhesive layer, a solution containing the adhesive composition P is applied to the peeling surface of the release sheet, and heat treatment is performed to form a coating film. The first retardation film 11 overlaps this coating film. When the above-mentioned coating film requires a curing period, the adhesive layer is formed at intervals of the curing period, and when the curing period is not required, the first adhesive layer 21 is directly formed. Thereby, the optical film 1B (with the release sheet attached) with the above-mentioned adhesive layer is obtained.

3.附有黏著劑層之光學薄膜的物性 3. Physical properties of optical film with adhesive layer

本實施形態之附有黏著劑層之光學薄膜1B的黏著力及表面電阻率與前述附有黏著劑層之光學薄膜1A相同。 The adhesive force and surface resistivity of the optical film 1B with an adhesive layer of this embodiment are the same as those of the optical film 1A with an adhesive layer.

4．附有黏著劑層之光學薄膜的使用 4. Use of optical film with adhesive layer

藉由使用附有黏著劑層之光學薄膜1B，例如能夠製造具備液晶單元及複合偏光板之液晶顯示裝置。 By using the optical film 1B with an adhesive layer, for example, a liquid crystal display device including a liquid crystal cell and a composite polarizing plate can be manufactured.

具體而言，將附有黏著劑層之光學薄膜1B的第1黏著劑層21(當積層有剝離片時，剝離該剝離片後被露出的第1黏著劑層21)重疊於液晶單元的所希望的面並進行壓著即可。藉此，能夠得到具備液晶單元與複合偏光板之液晶顯示裝 置。 Specifically, the first adhesive layer 21 of the optical film 1B with an adhesive layer (when a release sheet is laminated, the first adhesive layer 21 exposed after peeling off the release sheet) is overlaid on the liquid crystal cell. Just press the desired surface. By this, a liquid crystal display device including a liquid crystal cell and a composite polarizing plate can be obtained Set.

本實施形態之附有黏著劑層之光學薄膜1B的第1黏著劑層21，由於其耐久性優異，即使將所得到的液晶顯示裝置放置於高溫條件下、濕熱條件下或熱衝擊下，亦能夠抑制第1黏著劑層21的界面發生翹起或表面剝離。例如，當將貼附了附有黏著劑層之光學薄膜1B之玻璃板於85℃的高溫條件下或60℃、90%RH的濕熱條件下放置250小時的情況、或施加-35℃~70℃的熱衝擊(各30分鐘，200循環)的情況下，均能夠抑制發生翹起或表面剝離。 Since the first adhesive layer 21 of the optical film 1B with an adhesive layer of this embodiment has excellent durability, even if the resulting liquid crystal display device is placed under high temperature conditions, humid heat conditions or thermal shock, It can suppress that the interface of the first adhesive layer 21 is warped or the surface peels off. For example, when a glass plate with an optical film 1B with an adhesive layer attached is placed under high temperature conditions of 85°C or 60°C, 90%RH under humid heat for 250 hours, or -35°C to 70°C is applied In the case of a thermal shock at ℃ (200 cycles for 30 minutes each), the occurrence of warpage or surface peeling can be suppressed.

另外，本實施形態之附有黏著劑層之光學薄膜1B的第1黏著劑層21，由於其應力緩和性亦優異，所得到的液晶顯示裝置在高溫條件下亦不易翹曲、進而難以產生熱不均。例如，將貼附了附有黏著劑層之光學薄膜1B之玻璃板於高溫條件下(例如，80~85℃的條件下)放置250小時的情況下，亦不易翹曲，進而難以產生熱不均。尤其，即使複合偏光板為薄膜，液晶顯示裝置亦不易翹曲，另外，即使液晶單元為高精細者，亦不易產生熱不均。 In addition, the first adhesive layer 21 of the optical film 1B with an adhesive layer according to the present embodiment is also excellent in stress relaxation, and the resulting liquid crystal display device is also less likely to warp under high temperature conditions and thus hardly generate heat. Uneven. For example, when a glass plate with an optical film 1B with an adhesive layer attached is placed under high temperature conditions (for example, under conditions of 80 to 85° C.) for 250 hours, it is not easy to warp, and it is difficult to generate heat. all. In particular, even if the composite polarizer is a thin film, the liquid crystal display device is less likely to warp, and even if the liquid crystal cell is high-definition, it is less likely to cause thermal unevenness.

第1黏著劑層21所接觸的液晶單元的表面上亦可存在透明導電膜。作為該透明導電膜，例如可舉出，鉑、金、銀、銅等金屬、氧化錫、氧化銦、氧化鎘、氧化鋅、二氧化鋅等氧化物、錫摻雜氧化銦(ITO)、氧化鋅摻雜氧化銦、氟摻雜氧化銦、銻摻雜氧化錫、氟摻雜氧化錫、鋁摻雜氧化鋅等複合氧化物、硫屬化物、六硼化鑭、氮化鈦、碳化鈦等非氧化化合物等構成者。 A transparent conductive film may be present on the surface of the liquid crystal cell that the first adhesive layer 21 contacts. Examples of the transparent conductive film include metals such as platinum, gold, silver, and copper, oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide, and zinc oxide, tin-doped indium oxide (ITO), and oxide Zinc-doped indium oxide, fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide and other composite oxides, chalcogenides, lanthanum hexaboride, titanium nitride, titanium carbide, etc. Non-oxidized compounds and other constituents.

以上所說明之實施形態係為便於理解本發明而記載者，並非為限定本發明而記載者。因此，宗旨為上述實施形態中所揭示之各要素中亦包括屬於本發明的技術範圍之所有設計變更和等價物。 The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, the aim is to include all design changes and equivalents belonging to the technical scope of the present invention in the elements disclosed in the above-mentioned embodiments.

【實施例】 【Example】

以下，藉由實施例等進一步對本發明進行具體說明，但本發明的範圍並不限定於該等實施例等。 Hereinafter, the present invention will be further specifically described with examples and the like, but the scope of the present invention is not limited to these examples and the like.

〔實施例1〕 [Example 1]

1.光學薄膜(複合偏光板)的製造 1. Manufacture of optical film (composite polarizer)

(1)偏光子的製作 (1) Production of polarizer

將由平均聚合度約2,400、皂化度99.9莫耳%以上的聚乙烯醇構成的厚度為75μm的聚乙烯醇薄膜，以乾式單軸延伸方式延伸約5倍，進一步保持拉緊狀態下，於60℃的純水中浸漬1分鐘。之後，於碘/碘化鉀/水的質量比為0.05/5/100的水溶液中以28℃浸漬60秒。接著，於碘化鉀/硼酸/水的質量比為8.5/8.5/100的水溶液中以72℃浸漬300秒。然後，在用26℃的純水洗滌20秒以後，以65℃進行乾燥而得到碘吸附配向於聚乙烯醇的偏光子。 A polyvinyl alcohol film with a thickness of 75 μm composed of polyvinyl alcohol having an average degree of polymerization of about 2,400 and a saponification degree of 99.9 mol% or more is stretched by dry uniaxial stretching for about 5 times, and further maintained under tension at 60°C In pure water for 1 minute. After that, it was immersed in an aqueous solution having a mass ratio of iodine/potassium iodide/water of 0.05/5/100 at 28°C for 60 seconds. Next, it was immersed in an aqueous solution having a mass ratio of potassium iodide/boric acid/water of 8.5/8.5/100 at 72° C. for 300 seconds. Then, after washing with pure water at 26° C. for 20 seconds, it was dried at 65° C. to obtain a polarizer having iodine adsorbed and aligned to polyvinyl alcohol.

(2)偏光板的製作 (2) Fabrication of polarizing plates

製備將3質量份的羧基改質聚乙烯醇(KURARAY CO.,LTD製造，商品名“KL-318”)溶解於100質量份的水，並向該水溶液中添加了1.5質量份水溶性環氧樹脂，即聚醯胺環氧系添加劑(Taoka Chemical Co.,Ltd.製造，商品名“Sumirez Resin 650(30)”，固體成分濃度30質量%的水溶液)而得到的環氧系 接著劑。將該環氧系接著劑塗佈於藉由上述而得到的偏光子的一面。 Preparation of 3 parts by mass of carboxy-modified polyvinyl alcohol (manufactured by KURARAY CO., LTD, trade name "KL-318") was dissolved in 100 parts by mass of water, and 1.5 parts by mass of water-soluble epoxy was added to this aqueous solution Resin, that is, an epoxy-based additive of polyamide (made by Taoka Chemical Co., Ltd., trade name "Sumirez Resin 650(30)", an aqueous solution with a solid concentration of 30% by mass) Then agent. This epoxy-based adhesive is applied to one side of the polarizer obtained as described above.

於上述環氧系接著劑的塗佈層之上，貼合表面實施了皂化處理的厚度25μm的三乙醯纖維素薄膜(Konica Minolta Opto Products Co.,Ltd.製造，商品名“KC2UA”)作為保護層，從而得到積層保護層以及偏光子而成之偏光板。 On the coating layer of the above-mentioned epoxy-based adhesive, a 25 μm-thick triacetyl cellulose film (manufactured by Konica Minolta Opto Products Co., Ltd., trade name “KC2UA”) with a saponification surface bonded to it was used as A protective layer to obtain a polarizing plate formed by laminating a protective layer and a polarizer.

(3)含偏光板以及第2相位差板的積層體的製作 (3) Fabrication of a laminate including a polarizing plate and a second retardation plate

接著，於上述偏光板之偏光子的另一面，與上述相同地塗佈環氧系接著劑，並於該塗佈層之上，貼合厚度23μm的由環狀烯烴系樹脂構成的零相位差薄膜(Zeon Corporation製造，商品名“ZEONOR”)作為第2相位差板。之後以80℃乾燥5分鐘，藉此將上述第1保護層以及第2保護層接著於偏光子。接著之後，以40℃養護168小時，得到積層保護層(層厚25μm)、偏光子(延伸倍率5倍，層厚15μm)以及第2相位差板(層厚23μm)而成之總厚度63μm的積層體。 Next, on the other surface of the polarizer of the polarizer, an epoxy adhesive was applied in the same manner as above, and a phase retardation composed of a cyclic olefin resin having a thickness of 23 μm was laminated on the coating layer. A thin film (manufactured by Zeon Corporation, trade name "ZEONOR") is used as the second retardation plate. Then, it was dried at 80° C. for 5 minutes, thereby attaching the first protective layer and the second protective layer to the polarizer. After that, curing was carried out at 40°C for 168 hours to obtain a total thickness of 63 μm made up of a laminated protective layer (layer thickness 25 μm), polarizers (elongation magnification 5 times, layer thickness 15 μm) and a second retardation plate (layer thickness 23 μm) Layered body.

(4)活性能量射線硬化性黏著劑的塗膜的形成 (4) Formation of coating film of active energy ray hardening adhesive

共聚合丙烯酸正丁酯95質量份以及丙烯酸5質量份而製備(甲基)丙烯酸酯聚合物(X)。藉由後述方法測定該(甲基)丙烯酸酯聚合物(X)的分子量，結果重量平均分子量(Mw)為200萬。 95 parts by mass of n-butyl acrylate and 5 parts by mass of acrylic acid were copolymerized to prepare a (meth)acrylate polymer (X). The molecular weight of this (meth)acrylate polymer (X) was measured by the method described later, and as a result, the weight average molecular weight (Mw) was 2 million.

藉由將上述(甲基)丙烯酸酯聚合物(X)100質量份、作為活性能量射線硬化性化合物(Y)(多官能單體)的三(丙烯醯氧基乙基)異氰脲酸酯(TOAGOSEI CO.,LTD.製造，商品名“ARONIXM-315”)15質量份、作為交聯劑(Z)的三羥 甲基丙烷改質甲苯二異氰酸酯(Nippon Polyurethane Industry Co.,Ltd.製造，商品名“CORONATEL”)0.3質量份、作為聚合起始劑的將二苯甲酮以及1-羥基環己基苯基甲酮以1：1的質量比進行混合之混合物(Chiba Specialty Chemicals公司製造，商品名“IRGACURE 500”)1.5質量份、以及作為矽烷偶合劑的3-縮水甘油氧基丙基三甲氧基矽烷(Shin-Etsu Chemical Co.,Ltd.製造，商品名“KBM403”)0.2質量份進行混合，充分攪拌並用乙酸乙酯進行稀釋，得到活性能量射線硬化性黏著劑的塗佈溶液。 By using 100 parts by mass of the (meth)acrylate polymer (X) as the active energy ray-curable compound (Y) (multifunctional monomer), tris(acryloyloxyethyl)isocyanurate (Manufactured by TOAGOSEI CO., LTD., trade name "ARONIXM-315") 15 parts by mass of trihydroxy as a crosslinking agent (Z) Methylpropane modified toluene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "CORONATEL") 0.3 parts by mass, benzophenone and 1-hydroxycyclohexyl phenyl ketone as polymerization initiators 1.5 parts by mass of a mixture (manufactured by Chiba Specialty Chemicals, trade name "IRGACURE 500") mixed at a mass ratio of 1:1, and 3-glycidoxypropyltrimethoxysilane (Shin- Etsu Chemical Co., Ltd., trade name "KBM403") 0.2 parts by mass are mixed, sufficiently stirred and diluted with ethyl acetate to obtain a coating solution of an active energy ray-curable adhesive.

於聚對苯二甲酸乙二酯薄膜的一面被矽酮系剝離劑進行了剝離處理而得到的剝離片(LINTEC Corporation製造，SP-PET3811，厚度：38μm)的剝離處理面，用刀式塗佈機塗佈所得到的活性能量射線硬化性黏著劑的塗佈溶液之後，以90℃加熱處理1分鐘，從而形成活性能量射線硬化性黏著劑的塗膜。 The peeling surface of a peeling sheet (manufactured by LINTEC Corporation, SP-PET3811, thickness: 38 μm) obtained by peeling the silicone terephthalate film on one side of the polyethylene terephthalate film was coated with a knife After the obtained coating solution of the active energy ray-curable adhesive is machine-applied, heat treatment is performed at 90° C. for 1 minute to form a coating film of the active energy ray-curable adhesive.

(5)第1相位差板的製作 (5) Fabrication of the first phase difference plate

將配合有構成第1丙烯酸系樹脂層的平均粒徑200nm的丙烯酸系橡膠粒子約20質量%之甲基丙烯酸系樹脂(Sumitomo Chemical Co.,Ltd.製造，商品名“Technolloy S001”)、構成相位差表現層的苯乙烯-馬來酸酐系共聚合樹脂(NOVA Chemicals Corporation.，商品名“DYLARK D332”)、以及配合有構成第2丙烯酸系樹脂層的平均粒徑200nm的丙烯酸系橡膠粒子約20質量%之甲基丙烯酸系樹脂(Sumitomo Chemical Co.,Ltd.製造，商品名“Technolloy S001”)，按該順序進行3層共擠出，得 到3層結構的積層薄膜。將所得到的積層薄膜進行延伸，從而得到面內相位差值為60nm、厚度25μm的第1相位差板(第1丙烯酸系樹脂層/相位差表現層/第2丙烯酸系樹脂層)。 A methacrylic resin (manufactured by Sumitomo Chemical Co., Ltd., trade name "Technolloy S001") containing approximately 20% by mass of acrylic rubber particles constituting the first acrylic resin layer with an average particle diameter of 200 nm, and a phase The styrene-maleic anhydride-based copolymer resin (NOVA Chemicals Corporation., trade name "DYLARK D332") of the poor expression layer, and acrylic rubber particles containing an average particle diameter of 200 nm constituting the second acrylic resin layer are about 20 Mass% methacrylic resin (manufactured by Sumitomo Chemical Co., Ltd., trade name "Technolloy S001"), in this order, 3 layers of co-extrusion are obtained, Multilayer film with 3 layers. The obtained laminated film was stretched to obtain a first retardation plate (first acrylic resin layer/retardation expression layer/second acrylic resin layer) with an in-plane retardation value of 60 nm and a thickness of 25 μm.

(6)複合偏光板的製作 (6) Fabrication of composite polarizer

於藉由上述製程(3)得到的積層體之第2相位差板側的面，貼合藉由上述製程(4)得到的活性能量射線硬化性黏著劑的塗膜，透過上述剝離片在以下條件下照射紫外線，使上述黏著劑的塗膜硬化而成為第2黏著劑層。之後，從所得到的第2黏著劑層將剝離片剝離後，於所露出的第2黏著劑層的表面，貼合藉由上述製程(5)得到的第1相位差板之第2丙烯酸系樹脂層側的面。這樣，得到藉由積層保護層、偏光子、第2相位差板、第2黏著劑層以及第1相位差板而成之總厚度93μm的複合偏光板(光學薄膜)。另外，所形成的第2黏著劑層的厚度為5μm。 To the surface of the layered body obtained by the above process (3) on the second retardation plate side, a coating film of the active energy ray-curable adhesive obtained by the above process (4) is pasted through the release sheet as follows Irradiation of ultraviolet light under the conditions hardens the coating film of the above-mentioned adhesive to become the second adhesive layer. After that, after peeling off the release sheet from the obtained second adhesive layer, the second acrylic layer of the first retardation plate obtained by the above process (5) is bonded to the surface of the exposed second adhesive layer The surface on the resin layer side. In this way, a composite polarizing plate (optical film) with a total thickness of 93 μm formed by laminating a protective layer, polarizers, a second retardation plate, a second adhesive layer, and a first retardation plate was obtained. In addition, the thickness of the formed second adhesive layer was 5 μm.

<紫外線照射條件> <UV irradiation conditions>

．使用高壓水銀燈 . Use high-pressure mercury lamps

．照度300mW/cm2，光量300mJ/cm2 . Illumination 300mW/cm 2 , light intensity 300mJ/cm 2

．使用EYE GRAPHICS CO.,LTD.製造“UVPF-A1”的UV照度/光量計 . Using the UV Illumination/Light Meter of "UVPF-A1" manufactured by EYE GRAPHICS CO., LTD.

2.附有黏著劑層之光學薄膜的製造 2. Manufacture of optical film with adhesive layer

(1)(甲基)丙烯酸酯共聚物的製備 (1) Preparation of (meth)acrylate copolymer

將丙烯酸正丁酯87質量份、丙烯酸異冰片酯5質量份、丙烯酸2-苯基乙酯5質量份以及丙烯酸2-羥基乙酯3質量份進行共聚合來製備(甲基)丙烯酸酯共聚物(A)。用後述方法測 定該(甲基)丙烯酸酯共聚物(A)的分子量，結果重量平均分子量(Mw)為160萬。另外，根據上述配合可計算出該(甲基)丙烯酸酯共聚物(A)的羥值為14.49mgKOH/g，酸值為0mgKOH/g。 87 mass parts of n-butyl acrylate, 5 mass parts of isobornyl acrylate, 5 mass parts of 2-phenylethyl acrylate, and 3 mass parts of 2-hydroxyethyl acrylate were copolymerized to prepare a (meth)acrylate copolymer (A). Use the method described later When the molecular weight of this (meth)acrylate copolymer (A) was determined, the weight average molecular weight (Mw) was 1.6 million. In addition, the hydroxyl value of the (meth)acrylate copolymer (A) can be calculated from the above blending to be 14.49 mgKOH/g, and the acid value is 0 mgKOH/g.

(2)黏著性組成物的製備 (2) Preparation of adhesive composition

將藉由上述製程(1)得到的(甲基)丙烯酸酯共聚物(A)100質量份、作為交聯劑(B)的三羥甲基丙烷改質亞二甲苯基二異氰酸酯(Mitsui Chemicals,Inc.製造，商品名“TAKENATE D110N”)0.2質量份、作為含環氧基矽烷偶合劑(C1)的3-縮水甘油氧基丙基三甲氧基矽烷(Shin-Etsu Chemical Co.,Ltd.製造，商品名“KBM403”)0.2質量份、作為含巰基矽烷偶合劑(C2)的，3-巰基丙基三甲氧基矽烷與甲基三乙氧基矽烷的共縮合物(Shin-Etsu Chemical Co.,Ltd.製造，商品名“「X-411-1810”，巰基當量：450g/莫耳)0.2質量份、以及作為抗靜電劑(D)的N-辛基-4-甲基吡啶鎓六氟磷酸鹽(室溫下為固體的離子性化合物)2.0質量份進行混合，充分攪拌後用乙酸乙酯進行稀釋，從而得到黏著性組成物的塗佈溶液。 100 parts by mass of (meth)acrylate copolymer (A) obtained by the above process (1) and trimethylolpropane as crosslinking agent (B) were modified with xylylene diisocyanate (Mitsui Chemicals, Manufactured by Inc., trade name "TAKENATE D110N") 0.2 parts by mass, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as an epoxy-containing silane coupling agent (C1) , Trade name "KBM403") 0.2 parts by mass, as a mercaptosilane-containing coupling agent (C2), 3-mercaptopropyltrimethoxysilane and methyltriethoxysilane co-condensate (Shin-Etsu Chemical Co. , Ltd., trade name ""X-411-1810", mercapto equivalent: 450g/mol) 0.2 parts by mass, and N-octyl-4-methylpyridinium hexafluoro as an antistatic agent (D) Phosphate (ionic compound which is a solid ionic compound at room temperature) was mixed in 2.0 parts by mass, sufficiently stirred, and then diluted with ethyl acetate to obtain a coating solution of an adhesive composition.

在此，將(甲基)丙烯酸酯共聚物(A)為100質量份(固體成分換算值)時的黏著性組成物的各配合(固體成分換算值)示於表1。另外，表1中所記載之縮寫的詳細內容如下。 Here, Table 1 shows each blending (solid content conversion value) of the adhesive composition when the (meth)acrylate copolymer (A) is 100 parts by mass (solid content conversion value). In addition, the details of the abbreviations described in Table 1 are as follows.

[(甲基)丙烯酸酯共聚物] [(Meth)acrylate copolymer]

BA：丙烯酸正丁酯 BA: n-butyl acrylate

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

IBXA：丙烯酸異冰片酯 IBXA: isobornyl acrylate

PhEA：丙烯酸2-苯基乙酯 PhEA: 2-phenylethyl acrylate

CHA：丙烯酸環己酯 CHA: cyclohexyl acrylate

2EHA：丙烯酸2-乙基己酯 2EHA: 2-ethylhexyl acrylate

[異氰酸酯系交聯劑] [Isocyanate crosslinking agent]

XDI：三羥甲基丙烷改質亞二甲苯基二異氰酸酯(Mitsui Chemicals,Inc.製造，商品名“TAKENATE D110N”) XDI: Trimethylolpropane modified xylylene diisocyanate (manufactured by Mitsui Chemicals, Inc., trade name "TAKENATE D110N")

TDI：三羥甲基丙烷改質甲苯二異氰酸酯(Nippon Polyurethane Industry Co.,Ltd.製造，商品名“CORONATEL”) TDI: Trimethylolpropane modified toluene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "CORONATEL")

[抗靜電劑] [Antistatic agent]

Pry+PF6-：N-辛基-4-甲基吡啶鎓六氟磷酸鹽(室溫下為固體的離子性化合物) Pry+PF6-: N-octyl-4-methylpyridinium hexafluorophosphate (solid ionic compound at room temperature)

(3)附有黏著劑層之光學薄膜的製作 (3) Fabrication of optical film with adhesive layer

於聚對苯二甲酸乙二酯薄膜的一面被矽酮系剝離劑進行了剝離處理之剝離片(LINTEC Corporation製造，SP-PET3811，厚度：38μm)的剝離處理面，用刀式塗佈機塗佈所得到的黏著性組成物的塗佈溶液後，以90℃加熱處理1分鐘，從而形成黏著性組成物的塗膜。 The peeling surface of a peeling sheet (manufactured by LINTEC Corporation, SP-PET3811, thickness: 38 μm) on which one side of the polyethylene terephthalate film was peeled off with a silicone-based peeling agent was coated with a knife coater After coating the coating solution of the obtained adhesive composition, it was heated at 90°C for 1 minute to form a coating film of the adhesive composition.

接著，將藉由上述得到的複合偏光板以其第1相位差板之第1丙烯酸系樹脂層的表面與上述塗膜的露出面相接的方式，貼合上述塗膜，於23℃、50%RH下養護7天，從而得到於複合偏光板上形成黏著劑層之附有黏著劑層之光學薄膜。另外，該所形成的黏著劑層(第1黏著劑層)的厚度為20μm。 Next, the composite polarizer obtained by the above was laminated with the coating film so that the surface of the first acrylic resin layer of the first retardation plate was in contact with the exposed surface of the coating film, and the temperature was 23°C, 50 Cured at %RH for 7 days to obtain an optical film with an adhesive layer and an adhesive layer formed on the composite polarizing plate. In addition, the thickness of the formed adhesive layer (first adhesive layer) was 20 μm.

〔實施例2~13，比較例1〕 [Examples 2 to 13, Comparative Example 1]

除了將構成(甲基)丙烯酸酯共聚物(A)的各單體的種類以及比例、(甲基)丙烯酸酯共聚物(A)的重量平均分子量、以及交聯劑(B)的種類以及配合量進行了如表1所示的變更之外，與實施例1相同地製造附有黏著劑層之光學薄膜。 In addition to the types and proportions of the monomers constituting the (meth)acrylate copolymer (A), the weight average molecular weight of the (meth)acrylate copolymer (A), and the type and blending of the crosslinking agent (B) Except that the amount was changed as shown in Table 1, an optical film with an adhesive layer was produced in the same manner as in Example 1.

〔比較例2〕 [Comparative Example 2]

代替用於形成第1黏著劑層之黏著性組成物的塗膜，將向與第2黏著劑層相同組成的黏著劑中添加了抗靜電劑(D)者(參照表1)的塗膜形成於剝離片(LINTEC Corporation製造，SP-PET3811，厚度38μm)上，並以複合偏光板的第1相位差板的最外表面與上述塗膜的露出面相接的方式貼合，之後隔著剝離片於以下條件下照射紫外線，接著於23℃、50%RH下養護7天，除此之外，進行與實施例1相同的操作，來製造在複合偏光板上形成有黏著劑層(第1黏著劑層)之附有黏著劑層之光學薄膜。另外，該第1黏著劑層的厚度為20μm。 Instead of the coating film for forming the adhesive composition of the first adhesive layer, a coating film of an antistatic agent (D) (see Table 1) added to the adhesive with the same composition as the second adhesive layer will be formed On the peeling sheet (manufactured by LINTEC Corporation, SP-PET3811, thickness 38 μm), and the outermost surface of the first phase difference plate of the composite polarizer is in contact with the exposed surface of the coating film, and then peeled off The sheet was irradiated with ultraviolet light under the following conditions, followed by curing at 23°C and 50% RH for 7 days, except that the same operation as in Example 1 was carried out to produce an adhesive layer formed on the composite polarizing plate (the first Adhesive layer) optical film with adhesive layer attached. In addition, the thickness of the first adhesive layer is 20 μm.

<紫外線照射條件> <UV irradiation conditions>

．使用高壓水銀燈 . Use high-pressure mercury lamps

．照度300mW/cm2，光量300mJ/cm2 . Illumination 300mW/cm 2 , light intensity 300mJ/cm 2

．UV照度、光量計使用EYE GRAPHICS CO.,LTD.製造的“UVPF-A1” . The UV illuminance and light meter used "UVPF-A1" manufactured by EYE GRAPHICS CO., LTD.

在此，前述重量平均分子量(Mw)係使用凝膠滲透層析(GPC)在以下的條件下測定(GPC測定)的聚苯乙烯換算的重量平均分子量。 Here, the weight average molecular weight (Mw) is a polystyrene-equivalent weight average molecular weight measured (GPC measurement) using gel permeation chromatography (GPC) under the following conditions.

<測定條件> <Measurement conditions>

．GPC測定裝置：Tosoh Corporation製造，HLC-8020 . GPC measuring device: manufactured by Tosoh Corporation, HLC-8020

．GPC管柱(按以下順序通過)：Tosoh Corporation製造 . GPC string (passed in the following order): manufactured by Tosoh Corporation

TSK guard column HXL-H TSK guard column HXL-H

TSK gel GMHXL(×2) TSK gel GMHXL (×2)

TSK gel G2000HXL TSK gel G2000HXL

．測定溶劑：四氫呋喃 . Determination solvent: tetrahydrofuran

．測定溫度：40℃ . Measuring temperature: 40℃

〔試驗例1〕(凝膠分率的測定) [Test Example 1] (Measurement of gel fraction)

使用聚對苯二甲酸乙二酯的一面被矽酮系剝離劑進行了剝離處理之剝離片(LINTEC Corporation製造，SP-PET3801，厚度：38μm)，來製作黏著片，以代替實施例及比較例中製作附有黏著劑層之光學薄膜時使用之光學薄膜。具體而言，於由實施例或比較例的製造過程中所得到之剝離片/黏著性組成物(第1黏著劑層用)的塗膜構成之結構體之所露出之塗膜上，以上述剝離片與剝離處理面側相接的方式進行積層，於23℃、50%RH的條件下養護7天。藉此，製作由剝離片(SP-PET3801)/第1黏著劑層(厚度：20μm)/剝離片(SP-PET3811)的結構構成之黏著片。另外，在製作具有比較例2的第1黏著劑層(厚度：20μm)之黏著片時，與製作比較例2之附有黏著劑層之光學薄膜時相同地在養護前進行紫外線照射。 A peeling sheet (manufactured by LINTEC Corporation, SP-PET3801, thickness: 38 μm) using polyethylene terephthalate peeled on one side by a silicone-based peeling agent was used to produce an adhesive sheet instead of the examples and comparative examples The optical film used in the production of optical film with adhesive layer. Specifically, on the exposed coating film of the structure composed of the coating film of the release sheet/adhesive composition (for the first adhesive layer) obtained in the manufacturing process of the example or the comparative example, the above The peeling sheet was laminated so that the side of the peeling treatment surface was in contact, and cured at 23°C and 50% RH for 7 days. By this, an adhesive sheet composed of the structure of the release sheet (SP-PET3801)/first adhesive layer (thickness: 20 μm)/release sheet (SP-PET3811) was produced. In addition, when the adhesive sheet having the first adhesive layer (thickness: 20 μm) of Comparative Example 2 was produced, ultraviolet rays were irradiated before curing in the same manner as when the optical film with the adhesive layer attached to Comparative Example 2 was produced.

將所得到的黏著片裁切成80mm×80mm的大小，將該黏著劑層包覆於聚酯製網狀織物(mesh)(網狀織物大小200)，用精密天平稱量其質量，減去上述網狀織物單獨的質量，藉此算出只有黏著劑的質量。將此時的質量設為M1。 The obtained adhesive sheet was cut to a size of 80 mm × 80 mm, the adhesive layer was coated on a polyester mesh fabric (mesh fabric size 200), and its mass was weighed with a precision balance, minus The mass of the above mesh fabric alone is used to calculate the mass of only the adhesive. Let the mass at this time be M1.

接著，將包覆於上述聚酯製網狀織物的黏著劑，在室溫下(23℃)於乙酸乙酯中浸漬24小時。之後取出黏著劑，在溫度23℃、相對濕度50%的環境下，風乾24小時，進一步於80℃的烘箱中乾燥12小時。乾燥後，用精密天平稱量其質量，減去上述網狀織物單獨的質量，藉此算出只有黏著劑的質量。將此時的質量設為M2。凝膠分率(%)用(M2/M1)×100來表示。結果示於表2。 Next, the adhesive coated on the polyester mesh fabric was immersed in ethyl acetate at room temperature (23°C) for 24 hours. After that, the adhesive was taken out, air-dried for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%, and further dried in an oven at 80°C for 12 hours. After drying, weigh the mass with a precision balance and subtract the mass of the mesh fabric alone to calculate the mass of only the adhesive. Let the mass at this time be M2. The gel fraction (%) is represented by (M2/M1)×100. The results are shown in Table 2.

另外，對將實施例及比較例中所形成之活性能量射線硬化性黏著劑的塗膜硬化而成之第2黏著劑層，亦進行與上述相同的操作來測定凝膠分率(%)。結果示於表2。 In addition, the second adhesive layer formed by curing the coating film of the active energy ray-curable adhesive formed in Examples and Comparative Examples was also subjected to the same operation as described above to measure the gel fraction (%). The results are shown in Table 2.

〔試驗例2〕(儲存彈性模數的測定) [Test Example 2] (Measurement of storage elastic modulus)

進行與試驗例1相同的操作，製作由剝離片(SP-PET3801)/第1黏著劑層(厚度：20μm)/剝離片(SP-PET3811)的結構構成之黏著片。 The same operation as in Test Example 1 was carried out to prepare an adhesive sheet composed of the structure of a release sheet (SP-PET3801)/first adhesive layer (thickness: 20 μm)/release sheet (SP-PET3811).

另外，分別使用剝離片(SP-PET3801)及剝離片(SP-PET3811)來代替光學薄膜之偏光板及第1相位差板，除此之外，進行與實施例及比較例相同的操作，製作由剝離片(SP-PET3801)/第2黏著劑層(厚度：5μm)/剝離片(SP-PET3811)的結構構成之黏著片。 In addition, the peeling sheet (SP-PET3801) and the peeling sheet (SP-PET3811) were used instead of the polarizing plate and the first retardation plate of the optical film, except that the same operations as in the examples and comparative examples were performed to produce An adhesive sheet composed of a structure of a release sheet (SP-PET3801)/second adhesive layer (thickness: 5 μm)/release sheet (SP-PET3811).

將上述製程中形成之第1黏著劑層及第2黏著劑層分別以3mm厚度積層複數層。從所得到之黏著劑層的積層體沖切直径8mm的圓柱體(高度3mm)，並將此作為樣品。 A plurality of layers of the first adhesive layer and the second adhesive layer formed in the above-mentioned process are respectively stacked with a thickness of 3 mm. A cylindrical body (height 3 mm) with a diameter of 8 mm was punched from the obtained laminate of the adhesive layer, and this was used as a sample.

依照JISK7244-6，使用黏彈性測定裝置(RHEOMETRIC SCIENTIFIC製造，DYNAMIC ANALAYZER) 並利用扭轉剪切法，對上述樣品以下述條件測定儲存彈性模數(MPa)。結果示於表2。 According to JISK7244-6, a viscoelasticity measuring device (manufactured by RHEOMETRIC SCIENTIFIC, DYNAMIC ANALAYZER) is used The torsional shear method was used to measure the storage elastic modulus (MPa) of the above samples under the following conditions. The results are shown in Table 2.

測定頻率：1Hz Measuring frequency: 1Hz

測定溫度：85℃ Measuring temperature: 85℃

〔試驗例3〕(耐久性評價) [Test Example 3] (Durability Evaluation)

裁切實施例以及比較例中得到的附有黏著劑層之光學薄膜，製作150mm×200mm大小的樣品。從該樣品剝掉剝離片並隔著所露出的黏著劑層貼附於無鹼玻璃(Corning Incorporated製造，Eagle XG)後，用KURIHARA製作所製造的高壓釜於0.5MPa、50℃下加壓20分鐘。 The optical film with an adhesive layer obtained in Examples and Comparative Examples was cut to prepare a sample of 150 mm×200 mm. After peeling off the release sheet from the sample and attaching it to alkali-free glass (manufactured by Corning Incorporated, Eagle XG) via the exposed adhesive layer, the autoclave manufactured by KURIHARA was pressurized at 0.5 MPa and 50°C for 20 minutes. .

其後，投入到如下述三個耐久條件的環境下，250小時後用10倍放大鏡確認有無翹起或表面剝離。評價基準如下。結果示於表2。 After that, it was put into the environment of the three endurance conditions as described below, and after 250 hours, the presence or absence of warping or surface peeling was confirmed with a 10-fold magnifying glass. The evaluation criteria are as follows. The results are shown in Table 2.

◎：未確認到翹起或表面剝離。 ◎: No lifting or surface peeling was confirmed.

○：確認到0.5mm以下大小的翹起或表面剝離。 ○: Lifting of 0.5 mm or less or surface peeling was confirmed.

△：確認到超過0.5mm、1.0mm以下大小的翹起或表面剝離。 △: Lifting or surface peeling exceeding 0.5 mm and 1.0 mm or less was confirmed.

×：確認到超過1.0mm大小的翹起或表面剝離。 ×: Lifting or surface peeling exceeding 1.0 mm was confirmed.

<耐久條件> <durable condition>

．耐熱：85℃ dry . Heat resistance: 85℃ dry

．濕熱：60℃，相對濕度90%RH . Damp heat: 60℃, relative humidity 90%RH

．H.S.：-35℃

Figure 105106263-A0202-12-0065-8
70℃下各30分鐘的熱衝擊試驗，200循環 . HS: -35℃
Figure 105106263-A0202-12-0065-8
Thermal shock test at 70℃ for 30 minutes each, 200 cycles

〔試驗例4〕(耐翹曲性評價) [Test Example 4] (Evaluation of Warpage Resistance)

將實施例以及比較例中得到的附有黏著劑層之光學薄膜 裁切成長200mm、寬150mm。從該附有黏著劑層之光學薄膜剝掉剝離片，將所露出的黏著劑層貼合於長250mm、寬175mm、厚0.5mm的無鹼玻璃(Corning Incorporated製造，商品名“Eagle-XG”)的中央部，將此作為樣品。將該樣品於85℃、乾燥氣氛下放置250小時。其後，於25℃、50%RH的環境下取出，將光學薄膜側朝上地放置於水平台之上，測定樣品的各角(4點)距離台的翹曲量(角與台的距離)，將各角的翹曲量進行合計。根據其結果如下評價耐翹曲性。結果示於表2。 The optical film with an adhesive layer obtained in Examples and Comparative Examples The cutting length is 200mm and the width is 150mm. Peel off the release sheet from the optical film with an adhesive layer, and attach the exposed adhesive layer to alkali-free glass (made by Corning Incorporated, trade name "Eagle-XG") with a length of 250 mm, a width of 175 mm, and a thickness of 0.5 mm. ) In the central part of the sample. The sample was left at 85°C in a dry atmosphere for 250 hours. After that, take it out in an environment of 25°C and 50% RH, place the optical film side up on a water platform, and measure the amount of warpage (distance between the corner and the stage) of each corner (4 points) of the sample from the stage ), the warpage amount of each corner is added up. Based on the results, the warpage resistance was evaluated as follows. The results are shown in Table 2.

◎：翹曲量的合計為10mm以下 ◎: The total amount of warpage is 10 mm or less

○：翹曲量的合計超過10mm、15mm以下 ○: The total amount of warpage exceeds 10 mm and 15 mm or less

△：翹曲量的合計超過15mm、20mm以下 △: The total amount of warpage exceeds 15 mm and 20 mm or less

×：翹曲量的合計超過20mm ×: The total amount of warpage exceeds 20 mm

〔試驗例5〕(耐熱不均勻性的評價) [Test Example 5] (Evaluation of heat resistance unevenness)

將實施例以及比較例中得到的附有黏著劑層之光學薄膜，用裁切裝置(Ogino Seisakusho Co.,Ltd.製造的Super Cutter PN1-600)調整為200mm×150mm大小。剝掉剝離片並隔著所露出的黏著劑層貼附於無鹼玻璃(Corning Incorporated製造，Eagle XG)後，用KURIHARA製作所製造的高壓釜於0.5MPa、50℃下加壓20分鐘。另外，上述貼合係於無鹼玻璃的表面和背面，以使附有黏著劑層之光學薄膜的偏光軸成正交偏光狀態的方式(偏光軸：∠45°、∠135°)進行。以該狀態，在80℃乾燥(dry)環境下放置250小時後，於23℃、50%RH的環境下放置2小時，將此作為樣品，用以下所示之方法對耐熱不均勻性進行評價。結果示於表2。 The optical film with an adhesive layer obtained in Examples and Comparative Examples was adjusted to a size of 200 mm×150 mm using a cutting device (Super Cutter PN1-600 manufactured by Ogino Seisakusho Co., Ltd.). After peeling off the release sheet and attaching it to alkali-free glass (manufactured by Corning Incorporated, Eagle XG) via the exposed adhesive layer, the autoclave manufactured by KURIHARA was pressurized at 0.5 MPa and 50° C. for 20 minutes. In addition, the above-mentioned bonding is performed on the front and back surfaces of the alkali-free glass so that the polarizing axis of the optical film with the adhesive layer is orthogonally polarized (polarizing axis: ∠45°, ∠135°). In this state, after being left in a dry environment at 80°C for 250 hours, and then left in an environment of 23°C and 50% RH for 2 hours, this was used as a sample, and the heat unevenness was evaluated by the method shown below . The results are shown in Table 2.

<評價方法> <Evaluation method>

將上述樣品設置於平面照明裝置(FLAT ILLUMINATOR)(Raytronics Corp.，製造，HF-SL-A312LC，照度：26，000Lux，亮度：10，000cd)之上，用二維色彩亮度計(KONICA MINOLTA,INC.製造，CA-2000)進行拍攝，並用分析軟體(KONICA MINOLTA,INC.製造，CA-S20w)轉換成亮度分佈圖像。對所得到的樣品的亮度分佈圖像，基於圖4以及以下所示的評價基準進行評價。 The above sample was set on a flat illumination device (FLAT ILLUMINATOR) (manufactured by Raytronics Corp., HF-SL-A312LC, illuminance: 26,000 Lux, brightness: 10,000 cd), and a two-dimensional color brightness meter (KONICA MINOLTA, INC., manufactured by CA-2000), and converted into a brightness distribution image using analysis software (manufactured by KONICA MINOLTA, INC., CA-S20w). The brightness distribution image of the obtained sample was evaluated based on FIG. 4 and the evaluation criteria shown below.

◎：亮度分佈大致均勻。 ◎: The brightness distribution is roughly uniform.

○：四邊之亮度分佈有若干失真。 ○: There are some distortions in the brightness distribution on the four sides.

△：四邊之亮度分佈有明顯失真。 △: The brightness distribution on the four sides is obviously distorted.

×：四邊之亮度分佈有嚴重失真。 ×: The brightness distribution on the four sides is severely distorted.

〔試驗例6〕(黏著力測定-再處理性評價) [Test Example 6] (Measurement of Adhesion-Evaluation of Reprocessing)

從實施例以及比較例中得到的附有黏著劑層之光學薄膜切出25mm寬、100mm長的樣品，剝掉剝離片並隔著所露出的黏著劑層貼附於無鹼玻璃(Corning Incorporated製造，Eagle XG)後，用KURIHARA製作所製造的高壓釜於0.5MPa、50℃下加壓20分鐘。其後，在23℃、50%RH的條件下放置24小時，並使用拉伸試驗機(ORIENTEC Co.,Ltd.製造，TENSILON)，在剝離速度300mm/min、玻璃角度180度的條件下測定黏著力(貼附1天後的黏著力；N/25mm)。記錄於此之外的條件遵照JIS Z 0237：2009而進行測定。結果示於表2。 A 25 mm wide and 100 mm long sample was cut out from the optical film with an adhesive layer obtained in Examples and Comparative Examples, the peeling sheet was peeled off, and attached to an alkali-free glass (made by Corning Incorporated) through the exposed adhesive layer , Eagle XG), pressurized with an autoclave manufactured by KURIHARA at 0.5MPa, 50°C for 20 minutes. Thereafter, it was left for 24 hours under the conditions of 23° C. and 50% RH, and was measured under the conditions of a peeling speed of 300 mm/min and a glass angle of 180 degrees using a tensile tester (manufactured by ORIENTEC Co., Ltd., TENSILON). Adhesion (adhesion after 1 day of attachment; N/25mm). The conditions recorded outside are measured in compliance with JIS Z 0237:2009. The results are shown in Table 2.

在23℃、50%RH的條件下放置14天後，進一步與上述相同地測定黏著力(貼附14天後的黏著力；N/25mm)。 與其不同的是，在50℃、50%RH的條件下放置2天後，與上述相同地測定黏著力(50℃ 2天後的黏著力；N/25mm)。結果示於表2。 After leaving it under the conditions of 23° C. and 50% RH for 14 days, the adhesive force was further measured in the same manner as above (adhesive force after 14 days of attachment; N/25 mm). The difference is that, after being left under the conditions of 50° C. and 50% RH for 2 days, the adhesion is measured in the same manner as above (adhesion after 50 days at 50° C.; N/25 mm). The results are shown in Table 2.

基於上述貼附14天後的黏著力，用以下基準進行再處理性的評價。結果示於表2。 Based on the adhesive force 14 days after the above application, the reprocessing property was evaluated according to the following criteria. The results are shown in Table 2.

◎：貼附14天後的黏著力為8.8N/25mm以下 ◎: Adhesion after 14 days of application is 8.8N/25mm or less

○：貼附14天後的黏著力超過8.8N/25mm、未滿10N/25mm ○: The adhesive force after 14 days of application exceeds 8.8N/25mm and less than 10N/25mm

△：貼附14天後的黏著力為10N/25mm以上、未滿20N/25mm △: Adhesion force after 14 days of application is 10N/25mm or more and less than 20N/25mm

×：貼附14天後的黏著力為20N/25mm以上 ×: Adhesion after 14 days of application is 20N/25mm or more

〔試驗例7〕(黏著劑層的表面電阻率的測定) [Test Example 7] (Measurement of surface resistivity of adhesive layer)

將實施例以及比較例中得到的附有黏著劑層之光學薄膜切割成50mm×50mm的大小，將所得到的樣品於23℃的溫度、50%RH的濕度下放置24小時。其後，剝掉剝離片，於所露出的黏著劑層表面，使用電阻率計(Mitsubishi Chemical Analytech Co.,Ltd.製造，Hiresta UP MCP-HT450型)並依據JIS K6911來測定表面電阻率(Ω/sq)。結果示於表2。 The optical film with an adhesive layer obtained in Examples and Comparative Examples was cut into a size of 50 mm×50 mm, and the obtained sample was left at a temperature of 23° C. and a humidity of 50% RH for 24 hours. After that, the peeling sheet was peeled off, and the surface resistivity (Ω) was measured on the surface of the exposed adhesive layer using a resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., Hiresta UP MCP-HT450 type) according to JIS K6911. /sq). The results are shown in Table 2.

【表1】

Figure 105106263-A0202-12-0069-1
【Table 1】
Figure 105106263-A0202-12-0069-1

Figure 105106263-A0202-12-0069-3
Figure 105106263-A0202-12-0069-3

從表2可知，實施例中所得到的附有黏著劑層之光學薄膜的耐久性優異，並且在高溫下亦不易翹曲、不易產生熱不均。另外，實施例中所得到的附有黏著劑層之光學薄膜係黏著劑層的表面電阻率低且對液晶單元等的不利影響小者。進 而，實施例1~12中所得到的附有黏著劑層之光學薄膜之再處理性亦優異。 It can be seen from Table 2 that the optical film with an adhesive layer obtained in the examples is excellent in durability, and is also less likely to warp at high temperatures and less likely to cause thermal unevenness. In addition, the optical film with an adhesive layer obtained in the examples is one in which the surface resistivity of the adhesive layer is low and the adverse effect on the liquid crystal cell and the like is small. Into In addition, the adhesive film-attached optical films obtained in Examples 1 to 12 are also excellent in reprocessing properties.

【產業上的可利用性】 [Industry availability]

本發明之附有黏著劑層之光學薄膜適合於貼合已薄膜化的複合偏光板與液晶單元。 The optical film with an adhesive layer of the present invention is suitable for laminating a thin-film composite polarizing plate and a liquid crystal cell.

1A‧‧‧附有黏著劑層之光學薄膜 1A‧‧‧Optical film with adhesive layer

11‧‧‧第1相位差板 11‧‧‧First phase difference plate

12‧‧‧第2相位差板 12‧‧‧The second phase difference plate

21‧‧‧第1黏著劑層 21‧‧‧1st adhesive layer

22‧‧‧第2黏著劑層 22‧‧‧ 2nd adhesive layer

Claims (7)

一種附有黏著劑層之光學薄膜，其具備：第1相位差板；積層於前述第1相位差板的一面之第1黏著劑層；積層於前述第1相位差板之與前述第1黏著劑層側的面相反的一面側之第2黏著劑層；及積層於前述第2黏著劑層之與前述第1相位差板側的面相反的一面側之第2相位差板；前述附有黏著劑層之光學薄膜的特徵為：前述第1相位差板之與前述第1黏著劑層相接的面由丙烯酸系樹脂構成，構成前述第1黏著劑層之黏著劑的凝膠分率為55~90%，前述第1黏著劑層的85℃下之儲存彈性模數(G’)為0.03~0.25MPa，構成前述第2黏著劑層之黏著劑的凝膠分率為80~100%，前述第2黏著劑層的85℃下之儲存彈性模數(G’)為0.15~3.00MPa，構成前述第2黏著劑層之黏著劑的凝膠分率大於構成前述第1黏著劑層之黏著劑的凝膠分率，前述第2黏著劑層的85℃下之儲存彈性模數(G’)大於前述第1黏著劑層的85℃下之儲存彈性模數(G’)。 An optical film with an adhesive layer, comprising: a first phase difference plate; a first adhesive layer laminated on one side of the first phase difference plate; and a first adhesive layer laminated on the first phase difference plate The second adhesive layer on the side opposite to the side of the agent layer; and the second phase difference plate laminated on the side opposite to the side of the first phase difference plate layer of the second adhesive layer; the aforementioned is attached The optical film of the adhesive layer is characterized in that the surface of the first phase difference plate that is in contact with the first adhesive layer is composed of acrylic resin, and the gel fraction of the adhesive constituting the first adhesive layer is 55~90%, the storage elastic modulus (G') of the first adhesive layer at 85°C is 0.03~0.25MPa, and the gel fraction of the adhesive constituting the second adhesive layer is 80~100% The storage elastic modulus (G') of the second adhesive layer at 85° C. is 0.15 to 3.00 MPa, and the gel fraction of the adhesive constituting the second adhesive layer is greater than that of the first adhesive layer The gel fraction of the adhesive, the storage elastic modulus (G') at 85°C of the second adhesive layer is greater than the storage elastic modulus (G') at 85°C of the first adhesive layer. 如申請專利範圍第1項所述之附有黏著劑層之光學薄膜，其中前述第1相位差板之與前述第1黏著劑層相接之最外層由經由擠出成形而形成之丙烯酸系樹脂層構成。 The optical film with an adhesive layer as described in item 1 of the patent application scope, wherein the outermost layer of the first phase difference plate that is in contact with the first adhesive layer is an acrylic resin formed by extrusion molding Layer composition. 如申請專利範圍第2項所述之附有黏著劑層之光學薄膜，其中前述第1相位差板具備：前述丙烯酸系樹脂層；第2丙烯酸系樹脂層；及位於前述丙烯酸系樹脂層與前述第2丙烯酸系樹脂層之間之相位差表現層。 The optical film with an adhesive layer as described in item 2 of the patent application range, wherein the first phase difference plate includes: the acrylic resin layer; the second acrylic resin layer; and the acrylic resin layer and the foregoing The phase difference expression layer between the second acrylic resin layers. 如申請專利範圍第3項所述之附有黏著劑層之光學薄膜，其中前述相位差表現層由苯乙烯系樹脂構成。 The optical film with an adhesive layer as described in item 3 of the patent application range, wherein the phase difference expression layer is made of styrene resin. 如申請專利範圍第1項所述之附有黏著劑層之光學薄膜，其中前述第2相位差板由環狀烯烴系樹脂構成。 The optical film with an adhesive layer as described in item 1 of the patent application range, wherein the second phase difference plate is made of cyclic olefin resin. 如申請專利範圍第1項所述之附有黏著劑層之光學薄膜，其中前述第1黏著劑層由從黏著性組成物得到之黏著劑構成，前述黏著性組成物含有：(甲基)丙烯酸酯共聚物(A)含有含脂環式結構單體(a1)及含芳香環單體(a2)作為構成該共聚物之單體單元；以及交聯劑(B)。 The optical film with an adhesive layer as described in item 1 of the scope of the patent application, wherein the first adhesive layer is composed of an adhesive obtained from an adhesive composition, and the foregoing adhesive composition contains: (meth)acrylic acid The ester copolymer (A) contains an alicyclic structure-containing monomer (a1) and an aromatic ring-containing monomer (a2) as monomer units constituting the copolymer; and a crosslinking agent (B). 如申請專利範圍第1項所述之附有黏著劑層之光學薄膜，其中於前述第2相位差板之與前述第2黏著劑層側的面相反的一面側進一步積層有偏光板。 The optical film with an adhesive layer as described in item 1 of the patent application scope, wherein a polarizing plate is further laminated on the side of the second retardation plate opposite to the surface on the side of the second adhesive layer.
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