TWI735489B - Adhesive composition - Google Patents
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- TWI735489B TWI735489B TW105140825A TW105140825A TWI735489B TW I735489 B TWI735489 B TW I735489B TW 105140825 A TW105140825 A TW 105140825A TW 105140825 A TW105140825 A TW 105140825A TW I735489 B TWI735489 B TW I735489B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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Abstract
Description
本發明係有關於一種在被應用在液晶顯示裝置等之附黏著劑層的光學薄膜等中,有利於形成具有優異的耐久性之黏著劑層的黏著劑組成物。 The present invention relates to an adhesive composition that is useful for forming an adhesive layer with excellent durability in optical films, etc., which are applied to an adhesive layer of a liquid crystal display device.
以在偏光片的一面或兩面層積貼合透明樹脂薄膜而成之偏光板作為代表之光學薄膜,係被廣泛地使用作為構成液晶顯示裝置等的影像顯示裝置之光學構件。如偏光板的光學薄膜,多半是透過黏著劑層貼合在其它構件(例如在液晶顯示裝置之液晶胞等)而使用(參照專利文獻1)。因此,作為光學薄膜,已知一種在其中一面預先設置有黏著劑層之附黏著劑層的光學薄膜。 An optical film represented by a polarizer formed by laminating and laminating a transparent resin film on one or both sides of a polarizer is widely used as an optical member constituting an image display device such as a liquid crystal display device. Optical films such as polarizing plates are mostly used by bonding them to other members (for example, liquid crystal cells in liquid crystal display devices) through an adhesive layer (see Patent Document 1). Therefore, as an optical film, an optical film having an adhesive layer preliminarily provided with an adhesive layer on one side is known.
[專利文獻1]日本特開2010-229321號公報 [Patent Document 1] JP 2010-229321 A
近年來,液晶顯示裝置在以智慧型手機和平 板型終端設備作為代表之行動裝置用途和以汽車導航系統作為代表之車載用裝置用途不斷發展。因為相較於以往的屋內用TV用途,在此種用途時,會有曝露在較嚴酷的環境之可能性,所以提升裝置的耐久性係成為課題。 In recent years, liquid crystal display devices have been The use of tablet-type terminal equipment as a representative mobile device and the use of car navigation systems as a representative in-vehicle device continue to develop. Compared with the conventional indoor TV use, there is a possibility of exposure to a harsher environment in this use, so improving the durability of the device becomes a problem.
在構成液晶顯示裝置等之附黏著劑層的光學薄膜中,亦同樣地被要求耐久性。亦即,被組裝於液晶顯示裝置等之黏著劑層,會有被放置在高溫或高溫高濕環境下、或高溫與低溫反覆交替的環境下之情形,附黏著劑層的光學薄膜係被要求即便在該等環境下,亦能夠抑制在黏著劑層與其所貼合的光學構件之界面產生的浮起、剝落、黏著劑層的發泡等之缺陷,而且,亦被要求光學特性不會劣化。尤其是光學薄膜為偏光板時,因為在高溫環境下會產生較強大的收縮應力,所以黏著劑層被要求具有較一般的光學薄膜更高的耐久性能。因提升上述液晶顯示裝置的耐久性之需求日益增加,所以目前對於黏著劑層所要求的耐久性變為非常嚴格。 Durability is similarly required in optical films with adhesive layers constituting liquid crystal display devices and the like. That is, the adhesive layer assembled in the liquid crystal display device may be placed in a high temperature or high temperature and high humidity environment, or in an environment where high temperature and low temperature are alternated. Optical films with adhesive layers are required Even in these environments, it is possible to suppress defects such as floating, peeling, and foaming of the adhesive layer at the interface between the adhesive layer and the optical member to which it is bonded, and it is also required that the optical characteristics are not deteriorated . Especially when the optical film is a polarizing plate, the adhesive layer is required to have higher durability than ordinary optical films because of stronger shrinkage stress in a high temperature environment. Due to the increasing demand for improving the durability of the above-mentioned liquid crystal display device, the durability required for the adhesive layer has become very strict at present.
因而,本發明之目的係提供一種黏著劑組成物,其係即便在此種嚴酷的耐久條件下,亦能夠形成顯示優異的耐久性之黏著劑層者。 Therefore, the object of the present invention is to provide an adhesive composition that can form an adhesive layer exhibiting excellent durability even under such severe durability conditions.
為了解決上述課題,本發明人專心研討之結果,遂完成了本發明。 In order to solve the above-mentioned problems, the present inventors have completed the present invention as a result of intensive research.
亦即,本發明係包含下述的內容。 That is, the present invention includes the following contents.
[1]一種黏著劑組成物,係含有(甲基)丙烯酸系樹脂(A)、
交聯劑(B)、及矽烷化合物(C),其中,前述(甲基)丙烯酸系樹脂(A)係含有:源自下述式(a1)表示之含羥基的(甲基)丙烯酸酯之結構單元,與源自丙烯酸5-羥基戊酯之結構單元,
[2]如[1]所述之黏著劑組成物,其中,相對於構成(甲基)丙烯酸系樹脂之總結構單元100重量份,源自式(a1)表示之含羥基的(甲基)丙烯酸酯之結構單元的比率為1.5至4.5重量份,源自丙烯酸5-羥基戊酯之結構單元的比率為0.25至1.0重量份。 [2] The adhesive composition according to [1], wherein it is derived from the hydroxyl group-containing (methyl) represented by the formula (a1) relative to 100 parts by weight of the total structural units constituting the (meth)acrylic resin The ratio of structural units of acrylate is 1.5 to 4.5 parts by weight, and the ratio of structural units derived from 5-hydroxypentyl acrylate is 0.25 to 1.0 parts by weight.
[3]如[1]或[2]所述之黏著劑組成物,其中,(甲基)丙烯酸系樹脂係含有源自丙烯酸烷酯(a3)之結構單元,該源自丙烯酸烷酯(a3)之結構單元係包含:源自同元聚合物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3-1)之結構單元;及源自同元聚合物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a3-2)之結構單元。 [3] The adhesive composition according to [1] or [2], wherein the (meth)acrylic resin system contains a structural unit derived from alkyl acrylate (a3), which is derived from alkyl acrylate (a3 The structural units of) include: structural units derived from alkyl acrylate (a3-1) whose glass transition temperature is less than 0℃; and those whose glass transition temperature is above 0℃ derived from homopolymers Structural unit of alkyl acrylate (a3-2).
[4]如[3]所述之黏著劑組成物,其中,源自同元聚合物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3-1)之結構單元、與源自同元聚合物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a3-2)之結構單元之間的比率(重量比),為(a3-1)/(a3-2)=20/80至95/5。 [4] The adhesive composition according to [3], wherein the structural unit derived from the homopolymer of alkyl acrylate (a3-1) whose glass transition temperature is less than 0°C and the structural unit derived from the homopolymer The ratio (weight ratio) between the structural units of alkyl acrylate (a3-2) whose glass transition temperature is above 0℃ is (a3-1)/(a3-2)=20/80 to 95/5 .
[5]如[1]至[4]中任一者所述之黏著劑組成物,其中,(甲基)丙烯酸系樹脂的重量平均分子量經聚苯乙烯換算為6.0×105至2.5×106。 [5] The adhesive composition according to any one of [1] to [4], wherein the weight average molecular weight of the (meth)acrylic resin is 6.0×10 5 to 2.5×10 in terms of polystyrene 6 .
[6]如[1]至[5]中任一者所述之黏著劑組成物,其中,交聯劑(B)係芳香族異氰酸酯化合物及/或該芳香族異氰酸酯化合物加添多元醇化合物而得到的加成物。 [6] The adhesive composition according to any one of [1] to [5], wherein the crosslinking agent (B) is an aromatic isocyanate compound and/or the aromatic isocyanate compound is added with a polyol compound The adduct obtained.
[7]如[1]至[6]中任一者所述之黏著劑組成物,其中,相對於(甲基)丙烯酸系樹脂(A)100重量份,交聯劑(B)的比率為0.01至10重量份。 [7] The adhesive composition according to any one of [1] to [6], wherein the ratio of the crosslinking agent (B) to 100 parts by weight of the (meth)acrylic resin (A) is 0.01 to 10 parts by weight.
[8]如[1]至[7]中任一者所述之黏著劑組成物,其中,矽烷化合物(C)係下述式(c1)表示之矽烷化合物,
式中,B係表示碳數1至20的烷二基或碳數3至20的二價脂環式烴基,構成前述烷二基及前述脂環式烴基之-CH2-亦可置換成-O-或-CO-,R1係表示碳數1至5的烷基,R2、R3、R4、R5及R6係各自獨立地表示碳數1至5的烷基或碳數1至5的烷氧基。 In the formula, B represents an alkanediyl group having 1 to 20 carbons or a divalent alicyclic hydrocarbon group having 3 to 20 carbons, and -CH 2 -constituting the aforementioned alkanediyl group and the aforementioned alicyclic hydrocarbon group can also be substituted with- O- or -CO-, R 1 represents an alkyl group having 1 to 5 carbons, and R 2 , R 3 , R 4 , R 5 and R 6 each independently represent an alkyl group having 1 to 5 carbons or a carbon number Alkoxy from 1 to 5.
[9]如[8]所述之黏著劑組成物,其中,式(c1)之B係碳數1至10的烷二基,R1係碳數1至5的烷基,R2、R3、R4、R5及R6係各自獨立地表示碳數1至5的烷氧基。 [9] The adhesive composition according to [8], wherein B of the formula (c1) is an alkanediyl group having 1 to 10 carbons, R 1 is an alkyl group having 1 to 5 carbons, and R 2 , R 3 , R 4 , R 5 and R 6 each independently represent an alkoxy group having 1 to 5 carbon atoms.
[10]如[1]至[9]中任一者所述之黏著劑組成物,其中,相對於(甲基)丙烯酸系樹脂(A)100重量份,矽烷化合物(C)之比 率為0.01至10重量份。 [10] The adhesive composition according to any one of [1] to [9], wherein the ratio of the silane compound (C) to 100 parts by weight of the (meth)acrylic resin (A) The rate is 0.01 to 10 parts by weight.
[11]如[1]至[10]中任一者所述之黏著劑組成物,其中,由黏著劑組成物所形成之黏著劑的凝膠分率為50至95%。 [11] The adhesive composition according to any one of [1] to [10], wherein the gel fraction of the adhesive formed by the adhesive composition is 50 to 95%.
[12]如[1]至[11]中任一者所述之黏著劑組成物,其中,將由前述黏著劑組成物所形成之黏著劑層貼合在玻璃基板,在溫度23℃、相對濕度50%的條件下24小時後之前述黏著劑層的黏著力,係在剝離速度300mm/分鐘的情況下為0.5至10N/25mm。 [12] The adhesive composition according to any one of [1] to [11], wherein the adhesive layer formed of the aforementioned adhesive composition is bonded to a glass substrate at a temperature of 23°C and a relative humidity The adhesive force of the aforementioned adhesive layer after 24 hours under the condition of 50% is 0.5 to 10N/25mm at a peeling speed of 300mm/min.
[13]如[1]至[12]中任一者所述之黏著劑組成物,係使用於層積在光學薄膜之黏著劑層的形成。 [13] The adhesive composition described in any one of [1] to [12] is used to form an adhesive layer laminated on an optical film.
本發明的黏著劑組成物,其係即便在嚴酷的耐久條件下,亦能夠形成具有優異的耐久性之黏著劑層。 The adhesive composition of the present invention can form an adhesive layer with excellent durability even under severe durability conditions.
1、1a、1b‧‧‧附黏著劑層的光學薄膜 1, 1a, 1b‧‧‧Optical film with adhesive layer
2‧‧‧偏光片 2‧‧‧Polarizer
3‧‧‧第1樹脂薄膜 3‧‧‧The first resin film
4‧‧‧第2樹脂薄膜 4‧‧‧Second resin film
5、6、7、8、9‧‧‧光學積層體 5, 6, 7, 8, 9‧‧‧Optical laminate
10‧‧‧光學薄膜 10‧‧‧Optical Film
10a、10b‧‧‧偏光板 10a、10b‧‧‧Polarizer
20‧‧‧黏著劑層 20‧‧‧Adhesive layer
30‧‧‧金屬層 30‧‧‧Metal layer
40‧‧‧基板 40‧‧‧Substrate
50‧‧‧樹脂層 50‧‧‧Resin layer
第1圖係顯示附有由本發明之黏著劑組成物所形成之黏著劑層的光學薄膜的一例之概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing an example of an optical film with an adhesive layer formed of the adhesive composition of the present invention.
第2圖係顯示偏光板的層結構的一例之概略剖面圖。 Fig. 2 is a schematic cross-sectional view showing an example of the layer structure of the polarizing plate.
第3圖係顯示偏光板的層結構的其它例之概略剖面圖。 Fig. 3 is a schematic cross-sectional view showing another example of the layer structure of the polarizing plate.
第4圖係顯示包含附有由本發明之黏著劑組成物所形成之黏著劑層的光學薄膜之光學積層體的一例之概略剖面圖。 Fig. 4 is a schematic cross-sectional view showing an example of an optical laminate including an optical film with an adhesive layer formed of the adhesive composition of the present invention.
第5圖係顯示包含附有由本發明之黏著劑組成物所形 成之黏著劑層的光學薄膜之光學積層體的一例之概略剖面圖。 Fig. 5 shows the shape of the adhesive composition of the present invention A schematic cross-sectional view of an example of an optical laminate of an optical film of an adhesive layer.
第6圖係顯示包含附有由本發明之黏著劑組成物所形成之黏著劑層的光學薄膜之光學積層體之另一個其它例之概略剖面圖。 Fig. 6 is a schematic cross-sectional view showing another example of an optical laminate including an optical film with an adhesive layer formed of the adhesive composition of the present invention.
第7圖係顯示包含附有由本發明之黏著劑組成物所形成之黏著劑層的光學薄膜之光學積層體之別例之概略剖面圖。 FIG. 7 is a schematic cross-sectional view showing another example of an optical laminate including an optical film with an adhesive layer formed from the adhesive composition of the present invention.
第8圖係顯示包含附有由本發明之黏著劑組成物所形成之黏著劑層的光學薄膜之光學積層體之另一個別例之概略剖面圖。 FIG. 8 is a schematic cross-sectional view showing another example of an optical laminate including an optical film with an adhesive layer formed from the adhesive composition of the present invention.
本發明的黏著劑組成物係含有(甲基)丙烯酸系樹脂(A)、交聯劑(B)、及矽烷化合物(C)。 The adhesive composition of the present invention contains a (meth)acrylic resin (A), a crosslinking agent (B), and a silane compound (C).
(甲基)丙烯酸系樹脂(A),係以源自(甲基)丙烯酸系單體之結構單元作為主成分(較佳為含有50重量%以上)之聚合物或共聚物,其包含源自下述式(a1)表示之含羥基的(甲基)丙烯酸酯之結構單元,與源自丙烯酸5-羥基戊酯之結構單元,
亦即,因為本發明的(甲基)丙烯酸系樹脂(A)係在側鏈具有預定之碳鏈長不同的羥基烷基,所以推定由黏著劑組成物所形成之黏著劑層,係能夠使(甲基)丙烯酸系樹脂間的交聯密度最佳化。藉由該交聯密度的最佳化,能夠形成硬度及柔軟度的平衡性優異(或具有最佳硬度)之黏著劑層,所以能夠提升耐久性且即便在高溫環境亦能夠有效地抑制界面的剝落(或浮起)及發泡。而且,因為即便產生強大的收縮應力,黏著劑層亦能夠有效地緩和該應力,所以能夠防止隨著光學薄膜(例如偏向板)的收縮而產生的白斑。而且藉由該交聯密度的最佳化,亦能夠提升再加工性(剝離性)。又,在本說明書中,所謂耐久性係指例如在高溫環境下、高溫高濕環境下、高溫與低溫反覆交替之環境下等,能夠抑制在黏著劑層和與其隣接的光學構件之界面產生的浮起和剝落之特性(亦有稱為耐剝落性之情形)、及能夠抑制黏著劑層產生的發泡等缺陷之特性(亦有稱為耐發泡性之情形)。又,在本發明中,所謂耐凝聚破壞性係指能夠抑制黏著劑層的凝聚破壞(或破損)之特性。 That is, because the (meth)acrylic resin (A) of the present invention has hydroxyalkyl groups with predetermined carbon chain lengths in the side chain, it is estimated that the adhesive layer formed of the adhesive composition can make The crosslink density between (meth)acrylic resins is optimized. By optimizing the crosslinking density, an adhesive layer with an excellent balance of hardness and softness (or having the best hardness) can be formed, so durability can be improved and the interface can be effectively suppressed even in a high-temperature environment. Peeling (or floating) and foaming. Moreover, even if a strong shrinkage stress is generated, the adhesive layer can effectively alleviate the stress, so it is possible to prevent white spots caused by the shrinkage of the optical film (for example, deflection plate). Furthermore, by optimizing the crosslink density, reworkability (peelability) can also be improved. In addition, in this specification, the term “durability” means that, for example, in a high-temperature environment, a high-temperature and high-humidity environment, a high-temperature and low-temperature alternate environment, etc., it is possible to suppress the occurrence of the interface between the adhesive layer and the adjacent optical member. The characteristics of floating and peeling (also called resistance to peeling), and the characteristics of inhibiting defects such as foaming of the adhesive layer (also called resistance to foaming). In addition, in the present invention, the so-called anti-aggregation destruction property refers to the characteristic that can suppress the aggregation destruction (or breakage) of the adhesive layer.
在式(a1)中,X1係表示可具有取代基之亞甲基。作為該取代基,例如可舉出鹵原子(氟原子、氯原子、 溴原子、碘原子)、烷基(例如甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、戊基、己基等的C1-10烷基,較佳是C1-6烷基,更佳是C1-3烷基)、環烷基(環戊基、環己基等)、芳基[苯基、烷苯基(甲苯基、二甲苯基等)]芳烷基(苯甲基等)、烷氧基(例如甲氧基、乙氧基等的C1-4烷氧基)、聚氧伸烷基(例如二氧伸乙基等)、環烷氧基(例如環己氧基等的C5-10環烷氧基等)、芳氧基(例如苯氧基等)、芳烷氧基(例如,苯甲氧基等)、烷硫基(例如甲硫基、乙硫基等的C1-4烷硫基等)、環烷硫基(例如環己硫基等)、芳硫基(例如硫苯氧基等)、芳烷硫基(例如苯甲硫基等)、醯基(例如乙醯基等)、硝基、氰基等。該等之中,係以鹵原子、烷基、烷氧基、芳氧基等為佳,特別是以烷基(例如甲基、乙基等)為佳。 In the formula (a1), X 1 represents a methylene group which may have a substituent. Examples of the substituent include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), alkyl groups (for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, C 1-10 alkyl such as tertiary butyl, pentyl, hexyl, etc., preferably C 1-6 alkyl, more preferably C 1-3 alkyl), cycloalkyl (cyclopentyl, cyclohexyl, etc.) ), aryl [phenyl, alkyl phenyl (tolyl, xylyl, etc.)] aralkyl (benzyl, etc.), alkoxy (such as methoxy, ethoxy, etc. C 1-4 alkane Oxy), polyoxyalkylene (e.g., dioxyethylene, etc.), cycloalkoxy (e.g., C 5-10 cycloalkoxy such as cyclohexyloxy, etc.), aryloxy (e.g., phenoxy Etc.), aralkyloxy (e.g., benzyloxy, etc.), alkylthio (e.g., methylthio, ethylthio, etc. C 1-4 alkylthio, etc.), cycloalkylthio (e.g., cyclohexylthio Group, etc.), arylthio group (e.g. thiophenoxy group, etc.), aralkylthio group (e.g. benzylthio group, etc.), acyl group (e.g. acetyl group, etc.), nitro group, cyano group, and the like. Among them, halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, etc. are preferred, and alkyl groups (e.g., methyl, ethyl, etc.) are particularly preferred.
A1係表示氫原子或烷基,烷基可為X1所例示的烷基(較佳為甲基等)。 A 1 represents a hydrogen atom or an alkyl group, and the alkyl group may be an alkyl group exemplified by X 1 (preferably a methyl group or the like).
在式(a1)中,n係表示1至4的整數,較佳為1至3的整數,更佳為2。 In formula (a1), n represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 2.
作為含羥基的(甲基)丙烯酸酯(a1)之具體例,可舉出(甲基)丙烯酸1-羥基甲酯、(甲基)丙烯酸1-羥基乙酯、(甲基)丙烯酸1-羥基庚酯、(甲基)丙烯酸1-羥基丁酯、(甲基)丙烯酸1-羥基戊酯等的(甲基)丙烯酸1-羥基C1-8烷酯;(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸2-羥基戊酯、(甲基)丙烯酸2-羥基己酯等的(甲基)丙烯酸2-羥基C2-9 烷酯;(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸3-羥基戊酯、(甲基)丙烯酸3-羥基己酯、(甲基)丙烯酸3-羥基庚酯等的(甲基)丙烯酸3-羥基C3-10烷酯;(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸4-羥基戊酯、(甲基)丙烯酸4-羥基己酯、(甲基)丙烯酸4-羥基庚酯、(甲基)丙烯酸4-羥基辛酯等的(甲基)丙烯酸4-羥基C4-11烷酯;(甲基)丙烯酸2-氯-2-羥基丙酯、(甲基)丙烯酸3-氯-2-羥基丙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯等。該等之中,從耐久性的觀點而言,以(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯等n為2之含羥基的(甲基)丙烯酸酯;(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸3-羥基戊酯等n為3之含羥基的(甲基)丙烯酸酯為佳。以該n為2之含羥基的(甲基)丙烯酸酯為特佳,該等之中,係以(甲基)丙烯酸2-羥基乙酯為佳。 Specific examples of the hydroxyl-containing (meth)acrylate (a1) include 1-hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, and 1-hydroxy (meth)acrylate 1-hydroxy C 1-8 alkyl (meth)acrylate such as heptyl ester, 1-hydroxybutyl (meth)acrylate, 1-hydroxypentyl (meth)acrylate, etc.; 2-hydroxyethyl (meth)acrylate (Meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, etc. ) 2-hydroxy C 2-9 alkyl acrylate; 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 3-hydroxypentyl (meth)acrylate, (meth)acrylic acid 3-hydroxy C 3-10 alkyl (meth)acrylate such as 3-hydroxyhexyl ester, 3-hydroxyheptyl (meth)acrylate, etc.; 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid 4 -Hydroxypentyl, 4-hydroxyhexyl (meth)acrylate, 4-hydroxyheptyl (meth)acrylate, 4-hydroxyoctyl (meth)acrylate and other (meth)acrylic acid 4-hydroxy C 4- 11 Alkyl esters; 2-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate Wait. Among these, from the viewpoint of durability, n is 2 such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, etc. The hydroxyl-containing (meth)acrylate; 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 3-hydroxypentyl (meth)acrylate, etc. n is 3 hydroxyl-containing The (meth)acrylate is preferred. The hydroxyl-containing (meth)acrylate with n being 2 is particularly preferred, and among these, 2-hydroxyethyl (meth)acrylate is preferred.
相對於構成(甲基)丙烯酸系樹脂之總結構單元100重量份,源自式(a1)表示之含羥基的(甲基)丙烯酸酯之結構單元的比率,係以1.5至4.5重量份為佳,源自丙烯酸5-羥基戊酯(a2)之結構單元的比率,係以0.25至1.0重量份為佳。又,源自式(a1)表示之含羥基的(甲基)丙烯酸酯之結構單元、與源自丙烯酸5-羥基戊酯(a2)之結構單元之間的比率(重量比)係只要在上述範圍內即可,並沒有特別限定,較佳為(a1)/(a2)=13/1至3/1(例如11/1至3/1),更佳為9/1至4/1,特別是可為7/1至5/1。在上述範圍內時, 對於形成最佳交聯結構為有利,而且能夠提升耐久性等的特性。 The ratio of the structural units derived from the hydroxyl-containing (meth)acrylate represented by formula (a1) to 100 parts by weight of the total structural units constituting the (meth)acrylic resin is preferably 1.5 to 4.5 parts by weight , The ratio of the structural units derived from 5-hydroxypentyl acrylate (a2) is preferably 0.25 to 1.0 parts by weight. In addition, the ratio (weight ratio) between the structural unit derived from the hydroxyl-containing (meth)acrylate represented by formula (a1) and the structural unit derived from 5-hydroxypentyl acrylate (a2) is as long as It is within the range, and is not particularly limited, preferably (a1)/(a2)=13/1 to 3/1 (for example, 11/1 to 3/1), more preferably 9/1 to 4/1, In particular, it can be 7/1 to 5/1. When in the above range, It is advantageous for forming an optimal cross-linked structure and can improve characteristics such as durability.
(甲基)丙烯酸系樹脂(A)亦可含有源自丙烯酸烷酯(a3)之結構單元及源自含取代基的丙烯酸烷酯(a4)之結構單元。 The (meth)acrylic resin (A) may contain a structural unit derived from an alkyl acrylate (a3) and a structural unit derived from a substituent-containing alkyl acrylate (a4).
丙烯酸烷酯(a3)之中,就同元聚合物之玻璃轉移溫度(Tg)為未達0℃之丙烯酸烷酯(a3-1)而言,例如可舉出丙烯酸乙酯、丙烯酸正及異丙酯、丙烯酸正及異丁酯、丙烯酸正戊酯、丙烯酸正及異己酯、丙烯酸正庚酯、丙烯酸正及異辛酯、丙烯酸2-乙基己酯、丙烯酸正及異壬酯、丙烯酸正及異癸酯、丙烯酸正十二酯等烷基的碳數為2至12左右之直鏈狀或分枝鏈狀丙烯酸烷酯等。丙烯酸烷酯(a3)亦可為具有脂環式結構之丙烯酸烷酯(丙烯酸環烷酯),從對光學薄膜之追從性(或柔軟性和黏著性)等的觀點而言,係碳數為2至10的丙烯酸烷酯,較佳是碳數為3至8的丙烯酸烷酯,更佳是碳數為4至6的丙烯酸烷酯,特佳是丙烯酸正丁基烷酯。使用丙烯酸正丁基烷酯時,能夠提高追從性,例如對耐剝落性等為有利。該等丙烯酸烷酯(a3-1)係能夠單獨或組合二種以上而使用。 Among the alkyl acrylates (a3), for the alkyl acrylates (a3-1) whose glass transition temperature (Tg) of the homopolymer is less than 0°C, for example, ethyl acrylate, normal acrylate and isopropyl acrylate can be mentioned. Propyl ester, n- and isobutyl acrylate, n-pentyl acrylate, n- and isohexyl acrylate, n-heptyl acrylate, n- and isooctyl acrylate, 2-ethylhexyl acrylate, n- and isononyl acrylate, n-acrylate And isodecyl ester, n-lauryl acrylate and other straight-chain or branched-chain alkyl acrylates with the carbon number of the alkyl group from 2 to 12 or so. The alkyl acrylate (a3) may also be an alkyl acrylate (cycloalkyl acrylate) having an alicyclic structure. From the viewpoint of compliance (or flexibility and adhesion) to optical films, the number of carbon atoms is It is an alkyl acrylate having 2 to 10, preferably an alkyl acrylate having a carbon number of 3 to 8, more preferably an alkyl acrylate having a carbon number of 4 to 6, and particularly preferably an n-butyl alkyl acrylate. When n-butyl alkyl acrylate is used, it is possible to improve the followability, and for example, it is advantageous for the peeling resistance and the like. These alkyl acrylates (a3-1) can be used alone or in combination of two or more kinds.
就同元聚合物的Tg為0℃以上之丙烯酸烷酯(a3-2)而言,可舉出丙烯酸甲酯、丙烯酸環烷酯(例如丙烯酸環己酯、丙烯酸異莰酯)、丙烯酸硬脂酯、丙烯酸第三丁酯等,特別是以丙烯酸甲酯為特佳。使用丙烯酸甲酯時,能夠提高強度,例如對凝聚破壞為有利。該等丙烯酸烷酯 (a3-2)係能夠單獨或組合二種以上而使用。又,丙烯酸烷酯的同元聚合物之Tg,例如能夠參照POLYMER HANDBOOK(Wiley-Interscience)等的文獻值。 As for the alkyl acrylate (a3-2) whose Tg of the homopolymer is 0°C or higher, methyl acrylate, cycloalkyl acrylate (for example, cyclohexyl acrylate, isobornyl acrylate), and stearyl acrylate can be mentioned. Ester, tert-butyl acrylate, etc., especially methyl acrylate is particularly preferred. When methyl acrylate is used, the strength can be improved, which is advantageous for cohesion failure, for example. Alkyl acrylate (a3-2) It can be used individually or in combination of 2 or more types. In addition, for the Tg of the homopolymer of alkyl acrylate, for example, reference can be made to literature values such as POLYMER HANDBOOK (Wiley-Interscience).
在(甲基)丙烯酸系樹脂(A)中之源自丙烯酸烷酯的結構單元的比率,係從黏著劑層的耐久性及再加工性的觀點而言,相對於構成(甲基)丙烯酸系樹脂(A)之總結構單元100重量份例如為40重量份以上(例如50至98重量份),較佳為60重量份以上(例如70至95重量份),更佳為70重量份以上(例如80至90重量份)。 The ratio of the structural unit derived from alkyl acrylate in the (meth)acrylic resin (A) is relative to the structure of the (meth)acrylic from the viewpoint of durability and reworkability of the adhesive layer 100 parts by weight of the total structural unit of the resin (A) is, for example, 40 parts by weight or more (for example, 50 to 98 parts by weight), preferably 60 parts by weight or more (for example, 70 to 95 parts by weight), more preferably 70 parts by weight or more ( For example, 80 to 90 parts by weight).
若併用同元聚合物的Tg為未達0℃之丙烯酸烷酯、與同元聚合物的Tg為0℃以上的丙烯酸烷酯,則能夠兼具耐凝聚破壞性及追從性(耐發泡性及耐剝落性)且能夠提升對光學薄膜(例如偏光板)的尺寸變化之耐久性。 If the homopolymer has an alkyl acrylate whose Tg is less than 0°C, and the homopolymer has an alkyl acrylate whose Tg is 0°C or higher, it can have both cohesion resistance and compliance resistance (foaming resistance). Resistance and peeling resistance) and can improve the durability against dimensional changes of optical films (such as polarizing plates).
源自同元聚合物的玻璃轉移溫度為未達0℃之丙烯酸烷酯(a3-1)之結構單元、與源自玻璃轉移溫度為0℃以上之丙烯酸烷酯(a3-2)之結構單元之間的比率(重量比)為(a3-1)/(a3-2)=20/80至95/5(例如30/70至90/10),較佳為40/60至85/15,更佳為55/45至75/25。在上述範圍內時,能夠進一步提升耐久性。源自玻璃轉移溫度為未達0℃之丙烯酸烷酯(a3-1)之結構單元的比率越大時,追從性亦會越提升。源自玻璃轉移溫度為0℃以上之丙烯酸烷酯(a3-2)之結構單元的比率越大時,耐凝聚破壞性亦會越提升。 The structural unit derived from the alkyl acrylate (a3-1) whose glass transition temperature is less than 0℃ and the structural unit derived from the alkyl acrylate (a3-2) whose glass transition temperature is above 0℃ The ratio (weight ratio) between (a3-1)/(a3-2)=20/80 to 95/5 (for example, 30/70 to 90/10), preferably 40/60 to 85/15, More preferably, it is 55/45 to 75/25. Within the above range, durability can be further improved. The greater the ratio of structural units derived from the alkyl acrylate (a3-1) whose glass transition temperature is less than 0°C, the more the followability is improved. The greater the ratio of structural units derived from alkyl acrylate (a3-2) whose glass transition temperature is 0°C or higher, the greater the resistance to agglomeration destruction.
作為含取代基的丙烯酸烷酯(a4),例如可舉出在前述丙烯酸烷酯(a3-1)中之烷基導入有取代基(烷基的 氫原子被取代基取代)之丙烯酸烷酯。該取代基例如可為芳基(苯基等)、芳氧基(苯氧基)、烷氧基(例如甲氧基、乙氧基等)等。作為含取代基的丙烯酸烷酯(a3-3),例如可舉出丙烯酸烷氧基烷酯(例如丙烯酸2-甲氧基乙酯、丙烯酸乙氧基甲酯等)、丙烯酸芳氧基烷酯(例如丙烯酸苯氧基乙酯等)、芳氧基聚烷二醇單丙烯酸酯、聚烷二醇單丙烯酸酯等。該等丙烯酸烷酯(a3-3)係能夠單獨或組合2種以上而使用。藉由含有包含芳基、芳氧基等的芳香環之丙烯酸烷酯,能夠改善在耐久試驗時之偏光板所產生的白斑。又,芳氧基聚烷二醇單丙烯酸酯及聚烷二醇單丙烯酸酯的伸烷基,係例如可為亞甲基、伸乙基、伸丙基等C1-6伸烷基(較佳為伸乙基等)等,從由黏著劑組成物所形成的黏著層的耐久性之觀點而言,氧伸烷基的重複單元係例如可為2至7,較佳為2至5(特別是2)。在本發明,因為在黏著劑組成物中含有(甲基)丙烯酸系樹脂(A)及後述之交聯劑(B),能夠形成最佳交聯結構(或交聯密度),所以即便氧伸烷基的重複單元數較小,亦能夠顯示良好的再加工性。具體而言,例如可舉出苯氧基二乙二醇丙烯酸酯等的苯氧基二至七C1-3烷二醇丙烯酸酯、二乙二醇單丙烯酸酯等的二至七C1-3烷二醇單丙烯酸酯等。 As the substituent-containing alkyl acrylate (a4), for example, an alkyl acrylate in which a substituent (a hydrogen atom of the alkyl group is substituted by a substituent) is introduced into the alkyl group of the aforementioned alkyl acrylate (a3-1). The substituent may be, for example, an aryl group (such as a phenyl group), an aryloxy group (a phenoxy group), an alkoxy group (such as a methoxy group, an ethoxy group, etc.) and the like. As the substituent-containing alkyl acrylate (a3-3), for example, alkoxyalkyl acrylate (for example, 2-methoxyethyl acrylate, ethoxymethyl acrylate, etc.), aryloxyalkyl acrylate (For example, phenoxyethyl acrylate, etc.), aryloxy polyalkylene glycol monoacrylate, polyalkylene glycol monoacrylate, and the like. These alkyl acrylates (a3-3) can be used individually or in combination of 2 or more types. By containing an alkyl acrylate containing an aromatic ring containing an aryl group, an aryloxy group, etc., the white spots produced by the polarizing plate during the durability test can be improved. In addition, the alkylene groups of aryloxy polyalkylene glycol monoacrylate and polyalkylene glycol monoacrylate may be, for example, C 1-6 alkylene groups such as methylene, ethylene, and propylene (more Preferably, ethylene group, etc.), etc., from the viewpoint of durability of the adhesive layer formed by the adhesive composition, the repeating unit system of the oxyalkylene group may be, for example, 2 to 7, preferably 2 to 5 ( Especially 2). In the present invention, since the adhesive composition contains the (meth)acrylic resin (A) and the crosslinking agent (B) described later, the optimal crosslinking structure (or crosslinking density) can be formed, so even if oxygen stretches The alkyl group has a small number of repeating units and can also show good reworkability. Specific examples thereof include phenoxy diethylene glycol acrylate, phenoxy, a C 1-3 alkoxy two to seven glycol acrylate, diethylene glycol monoacrylate such as two to seven C 1- 3 Alkyl glycol monoacrylate and the like.
相對於構成(甲基)丙烯酸系樹脂(A)之總結構單元100重量份,源自含取代基之丙烯酸烷酯的結構單元的比率,係例如0至30重量份(例如1至25重量份),較佳為3至20重量份,更佳為5至15重量份。 The ratio of the structural unit derived from the substituent-containing alkyl acrylate relative to 100 parts by weight of the total structural unit constituting the (meth)acrylic resin (A) is, for example, 0 to 30 parts by weight (for example, 1 to 25 parts by weight) ), preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight.
(甲基)丙烯酸系樹脂(A)除了含有源自含羥基的(甲基)丙烯酸酯(a1)及丙烯酸5-羥基戊酯(a2)、丙烯酸烷酯(a3)及含取代基的丙烯酸烷酯(a4)之結構單元以外,亦能夠含有源自其它單體(a5)之結構單元。其它單體係能夠單獨或組合2種以上而使用。作為其它單體(a5),可舉出具有除了羥基以外的極性官能基之單體(a5-1)、丙烯醯胺系單體(a5-2)、甲基丙烯酸酯(甲基丙烯酸酯)(a5-3)、甲基丙烯醯胺系單體(a5-4)、苯乙烯系單體(a5-5)、乙烯系單體(a5-6)、及在分子內具有複數個(甲基)丙烯醯基之單體(a5-7)等。 (Meth) acrylic resin (A) in addition to containing hydroxyl-containing (meth)acrylate (a1) and 5-hydroxypentyl acrylate (a2), alkyl acrylate (a3) and alkyl acrylate containing substituents In addition to the structural unit of the ester (a4), a structural unit derived from another monomer (a5) can also be contained. Other single systems can be used alone or in combination of two or more kinds. Examples of other monomers (a5) include monomers having polar functional groups other than hydroxyl groups (a5-1), acrylamide-based monomers (a5-2), and methacrylates (methacrylates). (a5-3), methacrylamide-based monomer (a5-4), styrene-based monomer (a5-5), vinyl-based monomer (a5-6), and having a plurality of (formaldehyde) in the molecule Base) acryl monomer (a5-7) and so on.
作為具有羥基以外的極性官能基之單體(a5-1),可舉出具有羧基、取代或是未取代胺基、環氧基等雜環基等的取代基之(甲基)丙烯酸酯。具體而言,可舉出丙烯醯基嗎啉、乙烯基己內醯胺、N-乙烯基-2-吡咯啶酮、乙烯基吡啶、(甲基)丙烯酸四氫糠酯、己內酯改性丙烯酸四氫糠酯、(甲基)丙烯酸3,4-環氧基環己基甲酯、(甲基)丙烯酸縮水甘油酯、2,5-二氫呋喃等具有雜環基之單體;(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸二甲基胺基丙酯等具有取代或是未取代胺基之單體;(甲基)丙烯酸、順丁烯二酸、順丁烯二酸酐、反丁烯二酸、巴豆酸、(甲基)丙烯酸羧基烷酯(例如(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯)等具有羧基的單體。該等單體係能夠單獨或組合二種以上而使用。又,從能夠防止層積在黏著劑層之分離膜的剝離性低落之觀點而言,係以實質上不含有源自具有胺基的單體之結構單元為 佳。又,所謂實質上不含有係指相對於構成(甲基)丙烯酸系樹脂(A)之總結構單元100重量份為未達1.0重量份。 Examples of the monomer (a5-1) having a polar functional group other than a hydroxyl group include (meth)acrylates having a substituent such as a carboxyl group, a substituted or unsubstituted amino group, and a heterocyclic group such as an epoxy group. Specifically, acrylomorpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, tetrahydrofurfuryl (meth)acrylate, caprolactone modified Monomers with heterocyclic groups such as tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, glycidyl (meth)acrylate, 2,5-dihydrofuran, etc.; Yl)aminoethyl acrylate, N,N-dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate and other monomers with substituted or unsubstituted amino groups; (Meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, carboxyalkyl (meth)acrylate (e.g. carboxyethyl (meth)acrylate, (meth) Carboxypentyl acrylate) and other monomers having a carboxyl group. These single systems can be used alone or in combination of two or more. In addition, from the viewpoint of preventing deterioration of the peelability of the separation membrane laminated on the adhesive layer, the structural unit derived from a monomer having an amine group is not substantially contained as good. In addition, the term "substantially not contained" means that it is less than 1.0 part by weight with respect to 100 parts by weight of the total structural units constituting the (meth)acrylic resin (A).
在本發明,因為即便不含有被認為會使ITO腐蝕性增加之源自具有羧基的單體之結構單元(源自含羧基的(甲基)丙烯酸酯之結構單元),亦顯示較高的耐久性,所以能夠兼具耐久性及耐ITO腐蝕性。 In the present invention, even if it does not contain a structural unit derived from a monomer having a carboxyl group (a structural unit derived from a (meth)acrylate containing a carboxyl group) that is believed to increase the corrosiveness of ITO, it exhibits high durability. Performance, so it can have both durability and ITO corrosion resistance.
另一方面,含有源自具有羧基的單體之結構單元[源自含羧基的(甲基)丙烯酸酯之結構單元]時,能夠進一步提升耐久性。在本發明,因為即便源自含羧基的(甲基)丙烯酸酯之結構單元的比率較少,亦能夠有效地提升耐久性,所以在抑制ITO腐蝕之同時,能夠提升耐久性。 On the other hand, when a structural unit derived from a monomer having a carboxyl group [a structural unit derived from a (meth)acrylate containing a carboxyl group] is contained, durability can be further improved. In the present invention, even if the ratio of the structural unit derived from the carboxyl group-containing (meth)acrylate is small, the durability can be effectively improved. Therefore, the durability can be improved while suppressing the corrosion of ITO.
相對於源自(甲基)丙烯酸酯之結構單元100重量份,源自含羧基的(甲基)丙烯酸酯之結構單元的比率係例如5.0重量份以下(例如0至3重量份),較佳為1.0重量份以下(例如0至0.8重量份),更佳為0.5重量份以下(例如0.001至0.5重量份),又更佳為0.3重量份以下(例如0.005至0.3重量份),特別是0.2重量份以下(例如0.01至0.2重量份),尤其是0.15重量份以下(例如0.05至0.15重量份)。在上限值以下時,能夠抑制ITO腐蝕性,在下限值以上時則能夠提升耐久性。 The ratio of the structural unit derived from the carboxyl group-containing (meth)acrylate relative to 100 parts by weight of the structural unit derived from the (meth)acrylate is, for example, 5.0 parts by weight or less (for example, 0 to 3 parts by weight), preferably 1.0 parts by weight or less (for example, 0 to 0.8 parts by weight), more preferably 0.5 parts by weight or less (for example, 0.001 to 0.5 parts by weight), still more preferably 0.3 parts by weight or less (for example, 0.005 to 0.3 parts by weight), especially 0.2 Parts by weight or less (for example, 0.01 to 0.2 parts by weight), especially 0.15 parts by weight or less (for example, 0.05 to 0.15 parts by weight). When it is less than the upper limit, ITO corrosivity can be suppressed, and when it is more than the lower limit, durability can be improved.
作為丙烯醯胺系單體(a5-2),例如可舉出N-羥甲基丙烯醯胺、N-(2-羥乙基)丙烯醯胺、N-(3-羥丙基)丙烯醯胺、N-(4-羥丁基)丙烯醯胺、N-(5-羥戊基)丙烯醯胺、N-(6-羥己基)丙烯醯胺、N,N-二甲基丙烯醯胺、N,N-二乙基 丙烯醯胺、N-異丙基丙烯醯胺、N-(3-二甲胺基丙基)丙烯醯胺、N-(1,1-二甲基-3-側氧基丁基)丙烯醯胺、N-[2-(2-側氧基-1-咪唑啶基)乙基]丙烯醯胺、2-丙烯醯基胺基-2-甲基-1-丙磺酸、N-(甲氧基甲基)丙烯醯胺、N-(乙氧基甲基)丙烯醯胺、N-(丙氧基甲基)丙烯醯胺、N-(1-甲基乙氧基甲基)丙烯醯胺、N-(1-甲基丙氧基甲基)丙烯醯胺、N-(2-甲基丙氧基甲基)丙烯醯胺[別名:N-(異丁氧基甲基)丙烯醯胺]、N-(丁氧基甲基)丙烯醯胺、N-(1,1-二甲基乙氧基甲基)丙烯醯胺、N-(2-甲氧基乙基)丙烯醯胺、N-(2-乙氧基乙基)丙烯醯胺、N-(2-丙氧基乙基)丙烯醯胺、N-[2-(1-甲基乙氧基)乙基]丙烯醯胺、N-[2-(1-甲基丙氧基)乙基]丙烯醯胺、N-[2-(2-甲基丙氧基)乙基]丙烯醯胺[別名:N-(2-異丁氧基乙基)丙烯醯胺]、N-(2-丁氧基乙基)丙烯醯胺、N-[2-(1,1-二甲基乙氧基)乙基]丙烯醯胺等。該等之中,以N-(甲氧基甲基)丙烯醯胺、N-(乙氧基甲基)丙烯醯胺、N-(丙氧基甲基)丙烯醯胺、N-(丁氧基甲基)丙烯醯胺、N-(2-甲基丙氧基甲基)丙烯醯胺等為佳。 As the acrylamide-based monomer (a5-2), for example, N-methylol acrylamide, N-(2-hydroxyethyl) acrylamide, and N-(3-hydroxypropyl) acrylamide Amine, N-(4-hydroxybutyl)acrylamide, N-(5-hydroxypentyl)acrylamide, N-(6-hydroxyhexyl)acrylamide, N,N-dimethylacrylamide , N,N-Diethyl Acrylamide, N-isopropylacrylamide, N-(3-dimethylaminopropyl)acrylamide, N-(1,1-dimethyl-3-oxobutyl)acrylamide Amine, N-[2-(2-Pendant oxy-1-imidazolidinyl) ethyl] acrylamide, 2-propenylamino-2-methyl-1-propanesulfonic acid, N-(formaldehyde Oxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(1-methylethoxymethyl)acrylamide Amine, N-(1-methylpropoxymethyl)acrylamide, N-(2-methylpropoxymethyl)acrylamide [alias: N-(isobutoxymethyl)acrylamide Amine], N-(butoxymethyl)acrylamide, N-(1,1-dimethylethoxymethyl)acrylamide, N-(2-methoxyethyl)acrylamide , N-(2-ethoxyethyl) propylene amide, N-(2-propoxyethyl) propylene amide, N-[2-(1-methylethoxy) ethyl] propylene amide Amine, N-[2-(1-methylpropoxy)ethyl]acrylamide, N-[2-(2-methylpropoxy)ethyl]acrylamide [alias: N-(2 -Isobutoxyethyl)acrylamide], N-(2-butoxyethyl)acrylamide, N-[2-(1,1-dimethylethoxy)ethyl]acrylamide Amine etc. Among them, N-(methoxymethyl)acrylamide, N-(ethoxymeth)acrylamide, N-(propoxymeth)acrylamide, N-(butoxy Phenylmeth)acrylamide, N-(2-methylpropoxymeth)acrylamide, etc. are preferred.
作為甲基丙烯酸酯(methacrylic acid ester)(a5-3),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、甲基丙烯酸正辛酯、甲基丙烯酸月桂酯等的直鏈狀甲基丙烯酸烷酯;甲基丙烯酸異丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸異辛酯等的分枝鏈狀甲基丙烯酸烷酯;甲基丙烯酸異莰酯、甲基丙烯酸環己酯、甲基丙烯酸二環戊酯、甲基丙烯酸環十二酯、 甲基丙烯酸甲基環己酯、甲基丙烯酸三甲基環己酯、甲基丙烯酸第三丁基環己酯、甲基丙烯酸環己基苯酯等的甲基丙烯酸單或二環烷酯;甲基丙烯酸2-甲氧基乙酯、甲基丙烯酸乙氧基甲酯等的甲基丙烯酸烷氧基烷酯;甲基丙烯酸苯甲酯等的甲基丙烯酸芳烷酯等。 Examples of methacrylic acid ester (a5-3) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, and n-octyl methacrylate. Straight-chain alkyl methacrylate such as esters and lauryl methacrylate; branched-chain methacrylic acid such as isobutyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, etc. Alkyl ester; isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, cyclododecyl methacrylate, Mono- or dicycloalkyl methacrylates such as methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, cyclohexylphenyl methacrylate, etc.; Alkoxyalkyl methacrylate such as 2-methoxyethyl acrylate and ethoxymethyl methacrylate; Aralkyl methacrylate such as benzyl methacrylate.
作為甲基丙烯醯胺系單體(a5-4),例如可舉出與在(a5-2)所記載的丙烯醯胺系單體對應之甲基丙烯醯胺系單體等。 Examples of the methacrylamide-based monomer (a5-4) include methacrylamide-based monomers corresponding to the acrylamide-based monomers described in (a5-2).
作為苯乙烯系單體(a5-5),例如可舉出苯乙烯;甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、三乙基苯乙烯、丙基苯乙烯、丁基苯乙烯、己基苯乙烯、庚基苯乙烯、辛基苯乙烯等的烷基苯乙烯;氟苯乙烯、氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯等的鹵化苯乙烯;硝基苯乙烯;乙醯基苯乙烯;甲氧基苯乙烯;二乙烯基苯等。 As the styrene monomer (a5-5), for example, styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl Alkyl styrenes such as styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, and octyl styrene; fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, Halogenated styrene such as iodostyrene; nitrostyrene; acetoxystyrene; methoxystyrene; divinylbenzene, etc.
作為乙烯系單體(a5-6),例如可舉出乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯等的脂肪酸乙烯酯;氯乙烯、溴乙烯等的鹵化乙烯;偏二氯乙烯等的鹵化亞乙烯;乙烯基吡啶、乙烯基吡咯啶酮、乙烯基咔唑等的含氮芳香族乙烯;丁二烯、異戊二烯、氯丁二烯等的共軛二烯單體;丙烯腈、甲基丙烯腈等的不飽和腈等。 Examples of vinyl monomers (a5-6) include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate and other fatty acid vinyl esters; vinyl chloride , Vinyl bromide and other halogenated vinyl; vinylidene chloride and other halogenated vinylidene; vinyl pyridine, vinyl pyrrolidone, vinyl carbazole and other nitrogen-containing aromatic vinyl; butadiene, isoprene, chlorine Conjugated diene monomers such as butadiene; unsaturated nitriles such as acrylonitrile and methacrylonitrile.
作為在分子內具有複數個(甲基)丙烯醯基之單體(a5-7),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、1,9-壬二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等在分子內具有2個(甲基)丙烯醯基之單體;三羥甲基丙烷三(甲基)丙烯酸酯等在分子內具有3個(甲基)丙烯醯基之單體等。 Examples of monomers (a5-7) having plural (meth)acrylic groups in the molecule include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth) Acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, etc. have 2 (meth)acrylic acid monomers in the molecule; trimethylolpropane tris(meth) (Meth)acrylic acid esters and the like monomers having 3 (meth)acrylic acid groups in the molecule.
又,從黏著劑層的再加工性之觀點而言,(甲基)丙烯酸系樹脂(A)係以源自甲基丙烯酸酯(甲基丙烯酸酯)(a5-3)、甲基丙烯醯胺系單體(a5-4)等的甲基丙烯酸系單體之結構單元的比率(或含量)較小者為佳。亦即,相對於構成(甲基)丙烯酸系樹脂(A)之總結構單元100重量份,該結構單元的比率較佳為10重量份以下,更佳為5重量份以下,特別可為1重量份以下。 In addition, from the viewpoint of the reworkability of the adhesive layer, the (meth)acrylic resin (A) is derived from methacrylate (methacrylate) (a5-3), methacrylamide It is preferable that the ratio (or content) of the structural unit of the methacrylic monomer such as the monomer (a5-4) is smaller. That is, with respect to 100 parts by weight of the total structural units constituting the (meth)acrylic resin (A), the ratio of the structural units is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and particularly may be 1 part by weight The following.
而且,相對於構成(甲基)丙烯酸系樹脂(A)之總結構單元100重量份,源自其它單體(a5)的結構單元的比率,係例如可為0至20重量份,較佳為0至10重量份(例如0.001至10重量份),更佳為0至5重量份(例如0.01至3重量份)左右。 Furthermore, the ratio of the structural unit derived from the other monomer (a5) relative to 100 parts by weight of the total structural unit constituting the (meth)acrylic resin (A) may be, for example, 0 to 20 parts by weight, and is preferably 0 to 10 parts by weight (for example, 0.001 to 10 parts by weight), more preferably about 0 to 5 parts by weight (for example, 0.01 to 3 parts by weight).
(甲基)丙烯酸系樹脂(A),其藉由凝膠滲透層析法(GPC)所得到之經標準聚苯乙烯換算的重量平均分子量(Mw)係例如6.0×105至2.5×106(例如8.0×105至2.5×106),較佳為1.0×106至2.0×106,更佳為1.2×106至1.8×106(例如1.3×106至1.6×106)的範圍。Mw為上限值以下時,從將黏著劑組成物塗佈在基材時之塗佈性的觀點而言,乃是有 利,Mw為下限值以上時,係有利於提升黏著劑層對光學薄膜的尺寸變化之追從性。以重量平均分子量Mw與數量平均分子量Mn之比(Mw/Mn)表示之分子量分布通常為2至10,較佳為3至8,更佳為4至6。 (Meth)acrylic resin (A) whose weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) in terms of standard polystyrene is, for example, 6.0×10 5 to 2.5×10 6 (For example, 8.0×10 5 to 2.5×10 6 ), preferably 1.0×10 6 to 2.0×10 6 , more preferably 1.2×10 6 to 1.8×10 6 (for example, 1.3×10 6 to 1.6×10 6 ) Range. When Mw is less than the upper limit, it is advantageous from the viewpoint of coatability when the adhesive composition is applied to the substrate. When Mw is more than the lower limit, it is advantageous to improve the optical properties of the adhesive layer. The followability of the dimensional changes of the film. The molecular weight distribution expressed as the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw/Mn) is usually 2-10, preferably 3-8, more preferably 4-6.
又,(甲基)丙烯酸系樹脂(A)之在GPC之排出曲線上的Mw,係以在1.0×103至2.5×106的範圍具有單一譜峰為佳。使用該譜峰數為1之(甲基)丙烯酸系樹脂(A)時,對於提升黏著劑層的耐久性為有利。 In addition, the Mw of the (meth)acrylic resin (A) on the discharge curve of GPC preferably has a single peak in the range of 1.0×10 3 to 2.5×10 6. When the (meth)acrylic resin (A) with this number of peaks is 1 is used, it is advantageous to improve the durability of the adhesive layer.
在得到的排出曲線之上述範圍內,所謂「具有單一譜峰」係意味著在Mw1.0×103至2.5×106的範圍只具有一個極大值。在本說明書中,係將在GPC排出曲線內S/N比為30以上者定義為譜峰。又,GPC排出曲線的譜峰數及(甲基)丙烯酸系樹脂(A)的Mw及Mn,係能夠藉由在實施例項所記載的GPC測定條件來求取。 Within the above range of the obtained discharge curve, the so-called "having a single peak" means that there is only one maximum value in the range of Mw 1.0×10 3 to 2.5×10 6. In this specification, the spectrum peak is defined as the S/N ratio in the GPC discharge curve of 30 or more. In addition, the number of peaks of the GPC discharge curve and the Mw and Mn of the (meth)acrylic resin (A) can be determined by the GPC measurement conditions described in the section of the examples.
當(甲基)丙烯酸系樹脂(A)溶解在乙酸乙酯中且形成濃度20重量%的溶液時,其在25℃之黏度係以20Pa.s以下為佳,以0.1至7Pa.s為更佳。在該範圍的黏度時,從將黏著劑組成物塗佈在基材時之塗佈性的觀點而言,乃是有利。又,黏度係能夠藉由布氏(Brookfield)黏度計來測定。 When the (meth)acrylic resin (A) is dissolved in ethyl acetate and forms a solution with a concentration of 20% by weight, its viscosity at 25°C is 20Pa. s or less is better, 0.1 to 7Pa. s is better. When the viscosity is in this range, it is advantageous from the viewpoint of coatability when the adhesive composition is applied to the substrate. In addition, the viscosity can be measured with a Brookfield viscometer.
(甲基)丙烯酸系樹脂(A)的玻璃轉移溫度(Tg),係例如可為-60至0℃(例如-50至-10℃),較佳為-50至-20℃,更佳為-40至-20℃(例如-40至-25℃)。在該範圍時,對於提升耐久性為有利。又,玻璃轉移溫度係能夠藉 由差示掃描量熱儀(DSC)來測定。 The glass transition temperature (Tg) of the (meth)acrylic resin (A) can be, for example, -60 to 0°C (for example, -50 to -10°C), preferably -50 to -20°C, more preferably -40 to -20°C (for example, -40 to -25°C). In this range, it is advantageous to improve durability. In addition, the glass transition temperature can be used Measured by differential scanning calorimeter (DSC).
(甲基)丙烯酸系樹脂(A)可藉由例如溶液聚合法、塊狀聚合法、懸浮聚合法、乳化聚合法等的眾所周知的方法來製造,特別是以溶液聚合法為佳。作為溶液聚合法,例如可舉出將單體及有機溶劑混合,在氮氣環境下添加熱聚合起始劑,且在40至90℃(較佳為50至80℃)左右的溫度條件下攪拌3至15小時左右之方法。為了控制反應,亦可在聚合中連續性或間歇性地添加單體和熱聚合起始劑。該單體和熱起始劑亦可為已添加在有機溶劑之狀態。 The (meth)acrylic resin (A) can be produced by a well-known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, etc., and a solution polymerization method is particularly preferred. As a solution polymerization method, for example, a monomer and an organic solvent are mixed, a thermal polymerization initiator is added in a nitrogen atmosphere, and stirring is performed under a temperature condition of about 40 to 90°C (preferably 50 to 80°C). It takes about 15 hours. In order to control the reaction, the monomer and the thermal polymerization initiator may be added continuously or intermittently during the polymerization. The monomer and thermal initiator can also be added to the organic solvent.
作為聚合起始劑,能夠使用熱聚合起始劑、光聚合起始劑等。作為光聚合起始劑,例如可舉出4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮等。作為熱聚合起始劑,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-甲腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基-2,2’-偶氮雙(2-甲基丙酸酯)、2,2’-偶氮雙(2-羥甲基丙腈)等的偶氮系化合物;過氧化月桂醯、第三丁基過氧化氫、過氧化苯甲醯、過氧化苯甲酸第三丁酯、異丙苯過氧化氫、過氧化二碳酸二異丙酯、過氧化二碳酸二丙酯、過氧化新癸酸第三丁酯、過氧化三甲基乙酸第三丁酯、過氧化(3,5,5-三甲基己醯基)等的有機過氧化物;過硫酸鉀、過硫酸銨、過氧化氫等的無機過氧化物等。又,亦能夠使用將過氧化物與還原劑併用而成之氧化還原系起始劑等。 As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, and the like can be used. As a photopolymerization initiator, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone etc. are mentioned, for example. As the thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclo Hexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxy Valeronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile) and other azo compounds ; Laurel peroxide, tertiary butyl hydroperoxide, benzyl peroxide, tertiary butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dicarbonate peroxydicarbonate Organic peroxides such as propyl ester, t-butyl peroxyneodecanoate, t-butyl peroxy trimethyl acetate, and peroxy (3,5,5-trimethylhexyl); potassium persulfate , Ammonium persulfate, hydrogen peroxide and other inorganic peroxides. In addition, it is also possible to use a redox-based initiator obtained by using a peroxide and a reducing agent in combination.
相對於構成(甲基)丙烯酸系樹脂之單體的 總量100重量份,聚合起始劑的比率為0.001至5重量份左右。(甲基)丙烯酸系樹脂的聚合,亦可使用藉由活性能量線(例如紫外線等)所進行之聚合法。 Relative to the monomer constituting the (meth)acrylic resin The total amount is 100 parts by weight, and the ratio of the polymerization initiator is about 0.001 to 5 parts by weight. For the polymerization of (meth)acrylic resin, a polymerization method using active energy rays (for example, ultraviolet rays, etc.) can also be used.
作為有機溶劑,例如可舉出甲苯、二甲苯等的芳香族烴類;乙酸乙酯、乙酸丁酯等的酯類;丙醇、異丙醇等的脂肪族醇類;丙酮、甲基乙基酮、甲基異丁基酮等的酮類等。 Examples of organic solvents include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; acetone and methyl ethyl Ketones such as ketone, methyl isobutyl ketone, etc.
黏著劑組成物係含有交聯劑(B)。該交聯劑(B)係與(甲基)丙烯酸系樹脂(A)中之含羥基的極性官能基反應。本發明中,係被導入至(甲基)丙烯酸系樹脂(A)的側鏈之具有預定之不同的碳鏈之羥烷基的OH基(羥基)與交聯劑(B)產生反應,形成有利於耐久性及再加工性之交聯結構。 The adhesive composition contains a crosslinking agent (B). The crosslinking agent (B) reacts with the hydroxyl-containing polar functional group in the (meth)acrylic resin (A). In the present invention, the OH group (hydroxyl group) of the hydroxyalkyl group having a predetermined different carbon chain introduced into the side chain of the (meth)acrylic resin (A) reacts with the crosslinking agent (B) to form Cross-linked structure conducive to durability and reworkability.
作為交聯劑(B),可舉出慣用之交聯劑(例如:異氰酸酯化合物、環氧化合物、氮丙啶化合物,金屬螯合劑化合物,過氧化物等),尤其是由黏著劑組成物之適用期(pot life)及附黏著劑層之光學薄膜的耐久性、交聯速度等之觀點而言,以異氰酸酯化合物為佳。 As the crosslinking agent (B), conventional crosslinking agents (for example: isocyanate compounds, epoxy compounds, aziridine compounds, metal chelating agent compounds, peroxides, etc.) can be mentioned, especially those composed of adhesives. From the viewpoints of pot life and the durability of the optical film with the adhesive layer, and the crosslinking speed, isocyanate compounds are preferred.
作為異氰酸酯化合物,以在分子內具有至少2個異氰酸基(-NCO)之化合物為佳,例如,可舉出脂肪族異氰酸酯系化合物(例如六亞甲基二異氰酸酯等)、脂環族異氰酸酯系化合物(例如異佛酮二異氰酸酯)、芳香族異氰酸酯系化合物(例如甲苯二異氰酸酯、伸二甲苯二異氰酸 酯、氫化伸二甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、萘二異氰酸酯,三苯甲烷三異氰酸酯等)。而且,交聯劑(B)係可為上述異氰酸酯系化合物加添多元醇化合物而得到的加成物(additive compounds)[例如加添甘油、三羥甲基丙烷等而得到的加成物]、三聚異氰酸酯化合物、縮二脲型化合物、使與聚醚多元醇、聚酯多元醇、丙烯酸多元醇、聚丁二烯多元醇、聚異戊二烯多元醇等進行加成反應而得到的胺酯預聚物型之異氰酸酯化合物等的衍生物。交聯劑(B)係能夠單獨或組合二種以上而使用。此等之中,代表性地可舉出芳香族異氰酸酯系化合物(例如甲苯二異氰酸酯、伸二甲苯二異氰酸酯)、脂肪族異氰酸酯系化合物(例如六亞甲基二異氰酸酯)、或於此等加添多元醇化合物(甘油、三羥甲基丙烷)而得到的加成物。交聯劑(B)為芳香族異氰酸酯系化合物及/或於此等加添多元醇化合物而得到的加成物時,或許因有利於最佳交聯密度(或交聯構造)之形成而能夠提升黏著劑層之耐久性。特別是為甲苯二異氰酸酯系化合物及/或加添該等多元醇化合物而得到的加成物時,能夠進一步提升耐久性(例如使用於ITO基板時之黏著劑層的耐久性)。 As the isocyanate compound, a compound having at least two isocyanate groups (-NCO) in the molecule is preferred. For example, aliphatic isocyanate compounds (for example, hexamethylene diisocyanate, etc.) and alicyclic isocyanates are mentioned. Series compounds (e.g. isophorone diisocyanate), aromatic isocyanate compounds (e.g. toluene diisocyanate, xylene diisocyanate) Esters, hydrogenated xylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.). Furthermore, the crosslinking agent (B) may be an additive compound obtained by adding a polyol compound to the above-mentioned isocyanate compound [for example, an additive compound obtained by adding glycerin, trimethylolpropane, etc.], Trimeric isocyanate compound, biuret type compound, amine obtained by addition reaction with polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol, etc. Derivatives such as ester prepolymer type isocyanate compounds. The crosslinking agent (B) can be used alone or in combination of two or more kinds. Among these, representatively, aromatic isocyanate compounds (for example, toluene diisocyanate, xylene diisocyanate), aliphatic isocyanate compounds (for example, hexamethylene diisocyanate), or the addition of multiple An adduct obtained from an alcohol compound (glycerin, trimethylolpropane). When the crosslinking agent (B) is an aromatic isocyanate compound and/or an adduct obtained by adding a polyol compound to these, it may be useful for the formation of an optimal crosslink density (or crosslink structure) Improve the durability of the adhesive layer. Especially when it is a toluene diisocyanate-based compound and/or an adduct obtained by adding these polyol compounds, the durability (for example, the durability of the adhesive layer when used on an ITO substrate) can be further improved.
相對於(甲基)丙烯酸系樹脂(A)100重量份,交聯劑(B)的比率係例如可為0.01至10重量份(例如0.05至5重量份),較佳為0.1至3重量份(例如0.1至2重量份),更佳為0.2至1重量份(例如0.3至0.8重量份)。在上限值以下時,對提升追從性(或耐剝落性)越有利,在下限值以 上時,對提升耐凝聚性(或耐發泡性)和再加工性為有利。 Relative to 100 parts by weight of the (meth)acrylic resin (A), the ratio of the crosslinking agent (B) can be, for example, 0.01 to 10 parts by weight (for example, 0.05 to 5 parts by weight), preferably 0.1 to 3 parts by weight (E.g., 0.1 to 2 parts by weight), more preferably 0.2 to 1 part by weight (e.g., 0.3 to 0.8 parts by weight). Below the upper limit, it is more advantageous to improve the followability (or peel resistance), and the lower limit is less than When used, it is beneficial to improve cohesion resistance (or foam resistance) and reworkability.
黏著劑組成物係含有矽烷化合物(C)。藉由含有該矽烷化合物(C),能夠提升黏著劑層、與金屬層、透明電極、玻璃基板等之密著性(或接著性)。作為矽烷化合物(C),只要係能夠與(甲基)丙烯酸系樹脂(A)的反應性基(例如羥基的OH基)鍵結之矽烷化合物即可,例如可舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、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甲氧基矽烷、3-縮水甘油氧基丙基乙氧基二甲基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-氫硫基丙基三甲氧基矽烷、及1,3-雙(3’-三甲氧基丙基)脲等。 The adhesive composition contains a silane compound (C). By containing the silane compound (C), the adhesion (or adhesion) of the adhesive layer, the metal layer, the transparent electrode, the glass substrate, etc. can be improved. As the silane compound (C), any silane compound capable of bonding to the reactive group (for example, the OH group of the hydroxyl group) of the (meth)acrylic resin (A) may be used, for example, vinyl trimethoxy silane , Vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl triethoxy silane , 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsiloxane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-hydrothiopropyltrimethoxysilane Silane, and 1,3-bis(3'-trimethoxypropyl)urea, etc.
又,矽烷化合物(C)亦可為聚矽氧寡聚物型的化合物,以單體之間的組合記載該聚矽氧寡聚物時,例如可舉出3-氫硫基丙基二或三甲氧基矽烷-四甲氧基矽烷寡聚物、3-氫硫基甲基二或三甲氧基矽烷-四乙氧基矽烷寡聚物、3-氫硫基丙基二或三乙氧基矽烷-四甲氧基矽烷寡聚物、3-氫硫基甲基二或三乙氧基矽烷-四乙氧基矽烷寡聚物等的含氫硫基烷基的寡聚物;將該含氫硫基烷基的寡聚物的氫硫基烷基替換成為其它取代基[3-縮水甘油氧基丙 基、(甲基)丙烯醯氧基丙基、乙烯基、胺基等]而成之寡聚物等。 In addition, the silane compound (C) may be a polysiloxane oligomer type compound. When the polysiloxane oligomer is described as a combination of monomers, for example, 3-hydrothiopropyl bis or Trimethoxysilane-tetramethoxysilane oligomer, 3-hydrothiomethyl bis or trimethoxysilane-tetraethoxy silane oligomer, 3-hydrothiopropyl bis or triethoxy Silane-tetramethoxysilane oligomer, 3-hydrothiomethyl bis or triethoxy silane-tetraethoxy silane oligomer and other thioalkyl group-containing oligomers; The sulfhydryl alkyl of the oligomer of sulfhydryl alkyl is replaced with other substituents [3-glycidoxypropyl Group, (meth)acryloyloxypropyl, vinyl group, amine group, etc.].
矽烷化合物(C)較佳是可為下述式(c1)表示之矽烷化合物。黏著劑組成物含有下述式(c1)表示之矽烷化合物時,能夠進一步提升密著性(或接著性),所以能夠形成耐剝落性優異之黏著劑層。而且該黏著劑層亦具有優異的再加工性。尤其,即便在高溫環境下將黏著劑層應用(或層積)在透明電極(例如ITO基板等)之情況,亦能夠維持密著性(或接著性)且顯示較高的耐久性。 The silane compound (C) is preferably a silane compound represented by the following formula (c1). When the adhesive composition contains the silane compound represented by the following formula (c1), the adhesiveness (or adhesiveness) can be further improved, so an adhesive layer with excellent peeling resistance can be formed. Moreover, the adhesive layer also has excellent reworkability. In particular, even when an adhesive layer is applied (or laminated) to a transparent electrode (for example, an ITO substrate, etc.) under a high-temperature environment, it is possible to maintain adhesion (or adhesion) and exhibit high durability.
在式(c1)中,B係表示亞甲基、伸乙基、三亞甲基、四亞甲基、六亞甲基、七亞甲基、八亞甲基等碳數1至20的烷二基;伸環丁基(例如1,2-伸環丁基)、伸環戊基(例如1,2-伸環戊基、伸環己基(例如1,2-伸環己基)、伸環辛基(例如1,2-伸環辛基)等碳數3至20的二價脂環式烴基;或構成該等烷二基及前述脂環式烴基之-CH2-置換成
-O-或-CO-之基。較佳的B係碳數1至10的烷二基。R1係表示甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、戊基等碳數1至5的烷基,R2、R3、R4、R5及R6係各自獨立且表示在前述R1例示之碳數1至5的烷基;或甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、第二丁氧基、第三丁氧基等的碳數1至5的烷氧基。較佳的R2、R3、R4、R5及R6為碳數1至5的烷氧基。該等矽烷化合物(C)係能夠單獨或組合二種以上而使用。
In formula (c1), B series represents methylene, ethylene, trimethylene, tetramethylene, hexamethylene, heptamethylene, octamethylene and
作為具體的矽烷化合物(c1),例如可舉出(三甲氧基矽基)甲烷、1,2-雙(三甲氧基矽基)乙烷、1,2-雙(三乙氧基矽基)乙烷、1,3-雙(三甲氧基矽基)丙烷、1,3-雙(三乙氧基矽基)丙烷、1,4-雙(三甲氧基矽基)丁烷、1,4-雙(三乙氧基矽基)丁烷、1,5-雙(三甲氧基矽基)戊烷、1,5-雙(三乙氧基矽基)戊烷、1,6-雙(三甲氧基矽基)己烷、1,6-雙(三乙氧基矽基)己烷、1,6-雙(三丙氧基矽基)己烷、1,8-雙(三甲氧基矽基)辛烷、1,8-雙(三乙氧基矽基)辛烷、1,8-雙(三丙氧基矽基)辛烷等的雙(三C1-5烷氧基矽基)C1-10烷烴;雙(二甲氧基甲基矽基)甲烷、1,2-雙(二甲氧基甲基矽基)乙烷、1,2-雙(二甲氧基乙基矽基)乙烷、1,4-雙(二甲氧基甲基矽基)丁烷、1,4-雙(二甲氧基乙基矽基)丁烷、1,6-雙(二甲氧基甲基矽基)己烷、1,6-雙(二甲氧基乙基矽基)己烷、1,8-雙(二甲氧基甲基矽基)辛烷、1,8-雙(二甲氧基乙基矽基)辛烷等的雙(二C1-5烷氧基C1-5烷基矽基)C1-10烷烴;1,6-雙(甲氧基二甲基矽基)己烷、1,8-雙(甲氧基二甲基矽基)辛烷等 的雙(單C1-5烷氧基-二C1-5烷基矽基)C1-10烷烴等。該等之中,以1,2-雙(三甲氧基矽基)乙烷、1,3-雙(三甲氧基矽基)丙烷、1,4-雙(三甲氧基矽基)丁烷、1,5-雙(三甲氧基矽基)戊烷、1,6-雙(三甲氧基矽基)己烷、1,8-雙(三甲氧基矽基)辛烷等的雙(三C1-3烷氧基矽基)C1-10烷烴為佳,以1,6-雙(三甲氧基矽基)己烷、1,8-雙(三甲氧基矽基)辛烷為特佳。 Specific examples of the silane compound (c1) include (trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, and 1,2-bis(triethoxysilyl) Ethane, 1,3-bis(trimethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,4 -Bis(triethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,5-bis(triethoxysilyl)pentane, 1,6-bis( Trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,6-bis(tripropoxysilyl)hexane, 1,8-bis(trimethoxy) silicon based) octane, 1,8-bis (silicon based triethoxysilyl) octane, 1,8-bis (tripropoxy silicon based) octane, bis (C 1-5 alkoxy three silicon Group) C 1-10 alkanes; bis(dimethoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane, 1,2-bis(dimethoxyethyl) Silyl)ethane, 1,4-bis(dimethoxymethylsilyl)butane, 1,4-bis(dimethoxyethylsilyl)butane, 1,6-bis(dimethoxyethylsilyl)butane Methoxymethylsilyl)hexane, 1,6-bis(dimethoxyethylsilyl)hexane, 1,8-bis(dimethoxymethylsilyl)octane, 1,8 -Bis(di-C 1-5 alkoxy C 1-5 alkyl silyl) C 1-10 alkanes such as bis(dimethoxyethylsilyl)octane; 1,6-bis(methoxy) Dimethylsilyl)hexane, 1,8-bis(methoxydimethylsilyl)octane and other bis(mono-C 1-5 alkoxy-di C 1-5 alkylsilyl) C 1-10 alkanes and so on. Among them, 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane and other bis(triC) 1-3 alkoxysilyl) C 1-10 alkanes are preferred, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane are particularly preferred .
相對於(甲基)丙烯酸系樹脂(A)100重量份,矽烷化合物(C)的比率係例如0.01至10重量份(例如0.03至5重量份),較佳為0.05至3重量份,更佳為0.1至1重量份(例如0.2至0.5重量份)。在上限值以下時,對於抑制矽烷化合物(C)從黏著劑層的滲出為有利,在下限值以上時,黏著劑層、與金屬層、玻璃基板等之密著性(或接著性)的提升會變為容易,且對於提升耐剝落性等為有利。 The ratio of the silane compound (C) relative to 100 parts by weight of the (meth)acrylic resin (A) is, for example, 0.01 to 10 parts by weight (for example, 0.03 to 5 parts by weight), preferably 0.05 to 3 parts by weight, more preferably It is 0.1 to 1 part by weight (for example, 0.2 to 0.5 part by weight). When the value is below the upper limit, it is advantageous to suppress the exudation of the silane compound (C) from the adhesive layer. When the value is above the lower limit, the adhesion (or adhesion) of the adhesive layer, metal layer, glass substrate, etc. Lifting becomes easy, and it is advantageous for improving peeling resistance and the like.
黏著劑組成物亦可進一步含有抗靜電劑。藉由含有抗靜電劑,能夠提升黏著劑的抗靜電性(例如抑制因脫模膜、保護膜等剝離時所產生的靜電而引起的缺陷等)。作為抗靜電劑,可舉出慣用物,以離子性抗靜電劑為佳。作為構成離子性抗靜電劑之陽離子成分,可舉出有機陽離子、無機陽離子等。作為有機陽離子,例如可舉出吡啶鎓陽離子、咪唑鎓陽離子、銨陽離子、鋶陽離子、鏻陽離子等。作為無機陽離子,例如可舉出鋰陽離子、鉀陽離子、鈉陽離子、銫陽離子等的鹼金屬陽離子;鎂陽離子、鈣陽離子等的鹼 土金屬陽離子等。作為構成離子性抗靜電劑之陰離子成分,可為無機陰離子及有機陰離子之任一種,從具有優異的抗靜電性能而言,係以含有氟原子之陰離子成分為佳。作為含有氟原子之陰離子成分,例如可舉出六氟磷酸根陰離子(PF6-)、雙(三氟甲磺醯基)亞胺陰離子[(CF3SO2)2N-]、雙(氟磺醯基)亞胺陰離子[(FSO2)2N-]、四(五氟苯基)硼酸根陰離子[(C6F5)4B-]等。該等抗靜電劑係能夠單獨或組合二種以上而使用。特別是以雙(三氟甲磺醯基)亞胺陰離子[(CF3SO2)2N-]、雙(氟磺醯基)亞胺陰離子[(FSO2)2N-]、四(五氟苯基)硼酸根陰離子[(C6F5)4B-]為佳。 The adhesive composition may further contain an antistatic agent. By containing an antistatic agent, the antistatic property of the adhesive can be improved (for example, it is possible to suppress defects caused by static electricity generated when a release film, a protective film, etc. are peeled off). Examples of the antistatic agent include conventional ones, and ionic antistatic agents are preferred. Examples of cationic components constituting the ionic antistatic agent include organic cations and inorganic cations. As an organic cation, a pyridinium cation, an imidazolium cation, an ammonium cation, a sulfonium cation, a phosphonium cation, etc. are mentioned, for example. Examples of inorganic cations include alkali metal cations such as lithium cation, potassium cation, sodium cation, and cesium cation; alkaline earth metal cations such as magnesium cation and calcium cation. The anion component constituting the ionic antistatic agent can be either inorganic anion or organic anion. In terms of excellent antistatic performance, an anion component containing fluorine atoms is preferred. As an anion component containing a fluorine atom, for example, hexafluorophosphate anion (PF 6 -), bis(trifluoromethanesulfonyl)imide anion [(CF 3 SO 2 ) 2 N-], bis(fluorine Sulfonyl) imine anion [(FSO 2 ) 2 N-], tetrakis(pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B-], etc. These antistatic agents can be used alone or in combination of two or more kinds. Especially bis(trifluoromethanesulfonyl) imine anion [(CF 3 SO 2 ) 2 N-], bis(fluorosulfonyl) imine anion [(FSO 2 ) 2 N-], four (five Fluorophenyl) borate anion [(C 6 F 5 ) 4 B-] is preferred.
從黏著劑組成物的抗靜電性能具有優異的經時安定性而言,以在室溫為固體之離子性抗靜電劑為佳。 In terms of the antistatic properties of the adhesive composition and its excellent stability over time, ionic antistatic agents that are solid at room temperature are preferred.
相對於(甲基)丙烯酸系樹脂(A)100重量份,抗靜電劑的比率係例如可為0.01至10重量份,較佳為0.1至5重量份,更佳為1至3重量份。 The ratio of the antistatic agent relative to 100 parts by weight of the (meth)acrylic resin (A) can be, for example, 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 1 to 3 parts by weight.
黏著劑組成物,係能夠單獨含有或含有2種以上之溶劑、交聯觸媒、紫外線吸收劑、耐候安定劑、增黏劑(tackifier)、可塑劑、軟化劑、染料、顏料、無機填料、光散射性微粒子等的添加劑。又,對於在黏著劑組成物調配紫外線硬化性化合物而形成黏著劑層之後,照射紫外線使其硬化而成為更硬的黏著劑層亦是有用。作為交聯觸媒,例如可舉出六亞甲二胺、乙二胺、聚伸乙亞胺、六亞甲四 胺、二伸乙三胺、三伸乙四胺、異佛酮二胺、三亞甲二胺、聚胺基樹脂及三聚氰胺樹脂等的胺系化合物等。 The adhesive composition can contain two or more solvents, crosslinking catalysts, ultraviolet absorbers, weather stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, Additives such as light-scattering fine particles. It is also useful for forming an adhesive layer by blending an ultraviolet curable compound in the adhesive composition, and then irradiating it with ultraviolet rays to harden it to become a harder adhesive layer. As the crosslinking catalyst, for example, hexamethylene diamine, ethylene diamine, polyethyleneimine, hexamethylene tetramethylene Amine compounds such as amine, ethylene triamine, ethylene tetramine, isophorone diamine, trimethylene diamine, polyamine-based resin, and melamine resin.
從提高黏著劑層的耐金屬腐蝕性之觀點而言,黏著劑組成物係能夠含有防鏽劑。作為防鏽劑,例如可舉出苯并***系化合物等的***系化合物;苯并噻唑系化合物等的噻唑系化合物;苯甲基咪唑系化合物等的咪唑系化合物;咪唑啉系化合物;喹啉系化合物;吡啶系化合物;嘧啶系化合物;吲哚系化合物;胺系化合物;脲系化合物;苯甲酸鈉;苯甲基氫硫基系化合物;二-第二丁基硫醚;及二苯基亞碸等。 From the viewpoint of improving the metal corrosion resistance of the adhesive layer, the adhesive composition system can contain a rust inhibitor. Examples of the rust inhibitor include triazole-based compounds such as benzotriazole-based compounds; thiazole-based compounds such as benzothiazole-based compounds; imidazole-based compounds such as benzyl imidazole-based compounds; imidazoline-based compounds; Quinoline-based compounds; pyridine-based compounds; pyrimidine-based compounds; indole-based compounds; amine-based compounds; urea-based compounds; sodium benzoate; benzyl sulfide-based compounds; di-second butyl sulfide; and diphenyl Keaqi et al.
本發明的黏著劑組成物係能夠藉由施行表面活性化處理(例如電漿處理、電暈處理等)等來形成黏著劑層。通常,該黏著劑層係層積在光學薄膜的至少一面。 The adhesive composition system of the present invention can form an adhesive layer by performing surface activation treatment (for example, plasma treatment, corona treatment, etc.). Usually, the adhesive layer is laminated on at least one side of the optical film.
第1圖係顯示附有由本發明之黏著劑組成物所形成之黏著劑層的光學薄膜的一例之概略剖面圖。第1圖所顯示之附黏著劑層的光學薄膜1,係光學薄膜10、及在該光學薄膜的一面層積黏著劑層20而成之光學薄膜。該黏著劑層20通常係直接層積在光學薄膜10的表面。又,黏著劑層20亦可層積在光學薄膜10的兩面。
Fig. 1 is a schematic cross-sectional view showing an example of an optical film with an adhesive layer formed of the adhesive composition of the present invention. The
將黏著劑層20層積在光學薄膜10的表面時,係以使底漆層形成在光學薄膜10的貼合面及/或黏著劑層20的貼
合面、或施行前述表面活性化處理(例如電漿處理、電暈處理等)為佳,以施行電暈處理為特佳。
When the
光學薄膜10如第2圖所示為單面保護偏光板時,黏著劑層20通常係層積(較佳是直接層積)在偏光片面,亦即層積在偏光片2之與第1樹脂薄膜3為相反側之面。光學薄膜10如第3圖所示為兩面保護偏光板時,可將黏著劑層20層積在第1、第2樹脂薄膜3、4之任一者的外表面,亦可層積在雙方的外表面。
When the
在光學薄膜10與黏著劑層20之間亦可另外設置抗靜電層。作為抗靜電層,能夠使用聚矽氧烷等的矽系材料、錫摻雜氧化銦、錫摻雜氧化銻等的無機金屬系材料、聚噻吩、聚苯乙烯磺酸、聚苯胺等的有機高分子系材料。
An antistatic layer can also be additionally provided between the
附黏著劑層的光學薄膜1,亦可包含層積在黏著劑層20的外表面之分離膜(剝離膜)。該分離膜通常會在黏著劑層20的使用時(例如層積在透明導電極和玻璃基板時)被剝離除去。分離膜係例如可為在由聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚碳酸酯、聚芳酯等各種樹脂所構成的薄膜之要形成黏著劑層20之面,施行聚矽氧處理等的脫模處理者。
The adhesive layer-attached
附黏著劑層的光學薄膜1,係能夠藉由將構成上述黏著劑組成物之各成分溶解或分散在溶劑而成為含溶劑的黏著劑組成物,其次,將其塗佈在光學薄膜10的表面且乾燥而形成黏著劑層20來得到。又,附黏著劑層的光
學薄膜1,亦能夠藉由在分離膜的脫模處理面以與上述同樣的方式形成黏著劑層20,將該黏著劑層20層積(轉印)在光學薄膜10的表面來得到。
The adhesive layer-attached
黏著劑層的厚度通常為2至40μm,從附黏著劑層的光學薄膜之耐久性和附黏著劑層的光學薄膜之再加工性等之觀點而言,較佳為5至30μm,更佳為10至25μm。在上限值以下時,黏著劑層對光學薄膜的尺寸變化之追從性(或追隨性)變為良好,在下限值以上時,再加工性變為良好。 The thickness of the adhesive layer is usually 2 to 40 μm. From the viewpoints of the durability of the optical film with the adhesive layer and the reworkability of the optical film with the adhesive layer, it is preferably 5 to 30 μm, and more preferably 10 to 25μm. When it is below the upper limit, the followability (or followability) of the adhesive layer to the dimensional change of the optical film becomes good, and when it is above the lower limit, the reworkability becomes good.
黏著劑層係以在23至80℃的溫度範圍內顯示0.1至5MPa的儲存彈性模數者為佳。藉此,能夠更有效地提高附黏著劑層的光學薄膜之耐久性。所謂「在23至80℃的溫度範圍內顯示0.1至5MPa的儲存彈性模數」,係意味著在該範圍內的任一溫度,儲存彈性模數均為上述範圍內之值。因為儲存彈性模數通常會隨著溫度上升而漸減,所以只要在23℃及80℃之儲存彈性模數均在上述範圍內,就能夠設想在該範圍的溫度能夠顯示上述範圍內的儲存彈性模數。黏著劑層的儲存彈性模數,係能夠使用市售的黏彈性測定裝置,例如REOMETRIC公司製的黏彈性測定裝置「DYNAMIC ANALYZER RDA II」而測定。 The adhesive layer is preferably one that exhibits a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80°C. Thereby, the durability of the optical film with the adhesive layer can be more effectively improved. The so-called "showing a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80°C" means that at any temperature within this range, the storage elastic modulus is a value within the above range. Because the storage elastic modulus usually decreases as the temperature rises, as long as the storage elastic modulus at 23°C and 80°C is within the above range, it can be assumed that the temperature in this range can display the storage elastic modulus in the above range. number. The storage elastic modulus of the adhesive layer can be measured using a commercially available viscoelasticity measuring device, for example, a viscoelasticity measuring device "DYNAMIC ANALYZER RDA II" manufactured by REOMETRIC.
能夠使用凝膠分率作為交聯密度的一項指標。因為由本發明的黏著劑組成物所形成之黏著劑層,係具有預定的交聯密度,所以會顯示預定的凝膠分率。亦即,該黏著劑層的凝膠分率,係例如可為50至95重量%(例如 55至93重量%),較佳為60至90重量%(例如65至90重量%),更佳為70至85重量%(例如80至85重量%)。凝膠分率為下限值以上時,對黏著劑層的耐發泡性(耐凝聚破壞性)和再加工性為有利,凝膠分率為上限值以下時,對耐剝落性為有利。又,凝膠分率係能夠藉由在實施例之項所記載的方法來測定。 The gel fraction can be used as an index of crosslink density. Because the adhesive layer formed from the adhesive composition of the present invention has a predetermined crosslinking density, it will show a predetermined gel fraction. That is, the gel fraction of the adhesive layer can be, for example, 50 to 95% by weight (e.g. 55 to 93% by weight), preferably 60 to 90% by weight (for example, 65 to 90% by weight), more preferably 70 to 85% by weight (for example, 80 to 85% by weight). When the gel fraction is higher than the lower limit, it is advantageous for the foaming resistance (resistance to agglomeration destruction) and reworkability of the adhesive layer, and when the gel fraction is lower than the upper limit, it is advantageous for the peeling resistance. . In addition, the gel fraction can be measured by the method described in the section of Examples.
由本發明的黏著劑組成物所形成的黏著劑層係具有預定的黏著力。亦即,將前述黏著劑層貼合在玻璃基板,在溫度23℃、相對濕度50%的條件下24小時後之前述黏著劑層的黏著力,係在剝離速度300mm/分鐘的情況下例如可為0.5至25N(例如,0.5至20N),較佳為0.5至10N(例如1至10N),更佳為1至8N。黏著力為下限值以上時,黏著性(或接著性)會提升且對耐剝落性等為有利,黏著力為上限值以下時,對再加工性為有利。又,黏著力係能夠藉由在實施例之項所記載的方法來測定。 The adhesive layer formed by the adhesive composition of the present invention has a predetermined adhesive force. That is, the adhesive layer is attached to a glass substrate, and the adhesive force of the adhesive layer after 24 hours under the conditions of a temperature of 23°C and a relative humidity of 50% is set at a peeling speed of 300 mm/min. It is 0.5 to 25N (for example, 0.5 to 20N), preferably 0.5 to 10N (for example, 1 to 10N), and more preferably 1 to 8N. When the adhesive force is higher than the lower limit value, the adhesiveness (or adhesiveness) is improved and is advantageous for peeling resistance, etc., and when the adhesive force is lower than the upper limit value, it is advantageous for reworkability. In addition, the adhesive force can be measured by the method described in the section of Examples.
構成附黏著劑層的光學薄膜1之光學薄膜10,可為能夠組裝於液晶顯示裝置等的影像顯示裝置之各種光學薄膜(具有光學特性之薄膜)。該光學薄膜10可為單層結構(例如偏光片、相位差膜、亮度提升膜、防眩膜、抗反射膜、擴散膜、聚光膜等的光學功能性薄膜等),亦可為多層結構(例如偏光板、相位差板等)。光學薄膜10係以偏光板、偏光片、相位差板或相位差膜為佳,以偏光板或偏光片為特
佳。又,在本說明書中,所謂光學薄膜係意味著用以達成影像顯示(顯示畫面等)的功能之薄膜(例如達成提升影像的清晰度的功能之薄膜)。又,在本說明書中,所謂偏光板係意味著將樹脂薄膜或樹脂層層積在偏光片的至少一面而成者,所謂相位差板係意味著將樹脂薄膜或樹脂層層積在相位差膜的至少一面而成者。
The
第2圖及第3圖係顯示偏光板的層結構的例子之概略剖面圖。第2圖顯示之偏光板10a,係將第1樹脂薄膜3層積(或層積貼合)在偏光片2的一面而成之單面保護偏光板,而第3圖顯示之偏光板10b,係進一步將第2樹脂薄膜4層積(或層積貼合)在偏光片2的另一面而成之兩面保護偏光板。第1、第2樹脂薄膜3、4係能夠透過未圖示的接著劑層或黏著劑層而貼合在偏光片2。又,偏光板10a、10b亦可包含第1、第2樹脂薄膜3、4以外之其它薄膜或層。
2 and 3 are schematic cross-sectional views showing examples of the layer structure of the polarizing plate. The
偏光片2係具有下述性質之薄膜:亦即吸收具有與其吸收軸平行的振動面之直線偏光,而使具有與吸收軸正交(與穿透軸平行)的振動面之直線偏光穿透;例如能夠使用使二色性色素吸附配向在聚乙烯醇系樹脂薄膜而成之薄膜。作為二色性色素,例如可舉出碘、二色性有機染料等。
The
聚乙烯醇系樹脂係能夠藉由將聚乙酸乙烯酯系樹脂皂化來得到。作為聚乙酸乙烯酯系樹脂,例如可 舉出屬於乙酸乙烯酯的同元聚合物之聚乙酸乙烯酯、能夠與乙酸乙烯酯共聚合之單體(例如不飽和羧酸、烯烴、乙烯醚、不飽和磺酸、具有銨基之(甲基)丙烯醯胺等)和乙酸乙烯酯之共聚物等。 The polyvinyl alcohol-based resin system can be obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate resin, for example, Examples include polyvinyl acetate, which is a homopolymer of vinyl acetate, and monomers that can be copolymerized with vinyl acetate (e.g., unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (formaldehyde) Base) acrylamide, etc.) and vinyl acetate copolymer, etc.
聚乙烯醇系樹脂的皂化度通常為85至100莫耳%,較佳為98莫耳%以上。聚乙烯醇系樹脂可經改性,例如可為經醛類改性而成之聚乙烯甲醛或聚乙烯縮醛等。聚乙烯醇系樹脂的平均聚合度通常為1000至10000,較佳為1500至5000。又,聚乙烯醇系樹脂的平均聚合度係能夠依據JIS K 6726而求取。 The degree of saponification of the polyvinyl alcohol-based resin is generally 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, for example, polyvinyl formaldehyde or polyvinyl acetal modified by aldehydes. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 to 10,000, preferably 1,500 to 5,000. In addition, the average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726.
通常係將由聚乙烯醇系樹脂製膜而成者使用作為偏光片2的胚膜。聚乙烯醇系樹脂係能夠藉由眾所周知的方法製膜。胚膜的厚度通常為1至150μm,考慮延伸容易性等時,較佳為10μm以上。
Usually, a film made of a polyvinyl alcohol-based resin is used as the embryonic film of the
偏光片2係例如對胚膜施行進行單軸延伸之步驟、使用二色性色素將薄膜染色而使其吸附該二色性色素之步驟、使用硼酸水溶液處理薄膜之步驟、及將薄膜進行水洗之步驟,最後進行乾燥而製造。偏光片2的厚度通常為1至30μm,從附黏著劑層的光學薄膜1的薄膜化之觀點而言,較佳為20μm以下;更佳為15μm以下,特別是10μm以下。
The
使二色性色素吸附配向在聚乙烯醇系樹脂薄膜而成之偏光片2係能夠藉由下列方法來得到:1)使用聚乙烯醇系樹脂薄膜的單獨薄膜作為胚膜,對該薄膜施行
單軸延伸處理及二色性色素的染色處理之方法;以及2)將含有聚乙烯醇系樹脂的塗佈液(水溶液等)塗佈在基材薄膜且使其乾燥而得到具有聚乙烯醇系樹脂層之基材薄膜後,將其連同基材薄膜一起進行單軸延伸,對延伸後的聚乙烯醇系樹脂層施行二色性色素的染色處理,其次將基材薄膜剝離去除之方法。作為基材薄膜,係能夠使用由與後述能夠構成第1、第2樹脂薄膜3、4之熱可塑性樹脂同樣的熱可塑性樹脂所構成之薄膜,較佳是由聚對苯二甲酸乙二酯等的聚酯系樹脂、聚碳酸酯系樹脂、三乙酸纖維素等的纖維素系樹脂、降莰烯系樹脂等的環狀聚烯烴系樹脂、聚苯乙烯系樹脂等所構成之薄膜。利用上述2)的方法時,製造薄膜的偏光片2會變為容易,例如製造厚度7μm以下的偏光片2亦變為容易。
The
第1、第2樹脂薄膜3、4可以是各自獨立為具有透光性的熱可塑性樹脂,較佳為光學上透明的熱可塑性樹脂,例如鏈狀聚烯烴系樹脂(聚乙烯系樹脂、聚丙烯系樹脂等)、環狀聚烯烴系樹脂(降莰烯系樹脂等)等的聚烯烴系樹脂;纖維素系樹脂(纖維素酯系樹脂等);聚酯系樹脂(聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯等);聚碳酸酯系樹脂(例如2,2-雙(4-羥苯基)丙烷等由雙酚衍生之聚碳酸酯等);(甲基)丙烯酸系樹脂;聚苯乙烯系樹脂;聚醚醚酮系樹脂;聚碸系樹脂、或該等混合物、共聚物等所構成之薄膜。該等之中,第1、第2樹脂薄膜3、4係以各自可以是由環狀聚烯烴系樹脂、聚碳酸酯
系樹脂、纖維素系樹脂、聚酯系樹脂、及(甲基)丙烯酸系樹脂等所構成之薄膜為佳,以由纖維素系樹脂及環狀聚烯烴系樹脂等所構成之薄膜為特佳。
The first and
作為鏈狀聚烯烴系樹脂,例如可舉出聚乙烯樹脂、聚丙烯樹脂等的鏈狀烯烴的同元聚合物、由2種以上的鏈狀烯烴所構成之共聚物等。 Examples of chain polyolefin resins include homopolymers of chain olefins such as polyethylene resins and polypropylene resins, copolymers composed of two or more chain olefins, and the like.
環狀聚烯烴系樹脂係含有以降莰烯、四環十二烯(別名:二甲橋八氫萘)或該等的衍生物為代表例之環狀烯烴作為聚合單元之樹脂的總稱。作為環狀聚烯烴系樹脂,可舉出環狀烯烴的開環(共)聚合物及其氫化物、環狀烯烴的加成聚合物、環狀烯烴與乙烯、丙烯等鏈狀烯烴或具有乙烯基之芳香族化合物的共聚物、以及該等經不飽和羧酸或其衍生物改性而成之改性(共)聚合物等。該等之中,係以使用降莰烯、多環降莰烯系單體等的降莰烯系單體作為環狀烯烴之降莰烯系樹脂為佳。 Cyclic polyolefin-based resins are a general term for resins containing cyclic olefins as representative examples of norbornene, tetracyclododecene (alias: dimethyl octahydronaphthalene) or derivatives thereof as polymerized units. Examples of cyclic polyolefin resins include ring-opening (co)polymers of cyclic olefins and their hydrogenated products, addition polymers of cyclic olefins, cyclic olefins and chain olefins such as ethylene and propylene, or those having ethylene Copolymers of aromatic compounds based on the base, and these modified (co)polymers modified by unsaturated carboxylic acids or their derivatives. Among these, a norbornene-based resin using a norbornene-based monomer such as a norbornene and a polycyclic norbornene-based monomer as a cyclic olefin is preferred.
纖維素系樹脂較佳為纖維素酯系樹脂,亦即纖維素的部分或完全酯化物等,例如可舉出纖維素的乙酸酯、丙酸酯、丁酸酯、該等的混合酯等。該等之中,以三乙酸纖維素、二乙酸纖維素、乙酸丙酸纖維素、乙酸丁酸纖維素等為佳。 The cellulose resin is preferably a cellulose ester resin, that is, a partial or complete esterification of cellulose. Examples include acetate, propionate, butyrate, and mixed esters of cellulose. . Among them, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, etc. are preferred.
聚酯系樹脂係具有酯鍵之上述纖維素酯系樹脂以外的樹脂,通常係由多元羧酸或其衍生物與多元醇的聚縮合物所構成者。作為聚酯系樹脂,例如可舉出聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二 酯、聚萘二甲酸丁二酯、聚對苯二甲酸丙二酯、聚萘二甲酸丙二酯、聚對苯二甲酸環己烷二甲酯、聚萘二甲酸環己烷二甲酯等。 The polyester resin is a resin other than the above-mentioned cellulose ester resin having an ester bond, and is usually composed of a polycondensate of a polycarboxylic acid or a derivative thereof and a polyhydric alcohol. Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Esters, polybutylene naphthalate, polytrimethylene terephthalate, polypropylene naphthalate, polycyclohexane dimethyl terephthalate, polycyclohexane dimethyl naphthalate, etc. .
聚碳酸酯系樹脂係由碳酸及二醇或雙酚所形成之聚酯。該等之中,從耐熱性、耐候性及耐酸性的觀點而言,以在分子鏈具有二苯基烷烴之芳香族聚碳酸酯為佳。作為聚碳酸酯,例如可舉出由2,2-雙(4-羥苯基)丙烷(別名雙酚A)、2,2-雙(4-羥苯基)丁烷、1,1-雙(4-羥苯基)環己烷、1,1-雙(4-羥苯基)異丁烷、1,1-雙(4-羥苯基)乙烷等的雙酚所衍生之聚碳酸酯等。 The polycarbonate resin is a polyester formed from carbonic acid and glycol or bisphenol. Among these, from the viewpoints of heat resistance, weather resistance, and acid resistance, aromatic polycarbonates having diphenylalkanes in the molecular chain are preferred. Examples of polycarbonates include 2,2-bis(4-hydroxyphenyl)propane (alias bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis Polycarbonate derived from bisphenols such as (4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutane, 1,1-bis(4-hydroxyphenyl)ethane, etc. Ester etc.
能夠構成第1、第2樹脂薄膜3、4之(甲基)丙烯酸系樹脂,係能夠是將源自甲基丙烯酸酯之結構單元作為主體(例如含有其50重量%以上)之聚合物,而且以其與其它共聚合成分共聚合而成之共聚物為佳。
The (meth)acrylic resin that can constitute the first and
(甲基)丙烯酸系樹脂亦可含有2種以上之源自甲基丙烯酸酯的結構單元。作為甲基丙烯酸酯,可舉出甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯等甲基丙烯酸的C1至C4烷酯。 The (meth)acrylic resin may contain two or more types of structural units derived from methacrylate. Examples of methacrylates include C 1 to C 4 alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
作為能夠與甲基丙烯酸酯共聚合之共聚合成分,可舉出丙烯酸酯。丙烯酸酯較佳為丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等丙烯酸的C1至C8烷酯。作為其它共聚合成分的具體例,可舉出(甲基)丙烯酸等的不飽和酸類;苯乙烯、鹵化苯乙烯、α-甲基苯乙烯、乙烯基甲苯等的芳香族乙烯基化合物;(甲基)丙烯 腈等的乙烯基氰化合物;順丁烯二酸酐、檸康酸酐等的不飽和酸酐;苯基順丁烯二醯亞胺、環己基順丁烯二醯亞胺等的不飽和醯亞胺等在分子內具有1個聚合性碳-碳雙鍵之丙烯酸酯以外的化合物。亦可將在分子內具有2個以上的聚合性碳-碳雙鍵之化合物作為共聚合成分使用。共聚合成分係能夠單獨或組合二種以上而使用。 As a copolymerization component which can be copolymerized with methacrylate, an acrylate can be mentioned. The acrylate is preferably a C 1 to C 8 alkyl ester of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Specific examples of other copolymerization components include unsaturated acids such as (meth)acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene, and vinyl toluene; Base) vinyl cyanide compounds such as acrylonitrile; unsaturated acid anhydrides such as maleic anhydride and citraconic acid anhydride; unsaturated acid anhydrides such as phenyl maleimide and cyclohexyl maleimide Compounds other than acrylate having one polymerizable carbon-carbon double bond in the molecule, such as imine. A compound having two or more polymerizable carbon-carbon double bonds in the molecule can also be used as a copolymerization component. The copolymerization component system can be used individually or in combination of 2 or more types.
就能夠提高薄膜的耐久性而言,(甲基)丙烯酸樹脂可在高分子主鏈具有環結構。環結構係以環狀酸酐結構、環狀醯亞胺結構、內酯環結構等的雜環結構為佳。作為環狀酸酐結構的具體例,可舉出戊二酸酐結構、琥珀酸酐結構等,作為環狀醯亞胺結構的具體例,可舉出戊二醯亞胺(Glutarimide)結構、琥珀醯亞胺結構等,作為內酯環結構的具體例,可舉出丁內酯環結構、戊內酯環結構等。 In terms of improving the durability of the film, the (meth)acrylic resin may have a ring structure in the polymer main chain. The ring structure is preferably a heterocyclic structure such as a cyclic anhydride structure, a cyclic imine structure, and a lactone ring structure. Specific examples of the cyclic acid anhydride structure include a glutaric anhydride structure, a succinic anhydride structure, etc., and specific examples of a cyclic anhydride structure include a glutarimide structure and a succinic anhydride structure. The structure, etc., as specific examples of the lactone ring structure, a butyrolactone ring structure, a valerolactone ring structure, and the like can be given.
從對薄膜的製膜性、薄膜的耐衝撃性等的觀點而言,(甲基)丙烯酸系樹脂可含有丙烯酸系橡膠粒子。所謂丙烯酸系橡膠粒子,係將以丙烯酸酯為主體之彈性聚合物作為必要成分之粒子,可舉出實質上只有由該彈性聚合物所構成之單層結構者、或將彈性聚合物設作1層之多層結構者。作為彈性聚合物的例子,可舉出以丙烯酸烷酯作為主成分,使其與能夠共聚合的其它乙烯基單體及交聯性單體共聚合而成之交聯彈性共聚物。作為當作彈性聚合物的主成分之丙烯酸烷酯,例如,可舉出丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等丙烯酸的C1至C8烷酯。烷基的碳數係較佳為4以上。 The (meth)acrylic resin may contain acrylic rubber particles from the viewpoint of film-forming properties of the film, impact resistance of the film, and the like. The so-called acrylic rubber particles are particles that have an elastic polymer mainly composed of acrylate as an essential component. Examples include those having substantially only a single-layer structure composed of the elastic polymer, or the elastic polymer as 1 Layers of multi-layer structure. As an example of the elastic polymer, a crosslinked elastic copolymer obtained by copolymerizing an alkyl acrylate as a main component with another vinyl monomer and a crosslinkable monomer that can be copolymerized can be mentioned. As the alkyl acrylate which is the main component of the elastic polymer, for example, a C 1 to C 8 alkyl acrylate of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate can be cited. The carbon number of the alkyl group is preferably 4 or more.
作為能夠與丙烯酸烷酯共聚合的其它乙烯基單體,能夠舉出在分子內具有1個聚合性碳-碳雙鍵之化合物,更具體地,可舉出如甲基丙烯酸甲酯之甲基丙烯酸酯、如苯乙烯之芳香族乙烯化合物、如(甲基)丙烯腈之乙烯基氰化合物等。作為交聯性單體,能夠舉出在分子內具有至少2個聚合性碳-碳雙鍵之交聯性化合物,更具體地,可舉出乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯等多元醇的(甲基)丙烯酸酯、(甲基)丙烯酸烯丙酯等(甲基)丙烯酸的烯酯、及二乙烯基苯等。 Examples of other vinyl monomers that can be copolymerized with alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methyl methacrylate such as methyl methacrylate. Acrylates, aromatic vinyl compounds such as styrene, vinyl cyanide compounds such as (meth)acrylonitrile, etc. As the crosslinkable monomer, a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule can be cited, and more specifically, ethylene glycol di(meth)acrylate, butane diacrylate can be cited. (Meth)acrylates of polyhydric alcohols such as alcohol di(meth)acrylate, alkenyl esters of (meth)acrylic acid such as allyl (meth)acrylate, divinylbenzene, and the like.
相對於(甲基)丙烯酸系樹脂100重量份,丙烯酸系橡膠粒子的含量係以5重量份以上為佳,更佳為10重量份以上。丙烯酸系橡膠粒子的含量太多時,薄膜的表面硬度會降低,而且在對薄膜施行表面處理時,對表面處理劑中的有機溶劑之耐溶劑性降低。因而,相對於(甲基)丙烯酸系樹脂100重量份,丙烯酸系橡膠粒子的含量通常為80重量份以下,較佳為60重量份以下。 The content of the acrylic rubber particles is preferably 5 parts by weight or more, and more preferably 10 parts by weight or more with respect to 100 parts by weight of the (meth)acrylic resin. When the content of acrylic rubber particles is too large, the surface hardness of the film will decrease, and when the film is surface treated, the solvent resistance to the organic solvent in the surface treatment agent will decrease. Therefore, the content of the acrylic rubber particles is usually 80 parts by weight or less, preferably 60 parts by weight or less with respect to 100 parts by weight of the (meth)acrylic resin.
第1、第2樹脂薄膜3、4係能夠含有在本發明的技術領域之通常的添加劑。作為添加劑,例如可舉出紫外線吸收劑、紅外線吸收劑、有機系染料、顏料、無機系色素、抗氧化劑、抗靜電劑、界面活性劑、潤滑劑、分散劑、熱安定劑等。作為紫外線吸收劑,可舉出柳酸酯化合物、二苯基酮化合物、苯并***化合物、三化合物、氰基(甲基)丙烯酸酯化合物、鎳錯鹽等。
The first and
第1、第2樹脂薄膜3、4各自可為未延伸
的薄膜、或經單軸或是雙軸延伸的薄膜之任一種。第1樹脂薄膜3及/或第2樹脂薄膜4可為擔任保護偏光片2之保護膜,亦可為如後述的相位差膜的兼具光學功能之保護膜。又,第1樹脂薄膜3及第2樹脂薄膜4可為相同或不同的薄膜。
Each of the first and
又,第1樹脂薄膜3及/或第2樹脂薄膜4亦可在其外表面(與偏光片2為相反側的表面)具備硬塗層、防眩層、抗反射層、光擴散層、抗靜電層、防污層、導電層等的表面處理層(塗佈層)。該第1樹脂薄膜3及第2樹脂薄膜4的厚度各自通常為1至150μm,較佳為5至100μm(例如5至60μm),更佳為50μm以下(例如1至40μm),又更佳為30μm以下(例如5至25μm)。
In addition, the
特別是在如智慧型手機、平板型終端設備之中小型取向的偏光板時,從薄膜化的要求而言,多半是使用厚度30μm以下之較薄者作為第1樹脂薄膜3及/或第2樹脂薄膜4,但此種偏光板對抑制偏光片2的收縮力之力量較弱且耐久性容易變為不充分。將此種偏光板作為光學薄膜10使用時,本發明之附黏著劑層的光學薄膜1亦具有良好的耐久性。
Especially in the case of small-sized oriented polarizers in smart phones and tablet-type terminal devices, in terms of thin film requirements, most of them use thinner ones with a thickness of 30μm or less as the
第1、第2樹脂薄膜3、4係能夠透過接著劑層或黏著劑層而貼合在偏光片2。作為形成接著劑層之接著劑,能夠使用水系接著劑或活性能量線硬化性接著劑。
The first and
作為水系接著劑,可舉出慣用的水系接著劑(例如,由聚乙烯醇系樹脂水溶液所構成之接著劑、水系
二液型胺甲酸酯系乳液接著劑、醛化合物、環氧化合物、三聚氰胺系化合物、羥甲基化合物、異氰酸酯化合物、胺化合物、多價金屬鹽等的交聯劑等)。該等之中,能夠適當使用由聚乙烯醇系樹脂水溶液所構成之水系接著劑。又,使用水系接著劑時,係以將偏光片2與第1、第2樹脂薄膜3、4貼合後,實施用以將在水系接著劑中所含有的水除去之乾燥步驟為佳。乾燥步驟後,亦可設置在例如20至45℃左右的溫度熟化之熟化步驟。
As the water-based adhesive, a commonly used water-based adhesive (for example, an adhesive composed of a polyvinyl alcohol-based resin aqueous solution, water-based
Two-component urethane-based emulsion adhesives, aldehyde compounds, epoxy compounds, melamine-based compounds, methylol compounds, isocyanate compounds, amine compounds, crosslinking agents such as polyvalent metal salts, etc.). Among these, an aqueous adhesive composed of a polyvinyl alcohol-based resin aqueous solution can be suitably used. Moreover, when using a water-based adhesive, it is preferable to perform a drying step to remove water contained in the water-based adhesive after bonding the
上述所謂活性能量線硬化性接著劑係指藉由照射紫外線、電子束等的活性能量線而硬化之接著劑,例如可舉出含有聚合性化合物及光聚合起始劑之硬化性組成物、含有光反應性樹脂之硬化性組成物、含有黏結劑樹脂及光反應***聯劑之硬化性組成物等,較佳為紫外線硬化性接著劑。 The above-mentioned active energy ray curable adhesive means an adhesive that is cured by irradiating active energy rays such as ultraviolet rays, electron beams, etc., for example, a curable composition containing a polymerizable compound and a photopolymerization initiator, and The curable composition of a photoreactive resin, a curable composition containing a binder resin and a photoreactive crosslinking agent, etc., are preferably an ultraviolet curable adhesive.
使用活性能量線硬化性接著劑時,係進行下述硬化步驟:將偏光片2與第1、第2樹脂薄膜3、4貼合後,視需要進行乾燥步驟,其次照射活性能量線,藉此使活性能量線硬化性接著劑硬化。活性能量線的光源係沒有特別限定,以在波長400nm以下具有發光分布之紫外線為佳。
When an active energy ray curable adhesive is used, the following curing step is performed: after the
作為將偏光片2與第1、第2樹脂薄膜3、4貼合之方法,可舉出對該等之至少任一者之一貼合面施行皂化處理、電暈處理、電漿處理等的表面活性化處理之方法等。將樹脂薄膜貼合在偏光片2的兩面時,用以貼合該等樹脂薄膜之接著劑可為同種的接著劑,亦可為異種的接
著劑。
As a method of bonding the
偏光板10a、10b係能夠進一步含有其它薄膜或層。其具體例為後述之相位差膜、以及亮度提升薄膜、防眩薄膜、抗反射膜、擴散膜、聚光薄膜、黏著劑層20以外的黏著劑層、塗佈層、保護膜等。保護膜係用以保護偏光板等光學薄膜10的表面以避免刮傷及弄髒之目的而使用,而且在將附黏著劑層的光學薄膜1貼合在例如金屬層或基板上之後,通常會被剝離去除。
The
保護膜通常由:基材薄膜、及層積在其上之黏著劑層所構成。基材薄膜係能夠由熱可塑性樹脂、例如聚乙烯系樹脂、聚丙烯系樹脂等的聚烯烴系樹脂;聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等的聚酯系樹脂;聚碳酸酯系樹脂;(甲基)丙烯酸系樹脂等所構成。 The protective film is usually composed of a base film and an adhesive layer laminated on it. The base film can be made of thermoplastic resins, such as polyolefin resins such as polyethylene resins and polypropylene resins; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; Polycarbonate resin; (meth)acrylic resin, etc.
在相位差板所含有的相位差膜係如上述,為顯示光學異向性之光學薄膜,其可以是藉由將樹脂薄膜延伸至1.01至6倍左右而得到之延伸膜,該樹脂薄膜係由:在上述例示作為可使用在第1、第2樹脂薄膜3、4之熱可塑性樹脂、以及例如聚乙烯醇系樹脂、聚芳酯系樹脂、聚醯亞胺系樹脂、聚醚碸系樹脂、聚偏二氟乙烯(polvvinvlidene fluoride)/聚甲基丙烯酸甲酯系樹脂、液晶聚酯系樹脂、乙烯-乙酸乙烯酯共聚物皂化物、聚氯乙烯系樹脂等所構成者。該等之中,以將聚碳酸酯系樹脂薄膜或環狀烯烴系樹脂薄膜、(甲
基)丙烯酸系樹脂薄膜或纖維素系樹脂薄膜進行單軸延伸或雙軸延伸而成之延伸膜為佳。又,在本說明書中,亦將零遲滯值薄膜包含在相位差膜內(但是,亦能夠使用作為保護膜)。此外,被稱為單軸性相位差膜、廣視角相位差膜、低光彈性模數相位差膜等之薄膜,亦能夠應用作為相位差膜。
The retardation film contained in the retardation plate is an optical film exhibiting optical anisotropy as described above. It can be a stretched film obtained by stretching a resin film to about 1.01 to 6 times. The resin film is composed of : In the above examples, the thermoplastic resins that can be used in the first and
所謂零遲滯值薄膜係指面內相位差值Re及厚度方向相位差值Rth同時為-15至15nm之薄膜。該相位差膜係能夠適合使用在IPS模式的液晶顯示裝置。面內相位差值Re及厚度方向相位差值Rth係以同時為-10至10nm為佳,更佳是同時為-5至5nm。在此所稱的面內相位差值Re及厚度方向相位差值Rth係在波長590nm之值。 Called zero retardation value of the retardation value means the surface of the film R e and the thickness direction retardation R th value while a film of 15nm to -15. This retardation film system can be suitably used in an IPS mode liquid crystal display device. R e in-plane retardation value and the thickness direction retardation value R th lines simultaneously preferably -10 to 10nm, more preferably -5 to simultaneously 5nm. Referred to in this plane retardation value R e and the thickness direction retardation R th value of the 590nm wavelength system.
面內相位差值Re及厚度方向相位差值Rth係各自由下述式定義:Re=(nx-ny)×d R e in-plane retardation value and the thickness direction retardation value R th line are each defined by the following formula: R e = (n x -n y) × d
Rth=[(nx+ny)/2-nz]×d R th =[(n x +n y )/2-n z ]×d
式中,nx為薄膜面內的慢軸方向(x軸方向)之折射率,ny為薄膜面內的快軸方向(在面內與x軸正交之y軸方向)的折射率,nz為薄膜厚度方向(與薄膜面垂直的z軸方向)的折射率,d為薄膜厚度。 In the formula, n x is the refractive index in the slow axis direction (x-axis direction) in the film plane, and n y is the refractive index in the fast axis direction in the film plane (y-axis direction orthogonal to the x-axis in the plane), n z is the refractive index in the film thickness direction (the z-axis direction perpendicular to the film surface), and d is the film thickness.
零遲滯值薄膜中係能夠使用例如由纖維素系樹脂、鏈狀聚烯烴系樹脂及環狀聚烯烴系樹脂等的聚烯烴系樹脂、聚對苯二甲酸乙二酯系樹脂或(甲基)丙烯酸系樹脂所構成之樹脂薄膜。特別是因為相位差值容易控制且容易取得,故能夠適合使用纖維素系樹脂、聚烯烴系樹脂 或(甲基)丙烯酸系樹脂。 In the zero retardation film, for example, polyolefin resins such as cellulose resins, chain polyolefin resins, and cyclic polyolefin resins, polyethylene terephthalate resins, or (methyl) can be used. Resin film made of acrylic resin. In particular, because the retardation value is easy to control and easy to obtain, it can be suitable to use cellulose resins and polyolefin resins Or (meth)acrylic resin.
又,會因液晶性化合物的塗佈/配向而使光學異向性顯現之薄膜、及會因無機層狀化合物的塗佈而使光學異向性顯現之薄膜,均能夠使用作為相位差膜。此種相位差膜,係有:被稱為溫度補償型相位差膜者,又,JX日礦日石ENERGY(股)以「NH FILM」的商品名銷售之傾斜配向有棒狀液晶之薄膜、富士FILM(股)以「WV FILM」的商品名銷售之傾斜配向有圓盤狀液晶之薄膜、住友化學(股)以「VAC FILM」的商品名銷售之完全雙軸配向型的薄膜、及相同地由住友化學(股)以「new VAC FILM」的商品名銷售之雙軸配向型的薄膜等。又,層積在相位差膜的至少一面之樹脂薄膜,能夠是例如上述的保護膜。 In addition, a film that exhibits optical anisotropy due to coating/alignment of a liquid crystal compound and a film that exhibits optical anisotropy due to coating of an inorganic layered compound can be used as a retardation film. This kind of retardation film includes: what is called temperature compensation retardation film, and also, JX Nippon Mine Nippon Oil Energy Co., Ltd. sells a film with a rod-shaped liquid crystal in an oblique orientation, sold under the trade name of "NH FILM", Fuji Film Co., Ltd. sells a film with obliquely aligned disc-shaped liquid crystals under the brand name "WV FILM", and a fully biaxially oriented film sold under the brand name "VAC FILM" by Sumitomo Chemical Co., Ltd., and the same It is a biaxially oriented film sold by Sumitomo Chemical Co., Ltd. under the brand name "new VAC FILM". In addition, the resin film laminated on at least one surface of the retardation film can be, for example, the above-mentioned protective film.
第4圖至第8圖係顯示包含附有由本發明之黏著劑組成物所形成之黏著劑層的光學薄膜之光學積層體的一例之概略剖面圖。 FIGS. 4 to 8 are schematic cross-sectional views showing an example of an optical laminate including an optical film with an adhesive layer formed of the adhesive composition of the present invention.
第4圖顯示之光學積層體5,係將已層積在基板40上之金屬層30(或金屬線路層30)層積在前述附黏著劑層的光學薄膜1a(或附黏著劑層的偏光板1a)的黏著劑層側之面而成之光學積層體。前述附黏著劑層的光學薄膜1a係將黏著劑層20層積在前述偏光板10a的偏光片2側之面而成者。
The optical laminate 5 shown in Fig. 4 is a layer of the metal layer 30 (or metal circuit layer 30) laminated on the
第5圖顯示之光學積層體6,係將已層積在基板40上之金屬層30層積在附黏著劑層的光學薄膜1b(或
附黏著劑層的偏光板1b)的黏著劑層側之面而成之光學積層體。前述附黏著劑層的光學薄膜1b係將黏著劑層20層積在前述偏光板10b的第2樹脂薄膜4側之面而成之光學薄膜。
The
光學積層體5、6,係能夠藉由將附黏著劑層的光學薄膜(1a、1b)透過黏著劑層20而貼合金屬層30來得到,其中該金屬層30係層積在基板40上。
The
作為將金屬層30形成在基板40上之方法,例如可舉出濺鍍法等。基板40可為構成觸控輸入元件中所包含的液晶胞之透明基板,較佳為玻璃基板。作為該玻璃基板的材料,能夠使用鹼石灰玻璃、低鹼玻璃、無鹼玻璃等。金屬層30可形成在基板40的全面,亦可形成在其中一部分。
As a method of forming the
金屬層30係例如可為含有至少1種選自由鋁、銅、銀、鐵、錫、鋅、鎳、鉬、鉻、鎢、鉛及含有該等2種以上金屬的合金之金屬元素之層。該等之中,從導電性的觀點而言,較佳是可為含有選自鋁、銅、銀及金之至少1種金屬元素之層,從導電性及成本的觀點而言,較佳是可為含有鋁元素之層,更佳是可為含有以鋁元素作為主成分(占構成金屬層30之總金屬成分的50重量%以上)之層。
The
金屬層30係例如可為ITO(錫摻雜氧化銦)等的透明電極層,亦可同時具有金屬層30及由ITO等的金屬氧化物所構成之透明電極層。又,亦可使用在基板上配置細線的金屬線路層而成之金屬網狀物、或在黏結劑中
添加金屬奈米粒子、金屬奈米線材而成之層。
The
金屬層30的調製方法係沒有特別限定,可為金屬箔,亦可為藉由真空蒸鍍法、濺鍍法、離子噴鍍法、噴墨印刷法、凹版印刷法所形成者,以藉由濺鍍法、噴墨印刷法、凹版印刷法所形成的金屬層為佳,更佳是藉由濺鍍所形成的金屬層。金屬層30的厚度係沒有特別限定,通常為3μm以下,以1μm以下為佳,更佳為0.8μm以下,且通常為0.01μm以上。而且,金屬層30為金屬線路層(例如金屬網狀物)時,該金屬線路的線寬通常為10μm以下,以5μm以下為佳,更佳為3μm以下,且通常為0.5μm以上。
The preparation method of the
第6圖顯示之光學積層體7,係將前述附黏著劑層的光學薄膜1之黏著劑層20層積在基板40上而成之光學積層體。
The
第7圖顯示之光學積層體8,係將進一步層積在已層積在基板40上之金屬層30的表面上(與基板40為相反側的表面上)之樹脂層50,層積在前述附黏著劑層的光學薄膜1之黏著劑層20側的面而成之光學積層體。作為形成樹脂層50之樹脂,例如可舉出前述例示之構成第1或第2樹脂薄膜之樹脂等。
The optical laminate 8 shown in Fig. 7 is a
第8圖顯示之光學積層體9,係除了將複數之金屬層30以預定間隔往縱橫方向層積在基板40上,而且在該複數之金屬層30之間(或間隙)且該金屬層30的表面上(與基板40為相反側的表面上)形成(或層積)樹脂層50以外,其餘與光學積層體7同樣。該光學積層體8的形態(將
金屬層30圖案化成為預定形狀後之形態)時,金屬層30係例如亦可為觸控輸入式液晶顯示裝置所具有之觸控輸入元件的金屬線路層(亦即電極層)。
The optical laminate 9 shown in FIG. 8 is in addition to laminating a plurality of
在光學積層體8中,複數之金屬層30可全體或部分地接觸黏著劑層20,亦可不接觸。又,金屬層30亦可為含有上述金屬或合金之連續膜。又,亦可將樹脂層50省略。
In the optical layered body 8, the plurality of
將附黏著劑層的光學薄膜(1、1a、1b)、與基板40(玻璃基板、透明基板等)或金屬層30(透明電極層)貼合而製造光學積層體後,若產生某種不良情況時,有時必須將附黏著劑層的光學薄膜從基板40或金屬層30剝離,將其它的附黏著劑層的光學薄膜1重新貼合在基板40或金屬層30,亦即所謂的再加工作業。附有由本發明之黏著劑組成物所形成之黏著劑層的光學薄膜1,係在剝離後之玻璃基板或透明電極表面不易產生起雲、殘膠等,具有優異的再加工性。
After bonding the optical film (1, 1a, 1b) with the adhesive layer to the substrate 40 (glass substrate, transparent substrate, etc.) or the metal layer 30 (transparent electrode layer) to produce an optical laminate, if some kind of defect occurs In this case, it is sometimes necessary to peel off the optical film with the adhesive layer from the
本發明之液晶顯示裝置,係包含上述附有由本發明之黏著劑組成物所形成之黏著劑層的光學薄膜1,更典型地,係包含上述光學積層體。
The liquid crystal display device of the present invention includes the above-mentioned
因此,本發明之液晶顯示裝置係具有優異的耐久性。 Therefore, the liquid crystal display device of the present invention has excellent durability.
本發明之液晶顯示裝置,可為具有觸控面板功能之觸控輸入式液晶顯示裝置。觸控輸入式液晶顯示
裝置,係具備包含液晶胞之觸控輸入元件、及背光板。觸控面板的構成可為眾所周知的型式(例如外掛式(out-cell式)、內嵌式(on-cell式、in-cell式)等),又,觸控面板的動作方式,可為眾所周知的方式[例如電阻膜方式、靜電容量方式(表面型靜電容量方式、投影型靜電容量方式)等]。本發明之附黏著劑層的光學薄膜1可配置在觸控輸入元件(液晶胞)的辨識側,亦可配置在背光板側,亦可配置在雙方側。液晶胞的驅動方式可為TN方式、VA方式、IPS方式、多區域(Multi-Domain)方式、OCB方式等先前眾所周知的任何方式。又,在本發明之液晶顯示裝置,光學積層體所具有的基板40,可為上述液晶胞所包含之基板(典型上為玻璃基板)。
The liquid crystal display device of the present invention can be a touch input type liquid crystal display device with a touch panel function. Touch input LCD
The device is provided with a touch input element including a liquid crystal cell and a backlight panel. The structure of the touch panel can be a well-known type (for example, an out-cell type (out-cell type), an in-cell type (on-cell type, in-cell type), etc.), and the operation method of the touch panel can be a well-known type [For example, resistive film method, capacitance method (surface capacitance method, projection capacitance method), etc.]. The
以下,揭示實施例及比較例而更具體地說明本發明,但是本發明係不被該等例限定。以下只要未特別聲明,表示使用量、含量之份及%均為重量基準。 Hereinafter, examples and comparative examples are disclosed to explain the present invention more specifically, but the present invention is not limited by these examples. As long as there is no special statement below, the usage amount, content, and% are all based on weight.
在具備冷卻管、氮氣導入管、溫度計及攪拌機之反應容器,添加由表1顯示的組成(表1的數值為重量份)之單體混合與乙酸乙酯81.8份而得到的溶液。使用氮氣取代反應容器內的空氣後,使內溫成為60℃。隨後,添加使偶氮雙異丁腈0.12份溶解在乙酸乙酯10份而成的溶液。在同溫度保持1小時後,在內溫保持54至56℃的情況下,以 添加速度17.3份/Hr將乙酸乙酯連續地添加至反應容器內,以使聚合物的濃度成為大約35%。從乙酸乙酯添加開始起算至經過12小時為止,將內溫保持在54至56℃後,進一步添加乙酸乙酯,使聚合物的濃度調整成為20%,得到(甲基)丙烯酸系樹脂(A-1)的乙酸乙酯溶液。所得到的(甲基)丙烯酸系樹脂(A-1)之重量平均分子量Mw為139萬,重量平均分子量Mw與數量平均分子量Mn的比(Mw/Mn)為5.32。 In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, a solution obtained by mixing monomers of the composition shown in Table 1 (the value in Table 1 is parts by weight) and 81.8 parts of ethyl acetate was added. After replacing the air in the reaction vessel with nitrogen, the internal temperature was set to 60°C. Subsequently, a solution obtained by dissolving 0.12 parts of azobisisobutyronitrile in 10 parts of ethyl acetate was added. After keeping at the same temperature for 1 hour, when the internal temperature is kept at 54 to 56 ℃, Addition rate of 17.3 parts/Hr ethyl acetate was continuously added into the reaction vessel so that the concentration of the polymer became approximately 35%. From the start of ethyl acetate addition to 12 hours after the internal temperature was maintained at 54 to 56°C, ethyl acetate was further added to adjust the polymer concentration to 20% to obtain (meth)acrylic resin (A -1) The ethyl acetate solution. The weight average molecular weight Mw of the obtained (meth)acrylic resin (A-1) was 1.39 million, and the ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn was 5.32.
除了使單體的組成成為表1顯示之組成以外,其餘與製造例1同樣地進行,得到(甲基)丙烯酸系樹脂(A-2至12)的乙酸乙酯溶液(樹脂濃度:20%)。所得到的(甲基)丙烯酸系樹脂(A-2至12)之重量平均分子量Mw均為130萬至150萬的範圍,Mw/Mn為4至6的範圍。 Except that the composition of the monomers was set to the composition shown in Table 1, the rest was carried out in the same manner as in Production Example 1 to obtain an ethyl acetate solution of (meth)acrylic resins (A-2 to 12) (resin concentration: 20%) . The weight average molecular weight Mw of the obtained (meth)acrylic resins (A-2 to 12) was in the range of 1.3 million to 1.5 million, and Mw/Mn was in the range of 4 to 6.
在以上的製造例中,重量平均分子量Mw及數量平均分子量Mn,係將4支TOSOH(股)製的「TSKgel XL」、及1支昭和電工(股)製的「Shodex GPC KF-802」合計5支作為管柱,並以串聯連接的方式配置在GPC裝置,而且使用四氫呋喃作為洗提液,在試料濃度5mg/mL、試料導入量100μL、溫度40℃、流速1mL/分鐘的條件下,藉由標準聚苯乙烯換算來測定。得到GPC的排出曲線時之條件亦與其同樣。 In the above manufacturing example, the weight average molecular weight Mw and the number average molecular weight Mn are a total of 4 "TSKgel XL" manufactured by TOSOH and 1 "Shodex GPC KF-802" manufactured by Showa Denko Corporation. Five columns are used as columns and are connected in series in the GPC device, and tetrahydrofuran is used as the eluent. Under the conditions of a sample concentration of 5 mg/mL, a sample introduction volume of 100 μL, a temperature of 40°C, and a flow rate of 1 mL/min, borrow Measured by standard polystyrene conversion. The conditions for obtaining the discharge curve of GPC are also the same.
玻璃轉移溫度Tg係使用SII Nano Technology (股)製的差示掃描量熱計(DSC)「EXSTAR DSC6000」,在氮氣環境下、測定溫度範圍-80至50℃、升溫速度10℃/分鐘的條件下進行測定。 Glass transition temperature Tg uses SII Nano Technology The differential scanning calorimeter (DSC) "EXSTAR DSC6000" manufactured by Co., Ltd. is used for measurement under the conditions of a measurement temperature range of -80 to 50°C and a temperature rise rate of 10°C/min in a nitrogen atmosphere.
將在各製造例之單體的組成(表1的數值為重量份)顯示在表1。 Table 1 shows the composition of monomers in each production example (the values in Table 1 are parts by weight).
在表1的「單體組成」欄之簡稱係意味著下述的單體。 The abbreviation in the "monomer composition" column of Table 1 means the following monomers.
BA:丙烯酸丁酯(同元聚合物的玻璃轉移溫度:-54℃) BA: Butyl acrylate (Glass transition temperature of homopolymer: -54℃)
MA:丙烯酸甲酯(同元聚合物的玻璃轉移溫度:10℃) MA: Methyl acrylate (Glass transition temperature of homopolymer: 10°C)
HEA:丙烯酸2-羥基乙酯 HEA: 2-hydroxyethyl acrylate
4HBA:丙烯酸4-羥基丁酯 4HBA: 4-hydroxybutyl acrylate
5HPA:丙烯酸5-羥基戊酯 5HPA: 5-hydroxypentyl acrylate
PEA:丙烯酸苯氧基乙酯 PEA: phenoxyethyl acrylate
PEA2:苯氧基二乙二醇丙烯酸酯 PEA2: Phenoxydiethylene glycol acrylate
BMAA:丁氧基甲基丙烯醯胺 BMAA: Butoxy methacrylamide
AA:丙烯酸 AA: Acrylic
在上述製造例所得到之(甲基)丙烯酸系樹脂的乙酸乙酯溶液(樹脂濃度:20%)中,將相對於該溶液的固形物100份以表2顯示之量(重量份)的交聯劑(B)、矽烷化合物(C)、及離子性化合物(D)混合,而且以使固形物濃度成為14%之方式添加乙酸乙酯,得到黏著劑組成物。表2顯示之各調配成分的調配量,在所使用的商品含有溶劑等時,係設作其所含有的有效成分之重量份數。 In the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above production example, the amount (parts by weight) shown in Table 2 was added to 100 parts of the solid content of the solution. The coupling agent (B), the silane compound (C), and the ionic compound (D) are mixed, and ethyl acetate is added so that the solid content concentration becomes 14% to obtain an adhesive composition. The blending amount of each blending ingredient shown in Table 2 is set as the weight part of the active ingredient contained in the product used when the product contains a solvent or the like.
在表2以簡稱表示之各調配成分的詳細內 容係如下述。 In Table 2 the details of each compounding ingredient indicated by abbreviation The content is as follows.
B-1:甲苯二異氰酸酯的三羥甲基丙烷加成物的乙酸乙酯溶液(固形物濃度75%),從TOSOH(股)取得之商品名「CORONATE L」。 B-1: Ethyl acetate solution of trimethylolpropane adduct of toluene diisocyanate (solid content 75%), trade name "CORONATE L" obtained from TOSOH Co., Ltd.
B-2:伸二甲苯二異氰酸酯的三羥甲基丙烷加成物的乙酸乙酯溶液(固形物濃度75%),從三井化學(股)取得之商品名「TAKENATE D-110N」。 B-2: Ethyl acetate solution of trimethylolpropane adduct of xylene diisocyanate (solid content 75%), trade name "TAKENATE D-110N" obtained from Mitsui Chemicals Co., Ltd.
C-1:1,6-雙(三甲氧基矽基)己烷、C-2:1,8-雙(三甲氧基矽基)己烷、C-3:含甲基/甲氧基的聚矽氧寡聚物,從信越化學工業(股)取得之商品名「X-40-9250」、C-4:1,3-雙(3’-三甲氧基丙基)脲。 C-1: 1,6-bis(trimethoxysilyl)hexane, C-2: 1,8-bis(trimethoxysilyl)hexane, C-3: methyl/methoxy-containing Polysiloxane oligomer, trade name "X-40-9250", C-4: 1,3-bis(3'-trimethoxypropyl)urea obtained from Shin-Etsu Chemical Industry Co., Ltd.
D-1:雙(氟磺醯基)亞胺N-癸基吡啶鎓、D-2:雙(氟磺醯基)亞胺鉀、D-3:雙(三氟甲基磺醯基)亞胺鋰、D-4:四(五氟苯基)硼酸N-癸基吡啶鎓。 D-1: Bis(fluorosulfonyl)imide N-decylpyridinium, D-2: Bis(fluorosulfonyl)imide potassium, D-3: Bis(trifluoromethylsulfonyl)imide Lithium amide, D-4: N-decylpyridinium tetrakis(pentafluorophenyl)borate.
將在上述(1)所調製的各黏著劑組成物,使用塗佈器以使乾燥後的厚度成為20μm之方式,塗佈在已施行脫模處理之由聚對苯二甲酸乙二酯薄膜所構成的分離膜[從 LINTEC(股)取得之商品名「PLR-382051」]之脫模處理面,而且在100℃乾燥1分鐘而製造黏著劑層(黏著劑薄片)。 The adhesive composition prepared in (1) above was applied to a polyethylene terephthalate film that had been subjected to mold release treatment using an applicator so that the thickness after drying became 20 μm. Separation membrane [from The mold-releasing surface obtained by LINTEC (Stock) under the trade name "PLR-382051"], and dried at 100°C for 1 minute to produce an adhesive layer (adhesive sheet).
將平均聚合度約2400、皂化度99.9莫耳%、厚度60μm的聚乙烯醇薄膜[Kuraray(股)製的商品名「Kuraray Vinylon VF-PE # 6000」],浸漬在37℃的純水後,於30℃浸漬在含有碘及碘化鉀之水溶液(碘/碘化鉀/水(重量比)=0.04/1.5/100)中。隨後,於56.5℃浸漬在含有碘化鉀及硼酸之水溶液(碘化鉀/硼酸/水(重量比)=12/3.6/100)中。使用10℃的純水將薄膜洗淨後,在85℃乾燥,而得到在聚乙烯醇吸附配向有碘之厚度約23μm的偏光片。延伸主要是在碘染色及硼酸處理的步驟中進行且合計的延伸倍率為5.3倍。 A polyvinyl alcohol film with an average degree of polymerization of about 2400, a degree of saponification of 99.9 mol%, and a thickness of 60 μm [Kuraray Vinylon VF-PE # 6000, a trade name made by Kuraray Co., Ltd.] was immersed in pure water at 37°C. Immerse in an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio)=0.04/1.5/100) at 30°C. Subsequently, it was immersed in an aqueous solution containing potassium iodide and boric acid (potassium iodide/boric acid/water (weight ratio)=12/3.6/100) at 56.5°C. After washing the film with pure water at 10°C, it was dried at 85°C to obtain a polarizer with a thickness of about 23 μm in which iodine was adsorbed and aligned with polyvinyl alcohol. The stretching was mainly performed in the steps of iodine dyeing and boric acid treatment, and the total stretching magnification was 5.3 times.
將厚度25μm之由三乙酸纖維素薄膜所構成之透明保護膜[Konica Minolta(股)製的商品名「KC2UA」],透過由聚乙烯醇系樹脂的水溶液所構成之接著劑而貼合在所得到的偏光片之一面。其次,將厚度23μm之由環狀聚烯烴系樹脂所構成之零相位差膜[日本ZEON(股)製之商品名「ZEONOR」],透過由聚乙烯醇系樹脂的水溶液所構成之接著劑而貼合在上述偏光片之與三乙酸纖維素薄膜為相反側的面,而製造偏光板。其次,在零相位差膜之與偏光片接觸之面為相反側的面,施行用以提升密著性之電暈放電處理後,藉由貼合機將在上述(2)所製成的黏著劑層之與分離膜為相反側的面(黏著劑層面)貼合之後,在溫度23 ℃、相對濕度65%的條件下熟化7天,得到附黏著劑層的光學薄膜(P-1)。 A transparent protective film made of cellulose triacetate film [Konica Minolta Co., Ltd. product name "KC2UA"] with a thickness of 25μm is pasted on the surface through an adhesive made of an aqueous solution of a polyvinyl alcohol resin. One side of the obtained polarizer. Next, a 23μm thick zero retardation film made of cyclic polyolefin resin [trade name "ZEONOR" manufactured by ZEON, Japan] is passed through an adhesive made of an aqueous solution of polyvinyl alcohol resin. The above-mentioned polarizer was bonded to the surface on the opposite side to the cellulose triacetate film to produce a polarizing plate. Secondly, the surface of the zero retardation film that is in contact with the polarizer is on the opposite side, after corona discharge treatment to improve adhesion is performed, and the adhesive made in (2) above is bonded by a laminating machine. After bonding the agent layer on the opposite side of the separation membrane (adhesive layer), the temperature is 23 After curing for 7 days under the conditions of ℃ and 65% relative humidity, the optical film (P-1) with adhesive layer was obtained.
將上述(3)所製成之附黏著劑層的光學薄膜(P-1),以偏光板的延伸軸方向為長邊之方式裁成300mm×220mm的大小,而使分離膜剝離,將露出的黏著劑層面貼合在玻璃基板或附ITO(錫摻雜氧化銦)的玻璃基盤。將所得到之貼附有玻璃基板之試片(貼附有玻璃基板之附黏著劑層的光學薄膜),在高壓釜中、以溫度50℃、壓力5kg/cm2(490.3kPa)加壓20分鐘。玻璃基板係使用Corning公司製的無鹼玻璃商品名「Eagle XG」。又,作為附ITO的玻璃基板,係使用藉由ITO蒸鍍而使30nm的ITO層形成在Corning公司製的無鹼玻璃[商品名「Eagle XG」]而成者。 The optical film (P-1) with the adhesive layer produced in (3) above is cut into a size of 300mm×220mm with the extension axis direction of the polarizing plate as the long side, and the separation film is peeled off and exposed The adhesive layer is attached to the glass substrate or glass substrate with ITO (tin-doped indium oxide). The obtained glass substrate-attached test piece (optical film attached with the adhesive layer of the glass substrate) was pressurized in an autoclave at a temperature of 50°C and a pressure of 5 kg/cm 2 (490.3 kPa) for 20 minute. The glass substrate used the brand name "Eagle XG" of an alkali-free glass manufactured by Corning Corporation. In addition, as a glass substrate with ITO, a 30-nm ITO layer was formed on Corning Corporation's alkali-free glass [trade name "Eagle XG"] by ITO vapor deposition.
針對所得到的光學積層體,實施下述的3種耐久性試驗。 With respect to the obtained optical laminate, the following three types of durability tests were implemented.
‧在溫度95℃的乾燥條件下保持1000小時之耐熱試驗(玻璃基板),‧在溫度95℃的乾燥條件下保持1000小時之耐熱試驗(附ITO的玻璃),‧在溫度60℃、相對濕度90%的環境下保持1000小時之耐濕熱試驗(玻璃基板), ‧將在溫度85℃的乾燥條件下保持30分鐘,其次在溫度-40℃的乾燥條件下保持30分鐘之操作設作1循環,將其重複1000循環之耐熱震(HS)試驗(玻璃基板)。 ‧Heat resistance test for 1000 hours under dry conditions at 95℃ (glass substrate), ‧Heat resistance test for 1000 hours under dry conditions at 95℃ (glass with ITO), ‧At 60℃, relative humidity Moisture and heat resistance test (glass substrate) for 1000 hours under 90% of the environment, ‧Hold for 30 minutes under dry conditions at a temperature of 85°C, followed by a cycle of holding for 30 minutes under dry conditions at a temperature of -40°C, and repeat the heat shock (HS) test for 1000 cycles (glass substrate) .
目視觀察各試驗後的光學積層體,且以目視觀察黏著劑層有無浮起、剝落、發泡等的外觀變化,依照下述的評價基準而評價耐久性。將結果顯示在表3。 The optical laminate after each test was visually observed, and the adhesive layer was visually observed for changes in appearance such as floating, peeling, and foaming of the adhesive layer, and the durability was evaluated in accordance with the following evaluation criteria. The results are shown in Table 3.
5:完全未觀察到浮起、剝落、發泡等的外觀變化,4:幾乎未觀察到浮起、剝落、發泡等的外觀變化,3:浮起、剝落、發泡等的外觀變化稍微明顯,2:浮起、剝落、發泡等的外觀變化明顯,1:能夠明顯地觀察到浮起、剝落、發泡等的外觀變化。 5: No appearance changes such as floating, peeling, foaming, etc. are observed at all, 4: No appearance changes such as floating, peeling, foaming, etc. are observed at all, 3: Appearance changes such as floating, peeling, foaming, etc. are slightly changed Obviously, 2: Appearance changes such as floating, peeling, and foaming are obvious, 1: Appearance changes such as floating, peeling, and foaming can be clearly observed.
將上述(3)所製成之附黏著劑層的光學薄膜(P-1)裁成25mm×150mm的大小之試片。將隔離片從試片剝離,將其黏著劑面貼附在玻璃基板。將所得到之貼附有玻璃基板之試片(貼附有玻璃基板之附黏著劑層的光學薄膜),在高壓釜中、以溫度50℃、壓力5kg/cm2(490.3kPa)下加壓20分鐘。在溫度23℃、相對濕度50%的環境中保管24小時後,將光學薄膜與黏著劑層同時以300mm/分鐘的速度從試片往180°方向剝離。將剝離時的平均剝離力設作黏著力且顯示在表3。黏著力為10N以下時具有優異的再加工性,且0.5N以上時,即使從偏光板端部承受衝撃時亦不容易產生剝落。 The optical film (P-1) with the adhesive layer prepared in (3) above is cut into a test piece with a size of 25mm×150mm. The separator was peeled from the test piece, and its adhesive surface was attached to the glass substrate. The obtained glass substrate-attached test piece (optical film attached with the adhesive layer of the glass substrate) is pressurized in an autoclave at a temperature of 50°C and a pressure of 5kg/cm 2 (490.3kPa) 20 minutes. After storing for 24 hours in an environment with a temperature of 23° C. and a relative humidity of 50%, the optical film and the adhesive layer were simultaneously peeled from the test piece in the 180° direction at a speed of 300 mm/min. The average peel force during peeling was set as the adhesive force and shown in Table 3. When the adhesive force is 10N or less, it has excellent reworkability, and when it is 0.5N or more, it is not easy to peel off even when it is impacted from the end of the polarizing plate.
使用低電阻率計[三菱化學Analytech(股)製之商品名「Loresta AX」]測定附ITO層的玻璃基板之ITO層表面的表面電阻(試驗前表面電阻值)。其次,將上述(3)所製成之形成有黏著劑層之偏光板裁成20mm×40mm大小的試片,且透過黏著劑層而貼附在玻璃基板的ITO層側。將所得到的光學積層體,在溫度60℃、相對濕度90%的烘箱中保管500小時後,於溫度23℃、相對濕度50%的環境下在ITO層與黏著劑層之間進行剝離。測定剝離後之ITO層的表面電阻(試驗後表面電阻值)。依照下述式算出試驗前後的電阻變化率且基於以下的基準進行評價。電阻變化率越小時,ITO腐蝕性越低。將結果顯示在表3。 A low resistivity meter [trade name "Loresta AX" manufactured by Mitsubishi Chemical Analytech Co., Ltd.] was used to measure the surface resistance of the ITO layer surface of the glass substrate with the ITO layer (the surface resistance value before the test). Next, the polarizing plate with the adhesive layer formed in the above (3) was cut into a test piece with a size of 20 mm×40 mm, and the adhesive layer was passed through the adhesive layer and attached to the ITO layer side of the glass substrate. The obtained optical laminate was stored in an oven at a temperature of 60°C and a relative humidity of 90% for 500 hours, and then peeled between the ITO layer and the adhesive layer in an environment at a temperature of 23°C and a relative humidity of 50%. The surface resistance (surface resistance value after the test) of the ITO layer after peeling was measured. The resistance change rate before and after the test was calculated according to the following formula, and the evaluation was performed based on the following criteria. The smaller the resistance change rate, the lower the corrosiveness of ITO. The results are shown in Table 3.
電阻變化率(%)=[(試驗後表面電阻值)-(試驗前表面電阻值)]/[試驗前表面電阻值]×100 Resistance change rate (%)=[(Surface resistance value after test)-(Surface resistance value before test)]/[Surface resistance value before test]×100
○:電阻變化率未達50%,為ITO腐蝕性良好的光學積層體。 ○: The resistance change rate is less than 50%, and it is an optical laminate with good ITO corrosiveness.
×:電阻變化率為50%以上,光學積層體的ITO腐蝕性不良。 ×: The resistance change rate is 50% or more, and the ITO corrosiveness of the optical laminate is poor.
將所得到之附黏著劑層的偏光薄膜之隔離片剝離後, 使用表面固有電阻測定裝置[三菱化學(股)製的「Hiresta-up MCP-HT450」(商品名)]測定黏著劑的表面電阻值。在施加電壓250V、施加時間10秒的測定條件下實施。若表面電阻值為1.0×1012Ω/□以下,即能夠得到良好的抗靜電性。 After peeling off the separator of the obtained polarizing film with the adhesive layer, the surface resistance of the adhesive was measured using a surface resistance measuring device ["Hiresta-up MCP-HT450" (trade name) manufactured by Mitsubishi Chemical Corporation) value. It was implemented under the measurement conditions of an applied voltage of 250V and an applied time of 10 seconds. If the surface resistance value is 1.0×10 12 Ω/□ or less, good antistatic properties can be obtained.
揭示本發明的黏著劑薄片之凝膠分率評價方法。凝膠分率越大,則在黏著劑中會進行越多的交聯反應,能夠設作交聯密度的指標。凝膠分率係依照下述的(1)至(4)而測定之值。 The method for evaluating the gel fraction of the adhesive sheet of the present invention is disclosed. The larger the gel fraction, the more cross-linking reactions will proceed in the adhesive, which can be set as an index of cross-linking density. The gel fraction is a value measured in accordance with the following (1) to (4).
(1)將約8cm×約8cm的面積之黏著劑薄片、與約10cm×約10cm之由SUS304所構成之金屬網狀物(將其重量設作Wm)貼合。 (1) The adhesive sheet with an area of about 8cm×about 8cm is attached to a metal mesh of about 10cm×about 10cm made of SUS304 (the weight is set as Wm).
(2)將上述(1)所得到的貼合物進行稱量且將其重量設作Ws,其次,以將黏著劑薄片包入之方式折疊4次且使用釘書機(stapler)固定後稱量,將其重量設作Wb。 (2) Weigh the adhesive obtained in (1) above and set its weight as Ws. Next, fold it 4 times by wrapping the adhesive sheet and fix it with a stapler and weigh it. Set its weight as Wb.
(3)將上述(2)經釘書機固定後之網狀物放入玻璃容器,添加乙酸乙酯60mL進行浸漬之後,將該玻璃容器在室溫保管3天。 (3) Put the nets fixed by the stapler in the above (2) into a glass container, add 60 mL of ethyl acetate for immersion, and store the glass container at room temperature for 3 days.
(4)從玻璃容器將網狀物取出,於120℃乾燥24小時後進行稱量,將其重量設作Wa,基於下式而計算凝膠分率。 (4) The net was taken out from the glass container, dried at 120°C for 24 hours, and then weighed. The weight was set to Wa, and the gel fraction was calculated based on the following formula.
凝膠分率(重量%)=[{Wa-(Wb-Ws)-Wm}/(Ws-Wm)]×100 Gel fraction (weight%)=[{Wa-(Wb-Ws)-Wm}/(Ws-Wm)]×100
1‧‧‧附黏著劑層的光學薄膜 1‧‧‧Optical film with adhesive layer
10‧‧‧光學薄膜 10‧‧‧Optical Film
20‧‧‧黏著劑層 20‧‧‧Adhesive layer
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JP6066937B2 (en) * | 2014-01-28 | 2017-01-25 | 藤森工業株式会社 | Light diffusion adhesive layer and light diffusion adhesive film |
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JP6620325B2 (en) * | 2014-08-06 | 2019-12-18 | 藤森工業株式会社 | Adhesive layer and adhesive film |
JP6336897B2 (en) * | 2014-12-09 | 2018-06-06 | 藤森工業株式会社 | Adhesive layer and adhesive film |
-
2015
- 2015-12-15 JP JP2015244507A patent/JP6615597B2/en active Active
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2016
- 2016-11-21 CN CN201680073166.3A patent/CN108368404B/en active Active
- 2016-11-21 KR KR1020187019973A patent/KR102631155B1/en active IP Right Grant
- 2016-11-21 WO PCT/JP2016/084411 patent/WO2017104350A1/en active Application Filing
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201412545A (en) * | 2012-09-26 | 2014-04-01 | Fujimori Kogyo Co | Method for producing laminate, and laminate |
KR101529983B1 (en) * | 2014-09-25 | 2015-06-19 | 동우 화인켐 주식회사 | Adhesive composition |
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KR20180091091A (en) | 2018-08-14 |
WO2017104350A1 (en) | 2017-06-22 |
CN108368404B (en) | 2020-10-30 |
TW201726870A (en) | 2017-08-01 |
KR102631155B1 (en) | 2024-01-29 |
JP2017110076A (en) | 2017-06-22 |
CN108368404A (en) | 2018-08-03 |
JP6615597B2 (en) | 2019-12-04 |
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