TWI546364B - Adhesive composition, adhesive and adhesive sheet - Google Patents
Adhesive composition, adhesive and adhesive sheet Download PDFInfo
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- TWI546364B TWI546364B TW101106892A TW101106892A TWI546364B TW I546364 B TWI546364 B TW I546364B TW 101106892 A TW101106892 A TW 101106892A TW 101106892 A TW101106892 A TW 101106892A TW I546364 B TWI546364 B TW I546364B
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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
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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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
- C09J7/22—Plastics; Metallised plastics
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/005—Diaphragms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Description
本發明有關黏著性組成物，黏著性組成物的製造方法，黏著劑(黏著性組成物交聯了的材料)以及黏著片，特別是，有關用於偏振片等的光學部件的適宜的黏著性組成物，黏著性組成物的製造方法，黏著劑以及黏著片。 The present invention relates to an adhesive composition, a method for producing an adhesive composition, an adhesive (a material crosslinked by an adhesive composition), and an adhesive sheet, in particular, an appropriate adhesive property for an optical member for a polarizing plate or the like. The composition, the method of producing the adhesive composition, the adhesive, and the adhesive sheet.
一般，液晶面板中，多使用由將偏振片以及相位差板黏在玻璃基板等的黏著的性黏著劑組成物形成的黏著劑層。但是，偏振片以及相位差板等的光學部件因為熱等易產生收縮，出現熱變化造成的收縮，其結果，該光學部件上層疊的基黏著劑層不能跟隨該收縮，產生在界面的剝離(所謂浮起，剝離)，光學部件的收縮時的起因於應力的光學部件的光學軸偏離，從而產生漏光(所謂白斑)的問題。 In general, in the liquid crystal panel, an adhesive layer formed of an adhesive adhesive composition in which a polarizing plate and a phase difference plate are adhered to a glass substrate or the like is often used. However, optical members such as a polarizing plate and a phase difference plate are likely to shrink due to heat or the like, and shrinkage due to thermal change occurs. As a result, the base adhesive layer laminated on the optical member cannot follow the shrinkage, resulting in peeling at the interface ( In the case of shrinkage or peeling, the optical axis of the optical member due to stress is deviated during the contraction of the optical member, thereby causing a problem of light leakage (so-called white spot).
作為防止該問題的方法，可以例舉，(1)將黏著力高，並且，形態安定性優良的黏著劑層黏付於偏振片等的光學部件，由此使光學部件自身進行抑製的方法，或者，(2)使用光學部件的收縮時應力小的黏著劑層的方法。作為(1)的方法，如專利文獻1所示的那樣，使用儲能模量高的黏著劑層。另一方面，作為(2)的方法，使用對光學部件的變形能柔軟地對應的應力松馳率優良的黏著劑層。但是，以往，要形成這樣的應力松馳率優良的黏著劑層的場合，有必要將該黏著劑層中的交聯密度設低。這樣一來， 就會有黏著劑層自身的強度變低，耐久性為變差的問題。 As a method for preventing this problem, (1) a method in which an adhesive layer having a high adhesiveness and excellent form stability is adhered to an optical member such as a polarizing plate, thereby suppressing the optical member itself. Alternatively, (2) a method of using an adhesive layer having a small stress when shrinking an optical member. As a method of (1), as shown in Patent Document 1, an adhesive layer having a high storage modulus is used. On the other hand, as the method of (2), an adhesive layer excellent in stress relaxation rate which can flexibly correspond to deformation of an optical member is used. However, conventionally, in order to form such an adhesive layer excellent in stress relaxation rate, it is necessary to set the crosslinking density in the adhesive layer to be low. Thus, There is a problem that the strength of the adhesive layer itself is lowered and the durability is deteriorated.
由此，專利文獻2至4中，不是將黏著劑層的交聯密度設低，而是將可塑劑，流動石蠟，氨酯彈性體等添加於丙烯酸類黏著劑，由此使得到的黏著劑組成物適度地柔軟，對黏著劑層賦予應力松馳率，由此，想得到耐漏光性以及耐久性。 Therefore, in Patent Documents 2 to 4, instead of setting the crosslinking density of the adhesive layer to be low, a plasticizer, a flowing paraffin, a urethane elastomer, or the like is added to the acrylic adhesive, whereby the resulting adhesive is obtained. The composition is moderately soft, and the stress relaxation rate is imparted to the adhesive layer, whereby light leakage resistance and durability are desired.
但是，添加可塑劑或者流動石蠟的黏著劑組成物，形成的黏著劑層會隨著時間可塑劑以及流動石蠟滲出這一難點。並且，由此，黏著耐久性為變低，被黏著體的液晶單元被污染等，各種的問題被吾人所擔心。另外，添加氨酯彈性體的黏著劑組成物，如想維持相溶性，但是氨酯彈性體的添加量有上限，有應力松馳率的改善不充分的傾向。進一步，為了高應力松馳率，如增加氨酯彈性體的添加量，和丙烯酸類黏著劑的相溶性會變低，白濁等的問題發生。如此，以往的技術中，光學部件從根本上改善有黏著劑組成物形成的黏著劑層的耐漏光性以及耐久性是困難的。 However, the addition of a plasticizer or a fluid paraffin adhesive composition forms an adhesive layer that can ooze out over time with plasticizers and flowing paraffin. Further, as a result, the adhesive durability is lowered, and the liquid crystal cell of the adherend is contaminated, and various problems are caused by our problems. In addition, when the adhesive composition of the urethane elastomer is added, the compatibility of the urethane elastomer is increased, but the improvement of the stress relaxation rate tends to be insufficient. Further, in order to increase the rate of relaxation of the urethane elastomer, for example, the compatibility of the urethane elastomer is lowered, and the problem of white turbidity or the like occurs. As described above, in the prior art, it is difficult for the optical member to fundamentally improve the light leakage resistance and durability of the adhesive layer formed of the adhesive composition.
對此，專利文獻5中，提議使用從包括(甲基)丙烯酸酯80至96重量%，分子內1個的烯烴性雙鍵和至少具有1個的芳香環的不飽和單體3至15重量%，以及具有極性官能基的不飽和單體0.1至5重量%的單體混合物中得到的，重量平均分子量為100萬至200萬的丙烯酸樹脂為主成分的黏著劑組成物的帶有黏著劑的光學薄膜。 In this regard, in Patent Document 5, it is proposed to use 3 to 15 weights of an unsaturated monomer from 80 to 96% by weight of (meth) acrylate, one olefinic double bond in the molecule, and at least one aromatic ring. %, and 0.1 to 5% by weight of the unsaturated monomer having a polar functional group, the adhesive composition of the adhesive composition containing the acrylic resin as a main component having a weight average molecular weight of 1,000,000 to 2,000,000, with an adhesive Optical film.
[專利文獻1]特開2006-235568號公報 [Patent Document 1] JP-A-2006-235568
[專利文獻2]特開平5-45517號公報 [Patent Document 2] JP-A-5-45517
[專利文獻3]特開平9-137143號公報 [Patent Document 3] JP-A-9-137143
[專利文獻4]特開2005-194366號公報 [Patent Document 4] JP-A-2005-194366
[專利文獻5]特開2010-66755號公報 [Patent Document 5] JP-A-2010-66755
但是，專利文獻5的黏著劑中使用高分子量的單一的丙烯酸樹脂，耐漏光性以及耐久性的兩方並不一定優良，作為偏振片等的光學部件用其性能不充分。 However, in the adhesive of Patent Document 5, a single acrylic resin having a high molecular weight is used, and both of light leakage resistance and durability are not necessarily excellent, and the performance as an optical member such as a polarizing plate is insufficient.
本發明，就是鑒於此而產生的。本發明的目的就是提供一種在適用於偏振片等的光學部件時，耐漏光性和耐久性的兩方優良的黏著性組成物、該黏著性組成物的製造方法、黏著劑以及黏著片。 The present invention has been made in view of this. An object of the present invention is to provide an adhesive composition excellent in light leakage resistance and durability when applied to an optical member such as a polarizing plate, a method for producing the adhesive composition, an adhesive, and an adhesive sheet.
為了使上述目達成，首先，本發明為特徵為一種具有，重量平均分子量為50萬至300萬的第1(甲基)丙烯酸酯聚合物(A)、重量平均分子量為8000至30萬的第2(甲基)丙烯酸酯聚合物(B)以及交聯劑(C)和的黏著性組成物，上述第2(甲基)丙烯酸酯聚合物(B)，作為構成成分含有具有可以與交聯劑(C)反應的官能基(b1)的單體，上述第1(甲基)丙烯酸酯聚合物(A)，作為構成單體不含有具有與上述交聯劑(C)反應的反應的官能基的單體，或作為構成單體含有具有比上述第2(甲基)丙烯酸酯聚合物(B)的上述官能基(b1)還低的與上述交聯劑(C)的反應性的官能基(a1)，並且上述第1(甲基)丙烯酸酯聚合物(A)以及/或者上述第2(甲基)丙烯酸酯聚合物(B)，含有作為構成成分的具有芳香環的單體(發明1)。 In order to achieve the above object, first, the present invention is characterized by a first (meth) acrylate polymer (A) having a weight average molecular weight of 500,000 to 3,000,000 and a weight average molecular weight of 8,000 to 300,000. 2 (meth) acrylate polymer (B) and a crosslinking agent (C) and an adhesive composition, the second (meth) acrylate polymer (B) is contained as a constituent component and can be crosslinked The monomer of the functional group (b1) reacted with the agent (C), the first (meth) acrylate polymer (A), and the functional monomer do not contain a reaction having a reaction with the above-mentioned crosslinking agent (C) a monomer having a reactivity with the crosslinking agent (C) lower than the functional group (b1) of the second (meth) acrylate polymer (B) as a constituent monomer The group (a1), and the first (meth) acrylate polymer (A) and/or the second (meth) acrylate polymer (B) described above contain a monomer having an aromatic ring as a constituent component ( Invention 1).
上述發明(發明1)的黏著性組成物進行交聯得到的黏著劑，具有適宜的凝集力以及優良的應力松馳率。使用這種具有優良的應力松馳率的黏著劑，在適用於偏振片等的光學部件時，可以得到耐漏光性和耐久性的兩方都優良的黏著片。另外，得到的黏著劑，具有芳香環的成分均一的存在，折射率高，耐漏光性進一步變得優良。 The adhesive obtained by crosslinking the adhesive composition of the above invention (Invention 1) has an appropriate cohesive force and an excellent stress relaxation rate. By using such an adhesive having an excellent stress relaxation rate, when applied to an optical member such as a polarizing plate, an adhesive sheet excellent in both light leakage resistance and durability can be obtained. Further, the obtained adhesive has a uniform composition of an aromatic ring, a high refractive index, and further excellent light leakage resistance.
第2，本發明提供一種上述黏著性組成物(發明1)交聯而成得的黏著劑(發明2)。 Secondly, the present invention provides an adhesive obtained by crosslinking the above-mentioned adhesive composition (Invention 1) (Invention 2).
上述發明(發明2)的黏著劑，拉伸實驗中的斷裂拉伸度為1000%以上，凝膠比率為30至90%為較佳(發明3)。 In the adhesive of the above invention (Invention 2), the degree of elongation at break in the tensile test is 1000% or more, and the gel ratio is preferably 30 to 90% (Invention 3).
第3，本發明為一種具有基材以及黏著劑層的黏著片，其特徵在於上述黏著劑層，由上述黏著劑(發明2，3)形成(發明4)的。 Thirdly, the present invention is an adhesive sheet having a substrate and an adhesive layer, characterized in that the above-mentioned adhesive layer is formed of the above-mentioned adhesive (Invention 2, 3) (Invention 4).
上述發明(發明4)中，上述基材較佳為光學部件(發明5)。 In the above invention (Invention 4), the substrate is preferably an optical member (Invention 5).
第4，本發明為一種黏著劑片，包括2枚剝離片以及上述剝離片挾持的黏著劑層，由此與上述2枚剝離片的剝離面相接，上述黏著劑層由上述黏著劑(發明2，3)而成的(發明6)。 Fourthly, the present invention relates to an adhesive sheet comprising two release sheets and an adhesive layer held by the release sheet, thereby contacting the release faces of the two release sheets, and the adhesive layer is made of the above adhesive (inventive 2, 3) (Invention 6).
本發明的黏著性組成物交聯而成的黏著劑中，以往作為可塑劑使用的低分子量的聚合物被形成為化學交聯構造的三維網狀構造，該三維網狀構造，推測是使多個高分子量的聚合物***，高分子量的聚合物之間被約束，從而形成高分子量的聚合物之間的擬似交聯構造。由此，得到的 黏著劑具有適宜的凝集力和優良的應力松馳率。使用這種具有優良的應力松馳率的黏著劑，在適用於偏振片等的光學部件時，可以得到耐漏光性和耐久性的兩方都優良的黏著片。另外，得到的黏著劑，含有芳香環的成分被均一地含有，折射率高，耐漏光性進一步變得優良。 In the adhesive in which the adhesive composition of the present invention is crosslinked, a low molecular weight polymer which has been conventionally used as a plasticizer is formed into a three-dimensional network structure having a chemically crosslinked structure, and the three-dimensional network structure is presumably The high molecular weight polymer is intercalated and the high molecular weight polymer is constrained to form a pseudo-crosslinked structure between the high molecular weight polymers. Thus obtained The adhesive has a suitable cohesive force and an excellent stress relaxation rate. By using such an adhesive having an excellent stress relaxation rate, when applied to an optical member such as a polarizing plate, an adhesive sheet excellent in both light leakage resistance and durability can be obtained. Further, the obtained adhesive has a component containing an aromatic ring uniformly contained, and has a high refractive index and further excellent light leakage resistance.
以下，對本發明的實施形態進行說明。 Hereinafter, embodiments of the present invention will be described.
〔黏著性組成物〕 [adhesive composition]
本實施形態的黏著性組成物，包括重量平均分子量(Mw)為50萬至300萬的第1(甲基)丙烯酸酯聚合物(A)、重量平均分子量(Mw)為8000至30萬的第2(甲基)丙烯酸酯聚合物(B)以及交聯劑(C)，並且較佳為進一步含有矽烷偶聯劑(D)。本說明書中，(甲基)丙烯酸酯是指丙烯酸酯以及甲基丙烯酸酯的兩方。其他的類似用語也同樣。另外，「聚合物」也是含有「共聚合物」的概念。 The adhesive composition of the present embodiment includes a first (meth) acrylate polymer (A) having a weight average molecular weight (Mw) of 500,000 to 3,000,000 and a weight average molecular weight (Mw) of 8,000 to 300,000. The (meth) acrylate polymer (B) and the crosslinking agent (C), and preferably further contains a decane coupling agent (D). In the present specification, (meth) acrylate means both acrylate and methacrylate. The same is true for other similar terms. In addition, "polymer" also has the concept of "copolymer".
第1(甲基)丙烯酸酯聚合物(A)以及/或者第2(甲基)丙烯酸酯聚合物(B)，作為構成成分含有具有芳香環的單體。本實施形態的黏著性組成物，由於含有具有芳香環得成分，得到的黏著劑高折射率化。特別是(甲基)丙烯酸酯聚合物(A)以及/或者第2(甲基)丙烯酸酯聚合物(B)的構成單體為具有芳香環時，得到的黏著劑中可以使含有芳香環的成分均一分散。 The first (meth) acrylate polymer (A) and/or the second (meth) acrylate polymer (B) contain a monomer having an aromatic ring as a constituent component. In the adhesive composition of the present embodiment, since the component having an aromatic ring is contained, the obtained adhesive has a high refractive index. In particular, when the constituent monomer of the (meth) acrylate polymer (A) and/or the second (meth) acrylate polymer (B) has an aromatic ring, the obtained adhesive may contain an aromatic ring. The ingredients are uniformly dispersed.
較佳為，至少第2(甲基)丙烯酸酯聚合物(B)為，作為構成成分含有具有芳香環的單體，特佳為，第2(甲 基)丙烯酸酯聚合物(B)，含有具有芳香環的單體。如此，可以推定具有芳香環的成分被第2(甲基)丙烯酸酯聚合物(B)作為構成成分所含有，在高折射率化之上，在加上得到的黏著劑，使該聚合物(B)和交聯劑(C)而形成的三維網狀構造的構架安定化，得到的黏著劑的應力松馳率進一步高。其結果，具有芳香環的成分含在聚合物(B)中的場合，與聚合物(A)中含有的場合相比，即使少量也可以發揮同樣的効果。 It is preferable that at least the second (meth) acrylate polymer (B) contains a monomer having an aromatic ring as a constituent component, and particularly preferably, the second (A) The acrylate polymer (B) contains a monomer having an aromatic ring. In this way, it is presumed that the component having an aromatic ring is contained as a constituent component of the second (meth) acrylate polymer (B), and the obtained adhesive is added to the high refractive index to make the polymer ( B) The framework of the three-dimensional network structure formed by the crosslinking agent (C) is stabilized, and the obtained stress relaxation rate of the adhesive is further high. As a result, when the component having an aromatic ring is contained in the polymer (B), the same effect can be exhibited even in a small amount as compared with the case of containing the polymer (A).
並且，具有芳香環的成分，上述聚合物(A)以及/或者聚合物(B)含有的以外，作為其他的聚合物的構成成分的單體，也可以被含有，不作為聚合物的構成成分，作為獨立的成分也可以被含有。 Further, the component having an aromatic ring may be contained as a monomer which is a constituent component of another polymer, other than the polymer (A) and/or the polymer (B), and may not be a constituent component of the polymer. It can also be contained as an independent component.
第2(甲基)丙烯酸酯聚合物(B)，如作為構成成分含有具有可以與交聯劑(C)反應的官能基(b1)的單體，較佳為含有作為構成成分的具有芳香環的單體。使具有可以與交聯劑(C)反應的官能基(b1)的單體作為構成成分含有時，(1)使具有可以與交聯劑(C)反應的官能基(b1)的單體作為構成成分，該聚合物(B)為含有的，能與交聯劑(C)反應的官能基，實質上僅為官能基(b1)，(2)較佳為具有與交聯劑(C)的反應性為滿足下述式(I)的官能基(b1)的單體以及，較佳為具有與交聯劑(C)的反應性滿足下述式(I)的官能基(b2)的單體作為構成成分。 The second (meth) acrylate polymer (B) contains, as a constituent component, a monomer having a functional group (b1) reactive with the crosslinking agent (C), and preferably contains an aromatic ring as a constituent component. Monomer. When a monomer having a functional group (b1) reactive with the crosslinking agent (C) is contained as a constituent component, (1) a monomer having a functional group (b1) reactive with the crosslinking agent (C) is used as a constituent component, wherein the polymer (B) is a functional group capable of reacting with the crosslinking agent (C), and is substantially only a functional group (b1), and (2) preferably has a crosslinking agent (C). The reactivity is a monomer satisfying the functional group (b1) of the following formula (I), and preferably having a reactivity with the crosslinking agent (C) satisfying the functional group (b2) of the following formula (I) A monomer is used as a constituent component.
與交聯劑(C)的反應性：官能基(b2)<官能基(b1)．．．(I) Reactivity with crosslinker (C): functional group (b2) < functional group (b1). . . (I)
即，(2)的聚合物(B)中，官能基(b1)的與交聯劑(C)的反應性，比官能基(b2)的與交聯劑(C)反應性高。 That is, in the polymer (B) of (2), the reactivity of the functional group (b1) with the crosslinking agent (C) is higher than that of the functional group (b2) and the crosslinking agent (C).
上述(甲基)丙烯酸酯聚合物(A)或(B)較佳為，烷基的碳數為1至20的(甲基)丙烯酸烷基酯、具有與交聯劑(C)反應的官能基的單體(含有反應性官能基的單體)、以及根據需要，具有芳香環的單體(聚合物(A)以及聚合物(B)的至少一方必須)以及根據需要使用的其他的單體的共聚合物。並且，較佳也為第1(甲基)丙烯酸酯聚合物(A)，作為構成單位不含有上述反應性官能基的單體。 The (meth) acrylate polymer (A) or (B) is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms and having a function of reacting with the crosslinking agent (C). a monomer (a reactive functional group-containing monomer) and, if necessary, a monomer having an aromatic ring (at least one of the polymer (A) and the polymer (B)) and other singles used as needed The co-polymer of the body. Further, it is preferably a first (meth) acrylate polymer (A) as a monomer which does not contain the above-mentioned reactive functional group as a constituent unit.
作為烷基的碳數為1至20的(甲基)丙烯酸烷基酯，可以例舉(甲基)丙烯酸甲基酯、(甲基)丙烯酸乙基酯、(甲基)丙烯酸丙基酯、(甲基)丙烯酸n-丁基酯、(甲基)丙烯酸n-戊基酯、(甲基)丙烯酸n-己基酯、(甲基)丙烯酸環己基酯、(甲基)丙烯酸2-乙基己基酯、(甲基)丙烯酸異辛基酯、(甲基)丙烯酸n-葵基酯、(甲基)丙烯酸n-月桂基酯、(甲基)丙烯酸肉豆蔻基酯、(甲基)丙烯酸十六烷基酯以及(甲基)丙烯酸硬脂基酯等。這些可以1種單獨使用，也可以2種以上組合起來使用。 The (meth)acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate or propyl (meth)acrylate. N-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, isooctyl (meth)acrylate, n-sodium (meth)acrylate, n-lauryl (meth)acrylate, myristyl (meth)acrylate, (meth)acrylic acid Cetyl ester and stearyl (meth) acrylate. These may be used alone or in combination of two or more.
另一方面，作為含有反應性官能基的單體，分子內具有羥基的單體(含有羥基的單體)，分子內具有羧基的單 體(含有羧基的單體)，分子內具有氨基的單體(含有氨基的單體)等為較佳。 On the other hand, as a monomer having a reactive functional group, a monomer having a hydroxyl group in the molecule (a monomer having a hydroxyl group) and a monomer having a carboxyl group in the molecule The body (monomer having a carboxyl group), a monomer having an amino group in the molecule (a monomer having an amino group), and the like are preferable.
作為含有羥基的單體，可以例舉(甲基)丙烯酸2-羥基乙基酯、(甲基)丙烯酸2-羥基丙基酯、(甲基)丙烯酸3-羥基丙基酯、(甲基)丙烯酸2-羥基丁基酯、(甲基)丙烯酸3-羥基丁基酯以及(甲基)丙烯酸4-羥基丁基酯等的(甲基)丙烯酸羥基烷基酯等。這些可以1種單獨使用，也可以2種以上組合起來使用。 The hydroxyl group-containing monomer may, for example, be 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate or (methyl). A hydroxyalkyl (meth)acrylate such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate. These may be used alone or in combination of two or more.
作為含有羧基的單體，可以例舉，丙烯酸、甲基丙烯酸、巴豆酸、馬來酸、衣康酸以及檸康酸等的乙烯性不飽和羧酸。這些可以1種單獨使用，也可以2種以上組合起來使用。 The carboxyl group-containing monomer may, for example, be an ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or citraconic acid. These may be used alone or in combination of two or more.
作為含有氨基單體，可以例舉，(甲基)丙烯酸氨基乙基酯以及(甲基)丙烯酸n-丁基酯氨基乙基酯等。這些可以1種單獨使用，也可以2種以上組合起來使用。 The amino group-containing monomer may, for example, be aminoethyl (meth)acrylate or n-butyl (meth)acrylate or the like. These may be used alone or in combination of two or more.
另一方面，作為具有芳香環的單體，以具有芳香環的(甲基)丙烯酸酯為較佳。作為芳香環，可以例舉苯環、萘環、蒽環、聯苯基環以及芴環等，其中以苯環為較佳。作為具有苯環的(甲基)丙烯酸酯，可以例舉，(甲基)丙烯酸芐基酯、(甲基)丙烯酸芐基氧乙基酯、(甲基)丙烯酸苯氧乙基酯、(甲基)丙烯酸苯氧二乙二醇酯、氧化乙烯變性(甲基)丙烯酸對甲酚酯、氧化乙烯變性(甲基)丙烯酸的壬基酚酯、(甲基)丙烯酸聯苯基氧乙基酯以及苯乙烯等，其中(甲基)丙烯酸芐基酯以及(甲基) 丙烯酸苯氧乙基酯為較佳。這些可以1種單獨使用，也可以2種以上組合起來使用。 On the other hand, as the monomer having an aromatic ring, a (meth) acrylate having an aromatic ring is preferred. The aromatic ring may, for example, be a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring or an anthracene ring. Among them, a benzene ring is preferred. The (meth) acrylate having a benzene ring may, for example, be benzyl (meth) acrylate, benzyl oxyethyl (meth) acrylate or phenoxyethyl (meth) acrylate, (A) Phenyloxydiethylene glycol acrylate, ethylene oxide denatured (meth)acrylic acid p-cresol ester, ethylene oxide denatured (meth)acrylic acid nonylphenol ester, (meth)acrylic acid biphenyloxyethyl ester And styrene and the like, wherein benzyl (meth) acrylate and (methyl) Phenoxyethyl acrylate is preferred. These may be used alone or in combination of two or more.
進一步，作為上述其他的單體，例如，(甲基)丙烯酸環己基酯等的具有脂肪族環的(甲基)丙烯酸酯、丙烯酸酰胺以及甲基丙烯酰胺等的非交聯性的丙烯酸酰胺、(甲基)丙烯酸N，N-二甲基氨基乙基酯以及(甲基)丙烯酸N，N-二甲基氨基丙基酯等的含有非交聯性的叔胺基的(甲基)丙烯酸酯，醋酸乙烯基酯等。這些可以1種單獨使用，也可以2種以上組合起來使用。 Further, as the other monomer, for example, a non-crosslinkable acrylamide such as an aliphatic ring-containing (meth) acrylate such as cyclohexyl (meth) acrylate, an acrylamide or a methacrylamide, (meth)acrylic acid containing a non-crosslinkable tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate Ester, vinyl acetate, and the like. These may be used alone or in combination of two or more.
並且，含有第1(甲基)丙烯酸酯聚合物(A)使用的反應性官能基(a1)的單體以及含有第2(甲基)丙烯酸酯聚合物(B)使用的反應性官能基(b1)的單體以及含有反應性官能基(b2)的單體的選擇，與使用的交聯劑(C)的反應性的關系來決定。詳細下述。 Further, the monomer containing the reactive functional group (a1) used in the first (meth) acrylate polymer (A) and the reactive functional group used in the second (meth) acrylate polymer (B) ( The choice of the monomer of b1) and the monomer containing the reactive functional group (b2) is determined by the relationship with the reactivity of the crosslinking agent (C) to be used. The details are as follows.
在此，第2(甲基)丙烯酸酯聚合物(B)，較佳為含有上述反應性官能基(b1)的單體，超過1質量%，其上限為50質量%未滿。較佳為，含有上述反應性官能基(b1)單體3至40質量%，特佳為5至25質量%，更佳為含有10至20質量%。透過使含有反應性官能基(b1)的單體處於上述範圍，就會使第2(甲基)丙烯酸酯聚合物(B)的交聯的程度變得良好，第1(甲基)丙烯酸酯聚合物(A)和的組合中，得到的黏著劑的應力松馳率為優良。另外，如含有反應性官能基(b1)單體的含有量為1質量%以下，第2(甲基)丙烯酸酯聚合物(B)的交聯不充分，有造成的 耐久性為變低的可能。另一方面，如含有反應性官能基(b1)單體的含有量為50質量%以上，第2(甲基)丙烯酸酯聚合物(B)的交聯過度，這會造成向被黏著體的貼合適應性為變低的可能。並且，含有反應性官能基(b1)的單體的含有量的上限為40質量%時，得到的黏著片的耐漏光性更為優良。 Here, the second (meth) acrylate polymer (B) is preferably a monomer containing the reactive functional group (b1), and is more than 1% by mass, and the upper limit is 50% by mass. Preferably, the reactive functional group (b1) monomer is contained in an amount of from 3 to 40% by mass, particularly preferably from 5 to 25% by mass, more preferably from 10 to 20% by mass. When the monomer having the reactive functional group (b1) is in the above range, the degree of crosslinking of the second (meth) acrylate polymer (B) is improved, and the first (meth) acrylate is obtained. In the combination of the polymer (A) and the mixture, the obtained adhesive has excellent stress relaxation rate. In addition, when the content of the monomer containing the reactive functional group (b1) is 1% by mass or less, crosslinking of the second (meth) acrylate polymer (B) is insufficient, which is caused by Durability is low. On the other hand, if the content of the monomer containing the reactive functional group (b1) is 50% by mass or more, the crosslinking of the second (meth) acrylate polymer (B) is excessive, which causes sticking to the adherend. Appropriateness is the possibility of becoming lower. Further, when the upper limit of the content of the monomer containing the reactive functional group (b1) is 40% by mass, the obtained adhesive sheet is more excellent in light leakage resistance.
上述(1)的聚合物(B)中的「實質上僅為官能基(b1)」的意思，是指與交聯劑(C)反應的其他的官能基要在不妨害官能基(b1)和交聯劑(C)和的反應性的容許程度(這種場合，(1)的聚合物(B)和(2)的聚合物(B)重復)。即，第2(甲基)丙烯酸酯聚合物(B)，含有具有比上述官能基(b1)與交聯劑(C)和的反應性要低的官能基(b2)的單體(含有反應性官能基(b2)的單體)，作為構成成分不含有為特佳。含有反應性官能基(b2)的單體被作為構成成分含有的場合，作為質量比，為含有反應性官能基(b1)的單體的含有量的1/5以下的量，特別含有1/10以下的量為較佳。 In the polymer (B) of the above (1), "substantially only the functional group (b1)" means that other functional groups reactive with the crosslinking agent (C) are not harmful to the functional group (b1). The degree of reactivity with the crosslinking agent (C) and (in this case, the polymer (B) of (1) and the polymer (B) of (2) are repeated). In other words, the second (meth) acrylate polymer (B) contains a monomer having a functional group (b2) having a lower reactivity than the functional group (b1) and the crosslinking agent (C), and contains a reaction. The monomer of the functional group (b2) is not particularly preferable as a constituent component. When the monomer having a reactive functional group (b2) is contained as a constituent component, the mass ratio is 1/5 or less of the content of the monomer containing the reactive functional group (b1), and particularly contains 1/1. An amount of 10 or less is preferred.
第2(甲基)丙烯酸酯聚合物(B)具有的含有反應性官能基(b2)的單體，作為質量比，如超過含有反應性官能基(b1)的單體的含有量的1/5時，得到的黏著劑層的耐久性有變低的可能。第2(甲基)丙烯酸酯聚合物(B)中的反應性官能基(b2)多過時，由此形成的三維網狀構造體內反應性官能基(b2)剩余太多，該三維網狀構造體和第1(甲基)丙烯酸酯聚合物(A)的相溶性會發生變化 (推測)。其結果，海斯(Haze)值有上升的場合。另外，反應性官能基(b2)大量剩余的三維網狀構造體，該三維網狀構造體中***的基第1(甲基)丙烯酸酯聚合物(A)的可動性被過度限制(推測)。其結果，有耐久性為變差的場合。 The monomer having a reactive functional group (b2) which the second (meth) acrylate polymer (B) has has a mass ratio such as 1/1 of the content of the monomer containing the reactive functional group (b1). At 5 o'clock, the durability of the obtained adhesive layer was lowered. When the reactive functional group (b2) in the second (meth) acrylate polymer (B) is excessively lapsed, the three-dimensional network structure formed in the reactive functional group (b2) remains too much, and the three-dimensional network structure The compatibility of the body with the first (meth) acrylate polymer (A) will change. (presumed). As a result, there is a case where the Haze value rises. Further, the three-dimensional network structure in which a large amount of the reactive functional group (b2) remains, the mobility of the group-based (meth) acrylate polymer (A) inserted in the three-dimensional network structure is excessively restricted (presumed) . As a result, there is a case where the durability is deteriorated.
進一步，本實施形態的黏著性組成物在含有矽烷偶聯劑(D)的場合，矽烷偶聯劑(D)，與第1(甲基)丙烯酸酯聚合物(A)的反應性官能基(a1)(特別是羧基)反應，與高分子量的第1(甲基)丙烯酸酯聚合物(A)鍵合的場合，得到的黏著劑與被黏著體的玻璃基板等的密著性優良(推測)，第2(甲基)丙烯酸酯聚合物(B)具有含有反應性官能基(b2)的單體過剩的場合，矽烷偶聯劑(D)的烷氧基甲矽烷基等，與第2(甲基)丙烯酸酯聚合物(B)的反應性官能基(b2)(特別是羧基)也反應，與低分子量的第2(甲基)丙烯酸酯聚合物(B)鍵合(推測)。其結果，得到的黏著劑與被黏著體的玻璃基板等的密著性變差，由此造成黏著劑層的耐久性變低的可能。 Further, in the case where the adhesive composition of the present embodiment contains the decane coupling agent (D), the decane coupling agent (D) and the reactive functional group of the first (meth) acrylate polymer (A) ( When the a1) (particularly a carboxyl group) is bonded to the high molecular weight first (meth) acrylate polymer (A), the adhesion between the obtained adhesive and the glass substrate to be adhered is excellent (presumably When the second (meth) acrylate polymer (B) has an excess of a monomer containing a reactive functional group (b2), an alkoxymethyl sulfonyl group of a decane coupling agent (D), and the like The reactive functional group (b2) (particularly a carboxyl group) of the (meth) acrylate polymer (B) is also reacted and bonded to the low molecular weight second (meth) acrylate polymer (B) (presumed). As a result, the adhesion between the obtained adhesive and the glass substrate to be bonded is deteriorated, whereby the durability of the adhesive layer may be lowered.
第2(甲基)丙烯酸酯聚合物(B)，較佳為含有具有上述芳香環的單體1至40質量%，含有2至20質量%為特佳，含有5至15質量%為更佳。具有芳香環的單體為1質量%以上時，得到的黏著劑的折射率高，黏著劑的耐漏光性進一步變得優良。另一方面，具有芳香環的單體的含有量為40質量%超時，與第1(甲基)丙烯酸酯聚合物(B)等的相溶性變差，得到的黏著劑的海斯(Haze)值有上升的可 能。 The second (meth) acrylate polymer (B) preferably contains from 1 to 40% by mass of the monomer having the above aromatic ring, particularly preferably from 2 to 20% by mass, more preferably from 5 to 15% by mass. . When the monomer having an aromatic ring is 1% by mass or more, the obtained adhesive has a high refractive index and the light leakage resistance of the adhesive is further improved. On the other hand, the content of the monomer having an aromatic ring is 40% by mass, and the compatibility with the first (meth) acrylate polymer (B) or the like is deteriorated, and the obtained adhesive is Hays (Haze) ) the value has risen can.
在此，烷基的碳數為1至20的(甲基)丙烯酸烷基酯與含有具有與交聯劑(C)反應的官能基的單體與具有芳香環的單體聚合，得到的第2(甲基)丙烯酸酯聚合物(B)的聚合形式，隨機共聚合物也可，嵌段共聚合物也可。 Here, the alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms and a monomer having a functional group reactive with the crosslinking agent (C) are polymerized with a monomer having an aromatic ring, and the obtained The polymerized form of the (meth) acrylate polymer (B) may be a random copolymer or a block copolymer.
本實施形態中，上述的第2(甲基)丙烯酸酯類聚合物(B)，可以1種單獨使用，也可以2種以上組合起來使用。特別是，具有芳香環的單體作為構成成分的第2(甲基)丙烯酸酯類聚合物(B)與不含有將具有芳香環的單體作為構成成分(甲基)丙烯酸酯類聚合物(B)並用也是較佳的。由此，雖然具有芳香環的單體的使用量變低，但是，與將第2(甲基)丙烯酸酯類聚合物(B)全部作為構成成分使用具有芳香環的單體的聚合物(B)場合相比也具有同程度的耐久性以及耐漏光性。這種場合，將具有芳香環的單體作為構成成分的聚合物(B)和不將具有芳香環的單體作為構成成分的聚合物(B)的較佳組成比率，為質量比40：60至60：40。 In the present embodiment, the above-mentioned second (meth) acrylate-based polymer (B) may be used singly or in combination of two or more kinds. In particular, the second (meth) acrylate polymer (B) having a monomer having an aromatic ring as a constituent component and the monomer having no aromatic ring as a constituent component (meth) acrylate polymer ( B) Combined use is also preferred. Therefore, although the amount of the monomer having an aromatic ring is reduced, the polymer (B) having a monomer having an aromatic ring as the constituent component of the second (meth)acrylate polymer (B) is used as a constituent component. It also has the same degree of durability and light leakage resistance compared to the occasion. In this case, a preferred composition ratio of the polymer (B) having a monomer having an aromatic ring as a constituent component and the polymer (B) having no monomer having an aromatic ring as a constituent component is a mass ratio of 40:60. Until 60:40.
第2(甲基)丙烯酸酯聚合物(B)的重量平均分子量8000至30萬，較佳為1萬至20萬，特佳5萬至10萬。即，第2(甲基)丙烯酸酯聚合物(B)，低分子量聚合物成分構成的。並且，本說明書中的重量平均分子量，時用凝膠滲透色譜(GPC)法測定的聚苯乙烯換算的值。 The second (meth) acrylate polymer (B) has a weight average molecular weight of 8,000 to 300,000, preferably 10,000 to 200,000, and particularly preferably 50,000 to 100,000. That is, the second (meth) acrylate polymer (B) is composed of a low molecular weight polymer component. Further, the weight average molecular weight in the present specification is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
如第2(甲基)丙烯酸酯聚合物(B)的重量平均分子量在上述範圍內，在本實施形態的黏著性組成物中特有的 三維網狀構造形成，有利於得到優良的應力松馳率。即，第2(甲基)丙烯酸酯聚合物(B)的重量平均分子量為8000未滿，良好的三維網狀構造就不能得到。另一方面，第2(甲基)丙烯酸酯聚合物(B)的重量平均分子量超過30萬，相溶性變低，聚合物(A)向聚合物(B)而成的三維網狀構造體中的***就不充分，耐久性以及重復使用性就會變差。 When the weight average molecular weight of the second (meth) acrylate polymer (B) is within the above range, it is peculiar to the adhesive composition of the present embodiment. The formation of a three-dimensional network structure is advantageous for obtaining an excellent stress relaxation rate. That is, the weight average molecular weight of the second (meth) acrylate polymer (B) was less than 8,000, and a good three-dimensional network structure could not be obtained. On the other hand, the second (meth) acrylate polymer (B) has a weight average molecular weight of more than 300,000, and the compatibility is low, and the polymer (A) is in the three-dimensional network structure of the polymer (B). The insertion is insufficient, and the durability and reusability are deteriorated.
第1(甲基)丙烯酸酯聚合物(A)，作為構成成分不含有與交聯劑(C)和反應的官能基，或者作為構成成分含有比第2(甲基)丙烯酸酯聚合物(B)的上述官能基(b1)與交聯劑(C)的反應性為低的官能基(a1)的單體，並且較佳為，作為構成成分不含有具有比上述官能基(b1)與交聯劑(C)的反應性高的官能基的單體。並且，第1(甲基)丙烯酸酯聚合物(A)，代替第2(甲基)丙烯酸酯聚合物(B)，或者也可與第2(甲基)丙烯酸酯聚合物(B)一同，作為構成成分具有含有芳香環的單體。 The first (meth) acrylate polymer (A) does not contain a functional group reactive with the crosslinking agent (C) as a constituent component, or contains a second (meth) acrylate polymer as a constituent component (B). The functional group (b1) having a reactivity with the crosslinking agent (C) is a monomer having a low functional group (a1), and preferably, the constituent component does not contain a functional group (b1) A monomer having a highly reactive functional group of the crosslinking agent (C). Further, the first (meth) acrylate polymer (A) may be used in place of the second (meth) acrylate polymer (B), or may be used together with the second (meth) acrylate polymer (B). A monomer having an aromatic ring is contained as a constituent component.
第1(甲基)丙烯酸酯聚合物(A)，也可不含有具有與交聯劑(C)和反應的官能基的單體。但是，如含有具有比第2(甲基)丙烯酸酯聚合物(B)的反應性官能基(b1)反應性的低的反應性官能基(a1)的單體(含有反應性官能基(a1)單體)，有較佳的場合。上述聚合物(A)中如含有反應性官能基(a1)，可以促進第2(甲基)丙烯酸酯聚合物(B)和交聯劑(C)的反應，或者，矽烷偶聯劑(D)被使用的場合，第1(甲基)丙烯酸酯聚合物(A) 的反應性官能基(a1)與該矽烷偶聯劑(D)反應，得到的黏著劑的向液晶單元等的玻璃面的黏著耐久性會進一步高，因此有較佳的場合。 The first (meth) acrylate polymer (A) may not contain a monomer having a functional group reactive with the crosslinking agent (C). However, a monomer having a reactive functional group (a1) having a reactivity lower than that of the reactive functional group (b1) of the second (meth) acrylate polymer (B) (containing a reactive functional group (a1) ) Monomer), there are better occasions. The polymer (A) may contain a reactive functional group (a1) to promote the reaction of the second (meth) acrylate polymer (B) and the crosslinking agent (C), or a decane coupling agent (D). ) When used, the first (meth) acrylate polymer (A) The reactive functional group (a1) reacts with the decane coupling agent (D), and the obtained adhesive has a higher adhesion durability to the glass surface of the liquid crystal cell or the like, which is preferable.
第1(甲基)丙烯酸酯聚合物(A)含有具有上述反應性官能基(a1)單體的場合，其含有量，通常20質量%以下，15質量%以下為較佳，特佳為以10質量%以下。含有反應性官能基(a1)單體的含有量超過20質量%時，第1(甲基)丙烯酸酯聚合物(A)的玻璃転移溫度(Tg)過高，得到的黏著劑不能得到需要的應力松馳率。並且，黏著劑的重復使用性賦予的觀點，含有反應性官能基(a1)的單體的含有量15質量%以下為較佳。 When the first (meth) acrylate polymer (A) contains the monomer having the reactive functional group (a1), the content thereof is usually 20% by mass or less, preferably 15% by mass or less, and particularly preferably 10% by mass or less. When the content of the monomer having a reactive functional group (a1) exceeds 20% by mass, the glass transition temperature (Tg) of the first (meth) acrylate polymer (A) is too high, and the obtained adhesive cannot be obtained. Stress relaxation rate. Further, from the viewpoint of imparting reusability of the adhesive, the content of the monomer containing the reactive functional group (a1) is preferably 15% by mass or less.
另外，與第2(甲基)丙烯酸酯聚合物(B)含有具有反應性官能基(b1)的單體進行比較，第1(甲基)丙烯酸酯聚合物(A)含有的具有反應性官能基(a1)的單體的在該第1(甲基)丙烯酸酯聚合物(A)中的比率比第2(甲基)丙烯酸酯聚合物(B)的具有含有的反應性官能基(b1)的單體的在該第2(甲基)丙烯酸酯聚合物(B)中的比率小為較佳。由此，第1(甲基)丙烯酸酯聚合物(A)含有的反應性官能基(a1)對與交聯劑(C)的反應有抑製，可以使第2(甲基)丙烯酸酯聚合物(B)含有的反應性官能基(b1)和交聯劑(C)進行確實的反應。 Further, the first (meth) acrylate polymer (B) contains a reactive functional group (b1), and the first (meth) acrylate polymer (A) contains a reactive functional group. The ratio of the monomer of the group (a1) in the first (meth) acrylate polymer (A) is higher than that of the second (meth) acrylate polymer (B) (b1) The ratio of the monomer in the second (meth) acrylate polymer (B) is preferably small. Thereby, the reactive functional group (a1) contained in the first (meth) acrylate polymer (A) inhibits the reaction with the crosslinking agent (C), and the second (meth) acrylate polymer can be obtained. (B) The reactive functional group (b1) and the crosslinking agent (C) contained are subjected to a definite reaction.
第1(甲基)丙烯酸酯聚合物(A)，在分子內不含有具有與交聯劑(C)的反應性與第2(甲基)丙烯酸酯聚合物(B)的反應性官能基(b1)同等或以上的官能基的單體 為較佳，若含有的場合，在分子內具有該官能基的單體的含有量，在聚合物(A)中1質量%以下為較佳，0.5質量%以下為特佳。如該單體的含有量超過1質量%，就會有可能阻礙應優先反應的第2(甲基)丙烯酸酯聚合物(B)和交聯劑(C)的反應。 The first (meth) acrylate polymer (A) does not contain a reactive functional group having reactivity with the crosslinking agent (C) and the second (meth) acrylate polymer (B) in the molecule ( B1) Monomers having equal or higher functional groups In the case of containing, the content of the monomer having such a functional group in the molecule is preferably 1% by mass or less in the polymer (A), and particularly preferably 0.5% by mass or less. When the content of the monomer exceeds 1% by mass, the reaction of the second (meth) acrylate polymer (B) and the crosslinking agent (C) which are preferentially reacted may be inhibited.
第1(甲基)丙烯酸酯聚合物(A)含有具有上述芳香環的單體的場合，其含有量，1至20質量%為較佳，2至10質量%為特佳。具有上述芳香環的單體為1質量%以上的場合，得到的黏著劑高折射率化，耐漏光性也好。另一方面，具有上述芳香環的單體的含有量為20質量%時，與聚合物(B)等的成分的相溶性可保持良好。 When the first (meth) acrylate polymer (A) contains a monomer having the above aromatic ring, the content thereof is preferably from 1 to 20% by mass, particularly preferably from 2 to 10% by mass. When the monomer having the above aromatic ring is 1% by mass or more, the obtained adhesive has a high refractive index and good light leakage resistance. On the other hand, when the content of the monomer having the above aromatic ring is 20% by mass, the compatibility with the component such as the polymer (B) can be kept good.
在此，烷基的碳數為1至20的(甲基)丙烯酸烷基酯，如含有具有反應性官能基的單體，根據需要，與具有芳香環的單體進行聚合，得到的第1(甲基)丙烯酸酯聚合物(A)的聚合形式，為隨機共聚合物也可，為嵌段共聚合物也可。 Here, the alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms, such as a monomer having a reactive functional group, is polymerized with a monomer having an aromatic ring as needed, and the first one is obtained. The polymerized form of the (meth) acrylate polymer (A) may be a random copolymer or a block copolymer.
本實施形態中，上述的第1(甲基)丙烯酸酯聚合物(A)，可以1種單獨使用，也可以2種以上組合起來使用。 In the present embodiment, the first (meth) acrylate polymer (A) may be used singly or in combination of two or more kinds.
第1(甲基)丙烯酸酯聚合物(A)的重量平均分子量為50萬至300萬，較佳為70萬至250萬，特佳100萬至200萬。即，第1(甲基)丙烯酸酯聚合物(A)為高分子量聚合物成分。 The weight average molecular weight of the first (meth) acrylate polymer (A) is from 500,000 to 3,000,000, preferably from 700,000 to 2,500,000, and particularly preferably from 1,000,000 to 2,000,000. That is, the first (meth) acrylate polymer (A) is a high molecular weight polymer component.
如第1(甲基)丙烯酸酯聚合物(A)的重量平均分子量在上述範圍內，向第2(甲基)丙烯酸酯聚合物(B)形 成的三維網狀構造的該第1(甲基)丙烯酸酯聚合物(A)***良好，透過該聚合物(A)的2分子以上的擬似的交聯構造，聚合物(A)，為具有某種程度的自由度的狀態被約束(推測)。另外，聚合物(A)，如上述具有比較大的分子量，介於聚合物(B)形成三維網狀構造體，一邊維持擬似的交聯狀態，一邊作為分子鏈具有高的自由度。由此，形成的黏著劑，同時具有適宜的凝集力和優良的應力松馳率，其結果，該黏著劑，耐漏光性優良，另外，高溫．濕熱條件下的黏著耐久性充分，從而可以防止浮起以及剝離等。 The weight average molecular weight of the first (meth) acrylate polymer (A) is in the above range, and is formed into the second (meth) acrylate polymer (B). The first (meth) acrylate polymer (A) having a three-dimensional network structure is inserted well, and the polymer (A) has a pseudo-crosslinked structure of two or more molecules of the polymer (A). The state of a certain degree of freedom is constrained (presumed). Further, the polymer (A) has a relatively large molecular weight as described above, and forms a three-dimensional network structure in the polymer (B), and has a high degree of freedom as a molecular chain while maintaining a pseudo-crosslinked state. Thereby, the formed adhesive has both a suitable cohesive force and an excellent stress relaxation rate, and as a result, the adhesive is excellent in light leakage resistance and, in addition, high temperature. Adhesion durability under wet heat conditions is sufficient to prevent floating, peeling, and the like.
在此，如第1(甲基)丙烯酸酯聚合物(A)的重量平均分子量為50萬未滿，有可能使得到的黏著劑的凝集力變低，耐久性以及重復使用性變差。另外，如第1(甲基)丙烯酸酯聚合物(A)的重量平均分子量超過300萬，與第2(甲基)丙烯酸酯聚合物(B)等相溶性變差，海斯(Haze)值上升，難以得到需要的應力松馳率。 Here, when the weight average molecular weight of the first (meth) acrylate polymer (A) is less than 500,000, the cohesive force of the obtained adhesive may be lowered, and durability and reusability may be deteriorated. In addition, when the weight average molecular weight of the first (meth) acrylate polymer (A) exceeds 3,000,000, the compatibility with the second (meth) acrylate polymer (B) or the like is deteriorated, and the Haze value is obtained. Ascending, it is difficult to obtain the required stress relaxation rate.
對第1(甲基)丙烯酸酯聚合物(A)100質量份，第2(甲基)丙烯酸酯聚合物(B)的比率，5至40質量份為較佳，以10至30質量份為特佳。 The ratio of the first (meth) acrylate polymer (A) to 100 parts by mass of the second (meth) acrylate polymer (B) is preferably 5 to 40 parts by mass, and 10 to 30 parts by mass. Very good.
以上述比率含有第1(甲基)丙烯酸酯聚合物(A)以及第2(甲基)丙烯酸酯聚合物(B)黏著性組成物得到的黏著劑中，第2(甲基)丙烯酸酯聚合物(B)(低分子量聚合物)透過交聯劑(C)，三維網狀構造被形成，該三維網狀構造，為第1(甲基)丙烯酸酯聚合物(A)(高分子量聚合物)2分子以上***的構造，由此聚合物(A)為以 具有某種程度的自由度的狀態被約束擬似的交聯構造(推測)。由此，得到的黏著劑，具有適宜的凝集力，並具有優良的應力松馳率。由此，得到的黏著劑耐久性以及耐漏光性優良。 In the adhesive obtained by containing the first (meth) acrylate polymer (A) and the second (meth) acrylate polymer (B) adhesive composition in the above ratio, the second (meth) acrylate is polymerized. The (B) (low molecular weight polymer) is formed by a three-dimensional network structure through a crosslinking agent (C), which is a first (meth) acrylate polymer (A) (high molecular weight polymer) a structure in which two or more molecules are inserted, whereby the polymer (A) is A state with a certain degree of freedom is constrained to a pseudo-crosslinked structure (presumed). Thereby, the obtained adhesive has a suitable cohesive force and has an excellent stress relaxation rate. Thereby, the obtained adhesive is excellent in durability and light leakage resistance.
作為交聯劑(C)，較佳為例舉異氰酸酯類交聯劑，環氧類交聯劑，氮雜環丙烷類交聯劑，金屬螯合類交聯劑等。 The crosslinking agent (C) is preferably an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent or the like.
異氰酸酯類交聯劑，至少含有聚異氰酸酯化合物。作為聚異氰酸酯化合物，例如，亞芐基二異氰酸酯、二苯基甲基二異氰酸酯、對二甲苯基二異氰酸酯等的芳香族聚異氰酸酯、亞環己基二異氰酸酯等的脂肪族聚異氰酸酯、異氟而酮二異氰酸酯、加氫二苯基甲基二異氰酸酯等的酯環類聚異氰酸酯等、以及這些化合物的縮二脲體、異氰脲酸酯；進一步，乙二醇、丙二醇、新戊二醇、三羥甲基丙烷以及蓖麻油等的含有低分子活性氫的化合物的加成物等。 The isocyanate crosslinking agent contains at least a polyisocyanate compound. Examples of the polyisocyanate compound include an aromatic polyisocyanate such as benzylidene diisocyanate, diphenylmethyl diisocyanate or p-xylylene diisocyanate, or an aliphatic polyisocyanate such as cyclohexylene diisocyanate or isoflurane. An ester cyclic polyisocyanate such as a diisocyanate or a hydrogenated diphenylmethyl diisocyanate; and a biuret or isocyanurate of these compounds; further, ethylene glycol, propylene glycol, neopentyl glycol, and trishydroxyl An adduct of a compound containing a low molecular weight active hydrogen such as methyl propane or castor oil.
作為環氧類交聯劑，可能例舉1，3-雙(N，N’-二縮水甘油基氨基甲基)環己烷、N，N，N’，N’-四縮水甘油基m-對二甲苯基二胺、乙二醇二縮水甘油基醚、1，6-己二醇二縮水甘油基醚、三羥甲基丙烷二縮水甘油基醚、二縮水甘油基苯胺以及二縮水甘油基胺等。 As the epoxy-based crosslinking agent, 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl group m- may be exemplified. P-Xylylenediamine, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, and diglycidyl Amines, etc.
作為氮雜環丙烷類交聯劑，可以例舉二苯基甲基-4，4’-雙(1-氮雜環丙烷甲酰胺)、三羥甲基丙烷三β-氮雜環丙烷丙酸酯、四羥甲基甲烷三β-氮雜環丙烷丙酸酯、甲苯2，4-雙(1-氮雜環丙烷甲酰胺)、三亞乙基三聚氰氨、 雙異苯二甲基1-(2-甲基氮雜環丙烷)、三-1-(2-甲基氮雜環丙烷)膦以及三羥甲基丙烷三β-(2-甲基氮雜環丙烷)丙酸酯等。 As the aziridine-based crosslinking agent, diphenylmethyl-4,4'-bis(1-azabicyclopropanecarboxamide), trimethylolpropane tri-β-azepine propionic acid can be exemplified. Ester, tetramethylol methane tri-β-azepine propionate, toluene 2,4-bis(1-azacyclopropanecarboxamide), triethylene melamine, Diisophthalyl 1-(2-methylaziridine), tri-1-(2-methylaziridine)phosphine, and trimethylolpropane tri-β-(2-methylaza Cyclopropane) propionate and the like.
金屬螯合類交聯劑中，有金屬原子為鋁、鋯、鈦、鋅、鐵以及錫等的螯合化合物，從性能來看鋁螯合化合物為較佳。作為鋁螯合化合物，可以例舉二異丙氧基鋁單油醇乙酰乙酸鹽、單異丙氧基鋁雙油醇乙酰乙酸鹽、單異丙氧基鋁單油酸單乙基乙酰乙酸鹽、二異丙氧基鋁單月桂乙酰乙酸鹽、二異丙氧基鋁單硬脂基乙酰乙酸鹽以及二異丙氧基鋁單異硬脂基乙酰乙酸鹽等。 Among the metal chelate crosslinking agents, metal atoms are chelating compounds such as aluminum, zirconium, titanium, zinc, iron, and tin, and aluminum chelate compounds are preferred from the viewpoint of performance. As the aluminum chelate compound, diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum dioleyl acetoacetate, and monoisopropoxy aluminum monooleic acid monoethyl acetoacetate can be exemplified. , aluminum diisopropoxide, monolaurin acetoacetate, diisopropoxy aluminum monostearyl acetoacetate, and diisopropoxy aluminum monoisostearyl acetoacetate.
交聯劑(C)的含有量，對與該交聯劑(C)的交聯性基(例如，異氰酸酯基)為第2(甲基)丙烯酸酯聚合物(B)的反應性官能基(b1)(例如，羥基)的量，通常為0.05至5當量的量，較佳為0.1至3.5當量的量，特佳0.3至1.0當量的量。如上述交聯性基的量為0.05當量以上，得到的黏著劑的凝膠比率為30%以上，具有充分的凝集力，如上述交聯性基的量為0.1當量，特別是0.3當量以上時，得到的黏著劑的耐久性會進一步變得優良。另一方面，如上述交聯性基的量為3.5當量以下，得到的黏著劑得重復使用性優良，進一步如為1.0當量以下的話，聚合物(B)同類之間進行交聯，由此交聯劑(C)被消耗，從而，可以防止剩余交聯劑的聚合物(A)同種之間進行交聯，或者聚合物(A)和聚合物(B)進行交聯。 The content of the crosslinking agent (C) is such that the crosslinking group (for example, an isocyanate group) with the crosslinking agent (C) is a reactive functional group of the second (meth) acrylate polymer (B) ( The amount of b1) (e.g., a hydroxyl group) is usually an amount of from 0.05 to 5 equivalents, preferably from 0.1 to 3.5 equivalents, particularly preferably from 0.3 to 1.0 equivalents. When the amount of the crosslinkable group is 0.05 equivalent or more, the gel ratio of the obtained adhesive is 30% or more, and has sufficient cohesive force, and the amount of the crosslinkable group is 0.1 equivalent, particularly 0.3 equivalent or more. The durability of the obtained adhesive is further improved. On the other hand, when the amount of the crosslinkable group is 3.5 equivalents or less, the obtained adhesive is excellent in recyclability, and if it is 1.0 equivalent or less, the polymer (B) is crosslinked in the same manner. The crosslinking agent (C) is consumed, whereby crosslinking of the polymer (A) of the remaining crosslinking agent with the same species or crosslinking of the polymer (A) and the polymer (B) can be prevented.
另外，本實施形態中，作為交聯劑(C)，如果與反 應性官能基(b1)以及反應性官能基(a1)的兩方的反應性的關系為一致的場合，多種類的交聯基也可以並用。從第2(甲基)丙烯酸酯聚合物(B)形成的三維網狀構造的控製容易的觀點來看，例如就象說只可使用異氰酸酯類交聯劑那樣，只使用1類的交聯劑為較佳，進一步只使用1種交聯劑為特佳。 Further, in the present embodiment, as the crosslinking agent (C), if and When the relationship between the reactivity of the functional functional group (b1) and the reactive functional group (a1) is the same, a plurality of kinds of crosslinking groups may be used in combination. From the viewpoint of easy control of the three-dimensional network structure formed of the second (meth) acrylate polymer (B), for example, only one type of crosslinking agent can be used as in the case of using only an isocyanate crosslinking agent. Preferably, it is particularly preferable to use only one type of crosslinking agent.
在此，作為交聯劑(C)與，(甲基)丙烯酸酯聚合物(A)以及(B)的含有反應性官能基的單體和的組合，在交聯劑(C)為異氰酸酯類交聯劑的場合，作為含有聚合物(A)的反應性官能基(a1)的單體以含有羧基的單體為較佳，作為聚合物(B)的含有反應性官能基(b1)的單體，以含有羥基的單體或者含有氨基的單體為較佳。 Here, as the crosslinking agent (C) and the combination of the (meth) acrylate polymer (A) and the reactive functional group-containing monomer and (B), the crosslinking agent (C) is an isocyanate. In the case of a crosslinking agent, a monomer containing a carboxyl group as a monomer containing a reactive functional group (a1) of the polymer (A) is preferred, and a reactive functional group (b1) containing a reactive polymer (b1) as a polymer (B) is preferred. The monomer is preferably a monomer having a hydroxyl group or a monomer having an amino group.
另一方面，交聯劑(C)為環氧類交聯劑，氮雜環丙烷類交聯劑或者金屬螯合類交聯劑的場合，較佳為作為含有聚合物(A)的反應性官能基(a1)的單體為含有羥基的單體，作為含有聚合物(B)的反應性官能基(b1)含有單體為含有羧基的單體。 On the other hand, when the crosslinking agent (C) is an epoxy crosslinking agent, an aziridine crosslinking agent or a metal chelate crosslinking agent, it is preferably reactive as a polymer (A). The monomer of the functional group (a1) is a monomer having a hydroxyl group, and the reactive functional group (b1) containing the polymer (B) contains a monomer which is a carboxyl group-containing monomer.
交聯劑(C)和聚合物(B)之間形成的鍵的柔軟性，以及交聯反應的穩定性，進一步，聚合物(A)的反應性基與矽烷偶聯劑(D)進行適宜反應，對得到的黏著劑的凝集力高有貢獻的觀點，所以，使交聯劑(C)為異氰酸酯類交聯劑，使含有聚合物(A)的反應性官能基(a1)的單體為含有羧基的單體，使含有聚合物(B)的反應性官能基(b1)的單體為含有羥基的單體，不使用含有反應性官能基(b2) 的單體為特佳。 The flexibility of the bond formed between the crosslinking agent (C) and the polymer (B), and the stability of the crosslinking reaction, further, the reactive group of the polymer (A) and the decane coupling agent (D) are suitably Since the reaction contributes to a high cohesive force of the obtained adhesive, the crosslinking agent (C) is an isocyanate crosslinking agent, and the monomer containing the reactive functional group (a1) of the polymer (A) is obtained. The monomer having a carboxyl group-containing monomer, the monomer having the reactive functional group (b1) of the polymer (B) is a monomer having a hydroxyl group, and the reactive functional group (b2) is not used. The monomer is especially good.
本實施形態的黏著性組成物，較佳為，進一步含有矽烷偶聯劑(D)。如含有這種矽烷偶聯劑(D)，第1(甲基)丙烯酸酯聚合物(A)為有羧基的場合，矽烷偶聯劑(D)的有機反應性基等和第1(甲基)丙烯酸酯聚合物(A)的羧基反應，另一方面，矽烷偶聯劑(D)的烷氧基甲矽烷基等對玻璃基板等的被黏著體起作。由此，例如將偏振片在液晶玻璃單元等上貼合的場合，黏著劑和液晶玻璃單元之間的密著性會更為良好。 The adhesive composition of the present embodiment preferably further contains a decane coupling agent (D). When such a decane coupling agent (D) is contained, when the first (meth) acrylate polymer (A) has a carboxyl group, the organic reactive group of the decane coupling agent (D), etc., and the first (methyl group) The carboxy group of the acrylate polymer (A) is reacted. On the other hand, the alkoxycarbenyl group of the decane coupling agent (D) or the like acts on the adherend such as a glass substrate. Therefore, for example, when the polarizing plate is bonded to a liquid crystal glass unit or the like, the adhesion between the adhesive and the liquid crystal glass unit is further improved.
作為這種矽烷偶聯劑(D)，分子內至少具有一個烷氧基甲矽烷基的有機矽化合物，與黏著劑成分的相溶性好，並且為有光透過性的物質，例如實質上為透明的物質為佳。這樣的矽烷偶聯劑(D)的添加量，對第1(甲基)丙烯酸酯聚合物(A)100質量份，以0.01至0.5質量份為較佳，0.05至0.3質量份為特佳。 As such a decane coupling agent (D), an organic ruthenium compound having at least one alkoxycarbenyl group in the molecule has good compatibility with an adhesive component, and is a light-transmitting substance, for example, substantially transparent. The substance is better. The amount of the decane coupling agent (D) to be added is preferably from 0.01 to 0.5 parts by mass, preferably from 0.05 to 0.3 parts by mass, per 100 parts by mass of the first (meth) acrylate polymer (A).
作為矽烷偶聯劑(D)的具體例子，有乙烯基三甲氧基矽烷，乙烯基三乙氧基矽烷，甲基丙烯酰氧丙基三甲氧基矽烷等的含有聚合性不飽和基的矽化合物：3-環氧丙氧基丙基三甲氧基矽烷，2-(3，4-環氧環己基)乙基三甲氧基矽烷等的具有環氧構造的矽化合物；3-氨基丙基三甲氧基矽烷，N-(2-氨基乙基)-3-氨基丙基三甲氧基矽烷，N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基矽烷等的含有氨基的矽化合物；3-氯丙基三甲氧基矽烷，3-異氰酸酯丙基三乙氧基矽烷等。這些，可以1種單獨使用，也可以2種 以上組合起來使用。 Specific examples of the decane coupling agent (D) include a fluorene compound containing a polymerizable unsaturated group such as vinyl trimethoxy decane, vinyl triethoxy decane, methacryloxypropyl trimethoxy decane or the like. : an epoxy structure-containing hydrazine compound such as 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-aminopropyltrimethoxy Amino-containing, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, etc. Anthracene compound; 3-chloropropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, and the like. These can be used alone or in combination of two. The above is used in combination.
本實施形態的黏著性組成物，在作為獨立成分含有具有芳香環的成分的場合，作為該具有芳香環的成分，除了列舉的具有苯環(甲基)丙烯酸酯之外，還可以例舉苯乙烯類單體，雙苯酚A二縮水甘油基醚，芴化合物類等。其含有量，對聚合物(A)以及聚合物(B)的合計100質量份，以5質量份以下為較佳。但是，如將具有芳香環的成分作為獨立的成分添加的場合，有可能發生從黏著劑中滲出，或濃度不均的現象，所以，還是以作為聚合物(A)以及/或者聚合物(B)的構成成分在黏著劑中存在為較佳。 In the case where the adhesive composition of the present embodiment contains a component having an aromatic ring as an independent component, the benzene ring (meth) acrylate may be exemplified as the benzene ring (meth) acrylate. A vinyl monomer, a bisphenol A diglycidyl ether, an anthraquinone compound or the like. The content thereof is preferably 5 parts by mass or less based on 100 parts by mass of the total of the polymer (A) and the polymer (B). However, when a component having an aromatic ring is added as an independent component, bleed out from the adhesive or uneven concentration may occur, so that it is used as the polymer (A) and/or the polymer (B). The constituent components of the adhesive are preferably present in the adhesive.
上述黏著性組成物中，根據需要，可以添加丙烯酸類黏著劑通常使用的各種添加劑，例如黏著賦予劑，氧化防止劑，紫外線吸收劑，光安定劑，柔軟劑，充填劑，帯電防止劑，折射率調整劑等。 In the above adhesive composition, various additives commonly used for acrylic adhesives such as an adhesion-imparting agent, an oxidation preventive agent, an ultraviolet absorber, a light stabilizer, a softener, a filler, a antimony preventive agent, and a refraction may be added as needed. Rate adjuster, etc.
〔黏著性組成物的製造方法〕 [Method for Producing Adhesive Composition]
上述黏著性組成物，第1(甲基)丙烯酸酯聚合物(A)以及第2(甲基)丙烯酸酯聚合物(B)混合的同時，可以在任意的段階添加交聯劑(C)以及根據需要的矽烷偶聯劑(D)，由此而製造。 When the above-mentioned adhesive composition is mixed with the first (meth) acrylate polymer (A) and the second (meth) acrylate polymer (B), the crosslinking agent (C) can be added at any step. It is produced by the desired decane coupling agent (D).
作為較佳具體例，(甲基)丙烯酸酯聚合物(A)以及(B)，它們分別以通常的自由基聚合法製成。(甲基)丙烯酸酯聚合物(A)以及(B)的聚合，根據需要可以使用聚合引發劑，用溶液聚合法等製成。作為聚合溶媒，可以例舉醋酸乙基酯、醋酸n-丁基酯、醋酸異丁基酯、甲苯、 丙酮、己烷以及甲基乙基酮等，也可2種以上並用。 As a preferable specific example, the (meth) acrylate polymers (A) and (B) are each produced by a usual radical polymerization method. The polymerization of the (meth) acrylate polymers (A) and (B) can be carried out by a solution polymerization method or the like, if necessary, by using a polymerization initiator. The polymerization solvent may, for example, be ethyl acetate, n-butyl acetate, isobutyl acetate or toluene. Acetone, hexane, methyl ethyl ketone, or the like may be used in combination of two or more kinds.
作為聚合引發劑，可以例舉偶氮類化合物，有機過氧化物等，也可2種以上並用。偶氮類化合物，可以例舉2，2’-偶氮雙異丁腈、2，2’-偶氮雙(2-甲基丁腈)、1，1’-偶氮雙(環己烷1-腈)、2，2’-偶氮雙(2，4-二甲基腈)、2，2’-偶氮雙(2，4-二甲基4-甲氧基腈)、二甲基2，2’-偶氮雙(2-甲基丙酸酯)、4，4’-偶氮雙(4-氰基戊酸酯)、2，2’-偶氮雙(2-羥基甲基丙腈)以及2，2’-偶氮雙〔2-(2-咪唑琳2-基)丙烷〕等。 The polymerization initiator may, for example, be an azo compound or an organic peroxide, or may be used in combination of two or more kinds. The azo compound may, for example, be 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile) or 1,1'-azobis(cyclohexane1). - nitrile), 2,2'-azobis(2,4-dimethylcarbonitrile), 2,2'-azobis(2,4-dimethyl-4-methoxy nitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovalerate), 2,2'-azobis(2-hydroxymethyl) Propionitrile) and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].
有機過氧化物，可以例舉，苯甲酰過氧化物、t-丁基過氧化苯甲酯、過氧化氫異丙苯、過氧二碳酸二異丙基酯、過氧二碳酸二n-丙基酯、過氧二碳酸二(2-乙氧基乙基)酯、過氧新的卡酸t-丁基酯(t-butylperoxyneodecanoate)、過氧比巴酸t-丁基酯(t-butylperoxypyvalate)、(3，5，5-三甲基環戊酮基)過氧化物、二丙酰過氧化物以及二乙酰過氧化物等。 The organic peroxide may, for example, be benzoyl peroxide, t-butyl benzoyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate or din-peroxydicarbonate. Propyl ester, di(2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, peroxybutyrate t-butyl ester (t- Butylperoxypyvalate), (3,5,5-trimethylcyclopentanone) peroxide, dipropionyl peroxide, and diacetyl peroxide.
接著，將得到的聚合物(A)以及(B)的溶液混合，加入稀釋溶媒。其後，添加交聯劑(C)以及根據需要的矽烷偶聯劑(D)，充分混合，用溶媒稀釋，得到黏著性組成物(塗佈溶液)。 Next, the obtained solutions of the polymers (A) and (B) are mixed, and a diluted solvent is added. Thereafter, a crosslinking agent (C) and, if necessary, a decane coupling agent (D) are added, and the mixture is sufficiently mixed and diluted with a solvent to obtain an adhesive composition (coating solution).
將黏著性組成物稀釋成為塗佈溶液時使用的稀釋溶劑，可以例舉己烷，庚烷，環己烷等的脂肪族烴；甲苯，二甲苯等的芳香族烴；二氯甲烷，二氯乙烷等的鹵代烴；甲醇，乙醇，丙醇，丁醇，1-甲氧基2-丙醇等的醇；丙酮， 甲基乙基酮，2-戊醇，異氟而酮，環戊酮等的酮；醋酸乙基酯，醋酸丁基酯等的酯，乙基溶纖劑等的溶纖劑類溶劑等。 The diluent solvent used for diluting the adhesive composition into a coating solution may, for example, be an aliphatic hydrocarbon such as hexane, heptane or cyclohexane; an aromatic hydrocarbon such as toluene or xylene; or dichloromethane; a halogenated hydrocarbon such as ethane; an alcohol such as methanol, ethanol, propanol, butanol or 1-methoxy-2-propanol; acetone; A ketone such as methyl ethyl ketone, 2-pentanol, isoflurane or cyclopentanone; an ester such as ethyl acetate or butyl acetate; a cellosolve solvent such as ethyl cellosolve;
如此調製的塗佈溶液的濃度．黏度，只要處於塗佈可能的範圍就可以，沒有特別的限制，根據情況適宜選定即可。例如，可以將黏著性組成物的濃度稀釋為10至40質量%。並且，得到塗佈溶液時，稀釋溶劑等的添加並不是必要條件，黏著性組成物只要是可以塗佈的黏度，稀釋溶劑不添加也可。這種場合，可以用黏著性組成物直接進行塗佈。 The concentration of the coating solution thus prepared. The viscosity may be in the range of possible coating, and is not particularly limited, and may be appropriately selected depending on the circumstances. For example, the concentration of the adhesive composition can be diluted to 10 to 40% by mass. Further, when a coating solution is obtained, the addition of a diluent solvent or the like is not a requirement, and the adhesive composition may be a viscosity which can be applied, and the dilution solvent may not be added. In this case, the coating can be applied directly with the adhesive composition.
〔黏著劑〕 [adhesive]
本實施形態的黏著劑，為上述黏著性組成物交聯而得之物。上述黏著性組成物的交聯，加熱處理即可進行。並且，這種加熱處理，可以兼作使黏著性組成物的稀釋溶媒等揮發的幹燥處理。 The adhesive of the present embodiment is obtained by crosslinking the above-mentioned adhesive composition. The crosslinking of the above adhesive composition can be carried out by heat treatment. Further, this heat treatment can also serve as a drying treatment for volatilizing a diluted solvent or the like of the adhesive composition.
進行加熱處理的場合，加熱溫度，較佳為50至150℃，特佳是70至120℃。另外，加熱時間以30秒至3分為較佳，以50秒至2分為特佳。進一步，加熱處理後，設置在常溫(例如，23℃，50%RH)進行1至2周左右的熟成期為特佳。 In the case of heat treatment, the heating temperature is preferably from 50 to 150 ° C, particularly preferably from 70 to 120 ° C. Further, the heating time is preferably divided into 30 seconds to 3 minutes, and particularly preferably 50 seconds to 2 minutes. Further, after the heat treatment, it is particularly preferable to set the ripening period at a normal temperature (for example, 23 ° C, 50% RH) for about 1 to 2 weeks.
由上述的加熱處理(以及熟成)，交聯劑(C)將第2(甲基)丙烯酸酯聚合物(B)交聯，致密三維網狀構造得以形成(推測)。並且，該三維網狀構造中，2分子以上的第1(甲基)丙烯酸酯聚合物(A)不是直接的化學鍵，或 伴隨著極少的化學鍵得***，由此，該聚合物(A)被約束，形成擬似的交聯構造(推測)。另外，在第1(甲基)丙烯酸酯聚合物(A)為羧基的場合中，第1(甲基)丙烯酸酯聚合物(A)與矽烷偶聯劑(D)反應，得到的黏著劑的向液晶單元等的玻璃基板黏附時的黏著耐久性可以得以高。 By the above heat treatment (and aging), the crosslinking agent (C) crosslinks the second (meth) acrylate polymer (B), and a dense three-dimensional network structure is formed (presumed). Further, in the three-dimensional network structure, two or more molecules of the first (meth) acrylate polymer (A) are not direct chemical bonds, or Insertion with very few chemical bonds, whereby the polymer (A) is constrained to form a pseudo-crosslinked structure (presumed). Further, when the first (meth) acrylate polymer (A) is a carboxyl group, the first (meth) acrylate polymer (A) is reacted with the decane coupling agent (D) to obtain an adhesive. The adhesion durability when adhering to a glass substrate such as a liquid crystal cell can be made high.
本實施形態的黏著劑的拉伸實驗中的斷裂拉伸度，1000%以上為較佳，1500%以上為更佳，2000%以上為特佳，2500%以上為更佳。並且，上述斷裂拉伸度，是表示與基材等層疊的只有黏著劑層單獨進行測定的值。本實施形態的黏著劑有大的斷裂拉伸度，所以該黏著劑，表現出優良的應力松馳率，耐漏光性以及耐久性的兩方都優良。 In the tensile test of the adhesive of the present embodiment, the degree of elongation at break is preferably 1000% or more, more preferably 1500% or more, more preferably 2000% or more, and still more preferably 2500% or more. Further, the degree of elongation at break is a value indicating that only the pressure-sensitive adhesive layer is laminated alone with a substrate or the like. Since the adhesive of the present embodiment has a large degree of elongation at break, the adhesive exhibits excellent stress relaxation rate, excellent light leakage resistance, and durability.
上述拉伸實驗，具體地說，成形為厚度500μm，寬10mm，長75mm(其中，測定範圍為20mm)的黏著劑，在23℃，50%RH的環境下，以200mm/分的速度進行拉伸。 The above tensile test, specifically, an adhesive having a thickness of 500 μm, a width of 10 mm, and a length of 75 mm (in which the measurement range is 20 mm) was carried out at a rate of 200 mm/min in an environment of 23 ° C and 50% RH. Stretch.
並且，本實施形態的黏著劑，在進行上述的拉伸實驗時，1000%拉伸時的應力為3N以下為較佳，0.5至2.5N為特佳，另外，1500%拉伸時的應力以0.8至10N為較佳，1至5N為特佳。 Further, in the above-described tensile test, the adhesive of the present embodiment preferably has a stress at 1000% stretching of 3 N or less, more preferably 0.5 to 2.5 N, and a stress at 1500% elongation. 0.8 to 10N is preferred, and 1 to 5N is particularly preferred.
另外，本實施形態的黏著劑，凝膠比率以30至90%為較佳，以40至80%為特佳，進一步以45至75%為更佳。本實施形態的黏著劑的凝膠比率，即交聯的程度為在上述的範圍內的話，第2(甲基)丙烯酸酯聚合物(B)的交聯而成的三維網狀構造良好，黏著劑在耐漏光性以及耐久性兩方都優良。 Further, in the adhesive of the present embodiment, the gel ratio is preferably from 30 to 90%, particularly preferably from 40 to 80%, more preferably from 45 to 75%. When the gel ratio of the adhesive of the present embodiment, that is, the degree of crosslinking is within the above range, the three-dimensional network structure of the second (meth) acrylate polymer (B) is crosslinked, and the adhesion is good. The agent is excellent in both light leakage resistance and durability.
並且，黏著劑的凝膠比率，為黏付時(老化期間經過後)的值。具體地說，是將黏著性組成物在剝離片塗佈，加熱處理後，在23℃，50%RH的環境下進行7天保管後的凝膠比率。這是黏著劑的凝膠比率，老化期間經過前，其值是變動的。從這樣的觀點，如老化期間是否已經過不明的場合，再一次，在23℃，50%RH的環境下進行7天保管後，凝膠比率變為上述範圍即可。 Further, the gel ratio of the adhesive is a value at the time of sticking (after the aging period). Specifically, it is a gel ratio after the adhesive composition is applied to a release sheet and heat-treated, and then stored in an environment of 23° C. and 50% RH for 7 days. This is the gel ratio of the adhesive, and its value changes before the aging period passes. From such a viewpoint, if the aging period has not been known, the gel ratio may be changed to the above range after storage for another 7 days in an environment of 23° C. and 50% RH.
以上說明的黏著劑，作為光學部件用為較佳，例如，偏振片和相位差板的黏著，或者偏振片(偏振光薄膜)以及相位差板(相位差薄膜)和玻璃基的黏著最為適宜。上述黏著劑形成的黏著劑層，由於應力松馳率非常優良，被黏著體的尺寸變化大的場合，其尺寸變化而產生的應力可以被黏著劑層吸收．松馳，所以長期也不會從被黏著體剝離，同時如上述使用於光學部件時對漏光可以有効果地防止。即，本實施形態的黏著劑，耐漏光性和耐久性兩方可以同時達成。 The adhesive described above is preferably used as an optical member. For example, adhesion of a polarizing plate and a phase difference plate, or adhesion of a polarizing plate (polarizing film) and a phase difference plate (phase difference film) and a glass substrate are most suitable. The adhesive layer formed by the above adhesive agent is excellent in stress relaxation rate, and when the size of the adhesive body changes greatly, the stress generated by the dimensional change can be absorbed by the adhesive layer. When it is relaxed, it will not be peeled off from the adherend for a long period of time, and at the same time, it can be effectively prevented from leaking light when used as an optical member as described above. That is, the adhesive of the present embodiment can be simultaneously achieved both in light leakage resistance and durability.
〔黏著片〕 [adhesive sheet]
如圖1所示的那樣，第1實施形態的黏著片1A，以從下向上的順序，由剝離片12、剝離片12的剝離面層上疊的黏著劑層11以及黏著劑層11上層疊的基材13來構成。 As shown in Fig. 1, the adhesive sheet 1A of the first embodiment is laminated on the adhesive layer 11 and the adhesive layer 11 which are laminated on the release surface layer of the release sheet 12 and the release sheet 12 in the order from the bottom to the top. The base material 13 is constructed.
另外，圖2所示的那樣，第2實施形態的黏著片1B，包括2枚剝離片12a，12b，以及該2枚剝離片挾持的黏著劑層11來構成，由此黏著劑層11與12a，12b的剝離面相接。並且，本說明書中的所謂剝離片的剝離面包括剝離片 中有剝離性的面，實施了剝離處理的面以及即使不實施剝離處理也可以顯示出剝離性的面。 In addition, as shown in Fig. 2, the adhesive sheet 1B of the second embodiment includes two release sheets 12a and 12b and an adhesive layer 11 held by the two release sheets, whereby the adhesive layers 11 and 12a are formed. The peeling faces of 12b meet. Further, the peeling surface of the so-called release sheet in the present specification includes a release sheet. The surface having the peeling property, the surface subjected to the release treatment, and the surface which exhibits the peeling property even if the peeling treatment is not performed.
不管哪一個黏著片1A，1B所挾持的黏著劑層11，都是由上述的黏著性組成物交聯形成的黏著劑來構成的。 Regardless of which of the adhesive sheets 1A, 1B, the adhesive layer 11 is composed of an adhesive formed by crosslinking the above-mentioned adhesive composition.
黏著劑層11厚度，根據黏著片1A，1B的使用目的來適宜決定，通常為5至100μm，較佳為10至60μm的範圍，例如，作為光學部件，特別是作為偏振片用的黏著劑層使用的場合，以10至50μm，特別以10至30μm為較佳。 The thickness of the adhesive layer 11 is appropriately determined depending on the purpose of use of the adhesive sheets 1A, 1B, and is usually in the range of 5 to 100 μm, preferably 10 to 60 μm, for example, as an optical member, particularly as an adhesive layer for a polarizing plate. In the case of use, it is preferably 10 to 50 μm, particularly preferably 10 to 30 μm.
作為基材13，沒有特別限制，通常的作為黏著片的基材片使用的都可以使用，可以例舉根據需要而使用的光學部件之外，用人造絲、丙烯酸、聚酯等的纖維的紡織布或者無紡布；上質紙，玻璃紙，含浸紙，塗佈紙等的紙類；鋁，銅等的金屬箔；氨酯發泡體、聚乙烯發泡體等的發泡體；聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘酸乙醇酯等的聚酯薄膜；聚氨酯薄膜；聚乙烯薄膜；聚丙烯薄膜；三乙酰纖維素等的纖維素薄膜；聚二氯乙烯薄膜；聚氯化偏乙烯薄膜；聚乙烯基醇薄膜；乙烯醋酸乙烯基酯共聚合物薄膜；聚苯乙烯薄膜；聚碳酸酯薄膜；丙烯酸樹脂薄膜；聚冰片烯類樹脂薄膜；環烯烴樹脂薄膜等的塑料薄膜；這些的2種以上的層疊體等。塑料薄膜，一軸壓延或者二軸壓延之物也可。 The base material 13 is not particularly limited, and it can be used as a base material sheet for an adhesive sheet. For example, textiles made of rayon, acrylic, polyester, or the like may be used in addition to the optical members used as needed. Cloth or non-woven fabric; paper for upper quality paper, cellophane, impregnated paper, coated paper, etc.; metal foil of aluminum, copper, etc.; foam of urethane foam, polyethylene foam, etc.; Polyester film of ethylene glycol dicarboxylate, polybutylene terephthalate, polyethylene naphthalate, etc.; polyurethane film; polyethylene film; polypropylene film; cellulose film of triacetyl cellulose; Dichloroethylene film; polychloroethylene vinyl film; polyvinyl alcohol film; ethylene vinyl acetate copolymer film; polystyrene film; polycarbonate film; acrylic film; polybornene resin film; A plastic film such as an olefin resin film; or a laminate of two or more of these. Plastic film, one-axis rolling or two-axis rolling may also be used.
作為光學部件，可以例舉偏振片(偏振光薄膜)、偏光子、相位差板(相位差薄膜)、視角補償薄膜、亮度提 高薄膜、對比性提高薄膜、液晶聚合物薄膜等。其中，偏振片(偏振光薄膜)，易於收縮，尺寸變化大，從耐漏光性的觀點，作為本實施形態的黏著劑(上述黏著劑層11)的使用對象非常適宜。 The optical member may, for example, be a polarizing plate (polarized light film), a polarizer, a phase difference plate (phase difference film), a viewing angle compensation film, or a brightness enhancement. High film, contrast improving film, liquid crystal polymer film, and the like. Among them, the polarizing plate (polarizing film) is easy to shrink and has a large dimensional change, and is excellent in the use of the adhesive (the above-mentioned adhesive layer 11) of the present embodiment from the viewpoint of light leakage resistance.
基材13的厚度，根據其種類不同，例如在光學部件的場合，通常為10μm至500μm，較佳為50μm至300μm。 The thickness of the substrate 13 varies depending on the type thereof, and is, for example, in the case of an optical member, usually 10 μm to 500 μm, preferably 50 μm to 300 μm.
作為剝離片12，12a，12b，可以例舉聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯代乙烯薄膜、氯代乙烯共聚合物薄膜、聚對苯二甲酸乙二醇酯薄膜、聚萘酸乙醇酯薄膜、聚對苯二甲酸丁二醇酯薄膜、聚氨酯薄膜、乙烯醋酸乙烯基酯薄膜、離子鍵聚合物樹脂薄膜、乙烯．(甲基)丙烯酸共聚合物薄膜、乙烯．(甲基)丙烯酸酯共聚合物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚酰亞胺薄膜以及氟樹脂薄膜等。另外，這些物質的交聯薄膜也可以使用。進一步，這些物質的疊層薄膜也可使用。 Examples of the release sheets 12, 12a, and 12b include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a chloroethylene copolymer. Film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene. (meth)acrylic copolymer film, ethylene. (Meth) acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, and the like. Further, a crosslinked film of these materials can also be used. Further, a laminated film of these materials can also be used.
上述剝離片的剝離面(特別是與黏著劑層11相接的面)中，較佳為實施剝離處理。剝離處理所使用的剝離劑，可以例舉醇酸類、矽氧烷類、氟類化合物、不飽和聚酯類、聚烯烴類以及蠟類剝離劑。 In the release surface of the release sheet (particularly the surface in contact with the adhesive layer 11), it is preferred to carry out a release treatment. The release agent used for the release treatment may, for example, be an alkyd, a siloxane, a fluorine compound, an unsaturated polyester, a polyolefin or a wax release agent.
剝離片12，12a，12b的厚度沒有特別的限制，通常為20至150μm左右。 The thickness of the release sheets 12, 12a, 12b is not particularly limited and is usually about 20 to 150 μm.
上述黏著片1A的製造，為在剝離片12剝離面上，進行含有上述黏著性組成物的溶液(塗佈溶液)的塗佈，進 行加熱處理，黏著劑層11形成後，在該黏著劑層11上層疊基材13。其後，設置熟成期間為較佳。 The adhesive sheet 1A is produced by coating a solution (coating solution) containing the above-mentioned adhesive composition on the release surface of the release sheet 12 After the heat treatment, the adhesive layer 11 is formed, and the substrate 13 is laminated on the adhesive layer 11. Thereafter, it is preferred to set the ripening period.
並且，關於加熱處理以及熟成的條件，如上述。 Further, the conditions of the heat treatment and the ripening are as described above.
另外，上述黏著片1B的製造，是一個剝離片12a(或者12b)的剝離面，將上述含有黏著性組成物的塗佈溶液進行塗佈，進行加熱處理，黏著劑層11形成後，在該黏著劑層11上將另一個將剝離片12b(或者12a)的剝離面重合上。 Further, the adhesive sheet 1B is produced by peeling a release sheet 12a (or 12b), applying the coating solution containing the adhesive composition, and performing heat treatment. After the adhesive layer 11 is formed, the adhesive sheet 11 is formed. On the adhesive layer 11, the other peeling surface of the release sheet 12b (or 12a) is superposed.
作為上述塗佈溶液的塗佈的方法，可以例舉輥塗佈法，刮刀塗佈法，輥塗佈法，刮刀塗佈法，加壓塗佈法，凹版塗佈法等。 The method of applying the coating solution may, for example, be a roll coating method, a knife coating method, a roll coating method, a knife coating method, a pressure coating method, a gravure coating method, or the like.
在此，例如，在由液晶單元和偏振片構成的液晶表示裝置的製造中，作為黏著片1A的基材13，使用偏振片，將該黏著片1A的剝離片12剝離，將露出的黏著劑層11與液晶單元貼合即可。 Here, for example, in the production of a liquid crystal display device comprising a liquid crystal cell and a polarizing plate, a polarizing plate is used as the substrate 13 of the adhesive sheet 1A, and the release sheet 12 of the adhesive sheet 1A is peeled off to expose the adhesive. The layer 11 can be attached to the liquid crystal cell.
另外，例如，關於液晶單元和偏振片之間配置相位差板而成的液晶表示裝置的製造，作為一例，首先，黏著片1B的一方的剝離片12a(或者12b)剝離，將黏著片1B的露出的黏著劑層11與相位差板貼合。接著，作為基材13使用偏光板的黏著片1A的剝離片12剝離，黏著片1A的露出的黏著劑層11和上述相位差板貼合。進一步，從上述的黏著片B的黏著劑層11將另一剝離片12b(或者12a)剝離，將黏著片B的露出的黏著劑層11與液晶單元貼合。 Further, for example, in the production of a liquid crystal display device in which a retardation plate is disposed between a liquid crystal cell and a polarizing plate, as an example, first, one of the release sheets 12a (or 12b) of the adhesive sheet 1B is peeled off, and the adhesive sheet 1B is peeled off. The exposed adhesive layer 11 is bonded to the phase difference plate. Next, the release sheet 12 of the adhesive sheet 1A using the polarizing plate as the base material 13 is peeled off, and the exposed adhesive layer 11 of the adhesive sheet 1A is bonded to the retardation plate. Further, the other release sheet 12b (or 12a) is peeled off from the adhesive layer 11 of the above-mentioned adhesive sheet B, and the exposed adhesive layer 11 of the adhesive sheet B is bonded to the liquid crystal cell.
以上的黏著片1A，1B的黏著劑層11的應力松馳率非 常優良，例如在適用於偏振片的黏著的場合，偏振片的變形而產生的應力可以被黏著劑層11吸收．松馳，由此可以發揮優良的耐漏光性以及高的耐久性(推測)。 The stress relaxation rate of the adhesive layer 11 of the above adhesive sheets 1A, 1B is not Often excellent, for example, when applied to the adhesion of a polarizing plate, the stress generated by the deformation of the polarizing plate can be absorbed by the adhesive layer 11. By relaxing, it is possible to exhibit excellent light leakage resistance and high durability (presumed).
以上說明的實施形態，是為了使本發明更容易理解，並不對本發明構成限定。所以，上述實施形態記載的各要素，包括屬於本發明的技術的範圍的所有的設計變更以及等同物。 The embodiments described above are intended to facilitate the understanding of the present invention and are not intended to limit the invention. Therefore, each element described in the above embodiments includes all design changes and equivalents within the scope of the technology of the present invention.
例如，黏著片1A的剝離片12可以省略，黏著片1B中的剝離片12a，12b的一方也可以省略。 For example, the release sheet 12 of the adhesive sheet 1A can be omitted, and one of the release sheets 12a, 12b in the adhesive sheet 1B can be omitted.
以下，用實例等對本發明進行進一步的具體說明，本發明的範圍並不限於這些的實例等。 Hereinafter, the present invention will be further specifically described by way of examples and the like, and the scope of the present invention is not limited to the examples and the like.
〔實例1〕 [Example 1]
1.聚合物(A)的調製 1. Modulation of polymer (A)
向帶有攪拌機，溫度計，還流冷卻器，滴下裝置以及氮導入管的反應容器中，加入丙烯酸n-丁基酯95.0質量份，丙烯酸5.0質量份，醋酸乙基酯200質量份，以及2，2’-偶氮雙異丁腈0.08質量份。上述反應容器內的空氣用氮氣置換。在這種氮氛圍氣下一邊攪拌，一邊將反應溶液升溫至60℃，16小時反應後，冷卻至室溫。在此，將得到的溶液的一份用下述的方法GPC進行測定，確認到重量平均分子量150萬的聚合物(A)被生成。 To a reaction vessel equipped with a stirrer, a thermometer, a reflow cooler, a dropping device, and a nitrogen introduction tube, 95.0 parts by mass of n-butyl acrylate, 5.0 parts by mass of acrylic acid, 200 parts by mass of ethyl acetate, and 2, 2 were added. '-Azobisisobutyronitrile 0.08 parts by mass. The air in the above reaction vessel was replaced with nitrogen. The reaction solution was heated to 60 ° C while stirring under such a nitrogen atmosphere, and after 16 hours of reaction, it was cooled to room temperature. Here, a part of the obtained solution was measured by the following method GPC, and it was confirmed that the polymer (A) having a weight average molecular weight of 1.5 million was formed.
2.聚合物(B)的調製 2. Modulation of polymer (B)
向具有攪拌機，溫度計，還流冷卻器，滴下裝置以及氮導入管的反應容器中，加入丙烯酸n-丁基酯75.0質量份，丙烯酸2-羥基乙基酯15.0質量份，丙烯酸苯氧乙基酯10.0質量份，醋酸乙基酯200質量份，2，2’-偶氮雙異丁腈0.16質量份，以及2-巰基乙醇0.3質量份。上述反應容器內的空氣用氮氣置換。在這種氮氛圍氣下邊攪拌，邊將反應溶液升溫至70℃，進行6小時反應後，冷卻到室溫。在此，將得到的溶液的一份用下述的方法進行GPC測定，確認到重量平均分子量為6萬的聚合物(B)被生成。 To a reaction vessel having a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen introduction tube, 75.0 parts by mass of n-butyl acrylate, 15.0 parts by mass of 2-hydroxyethyl acrylate, and phenoxyethyl acrylate 10.0 were added. Parts by mass, 200 parts by mass of ethyl acetate, 0.16 parts by mass of 2,2'-azobisisobutyronitrile, and 0.3 parts by mass of 2-mercaptoethanol. The air in the above reaction vessel was replaced with nitrogen. The reaction solution was heated to 70 ° C while stirring under such a nitrogen atmosphere, and after reacting for 6 hours, it was cooled to room temperature. Here, a part of the obtained solution was subjected to GPC measurement by the following method, and it was confirmed that a polymer (B) having a weight average molecular weight of 60,000 was formed.
3.黏著性組成物的調製 3. Modulation of adhesive composition
將在上述工序(1)中得到的聚合物(A)100質量份(固體成分換算值)和在上述工序(2)中得到的聚合物(B)15質量份(固體成分換算值)混合後，作為交聯劑(C)，添加相當於聚合物(B)的羥基的0.6當量的三羥甲基丙烷的亞芐基二異氰酸酯(TDI類)加成物(日本聚氨酯公司製，商品名「(CORONATE)L」)1.7質量份。最後，作為矽烷偶聯劑(D)，3-環氧丙氧基丙基三甲氧基矽烷(信越化學工業公司製，商品名「KBM403」)0.2質量份添加，充分攪拌，得到黏著性組成物的稀釋溶液。 100 parts by mass (solid content converted value) of the polymer (A) obtained in the above step (1) and 15 parts by mass (solid content converted value) of the polymer (B) obtained in the above step (2) are mixed. To the crosslinking agent (C), a benzylidene diisocyanate (TDI-based) adduct of 0.6 equivalents of trimethylolpropane corresponding to the hydroxyl group of the polymer (B) (manufactured by Nippon Polyurethane Co., Ltd., trade name " (CORONATE) L") 1.7 parts by mass. Finally, 0.2 parts by mass of 3-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM403") was added as a decane coupling agent (D), and the mixture was sufficiently stirred to obtain an adhesive composition. Diluted solution.
在此，該黏著性組成物的配比如表1所示。並且，表1中記載的略號等的意思如下。 Here, the composition of the adhesive composition is shown in Table 1. Further, the meanings of the abbreviations and the like described in Table 1 are as follows.
[聚合物(A)以及(B)] [Polymer (A) and (B)]
BA：丙烯酸n-丁基酯 BA: n-butyl acrylate
AA：丙烯酸 AA: Acrylic
HEA：丙烯酸2-羥基乙基酯 HEA: 2-hydroxyethyl acrylate
PhEA：丙烯酸苯氧乙基酯 PhEA: phenoxyethyl acrylate
BzA：丙烯酸芐基酯 BzA: benzyl acrylate
[可塑劑] [plasticizer]
．ADEKASIZER-C-8：偏苯三酸酯類可塑劑(三(2-乙基己基)偏苯三酸酯)(旭電化工業公司製，商品名「ADEKASIZER-C-8) . ADEKASIZER-C-8: trimellitate plasticizer (tris(2-ethylhexyl) trimellitate) (made by Asahi Kasei Kogyo Co., Ltd., trade name "ADEKASIZER-C-8")
[交聯劑(C)] [Crosslinking agent (C)]
．異氰酸酯類交聯劑 . Isocyanate crosslinker
CORONATE-L：三羥甲基丙烷的亞芐基二異氰酸酯加成物(日本聚氨酯公司製，商品名：CORONATE-L) CORONATE-L: a benzylidene diisocyanate adduct of trimethylolpropane (manufactured by Nippon Polyurethane Co., Ltd., trade name: CORONATE-L)
TAKENATE-D-110N：三羥甲基丙烷的二甲苯二異氰酸酯加成物(三井化學聚氨酯公司製，商品名：TAKENATE)D-110N) TAKENATE-D-110N: a xylene diisocyanate adduct of trimethylolpropane (manufactured by Mitsui Chemicals, Inc., trade name: TAKENATE) D-110N)
[矽烷偶聯劑(D)] [Hydrane coupling agent (D)]
KBM403：3-環氧丙氧基丙基三甲氧基矽烷(信越化學工業公司製，商品名：KBM403) KBM403: 3-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM403)
KBE9007：3-異氰酸酯丙基三乙氧基矽烷(信越化學工業公司製，商品名：KBE9007) KBE9007: 3-isocyanate propyl triethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE9007)
刮刀塗佈機將得到的黏著性組成物的稀釋溶液，塗佈在對聚對苯二甲酸乙二醇酯薄膜的單面用矽氧烷類剝離劑進行了剝離處理的剝離片(琳得科公司製，SP-PET3811，厚度：38μm)的剝離處理面上，該塗佈要使幹燥後的厚度 為25μm，此後90℃進行1分鐘加熱處理，黏著劑層形成。 A dilute solution of the obtained adhesive composition was applied to a release sheet which was subjected to a release treatment on a single side of a polyethylene terephthalate film with a decane-based release agent by a knife coater (Lindeke). The company's system, SP-PET3811, thickness: 38μm) on the peeling surface, the coating should be made after drying It was 25 μm, and then heat treatment was performed at 90 ° C for 1 minute, and an adhesive layer was formed.
接著，將由帶有圓盤液晶層的偏振光薄膜構成的，偏振光薄膜和視角擴大薄膜一體化的偏振片進行貼合，由此使黏著劑層和圓盤液晶層相接，23℃，50%RH進行7天熟成，得到具有黏著劑層的偏振片。 Next, the polarizing film composed of the polarizing film with the disk liquid crystal layer and the polarizing film integrated with the viewing angle expanding film are bonded together, thereby bonding the adhesive layer and the liquid crystal layer of the disk, 23 ° C, 50 The %RH was aged for 7 days to obtain a polarizing plate having an adhesive layer.
〔實例2至16，比較例1至2〕 [Examples 2 to 16, Comparative Examples 1 to 2]
除了將構成黏著性組成物的各單體的種類以及比率，交聯劑以及矽烷偶聯劑的種類以及添加量，聚合物(A)以及聚合物(B)的組成比如表1所示那樣變更的以外，於實例1同樣，製造具有黏著劑層的偏振片。 The composition of the polymer (A) and the polymer (B) was changed as shown in Table 1, except for the type and ratio of each monomer constituting the adhesive composition, the type and amount of the crosslinking agent and the decane coupling agent. In the same manner as in Example 1, a polarizing plate having an adhesive layer was produced.
在此，上述的重量平均分子量(Mw)，是用凝膠滲透色譜(GPC)按以下的條件進行測定(GPC測定)的聚苯乙烯換算的重量平均分子量。 Here, the weight average molecular weight (Mw) is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions (GPC measurement).
<測定條件> <Measurement conditions>
．GPC測定裝置：Tosoh公司製，HLC-8020 . GPC measuring device: manufactured by Tosoh Corporation, HLC-8020
．GPC柱(按以下的順序通過)：Tosoh公司製 . GPC column (passed in the following order): made by Tosoh
TSK guard column HXL-H TSK guard column HXL-H
TSK gel GMHXL(×2) TSK gel GMHXL (×2)
TSK gel G2000HXL TSK gel G2000HXL
．測定溶媒：四氫呋喃 . Determination of solvent: tetrahydrofuran
．測定溫度：40℃ . Measuring temperature: 40 ° C
〔實驗例1〕(凝膠比率的測定) [Experimental Example 1] (Measurement of gel ratio)
將在實例或者比較例的製造帶有黏著劑層的偏振片的製作中使用偏振片換掉，使用聚對苯二甲酸乙二醇酯薄 膜的單面用矽氧烷類剝離劑進行了剝離處理的剝離片(琳得科公司製，SP-PET3801，厚度：38μm)，製作黏著片。具體地說，就是將在實例或者比較例的製造過程得到的由剝離片/黏著劑層(厚度：25μm)構成的構成體的露出的黏著劑層上，層疊上上述剝離片(要使剝離處理面與黏著劑層相接)。由此，製得由剝離片/黏著劑層/剝離片的順序構成的黏著片。 The polarizing plate will be replaced in the production of a polarizing plate with an adhesive layer in the example or the comparative example, using polyethylene terephthalate thin. A release sheet (SP-PET3801, thickness: 38 μm, manufactured by Linde Co., Ltd.) which was subjected to a release treatment with a phthalic acid-based release agent on one side of the film was prepared to prepare an adhesive sheet. Specifically, the release sheet is laminated on the exposed adhesive layer of the structure composed of the release sheet/adhesive layer (thickness: 25 μm) obtained in the production process of the example or the comparative example (to be peeled off) The surface is in contact with the adhesive layer). Thus, an adhesive sheet composed of the release sheet/adhesive layer/release sheet in this order was obtained.
得到的黏著片，23℃，50%RH的條件下進行7天熟成。其後，該黏著片做成80mm×80mm尺寸的試樣，其黏著劑層用聚酯製網(網尺寸200)包上，僅對黏著劑的質量用精密天平秤量。將這時的質量作為M1。 The obtained adhesive sheet was aged for 7 days under conditions of 23 ° C and 50% RH. Thereafter, the adhesive sheet was made into a sample having a size of 80 mm × 80 mm, and the adhesive layer was wrapped with a polyester mesh (mesh size 200), and only the quality of the adhesive was weighed with a precision balance. Take the quality at this time as M1.
接著，將包在上述聚酯製網中的黏著劑，室溫下(23℃)，在醋酸乙基酯中進行24小時浸漬。其後將黏著劑取出，在溫度23℃，相對濕度50%的環境下，24小時風幹，進一步在80℃的烘箱中進行12小時幹燥。僅對幹燥後的黏著劑的質量用精密天平秤量。將這時的質量作為M2。凝膠比率(%)用(M2/M1)×100計算。結果如表2所示。 Next, the adhesive wrapped in the above polyester web was immersed in ethyl acetate for 24 hours at room temperature (23 ° C). Thereafter, the adhesive was taken out, air-dried at a temperature of 23 ° C and a relative humidity of 50% for 24 hours, and further dried in an oven at 80 ° C for 12 hours. Only the quality of the dried adhesive is weighed with a precision balance. Take the quality at this time as M2. The gel ratio (%) was calculated by (M2/M1) × 100. The results are shown in Table 2.
〔實驗例2〕(光學性能的測定) [Experimental Example 2] (Measurement of optical properties)
作為測定試樣，準備與凝膠比率的測定時使用的黏著片同樣的黏著片(進行了7天熟成)。關於該黏著片的黏著劑層，用海斯(Haze)儀(日本電色工業公司製，NDH2000)，按照JIS K7105進行海斯(Haze)值(%)(也可略稱為Hz(%))。結果如表2所示。並且，較佳海斯(Haze)值的範圍為0至5%。 As the measurement sample, an adhesive sheet similar to the adhesive sheet used for the measurement of the gel ratio was prepared (cooked for 7 days). With regard to the adhesive layer of the adhesive sheet, a Haze value (%) is also performed in accordance with JIS K7105 using a Haze instrument (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) (may also be abbreviated as Hz (%) ). The results are shown in Table 2. Also, a preferred Haze value ranges from 0 to 5%.
〔實驗例3〕(耐漏光性實驗) [Experimental Example 3] (Light leakage resistance test)
將在實例或者比較例中得到的具有黏著劑層的偏振片，用裁斷裝置(荻野製作所公司製超級刀，PN1-600)製成233mm×309mm尺寸的試樣。將剝離片剝離，介於露出的黏著劑層，黏付於無堿玻璃(康寧公司製，鷹XG)，此後，用栗原製作所製高壓釜進行0.5MPa，50℃下，進行20分加壓。並且，上述貼合，在無堿玻璃的表裏，要使具有黏著劑層的偏振片成偏光軸為尼科爾十字狀態(偏光軸：∠45°，∠135°)。這種狀態，80℃幹燥環境下進行250小時放置。此後，在23℃，50%RH的環境下進行2小時放置，以此為試樣，用以下所示的方法進行漏光性的評價。結果如表2所示。 A polarizing plate having an adhesive layer obtained in the examples or the comparative examples was molded into a sample having a size of 233 mm × 309 mm by a cutting device (Super Knife, manufactured by Takino Seisakusho Co., Ltd., PN1-600). The release sheet was peeled off, and the exposed adhesive layer was adhered to an aluminum-free glass (Eagle XG, manufactured by Corning Co., Ltd.). Thereafter, the autoclave made by Kurihara Co., Ltd. was subjected to 0.5 MPa, and at 50 ° C, pressure was applied for 20 minutes. Further, in the above-described bonding, in the surface of the enamel-free glass, the polarizing plate having the adhesive layer has a polarization axis in a Nicols cross state (polarizing axis: ∠45°, ∠135°). In this state, it was placed in a dry environment at 80 ° C for 250 hours. Thereafter, the film was allowed to stand for 2 hours in an environment of 23° C. and 50% RH, and this was used as a sample, and the light leakage property was evaluated by the method shown below. The results are shown in Table 2.
<漏光性評價：△L*> <Light leakage evaluation: △L*>
用大冢電子公司製的MCPD-2000，對上述試樣中的圖3所示各領域的明度L*進行測定，明度差△L*，用下式進行計算：△L*=〔(b+c+d+e)/4〕-a(但是，a，b，c，d以及e，分別為A領域，B領域，C領域，D領域以及E領域的預先規定的測定點(各領域的中央部1處)中的明度)，將其作為漏光性。△L*的值越小，漏光越少。並且，L*max，為上述全部領域中的最大的明度。 Using the MCPD-2000 manufactured by Otsuka Electronics Co., Ltd., the brightness L* of each field shown in Fig. 3 in the above sample was measured, and the difference in brightness was ΔL*, which was calculated by the following formula: ΔL* = [(b+ c+d+e)/4]-a (however, a, b, c, d, and e are pre-specified measurement points in the A field, B field, C field, D field, and E field, respectively (in each field) Lightness in one of the central parts) is used as light leakage. The smaller the value of ΔL*, the less light leakage. Moreover, L*max is the maximum brightness in all of the above fields.
<漏光性評價：目視> <Light leakage evaluation: visual inspection>
將上述試樣設置在平板照明燈(電通產業公司製， HF-SL-A312LC，照度：26，000Lux，亮度：10，000cd)上，用二維色彩亮度計(可尼卡美能達公司製，CA-2000)進行撮影，用解析軟件(可尼卡美能達公司製，CA-S20w)變換成亮度分布圖像。得到的試樣的亮度分布圖像，按圖4所示評價基準評價。 The above sample was set in a flat panel lighting lamp (manufactured by Dentsu Industry Co., Ltd. HF-SL-A312LC, illuminance: 26,000 Lux, brightness: 10,000 cd), using a two-dimensional color luminance meter (manufactured by Konica Minolta, CA-2000) for shadowing, using analysis software (Konica Minolta) The company system, CA-S20w) is transformed into a brightness distribution image. The luminance distribution image of the obtained sample was evaluated according to the evaluation criteria shown in Fig. 4 .
〔實驗例4〕(耐久性評價) [Experimental Example 4] (Durability Evaluation)
將實例或者比較例中得到的具有黏著劑層的偏振片，用裁斷裝置(荻野製作所公司製超級刀，PN1-600)調整為233mm×309mm尺寸調整。將剝離片進行剝離，介於露出的黏著劑層，黏付於無堿玻璃(康寧公司製，鷹XG)之後，在栗原製作所製高壓釜中在0.5MPa，50℃下，進行20分加壓。 The polarizing plate having the adhesive layer obtained in the example or the comparative example was adjusted to a size of 233 mm × 309 mm by a cutting device (Super Knife, manufactured by Takino Seisakusho Co., Ltd., PN1-600). The release sheet was peeled off, and the exposed adhesive layer was adhered to the flawless glass (manufactured by Corning Co., Ltd., Eagle XG), and then subjected to pressurization at 0.5 MPa and 50 ° C in an autoclave manufactured by Kurihara Seisakusho Co., Ltd. .
其後，投入到下述的各耐久條件的環境下，500小時後用10倍放大鏡進行觀察。外觀變化以以下為基準。結果如表2所示。 Thereafter, the mixture was placed in an environment of each of the following durability conditions, and after 500 hours, it was observed with a magnifying glass of 10 times. Appearance changes are based on the following. The results are shown in Table 2.
◎：4邊中，無問題 ◎: 4 sides, no problem
○：4邊中，從外周端部到0.6mm以上的部位無問題 ○: There are no problems in the four sides from the outer peripheral end to the 0.6 mm or more.
×：4邊的至少1邊中，外周端部到0.6mm以上的部位，有浮起，剝離，發泡，條紋等的0.1mm以上的黏著劑的外觀異常 In the case where at least one of the four sides is at least one side, the outer peripheral end portion is at least 0.6 mm or more, and the appearance of the adhesive of 0.1 mm or more, such as floating, peeling, foaming, and streaking, is abnormal.
<耐久條件> <endurance condition>
．80℃幹燥 . Dry at 80 ° C
．60℃，相對濕度90%RH . 60 ° C, relative humidity 90% RH
〔實驗例5〕(拉伸實驗) [Experimental Example 5] (tensile experiment)
將單面用矽氧烷類剝離劑進行了剝離處理的聚對苯二甲酸乙二醇酯剝離片(琳得科公司製，SP-PET3811)的剝離處理面塗佈在實例以及比較例調製的黏著性組成物，幹燥後的塗佈厚度為25μm，100℃進行1分鐘加熱，形成黏著劑層。其黏著劑層和別的聚對苯二甲酸乙二醇酯剝離片(琳得科公司製，SP-PET3801)的剝離處理面貼合，得到黏著片。 The peeling-treated surface of a polyethylene terephthalate release sheet (SP-PET3811, manufactured by Linde Co., Ltd.) which was subjected to a release treatment with a decane-based release agent on one side was applied to the examples and comparative examples. The adhesive composition was applied to a thickness of 25 μm after drying, and heated at 100 ° C for 1 minute to form an adhesive layer. The adhesive layer was bonded to a peeling-treated surface of another polyethylene terephthalate release sheet (SP-PET3801 manufactured by Linde Co., Ltd.) to obtain an adhesive sheet.
將上述黏著劑層進行多層層疊，使上述黏著片中的黏著劑層的合計厚度為500μm，並且僅層疊體的最表層的剝離片留下，在23℃，50%RH的氛圍氣下放置2周。其後，從上述黏著劑層多層層疊的黏著片切出10mm寬×75mm長的試樣，將層疊在層疊體的最表層的剝離片剝離，安裝試樣，使其測定範圍為10mm寬×20mm長，23℃，50%RH的環境下用拉伸實驗機(奧瑞公司製，tensilon)以200mm/分的拉伸速度拉伸，對1000%伸長時，1500%伸長時，2000%伸長時以及2500%伸長時的應力(N)進行測定。結果如表2所示。 The adhesive layer was laminated in multiple layers so that the total thickness of the adhesive layer in the adhesive sheet was 500 μm, and only the outermost release sheet of the laminate was left, and placed under an atmosphere of 23 ° C and 50% RH. week. Thereafter, a sample having a thickness of 10 mm and a length of 75 mm was cut out from the adhesive sheet in which the pressure-sensitive adhesive layer was laminated, and the release sheet laminated on the outermost layer of the laminate was peeled off, and the sample was attached to have a measurement range of 10 mm wide by 20 mm. Long, 23 ° C, 50% RH environment was stretched at a tensile speed of 200 mm/min using a tensile tester (tensilon), for 1000% elongation, 1500% elongation, 2000% elongation. And the stress (N) at 2500% elongation was measured. The results are shown in Table 2.
從表2可以明確得知，實例中得到的具有黏著劑層的偏振片中，黏著劑即使1000%以上拉伸，其應力也小，斷裂拉伸度超過2500%，耐漏光性以及耐久性的都優良。另一方面，比較例中得到的具有黏著劑層的偏振片中，黏著劑的斷裂拉伸度為1000%未滿，或者雖然黏著劑可以伸長1000%，但此時的應力與實例相比其值要大，並且耐漏光性低下，另外耐久性不充分。並且，比較例中的黏著劑，都在1500%伸長前斷裂。 It can be clearly seen from Table 2 that in the polarizing plate having an adhesive layer obtained in the examples, even if the adhesive is stretched by 1000% or more, the stress is small, the tensile elongation at break exceeds 2500%, and the light leakage resistance and durability are improved. All are fine. On the other hand, in the polarizing plate having the adhesive layer obtained in the comparative example, the elongation at break of the adhesive is 1000% or less, or although the adhesive can be elongated by 1000%, the stress at this time is compared with the example. The value is large, and the light leakage resistance is low, and the durability is insufficient. Further, the adhesive in the comparative example was broken before the 1500% elongation.
本發明的黏著性組成物以及黏著劑，光學部件適宜於例如偏振片以及相位差板的黏結，另外，本發明的黏著片，作為偏振片以及相位差板等的光學部件用的黏著片，適宜。 In the adhesive composition and the adhesive of the present invention, the optical member is suitable for bonding, for example, a polarizing plate and a phase difference plate, and the adhesive sheet of the present invention is suitable as an adhesive sheet for optical members such as a polarizing plate and a phase difference plate. .
1A，1B‧‧‧黏著片 1A, 1B‧‧‧Adhesive tablets
11‧‧‧黏著劑層 11‧‧‧Adhesive layer
12，12a，12b‧‧‧剝離片 12,12a,12b‧‧‧ peeling film
13‧‧‧基材 13‧‧‧Substrate
圖1本發明的第1實施形態的黏著片的剖面圖。 Fig. 1 is a cross-sectional view showing an adhesive sheet according to a first embodiment of the present invention.
圖2本發明的第2實施形態的黏著片的剖面圖。 Fig. 2 is a cross-sectional view showing an adhesive sheet according to a second embodiment of the present invention.
圖3表示具有黏著劑層附的偏振片中的耐漏光性實驗的測定領域的圖。 Fig. 3 is a view showing the field of measurement of the light leakage resistance test in the polarizing plate with the adhesive layer attached.
圖4附有黏著劑層的偏振片中的耐漏光性實驗(目視)的評價基準的表示圖。 Fig. 4 is a view showing the evaluation criteria of the light leakage resistance test (visual) in the polarizing plate to which the adhesive layer is attached.
1A‧‧‧黏著片 1A‧‧‧Adhesive tablets
11‧‧‧黏著劑層 11‧‧‧Adhesive layer
12‧‧‧剝離片 12‧‧‧ peeling film
13‧‧‧基材 13‧‧‧Substrate
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| CN105848879B (en) * | 2013-12-27 | 2018-05-11 | 日本瑞翁株式会社 | Optical laminates and planar light source device |
| CN106414644B (en) * | 2015-03-20 | 2018-04-17 | 东洋油墨Sc控股株式会社 | Sticker and adhesive tape |
| KR102047288B1 (en) * | 2015-12-10 | 2019-11-21 | 주식회사 엘지화학 | Pressure sensitive adhesive composition |
| KR102024256B1 (en) | 2016-09-23 | 2019-11-04 | 주식회사 엘지화학 | Pressure sensitive adhsive composition |
| JP6307189B2 (en) * | 2017-03-02 | 2018-04-04 | リンテック株式会社 | Adhesive composition, adhesive and adhesive sheet |
| JP2022179185A (en) * | 2021-05-21 | 2022-12-02 | 日東電工株式会社 | Adhesive sheet, optical laminate and image display device |
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| JP3533589B2 (en) * | 1997-04-09 | 2004-05-31 | 綜研化学株式会社 | Pressure-sensitive adhesive composition for polarizing plate and polarizing plate |
| JP2000109771A (en) * | 1998-10-07 | 2000-04-18 | Lintec Corp | Adhesive sheet |
| JP4072309B2 (en) * | 2000-10-13 | 2008-04-09 | 日本カーバイド工業株式会社 | Adhesive composition for polarizing film and polarizing film |
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