TW201443182A - Adhesive composition, adhesive and adhesive sheet - Google Patents
Adhesive composition, adhesive and adhesive sheet Download PDFInfo
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- TW201443182A TW201443182A TW103106696A TW103106696A TW201443182A TW 201443182 A TW201443182 A TW 201443182A TW 103106696 A TW103106696 A TW 103106696A TW 103106696 A TW103106696 A TW 103106696A TW 201443182 A TW201443182 A TW 201443182A
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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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C09J7/00—Adhesives in the form of films or foils
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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]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/205—Compounds containing groups, e.g. carbamates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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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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- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本發明是關於一種黏接性組合物、黏接劑(使黏接性組合物架橋的材料)以及黏接片，特別是關於一種適合作為光學構件用的黏接性組合物、黏接劑以及黏接片。 The present invention relates to an adhesive composition, an adhesive (a material for bridging an adhesive composition), and an adhesive sheet, and more particularly to an adhesive composition suitable for use as an optical member, an adhesive, and Adhesive sheet.
近年在各種電子設備中，多使用兼具顯示裝置與輸入手段的觸控面板。觸控面板的種類主要有電阻式、電容式、光學式以及超聲波式。電阻式觸控面板有模擬數據電阻式以及母體電阻式。電容式觸控面板有表面型以及投影型。 In recent years, in various electronic devices, a touch panel having both a display device and an input means has been frequently used. The types of touch panels are mainly resistive, capacitive, optical, and ultrasonic. The resistive touch panel has analog data resistance and mother resistance. The capacitive touch panel has a surface type and a projection type.
最近受到注目的智慧手機、平板電腦終端等移動式電子設備的觸控面板，多使用投影型電容式的觸控面板。作為上述移動電子機器的投影型電容式觸控面板，例如，有研究提出了從下向上按順序積層液晶顯示裝置(LCD)、黏接劑層、透明導電膜(氧化銦錫：ITO)、玻璃基板、透明導電膜(ITO)、及強化玻璃等保護層的觸控面板。 The touch panel of mobile electronic devices such as smart phones and tablet terminals that have recently attracted attention has mostly used projection type capacitive touch panels. As a projection type capacitive touch panel of the above mobile electronic device, for example, research has been proposed to laminate a liquid crystal display device (LCD), an adhesive layer, a transparent conductive film (indium tin oxide: ITO), and glass in order from bottom to top. A touch panel of a protective layer such as a substrate, a transparent conductive film (ITO), or a tempered glass.
作為上述構成液晶顯示裝置的光學構件，一般使用液晶組件。液晶組件一般是將形成配向層的兩片透明電極基板的配向層作為內側，通過間隔片，以形成所定間隔的方式，進行配置，將其周邊密封，在兩片透明電極基板之間夾持液晶材料的組件。通常，在液晶組件中的兩片透明電極基板的外 側，分別介於黏接劑而黏接偏光板。 As the optical member constituting the liquid crystal display device described above, a liquid crystal module is generally used. In the liquid crystal module, the alignment layer of the two transparent electrode substrates forming the alignment layer is generally disposed inside, and is disposed so as to form a predetermined interval by the spacers, and the periphery thereof is sealed to sandwich the liquid crystal between the two transparent electrode substrates. The components of the material. Usually, outside the two transparent electrode substrates in the liquid crystal module On the side, the adhesive is bonded to the polarizing plate.
作為在觸控面板中所使用的黏接劑，例如，已知有專利文獻1所示的黏接劑。該黏接劑，作為單體單元，相對於具有碳原子數4~14的烷基的烷基(甲基)丙烯酸酯100重量份，含有將含有羧基的單體0.2重量份~20重量份作為共聚合成分而成的(甲基)丙烯類聚合物，以及相對於(甲基)丙烯類聚合物100重量份，作為架橋劑，含有過氧化物0.02重量份~2重量份，以及含有環氧類架橋劑0.005重量份~5重量份。 As the adhesive used in the touch panel, for example, an adhesive shown in Patent Document 1 is known. The binder contains, as a monomer unit, 0.2 parts by weight to 20 parts by weight of the carboxyl group-containing monomer, based on 100 parts by weight of the alkyl (meth) acrylate having an alkyl group having 4 to 14 carbon atoms. (meth) propylene-based polymer obtained by copolymerizing a component, and 100 parts by weight of a (meth) propylene-based polymer, containing 0.02 parts by weight to 2 parts by weight of a peroxide as a bridging agent, and containing an epoxy resin The bridging agent is 0.005 parts by weight to 5 parts by weight.
【專利文獻1】日本特開2009-242786號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-242786
在如上所述的觸控面板中，通過黏接劑，特別是丙烯酸類黏接劑貼合各種光學構件。此處光學構件的折射率一般較高，例如為1.50以上，但丙烯酸類黏接劑的折射率通常為1.47左右。因此，光學構件與黏接劑層的折射率差大，在其介面上有產生反射的問題。 In the touch panel as described above, various optical members are bonded by an adhesive, particularly an acrylic adhesive. Here, the refractive index of the optical member is generally high, for example, 1.50 or more, but the refractive index of the acrylic adhesive is usually about 1.47. Therefore, the refractive index difference between the optical member and the adhesive layer is large, and there is a problem that reflection occurs on the interface.
另外，在以往用於觸控面板的黏接劑中，觸控面板如果放置於高溫高濕的環境下，則黏接劑層中有水分浸入，觸控面板恢複到常溫時黏接劑層白化，有透明性降低的問題。 In addition, in the conventional adhesive for a touch panel, if the touch panel is placed in a high-temperature and high-humidity environment, moisture is immersed in the adhesive layer, and the adhesive layer is whitened when the touch panel returns to normal temperature. There is a problem of reduced transparency.
本發明是鑒於這樣的現狀而進行的，目的在於提供一種適用於光學構件用，折射率高，並且可抑制在實施高溫高濕條件後，恢複到常溫時的白化的黏接性組合物、黏接劑以 及黏接片。 The present invention has been made in view of such circumstances, and it is an object of the present invention to provide an adhesive composition and a viscous composition which are suitable for use in an optical member and which have a high refractive index and can be prevented from being whitened when subjected to high temperature and high humidity conditions. Ingredients And bonding sheets.
為了達成上述目的，第一，本發明提供一種黏接性組合物，其特徵在於：其為以(甲基)丙烯酸酯聚合物作為主成分的黏接性組合物，上述(甲基)丙烯酸酯聚合物，作為構成聚合物的單體單元，含有具有複數芳香環的單體，同時，含有具有羥基的單體或具有羧基的單體。上述(甲基)丙烯酸酯聚合物中，上述具有芳香環的單體的含有量為10質量%~70質量%，上述(甲基)丙烯酸酯聚合物，作為構成該聚合物的單體單元，在含有上述具有羥基的單體的情況時，上述(甲基)丙烯酸酯聚合物中上述具有羥基的單體的含有量為12質量%~50質量%，上述(甲基)丙烯酸酯聚合物，作為構成該聚合物的單體單元，在含有上述具有羧基的單體的情況時，上述(甲基)丙烯酸酯聚合物中上述具有羧基的單體的含有量為7質量%~40質量%(發明1)。 In order to achieve the above object, a first aspect of the present invention provides an adhesive composition characterized in that it is an adhesive composition containing a (meth) acrylate polymer as a main component, and the above (meth) acrylate The polymer, as a monomer unit constituting the polymer, contains a monomer having a plurality of aromatic rings, and contains a monomer having a hydroxyl group or a monomer having a carboxyl group. In the above (meth) acrylate polymer, the content of the monomer having an aromatic ring is 10% by mass to 70% by mass, and the (meth) acrylate polymer is a monomer unit constituting the polymer. In the case where the monomer having a hydroxyl group is contained, the content of the monomer having a hydroxyl group in the (meth)acrylate polymer is from 12% by mass to 50% by mass based on the (meth)acrylate polymer. When the monomer having a carboxyl group is contained in the monomer unit constituting the polymer, the content of the monomer having a carboxyl group in the (meth) acrylate polymer is 7 mass% to 40 mass% ( Invention 1).
上述發明(發明1)中的黏接性組合物的(甲基)丙烯酸酯聚合物，作為構成單體單元，通過含有所定量的具有複數芳香環的單體，所得到的黏接劑的折射率高。另外，上述發明(發明1)中的黏接性組合物的(甲基)丙烯酸酯聚合物，作為構成單體單元，通過含有所定量的具有羥基的單體或具有羧基的單體，所得到的黏接劑，可抑制在實施高溫高濕條件後，恢複到常溫常濕時的白化。 The (meth) acrylate polymer of the adhesive composition in the above invention (Invention 1), as a constituent monomer unit, contains a predetermined amount of a monomer having a plurality of aromatic rings, and the obtained adhesive is refracted. The rate is high. Further, the (meth) acrylate polymer of the adhesive composition in the above invention (Invention 1) is obtained as a constituent monomer unit by containing a predetermined monomer having a hydroxyl group or a monomer having a carboxyl group. The adhesive can suppress whitening when returning to normal temperature and humidity after performing high temperature and high humidity conditions.
在上述發明(發明1)中，上述具有複數芳香環的單體優選具有聯苯環的單體(發明2)。 In the above invention (Invention 1), the monomer having a plurality of aromatic rings is preferably a monomer having a biphenyl ring (Invention 2).
在上述發明(發明2)中，上述具有聯苯環的單體優選含有聯苯結構的(甲基)丙烯酸酯(發明3)。 In the above invention (Invention 2), the monomer having a biphenyl ring preferably contains a (meth) acrylate having a biphenyl structure (Invention 3).
在上述發明(發明1~發明3)中，上述黏接性組合物進一步優選含有架橋劑(發明4)。 In the above invention (Invention 1 to Invention 3), the adhesive composition further preferably contains a bridging agent (Invention 4).
在上述發明(發明4)中，上述架橋劑優選為由異氰酸酯類架橋劑、環氧類架橋劑以及氮丙啶類架橋劑所構成的群中選擇的至少一種(發明5)。 In the above invention (Invention 4), the bridging agent is preferably at least one selected from the group consisting of an isocyanate-based bridging agent, an epoxy-based bridging agent, and an aziridine-based bridging agent (Invention 5).
在上述發明(發明4，發明5)中，上述黏接性組合物中的上述架橋劑的含有量，相對於上述(甲基)丙烯酸酯聚合物100質量份，優選為0.001質量份~5質量份(發明6)。 In the above invention (Invention 4, Invention 5), the content of the bridging agent in the adhesive composition is preferably 0.001 part by mass to 5 parts by mass based on 100 parts by mass of the (meth) acrylate polymer. (Invention 6).
在上述發明(發明1~發明6)中，上述(甲基)丙烯酸酯聚合物的重均分子量優選為20萬~200萬(發明7)。 In the above invention (Invention 1 to Invention 6), the weight average molecular weight of the (meth) acrylate polymer is preferably 200,000 to 2,000,000 (Invention 7).
第二，本發明提供一種將上述黏接性組合物(發明1~發明7)架橋所構成的黏接劑(發明8)。 Secondly, the present invention provides an adhesive comprising the above-mentioned adhesive composition (Invention 1 to Invention 7). (Invention 8).
在上述發明(發明8)中，上述黏接劑的折射率優選為1.50以上(發明9)。 In the above invention (Invention 8), the refractive index of the above-mentioned binder is preferably 1.50 or more (Invention 9).
在上述發明(發明8，發明9)中，用兩片厚度為1.1mm的無堿玻璃夾住的厚度為50μm的上述黏接劑，在85℃、85%RH的條件下保管120小時後，恢複到23℃、50%RH的常溫常濕時，上述黏接劑的霧度值優選為1.0%以下(發明10)。 In the above invention (Invention 8, Invention 9), the above-mentioned adhesive having a thickness of 50 μm sandwiched between two sheets of non-twisted glass having a thickness of 1.1 mm is stored at 85 ° C and 85% RH for 120 hours. When the temperature is normalized to normal temperature of 23 ° C and 50% RH, the haze value of the above-mentioned adhesive is preferably 1.0% or less (Invention 10).
第三，本發明提供一種黏接片，其特徵在於：為具有基材與黏接劑層的黏接片，上述黏接劑層由上述黏接劑(發明8~發明10)構成(發明11)。 Thirdly, the present invention provides a bonding sheet characterized in that it is an adhesive sheet having a substrate and an adhesive layer, and the adhesive layer is composed of the above-mentioned adhesive (Invention 8 to Invention 10) (Invention 11) ).
上述發明(發明11)中，上述基材優選為光學構件(發明12)。 In the above invention (Invention 11), the substrate is preferably an optical member (Invention 12).
第四，本發明提供一種黏接片，其特徵在於：其具備兩片剝離片和以上述兩片剝離片的剝離面相接的方式夾持上述剝離片的黏接劑層，上述黏接劑層由上述黏接劑(發明8~發明10)構成(發明13)。 Fourthly, the present invention provides a bonding sheet comprising two release sheets and an adhesive layer for holding the release sheet in contact with the release faces of the two release sheets, the adhesive The layer is composed of the above-mentioned binder (Invention 8 to Invention 10) (Invention 13).
上述發明(發明13)中，上述黏接片優選為貼合兩片玻璃基板的黏接片(發明14)。 In the above invention (Invention 13), the adhesive sheet is preferably an adhesive sheet to which two glass substrates are bonded (Invention 14).
根據本發明所述黏接性組合物，可以獲得適用於光學構件用的折射率高、可抑制在實施高溫高濕條件後，恢複到常溫常濕時的白化的黏接劑以及黏接片。 According to the adhesive composition of the present invention, it is possible to obtain an adhesive and a pressure-sensitive adhesive sheet which have a high refractive index and can suppress whitening when returning to normal temperature and normal humidity after performing high temperature and high humidity conditions.
1A，1B‧‧‧黏接片 1A, 1B‧‧‧bonding strips
11‧‧‧黏接劑層 11‧‧‧Adhesive layer
12，12a，12b‧‧‧剝離片 12,12a,12b‧‧‧ peeling film
13‧‧‧基材 13‧‧‧Substrate
圖1為本發明第1實施形態所有關的黏接片的剖面圖。 Fig. 1 is a cross-sectional view showing an adhesive sheet according to a first embodiment of the present invention.
圖2為本發明第2實施形態所有關的黏接片的剖面圖。 Fig. 2 is a cross-sectional view showing a bonding sheet according to a second embodiment of the present invention.
以下，關於本發明的實施形態進行說明。 Hereinafter, embodiments of the present invention will be described.
本實施形態所有關的黏接性組合物(以下稱為「黏接性組合物P」)，以(甲基)丙烯酸酯聚合物(A)作為主成分，上述(甲基)丙烯酸酯聚合物(A)，作為構成聚合物的單體單元，含有具有複數芳香環的單體(含有複數芳香環單體)，同時，含有具有羥基的單體(含有羥基單體)或具有羧基的單體(含有羧基單 體)。優選為進一步含有架橋劑(B)。另外，本說明書中所說的(甲基)丙烯酸酯，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，在「聚合物」中，也包括「共聚物」的概念。另外，「主成分」指，黏接性組合物的不揮發成分占總量通常為50質量%以上，優選為占80質量%以上，特別優選為占90質量%以上的成分。 The adhesive composition (hereinafter referred to as "adhesive composition P") according to the present embodiment has the (meth) acrylate polymer (A) as a main component and the (meth) acrylate polymer. (A), as a monomer unit constituting a polymer, a monomer having a plurality of aromatic rings (containing a plurality of aromatic ring monomers), and a monomer having a hydroxyl group (containing a hydroxyl group monomer) or a monomer having a carboxyl group (containing carboxyl group body). Preferably, the bridging agent (B) is further contained. Further, the term "(meth)acrylate" as used herein means both acrylate and methacrylate. The same is true for other similar terms. In addition, the concept of "copolymer" is also included in "polymer". In addition, the "main component" means that the non-volatile component of the adhesive composition is usually 50% by mass or more, preferably 80% by mass or more, and particularly preferably 90% by mass or more.
(甲基)丙烯酸酯聚合物(A)通過含有具有複數芳香環的單體，將黏接性組合物P架橋所得到的黏接劑，折射率高。具體而言，折射率為1.50以上，特別優選為1.51以上。另外，折射率的測定方法如後所述。 The (meth) acrylate polymer (A) has a high refractive index by a binder obtained by bridging the adhesive composition P with a monomer having a plurality of aromatic rings. Specifically, the refractive index is 1.50 or more, and particularly preferably 1.51 or more. In addition, the method of measuring the refractive index will be described later.
作為含有複數芳香環的單體的芳香環，例如，可以列舉出萘環、蒽環、芴環、聯苯環、三聯苯環、薁環、菲環、三亞苯環、芘環、屈環、並四苯環、苝環、並五苯環、並六苯環、蒄環、三萘環、中氮茚環、喹啉環、異吲哚環、吲哚環、異喹啉環、酞環、嘌呤環、萘啶環、喹喔啉環、喹唑啉環、噌啉環、蝶啶環、哢唑環、菲啶環、吖啶環、嘧啶環、鄰菲羅啉環、吩嗪環、亞苯環等。其中，優選碳原子數為10~18的芳香環，特別是優選碳原子數為12的芳香環，具體而言，優選為聯苯環、萘環、蒽環、三亞苯環等，特別是優選為聯苯環。通過含有聯苯環的單體，可在保持良好的黏接物性的同時獲得高折射率。 Examples of the aromatic ring of the monomer having a plurality of aromatic rings include a naphthalene ring, an anthracene ring, an anthracene ring, a biphenyl ring, a terphenyl ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, an anthracene ring, and a ring. Tetraphenyl ring, anthracene ring, pentacene ring, hexaphenyl ring, anthracene ring, trinaphthyl ring, mesoindol ring, quinoline ring, isoindole ring, anthracene ring, isoquinoline ring, anthracene ring , anthracene ring, naphthyridine ring, quinoxaline ring, quinazoline ring, porphyrin ring, pteridine ring, carbazole ring, phenanthridine ring, acridine ring, pyrimidine ring, phenanthroline ring, phenazine ring, sub Benzene ring and the like. Among them, an aromatic ring having 10 to 18 carbon atoms is preferable, and an aromatic ring having 12 carbon atoms is preferable, and specifically, a biphenyl ring, a naphthalene ring, an anthracene ring, a triphenylene ring or the like is preferable, and particularly preferred. It is a biphenyl ring. By the monomer containing a biphenyl ring, a high refractive index can be obtained while maintaining good adhesiveness.
作為含有複數芳香環的單體，例如，可以列舉出含有聯苯環(甲基)丙烯酸酯、含有萘環(甲基)丙烯酸酯、含有蒽環(甲基)丙烯酸酯、含有三苯環(甲基)丙烯酸酯、含有乙烯 基聯苯、含有乙烯基萘、含有乙烯基蒽等，其中優選為在保持良好的黏接物性的同時可獲得高折射率的含有聯苯環(甲基)丙烯酸酯。這些可以單獨使用，也可以組合兩種以上使用。 Examples of the monomer having a plurality of aromatic rings include a biphenyl ring (meth) acrylate, a naphthalene ring (meth) acrylate, an anthracene ring (meth) acrylate, and a triphenyl ring ( Methyl) acrylate, containing ethylene The phenyl group, vinyl naphthalene, vinyl fluorene or the like is preferable, and among them, a biphenyl ring (meth) acrylate having a high refractive index is preferably obtained while maintaining good adhesion properties. These may be used alone or in combination of two or more.
在此，作為含有聯苯環(甲基)丙烯酸酯，具體而言，可以列舉出o-甲氧基聯苯(甲基)丙烯酸酯、m-甲氧基聯苯(甲基)丙烯酸酯、p-甲氧基聯苯(甲基)丙烯酸酯、o-乙氧基聯苯(甲基)丙烯酸酯、m-乙氧基聯苯(甲基)丙烯酸酯、p-乙氧基聯苯(甲基)丙烯酸酯、o-丙氧基聯苯(甲基)丙烯酸酯、m-丙氧基聯苯(甲基)丙烯酸酯、p-丙氧基聯苯(甲基)丙烯酸酯、(o-聯苯氧基)二甘醇(甲基)丙烯酸酯、(m-聯苯氧基)二甘醇(甲基)丙烯酸酯、(p-聯苯氧基)二甘醇(甲基)丙烯酸酯、(o-聯苯氧基)一縮二丙二醇(甲基)丙烯酸酯、(m-聯苯氧基)一縮二丙二醇(甲基)丙烯酸酯、(p-聯苯氧基)一縮二丙二醇(甲基)丙烯酸酯、(o-聯苯氧基)聚乙二醇(甲基)丙烯酸酯、(m-聯苯氧基)聚乙二醇(甲基)丙烯酸酯、(p-聯苯氧基)聚乙二醇(甲基)丙烯酸酯、(o-聯苯氧基)聚丙二醇(甲基)丙烯酸酯、(m-聯苯氧基)聚丙二醇(甲基)丙烯酸酯、(p-聯苯氧基)聚丙二醇(甲基)丙烯酸酯等。其中，從所得到的黏接劑的透明性和高折射率化並存的觀點考慮，優選為乙氧基聯苯(甲基)丙烯酸酯，特別是優選為o-乙氧基聯苯(甲基)丙烯酸酯。 Here, specific examples of the biphenyl ring-containing (meth) acrylate include o-methoxybiphenyl (meth) acrylate and m-methoxybiphenyl (meth) acrylate. P-methoxybiphenyl (meth) acrylate, o-ethoxybiphenyl (meth) acrylate, m-ethoxybiphenyl (meth) acrylate, p-ethoxybiphenyl ( Methyl) acrylate, o-propoxy biphenyl (meth) acrylate, m-propoxy biphenyl (meth) acrylate, p-propoxy biphenyl (meth) acrylate, (o -biphenoxy)diethylene glycol (meth) acrylate, (m-biphenyloxy) diglycol (meth) acrylate, (p-biphenyloxy) diglycol (meth) acrylate Ester, (o-biphenyloxy) dipropylene glycol (meth) acrylate, (m-biphenoxy) dipropylene glycol (meth) acrylate, (p-biphenyloxy) condensate Dipropylene glycol (meth) acrylate, (o-biphenyloxy) polyethylene glycol (meth) acrylate, (m-biphenoxy) polyethylene glycol (meth) acrylate, (p- Biphenyloxy) polyethylene glycol (meth) acrylate, (o-biphenyloxy) polypropylene glycol (meth) acrylate, (m-biphenyloxy) polypropylene glycol (methyl) Acrylate, (p- biphenyl-yloxy) glycol (meth) acrylate. Among them, from the viewpoint of the transparency of the obtained adhesive and the high refractive index, ethoxybiphenyl (meth) acrylate is preferable, and o-ethoxybiphenyl (methyl) is particularly preferable. )Acrylate.
(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，含有10質量%~70質量%具有芳香環的單體，優選為含有20質量%~65質量%，特別優選為含有25質量%~60質量%。含有芳香環單體的含有量如果小於10質量%，則所得 到的黏接劑的折射率不會充分提高。另一方面，含有芳香環單體的含有量如果超過70質量%，則得不到適用於光學用途的黏接性。 The (meth) acrylate polymer (A) contains 10% by mass to 70% by mass of a monomer having an aromatic ring as a monomer unit constituting the polymer, and preferably contains 20% by mass to 65% by mass, particularly preferably It is contained in an amount of 25% by mass to 60% by mass. If the content of the aromatic ring-containing monomer is less than 10% by mass, the result is The refractive index of the resulting adhesive does not increase sufficiently. On the other hand, when the content of the aromatic ring-containing monomer exceeds 70% by mass, the adhesiveness suitable for optical use cannot be obtained.
另外，(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，在含有具有羥基的單體的情況時，含有12質量%~50質量%的該具有羥基的單體，優選為含有15質量%~40質量%，特別優選為含有17質量%~35質量%。另外，(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，在含有具有羧基的單體的情況時，含有7質量%~40質量%的該具有羧基的單體，優選為含有10質量%~35質量%，特別優選為含有10質量%~20質量%。 In addition, when the (meth) acrylate polymer (A) contains a monomer having a hydroxyl group as a monomer unit constituting the polymer, it contains 12% by mass to 50% by mass of the monomer having a hydroxyl group. It is preferably contained in an amount of 15% by mass to 40% by mass, particularly preferably 17% by mass to 35% by mass. In addition, when the (meth) acrylate polymer (A) contains a monomer having a carboxyl group as a monomer unit constituting the polymer, it contains 7 mass% to 40 mass% of the monomer having a carboxyl group. It is preferably contained in an amount of 10% by mass to 35% by mass, particularly preferably 10% by mass to 20% by mass.
(甲基)丙烯酸酯聚合物(A)通過以上述的量含有具有羥基的單體或具有羧基的單體，將黏接性組合物P架橋，所得到的黏接劑可抑制在實施高溫高濕條件後，恢複到常溫常濕時的白化。高溫高濕條件的詳細情況如後所述。 When the (meth) acrylate polymer (A) contains a monomer having a hydroxyl group or a monomer having a carboxyl group in the above amount, the adhesive composition P is bridged, and the obtained adhesive can be suppressed from being subjected to high temperature. After the wet condition, it returns to whitening at normal temperature and humidity. The details of the high temperature and high humidity conditions are as described later.
(甲基)丙烯酸酯聚合物(A)如果以上述的量含有具有羥基的單體或具有羧基的單體，則將黏接性組合物P架橋，所得到的黏接劑中有所定量的羥基或羧基殘留。羥基以及羧基為親水性官能基，如果這種親水性官能基以所定量存在於黏接劑中，則黏接劑即使放置在高溫高濕條件下，在高溫高濕條件下侵入於黏接劑中的水分，在恢複到常溫常濕時，容易從黏接劑上脫落，從而抑制黏接劑的白化。(甲基)丙烯酸酯聚合物(A)中，含有羥基單體或含有羧基單體的含有量如果小於上述範圍，則無法獲得上述效果，如果大於上述範圍，則耐久性降低 或無法充分提高折射率。 When the (meth) acrylate polymer (A) contains a monomer having a hydroxyl group or a monomer having a carboxyl group in the above amount, the adhesive composition P is bridged, and the obtained adhesive is quantitatively determined. Hydroxyl or carboxyl groups remain. The hydroxyl group and the carboxyl group are hydrophilic functional groups. If the hydrophilic functional group is present in the binder in a quantitative amount, the binder invades the binder under high temperature and high humidity conditions even under high temperature and high humidity conditions. The water in the water is easily detached from the adhesive when it is returned to normal temperature and humidity, thereby suppressing whitening of the adhesive. In the (meth) acrylate polymer (A), if the content of the hydroxy monomer or the carboxyl group-containing monomer is less than the above range, the above effect cannot be obtained, and if it is more than the above range, the durability is lowered. Or the refractive index cannot be sufficiently increased.
另外，黏接性組合物P在含有架橋劑(B)的情況時，(甲基)丙烯酸酯聚合物(A)中，含有羥基單體或含有羧基單體的含有量如果在上述範圍內，則在保持上述效果的同時，所形成的架橋結構變得良好，所得到的黏接劑具有優異的耐久性。 When the binder composition (B) contains the bridging agent (B), the content of the hydroxyl group-containing monomer or the carboxyl group-containing monomer in the (meth) acrylate polymer (A) is within the above range. Further, while maintaining the above effects, the bridging structure formed becomes good, and the obtained adhesive has excellent durability.
作為含羥基單體，例如，可以列舉(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、(甲基)丙烯酸4-羥基丁基酯等的(甲基)丙烯酸羥基烷基酯等，其中，從與架橋劑(B)的反應性以及貯存期的觀點考慮，優選(甲基)丙烯酸2-羥基乙基酯。這些可以單獨使用，也可以組合兩種以上使用。 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (methyl). a hydroxyalkyl (meth) acrylate such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate, and the like, and a bridging agent From the viewpoint of the reactivity of (B) and the storage period, 2-hydroxyethyl (meth)acrylate is preferred. These may be used alone or in combination of two or more.
作為含羧基單體，例如，可以列舉優選丙烯酸、甲基丙烯酸、巴豆酸、馬來酸、衣康酸、檸康酸等的乙烯性不飽和羧酸等。這些可以單獨使用，也可以組合兩種以上使用。 Examples of the carboxyl group-containing monomer include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. These may be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，除上述含羥基單體、含羧基單體以及含芳香環單體外，優選含有烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯。另外，根據需要，還可以含有其他的單體。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, preferably has an alkyl group in addition to the above-mentioned hydroxyl group-containing monomer, carboxyl group-containing monomer, and aromatic ring-containing monomer. 1 to 20 alkyl (meth)acrylate. Further, other monomers may be contained as needed.
(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，通過含有烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，可以表現優選的黏接性。作為烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，例如，可以列舉出(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)丙烯酸正丁基酯、(甲基)丙烯酸正戊基酯、(甲基)丙烯酸正己基酯、(甲基)丙烯酸2-乙基己基酯、(甲基)丙烯酸異辛基酯、(甲基)丙烯酸正癸基酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸肉豆蔻基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂基等。其中，從更加提高黏接性的觀點考慮，優選烷基的碳原子數為1~8的(甲基)丙烯酸酯，特別優選(甲基)丙烯酸甲酯及(甲基)丙烯酸正丁酯。而且，這些可以單獨使用，也可以組合兩種以上使用。 The (meth) acrylate polymer (A), as a monomer unit constituting the polymer, can exhibit a preferred adhesion by an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms. Sex. Examples of the (meth)acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group include (meth)acrylic acid. a base ester, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, (meth)acrylic acid Myristyl ester, hexadecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Among them, from the viewpoint of further improving the adhesion, a (meth) acrylate having an alkyl group having 1 to 8 carbon atoms is preferable, and methyl (meth)acrylate and n-butyl (meth)acrylate are particularly preferable. Further, these may be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(A)，作為構成該聚合物的單體單元，優選含有18質量%~78質量%的烷基的碳原子數為1~20的(甲基)丙烯酸烷基酯，特別優選含有20質量%~65質量%，進一步優選含有23質量%~58質量%。 The (meth) acrylate polymer (A) preferably contains, as a monomer unit constituting the polymer, an alkyl (meth) acrylate having 1 to 20 carbon atoms in an alkyl group of 18% by mass to 78% by mass. The ester is particularly preferably contained in an amount of 20% by mass to 65% by mass, and more preferably 23% by mass to 58% by mass.
作為上述其他的單體，為了不妨礙上述含羥基單體或上述含羧基單體的作用，優選不包含具有反應性官能基的單體。作為這樣的其他單體，例如，可以列舉(甲基)丙烯酸甲氧基乙基、(甲基)丙烯酸乙氧基乙基等的(甲基)丙烯酸烷氧基烷基酯、(甲基)丙烯酸環己基等的具有脂環族環的(甲基)丙烯酸酯、丙烯醯胺、甲基丙烯醯胺等的非架橋性的丙烯醯胺、(甲基)丙烯酸N、N-二甲基氨基乙基、(甲基)丙烯酸N、N-二甲基氨基丙基等的具有非架橋性的3級氨基的(甲基)丙烯酸酯、乙酸乙烯酯、苯乙烯等。這些可以單獨使用，也可以組合兩種以上使用。 The above other monomer preferably does not contain a monomer having a reactive functional group in order not to hinder the action of the hydroxyl group-containing monomer or the carboxyl group-containing monomer. Examples of such other monomers include (meth)acrylic acid alkoxyalkyl groups such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate, and (methyl). A non-branching acrylamide or a (meth)acrylic acid N,N-dimethylamino group such as an alicyclic ring-derived (meth) acrylate such as cyclohexyl acrylate, acrylamide or methacrylamide. A (meth) acrylate having a non-branching tertiary amino group such as an ethyl group or an N,N-dimethylaminopropyl group (meth)acrylate, vinyl acetate, styrene or the like. These may be used alone or in combination of two or more.
(甲基)丙烯酸酯聚合物(A)的聚合方式，可以為無 規共聚物，也可以為嵌段共聚物。 The polymerization mode of the (meth) acrylate polymer (A) may be none The copolymer may also be a block copolymer.
(甲基)丙烯酸酯聚合物(A)的重均分子量優選為為20萬~200萬，特別優選為20萬~100萬，進一步優選為30萬~70萬。另外，本說明書中的重均分子量，為根據凝膠滲透色譜法(GPC)法所測定的聚苯乙烯換算的值。 The weight average molecular weight of the (meth) acrylate polymer (A) is preferably 200,000 to 2,000,000, particularly preferably 200,000 to 1,000,000, and more preferably 300,000 to 700,000. The weight average molecular weight in the present specification is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
(甲基)丙烯酸酯聚合物(A)的重均分子量如果小於20萬，則所得到的黏接劑放置在白化試驗等高溫高濕條件時，有發生發泡等的情況。另外，(甲基)丙烯酸酯聚合物(A)的重均分子量如果超過200萬，則所得到的黏接劑，在實施高溫高濕條件後，恢複到常溫常濕時，有無法抑制白化的情況。 When the weight average molecular weight of the (meth) acrylate polymer (A) is less than 200,000, when the obtained adhesive is placed under conditions of high temperature and high humidity such as a whitening test, foaming or the like may occur. When the weight average molecular weight of the (meth) acrylate polymer (A) exceeds 2,000,000, the obtained adhesive can be prevented from whitening when it is returned to normal temperature and normal humidity after high temperature and high humidity conditions. Happening.
另外，在黏接性組合物P中，(甲基)丙烯酸酯聚合物(A)可以單獨使用一種，也可以組合兩種以上使用。另外，黏接性組合物P可進一步含有，作為構成含羥基單體以及含羧基單體單體單元，不含有的(甲基)丙烯酸酯聚合物，以及作為構成含芳香環單體的單體單元，不含有的(甲基)丙烯酸酯聚合物。 Further, in the adhesive composition P, the (meth) acrylate polymer (A) may be used alone or in combination of two or more. Further, the adhesive composition P may further contain, as a monomer component constituting the hydroxyl group-containing monomer and the carboxyl group-containing monomer unit, a (meth) acrylate polymer which is not contained, and a monomer constituting the aromatic ring-containing monomer. Unit, (meth) acrylate polymer not contained.
黏接性組合物P優選為含有架橋劑(B)，通過含有該架橋劑(B)，將(甲基)丙烯酸酯聚合物(A)架橋，形成三維網絡結構，可提高所得到的黏接劑的耐久性。 The adhesive composition P preferably contains a bridging agent (B), and by bridging the (meth) acrylate polymer (A) by the bridging agent (B) to form a three-dimensional network structure, the obtained bonding can be improved. The durability of the agent.
作為架橋劑(B)，只要為對於(甲基)丙烯酸酯聚合物(A)所具有的官能基，即，羥基或羧基具有反應性的架橋劑即可，例如，可以列舉出異氰酸酯類架橋劑、環氧類架橋劑、胺類架橋劑、三聚氰胺類架橋劑、氮丙啶類架橋劑、肼類架橋劑、醛類架橋劑、惡唑啉類架橋劑、金屬醇鹽類架橋劑、金屬 螯合物類架橋劑、金屬鹽類架橋劑、銨鹽類架橋劑等。其中，優選為使用異氰酸酯類架橋劑、環氧類架橋劑或者氮丙啶類架橋劑。架橋劑(B)可以單獨使用一種，或者也可以組合兩種以上使用。 The bridging agent (B) may be a bridging agent which is reactive with a functional group which is a (meth)acrylate polymer (A), that is, a hydroxyl group or a carboxyl group, and examples thereof include an isocyanate bridging agent. , epoxy bridging agent, amine bridging agent, melamine bridging agent, aziridine bridging agent, anthraquinone bridging agent, aldehyde bridging agent, oxazoline bridging agent, metal alkoxide bridging agent, metal Chelate bridging agents, metal salt bridging agents, ammonium salt bridging agents, and the like. Among them, an isocyanate bridging agent, an epoxy bridging agent or an aziridine bridging agent is preferably used. The bridging agent (B) may be used singly or in combination of two or more.
在此，(甲基)丙烯酸酯聚合物(A)具有羥基的情況時，優選為使用與該羥基的反應性優異的異氰酸酯類架橋劑，(甲基)丙烯酸酯聚合物(A)具有羧基的情況時，優選為使用與該羧基的反應性優異的環氧類架橋劑及/或氮丙啶類架橋劑。 When the (meth) acrylate polymer (A) has a hydroxyl group, it is preferred to use an isocyanate bridging agent which is excellent in reactivity with the hydroxy group, and the (meth) acrylate polymer (A) has a carboxyl group. In the case, it is preferred to use an epoxy type bridging agent and/or an aziridine type bridging agent which is excellent in reactivity with the carboxyl group.
異氰酸酯類架橋劑為至少含有聚異氰酸酯化合物的架橋劑。作為聚異氰酸酯化合物，例如，可以列舉出甲次苯基二異氰酸酯、二苯甲烷二異氰酸酯、伸二甲苯二異氰酸酯等的芳香族聚異氰酸酯、六亞甲基二異氰酸酯等的脂環族聚異氰酸酯、異佛爾酮二異氰酸酯、氫化二苯甲烷二異氰酸酯等的脂環式聚異氰酸酯等、以及這些的雙縮脲體、異氰酸酯體、進一步可以列舉乙二醇、丙二醇、新戊二醇、三羥甲基丙烷、蓖麻油等的作為與含有低分子活性氫化合物的反應物的加和物體等。 The isocyanate bridging agent is a bridging agent containing at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as methylphenyl diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate, and alicyclic polyisocyanates such as hexamethylene diisocyanate. Examples of the alicyclic polyisocyanate such as ketone diisocyanate and hydrogenated diphenylmethane diisocyanate, and the biuret or isocyanate of these, and further examples thereof include ethylene glycol, propylene glycol, neopentyl glycol, and trimethylolpropane. An additive such as castor oil or the like which is a reactant containing a low molecular weight active hydrogen compound.
作為環氧類架橋劑，例如，可以列舉出1,3-雙(N，N’-二縮水甘油基氨基甲基)環己烷、N，N，N’，N’-四縮水甘油基間二甲苯二胺、乙二醇二縮水甘油醚、1,6-己二醇縮水甘油醚、三羥甲基丙烷二縮水甘油醚、二縮水甘油苯胺、二縮水甘油胺等。 Examples of the epoxy-based bridging agent include 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane and N,N,N',N'-tetraglycidyl group. Xylene diamine, ethylene glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidylamine, and the like.
作為氮丙啶類架橋劑，例如，可以列舉出二苯基甲烷-4,4’-二(1-氮丙啶甲醯胺丁卡)、三羥甲基丙烷三-β-氮丙 啶基丙酸酯、四羥甲基甲烷三-β-氮丙啶基丙酸酯、甲苯-2,4-二(1-氮丙啶甲醯胺丁卡)、三乙烯三聚氰胺、間苯二-1-(2-甲基氮丙啶)、三-1-(2-甲基氮丙啶)磷化氫、三羥甲基丙烷三-β-(2-甲基氮丙啶基)丙酸酯等。 Examples of the aziridine-based bridging agent include diphenylmethane-4,4'-bis(1-aziridinecarbamidine) and trimethylolpropane tris-β-aza-propane. Pyridyl propionate, tetramethylol methane tri-β-aziridine propionate, toluene-2,4-di(1-aziridinecarbamidine), triethylene melamine, isophthalic acid 1-(2-methylaziridine), tri-1-(2-methylaziridine) phosphine, trimethylolpropane tri-β-(2-methylaziridine)propane Acid esters, etc.
黏接性組合物P中，架橋劑(B)的含有量，相對於(甲基)丙烯酸酯聚合物(A)100質量份，優選為0.001質量份~5質量份，特別優選為0.005質量份~2質量份，進一步優選為0.01質量份~1質量份。架橋劑(B)的含有量如果為0.001質量份以上，通過該架橋劑(B)可獲得耐久性提高的效果。架橋劑(B)的含有量如果超過5質量份，則(甲基)丙烯酸酯聚合物(A)所具有的羥基或羧基大量與架橋劑(B)反應，黏接劑中殘留的量變少，有無法獲得如上所述的抑制白化效果的可能性。 In the adhesive composition P, the content of the bridging agent (B) is preferably 0.001 parts by mass to 5 parts by mass, particularly preferably 0.005 parts by mass, per 100 parts by mass of the (meth) acrylate polymer (A). ~2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass. When the content of the bridging agent (B) is 0.001 part by mass or more, the effect of improving durability can be obtained by the bridging agent (B). When the content of the bridging agent (B) exceeds 5 parts by mass, a large amount of a hydroxyl group or a carboxyl group of the (meth) acrylate polymer (A) reacts with the bridging agent (B), and the amount remaining in the binder decreases. There is a possibility that the whitening effect as described above cannot be obtained.
黏接性組合物P中，可以添加在丙烯酸類黏接劑中通常使用的各種添加劑，例如可以添加矽烷偶聯劑、帶電防止劑、黏接賦予劑、氧化防止劑、紫外線吸收劑、光穩定劑、軟化劑、充填劑、折射率調整劑等。 In the adhesive composition P, various additives commonly used in acrylic adhesives may be added, and for example, a decane coupling agent, a charge preventing agent, an adhesion-imparting agent, an oxidation preventing agent, an ultraviolet absorber, and light stabilization may be added. Agent, softener, filler, refractive index modifier, and the like.
作為矽烷偶聯劑，為分子內至少具有一個烷氧基甲矽烷基的有機矽化合物，與黏接劑成分的相溶性良好，且具有光透過性，例如優選實質上為透明者。 The decane coupling agent is an organic ruthenium compound having at least one alkoxycarbenyl group in the molecule, and has good compatibility with the binder component and has light permeability. For example, it is preferably substantially transparent.
作為上述矽烷偶聯劑，例如，可以列舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、甲基丙烯醯氧丙基三甲氧基矽烷等的聚合性含不飽和基團矽化合物、3-環氧丙氧基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等的具有環氧結構的矽化合物、3-巰基丙基三甲氧基矽烷、3-巰基丙基 三乙氧基矽烷、3-巰基丙基甲基二甲氧基矽烷等的含有巰基的矽化合物、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、或這些中的至少一種與甲基三乙氧基矽烷、乙基三乙氧基矽烷、甲基三甲氧基矽烷、乙基三甲氧基矽烷等的含有烷基的矽化合物的縮合物等。這些可以單獨使用一種，也可以組合兩種以上使用。 The decane coupling agent may, for example, be a polymerizable unsaturated group-containing oxime compound such as vinyltrimethoxydecane, vinyltriethoxysilane or methacryloxypropyltrimethoxynonane. An anthracene compound having an epoxy structure such as 3-glycidoxytrimethoxydecane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyl A mercapto group-containing anthracene compound such as triethoxydecane or 3-mercaptopropylmethyldimethoxydecane, 3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropane Amino-containing hydrazine compound such as trimethoxy decane or N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-isocyanate C An alkyl group-containing oxime such as at least one of methyl triethoxy decane or at least one of these and methyl triethoxy decane, ethyl triethoxy decane, methyl trimethoxy decane, ethyl trimethoxy decane a condensate of the compound or the like. These may be used alone or in combination of two or more.
矽烷偶聯劑的添加量，相對於(甲基)丙烯酸酯聚合物(A)100質量份，優選為0.01質量份~1質量份，特別是優選為0.05質量份~0.5質量份。 The amount of the decane coupling agent to be added is preferably 0.01 parts by mass to 1 part by mass, particularly preferably 0.05 parts by mass to 0.5 parts by mass, per 100 parts by mass of the (meth) acrylate polymer (A).
黏接性組合物P可以通過製造(甲基)丙烯酸酯聚合物(A)，在所得到的(甲基)丙烯酸酯聚合物(A)中添加架橋劑(B)或添加劑來製造。 The adhesive composition P can be produced by adding a bridging agent (B) or an additive to the obtained (meth) acrylate polymer (A) by producing a (meth) acrylate polymer (A).
(甲基)丙烯酸酯聚合物(A)，可以通過用通常的自由基聚合法，聚合構成聚合物的單體來製造。(甲基)丙烯酸酯聚合物(A)的聚合，可使用聚合引發劑，由溶液聚合法等進行。作為聚合溶劑，例如可以舉出乙酸乙酯、乙酸正丁基酯、乙酸異丁基酯、甲苯、丙酮、己烷、甲基乙基酮等，可以並用兩種以上。 The (meth) acrylate polymer (A) can be produced by polymerizing a monomer constituting the polymer by a usual radical polymerization method. The polymerization of the (meth) acrylate polymer (A) can be carried out by a solution polymerization method or the like using a polymerization initiator. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone, and the like, and two or more kinds thereof may be used in combination.
作為聚合引發劑，可以列舉偶氮類化合物、有機過氧化物等，可以同時使用兩種以上。作為偶氮類化合物，可以列舉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(2，4-二甲基戊腈)、2，2’-偶氮雙(2，4-二甲基-4-甲氧基戊腈)、二甲基2，2’-偶氮雙(2-甲基丙酸酯)、4，4’-偶氮雙(4-氰基纈草酸)、2，2’-偶氮雙(2-羥基甲基丙腈)、2，2’-偶氮雙〔2-(2-咪唑琳-2-基)丙烷〕等。 Examples of the polymerization initiator include an azo compound and an organic peroxide, and two or more kinds thereof can be used at the same time. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1, 1'-azobis(cyclohexane1-nitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl 4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanoshikimate), 2 2'-Azobis(2-hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane, and the like.
作為有機過氧化物，例如，可以列舉出苯甲醯過氧化物、過氧苯甲酸叔丁基酯、異丙苯過氧化氫、二異丙基過氧二碳酸酯、二正丙基過氧二碳酸酯、二(2-乙氧基乙基)過氧二碳酸酯、過氧新葵酸叔丁基酯、過氧特戊酸叔丁基酯、(3，5，5-三甲基己醯基)過氧化物、二丙醯過氧化物、二乙醯過氧化物等。 Examples of the organic peroxide include benzamidine peroxide, t-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, and di-n-propyl peroxygen. Dicarbonate, bis(2-ethoxyethyl)peroxydicarbonate, tert-butyl peroxy neopentate, tert-butyl peroxypivalate, (3,5,5-trimethyl Benzyl) peroxide, dipropylene peroxide, diethyl hydrazine peroxide, and the like.
另外，在上述聚合步驟中，通過搭配2-巰基乙醇等的鏈移動劑，可以對得到的聚合物的重量平均分子量進行調節。 Further, in the above polymerization step, the weight average molecular weight of the obtained polymer can be adjusted by mixing a chain shifting agent such as 2-mercaptoethanol.
得到(甲基)丙烯酸酯聚合物(A)後，在(甲基)丙烯酸酯聚合物(A)的溶液中，添加稀釋溶劑以及架橋劑(B)或添加劑，進行充分混合，得到用溶劑稀釋了的黏接性組合物P(塗布溶液)。 After obtaining the (meth) acrylate polymer (A), a dilution solvent, a bridging agent (B) or an additive is added to the solution of the (meth) acrylate polymer (A), and the mixture is sufficiently mixed to obtain a solvent-diluted solution. Adhesive composition P (coating solution).
作為對黏接性組合物P進行稀釋，得到塗布溶液的稀釋溶劑，可以使用己烷、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-戊酮、異佛爾酮、環己酮等的酮類；乙酸乙酯、乙酸丁基酯等的酯；乙基溶纖劑等的溶纖劑類溶劑等。 As a diluent solvent for diluting the adhesive composition P to obtain a coating solution, an aliphatic hydrocarbon such as hexane, heptane or cyclohexane; an aromatic hydrocarbon such as toluene or xylene; methylene chloride or two may be used. Halogenated hydrocarbon such as ethyl chloride; alcohol such as methanol, ethanol, propanol, butanol or 1-methoxy-2-propanol; acetone, methyl ethyl ketone, 2-pentanone, isophorone a ketone such as cyclohexanone; an ester such as ethyl acetate or butyl acetate; a cellosolve solvent such as ethyl cellosolve;
作為如此調製的塗布溶液的濃度、黏度，只要為 在塗布可能的範圍內即可，沒有特別的限制，可以根據情況進行適宜選擇。例如，黏接性組合物P的濃度可以稀釋到10質量%~40質量%。另外，得到塗布溶液時，稀釋溶劑等的添加不是必要條件，黏接性組合物P只要是塗布可能的黏度等，稀釋溶劑不添加也可。該情況時黏接性組合物P可以直接作為塗布溶液。 The concentration and viscosity of the coating solution thus prepared are as long as It may be within 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 P can be diluted to 10% by mass to 40% by mass. In addition, when a coating solution is obtained, the addition of a diluent solvent or the like is not a requirement, and the adhesive composition P may be added without any addition as long as it is a coating viscosity. In this case, the adhesive composition P can be directly used as a coating solution.
本實施形態所述的黏接劑，是將黏接性組合物P架橋所構成。在此，黏接性組合物P含有架橋劑(B)的情況時，黏接劑是將黏接性組合物P架橋而構成的。黏接性組合物P的架橋可通過加熱處理進行。另外，此加熱處理還可兼用作對黏接性組合物P的稀釋溶劑等進行揮發時的乾燥處理。 The adhesive according to the present embodiment is formed by bridging the adhesive composition P. Here, when the adhesive composition P contains the bridging agent (B), the adhesive agent is formed by bridging the adhesive composition P. The bridging of the adhesive composition P can be carried out by heat treatment. In addition, this heat treatment can also serve as a drying treatment for volatilizing a dilution solvent or the like of the adhesive composition P.
在進行加熱處理的情況時，加熱溫度優選為50℃~150℃，特別優選為70℃~120℃。另外，加熱時間優選為10秒~10分，特別優選為50秒~2分。進一步優選為加熱處理後，在常溫(例如23℃、50%RH)下放置1~2周左右的熟成期間。 In the case of heat treatment, the heating temperature is preferably from 50 ° C to 150 ° C, particularly preferably from 70 ° C to 120 ° C. Further, the heating time is preferably from 10 seconds to 10 minutes, particularly preferably from 50 seconds to 2 minutes. More preferably, after the heat treatment, the ripening period is left at a normal temperature (for example, 23 ° C, 50% RH) for about 1 to 2 weeks.
通過上述加熱處理(以及熟成)，(甲基)丙烯酸酯聚合物(A)被架橋。黏接性組合物P在含有架橋劑(B)的情況時，(甲基)丙烯酸酯聚合物(A)通過架橋劑(B)被架橋，形成三維網絡結構。 The (meth) acrylate polymer (A) is bridged by the above heat treatment (and aging). When the adhesive composition P contains the bridging agent (B), the (meth) acrylate polymer (A) is bridged by the bridging agent (B) to form a three-dimensional network structure.
將黏接性組合物P架橋所得到的黏接劑，通過具有構成(甲基)丙烯酸酯聚合物(A)的含芳香環單體中所帶有的複數的芳香環，具有高折射率。具體而言，折射率為1.50以 上，特別優選為1.51以上。在此，本說明書中的折射率，是在測定波長為589nm、測定溫度為23℃的條件下，使用阿貝折射儀(試驗例中使用愛宕公司產品)測定的值。另外，折射率的上限沒有特別的限制，但通常為1.9以下。 The adhesive obtained by bridging the adhesive composition P has a high refractive index by passing through a plurality of aromatic rings carried in the aromatic ring-containing monomer constituting the (meth) acrylate polymer (A). Specifically, the refractive index is 1.50. In particular, it is particularly preferably 1.51 or more. Here, the refractive index in the present specification is a value measured using an Abbe refractometer (product of Aiwa Co., Ltd. in the test example) under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 23 °C. Further, the upper limit of the refractive index is not particularly limited, but is usually 1.9 or less.
本實施形態所述的黏接劑的凝膠分率，優選為15%~90%，特別優選為20%~80%，進一步優選為30%~70%。凝膠分率如果小於15%，則黏接劑的凝集力不足，有耐久性以及再加工性降低的情況。另一方面，凝膠分率如果超過90%，則黏接力變得過低，有耐久性降低的情況。另外，上述凝膠分率是熟成期間經過後(例如，在23℃、50%RH的環境下保管7天後)形成的黏接劑的值。在不明是否為熟成期間的情況時，只要重新在23℃、50%RH的環境下保管7天後，如果凝膠分率在上述範圍內即可。 The gel fraction of the adhesive according to the present embodiment is preferably 15% to 90%, particularly preferably 20% to 80%, and more preferably 30% to 70%. When the gel fraction is less than 15%, the cohesive force of the adhesive is insufficient, and durability and reworkability are deteriorated. On the other hand, when the gel fraction exceeds 90%, the adhesive strength becomes too low, and the durability may be lowered. Further, the gel fraction is a value of the adhesive formed after the passage of the ripening period (for example, after storage for 7 days in an environment of 23° C. and 50% RH). When it is not known whether it is a ripening period, if it is stored in the environment of 23 ° C and 50% RH for 7 days, the gel fraction may be within the above range.
如圖1所示，第1實施形態所述的黏接片1A，按照從下往上的順序，由剝離片12、積層於剝離片12的剝離面上的黏接劑層11、以及積層於黏接劑層11上的基材13所構成。 As shown in Fig. 1, the adhesive sheet 1A according to the first embodiment is composed of a release sheet 12, an adhesive layer 11 laminated on the release surface of the release sheet 12, and a laminate layer in the order from the bottom to the top. The substrate 13 on the adhesive layer 11 is composed of a substrate 13 .
另外，如圖2所示，第2實施形態所述的黏接片1B，由兩片剝離片12a、12b，以及以與這兩片剝離片12a、12b的剝離面相接的方式，被這兩片剝離片12a、12b所夾持的黏接劑層11所構成。另外，本說明書中所謂的剝離片的剝離面，是指剝離片中具有剝離性的面，包括實施了剝離處理的面以及即使未實施剝離處理也顯示出剝離性的面這兩者。 Further, as shown in Fig. 2, the adhesive sheet 1B according to the second embodiment is formed by the two release sheets 12a and 12b and the peeling surfaces of the two release sheets 12a and 12b. The adhesive layer 11 sandwiched between the two release sheets 12a and 12b is formed. In addition, the peeling surface of the peeling sheet in this specification is the surface which has the peeling property in the peeling sheet, and the surface which carried out the peeling process, and the surface which shows the peeling-
在黏接片1A、1B的兩者中，黏接劑層11都是由 架橋上述黏接性組合物P所成的黏接劑構成。 In both of the bonding sheets 1A, 1B, the adhesive layer 11 is composed of The bridging agent formed by the above adhesive composition P is bridged.
黏接劑層11的厚度，根據黏接片1A、1B的使用目的而適宜決定，但是通常為5μm~100μm，優選為10μm~60μm的範圍。例如，在作為光學構件，特別是作為偏光板用的黏接劑層使用的情況時，優選為10μm~50μm，特別優選為15μm~30μm。 The thickness of the adhesive layer 11 is appropriately determined depending on the purpose of use of the adhesive sheets 1A and 1B, but is usually in the range of 5 μm to 100 μm, preferably 10 μm to 60 μm. For example, when it is used as an optical member, particularly as an adhesive layer for a polarizing plate, it is preferably 10 μm to 50 μm, and particularly preferably 15 μm to 30 μm.
作為基材13，沒有特別的限制，作為通常的黏接片的基材片所使用的基材都可以使用。例如，除所希望的光學構件之外，可以列舉出人造絲、丙烯以及聚酯等使用了纖維的織布或者不織布；合成紙；上質紙、玻璃紙、含浸紙、銅板紙等的紙類；鋁、銅等的金屬箔；氨基甲酸酯發泡體、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、聚萘二酸乙二醇酯等的聚酯薄膜；聚氨酯薄膜、聚乙烯薄膜、聚丙烯薄膜、三乙醯纖維素等的纖維素薄膜；聚氯乙烯薄膜、聚偏氯乙烯薄膜、聚乙烯基醇薄膜、乙烯-乙酸乙烯基共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、丙烯酸樹脂薄膜、降冰片烯類樹脂薄膜、環烯烴樹脂薄膜等的塑膠薄膜；這些的兩種以上的積層體等。塑膠薄膜可以為單軸壓延的薄膜或者雙軸壓延的薄膜。 The base material 13 is not particularly limited, and any substrate used as a base material sheet of a usual adhesive sheet can be used. For example, in addition to the desired optical member, woven or non-woven fabrics using rayon, acryl, and polyester, and the like; synthetic paper; paper of upper quality paper, cellophane, impregnated paper, copper paper, etc.; Metal foil such as copper; foam of urethane foam or polyethylene foam; polyethylene terephthalate, polybutylene terephthalate, polynaphthalene dicarboxylic acid Polyester film such as ethylene glycol ester; cellulose film such as polyurethane film, polyethylene film, polypropylene film, triacetyl cellulose; polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene - a plastic film such as a vinyl acetate copolymer film, a polystyrene film, a polycarbonate film, an acrylic resin film, a norbornene resin film, or a cycloolefin resin film; or a laminate of two or more of these. The plastic film may be a uniaxially rolled film or a biaxially rolled film.
作為光學構件，例如可以列舉出偏光板(偏光薄膜)、偏光子、相位差板(相位差薄膜)、視野角補償薄膜、提高輝度薄膜、提高對比度薄膜、液晶聚合物薄膜、擴散薄膜、半透過反射薄膜等。 Examples of the optical member include a polarizing plate (polarizing film), a polarizer, a retardation film (retardation film), a viewing angle compensation film, a brightness enhancement film, a contrast film, a liquid crystal polymer film, a diffusion film, and a semi-transmission. Reflective film, etc.
基材13的厚度，根據其種類而有所不同，但是， 在例如光學構件的情況時，通常為10μm~500μm，優選為50μm~300μm。 The thickness of the substrate 13 varies depending on the type thereof, however, In the case of, for example, an optical member, it is usually 10 μm to 500 μm, preferably 50 μm to 300 μm.
作為剝離片12、12a、12b，可以使用例如聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯基薄膜、氯乙烯基共聚物薄膜、聚對苯二甲酸乙二醇酯薄膜、聚萘二酸乙二醇酯薄膜、聚對苯二甲酸丁二醇酯薄膜、聚氨酯薄膜、乙烯乙酸乙烯基薄膜、離聚物樹脂薄膜、乙烯-(甲基)丙烯酸共聚物薄膜、乙烯-(甲基)丙烯酸酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜、氟樹脂薄膜等。另外，也可以使用這些的架橋薄膜。進一步，也可以為這些的積層薄膜。 As the release sheets 12, 12a, 12b, for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film can be used. , polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, 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. In addition, these bridge films can also be used. Further, it is also possible to laminate these films.
上述剝離片的剝離面(特別是與黏接劑層11相接的面)，優選為實施有剝離處理。作為剝離處理所使用的剝離劑，例如可以列舉出醇酸類、矽酮類、氟類、不飽和聚酯類、聚烯烴類以及蠟類的剝離劑。 It is preferable that the peeling surface of the peeling sheet (particularly the surface in contact with the adhesive layer 11) is subjected to a peeling treatment. Examples of the release agent used for the release treatment include a release agent of an alkyd, an anthrone, a fluorine, an unsaturated polyester, a polyolefin, and a wax.
關於剝離片12、12a、12b的厚度，沒有特別的限制，通常為20μm~150μm左右。 The thickness of the release sheets 12, 12a, and 12b is not particularly limited, but is usually about 20 μm to 150 μm.
在製造上述黏接片1A中，在剝離片12的剝離面上，將含有上述黏接性組合物P的溶液(塗布溶液)進行塗布、加熱處理，在形成塗布層後，在其塗布層上將基材13進行積層。在需要熟成期間的情況時，通過保留熟成期間，在不需要熟成期間的情況時，上述塗布層直接成為黏接劑層11。由此，得到上述黏接片1A。另外，關於加熱處理以及熟成的條件如上所述。 In the production of the above-mentioned adhesive sheet 1A, the solution (coating solution) containing the above-mentioned adhesive composition P is applied and heat-treated on the release surface of the release sheet 12, and after the coating layer is formed, on the coating layer. The substrate 13 is laminated. When the ripening period is required, the coating layer directly becomes the adhesive layer 11 by retaining the ripening period, when the ripening period is not required. Thereby, the above-mentioned adhesive sheet 1A is obtained. Further, the conditions regarding the heat treatment and the ripening are as described above.
另外，在製造上述黏接片1B中，在一個剝離片12a(或者12b)的剝離面上，將含有上述黏接性組合物P的塗布溶液進行塗布、加熱處理，在形成塗布層後，在其塗布層上，將另一個剝離片12b(或者12a)的剝離面聚合。在需要熟成期間的情況時，通過保留熟成期間，在不需要熟成期間的情況時，上述塗布層直接成為黏接劑層11。由此，得到上述黏接片1B。 Further, in the production of the above-mentioned adhesive sheet 1B, the coating solution containing the above-mentioned adhesive composition P is applied and heat-treated on the peeling surface of one of the release sheets 12a (or 12b), and after the coating layer is formed, On the coating layer, the peeling surface of the other release sheet 12b (or 12a) is polymerized. When the ripening period is required, the coating layer directly becomes the adhesive layer 11 by retaining the ripening period, when the ripening period is not required. Thereby, the above-mentioned adhesive sheet 1B is obtained.
作為塗布上述塗布溶液的方法，例如可以利用棒塗布法、刮刀塗布法、輥塗布法、板塗布法、模具塗布法、凹板塗布法等。 As a method of applying the above coating solution, for example, a bar coating method, a knife coating method, a roll coating method, a plate coating method, a die coating method, a gravure coating method, or the like can be used.
在此，例如，在製造由液晶組件和偏光板所構成的液晶顯示裝置中，作為黏接片1A的基材13，使用偏光板，將該黏接片1A的剝離片12剝離，將露出的黏接劑層11和液晶組件進行貼合即可。 Here, for example, in the liquid crystal display device including the liquid crystal module and the polarizing plate, a polarizing plate is used as the substrate 13 of the bonding sheet 1A, and the peeling sheet 12 of the bonding sheet 1A is peeled off to be exposed. The adhesive layer 11 and the liquid crystal module may be attached.
另外，例如，製造在液晶組件和偏光板之間配置有相位差板的液晶顯示裝置中，作為一例，首先，將黏接片1B的一個剝離片12a(或者12b)剝離，將黏接片1B露出的黏接劑層11和相位差板進行貼合。然後，將作為基材13使用偏光板的黏接片1A的剝離片12剝離，將黏接片1A露出的黏接劑層11和上述相位差板進行貼合。另外，從上述黏接片B的黏接劑層11，將另一個剝離片12b(或者12a)剝離，將黏接片B露出的黏接劑層11和液晶組件貼合。 Further, for example, in 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 peeling sheet 12a (or 12b) of the bonding sheet 1B is peeled off, and the bonding sheet 1B is peeled off. The exposed adhesive layer 11 and the phase difference plate are bonded together. Then, the release sheet 12 of the adhesive sheet 1A using the polarizing plate as the base material 13 is peeled off, and the adhesive layer 11 exposed by the adhesive sheet 1A and the phase difference plate are bonded together. 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 adhesive layer 11 from which the adhesive sheet B is exposed is bonded to the liquid crystal module.
另外，例如，製造帶有玻璃基板的液晶組件和帶有所希望的功能層的玻璃基板的積層體中，作為一例，首先，將接片1B的一個剝離片12a(或者12b)剝離，將黏接片1B露 出的黏接劑層11和玻璃基板的功能層側的面貼合。然後，將另一個剝離片12b(或者12a)從黏接片B的黏接劑層11上剝離，將黏接片B露出的黏接劑層11和液晶組件的玻璃基板貼合。 Further, for example, in a laminate in which a liquid crystal module having a glass substrate and a glass substrate having a desired functional layer are produced, as an example, first, one release sheet 12a (or 12b) of the tab 1B is peeled off, and the adhesive is adhered. Tab 1B The adhesive layer 11 and the surface of the functional layer side of the glass substrate are bonded together. Then, the other release sheet 12b (or 12a) is peeled off from the adhesive layer 11 of the adhesive sheet B, and the adhesive layer 11 exposed by the adhesive sheet B is bonded to the glass substrate of the liquid crystal module.
上述玻璃基板的種類，沒有特別的限制，例如，可以列舉無堿玻璃、石英玻璃、鈉鈣玻璃、含鋇鍶玻璃、鋁矽酸鹽玻璃、鉛玻璃、硼矽玻璃、鋇硼矽酸鹽玻璃等。玻璃基板的厚度，沒有特別的限制，但通常為0.1mm~5mm，優選為0.2mm~2mm。 The type of the glass substrate is not particularly limited, and examples thereof include bismuth-free glass, quartz glass, soda-lime glass, bismuth-containing glass, aluminosilicate glass, lead glass, borosilicate glass, and bismuth borate glass. Wait. The thickness of the glass substrate is not particularly limited, but is usually 0.1 mm to 5 mm, preferably 0.2 mm to 2 mm.
在此，黏接片1A、1B中的黏接劑層11，如上所述，(甲基)丙烯酸酯聚合物(A)通過具有所定量的羥基或羧基，可抑制在實施高溫高濕條件後，恢複到常溫時的白化。例如，用兩片厚度為1.1mm的無堿玻璃夾住的厚度為50μm的上述黏接劑層11，在85℃、85%RH的條件下保管120小時後，恢複到23℃、50%RH的常溫常濕時，可抑制上述黏接劑層11的白化。具體而言，此時的霧度值(基於JIS K7136：2000測定出的值)優選為1.0%以下，特別優選為0.9%以下，進一步優選為0.8%以下。 Here, the adhesive layer 11 in the adhesive sheets 1A, 1B, as described above, the (meth) acrylate polymer (A) having a certain amount of a hydroxyl group or a carboxyl group can be suppressed from being subjected to high temperature and high humidity conditions. , return to whitening at normal temperature. For example, the above-mentioned adhesive layer 11 having a thickness of 50 μm sandwiched between two sheets of non-twisted glass having a thickness of 1.1 mm is stored at 85 ° C and 85% RH for 120 hours, and then restored to 23 ° C, 50% RH. When the temperature is normal and normal, the whitening of the above-mentioned adhesive layer 11 can be suppressed. Specifically, the haze value (value measured based on JIS K7136:2000) at this time is preferably 1.0% or less, particularly preferably 0.9% or less, and further preferably 0.8% or less.
另外，上述黏接劑層11，在正常情況下也優選為具有如上所述的霧度值。霧度值如果為1.0%以下，則透明性極高，適合用於光學用途。 Further, it is preferable that the above-mentioned adhesive layer 11 has a haze value as described above under normal conditions. When the haze value is 1.0% or less, the transparency is extremely high and it is suitable for optical use.
另外，黏接片1A相對於無堿玻璃的黏接力優選為0.1N/25mm~50N/25mm，特別優選為2N/25mm~20N/25mm。通過使黏接力在上述的範圍內，則在與玻璃板等的被黏物之 間，可以防止浮起或剝離等。另外，在此所說的黏接力，基本上是指通過基於JIS Z0237：2009的180°剝離法所測定的黏接力，但是將測定樣品切成寬25mm、長100mm，使該測定樣品相對於被黏物(無堿玻璃)，在0.5MPA、50℃，加壓20分貼附之後，以常壓23℃、50%RH的條件下放置24小時之後，以剝離速度300mm/min進行測定所得到的黏接力。 Further, the adhesive force of the adhesive sheet 1A with respect to the beryllium-free glass is preferably 0.1 N/25 mm to 50 N/25 mm, and particularly preferably 2 N/25 mm to 20 N/25 mm. When the adhesive force is within the above range, it is adhered to a adherend such as a glass plate. In between, it can prevent floating or peeling. In addition, the adhesive force referred to here basically means the adhesive force measured by the 180° peeling method based on JIS Z0237:2009, but the measurement sample is cut into a width of 25 mm and a length of 100 mm so that the measurement sample is opposed to the The adhesive (no glass) was placed at 0.5 MPA, 50 ° C, and pressed for 20 minutes, and then allowed to stand under normal pressure of 23 ° C and 50% RH for 24 hours, and then measured at a peeling speed of 300 mm/min. Adhesion.
通過上述黏接片1A、1B，由於黏接劑層11的折射率高，該黏接劑層11與光學構件的折射率差小，可抑制在這些介面上發生的反射。 With the above-mentioned adhesive sheets 1A and 1B, since the refractive index of the adhesive layer 11 is high, the refractive index difference between the adhesive layer 11 and the optical member is small, and reflection occurring on these interfaces can be suppressed.
以上說明的實施形態，是為了易於對本發明的理解而記述的，並不是對本發明進行限定而進行的記述。因此，上述實施形態中所公開的各要素，也包括屬於本發明的技術範圍的所有設計變更以及均等物。 The embodiments described above are described in order to facilitate understanding of the present invention, and are not intended to limit the present invention. Therefore, each of the elements disclosed in the above embodiments includes all design changes and equivalents belonging to the technical scope of the present invention.
例如，黏接片1A的剝離片12可以省略，黏接片1B中的剝離片12a，12b的任意一方也可以省略。 For example, the release sheet 12 of the adhesive sheet 1A can be omitted, and either one of the release sheets 12a and 12b in the adhesive sheet 1B can be omitted.
以下，通過實施例等進一步對本發明進行具體說明，但是本發明的範圍並不受這些實施例等的限定。 The present invention will be specifically described by the following examples, but the scope of the present invention is not limited by the examples and the like.
1.(甲基)丙烯酸酯聚合物的調製 1. Modulation of (meth) acrylate polymer
向具備攪拌機、溫度計、回流冷卻器、滴下裝置及氮氣導入管的反應容器中，裝入丙烯酸正丁基酯40質量份、o-乙氧基聯苯丙烯酸酯(新中村化學公司製，ALEN10)50質量份、丙烯酸10質量份、乙酸乙酯200質量份以及2,2'-偶氮二異丁 腈0.18質量份，將上述反應容器內的空氣置換成氮氣。在該氮氣氣氛下一邊攪拌，一邊將反應溶液升溫至60℃，使反應進行16小時後，冷卻至室溫。在此，將所得的溶液的一部分，用後述的方法測定分子量，確認到生成有重均分子量(Mw)40萬的(甲基)丙烯酸酯聚合物(A)。 40 parts by mass of n-butyl acrylate and o-ethoxybiphenyl acrylate (ALEN10, manufactured by Shin-Nakamura Chemical Co., Ltd.) were placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen gas introduction tube. 50 parts by mass, 10 parts by mass of acrylic acid, 200 parts by mass of ethyl acetate, and 2,2'-azobisisobutyl 0.18 parts by mass of the nitrile was replaced with nitrogen in the reaction vessel. The reaction solution was heated to 60 ° C while stirring in a nitrogen atmosphere, and the reaction was allowed to proceed for 16 hours, followed by cooling to room temperature. Here, a part of the obtained solution was measured for molecular weight by a method described later, and it was confirmed that a (meth) acrylate polymer (A) having a weight average molecular weight (Mw) of 400,000 was formed.
2.黏接性組合物的調製 2. Modulation of adhesive composition
在上述步驟(1)中獲得的(甲基)丙烯酸酯聚合物(A)100質量份(固體成分換算值；以下同)；作為環氧類架橋劑(B)，將N，N，N’，N’-四縮水甘油基間二甲苯二胺(綜研化學工程公司製，商品名「E-AX」)0.05質量份進行混合，充分地攪拌，通過用乙酸乙酯進行稀釋，獲得黏接性組合物的塗布溶液。 100 parts by mass of the (meth) acrylate polymer (A) obtained in the above step (1) (solid content conversion value; the same applies hereinafter); as the epoxy type bridging agent (B), N, N, N' , N'-tetraglycidyl-m-xylenediamine (manufactured by Soken Chemical Engineering Co., Ltd., trade name "E-AX"), 0.05 parts by mass, mixed well, and diluted with ethyl acetate to obtain adhesiveness A coating solution for the composition.
在此，該黏接性組合物的搭配表示於表1。另外，表1所記載的縮寫符號等的詳細情況如下所述。 Here, the combination of the adhesive composition is shown in Table 1. The details of the abbreviations and the like described in Table 1 are as follows.
[(甲基)丙烯酸酯聚合物] [(Meth)acrylate polymer]
BA：丙烯酸正丁基酯 BA: n-butyl acrylate
ALEN10：o-乙氧基聯苯丙烯酸酯 ALEN10: o-ethoxybiphenyl acrylate
AA：丙烯酸 AA: Acrylic
HEA：丙烯酸2-羥基乙基酯 HEA: 2-hydroxyethyl acrylate
3.黏接片的製造 3. Manufacture of adhesive sheets
將所得到的黏接性組合物的塗布溶液，在將聚對苯二甲酸乙二醇酯薄膜的一個面，用矽酮類剝離劑進行了剝離處理的剝離片(琳得科株式公司製，SP-PET3811，厚度：38μm)的剝離處理面上，用刮刀塗布器進行塗布之後，使乾燥後的厚度為25μm，用90℃進行1分鍾加熱處理而形成的塗布層。 The coating solution of the obtained adhesive composition was peeled off by the one side of the polyethylene terephthalate film by the ketone type release agent (The Linde Co., Ltd. product, SP-PET 3811, thickness: 38 μm) The coating layer formed by coating with a knife coater, and having a thickness of 25 μm after drying and heat treatment at 90 ° C for 1 minute.
接著，在將聚對苯二甲酸乙二醇酯薄膜的一個面，用矽酮類剝離劑進行了剝離處理的剝離片(琳得科株式公司製，SP-PET3801，厚度：38μm)貼合，使該剝離片的剝離處理面與上述塗布層露出的面一側貼合，通過在23℃、50%RH的條件下熟成7天，來製作由剝離片/黏接劑層(厚度：25μm)/剝離片的構成所形成的黏接片。 Next, a release sheet (SP-PET3801, thickness: 38 μm, manufactured by Linda Co., Ltd.) which was peeled off with an anthrone-based release agent was attached to one surface of the polyethylene terephthalate film. The release-treated surface of the release sheet was bonded to the surface on which the coating layer was exposed, and the laminate was aged for 7 days under conditions of 23° C. and 50% RH to prepare a release sheet/adhesive layer (thickness: 25 μm). / Adhesive sheet formed by the composition of the release sheet.
除將構成(甲基)丙烯酸酯聚合物(A)的各單體的種類、比例以及架橋劑(B)的種類及配合量按照表1所示進行變更外，與實施例1同樣地進行操作，製造黏接片。 The operation was carried out in the same manner as in Example 1 except that the type and ratio of each monomer constituting the (meth) acrylate polymer (A) and the type and amount of the bridging agent (B) were changed as shown in Table 1. , manufacturing adhesive sheets.
另外，表1中所述的架橋劑的詳細情況如下所述。 In addition, the details of the bridging agent described in Table 1 are as follows.
：N，N，N’，N’-四縮水甘油基間二甲苯二胺(綜研化學工程公司製，商品名「E-AX」) :N,N,N',N'-tetraglycidyl-m-xylenediamine (manufactured by Amika Chemical Engineering Co., Ltd., trade name "E-AX")
氮丙啶類架橋劑：三羥甲基丙烷三-β-氮丙啶基丙酸酯(東洋油墨公司製，商品名「BXX5172」) Aziridine-type bridging agent: trimethylolpropane tri-β-aziridine propionate (manufactured by Toyo Ink Co., Ltd., trade name "BXX5172")
異氰酸酯類架橋劑：三羥甲基丙烷加合物伸二甲苯二異氰酸酯(綜研化學工程公司製，商品名「TD-75」) Isocyanate bridging agent: trimethylolpropane adduct xylene diisocyanate (manufactured by Soken Chemical Engineering Co., Ltd., trade name "TD-75")
在此，上述的重均分子量(Mw)，為使用凝膠滲透色譜法(GPC)在以下的條件下測定(GPC測定)的聚苯乙烯換算的重均分子量。 Here, the above-mentioned 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).
．GPC測定裝置：Tosoh公司製，HLC-8020 . GPC measuring device: manufactured by Tosoh Corporation, HLC-8020
．GPC柱(以下的順序通過)：Tosoh公司製 . GPC column (the following sequence is passed): 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
．測定溶劑：四氫呋喃 . Determination of solvent: tetrahydrofuran
．測定溫度：40℃ . Measuring temperature: 40 ° C
將在實施例或比較例中得到的黏接片，製成80mm×80mm尺寸的樣品，將其黏接劑層用聚酯制網(網尺寸200)包裹，僅將黏接劑的質量用精密天平進行稱量。將此時的質量作為M1。 The adhesive sheet obtained in the examples or the comparative examples was made into a sample of 80 mm×80 mm size, and the adhesive layer was wrapped with a polyester mesh (mesh size 200), and only the quality of the adhesive was precision. The balance is weighed. The mass at this time is taken as M1.
接著，將上述聚酯制網包裹的黏接劑，在室溫(23℃)下，在乙酸乙酯中進行24小時浸漬。之後將黏接劑取出，在溫度23℃、相對濕度50%的環境下，進行24小時風乾，進一步在80℃的烘箱中進行12小時乾燥。僅將乾燥後的黏接劑的質量用精密天平進行稱量。將此時的質量作為M2。凝膠分率(%)用(M2/M1)×100來表示。將結果示於表2。 Next, the above-mentioned polyester net-wrapped adhesive was immersed in ethyl acetate at room temperature (23 ° C) for 24 hours. Thereafter, the adhesive was taken out, air-dried for 24 hours in an environment of a temperature of 23 ° C and a relative humidity of 50%, and further dried in an oven at 80 ° C for 12 hours. Only the quality of the dried adhesive was weighed with a precision balance. The mass at this time is taken as M2. The gel fraction (%) is represented by (M2/M1) × 100. The results are shown in Table 2.
從實施例或比較例中得到的黏接片上，將一片剝離片剝離露出的黏接劑層，在具有該黏接層的聚對苯二甲酸乙二醇酯薄膜(東洋紡公司製，PET100A4300，厚度：100μm)上貼合後，將該積層體裁斷，製作寬25mm、長100mm的樣品。從該樣品把剝離片剝離，介於露出的黏接劑層，在無堿玻璃(康寧公司製，鷹XG)上將該樣品進行貼附之後，用用栗原製作所制的高壓鍋，在0.5MPA、50℃，加壓20分鍾。之後，在23℃、50%RH的條件下放置24小時後，使用拉力試驗機(奧瑞公司製， TENSILON)，以剝離速度300mm/min、剝離角度180°的條件下對黏接力(N/25mm)進行測定。將結果示於表2。 From the adhesive sheet obtained in the examples or the comparative examples, a piece of the release sheet was peeled off the exposed adhesive layer, and a polyethylene terephthalate film having the adhesive layer (PET100A4300, manufactured by Toyobo Co., Ltd., thickness) was used. : 100 μm) After bonding, the laminate was cut to prepare a sample having a width of 25 mm and a length of 100 mm. The peeling sheet was peeled off from the sample, and the exposed adhesive layer was attached to the sample, and the sample was attached to a glass-free glass (manufactured by Corning Co., Ltd., Eagle XG), and then an autoclave made of Kurihara was used at 0.5 MPA. Pressurize at 50 ° C for 20 minutes. Thereafter, after standing at 23 ° C and 50% RH for 24 hours, a tensile tester (manufactured by Orui Co., Ltd., TENSILON) The adhesion (N/25 mm) was measured under the conditions of a peeling speed of 300 mm/min and a peeling angle of 180°. The results are shown in Table 2.
另外，在上述試驗中剝離樣品時，確認撕裂的發生，根據如下基準進行評價。另外，所謂撕裂是指，從被黏物將黏接片剝離時，無法連續順利剝離，產生剝離音或在黏接劑層形成剝離線紋，如果發生撕裂，剝離性以及貼附性變差。將結果示於表2。 Further, when the sample was peeled off in the above test, the occurrence of tear was confirmed, and evaluation was performed based on the following criteria. In addition, the term "tear" means that when the adhesive sheet is peeled off from the adherend, it is not possible to continuously peel off smoothly, and a peeling sound is generated or a peeling line is formed in the adhesive layer. If tearing occurs, peeling property and adhesion property change. difference. The results are shown in Table 2.
○：沒有撕裂發生 ○: no tearing occurred
△：撕裂一定程度發生(剝離性以及貼附性沒有問題的程度) △: The tearing occurs to a certain extent (the degree of peeling and adhesion is not problematic)
×：撕裂發生(剝離性以及貼附性有問題的程度) ×: tearing occurred (degree of peelability and adhesion)
對於實施例或比較例中得到的黏接片的黏接劑層，在測定波長為589nm、測定溫度為23℃的條件下，使用阿貝折射儀(愛宕公司製)對折射率進行測定。將結果示於表2。 The adhesive layer of the adhesive sheet obtained in the example or the comparative example was measured using the Abbe refractometer (manufactured by Aiko Co., Ltd.) under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 23 °C. The results are shown in Table 2.
將實施例或比較例中得到的黏接片的黏接劑層積層2層，製作膜厚度為50μm的黏接劑層。將該黏接劑層，用兩片厚度為1.1mm的無堿玻璃夾住，將其積層體作為樣品。將所得到的樣品在85℃、85%RH的條件下保管120小時。然後，恢複到23℃、50%RH的常溫常濕，用肉眼按以下基準確認有無白化，在評價耐濕熱白化性的同時，測定黏接劑層的霧度值。霧度值為將樣品恢複到常溫常濕的30分鍾內，基於JIS K7136：2000進行測定。將結果示於表2。 The adhesive of the adhesive sheet obtained in the Example or the comparative example was laminated|stacked two layers, and the adhesive layer of the film thickness of 50 micrometer was formed. The adhesive layer was sandwiched between two sheets of non-twisted glass having a thickness of 1.1 mm, and the laminate was used as a sample. The obtained sample was stored under the conditions of 85 ° C and 85% RH for 120 hours. Then, it was returned to normal temperature and humidity of 23° C. and 50% RH, and whitening was confirmed with the naked eye according to the following criteria, and the haze value of the adhesive layer was measured while evaluating the wet heat whitening resistance. The haze value was measured within 30 minutes of returning the sample to normal temperature and normal humidity, and was measured based on JIS K7136:2000. The results are shown in Table 2.
◎：恢複到常溫常濕之後起完全沒有白化。 ◎: There was no whitening at all after returning to normal temperature and humidity.
○：一部分白化，但在恢複常溫常濕後2小時內白化消失。 ○: Part of the whitening, but whitening disappeared within 2 hours after returning to normal temperature and humidity.
×：整體全部白化。或一部分白化後，在常溫常濕下保管也無法恢複原來狀態。 ×: The whole is whitened. Or after a part of whitening, it cannot be restored to its original state when stored under normal temperature and humidity.
由表2可知，在實施例中所得到的黏接劑層的黏接劑，具有良好的黏接力和高折射率(1.51以上)，同時耐濕熱白化性優異。 As is apparent from Table 2, the adhesive of the adhesive layer obtained in the examples had good adhesion and high refractive index (1.51 or more) and was excellent in wet heat whitening resistance.
本發明的黏接劑適宜用於偏光板、玻璃基板等的光學構件的黏接，而且，本發明的黏接片適宜作為偏光板、玻璃基板等的光學構件用的黏接片。 The adhesive of the present invention is suitably used for bonding optical members such as a polarizing plate and a glass substrate, and the adhesive sheet of the present invention is suitably used as an adhesive sheet for an optical member such as a polarizing plate or a glass substrate.
1A‧‧‧黏接片 1A‧‧‧bonding strip
11‧‧‧黏接劑層 11‧‧‧Adhesive layer
12‧‧‧剝離片 12‧‧‧ peeling film
13‧‧‧基材 13‧‧‧Substrate
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-
2014
- 2014-02-21 KR KR1020140020094A patent/KR102314962B1/en active IP Right Grant
- 2014-02-27 TW TW103106696A patent/TWI628250B/en active
- 2014-03-04 CN CN201710583306.8A patent/CN107216837B/en active Active
- 2014-03-04 CN CN201410075584.9A patent/CN104031582B/en active Active
-
2021
- 2021-09-01 KR KR1020210116182A patent/KR20210112281A/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI806823B (en) * | 2016-01-27 | 2023-07-01 | 日商日東電工股份有限公司 | Adhesive composition, adhesive member, optical member, and electronic member |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102314962B1 (en) | 2021-10-19 |
| JP2014169382A (en) | 2014-09-18 |
| KR20210112281A (en) | 2021-09-14 |
| CN107216837B (en) | 2020-01-17 |
| TWI628250B (en) | 2018-07-01 |
| JP6216519B2 (en) | 2017-10-18 |
| CN107216837A (en) | 2017-09-29 |
| CN104031582B (en) | 2018-05-15 |
| CN104031582A (en) | 2014-09-10 |
| KR20140109265A (en) | 2014-09-15 |
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