TWI737849B - Adhesive composition and surface-protective film - Google Patents
Adhesive composition and surface-protective film Download PDFInfo
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- TWI737849B TWI737849B TW106138599A TW106138599A TWI737849B TW I737849 B TWI737849 B TW I737849B TW 106138599 A TW106138599 A TW 106138599A TW 106138599 A TW106138599 A TW 106138599A TW I737849 B TWI737849 B TW I737849B
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- 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
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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
- C09J133/06—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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- 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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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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
- C08K5/0091—Complexes with metal-heteroatom-bonds
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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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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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
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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
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- C09J2433/00—Presence of (meth)acrylic polymer
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- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
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Abstract
Description
本發明涉及一種含有抗靜電劑的黏著劑組合物及表面保護膜。更詳細而言，為一種含有離子化合物作為抗靜電劑從而具有優異的抗靜電性能和耐污染性的黏著劑組合物及使用了該黏著劑組合物的表面保護膜，所述離子化合物具有九氟丁烷磺酸根等特定的磺酸根陰離子。 The invention relates to an adhesive composition and a surface protective film containing an antistatic agent. In more detail, it is an adhesive composition containing an ionic compound as an antistatic agent to have excellent antistatic performance and pollution resistance, and a surface protective film using the adhesive composition. The ionic compound has nonafluoro Specific sulfonate anions such as butane sulfonate.
以往以來，在電子設備部件、光學設備部件、圖像顯示面板等精密部件及構件的製造加工和組裝工序中，為了暫時保護這些精密部件及構件的表面，以防止來自作業環境氣氛的粒子(particle)‧氣體狀的污染物質的附著，或者刮痕、凹陷的產生，在精密部件及構件的表面上貼附有表面保護膜。 In the past, in the manufacturing, processing and assembly processes of precision parts and components such as electronic equipment parts, optical equipment parts, image display panels, etc., in order to temporarily protect the surfaces of these precision parts and components to prevent particles from the working environment. ) ‧ Adhesion of gaseous pollutants, or the occurrence of scratches or dents, a surface protective film is attached to the surface of precision parts and components.
例如，對於在製造作為構成液晶顯示器的構件的偏振片、相位差板等光學構件的工序中所使用的表面保護膜而言，雖然在具有光學透明性的聚對苯二甲酸乙二醇酯(PET)樹脂膜的單面上形成有黏著劑層，但是在貼合於光學構件上之前，在黏著劑層上貼合有用於保護該黏著劑層的經剝離處理的離型膜。 For example, as for the surface protection film used in the process of manufacturing optical members such as polarizers and retardation plates that constitute liquid crystal displays, there are optically transparent polyethylene terephthalate (polyethylene terephthalate). An adhesive layer is formed on one side of the PET) resin film, but before bonding to the optical member, a release film that has been peeled off to protect the adhesive layer is bonded to the adhesive layer.
此外，偏振片、相位差板等光學構件以貼合有表面保護膜的狀態，進行伴隨液晶顯示板的顯示能力、色調、對 比度、異物混入等光學性評價的產品檢查。因此，作為對表面保護膜的需求性能，要求無氣泡或異物附著於黏著劑層。 In addition, optical components such as polarizers and retardation plates are bonded with surface protection films, and product inspections are carried out with optical evaluation of the display ability, color tone, contrast, and foreign matter incorporation of the liquid crystal display panel. Therefore, as a required performance for the surface protective film, it is required that no bubbles or foreign matter adhere to the adhesive layer.
此外，近年來，認為在將表面保護膜從偏振片、相位差板等光學構件上剝離時，隨著從被黏物上剝離黏著劑層時產生的靜電而產生的剝離靜電可能會對液晶顯示器的電氣控制線路的故障產生影響。因此，對黏著劑層要求優異的抗靜電性能。 In addition, in recent years, it is considered that when the surface protection film is peeled from the polarizer, the retardation plate and other optical members, the peeling static electricity generated by the static electricity generated when the adhesive layer is peeled from the adherend may affect the liquid crystal display. The failure of the electrical control circuit has an impact. Therefore, excellent antistatic properties are required for the adhesive layer.
如上所述，近年來，作為對構成表面保護膜的黏著劑層的需求性能，從使用表面保護膜時的使用難易度的角度出發，要求優異的抗靜電性能及污染防止性能等。 As described above, in recent years, as the performance required for the adhesive layer constituting the surface protective film, from the viewpoint of ease of use when using the surface protective film, excellent antistatic performance and pollution prevention performance are required.
關於優異的抗靜電性能，作為用於賦予表面保護膜抗靜電性的方法，公開有向基材膜中捏合抗靜電劑的方法等，作為抗靜電劑，公開有例如：(a)具有4級銨鹽、吡啶鎓鹽、1級~3級胺基等陽離子基團的各種陽離子抗靜電劑；(b)具有磺酸鹽基、硫酸酯鹽基、磷酸酯鹽基、膦酸鹽基等陰離子基團的陰離子抗靜電劑；(c)氨基酸系、氨基硫酸酯系等兩性抗靜電劑；(d)氨基醇系、甘油系、聚乙二醇系等非離子抗靜電劑；(e)將如上所述的抗靜電劑高分子量化而成的高分子型抗靜電劑等(專利文獻1)。 Regarding excellent antistatic performance, as a method for imparting antistatic properties to a surface protective film, a method of kneading an antistatic agent into a base film is disclosed. As an antistatic agent, for example: (a) having 4 levels Various cationic antistatic agents with cationic groups such as ammonium salts, pyridinium salts, and 1--3 amine groups; (b) anions with sulfonate, sulfate, phosphate, phosphonate and other anions Group of anionic antistatic agents; (c) amphoteric antistatic agents such as amino acid series and aminosulfate series; (d) amino alcohol series, glycerin series, polyethylene glycol series and other nonionic antistatic agents; (e) The above-mentioned antistatic agent is a high molecular weight polymer type antistatic agent, etc. (Patent Document 1).
此外，近年來提出了，不使這樣的抗靜電劑包含於基材膜中，或者不將其塗布於基材膜的表面上，而是直接使其包含於黏著劑層中(專利文獻2)。 In addition, in recent years, it has been proposed that such an antistatic agent is not included in the substrate film, or is not coated on the surface of the substrate film, but directly included in the adhesive layer (Patent Document 2) .
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
專利文獻1：日本特開平11-070629號公報 Patent Document 1: Japanese Patent Laid-Open No. 11-070629
專利文獻2：日本特開2000-129235號公報 Patent Document 2: Japanese Patent Application Publication No. 2000-129235
然而，對於用於LR(低反射)偏振片或AG(防眩)-LR偏振片等光學膜的表面保護膜而言，由於光學膜的表面被施以了基於聚矽氧化合物或氟化合物等的防汙處理或低反射表面處理，因此將表面保護膜從作為被黏物的光學膜上剝離時的剝離靜電電壓變高。 However, for the surface protection film used for optical films such as LR (low reflection) polarizer or AG (anti-glare)-LR polarizer, the surface of the optical film is applied based on polysiloxane or fluorine compound, etc. Anti-fouling treatment or low-reflection surface treatment, so the peeling electrostatic voltage when the surface protective film is peeled from the optical film as the adherend becomes higher.
此外，具備抗靜電性能的黏著劑組合物及使用了該黏著劑組合物的表面保護膜的抗靜電性能與對被黏物的耐污染性的關係為此消彼長(trade-off)的關係，難以在維持抗靜電性能的同時改善耐污染性。 In addition, there is a trade-off relationship between the antistatic performance of the adhesive composition with antistatic properties and the surface protective film using the adhesive composition and the stain resistance of the adherend. , It is difficult to improve stain resistance while maintaining antistatic performance.
因此，在用於LR偏振片或AG-LR偏振片等光學膜的表面保護膜用的黏著劑組合物中，尋求一種即使在光學膜的表面被施以了基於聚矽氧化合物或氟化合物等的防汙處理或低反射表面處理的情況下，也可將表面保護膜從光學膜上剝離時的剝離靜電電壓抑制為較低、並且被黏物的污染少的黏著劑組合物。 Therefore, in the adhesive composition used for the surface protection film of optical film such as LR polarizer or AG-LR polarizer, it is sought for an adhesive composition based on polysiloxane or fluorine compound, etc., even if the surface of the optical film is applied In the case of anti-fouling treatment or low-reflection surface treatment, the peeling electrostatic voltage when the surface protective film is peeled from the optical film can be suppressed to a low adhesive composition with less contamination of the adherend.
本發明是鑒於上述情況而完成的，本發明提供一種黏著劑組合物及使用了該黏著劑組合物的表面保護膜，所述黏著劑組合物可在利用含有氟化合物的組合物對被黏物施以表面處理的情況下，同時實現優異的抗靜電性能和耐污染性。 The present invention was completed in view of the above circumstances. The present invention provides an adhesive composition and a surface protective film using the adhesive composition. The adhesive composition can be used to When surface treatment is applied, excellent antistatic performance and pollution resistance are achieved at the same time.
本申請的發明人製備了一種新的黏著劑組合物，其含有：將構成黏著劑組合物的丙烯酸系聚合物的(甲基)丙 烯酸烷基酯的烷基的碳原子數限定為特定的範圍、並使特定的組合的兩種以上的(甲基)丙烯酸烷基酯共聚而成的共聚物；以及由具有九氟丁烷磺酸根等特定的磺酸根陰離子的熔點為25℃以上的離子化合物形成的抗靜電劑。由此，發現可得到一種與以往的表面保護膜用黏著劑組合物相比，具有優異的耐污染性，並且具有不發生經時劣化的優異的抗剝離靜電性能的黏著劑組合物，從而完成了本發明。 The inventor of the present application has prepared a new adhesive composition containing: limiting the number of carbon atoms of the alkyl group of the alkyl (meth)acrylate of the acrylic polymer constituting the adhesive composition to a specific range , And the copolymer of two or more (meth)acrylic acid alkyl esters in a specific combination; and an ionic compound having a specific sulfonate anion such as nonafluorobutanesulfonate with a melting point of 25°C or higher Antistatic agent formed. As a result, it was found that an adhesive composition that has excellent stain resistance compared to conventional adhesive compositions for surface protective films, and has excellent anti-peeling electrostatic performance without deterioration over time, was completed. The present invention.
特別是已明確：在被黏物具有積層於光學膜的表面上的、含有氟化合物的防汙層或者使用含有氟化合物的低折射率形成用的組合物而形成的低折射率層的情況下，與現有技術相比，本發明涉及的表面保護膜具有優異的耐污染性，並且具有不發生經時劣化的優異的抗剝離靜電性能。即，可得到一種具有同時實現抗靜電性能和耐污染性的效果的表面保護膜。 In particular, it has been clarified that when the adherend has an antifouling layer containing a fluorine compound laminated on the surface of the optical film or a low refractive index layer formed using a composition for forming a low refractive index containing a fluorine compound Compared with the prior art, the surface protective film of the present invention has excellent pollution resistance, and has excellent anti-peeling electrostatic performance without deterioration over time. That is, it is possible to obtain a surface protective film having the effects of simultaneously achieving antistatic performance and stain resistance.
為了解決所述技術問題，本發明提供一種黏著劑組合物，其含有丙烯酸系聚合物、抗靜電劑及(D)交聯劑，其特徵在於，所述丙烯酸系聚合物具有0℃以下的玻璃轉移溫度，所述(D)交聯劑為三官能以上的異氰酸酯化合物，所述抗靜電劑為由陽離子和陰離子形成的熔點為25℃以上的離子化合物，所述陰離子為選自由三氟甲烷磺酸根陰離子、五氟乙烷磺酸根陰離子、七氟丙烷磺酸根陰離子、九氟丁烷磺酸根陰離子組成的組中的一種，相對於100重量份的所述丙烯酸系聚合物，以0.01~10重量份的比例含有所述抗靜電劑作為必需成分。 In order to solve the technical problem, the present invention provides an adhesive composition containing an acrylic polymer, an antistatic agent and (D) a crosslinking agent, characterized in that the acrylic polymer has a glass temperature of 0°C or less For the transition temperature, the (D) crosslinking agent is an isocyanate compound with three or more functions, the antistatic agent is an ionic compound formed of a cation and an anion with a melting point of 25° C. or more, and the anion is selected from the group consisting of trifluoromethane sulfonate One of the acid radical anion, pentafluoroethane sulfonate anion, heptafluoropropane sulfonate anion, nonafluorobutane sulfonate anion, relative to 100 parts by weight of the acrylic polymer, 0.01 to 10 parts by weight The ratio contains the antistatic agent as an essential ingredient.
此外，優選：所述丙烯酸系聚合物為使下列單體共聚而成的共聚物的丙烯酸系聚合物：(A)烷基的碳原子數為C1~18的(甲基)丙烯酸酯單體中的至少兩種以上，其以1~50重量份的比例含有(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體中的至少一種，並以50~99重量份的比例含有(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中的至少一種，所述(a1)與所述(a2)的總計為100重量份；(B)含有羥基和/或羧基的共聚性乙烯基單體中的至少一種以上；及(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體中的至少一種以上，所述(a2)中，以50重量份以上的比例含有選自由(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸-2-乙基己酯組成的組中的至少一種，所述黏著劑組合物進一步含有(E)金屬螯合化合物的交聯促進劑和(F)酮-烯醇互變異構體化合物。 In addition, it is preferable that the acrylic polymer is an acrylic polymer of a copolymer obtained by copolymerizing the following monomers: (A) among the (meth)acrylate monomers having C1-18 carbon atoms in the alkyl group At least two or more of (a1) alkyl (meth)acrylate monomers with C1-C4 carbon atoms in a ratio of 1-50 parts by weight, and 50-99 parts by weight The ratio of (a2) contains at least one of the (meth)acrylate monomers with C5 to C18 alkyl carbon atoms, and the total of (a1) and (a2) is 100 parts by weight; (B) ) At least one or more of copolymerizable vinyl monomers containing hydroxyl and/or carboxyl groups; and (C) at least one or more of mono(meth)acrylate monomers containing polyalkylene glycol chain, said (a2) In the ratio of 50 parts by weight or more, it contains isooctyl (meth)acrylate, isononyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. At least one, the adhesive composition further contains (E) a crosslinking accelerator of a metal chelate compound and (F) a keto-enol tautomer compound.
所述陽離子優選為選自由吡啶鎓、咪唑鎓、鏻、鋶、吡咯啶鎓、胍鎓、銨、異脲鎓(isouronium)、硫脲鎓(thiouronium)、呱啶鎓、吡唑鎓(pyrazolium)、甲基鎓(methylium)、鋰、嗎啉鎓(morpholinium)組成的組中的一種。 The cation is preferably selected from pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium (isouronium), thiouronium (thiouronium), pyridinium, pyrazolium (pyrazolium) , One of the group consisting of methylium, lithium, and morpholinium.
優選：使所述黏著劑組合物交聯而成的黏著劑層的表面電阻率為1.0×10+12Ω/□以下，相對於使用含有氟化合物的低折射率層形成用的組合物而形成的低折射率層的、所述黏 著劑層的剝離靜電電壓為-0.3~+0.3kV。 Preferably: the adhesive layer formed by cross-linking the adhesive composition has a surface resistivity of 1.0×10 +12 Ω/□ or less, compared to a composition for forming a low refractive index layer containing a fluorine compound The peeling electrostatic voltage of the low refractive index layer of the adhesive layer is -0.3~+0.3kV.
優選：所述(B)含有羥基和/或羧基的共聚性乙烯基單體為選自由含有羥基的可共聚單體、及含有羧基的可共聚單體組成的組中的至少一種以上，其中，所述含有羥基的可共聚單體為選自由(甲基)丙烯酸-8-羥基辛酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-2-羥基乙酯、N-羥基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺組成的化合物組中的至少一種以上，所述含有羧基的可共聚單體為選自由(甲基)丙烯酸、羧乙基(甲基)丙烯酸酯、羧戊基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基馬來酸、羧基聚己內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基四氫鄰苯二甲酸組成的化合物組中的至少一種以上。 Preferably: (B) the copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group is at least one or more selected from the group consisting of a copolymerizable monomer containing a hydroxyl group and a copolymerizable monomer containing a carboxyl group, wherein, The hydroxy-containing copolymerizable monomer is selected from the group consisting of (meth) acrylate-8-hydroxyoctyl ester, (meth) acrylate-6-hydroxyhexyl ester, (meth) acrylate-4-hydroxybutyl ester, (meth) acrylate Group) 2-hydroxyethyl acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide At least one of the carboxyl-containing copolymerizable monomers is selected from (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(methyl) Acrylic oxyethyl hexahydro phthalic acid, 2-(meth) acryloxy propyl hexahydro phthalic acid, 2-(meth) acryloxy ethyl phthalic acid, 2 -(Meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylmaleic acid, carboxypolycaprolactone mono(meth)acrylate, 2-(meth)propylene At least one or more of the compound group consisting of acetoxyethyltetrahydrophthalic acid.
優選：對於所述(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體而言，構成聚亞烷基二醇鏈的環氧烷(alkylene oxide)的平均重複單元數為3~14，所述(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體中的二酯組分為0.2%以下，相對於總計為100重量份的所述(A)烷基的碳原子數為C1~18的(甲基)丙烯酸酯單體中的至少兩種以上，以1~50重量份的比例含有選自由聚亞烷基二醇單(甲基)丙烯酸酯、 甲氧基聚亞烷基二醇(甲基)丙烯酸酯、乙氧基聚亞烷基二醇(甲基)丙烯酸酯組成的組中的至少一種以上作為所述(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體。 Preferably: for the (C) polyalkylene glycol chain-containing mono(meth)acrylate monomer, the average number of repeating units of alkylene oxide constituting the polyalkylene glycol chain The diester component in the (C) polyalkylene glycol chain-containing mono(meth)acrylate monomer is 0.2% or less, relative to a total of 100 parts by weight of the ( A) At least two or more of the (meth)acrylate monomers with C1-18 carbon atoms in the alkyl group are contained in a ratio of 1-50 parts by weight selected from polyalkylene glycol mono(methyl) At least one of the group consisting of acrylate, methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acrylate is used as the (C) containing poly(meth)acrylate Mono(meth)acrylate monomer of alkylene glycol chain.
優選：所述(E)交聯促進劑為選自由鋁螯合化合物、鈦螯合化合物、鐵螯合化合物組成的組中的至少一種以上，相對於100重量份的所述丙烯酸系聚合物，以0.001~0.5重量份的比例含有所述(E)交聯促進劑、並以0.1~300重量份的比例含有所述(F)酮-烯醇互變異構體化合物，所述(F)/所述(E)的重量份比為70~1000。 Preferably: the (E) crosslinking accelerator is at least one selected from the group consisting of aluminum chelating compounds, titanium chelating compounds, and iron chelating compounds, relative to 100 parts by weight of the acrylic polymer, The (E) crosslinking accelerator is contained in a ratio of 0.001 to 0.5 parts by weight, and the (F) keto-enol tautomer compound is contained in a ratio of 0.1 to 300 parts by weight, and the (F)/ The weight ratio of the (E) is 70-1000.
此外，本發明提供一種黏著膜，其特徵在於，在樹脂膜的單面上積層有使上述的黏著劑組合物交聯而成的黏著劑層。 In addition, the present invention provides an adhesive film characterized in that an adhesive layer formed by crosslinking the above-mentioned adhesive composition is laminated on one side of a resin film.
此外，本發明提供一種表面保護膜，其使用了上述的黏著膜。 In addition, the present invention provides a surface protection film using the above-mentioned adhesive film.
此外，本發明提供一種偏振片用的表面保護膜，其使用了上述的黏著膜。 In addition, the present invention provides a surface protective film for a polarizing plate, which uses the above-mentioned adhesive film.
此外，本發明提供一種帶黏著劑層的光學膜，其在光學膜的至少一側的面上積層有使上述的黏著劑組合物交聯而成的黏著劑層。 In addition, the present invention provides an optical film with an adhesive layer, in which an adhesive layer formed by crosslinking the above-mentioned adhesive composition is laminated on at least one surface of the optical film.
此外，本發明提供一種黏著膜，其中，在所述樹脂膜的單面、即與積層有所述黏著劑層的一側相反的面上實施有抗靜電處理及防汙處理。 In addition, the present invention provides an adhesive film in which an antistatic treatment and an antifouling treatment are applied to one side of the resin film, that is, the side opposite to the side on which the adhesive layer is laminated.
本發明提供一種可同時實現優異的抗靜電性能和 耐污染性的黏著劑組合物及表面保護膜。 The present invention provides an adhesive composition and a surface protective film that can achieve excellent antistatic performance and stain resistance at the same time.
在被黏物具有積層於光學膜的表面上的、含有氟化合物的防汙層或者使用含有氟化合物的低折射率層形成用的組合物而形成的低折射率層的情況下，與現有技術相比，本發明涉及的黏著劑組合物及使用了該黏著劑組合物的表面保護膜具有優異的耐污染性，並且具有不發生經時劣化的優異的抗剝離靜電性能。 When the adherend has an antifouling layer containing a fluorine compound laminated on the surface of the optical film or a low refractive index layer formed using a composition for forming a low refractive index layer containing a fluorine compound, it is consistent with the prior art In contrast, the adhesive composition of the present invention and the surface protective film using the adhesive composition have excellent pollution resistance, and have excellent anti-peeling electrostatic performance without deterioration over time.
即，本發明涉及的黏著劑組合物及使用了該黏著劑組合物的表面保護膜由於具備優異的抗靜電性能和耐污染性，因此在產業上的利用價值極大。 That is, since the adhesive composition of the present invention and the surface protective film using the adhesive composition have excellent antistatic performance and stain resistance, they have great industrial utility value.
以下，基於適宜的實施方式，對本發明進行說明。 Hereinafter, the present invention will be described based on suitable embodiments.
本實施方式的黏著劑組合物是含有丙烯酸系聚合物、抗靜電劑及(D)交聯劑的黏著劑組合物，所述丙烯酸系聚合物具有0℃以下的玻璃轉移溫度，所述(D)交聯劑為三官能以上的異氰酸酯化合物，所述抗靜電劑為由陽離子和陰離子形成的熔點為25℃以上的離子化合物，所述陰離子為選自由三氟甲烷磺酸根陰離子、五氟乙烷磺酸根陰離子、七氟丙烷磺酸根陰離子、九氟丁烷磺酸根陰離子組成的組中的一種；相對於100重量份的所述丙烯酸系聚合物，以0.01~10重量份的比例含有所述抗靜電劑作為必需成分。 The adhesive composition of the present embodiment is an adhesive composition containing an acrylic polymer, an antistatic agent, and (D) a crosslinking agent. The acrylic polymer has a glass transition temperature of 0°C or less, and the (D) ) The crosslinking agent is an isocyanate compound with more than three functions, the antistatic agent is an ionic compound formed of cations and anions with a melting point of 25° C. or more, and the anion is selected from the group consisting of trifluoromethanesulfonate anion and pentafluoroethane One of the group consisting of sulfonate anion, heptafluoropropane sulfonate anion, and nonafluorobutane sulfonate anion; relative to 100 parts by weight of the acrylic polymer, the antistatic agent is contained in a ratio of 0.01 to 10 parts by weight As an essential ingredient.
此外，優選所述抗靜電劑是在25℃的溫度下為固體的、熔 點為25℃以上的離子化合物，進一步優選所述抗靜電劑的熔點為450℃以下。 In addition, it is preferable that the antistatic agent is an ionic compound that is solid at a temperature of 25°C and has a melting point of 25°C or higher, and it is more preferable that the melting point of the antistatic agent is 450°C or lower.
本實施方式的黏著劑組合物中使用的丙烯酸系聚合物具有0℃以下的玻璃轉移溫度。此外，丙烯酸系聚合物優選為以(A)烷基的碳原子數為C1~18的(甲基)丙烯酸酯單體作為主要成分的共聚物。 The acrylic polymer used in the adhesive composition of this embodiment has a glass transition temperature of 0°C or less. In addition, the acrylic polymer is preferably a copolymer having (A) an alkyl (meth)acrylate monomer having C1 to 18 carbon atoms as a main component.
此外，作為(A)烷基的碳原子數為C1~18的(甲基)丙烯酸酯單體，可列舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯等。(甲基)丙烯酸烷基酯單體的烷基為直鏈、分支狀、環狀中的任意一種均可。 In addition, examples of (A) alkyl (meth)acrylate monomers having C1-18 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate Ester, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, ( Undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate Alkyl ester, cetyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, (meth)acrylate Cyclohexyl acrylate, etc. The alkyl group of the (meth)acrylic acid alkyl ester monomer may be any of linear, branched, and cyclic.
此外，相對於總計為100重量份的(A)烷基的碳原子數為C1~18的(甲基)丙烯酸酯單體，(a1)烷基的碳原子數為C1~C4的(甲基)丙烯酸酯單體中的至少一種的比例優選為1~50重量份、(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中的至少一種的比例優選為50~99重量 份。此外，相對於總計為100重量份的(A)烷基的碳原子數為C1~18的(甲基)丙烯酸酯單體，(a2)烷基的碳原子數為C5~C18的(甲基)丙烯酸酯單體中，優選以50重量份以上的比例含有選自由(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸-2-乙基己酯組成的組中的至少一種。 In addition, with respect to a total of 100 parts by weight of (A) alkyl (meth)acrylate monomers with C1-18 carbon atoms, (a1) (a1) alkyl (meth)acrylate monomers with C1-C4 carbon atoms ) The ratio of at least one of the acrylate monomers is preferably 1 to 50 parts by weight, and the ratio of (a2) at least one of the (meth)acrylate monomers having C5 to C18 alkyl groups is preferably 50 parts by weight. ~99 parts by weight. In addition, with respect to a total of 100 parts by weight of (A) alkyl (meth)acrylate monomers having C1 to 18 carbon atoms, (a2) (methyl) alkyl groups having C5 to C18 carbon atoms ) In the acrylic acid ester monomers, it is preferable to contain a ratio of 50 parts by weight or more selected from the group consisting of isooctyl (meth)acrylate, isononyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate At least one of the group.
本實施方式的黏著劑組合物中使用的丙烯酸系聚合物可以使(B)含有羥基和/或羧基的共聚性乙烯基單體中的至少一種作為任意成分共聚而成。作為(B)含有羥基和/或羧基的共聚性乙烯基單體，可列舉出選自由含有羥基的可共聚單體(含羥基單體)及含有羧基的可共聚單體(含羧基單體)組成的組中的至少一種以上。即，可以僅選擇含羥基單體或含羧基單體中的任意一者而進行共聚，也可以使含羥基單體及含羧基單體這兩者共聚。 The acrylic polymer used in the adhesive composition of the present embodiment can be obtained by copolymerizing at least one of (B) a hydroxyl group and/or carboxyl group-containing copolymerizable vinyl monomer as an optional component. (B) The copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group may be selected from a copolymerizable monomer containing a hydroxyl group (a hydroxyl group-containing monomer) and a copolymerizable monomer containing a carboxyl group (a carboxyl group-containing monomer) At least one of the group consisting of. That is, only one of the hydroxyl group-containing monomer and the carboxyl group-containing monomer may be selected and copolymerized, or both the hydroxyl group-containing monomer and the carboxyl group-containing monomer may be copolymerized.
此外，作為含羥基單體，可列舉出選自由(甲基)丙烯酸-8-羥基辛酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-2-羥基乙酯、N-羥基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺等組成的化合物組中的至少一種以上。相對於總計為100重量份的(A)烷基的碳原子數為C1~18的(甲基)丙烯酸酯單體中的至少兩種以上，本實施方式的黏著劑組合物中含有的含羥基單體的比例優選為0.1~20重量份的比例，更優選為4.1~16重量份的比例，特別優選為5.1~14重量份的比例。 In addition, as the hydroxyl group-containing monomers, exemplified are selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, ( It is composed of 2-hydroxyethyl methacrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, etc. At least one of the compound group. With respect to at least two or more of the (meth)acrylate monomers having C1 to 18 carbon atoms in the alkyl group (A) totaling 100 parts by weight, the adhesive composition of the present embodiment contains a hydroxyl group The ratio of the monomers is preferably 0.1 to 20 parts by weight, more preferably 4.1 to 16 parts by weight, and particularly preferably 5.1 to 14 parts by weight.
此外，作為含羧基單體，可列舉出選自由(甲基)丙烯酸、羧乙基(甲基)丙烯酸酯、羧戊基(甲基)丙烯酸酯、 2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基馬來酸、羧基聚己內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基四氫鄰苯二甲酸等組成的化合物組中的至少一種以上。相對於總計為100重量份的(A)烷基的碳原子數為C1~18的(甲基)丙烯酸酯單體中的至少兩種以上，本實施方式涉及的黏著劑組合物中的含羧基單體的比例優選為0~5.0重量份(也允許未使含羧基單體共聚的情況)，在使含羧基單體共聚的情況下，更優選為0.01~5.0重量份的比例，特別優選為0.02~1.3重量份的比例，最優選為0.02~0.8重量份的比例。 In addition, examples of carboxyl group-containing monomers include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)acryloyloxyethyl Hexahydrophthalic acid, 2-(meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(methyl) Acrylic oxyethyl succinic acid, 2-(meth) acryloxy ethyl maleic acid, carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acryloxyethyl At least one or more of the compound group consisting of tetrahydrophthalic acid and the like. With respect to at least two or more of the (meth)acrylate monomers having C1 to 18 carbon atoms in the alkyl group (A) totaling 100 parts by weight, the adhesive composition according to the present embodiment contains a carboxyl group The ratio of the monomers is preferably 0 to 5.0 parts by weight (the case where the carboxyl group-containing monomer is not copolymerized is also allowed). In the case of copolymerizing the carboxyl group-containing monomer, the ratio is more preferably 0.01 to 5.0 parts by weight, and particularly preferably The ratio of 0.02 to 1.3 parts by weight is most preferably the ratio of 0.02 to 0.8 parts by weight.
本實施方式的黏著劑組合物中使用的丙烯酸系聚合物可以使(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體作為任意成分而共聚。作為(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體，只要為聚亞烷基二醇所具有的多個羥基中的一個羥基被酯化為(甲基)丙烯酸酯而成的化合物即可。由於(甲基)丙烯酸酯基為聚合性基團，因此能夠與所述丙烯酸系聚合物共聚。本實施方式中，即使為其他的羥基仍為OH的聚亞烷基二醇單(甲基)丙烯酸酯，也不將其分類為(B)含有羥基和/或羧基的共聚性乙烯基單體。(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體也可以為其他的羥基變換成烷基醚的烷氧基聚亞烷基二醇單(甲基)丙烯酸酯等。 The acrylic polymer used in the adhesive composition of the present embodiment can copolymerize (C) a polyalkylene glycol chain-containing mono(meth)acrylate monomer as an optional component. As (C) a polyalkylene glycol chain-containing mono(meth)acrylate monomer, as long as one of the multiple hydroxyl groups possessed by the polyalkylene glycol is esterified to (meth)acrylic acid What is necessary is just a compound which consists of an ester. Since the (meth)acrylate group is a polymerizable group, it can be copolymerized with the acrylic polymer. In this embodiment, even if it is a polyalkylene glycol mono(meth)acrylate whose other hydroxyl group is still OH, it is not classified as (B) a copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group . (C) The polyalkylene glycol chain-containing mono(meth)acrylate monomer may also be an alkoxy polyalkylene glycol mono(meth)acrylate in which other hydroxyl groups are converted to alkyl ethers, etc. .
此外，作為構成聚亞烷基二醇鏈的聚亞烷基二醇，只要為具有一種或兩種以上的亞烷基的二元醇化合物即 可，例如可列舉出聚乙二醇、聚丙二醇、聚丁二醇、聚乙二醇-聚丙二醇、聚乙二醇-聚丁二醇、聚丙二醇-聚丁二醇、聚乙二醇-聚丙二醇-聚丁二醇等。 In addition, the polyalkylene glycol constituting the polyalkylene glycol chain may be a glycol compound having one or two or more alkylene groups, and examples thereof include polyethylene glycol and polypropylene glycol. , Polybutylene glycol, polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, polyethylene glycol-polypropylene glycol-polybutylene glycol, etc.
此外，對於(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體而言，優選構成聚亞烷基二醇鏈的環氧烷的平均重複單元數為3~14。“環氧烷的平均重複單元數”是指在(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體的分子結構中所包含的“聚亞烷基二醇鏈”的部分中，環氧烷單元重複的平均數。此外，優選(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體中的二酯組分為0.2%以下。“單體中的二酯組分”是指(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體中所包含的聚亞烷基二醇二(甲基)丙烯酸酯的含有率(重量%)。 In addition, it is preferable that (C) the polyalkylene glycol chain-containing mono(meth)acrylate monomer has an average number of repeating units of the alkylene oxide constituting the polyalkylene glycol chain of 3-14. The "average number of repeating units of alkylene oxide" refers to the "polyalkylene glycol chain" contained in the molecular structure of (C) a polyalkylene glycol chain-containing mono(meth)acrylate monomer In the part, the average number of repeating alkylene oxide units. In addition, it is preferable that the diester component in the (C) polyalkylene glycol chain-containing mono(meth)acrylate monomer is 0.2% or less. "The diester component in the monomer" means (C) the polyalkylene glycol di(meth)acrylate contained in the polyalkylene glycol chain-containing mono(meth)acrylate monomer The content rate (weight%).
此外，作為(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體，優選為選自由聚亞烷基二醇單(甲基)丙烯酸酯、甲氧基聚亞烷基二醇(甲基)丙烯酸酯、乙氧基聚亞烷基二醇(甲基)丙烯酸酯組成的組中的至少一種以上。 In addition, (C) the polyalkylene glycol chain-containing mono(meth)acrylate monomer is preferably selected from the group consisting of polyalkylene glycol mono(meth)acrylate and methoxypolyalkylene At least one kind selected from the group consisting of glycol (meth)acrylate and ethoxy polyalkylene glycol (meth)acrylate.
相對於總計為100重量份的(A)烷基的碳原子數為C1~18的(甲基)丙烯酸酯單體中的至少兩種以上，本實施方式涉及的黏著劑組合物中的(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體的比例優選為1~50重量份的比例，更優選為1~30重量份的比例，特別優選為2~25重量份的比例。 (C ) The ratio of the polyalkylene glycol chain-containing mono(meth)acrylate monomer is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 2 to 25 parts by weight proportion.
本實施方式涉及的黏著劑組合物中含有的丙烯酸系聚合物的製備方法沒有特別的限定，可使用溶液聚合法、乳液聚合法等適宜且已知的聚合方法。對於本實施方式涉及的黏 著劑組合物而言，優選所使用的丙烯酸系聚合物的共聚物的重均分子量為100~300萬。 The preparation method of the acrylic polymer contained in the adhesive composition according to this embodiment is not particularly limited, and a suitable and known polymerization method such as a solution polymerization method and an emulsion polymerization method can be used. For the adhesive composition according to the present embodiment, the weight average molecular weight of the acrylic polymer copolymer used is preferably 1 to 3 million.
為了獲得抗靜電性能，本實施方式涉及的黏著劑組合物含有(G)抗靜電劑。(G)抗靜電劑為由陽離子和陰離子形成的熔點為25℃以上的離子化合物，該陰離子為選自由三氟甲烷磺酸根陰離子(CF3SO3 -)、五氟乙烷磺酸根陰離子(CF3CF2SO3 -)、七氟丙烷磺酸根陰離子(CF3CF2CF2SO3 -)、九氟丁烷磺酸根陰離子(CF3CF2CF2CF2SO3 -)組成的群組中的一種。相對於100重量份的丙烯酸系聚合物，本實施方式涉及的黏著劑組合物優選以0.01~10重量份的比例含有(G)抗靜電劑作為必需成分，在需要進一步提高黏著劑層的抗靜電性能從而使表面電阻率的下限值降低至1.0×10+10Ω/□以下的情況下，更優選以0.01~15重量份的比例含有(G)抗靜電劑。 In order to obtain antistatic performance, the adhesive composition according to this embodiment contains (G) an antistatic agent. (G) an antistatic agent cation and an anion formed by the melting point is above 25 ℃ ionic compound the anion is selected from the group consisting of trifluoromethanesulfonic acid anion (CF 3 SO 3 -), pentafluoroethane sulfonate anion (CF 3 CF 2 SO 3 -), heptafluoropropane sulfonate anion (CF 3 CF 2 CF 2 SO 3 -), nonafluorobutanesulfonic acid anion (CF 3 CF 2 CF 2 CF 2 SO 3 - group) consisting of A sort of. With respect to 100 parts by weight of the acrylic polymer, the adhesive composition according to the present embodiment preferably contains (G) an antistatic agent as an essential component in a ratio of 0.01 to 10 parts by weight, and when it is necessary to further improve the antistatic properties of the adhesive layer When the performance reduces the lower limit of the surface resistivity to 1.0×10 +10 Ω/□ or less, it is more preferable to contain the (G) antistatic agent in a ratio of 0.01 to 15 parts by weight.
此外，作為離子化合物所含有的陽離子，可列舉出選自由吡啶鎓、咪唑鎓、鏻、鋶、吡咯啶鎓、胍鎓、銨、異脲鎓、硫脲鎓、呱啶鎓、吡唑鎓、甲基鎓、鋰、嗎啉鎓組成的組中的一種。 In addition, the cation contained in the ionic compound may be selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, pyridinium, pyrazolium, One of the group consisting of methyl onium, lithium, and morpholinium.
此外，作為(G)抗靜電劑的具體例，可列舉出三氟甲烷磺酸鋰、九氟丁烷磺酸鋰、1-甲基-3-辛基吡啶鎓 三氟甲烷磺酸鹽、3-甲基-1-辛基吡啶鎓 三氟甲烷磺酸鹽、1-甲基-4-辛基吡啶鎓 九氟丁烷磺酸鹽、4-甲基-1-辛基吡啶鎓 九氟丁烷磺酸鹽、二甲基二辛基銨 五氟乙烷磺酸鹽、1-甲基-3-辛基吡啶鎓 七氟丙烷磺酸鹽、3-甲基-1-辛基吡啶鎓 七氟丙烷磺酸鹽、1-甲基-3-辛基吡啶鎓 九氟丁烷磺酸鹽、3-甲基-1-辛基吡 啶鎓 九氟丁烷磺酸鹽、1-辛基-3-甲基咪唑鎓 九氟丁烷磺酸鹽等。 In addition, as specific examples of the (G) antistatic agent, lithium trifluoromethanesulfonate, lithium nonafluorobutanesulfonate, 1-methyl-3-octylpyridinium trifluoromethanesulfonate, 3 -Methyl-1-octylpyridinium trifluoromethanesulfonate, 1-methyl-4-octylpyridinium nonafluorobutanesulfonate, 4-methyl-1-octylpyridinium nonafluorobutane Alkyl sulfonate, dimethyl dioctyl ammonium pentafluoroethane sulfonate, 1-methyl-3-octylpyridinium heptafluoropropane sulfonate, 3-methyl-1-octylpyridinium heptafluoropropane sulfonic acid Salt, 1-methyl-3-octylpyridinium nonafluorobutanesulfonate, 3-methyl-1-octylpyridinium nonafluorobutanesulfonate, 1-octyl-3-methylimidazole Onium nonafluorobutane sulfonate and the like.
本實施方式涉及的黏著劑組合物進一步含有三官能以上的異氰酸酯化合物作為(D)交聯劑。 The adhesive composition according to this embodiment further contains a trifunctional or higher isocyanate compound as the (D) crosslinking agent.
作為三官能以上的異氰酸酯化合物，例如可列舉出六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、二苯基甲烷二異氰酸酯、甲苯二異氰酸酯、二甲苯撐基(xylylene)二異氰酸酯等二異氰酸酯系的縮二脲改性體或異氰脲酸酯改性體，與三羥甲基丙烷或甘油等三元以上的多元醇的加合物等。 As trifunctional or higher isocyanate compounds, for example, diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate, etc. The biuret modified body or isocyanurate modified body, and trimethylolpropane or glycerin and other trivalent or more polyhydric alcohol adducts.
作為(D)交聯劑的比例，例如可列舉出相對於100重量份的丙烯酸系聚合物為0.01~5重量份的比例。 As a ratio of (D) crosslinking agent, the ratio of 0.01-5 weight part with respect to 100 weight part of acrylic polymers is mentioned, for example.
本實施方式涉及的黏著劑組合物也可含有(E)交聯促進劑。將聚異氰酸酯化合物作為交聯劑的情況下，(E)交聯促進劑只要為作為催化劑而對所述丙烯酸系聚合物與交聯劑的反應(交聯反應)發揮作用的物質即可，可列舉出3級胺等胺系化合物、金屬螯合化合物、有機錫化合物、有機鉛化合物、有機鋅化合物等有機金屬化合物等。本實施方式中，作為交聯促進劑，優選金屬螯合化合物。 The adhesive composition according to this embodiment may contain (E) a crosslinking accelerator. When a polyisocyanate compound is used as a crosslinking agent, the (E) crosslinking accelerator may be a substance that acts as a catalyst for the reaction (crosslinking reaction) between the acrylic polymer and the crosslinking agent, and it may be Examples include amine compounds such as tertiary amines, metal chelate compounds, organic tin compounds, organic lead compounds, organic zinc compounds, and other organic metal compounds. In this embodiment, as the crosslinking accelerator, a metal chelate compound is preferable.
此外，作為金屬螯合化合物，為在中心金屬原子M上鍵合有1個以上的多齒配體L的化合物。金屬螯合化合物可以具有1個以上的鍵合於金屬原子M上的單齒配體X，也可以不具有單齒配體X。例如，將金屬原子M為1個的金屬螯合化合物的通式用M(L)m(X)n表示時，m
此外，作為金屬原子M，可列舉出Fe，Ni，Mn，Cr，V，Ti，Ru，Zn，Al，Zr，Sn等。 In addition, examples of the metal atom M include Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, Sn, and the like.
作為多齒配體L，可列舉出乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油醇酯(oleyl acetoacetate)、乙醯乙酸月桂酯、乙醯乙酸硬脂醯酯等β-酮酯、乙醯丙酮(別名2,4-戊二酮)、2,4-己二酮、苯甲醯丙酮等β-二酮。這些多齒配體L為酮-烯醇互變異構體化合物，對於多齒配體L而言，也可以為烯醇脫質子而成的烯醇化合物(例如乙醯丙酮化物)。 Examples of the multidentate ligand L include methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, and stearyl acetoacetate. Β-ketoesters such as acetone, β-diketones such as acetone (also known as 2,4-pentanedione), 2,4-hexanedione, and benzacetone. These multidentate ligands L are keto-enol tautomer compounds, and the multidentate ligand L may also be an enol compound obtained by deprotonation of an enol (for example, acetylacetonate).
作為單齒配體X，可列舉出氯原子、溴原子等鹵素原子；戊醯基、己醯基、2-乙基己醯基、辛醯基、壬醯基、癸醯基、十二醯基、十八醯基等醯氧基；甲氧基、乙氧基、正丙氧基、異丙氧基、丁氧基等烷氧基等。 Examples of the monodentate ligand X include halogen atoms such as chlorine atoms and bromine atoms; Alkoxy groups such as octadecanoyl group; alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, butoxy and the like.
此外，作為金屬螯合化合物的具體例，可列舉出三(2,4-戊二酮)鐵(III)、三乙醯丙酮鐵、三乙醯丙酮鈦、三乙醯丙酮釕、雙乙醯丙酮鋅、三乙醯丙酮鋁、四乙醯丙酮鋯、三(2,4-己二酮)鐵(III)、雙(2,4-己二酮)鋅、三(2,4-己二酮)鈦、三(2,4-己二酮)鋁、四(2,4-己二酮)鋯等。 In addition, specific examples of metal chelate compounds include tris(2,4-pentanedione) iron (III), triacetone iron, triacetone titanium, triacetone ruthenium, and diacetone Zinc acetone, aluminum triacetone acetone, zirconium tetraacetone, tris(2,4-hexanedione) iron(III), bis(2,4-hexanedione) zinc, tris(2,4-hexanedi) Ketone) titanium, tris (2,4-hexanedione) aluminum, tetrakis (2,4-hexanedione) zirconium, etc.
此外，作為(E)交聯促進劑，優選為選自由鋁螯合化合物、鈦螯合化合物、鐵螯合化合物組成的組中的至少一種以上。相對於100重量份的丙烯酸系聚合物，本實施方式涉及的黏著劑組合物優選以0.001~0.5重量份的比例含有(E)交聯促進劑。 In addition, the (E) crosslinking accelerator is preferably at least one selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds. It is preferable that the adhesive composition concerning this embodiment contains (E) a crosslinking accelerator in the ratio of 0.001-0.5 weight part with respect to 100 weight part of acrylic polymers.
本實施方式涉及的黏著劑組合物也可以含有(F)酮-烯醇互變異構體化合物。作為(F)酮-烯醇互變異構體化合物，可列舉出乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油醇酯、乙醯乙酸月桂酯、乙醯乙酸硬脂醯酯等β-酮酯；乙醯丙酮、2,4-己二酮、苯甲醯丙酮等β-二酮。在將聚異氰酸酯化合物作為交聯劑的黏著劑組合物中，這些酮-烯醇互變異構體化合物藉由封端(block)交聯劑所具有的異氰酸酯基，能夠抑制摻合交聯劑後的黏著劑組合物的過度的黏度上升或凝膠化，能夠延長黏著劑組合物的貯存期。 The adhesive composition according to this embodiment may contain (F) a keto-enol tautomer compound. (F) Keto-enol tautomer compounds include methyl acetylacetate, ethyl acetylacetate, octyl acetylacetate, oleyl acetylacetate, lauryl acetylacetate, and acetylacetate. Β-ketoesters such as stearyl acetate; β-diketones such as acetone, 2,4-hexanedione, and benzylacetone. In the adhesive composition using a polyisocyanate compound as a crosslinking agent, these keto-enol tautomer compounds block the isocyanate group possessed by the crosslinking agent to prevent the crosslinking agent from being blended. Excessive viscosity rise or gelation of the adhesive composition can prolong the shelf life of the adhesive composition.
相對於100重量份的丙烯酸系聚合物，本實施方式涉及的黏著劑組合物優選以0.1~300重量份的比例含有(F)酮-烯醇互變異構體化合物。 The adhesive composition according to this embodiment preferably contains (F) the keto-enol tautomer compound in a ratio of 0.1 to 300 parts by weight relative to 100 parts by weight of the acrylic polymer.
此外，與(E)交聯促進劑相反，(F)酮-烯醇互變異構體化合物具有抑制交聯的效果，因此優選對(F)酮-烯醇互變異構體化合物相對於(E)交聯促進劑的比例進行適當地設定。為了延長黏著劑組合物的貯存期、提高貯存穩定性，(F)/(E)的重量份比優選為70~1000，更優選為70~700，特別優選為80~600。此處，(F)/(E)的重量份比是指(F)的重量份除以(E)的重量份而計算所得的商的值。 In addition, in contrast to the (E) crosslinking accelerator, (F) the keto-enol tautomer compound has an effect of inhibiting crosslinking, and therefore it is preferable that the (F) keto-enol tautomer compound is relative to (E) ) The ratio of the crosslinking accelerator is appropriately set. In order to extend the shelf life of the adhesive composition and improve storage stability, the weight ratio of (F)/(E) is preferably 70 to 1,000, more preferably 70 to 700, and particularly preferably 80 to 600. Here, the weight part ratio of (F)/(E) means the value of the quotient calculated by dividing the weight part of (F) by the weight part of (E).
除了上述的添加劑以外，本實施方式的黏著劑組合物也可以適當摻合抗氧化劑、表面活性劑、固化促進劑、增塑劑、填充劑、固化延遲劑、加工助劑、抗老化劑等公知的添加劑。這些添加劑可單獨使用或合併使用兩種以上。 In addition to the above-mentioned additives, the adhesive composition of the present embodiment may also appropriately incorporate known antioxidants, surfactants, curing accelerators, plasticizers, fillers, curing retarders, processing aids, anti-aging agents, etc. Of additives. These additives can be used alone or in combination of two or more.
對於使本實施方式的黏著劑組合物交聯而成的黏 著劑層而言，優選黏著劑層的表面電阻率為1.0×10+12Ω/□以下，更優選表面電阻率為5.0×10+11Ω/□以下，特別優選表面電阻率為2.0×10+11Ω/□以下。若表面電阻率大，則將黏著劑層從被黏物上剝離時，釋放因帶電而產生的靜電的性能差。因此，藉由充分地減小黏著劑層的表面電阻率，能夠降低伴隨將黏著劑層從被黏物上剝離時產生的靜電而產生的剝離靜電電壓、抑制對被黏物的影響。 For the adhesive layer formed by crosslinking the adhesive composition of the present embodiment, the surface resistivity of the adhesive layer is preferably 1.0×10 +12 Ω/□ or less, and the surface resistivity is more preferably 5.0×10 + 11 Ω/□ or less, and particularly preferably a surface resistivity of 2.0×10 +11 Ω/□ or less. If the surface resistivity is high, when the adhesive layer is peeled from the adherend, the performance of discharging static electricity generated by charging is poor. Therefore, by sufficiently reducing the surface resistivity of the adhesive layer, it is possible to reduce the peeling electrostatic voltage generated by the static electricity generated when the adhesive layer is peeled from the adherend and suppress the influence on the adherend.
對於使本實施方式的黏著劑組合物交聯而成的黏著劑層而言，優選相對於使用含有氟化合物的低折射率層形成用的組合物而形成的低折射率層、黏著劑層的剝離靜電電壓在-0.3~+0.3kV的範圍內。作為低折射率層形成用的組合物中使用的氟化合物，可列舉出作為氟化烯烴系、氟化乙烯基醚系、(甲基)丙烯酸氟化烷基酯等中的一種或兩種以上的聚合物的含氟共聚物、含氟化烷基的矽烷化合物等縮合物。含氟共聚物除了經氟化的單體以外，還可以共聚有烯烴系、乙烯基醚系、(甲基)丙烯酸酯等未經氟化的單體。低折射率層也可以與高折射率層等組合而構成防反射層。 For the adhesive layer formed by crosslinking the adhesive composition of the present embodiment, it is preferable that the low refractive index layer and the adhesive layer formed using the composition for forming a low refractive index layer containing a fluorine compound are used. The stripping electrostatic voltage is in the range of -0.3~+0.3kV. Examples of the fluorine compound used in the composition for forming the low refractive index layer include one or two or more of fluorinated olefins, fluorinated vinyl ethers, and fluorinated alkyl (meth)acrylates. Condensates such as fluorine-containing copolymers and fluorinated alkyl-containing silane compounds. In addition to fluorinated monomers, the fluorinated copolymer may also copolymerize non-fluorinated monomers such as olefins, vinyl ethers, and (meth)acrylates. The low refractive index layer may be combined with a high refractive index layer or the like to form an anti-reflection layer.
本實施方式的黏著膜為在基材膜的單面上積層有使本實施方式的黏著劑組合物交聯而成的黏著劑層的黏著膜。本實施方式的黏著膜能夠適宜地用於表面保護膜、偏振片用的表面保護膜、光學膜用的表面保護膜中。藉由在光學膜的至少一側的面上積層使本實施方式的黏著劑組合物交聯而成的黏著劑層，可得到帶黏著劑層的光學膜。作為光學膜，可列舉出偏振膜、相位差膜、防反射膜、防眩(anti-glare)膜、紫 外線吸收膜、紅外線吸收膜、光學補償膜、亮度提高膜等。作為光學構件所適用的設備，可列舉出液晶面板、有機EL面板、觸控面板等。 The adhesive film of the present embodiment is an adhesive film in which an adhesive layer formed by crosslinking the adhesive composition of the present embodiment is laminated on one side of a base film. The adhesive film of this embodiment can be used suitably for a surface protective film, the surface protective film for polarizing plates, and the surface protective film for optical films. By laminating an adhesive layer formed by crosslinking the adhesive composition of the present embodiment on at least one surface of the optical film, an optical film with an adhesive layer can be obtained. Examples of the optical film include a polarizing film, a retardation film, an anti-reflection film, an anti-glare film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensation film, and a brightness improving film. Examples of equipment to which the optical member is applied include liquid crystal panels, organic EL panels, touch panels, and the like.
作為黏著劑層的基材膜或保護黏著面的離型膜(隔離膜)，可使用聚脂膜等樹脂膜等。 As the base film of the adhesive layer or the release film (separation film) for protecting the adhesive surface, a resin film such as a polyester film or the like can be used.
對於基材膜而言，可在樹脂膜的與形成有黏著劑層的一側相反的面上實施基於聚矽氧系、氟系的離型劑或塗布劑、二氧化矽微粒等的防汙處理，基於抗靜電劑的塗布或捏合等的抗靜電處理。 For the base film, antifouling based on silicone-based, fluorine-based release agents or coating agents, silica particles, etc., can be implemented on the surface of the resin film opposite to the side on which the adhesive layer is formed. Treatment, antistatic treatment based on coating or kneading of an antistatic agent.
對於離型膜而言，利用聚矽氧系、氟系的離型劑等在與黏著劑層的黏著面貼合的一側的面上實施離型處理。 For the release film, a release treatment is performed on the surface on the side that is bonded to the adhesive surface of the adhesive layer with a silicone-based, fluorine-based release agent, or the like.
偏振片用的表面保護膜等光學用的表面保護膜中的情況下，優選基材膜及黏著劑層具有充分的透明性。 In the case of an optical surface protective film such as a surface protective film for a polarizing plate, it is preferable that the base film and the adhesive layer have sufficient transparency.
[實施例] [Example]
以下，利用實施例對本發明進行具體地說明。 Hereinafter, the present invention will be specifically explained using examples.
<丙烯酸系聚合物的製備> <Preparation of acrylic polymer>
[實施例1] [Example 1]
向具備攪拌機、溫度計、回流冷卻器及氮氣導入管的反應裝置中導入氮氣，利用氮氣置換了反應裝置內的空氣。然後，向反應裝置中加入12重量份的丙烯酸甲酯、88重量份的丙烯酸-2-乙基己酯、12.0重量份的丙烯酸-8-羥基辛酯、0.1重量份的丙烯酸、20重量份的聚丙二醇單丙烯酸酯(環氧烷的平均重複單元數n=12)，同時加入了100重量份的溶劑(乙酸乙酯)。然後，以2小時滴加作為聚合起始劑的0.1重量份的偶氮二異 丁腈，於65℃下反應8小時，得到了實施例1的丙烯酸系聚合物溶液。 Nitrogen was introduced into a reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen introduction pipe, and the air in the reaction device was replaced with nitrogen. Then, 12 parts by weight of methyl acrylate, 88 parts by weight of 2-ethylhexyl acrylate, 12.0 parts by weight of 8-hydroxyoctyl acrylate, 0.1 parts by weight of acrylic acid, and 20 parts by weight of acrylic acid were added to the reaction device. Polypropylene glycol monoacrylate (the average number of repeating units of alkylene oxide n=12), and 100 parts by weight of solvent (ethyl acetate) were added at the same time. Then, 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours and reacted at 65°C for 8 hours to obtain the acrylic polymer solution of Example 1.
[實施例2~6及比較例1~3] [Examples 2 to 6 and Comparative Examples 1 to 3]
除了將單體的組成分別設為如表1所記載以外，以與上述的實施例1中使用的丙烯酸系聚合物溶液同樣的方式，得到了實施例2~6及比較例1~3中使用的丙烯酸系聚合物溶液。 Except that the composition of the monomers was set as described in Table 1, in the same manner as the acrylic polymer solution used in Example 1 above, Examples 2 to 6 and Comparative Examples 1 to 3 were obtained. Acrylic polymer solution.
<黏著劑組合物及表面保護膜的製備> <Preparation of Adhesive Composition and Surface Protective Film>
[實施例1] [Example 1]
向如上所述而製備的實施例1的丙烯酸系聚合物溶液中，加入2.0重量份的交聯劑(CORONATE HX)、1.0重量份的抗靜電劑(九氟丁烷磺酸鋰)、0.1重量份的交聯促進劑(三乙醯丙酮鈦)、以及9重量份的酮-烯醇互變異構體化合物(乙醯丙酮)，進行攪拌混合，得到了實施例1的黏著劑組合物。將該黏著劑組合物塗布在由已塗布聚矽氧樹脂的聚對苯二甲酸乙二醇酯(PET)膜形成的離型膜上後，於90℃下進行乾燥，從而將溶劑去除，得到了厚度為20μm的黏著劑層。然後，使帶離型膜的黏著劑層轉印於對一側的面實施了抗靜電及防汙處理的由聚對苯二甲酸乙二醇酯(PET)膜形成的基材膜的、與實施了抗靜電及防汙處理的面相反的面上，得到了具有基材膜/黏著劑層/離型膜的積層結構的實施例1的表面保護膜。 To the acrylic polymer solution of Example 1 prepared as described above, 2.0 parts by weight of crosslinking agent (CORONATE HX), 1.0 parts by weight of antistatic agent (lithium nonafluorobutane sulfonate), and 0.1 parts by weight were added Parts of the crosslinking accelerator (titanium triacetone) and 9 parts by weight of the keto-enol tautomer compound (acetone) were stirred and mixed to obtain the adhesive composition of Example 1. After coating the adhesive composition on a release film formed of a polyethylene terephthalate (PET) film coated with a silicone resin, it was dried at 90°C to remove the solvent to obtain The thickness of the adhesive layer is 20μm. Then, the adhesive layer with a release film is transferred to a base film formed of a polyethylene terephthalate (PET) film that has been subjected to antistatic and antifouling treatment on the opposite surface, and The surface protection film of Example 1 which has a laminated structure of a base film/adhesive layer/release film on the surface opposite to the surface which was given antistatic and antifouling treatment was obtained.
[實施例2~6及比較例1~3] [Examples 2 to 6 and Comparative Examples 1 to 3]
除了將添加劑的組成分別設為如表1所記載以外，以與上述的實施例1的表面保護膜同樣的方式，得到了實施例2~6及比較例1~3的表面保護膜。 Except that the composition of the additives was as described in Table 1, the surface protective films of Examples 2 to 6 and Comparative Examples 1 to 3 were obtained in the same manner as the surface protective film of Example 1 described above.
表1中，各成分的重量份是藉由將作為(A)烷基的碳原子數為C1~18的(甲基)丙烯酸酯單體的(a1)和(a2)的總計設為100重量份而求得的。 In Table 1, the parts by weight of each component are made by setting the total of (a1) and (a2) as the (meth)acrylate monomer having C1-18 carbon atoms as the alkyl group as 100 weight. For the share.
另外，在表1中，(D)、(G)、(E)、(F)的各欄中，將丙烯酸系聚合物設為100重量份，以括弧( )內的數值表示了各成分的含有比例(重量份)。 In addition, in Table 1, in each column of (D), (G), (E), and (F), the acrylic polymer is set to 100 parts by weight, and the values in parentheses () indicate the content of each component Containing ratio (parts by weight).
此外，將表1中使用的各成分的縮寫符號的化合物名稱示於表2。(C)含聚亞烷基二醇鏈的單(甲基)丙烯酸酯單體中，對於C-1~C-5，單體中的二酯組分為0.2%以下；對於C-6，單體中的二酯組分為0.8%。G-1~G-6均是熔點為25℃以上、在25℃下為固體的離子化合物；G-7是熔點為15℃、在25℃下為液體的離子化合物。 In addition, the compound name of the abbreviation symbol of each component used in Table 1 is shown in Table 2. (C) In the mono(meth)acrylate monomer containing polyalkylene glycol chain, for C-1~C-5, the diester component in the monomer is 0.2% or less; for C-6, The diester component in the monomer is 0.8%. G-1~G-6 are ionic compounds with a melting point of 25°C or higher and solid at 25°C; G-7 is an ionic compound with a melting point of 15°C and liquid at 25°C.
另外，CORONATE(註冊商標)HX、CORONATE HL及CORONATE L為TOSOH CORPORATION的商品名稱，D-127N、TAKENATE(註冊商標)D-140N為Mitsui Chemicals,Inc.的商品名稱。此外，HDI是指六亞甲基二異氰酸酯，IPDI是指異佛爾酮二異氰酸酯，XDI是指二甲苯撐基二異氰酸酯，TDI是指甲苯二異氰酸酯，TMP是指三羥甲基丙烷。 In addition, CORONATE (registered trademark) HX, CORONATE HL, and CORONATE L are trade names of TOSOH CORPORATION, and D-127N and TAKENATE (registered trademark) D-140N are trade names of Mitsui Chemicals, Inc. In addition, HDI refers to hexamethylene diisocyanate, IPDI refers to isophorone diisocyanate, XDI refers to xylene diisocyanate, TDI refers to toluene diisocyanate, and TMP refers to trimethylolpropane.
<試驗方法及評價> <Test Method and Evaluation>
將實施例1~6及比較例1~3中的表面保護膜分別在23℃、50%RH的氣氛下熟化7天後，利用以下的試驗方法進行了評價。 The surface protective films in Examples 1 to 6 and Comparative Examples 1 to 3 were each cured in an atmosphere of 23° C. and 50% RH for 7 days, and then evaluated by the following test method.
<黏著力的試驗方法> <Test method of adhesion>
將離型膜剝下，將露出黏著劑層的表面保護膜經由黏著劑層而貼合於偏振片(使用偏光鏡的保護層為TAC的偏振片)的表面上，放置1天後，於50℃、5個大氣壓下進行20分鐘壓熱處理，進一步於室溫下放置了12小時後，作為了黏著力的測定樣品。被黏物的所述偏振片為LR偏振片或AG-LR偏振片。用拉伸試驗機以低速度(0.3m/分鐘)或高速度(30m/分鐘)將在上述所得到的測定樣品沿180°方向剝下，將測定得到的剝離強度作為了黏著力。 The release film is peeled off, and the surface protection film with the adhesive layer exposed is pasted on the surface of the polarizer (the protective layer of the polarizer is a TAC polarizer) through the adhesive layer, and left for 1 day. After performing autoclave heat treatment at ℃ and 5 atmospheres for 20 minutes, and further leaving it at room temperature for 12 hours, it was used as a sample for measuring adhesion. The polarizer of the adherend is an LR polarizer or an AG-LR polarizer. The measurement sample obtained above was peeled off at a low speed (0.3 m/min) or a high speed (30 m/min) with a tensile tester in the 180° direction, and the measured peel strength was used as the adhesive force.
此處，對於上述的LR偏振片及AG-LR偏振片，用含有氟化合物的組合物對所述偏振片的表面實施低反射表面處理。 Here, for the above-mentioned LR polarizer and AG-LR polarizer, the surface of the polarizer is treated with a low-reflection surface treatment with a composition containing a fluorine compound.
<表面電阻率的試驗方法> <Test method of surface resistivity>
將表面保護膜熟化後，在將其貼合於被黏物上之前，將離型膜剝下，露出黏著劑層，利用電阻率計HIRESTA UP-HT450(Mitsubishi Chemical Analytech Co.,Ltd製造)對黏著劑層的 表面電阻率進行了測定。 After the surface protective film is cured, before attaching it to the adherend, peel off the release film to expose the adhesive layer, and use the resistivity meter HIRESTA UP-HT450 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) The surface resistivity of the adhesive layer was measured.
<剝離靜電電壓的試驗方法> <Test method of peeling electrostatic voltage>
將離型膜剝下，將露出黏著劑層的表面保護膜貼合於被黏物上，所述被黏物在被黏面上具有使用含有氟化合物的低折射率層形成用的組合物而形成的低折射率層。以30m/分鐘的拉伸速度對表面保護膜進行180°剝離時，使用高精度靜電感應器SK-035、SK-200(KEYENCE CORPORATION製造)測定被黏物帶電而產生的電壓(靜電電壓)，將測定值的最大值作為了剝離靜電電壓。 The release film is peeled off, and the surface protection film exposing the adhesive layer is attached to the adherend. The adherend has a composition for forming a low refractive index layer containing a fluorine compound on the adherend. The low refractive index layer formed. When peeling the surface protection film 180° at a stretching speed of 30m/min, use high-precision electrostatic sensors SK-035, SK-200 (manufactured by KEYENCE CORPORATION) to measure the voltage (electrostatic voltage) generated by the adherend. The maximum value of the measured value was used as the peeling electrostatic voltage.
<耐污染性的試驗方法> <Test method for contamination resistance>
使用貼合機，將所述實施了低反射表面處理的LR偏振片、或者所述實施了低反射表面處理的AG-LR偏振片(使用偏光鏡的保護層為TAC的偏振片)經由黏著劑層(雙面黏著膠帶)貼合於玻璃板的單面上。然後，使用貼合機將表面保護膜貼合於所述偏振片的表面上。於23℃、50%RH的環境下進行了3天及30天的期間的保管後，將所述表面保護膜剝下，對所述偏振片的表面的污染狀態進行了目視觀察。耐污染性的判斷基準為：將對所述偏振片的表面無污染的情況評價為“○”；將存在少許污染的情況評價為“△”；將存在污染的情況評價為“×”。 Using a laminating machine, pass the low-reflection surface treatment LR polarizer or the low-reflection surface treatment AG-LR polarizer (the protective layer of the polarizer is a TAC polarizer) through the adhesive The layer (double-sided adhesive tape) is attached to one side of the glass plate. Then, the surface protection film was bonded to the surface of the polarizing plate using a bonding machine. After storage for a period of 3 days and 30 days in an environment of 23° C. and 50% RH, the surface protective film was peeled off, and the contamination state of the surface of the polarizing plate was visually observed. The criteria for judging stain resistance are: the case where there is no contamination on the surface of the polarizer is evaluated as "○"; the case where there is a little contamination is evaluated as "△"; the case where there is contamination is evaluated as "x".
將關於實施例1~6及比較例1~3中的表面保護膜的評價結果示於表3。“表面電阻率”藉由將“m×10+n”記作“mE+n”的方式(其中，m為任意的實數值，n為正整數)而進行了表示。“表面處理”欄表示黏著力的試驗中使用的被黏物的 偏振片的種類。 Table 3 shows the evaluation results of the surface protective films in Examples 1 to 6 and Comparative Examples 1 to 3. "Surface resistivity" is represented by a method of writing "m×10 +n " as "mE+n" (where m is an arbitrary real value, and n is a positive integer). The “surface treatment” column indicates the type of polarizer of the adherend used in the adhesion test.
實施例1~6的表面保護膜對作為被黏物的偏振片的、在低速的剝離速度為0.3m/分鐘時的黏著力為0.03~0.05N/25mm(例如，0.01~0.1N/25mm)，在高速的剝離速度為30m/分鐘時的黏著力為0.4~0.6N/25mm(例如，1.0N/25mm以下)，具有適當的黏著力，黏著性能優異。 The surface protection film of Examples 1 to 6 has an adhesive force of 0.03 to 0.05N/25mm (for example, 0.01 to 0.1N/25mm) to the polarizer as an adherend at a low-speed peeling speed of 0.3m/min. , When the high-speed peeling speed is 30m/min, the adhesive force is 0.4~0.6N/25mm (for example, 1.0N/25mm or less), with proper adhesive force and excellent adhesive performance.
此外，實施例1~6的表面保護膜的黏著劑層的表面電阻率為1.0×10+12Ω/□以下，相對於使用含有氟化合物的低折射率層形成用的組合物而形成的低折射率層的、黏著劑層的剝離靜電電壓在-0.3~+0.3kV的範圍內，抗靜電性能優異。 In addition, the surface resistivity of the adhesive layer of the surface protection films of Examples 1 to 6 is 1.0×10 +12 Ω/□ or less, which is lower than that of the composition for forming a low refractive index layer containing a fluorine compound. The peeling electrostatic voltage of the refractive index layer and the adhesive layer is in the range of -0.3~+0.3kV, and the antistatic performance is excellent.
進一步，實施例1~6的表面保護膜即使在進行了3天及30天的期間的保管後，也沒有對作為被黏物的偏振片的污染，耐污染性優異。 Furthermore, the surface protection films of Examples 1 to 6 did not contaminate the polarizing plate as an adherend even after storage for a period of 3 days and 30 days, and were excellent in contamination resistance.
即，表3所示的關於實施例1~6的表面保護膜的評價結果，證實了能夠解決本發明的技術問題。 That is, the evaluation results of the surface protective films of Examples 1 to 6 shown in Table 3 proved that the technical problems of the present invention can be solved.
比較例1~3的表面保護膜由於使用了液體的離子化合物作為(G)抗靜電劑，因此黏著劑層的表面電阻率高、耐污染性差。 Since the surface protective films of Comparative Examples 1 to 3 used a liquid ionic compound as the (G) antistatic agent, the adhesive layer had high surface resistivity and poor contamination resistance.
此外，比較例1~2的表面保護膜由於黏著劑層的表面電阻率高，因此剝離靜電電壓高。關於比較例3的表面保護膜，雖然未測定剝離靜電電壓，但由於黏著劑層的表面電阻率高，因此可推測剝離靜電電壓高。 In addition, since the surface protection films of Comparative Examples 1 and 2 had high surface resistivity of the adhesive layer, the peeling electrostatic voltage was high. Regarding the surface protective film of Comparative Example 3, although the peeling electrostatic voltage was not measured, since the surface resistivity of the adhesive layer is high, it can be estimated that the peeling electrostatic voltage is high.
進一步，對於比較例2的表面保護膜而言，黏著劑組合物中所含有的丙烯酸系聚合物的玻璃轉移溫度大於0℃(計算值為+2℃)。因此，黏著性能差，黏著力過大。另外，比較例2中使用的丙烯酸系聚合物中，均聚物的玻璃轉移溫度為高值(大於0℃)的丙烯酸甲酯及丙烯酸的比例較多。 Furthermore, in the surface protective film of Comparative Example 2, the glass transition temperature of the acrylic polymer contained in the adhesive composition was greater than 0°C (calculated value +2°C). Therefore, the adhesive performance is poor and the adhesive force is too large. In addition, among the acrylic polymers used in Comparative Example 2, there are many ratios of methyl acrylate and acrylic acid whose homopolymer has a high glass transition temperature (greater than 0°C).
如上所述，比較例1~3的表面保護膜，無法解決本發明的技術問題。 As described above, the surface protection films of Comparative Examples 1 to 3 cannot solve the technical problems of the present invention.
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