TWI838402B - Optical film with adhesive layer, image display panel and image display device - Google Patents
Optical film with adhesive layer, image display panel and image display device Download PDFInfo
- Publication number
- TWI838402B TWI838402B TW108133616A TW108133616A TWI838402B TW I838402 B TWI838402 B TW I838402B TW 108133616 A TW108133616 A TW 108133616A TW 108133616 A TW108133616 A TW 108133616A TW I838402 B TWI838402 B TW I838402B
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- TW
- Taiwan
- Prior art keywords
- adhesive layer
- film
- optical film
- meth
- mass
- Prior art date
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- 239000012790 adhesive layer Substances 0.000 title claims abstract description 224
- 239000012788 optical film Substances 0.000 title claims abstract description 163
- 239000010408 film Substances 0.000 claims abstract description 243
- 239000000178 monomer Substances 0.000 claims abstract description 152
- 230000001681 protective effect Effects 0.000 claims abstract description 97
- 230000001070 adhesive effect Effects 0.000 claims abstract description 67
- 239000000853 adhesive Substances 0.000 claims abstract description 64
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 60
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 53
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- 125000000217 alkyl group Chemical group 0.000 claims description 54
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- 239000003431 cross linking reagent Substances 0.000 claims description 27
- 239000004593 Epoxy Substances 0.000 claims description 19
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 17
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 17
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- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 10
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- RKYSDIOEHLMYRS-UHFFFAOYSA-N triethoxy(hex-5-enyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCC=C RKYSDIOEHLMYRS-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- 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
-
- 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
-
- 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
-
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09J133/16—Homopolymers or copolymers of esters containing halogen atoms
-
- 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
- C09J133/18—Homopolymers or copolymers of nitriles
- C09J133/20—Homopolymers or copolymers of acrylonitrile
-
- 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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- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Liquid Crystal (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Polarising Elements (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Electroluminescent Light Sources (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Holo Graphy (AREA)
Abstract
本發明附黏著劑層之光學薄膜係使用於薄型偏光件之單面具有透明保護薄膜(惟,不含相位差薄膜)的單面保護偏光薄膜者;前述黏著劑層係由下述黏著劑組成物所形成:該黏著劑組成物係含有(甲基)丙烯酸系聚合物(A)且含有矽烷耦合劑(B),並且不含有具聚醚骨架且具反應性矽基之聚醚化合物者,該(甲基)丙烯酸系聚合物(A)含有80質量%以上之預定單體(a)作為單官能性單體單元,且預定單體(a)中含有20質量%以上之丙烯酸正丁酯、或含有70質量%以上之(甲基)丙烯酸烷氧基烷基酯。本發明即使是在已有油脂或乳油成分接觸黏著劑層之狀態下置於加濕環境下時仍可抑制剝落,且可抑制於偏光薄膜的透明保護薄膜產生裂痕。The optical film with adhesive layer of the present invention is a single-sided protective polarizing film used for thin polarizers having a transparent protective film on one side (but not containing a phase difference film); the adhesive layer is formed by the following adhesive composition: the adhesive composition contains a (meth) acrylic polymer (A) and a silane coupling agent (B), and does not contain a polyether compound with a polyether skeleton and reactive silicon groups, the (meth) acrylic polymer (A) contains 80% by mass or more of a predetermined monomer (a) as a monofunctional monomer unit, and the predetermined monomer (a) contains 20% by mass or more of n-butyl acrylate, or contains 70% by mass or more of (meth) alkoxyalkyl acrylate. The present invention can inhibit peeling even when the adhesive layer is placed in a humidified environment with a grease or emulsion component in contact with the adhesive layer, and can inhibit cracks from being generated in the transparent protective film of the polarizing film.
Description
本發明涉及附黏著劑層之光學薄膜。本發明之附黏著劑層之光學薄膜可應用於影像顯示面板,且該影像顯示面板可形成液晶顯示裝置(LCD)、有機EL顯示裝置等影像顯示裝置。且,前述影像顯示面板可作為於影像顯示面板外側具備邊框作為外框之附邊框之影像顯示面板來使用。 The present invention relates to an optical film with an adhesive layer. The optical film with an adhesive layer of the present invention can be applied to an image display panel, and the image display panel can form an image display device such as a liquid crystal display device (LCD), an organic EL display device, etc. Moreover, the aforementioned image display panel can be used as an image display panel with a frame as an outer frame on the outer side of the image display panel.
發明背景 Invention background
液晶顯示面板等之影像顯示面板由其影像形成方式,而於液晶單元等影像顯示部配置有偏光薄膜。一般而言,影像顯示面板中係於影像顯示部透過黏著劑層至少貼合有偏光薄膜。 Image display panels such as liquid crystal display panels have polarizing films arranged on the image display portion such as liquid crystal cells due to their image forming method. Generally speaking, in image display panels, at least a polarizing film is attached to the image display portion through an adhesive layer.
前述黏著劑層之形成通常係使用含有基底聚合物及交聯劑之黏著劑。前述基底聚合物係利用使用了丙烯酸系聚合物之丙烯酸系黏著劑。對於所述黏著劑,要求具有再剝離性(重工性),使其在將偏光薄膜貼合至影像顯示部時,即使在貼合位置有誤或貼合面有咬入異物這般情況下仍可輕易剝離。又,對於前述黏著劑層,除了要求重工性之外,還要求改善泛白(周邊不均)或提升耐久性等, 而作為可提升前述特性的黏著劑組成物,已有文獻提議於丙烯酸系聚合物中摻混具有反應性矽基的聚醚化合物(專利文獻1)。 The adhesive layer is usually formed by using an adhesive containing a base polymer and a crosslinking agent. The base polymer is an acrylic adhesive using an acrylic polymer. The adhesive is required to have re-peelability (reworkability) so that when the polarizing film is bonded to the image display part, it can be easily peeled off even if there is an error in the bonding position or a foreign object is bitten into the bonding surface. In addition, the adhesive layer is required to improve whitening (peripheral unevenness) or improve durability in addition to reworkability. As an adhesive composition that can improve the above characteristics, there is a document that proposes mixing a polyether compound with a reactive silicon group into an acrylic polymer (Patent Document 1).
又,前述影像顯示面板之外側由處置性等觀點來看,通常具備有邊框(外框)。近年來重視設計性而有將邊框進行窄邊框化之傾向(專利文獻2、3)。 In addition, the outer side of the aforementioned image display panel usually has a frame (outer frame) from the perspective of handling. In recent years, there has been a trend to narrow the frame due to emphasis on design (Patent Documents 2, 3).
先前技術文獻 Prior art literature
專利文獻 Patent Literature
專利文獻1:日本特開2010-275522號公報 Patent document 1: Japanese Patent Publication No. 2010-275522
專利文獻2:日本特開2012-014000號公報 Patent document 2: Japanese Patent Publication No. 2012-014000
專利文獻3:日本特開2016-004214號公報 Patent document 3: Japanese Patent Publication No. 2016-004214
在將上述邊框經窄邊框化的影像顯示面板應用於行動電話等影像顯示裝置時,該影像顯示面板的最表面會配置有蓋玻璃等,但在應用於筆記型電腦等開合式影像顯示裝置時,該影像顯示面板的最表面則通常不會配置蓋玻璃等,因此影像顯示面板之視辨側表面的強度說不上充足。作為對策,會基於在使用筆記型電腦等時防止影像顯示面板在關閉時的狀態下與影像顯示裝置本體直接接觸之目的,而例如於邊框上部設置彈性體。然而在已將邊框進行窄邊框化時,有時會難以於邊框上部設置前述彈性體。因此,在使用經窄邊框化之邊框時,亦研討了以下態樣:於 前述影像顯示面板之端面與邊框之間設置較影像顯示面板之視辨側的最表面更突出的彈性中間層。 When the image display panel with a narrow frame is used in an image display device such as a mobile phone, a cover glass or the like is disposed on the outermost surface of the image display panel. However, when it is used in an openable image display device such as a notebook computer, a cover glass or the like is usually not disposed on the outermost surface of the image display panel, so the strength of the visual side surface of the image display panel is not sufficient. As a countermeasure, an elastic body is disposed on the upper part of the frame, for example, in order to prevent the image display panel from directly contacting the image display device body when the laptop computer is closed. However, when the frame has been narrowed, it is sometimes difficult to dispose the elastic body on the upper part of the frame. Therefore, when using a narrow frame, the following aspect is also considered: a flexible middle layer that protrudes more than the outermost surface of the viewing side of the image display panel is provided between the end surface of the aforementioned image display panel and the frame.
一般而言在開關筆記型電腦等之影像顯示面板時,多會赤手接觸影像顯示面板的外緣部。赤手具有源於皮脂的油脂成分(油酸等),且使用過保濕乳、防曬乳等後,該等乳油成分有時會殘留於赤手上。已知在這種情況下,若赤手開關使用有設有前述彈性中間層的附邊框之影像顯示面板的筆記型電腦等,前述油脂或乳油成分會有透過前述彈性中間層直接或間接到達將偏光薄膜等貼合於影像顯示部的黏著劑層之虞,從而前述黏著劑層會吸收前述成分而膨脹。尤其是在加濕環境下,吸收了前述成分的黏著劑層會更容易膨脹,而有前述黏著劑層從影像顯示部剝落之問題。而由上述專利文獻1記載之黏著劑組成物所形成的黏著劑層並無法解決前述剝落之問題。 Generally speaking, when turning on and off the image display panel of a laptop or the like, the outer edge of the image display panel is often touched with bare hands. Bare hands contain oil components (oleic acid, etc.) derived from sebum, and after using moisturizers, sunscreens, etc., these cream components may remain on bare hands. It is known that in this case, if a laptop or the like having an image display panel with a frame provided with the above-mentioned elastic intermediate layer is turned on and off with bare hands, the above-mentioned oil or cream components may directly or indirectly reach the adhesive layer that adheres the polarizing film, etc. to the image display part through the above-mentioned elastic intermediate layer, and the above-mentioned adhesive layer may absorb the above-mentioned components and expand. Especially in a humidified environment, the adhesive layer that absorbs the aforementioned components will swell more easily, and there is a problem that the aforementioned adhesive layer peels off from the image display part. However, the adhesive layer formed by the adhesive composition described in the above-mentioned patent document 1 cannot solve the aforementioned peeling problem.
又,亦已知該黏著劑層會因到達前述黏著劑層的油脂或乳油成分而膨潤,進而貼合有該黏著劑層之偏光薄膜的透明保護薄膜會吸收油脂或乳油成分而膨潤,從而發生透明保護薄膜龜裂所造成之白化(產生裂痕)。該等不良情況會使油脂或乳油成分容易介入黏著劑層與透明保護薄膜之界面,並且亦會有透明保護薄膜面發生變形之情形。亦已知結果會有誘發黏著劑層與透明保護薄膜剝落之虞。 In addition, it is also known that the adhesive layer will swell due to the oil or emulsion components reaching the aforementioned adhesive layer, and then the transparent protective film of the polarizing film bonded with the adhesive layer will absorb the oil or emulsion components and swell, thereby causing whitening (cracks) caused by cracking of the transparent protective film. Such adverse conditions will make it easy for the oil or emulsion components to intervene in the interface between the adhesive layer and the transparent protective film, and there will also be a situation where the surface of the transparent protective film is deformed. It is also known that the result may induce the adhesive layer and the transparent protective film to peel off.
本發明之目的在於提供一種附黏著劑層之光學薄膜,其可應用於影像顯示面板等,且該附黏著劑層 之光學薄膜即使在加濕環境下,有油脂或乳油成分到達該附黏著劑層之光學薄膜的黏著劑層時,仍可抑制前述黏著劑層剝落,且可抑制於光學薄膜所含偏光薄膜的透明保護薄膜產生裂痕(具有耐裂痕性)。 The purpose of the present invention is to provide an optical film with an adhesive layer, which can be applied to image display panels, etc., and the optical film with an adhesive layer can inhibit the peeling of the adhesive layer even in a humidified environment when grease or emulsion components reach the adhesive layer of the optical film with an adhesive layer, and can inhibit the generation of cracks in the transparent protective film of the polarizing film contained in the optical film (having crack resistance).
又,本發明目的在於提供使用有前述附黏著劑層之光學薄膜的影像顯示面板,並且提供使用有該影像顯示面板之影像顯示裝置。 Furthermore, the present invention aims to provide an image display panel using the optical film with the aforementioned adhesive layer, and to provide an image display device using the image display panel.
本發明人等為了解決前述課題而積極努力研討後,發現藉由下述附黏著劑層之光學薄膜等可解決上述課題,遂而完成本發明。 After actively studying and researching to solve the above-mentioned problems, the inventors found that the above-mentioned problems can be solved by the following optical film with adhesive layer, and thus completed the present invention.
亦即,本發明涉及一種附邊框之影像顯示面板,其係具有光學薄膜及黏著劑層者;該附黏著劑層之光學薄膜之特徵在於:前述光學薄膜之厚度為75μm以上;前述光學薄膜包含單面保護偏光薄膜,該單面保護偏光薄膜於厚度10μm以下的偏光件之單面具有透明保護薄膜(惟,不含相位差薄膜),且前述黏著劑層設於前述單面保護偏光薄膜之不具有前述透明保護薄膜之側;前述黏著劑層係由下述黏著劑組成物所形成:該黏著劑組成物含有(甲基)丙烯酸系聚合物(A)作為基底聚合物,該(甲基)丙烯酸系聚合物(A)含有80質量%以上之單體(a)作為單官能性單體單元,該單體(a)選自具碳數1~4烷基之(甲基)丙烯酸烷基酯、(甲基)丙烯酸烷氧基烷 基酯、含氟單體及丙烯腈中之任意至少1種,且作為單官能性單體單元含有20質量%以上之丙烯酸正丁酯、或含有70質量%以上之(甲基)丙烯酸烷氧基烷基酯,且含有矽烷耦合劑(B),並且不含有具聚醚骨架且於至少1末端具反應性矽基之聚醚化合物。 That is, the present invention relates to an image display panel with a border frame, which has an optical film and an adhesive layer; the optical film with an adhesive layer is characterized in that: the thickness of the optical film is greater than 75 μm; the optical film includes a single-sided protective polarizing film, the single-sided protective polarizing film has a transparent protective film (but does not contain a phase difference film) on one side of a polarizer with a thickness of less than 10 μm, and the adhesive layer is arranged on the side of the single-sided protective polarizing film that does not have the transparent protective film; the adhesive layer is formed by the following adhesive composition: the adhesive composition contains a (meth) acrylic polymer ( A) as a base polymer, the (meth) acrylic polymer (A) contains 80% by mass or more of a monomer (a) as a monofunctional monomer unit, the monomer (a) is selected from at least one of a (meth) acrylic acid alkyl ester having an alkyl group with 1 to 4 carbon atoms, a (meth) acrylic acid alkoxyalkyl ester, a fluorinated monomer and acrylonitrile, and contains 20% by mass or more of n-butyl acrylate or 70% by mass or more of a (meth) acrylic acid alkoxyalkyl ester as a monofunctional monomer unit, contains a silane coupling agent (B), and does not contain a polyether compound having a polyether skeleton and a reactive silicon group at at least one end.
前述附黏著劑層之光學薄膜中,可使用前述黏著劑層隔著相位差薄膜設於單面保護偏光薄膜者。 In the aforementioned optical film with adhesive layer, the aforementioned adhesive layer can be provided on a single-sided protective polarizing film via a phase difference film.
前述附黏著劑層之光學薄膜中,可使用前述黏著劑層直接設於單面保護偏光薄膜之偏光件者。 Among the optical films with adhesive layers, the aforementioned adhesive layer can be directly provided on the polarizing element of the single-sided protective polarizing film.
前述附黏著劑層之光學薄膜中,前述光學薄膜宜為於視辨側的最表面具有表面處理層者。 In the aforementioned optical film with an adhesive layer, the aforementioned optical film preferably has a surface treatment layer on the outermost surface of the viewing side.
前述附黏著劑層之光學薄膜中,前述光學薄膜的厚度宜為300μm以下。 In the optical film with the adhesive layer, the thickness of the optical film should be less than 300μm.
前述附黏著劑層之光學薄膜中,前述黏著劑層的厚度宜為10~30μm。 In the optical film with the adhesive layer, the thickness of the adhesive layer is preferably 10~30μm.
前述附黏著劑層之光學薄膜中,前述黏著劑層亦適於油酸膨潤度大於130%且為190%以下之情況。 In the aforementioned optical film with an adhesive layer, the aforementioned adhesive layer is also suitable for the case where the oleic acid swelling degree is greater than 130% and less than 190%.
前述附黏著劑層之光學薄膜中,可使用:前述單體(a)全為前述具碳數1~4烷基之(甲基)丙烯酸烷基酯,並且作為前述單體單元含有30質量%以上之丙烯酸正丁酯者(態樣(1))。 In the optical film with the adhesive layer, the monomers (a) are all the (meth) acrylate alkyl esters with 1 to 4 carbon atoms, and the monomer units contain 30% by mass or more of n-butyl acrylate (aspect (1)).
可使用:上述態樣(1)中,前述具碳數1~4烷基之(甲基)丙烯酸烷基酯全為丙烯酸正丁酯,並且作為前 述單體單元含有70質量%以上之丙烯酸正丁酯者(態樣(10))。 It can be used: In the above-mentioned aspect (1), the aforementioned (meth) alkyl acrylate having an alkyl group with 1 to 4 carbon atoms is all n-butyl acrylate, and the aforementioned monomer unit contains 70% by mass or more of n-butyl acrylate (aspect (10)).
又可使用:上述態樣(10)中,前述具碳數1~4烷基之(甲基)丙烯酸烷基酯含有具碳數1~4烷基之(甲基)丙烯酸烷基酯(惟,除丙烯酸正丁酯外)及丙烯酸正丁酯者(態樣(11))。 It is also possible to use: In the above aspect (10), the aforementioned (meth)acrylic acid alkyl ester having an alkyl group with 1 to 4 carbon atoms contains (meth)acrylic acid alkyl ester having an alkyl group with 1 to 4 carbon atoms (except for n-butyl acrylate) and n-butyl acrylate (aspect (11)).
並且可使用:上述態樣(11)中,作為前述單體單元含有4~60質量%之前述具碳數1~4烷基之(甲基)丙烯酸烷基酯(惟,除丙烯酸正丁酯外)與30質量%以上之丙烯酸正丁酯者。 And it can be used: In the above aspect (11), as the aforementioned monomer unit, the one containing 4 to 60% by mass of the aforementioned (meth) alkyl acrylate having an alkyl group with 1 to 4 carbon atoms (except for n-butyl acrylate) and 30% by mass or more of n-butyl acrylate.
並且可使用:上述態樣(11)中,作為前述單體單元含有15~60質量%之前述具碳數1~4烷基之丙烯酸烷基酯(惟,除丙烯酸正丁酯外)與30質量%以上之丙烯酸正丁酯者(態樣(11A))。 Furthermore, the above-mentioned aspect (11) may be used, wherein the monomer unit contains 15-60% by mass of the above-mentioned alkyl acrylate having an alkyl group with 1-4 carbon atoms (except n-butyl acrylate) and 30% by mass or more of n-butyl acrylate (aspect (11A)).
並且可使用:上述態樣(11)中,作為前述單體單元含有5~15質量%之前述具碳數1~4烷基之甲基丙烯酸烷基酯與70質量%以上之丙烯酸正丁酯者(態樣(11B))。 Furthermore, the above-mentioned aspect (11) can be used, wherein the monomer unit contains 5-15% by mass of the above-mentioned alkyl methacrylate having an alkyl group with 1-4 carbon atoms and 70% by mass or more of n-butyl acrylate (aspect (11B)).
又,前述附黏著劑層之光學薄膜中可使用:前述單體(a)含有前述具碳數1~4烷基之(甲基)丙烯酸烷基酯及前述含氟單體,並且作為前述單體單元含有30質量%以上之前述具碳數1~4烷基之(甲基)丙烯酸烷基酯與25質量%以上之含氟單體,且含有30質量%以上之丙烯酸正丁酯者(態樣(21))。 In addition, the optical film with the adhesive layer may include: the monomer (a) contains the alkyl (meth)acrylate with a carbon number of 1 to 4 alkyl group and the fluorine-containing monomer, and the monomer unit contains 30% by mass or more of the alkyl (meth)acrylate with a carbon number of 1 to 4 alkyl group and 25% by mass or more of the fluorine-containing monomer, and contains 30% by mass or more of n-butyl acrylate (Aspect (21)).
又,前述附黏著劑層之光學薄膜中可使用: 前述單體(a)含有前述具碳數1~4烷基之(甲基)丙烯酸烷基酯及丙烯腈,並且作為前述單體單元含有70質量%以上之前述具碳數1~4烷基之(甲基)丙烯酸烷基酯與5質量%以上丙烯腈,且含有70質量%以上之丙烯酸正丁酯者(態樣(22))。 In addition, the optical film with the adhesive layer may include: The monomer (a) contains the aforementioned (meth) acrylate alkyl ester with a carbon number of 1 to 4 and acrylonitrile, and the monomer unit contains 70% by mass or more of the aforementioned (meth) acrylate alkyl ester with a carbon number of 1 to 4 and 5% by mass or more of acrylonitrile, and contains 70% by mass or more of n-butyl acrylate (Aspect (22)).
又,前述附邊框之影像顯示面板中可使用前述單體(a)含有70質量%以上之前述(甲基)丙烯酸烷氧基烷基酯者(態樣(23))。 Furthermore, the aforementioned image display panel with borders may contain the aforementioned monomer (a) containing 70% by mass or more of the aforementioned alkoxyalkyl (meth)acrylate (aspect (23)).
前述附黏著劑層之光學薄膜中,前述矽烷耦合劑(B)宜為選自含環氧基之矽烷耦合劑(b1)及含巰基之矽烷耦合劑(b2)中之至少1種。前述含環氧基之矽烷耦合劑(b1)宜為低分子型含環氧基之矽烷耦合劑(b1)。又,前述含巰基之矽烷耦合劑(b2)宜為寡聚物型含巰基之矽烷耦合劑(b2)。 In the optical film with the adhesive layer, the silane coupling agent (B) is preferably at least one selected from an epoxy-containing silane coupling agent (b1) and a silane coupling agent (b2). The epoxy-containing silane coupling agent (b1) is preferably a low molecular weight epoxy-containing silane coupling agent (b1). Moreover, the silane coupling agent (b2) is preferably an oligomer silane coupling agent (b2).
前述附黏著劑層之光學薄膜中,前述黏著劑組成物可含有交聯劑。 In the optical film with the adhesive layer, the adhesive composition may contain a crosslinking agent.
又本發明係涉及一種影像顯示面板,其特徵在於具有影像顯示部及前述附黏著劑層之光學薄膜。前述影像顯示面板可在以下態樣下作使用:前述附黏著劑層之光學薄膜透過該附黏著劑層之光學薄膜的黏著劑層配置於前述影像顯示部之視辨側。 The present invention also relates to an image display panel, which is characterized by having an image display portion and an optical film with the adhesive layer. The image display panel can be used in the following manner: the optical film with the adhesive layer is arranged on the visual recognition side of the image display portion through the adhesive layer of the optical film with the adhesive layer.
又本發明涉及一種具有前述影像顯示面板之液晶顯示裝置。 The present invention also relates to a liquid crystal display device having the aforementioned image display panel.
本發明附黏著劑層之光學薄膜具有預定範圍以上之厚度的光學薄膜,故可防止或在某程度上防止油脂或乳油成分到達、接觸黏著劑層。又,本發明附黏著劑層之光學薄膜中,前述黏著劑層係由含有丙烯酸系聚合物作為基底聚合物且含有矽烷耦合劑的黏著劑層所形成,且該丙烯酸系聚合物使用了預定比率以上的預定單體,因此即使在加濕環境下有油脂或乳油成分到達黏著劑層時,仍可抑制黏著劑層因膨潤而從被黏體剝落。 The optical film with adhesive layer of the present invention has an optical film with a thickness above a predetermined range, so it can prevent or to some extent prevent grease or cream components from reaching and contacting the adhesive layer. In addition, in the optical film with adhesive layer of the present invention, the adhesive layer is formed by an adhesive layer containing an acrylic polymer as a base polymer and a silane coupling agent, and the acrylic polymer uses a predetermined monomer above a predetermined ratio, so even if grease or cream components reach the adhesive layer in a humidified environment, the adhesive layer can be prevented from being peeled off from the adherend due to swelling.
又,本發明附黏著劑層之光學薄膜係使用於偏光件之單面具有透明保護薄膜(惟,不含相位差薄膜)的單面保護偏光薄膜作為偏光薄膜,且前述黏著劑層係設於前述單面保護偏光薄膜之不具有前述透明保護薄膜之側,因此即使是在前述黏著劑層在加濕環境下吸收油脂或乳油成分而膨潤時,由於用以貼合前述黏著劑層之側不具有透明保護薄膜而可有效抑制於透明保護薄膜產生裂痕。又,前述偏光件係厚度為10μm以下的薄型偏光件,因此可將加濕環境下之偏光件收縮抑制得較小,而不易發生偏光件與黏著劑層之剝落。 Furthermore, the optical film with adhesive layer of the present invention is a single-sided protective polarizing film with a transparent protective film (but not including a phase difference film) on one side of the polarizer as a polarizing film, and the adhesive layer is provided on the side of the single-sided protective polarizing film without the transparent protective film, so even when the adhesive layer absorbs oil or emulsion components and swells in a humidified environment, the side for bonding the adhesive layer does not have a transparent protective film, so cracks in the transparent protective film can be effectively suppressed. Furthermore, the polarizer is a thin polarizer with a thickness of less than 10μm, so the shrinkage of the polarizer in a humidified environment can be suppressed to a small extent, and the polarizer and the adhesive layer are not easy to peel off.
A:影像顯示面板 A: Image display panel
1:影像顯示部 1: Image display unit
2:光學薄膜(包含偏光薄膜) 2: Optical films (including polarizing films)
3:黏著劑層(影像顯示部側) 3: Adhesive layer (image display side)
4:彈性中間層 4: Elastic middle layer
5:外部邊框 5: External border
6:內部邊框 6: Inner border
7:空室 7: Empty room
8:黏著劑層(蓋玻璃側) 8: Adhesive layer (covering the glass side)
9:蓋玻璃 9: Cover with glass
41:保持部 41:Maintenance Department
42:凸部 42: convex part
S:間隙 S: Gap
a:最表面 a: The most superficial
t:距離 t: distance
圖1A係顯示本發明附黏著劑層之光學薄膜可應用之附邊框之影像顯示面板之一例的截面圖的一部分。 FIG. 1A is a partial cross-sectional view showing an example of an image display panel with a frame to which the optical film with an adhesive layer of the present invention can be applied.
圖1B係顯示圖1A之附邊框之影像顯示面板之一例的俯視圖。 FIG. 1B is a top view showing an example of an image display panel with a border of FIG. 1A .
圖2A係顯示本發明附黏著劑層之光學薄膜可應用之附邊框之影像顯示面板之一例的截面圖的一部分。 FIG. 2A is a partial cross-sectional view showing an example of an image display panel with a frame to which the optical film with an adhesive layer of the present invention can be applied.
圖2B係顯示圖2A之附邊框之影像顯示面板之一例的俯視圖。 FIG. 2B is a top view showing an example of an image display panel with a border as shown in FIG. 2A .
圖3A係顯示本發明附黏著劑層之光學薄膜可應用之附邊框之影像顯示面板之一例的截面圖的一部分。 FIG. 3A is a partial cross-sectional view showing an example of an image display panel with a frame to which the optical film with an adhesive layer of the present invention can be applied.
圖3B係顯示圖3A之附邊框之影像顯示面板之一例的俯視圖。 FIG. 3B is a top view showing an example of an image display panel with a border as shown in FIG. 3A .
圖4係顯示框狀彈性中間層之一例的俯視圖。 FIG4 is a top view showing an example of a frame-shaped elastic middle layer.
圖5係顯示比較例之附邊框之影像顯示面板之一例的截面圖的一部分。 FIG5 is a partial cross-sectional view showing an example of an image display panel with a frame as a comparative example.
用以實施發明之形態 The form used to implement the invention
以下參照圖示來說明可應用本發明之附黏著劑層之光學薄膜的影像顯示面板。於下述,針對將附黏著劑層之光學薄膜應用於附邊框之影像顯示面板之情況進行說明。 The following diagrams are used to illustrate an image display panel to which the optical film with an adhesive layer of the present invention can be applied. In the following, the application of the optical film with an adhesive layer to an image display panel with a frame is described.
例如,應用了本發明附黏著劑層之光學薄膜的附邊框之影像顯示面板如圖1A之截面圖所示,具有影像顯示面板A與位於前述影像顯示面板A之端面外側的外部邊框5,該影像顯示面板A具有影像顯示部1及光學薄膜2,該光學薄膜2係透過黏著劑層3配置於該影像顯示部1之視辨側。圖1A係顯示附邊框之影像顯示面板之一例的截面圖的一部分,顯示單側的端邊部。圖1B係顯示應用了本發明附黏著劑層之光學薄膜之附邊框之影像顯示面板之的俯視圖。外 部邊框5係隔著彈性中間層4而設置。彈性中間層4係設置成較前述影像顯示面板A(光學薄膜2)之視辨側的最表面a更突出,且外部邊框5係設置成不覆蓋彈性中間層4。由窄邊框化、顯示面積擴大化之觀點,或防止水分、油脂或乳油成分滲入之觀點,以及在使影像顯示裝置整體厚度薄化後防止龜裂從影像顯示面板端部產生之觀點等來看,宜在前述影像顯示面板A之端面與前述彈性中間層4接觸之態樣下作使用。前述外部邊框5可藉由接著劑固定於前述彈性中間層4。 For example, the image display panel with a border frame using the optical film with an adhesive layer of the present invention is shown in the cross-sectional view of FIG1A, and has an image display panel A and an external border frame 5 located outside the end surface of the aforementioned image display panel A. The image display panel A has an image display portion 1 and an optical film 2, and the optical film 2 is arranged on the visual side of the image display portion 1 through an adhesive layer 3. FIG1A is a part of a cross-sectional view of an example of an image display panel with a border frame, showing the end portion of one side. FIG1B is a top view of an image display panel with a border frame using the optical film with an adhesive layer of the present invention. The external border frame 5 is provided via an elastic intermediate layer 4. The elastic middle layer 4 is arranged to protrude more than the outermost surface a of the visual side of the image display panel A (optical film 2), and the outer frame 5 is arranged not to cover the elastic middle layer 4. From the perspective of narrowing the frame and expanding the display area, or preventing the penetration of moisture, grease or emulsion components, and preventing cracks from occurring at the end of the image display panel after the overall thickness of the image display device is thinned, it is suitable to use the image display panel A in a state of contact with the elastic middle layer 4. The outer frame 5 can be fixed to the elastic middle layer 4 by an adhesive.
另一方面,由可使面板嵌入框體來設置之製造步驟簡易的觀點來看,前述影像顯示面板A之端面與前述彈性中間層4可如圖2A所示設置間隙S。圖2B係顯示應用了本發明附黏著劑層之光學薄膜之附邊框之影像顯示面板之的俯視圖。間隙S宜在2000μm以下之範圍內設計。在具有前述間隙S時,水分、油脂或乳油成分會容易滲入該間隙S,但利用本發明附邊框之影像顯示面板的話,即使是在置於加濕環境下之情況時,仍可抑制黏著劑層剝落。且不論有無間隙S,都可對光學薄膜2之端面施行使用丙烯酸系樹脂、胺甲酸酯系樹脂、聚矽氧系、氟系樹脂等進行之端部塗佈。 On the other hand, from the viewpoint of simplifying the manufacturing steps by embedding the panel into the frame, a gap S can be provided between the end face of the image display panel A and the elastic intermediate layer 4 as shown in FIG2A. FIG2B is a top view of an image display panel with a frame to which the optical film with the adhesive layer of the present invention is applied. The gap S is preferably designed within a range of less than 2000 μm. When the gap S is provided, moisture, grease or emulsion components can easily penetrate into the gap S, but when the image display panel with the frame of the present invention is used, the peeling of the adhesive layer can be suppressed even when placed in a humidified environment. Regardless of whether there is a gap S or not, the end surface of the optical film 2 can be coated with an acrylic resin, urethane resin, silicone resin, fluorine resin, etc.
又,應用了本發明附黏著劑層之光學薄膜之附邊框之影像顯示面板如圖3A之截面圖所示,可於上述圖1A或圖1B所示態樣中,進一步於前述影像顯示面板A之端面部中於較前述彈性中間層4更內側之最表面a具有內部 邊框6。圖3B係顯示應用了本發明附黏著劑層之光學薄膜之附邊框之影像顯示面板之的俯視圖。該態樣中,前述彈性中間層4亦係在較前述內部邊框6更突出之態樣下作使用。圖3A所示態樣中,係例示於前述影像顯示面板A之端面與前述彈性中間層4之間設有空室7之情形,惟在圖3A所示態樣中,亦可在前述影像顯示面板A之端面與前述彈性中間層4接觸之態樣下作使用。在圖3A所示態樣中設置空室7時,可於該空室7之處配置附屬品(相機鏡頭、排線、調光感測器、面部辨識感測器等),並使其隔著其上面之內部邊框6發揮功能。內部邊框6可藉由接著劑固定於前述影像顯示面板A之最表面a、前述彈性中間層4。 In addition, as shown in the cross-sectional view of FIG3A, the image display panel with a frame of the optical film with an adhesive layer of the present invention can be further provided with an inner frame 6 on the outermost surface a of the end face of the image display panel A which is further inward than the elastic intermediate layer 4 in the embodiment shown in FIG1A or FIG1B. FIG3B is a top view of the image display panel with a frame of the optical film with an adhesive layer of the present invention. In this embodiment, the elastic intermediate layer 4 is also used in an embodiment that is more protruding than the inner frame 6. In the embodiment shown in FIG. 3A, a case where a chamber 7 is provided between the end surface of the image display panel A and the elastic middle layer 4 is illustrated. However, in the embodiment shown in FIG. 3A, the end surface of the image display panel A and the elastic middle layer 4 can also be used in a state where the end surface of the image display panel A is in contact with the elastic middle layer 4. When the chamber 7 is provided in the embodiment shown in FIG. 3A, accessories (camera lens, flat cable, dimming sensor, facial recognition sensor, etc.) can be arranged in the chamber 7, and the inner frame 6 above it can be used to perform its function. The inner frame 6 can be fixed to the outermost surface a of the image display panel A and the elastic middle layer 4 by an adhesive.
又,應用了本發明附黏著劑層之光學薄膜之附邊框之影像顯示面板中,前述影像顯示面板A(光學薄膜2)之視辨側的最表面a與前述黏著劑層3之間的距離t(對應光學薄膜2的厚度)係設定成75μm以上。若前述距離t小於75μm,則會難以在有油脂或乳油成分與前述彈性中間層接觸之虞的加濕環境下仍抑制黏著劑層3剝落。前述距離t以可抑制黏著劑層3之剝落來看,宜為100μm以上,且120μm以上更佳。另一方面,若前述距離t變長(亦即若光學薄膜之厚度變厚),則光學薄膜在加濕環境下之尺寸收縮會變大,而有容易發生翹曲之傾向,因此前述距離t宜為300μm以下,且250μm以下更佳。前述距離t係對應光學薄膜之厚度,而本發明附黏著劑層之光學薄膜中光學薄膜之厚度為75μm以上,另一方面,厚度宜在300μm以下。 Furthermore, in the image display panel with a frame using the optical film with an adhesive layer of the present invention, the distance t (corresponding to the thickness of the optical film 2) between the outermost surface a of the visual side of the image display panel A (optical film 2) and the adhesive layer 3 is set to be greater than 75 μm. If the distance t is less than 75 μm, it will be difficult to suppress the peeling of the adhesive layer 3 in a humidified environment where there is a risk of contact between grease or emulsion components and the elastic intermediate layer. In order to suppress the peeling of the adhesive layer 3, the distance t is preferably greater than 100 μm, and more preferably greater than 120 μm. On the other hand, if the aforementioned distance t becomes longer (that is, if the thickness of the optical film becomes thicker), the dimensional shrinkage of the optical film in a humidified environment will become larger, and there is a tendency to bend easily. Therefore, the aforementioned distance t is preferably less than 300μm, and more preferably less than 250μm. The aforementioned distance t corresponds to the thickness of the optical film, and the thickness of the optical film in the optical film with an adhesive layer of the present invention is more than 75μm. On the other hand, the thickness is preferably less than 300μm.
又,由附邊框之影像顯示面板的窄邊框化之觀點來看,外部邊框5、彈性中間層4的寬度宜皆小。外部邊框5、彈性中間層4的寬度係因應影像顯示面板A的尺寸適當設定,一般來說外部邊框5的寬度為5mm以下,宜為0.5~5mm,且宜為0.5~3mm。而彈性中間層4的寬度為5mm以下,宜為0.5~5mm,且宜為0.5~3mm。又,關於內部邊框6,由窄邊框化之觀點來看亦宜小。一般而言,內部邊框6的寬度宜為1~20mm,且1~15mm更佳。又,設置空室7時,其寬度宜為1~20mm,且1~15mm更佳。在具有內部邊框6時,即使是在已有油脂或乳油成分接觸前述彈性中間層4之情況時,前述成分到達、接觸前述黏著劑層3之可能性仍會減少,因此空室7之寬度宜為1mm以上。 Furthermore, from the perspective of narrowing the frame of the image display panel with a frame, the widths of the external frame 5 and the elastic middle layer 4 should both be small. The widths of the external frame 5 and the elastic middle layer 4 are appropriately set according to the size of the image display panel A. Generally speaking, the width of the external frame 5 is less than 5 mm, preferably 0.5~5 mm, and preferably 0.5~3 mm. The width of the elastic middle layer 4 is less than 5 mm, preferably 0.5~5 mm, and preferably 0.5~3 mm. Furthermore, regarding the internal frame 6, from the perspective of narrowing the frame, it should also be small. Generally speaking, the width of the internal frame 6 should be 1~20 mm, and 1~15 mm is better. Furthermore, when the empty chamber 7 is provided, its width should be 1~20 mm, and 1~15 mm is better. When there is an inner frame 6, even when the grease or emulsion component has contacted the elastic intermediate layer 4, the possibility of the component reaching and contacting the adhesive layer 3 will still be reduced, so the width of the empty chamber 7 is preferably greater than 1 mm.
又,前述彈性中間層4在上述圖1A所示態樣中,係在較前述影像顯示面板A(光學薄膜2)之視辨側的最表面a更突出之態樣下作使用,而在上述圖3A所示態樣中,係在較前述內部邊框6更突出之態樣下作使用。藉由該突出,可避免影像顯示面板與影像顯示裝置之本體直接接觸。前述突出部的高度一般宜為0.5~5mm,且0.5~3mm更佳。又,前述彈性中間層4在上述圖1B所示俯視圖、上述圖3B所示俯視圖中係設於前述影像顯示面板A之端面外側全部,但本發明在前述彈性中間層4用於其至少一部分之情況時亦有效。 Furthermore, the elastic middle layer 4 is used in a state where it protrudes more than the outermost surface a of the visual side of the image display panel A (optical film 2) in the state shown in the above FIG. 1A, and is used in a state where it protrudes more than the inner frame 6 in the state shown in the above FIG. 3A. By protruding, the image display panel and the body of the image display device can be prevented from directly contacting. The height of the protruding portion is generally preferably 0.5 to 5 mm, and 0.5 to 3 mm is more preferred. Furthermore, the elastic middle layer 4 is provided on the entire outer side of the end surface of the image display panel A in the top view shown in the above FIG. 1B and the top view shown in the above FIG. 3B, but the present invention is also effective when the elastic middle layer 4 is used for at least a part thereof.
又,如圖1A、圖2A、圖3A所示,可於前述彈性中間層4之下側具有用以保持前述影像顯示面板A之 保持部41。前述彈性中間層4與保持部41亦可一體成型。前述保持部41的寬度中,不接觸彈性中間層4之底部之處的寬度由窄邊框、輕量化等之觀點來看宜為5mm以下,且以3mm以下為佳。另一方面,由保持前述影像顯示面板A之觀點來看,前述保持部41的寬度(不接觸彈性中間層4之底部之處的寬度)宜為0.1mm以上,且0.3mm以上更佳。圖2係例示前述彈性中間層4的保持部41中,於前述影像顯示面板A之端面與前述彈性中間層4之間設置間隙S,且影像顯示面板A之緣部被保持部41保持的情形,而在設置間隙S時,宜設計成使前述保持部41之不與彈性中間層4的底部接觸之處的寬度較間隙S的寬度更長。 Furthermore, as shown in Fig. 1A, Fig. 2A, and Fig. 3A, a holding portion 41 for holding the image display panel A may be provided on the lower side of the elastic intermediate layer 4. The elastic intermediate layer 4 and the holding portion 41 may also be formed as one piece. The width of the holding portion 41, which does not contact the bottom of the elastic intermediate layer 4, is preferably 5 mm or less, and preferably 3 mm or less, from the viewpoint of narrow frame and light weight. On the other hand, from the viewpoint of holding the image display panel A, the width of the holding portion 41 (the width of the bottom of the elastic intermediate layer 4) is preferably 0.1 mm or more, and more preferably 0.3 mm or more. FIG2 illustrates a case where a gap S is provided between the end surface of the image display panel A and the elastic middle layer 4 in the retaining portion 41 of the elastic middle layer 4, and the edge of the image display panel A is retained by the retaining portion 41. When the gap S is provided, it is preferable to design the width of the retaining portion 41 where it does not contact the bottom of the elastic middle layer 4 to be longer than the width of the gap S.
如圖1B、圖2B、圖3B所示,彈性中間層4、外部邊框5、內部邊框6可以框狀設置。又,彈性中間層4如圖4所示以框狀(圖4為俯視圖,因此一併記載具有彈性中間層4且同時具有保持部41之情形)使用時,由處置性等之觀點來看可省略一部分的邊。並且,彈性中間層4之內側亦可具有為了固定於框體而用於嵌入的凸部42。例如在圖4中係於框內側的三邊各設置2個凸部42。前述凸部42可任意設定其數量。 As shown in Fig. 1B, Fig. 2B, and Fig. 3B, the elastic middle layer 4, the outer frame 5, and the inner frame 6 can be arranged in a frame shape. Moreover, when the elastic middle layer 4 is used in a frame shape as shown in Fig. 4 (Fig. 4 is a top view, so the case where the elastic middle layer 4 and the retaining portion 41 are simultaneously recorded), a part of the sides can be omitted from the perspective of handling, etc. Moreover, the inner side of the elastic middle layer 4 can also have a protrusion 42 for embedding in order to fix it to the frame. For example, in Fig. 4, two protrusions 42 are arranged on each of the three sides of the inner side of the frame. The number of the protrusions 42 can be set arbitrarily.
<外部邊框、內部邊框> <Outer border, inner border>
外部邊框係在影像顯示面板之端面外側形成外框進行保護者,通常可無特別限制地使用適用於影像顯示面板者。而內部邊框係在前述影像顯示面板之端面部保護最表面者,通常可無特別限制地使用適用於影像顯示面板者。 The external frame is formed on the outer side of the end surface of the image display panel for protection, and can usually be used without special restrictions for image display panels. The internal frame is formed on the outermost surface of the end surface of the aforementioned image display panel for protection, and can usually be used without special restrictions for image display panels.
<彈性中間層> <Elastic middle layer>
彈性中間層係如同上述用於避免影像顯示面板與影像顯示裝置本體直接接觸,只要是在關閉筆記型電腦等時可緩和前述接觸所帶來之衝擊的材料即無特別限制。形成彈性中間層之材料可使用例如用於橡膠襯墊等之腈橡膠、氟橡膠、胺甲酸酯橡膠、聚矽氧橡膠、乙烯丙烯橡膠、氫化腈橡膠、氯丁二烯橡膠、丙烯酸橡膠、丁基橡膠、氯磺化聚乙烯、表氯醇橡膠、天然橡膠等橡膠材料。除此之外,彈性中間層的材料還可舉例如氯乙烯樹脂、胺甲酸酯樹脂等彈性塑膠、緩衝泡沫發泡體等。 As mentioned above, the elastic middle layer is used to prevent the image display panel from directly contacting the image display device body. There is no particular limitation as long as the material can mitigate the impact caused by the aforementioned contact when the laptop is closed. The material forming the elastic middle layer can be a rubber material such as nitrile rubber, fluoro rubber, urethane rubber, silicone rubber, ethylene propylene rubber, hydrogenated nitrile rubber, chloroprene rubber, acrylic rubber, butyl rubber, chlorosulfonated polyethylene, epichlorohydrin rubber, natural rubber, etc., which are used for rubber pads. In addition, the material of the elastic middle layer can also include elastic plastics such as vinyl chloride resin, urethane resin, and cushioning foam.
<光學薄膜> <Optical film>
以下說明本發明之光學薄膜。如上述,本發明之光學薄膜係含有偏光薄膜者。本發明之光學薄膜可以偏光薄膜單獨形成,亦可以偏光薄膜與其他薄膜組合而成之積層光學薄膜之型態形成。前述光學薄膜(為積層光學薄膜時亦同)的厚度係設計成滿足75μm以上。另一方面,宜將前述厚度設計為300μm以下。 The optical film of the present invention is described below. As mentioned above, the optical film of the present invention is a film containing a polarizing film. The optical film of the present invention can be formed by a polarizing film alone, or can be formed by a laminated optical film composed of a polarizing film and other films. The thickness of the aforementioned optical film (the same applies to laminated optical films) is designed to meet 75μm or more. On the other hand, the aforementioned thickness is preferably designed to be less than 300μm.
《偏光薄膜》 《Polarizing Film》
前述光學薄膜含有之偏光薄膜可使用僅於偏光件之單面具有透明保護薄膜(惟,不包含相位差薄膜)之單面保護偏光薄膜。該單面保護偏光薄膜中,係將前述黏著劑層設在前述單面保護偏光薄膜之不具有前述透明保護薄膜之側。 The polarizing film contained in the aforementioned optical film may be a single-sided protected polarizing film having a transparent protective film (but not including a phase difference film) on only one side of the polarizing element. In the single-sided protected polarizing film, the aforementioned adhesive layer is disposed on the side of the aforementioned single-sided protected polarizing film that does not have the aforementioned transparent protective film.
前述黏著劑層直接設於單面保護偏光薄膜 之偏光件的情況時,單面保護偏光薄膜與黏著劑層之層構成(1)顯示如下。 In the case of a polarizing element in which the aforementioned adhesive layer is directly provided on a single-sided protective polarizing film, the layer structure (1) of the single-sided protective polarizing film and the adhesive layer is shown as follows.
層構成(1):透明保護薄膜/偏光件/黏著劑層 Layer composition (1): transparent protective film/polarizer/adhesive layer
而前述黏著劑層隔著相位差薄膜設於單面保護偏光薄膜的情況時,單面保護偏光薄膜與黏著劑層之層構成(2)顯示如下。 When the aforementioned adhesive layer is provided on the single-sided protective polarizing film via a phase difference film, the layer structure (2) of the single-sided protective polarizing film and the adhesive layer is shown as follows.
層構成(2):透明保護薄膜/偏光件/相位差薄膜/黏著劑層 Layer composition (2): transparent protective film/polarizer/phase difference film/adhesive layer
前述偏光件並無特別限制,可使用各種偏光件。作為偏光件,可舉如使聚乙烯醇系薄膜、部分縮甲醛化聚乙烯醇系薄膜、乙烯-乙酸乙烯酯共聚物系部分皂化薄膜等親水性高分子薄膜吸附碘或二色性染料之二色性物質並進行單軸延伸者,以及聚乙烯醇之脫水處理物或聚氯乙烯之脫鹽酸處理物等多烯系定向薄膜等。該等之中又以由聚乙烯醇系薄膜與碘等的二色性物質構成之偏光件較適宜。 The aforementioned polarizer is not particularly limited, and various polarizers can be used. As polarizers, hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and partially saponified films of ethylene-vinyl acetate copolymers adsorb dichroic substances such as iodine or dichroic dyes and are uniaxially stretched, as well as polyene oriented films such as dehydrated polyvinyl alcohol or dehydrogenated polyvinyl chloride. Among these, polarizers composed of polyvinyl alcohol films and dichroic substances such as iodine are more suitable.
又,偏光件宜使用厚度10μm以下的薄型偏光件。尤宜於前述單面保護偏光薄膜使用薄型偏光件。以可抑制黏著劑層因油脂或乳油成分而剝落來看,偏光件之厚度在3μm以上為佳。又,由抑制在加濕環境下之尺寸收縮之觀點來看,偏光件的厚度宜為10μm以下。厚度3~10μm的薄型偏光件因厚度參差少,視辨性佳,且尺寸變化少故耐久性優異,而且在作為偏光薄膜的厚度上亦能力求薄型化,就此等觀點來看較為理想。 In addition, the polarizer should preferably be a thin polarizer with a thickness of less than 10μm. It is particularly suitable to use a thin polarizer for the aforementioned single-sided protective polarizing film. From the perspective of suppressing the peeling of the adhesive layer due to grease or emulsion components, the thickness of the polarizer is preferably above 3μm. From the perspective of suppressing dimensional shrinkage in a humidified environment, the thickness of the polarizer should be less than 10μm. A thin polarizer with a thickness of 3~10μm has less thickness variation, better visibility, and less dimensional change, so it has excellent durability. In addition, it can also be thinned in thickness as a polarizing film, which is more ideal from these perspectives.
作為構成透明保護薄膜的材料,可使用例如透明性、機械強度、熱穩定性、抗濕性、各向同性等優異之熱塑性樹脂。所述熱塑性樹脂的具體例可舉例如三醋酸纖維素等之纖維素樹脂、聚酯樹脂、聚醚碸樹脂、聚碸樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚烯烴樹脂、(甲基)丙烯酸樹脂、環狀聚烯烴樹脂(降莰烯系樹脂)、聚芳酯樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂及該等之混合物。此外,在偏光件的單側,透明保護薄膜是藉由接著劑層而貼合,而在另一側,透明保護薄膜可使用(甲基)丙烯酸系、胺甲酸酯系、丙烯酸胺甲酸酯系、環氧系、聚矽氧系等熱硬化性樹脂或紫外線硬化型樹脂。 As the material constituting the transparent protective film, a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture resistance, isotropy, etc. can be used. Specific examples of the thermoplastic resin include cellulose resins such as cellulose triacetate, polyester resins, polyether resins, polyester resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, cyclic polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. In addition, on one side of the polarizer, the transparent protective film is bonded by an adhesive layer, and on the other side, the transparent protective film can use a thermosetting resin or UV-curing resin such as (meth) acrylic, urethane, acrylic urethane, epoxy, or silicone.
前述透明保護薄膜的材料宜為纖維素樹脂、(甲基)丙烯酸樹脂。(甲基)丙烯酸樹脂宜使用具有內酯環結構之(甲基)丙烯酸系樹脂。具有內酯環結構之(甲基)丙烯酸系樹脂可列舉日本特開2000-230016號公報、日本特開2001-151814號公報、日本特開2002-120326號公報、日本特開2002-254544號公報、日本特開2005-146084號公報等中記載之具有內酯環結構的(甲基)丙烯酸系樹脂。尤其是纖維素樹脂相較於(甲基)丙烯酸樹脂,在抑制僅於偏光件之單面具有透明保護薄膜的單面保護薄膜中成為課題之偏光件裂痕上更為有效,就此觀點來看較佳。前述透明保護薄膜的厚度一般宜為10~100μm,且以20~50μm為佳,30~50μm更佳。尤其在使用纖維素樹脂作為透明保護薄膜之材料時,將厚度控制在100μm以下能抑制加濕環 境下之尺寸收縮,由此來看較佳。 The material of the transparent protective film is preferably a cellulose resin or a (meth) acrylic resin. The (meth) acrylic resin is preferably a (meth) acrylic resin having a lactone ring structure. Examples of the (meth) acrylic resin having a lactone ring structure include the (meth) acrylic resin having a lactone ring structure described in Japanese Patent Publication No. 2000-230016, Japanese Patent Publication No. 2001-151814, Japanese Patent Publication No. 2002-120326, Japanese Patent Publication No. 2002-254544, Japanese Patent Publication No. 2005-146084, etc. In particular, cellulose resin is more effective than (meth) acrylic resin in suppressing polarizer cracks, which is a problem in a single-sided protective film having a transparent protective film on only one side of the polarizer, and is therefore preferred from this point of view. The thickness of the aforementioned transparent protective film is generally preferably 10~100μm, preferably 20~50μm, and more preferably 30~50μm. In particular, when using cellulose resin as the material for the transparent protective film, controlling the thickness to less than 100μm can suppress dimensional shrinkage in a humidified environment, and is therefore preferred.
前述透明保護薄膜中不包含相位差薄膜。不包含相位差薄膜之透明保護薄膜顯示「在光學上為各向同性」,意指面內相位差Re(550)為0nm~10nm,且厚度方向之相位差Rth(550)為-10nm~+10nm。 The aforementioned transparent protective film does not include a phase difference film. The transparent protective film without a phase difference film is "optically isotropic", which means that the in-plane phase difference Re(550) is 0nm~10nm, and the phase difference Rth(550) in the thickness direction is -10nm~+10nm.
(用語及符號之定義) (Definition of terms and symbols)
本說明書中之用語及符號之定義如下。 The definitions of terms and symbols in this manual are as follows.
(1)折射率(nx、ny、nz) (1) Refractive index (nx, ny, nz)
「nx」為面內折射率成最大的方向(亦即慢軸方向)之折射率,「ny」為在面內與慢軸正交之方向(亦即快軸方向)之折射率,而「nz」為厚度方向之折射率。 "nx" is the refractive index in the direction where the refractive index is the largest in the plane (i.e. the slow axis direction), "ny" is the refractive index in the direction orthogonal to the slow axis in the plane (i.e. the fast axis direction), and "nz" is the refractive index in the thickness direction.
(2)面內相位差(Re) (2) In-plane phase difference (Re)
「Re(λ)」係於23℃下以波長λ nm之光測得之薄膜的面內相位差。例如,「Re(450)」係於23℃下以波長450nm之光測得之薄膜的面內相位差。Re(λ)可於令薄膜之厚度為d(nm)時,藉由式:Re=(nx-ny)×d求得。 "Re(λ)" is the in-plane phase difference of the film measured at 23°C with light of wavelength λ nm. For example, "Re(450)" is the in-plane phase difference of the film measured at 23°C with light of wavelength 450nm. Re(λ) can be obtained by the formula: Re=(nx-ny)×d when the thickness of the film is d(nm).
(3)厚度方向之相位差(Rth) (3) Phase difference in thickness direction (Rth)
「Rth(λ)」係於23℃下以波長550nm之光測得之薄膜在厚度方向的相位差。例如,「Rth(450)」係於23℃下以波長450nm之光測得之薄膜在厚度方向的相位差。Rth(λ)可於令薄膜厚度為d(nm)時,藉由式:Rth=(nx-nz)×d求得。 "Rth(λ)" is the phase difference of the film in the thickness direction measured at 23°C with light of 550nm wavelength. For example, "Rth(450)" is the phase difference of the film in the thickness direction measured at 23°C with light of 450nm wavelength. Rth(λ) can be obtained by the formula: Rth=(nx-nz)×d when the film thickness is d(nm).
用於前述偏光件與透明保護薄膜的貼合之接著劑只要在光學上是透明的,則可無特別限制地使用水 系、溶劑系、熱熔膠系、自由基硬化型、陽離子硬化型之各種形態的接著劑,惟水系接著劑或自由基硬化型接著劑較適宜。 As long as the adhesive used for bonding the polarizer and the transparent protective film is optically transparent, various forms of adhesives such as water-based, solvent-based, hot melt adhesive-based, free radical curing, and cationic curing can be used without particular restrictions, but water-based adhesives or free radical curing adhesives are more suitable.
≪表面處理層≫ ≪Surface treatment layer≫
亦可於前述光學薄膜之最表面設置表面處理層。表面處理層可舉硬塗層、抗反射層、抗黏結層、擴散層或防眩層等機能層。表面處理層可設於偏光薄膜所用之透明保護薄膜上,除此之外亦可另外設於與前述透明保護薄膜相異之另一基材上。另一基材可使用與前述透明保護薄膜相同之物。另外設置表面處理層時,可利用以往習知之黏著劑層等來貼合於前述偏光薄膜。前述表面處理層係在前述光學薄膜之前述偏光薄膜中,設於與設置前述黏著劑層之側相反之側。 A surface treatment layer may also be provided on the outermost surface of the aforementioned optical film. The surface treatment layer may be a functional layer such as a hard coating layer, an anti-reflection layer, an anti-adhesion layer, a diffusion layer or an anti-glare layer. The surface treatment layer may be provided on a transparent protective film used for the polarizing film, or may be provided on another substrate different from the aforementioned transparent protective film. The other substrate may be the same as the aforementioned transparent protective film. When the surface treatment layer is provided, an adhesive layer known in the past may be used to adhere to the aforementioned polarizing film. The aforementioned surface treatment layer is provided on the side opposite to the side on which the aforementioned adhesive layer is provided in the aforementioned polarizing film of the aforementioned optical film.
以作為前述表面處理層設置之硬塗層的形成材料可使用例如熱塑性樹脂、可藉由熱或放射線硬化之材料。前述材料可列舉熱硬化型樹脂或紫外線硬化型樹脂、電子射線硬化型樹脂等的放射線硬化性樹脂。該等中又以紫外線硬化型樹脂為宜,該紫外線硬化型樹脂可藉由利用紫外線照射進行的硬化處理,以簡單的加工操作有效率地形成硬化樹脂層。該等硬化型樹脂可舉聚酯系、丙烯酸系、胺甲酸酯系、醯胺系、聚矽氧系、環氧系、三聚氰胺系等各種樹脂,且包含該等之單體、寡聚物、聚合物等。從加工速度的迅速性、對基材之熱損少的觀點來看,尤以放射線硬化型樹脂、特別是紫外線硬化型樹脂為宜。可適宜使 用的紫外線硬化型樹脂可舉例如具有紫外線聚合性官能基者,其中包含具有2個以上該官能基、特別是具有3~6個該官能基之丙烯酸系單體或寡聚物成分者。又,紫外線硬化型樹脂中摻混有光聚合起始劑。 The material used to form the hard coating layer provided as the surface treatment layer may be, for example, a thermoplastic resin or a material that can be cured by heat or radiation. Examples of the material include heat-curing resins, ultraviolet-curing resins, electron-ray-curing resins, and other radiation-curing resins. Among these, ultraviolet-curing resins are preferred, and the ultraviolet-curing resins can be cured by ultraviolet irradiation to efficiently form a cured resin layer with a simple processing operation. Examples of these curing resins include various resins such as polyesters, acrylics, urethanes, amides, silicones, epoxys, and melamines, and include monomers, oligomers, and polymers thereof. From the perspective of rapid processing speed and less heat damage to the substrate, radiation-curing resins, especially UV-curing resins, are particularly suitable. Suitable UV-curing resins include, for example, those having UV-polymerizable functional groups, including acrylic monomers or oligomer components having two or more such functional groups, especially 3 to 6 such functional groups. In addition, the UV-curing resin is mixed with a photopolymerization initiator.
又,就前述表面處理層來說,可設置以提升視辨性為目的之防眩處理層或抗反射層。且可於前述硬塗層上設置防眩處理層或抗反射層。防眩處理層之構成材料無特別限定,譬如可使用放射線硬化型樹脂、熱硬化型樹脂、熱塑性樹脂等。抗反射層可使用氧化鈦、氧化鋯、氧化矽、氟化鎂等。抗反射層可設置多層。除此之外,表面處理層還可舉抗黏結層等。 In addition, as for the aforementioned surface treatment layer, an anti-glare treatment layer or an anti-reflection layer can be provided for the purpose of improving visibility. And an anti-glare treatment layer or an anti-reflection layer can be provided on the aforementioned hard coating layer. The constituent material of the anti-glare treatment layer is not particularly limited, for example, radiation-hardening resins, thermosetting resins, thermoplastic resins, etc. can be used. The anti-reflection layer can use titanium oxide, zirconium oxide, silicon oxide, magnesium fluoride, etc. The anti-reflection layer can be provided in multiple layers. In addition, the surface treatment layer can also provide an anti-adhesive layer, etc.
≪其他層≫ ≪Other layers≫
前述光學薄膜(積層光學薄膜)上,除前述各層外,亦可積層相位差薄膜(包含1/2或1/4等波長板)、視覺補償薄膜等。又,可於前述偏光薄膜或其他光學層上設置錨固層、易接著層,或施行電暈處理、電漿處理等各種易接著處理。 In addition to the aforementioned layers, the aforementioned optical film (laminated optical film) may also be laminated with a phase difference film (including 1/2 or 1/4 equal wavelength plates), a visual compensation film, etc. In addition, an anchoring layer, an easy-to-bond layer, or various easy-to-bond treatments such as corona treatment and plasma treatment may be provided on the aforementioned polarizing film or other optical layers.
如前述層構成(2)所示,前述黏著劑層可隔著相位差薄膜設於單面保護偏光薄膜。作為相位差薄膜,可舉如將高分子素材進行單軸或雙軸延伸處理而成之雙折射性薄膜、液晶聚合物之定向薄膜、以薄膜支持液晶聚合物之定向層者等。該等相位差薄膜可單獨1層或組合或2層以上。 As shown in the aforementioned layer structure (2), the aforementioned adhesive layer can be provided on the single-sided protective polarizing film via a phase difference film. As the phase difference film, for example, there can be a birefringent film obtained by uniaxial or biaxial stretching of a polymer material, an oriented film of a liquid crystal polymer, an oriented layer of a liquid crystal polymer supported by a film, etc. Such phase difference films can be a single layer or a combination or more than two layers.
在將附黏著劑層之光學薄膜應用於PC用影像顯示面板時,相位差薄膜由視角補償、低反射率等觀點 來看,宜設於偏光件與影像顯示部之間,而與上述透明保護薄膜差異化。又,相位差薄膜一般而言可使用厚度4~150μm者,但由抑制黏著劑層在加濕環境下之剝落或相位差薄膜之裂痕來看,前述厚度在適當範圍內較薄較為有利,例如相位差薄膜之厚度(合計)為2~25μm,且4~24μm更佳。 When an optical film with an adhesive layer is applied to an image display panel for a PC, the phase difference film is preferably placed between the polarizer and the image display part from the perspective of viewing angle compensation and low reflectivity, and is differentiated from the above-mentioned transparent protective film. In addition, the phase difference film can generally be used with a thickness of 4 to 150 μm, but from the perspective of suppressing the peeling of the adhesive layer in a humidified environment or cracks in the phase difference film, it is more advantageous to have a thinner thickness within an appropriate range, for example, the thickness (total) of the phase difference film is 2 to 25 μm, and 4 to 24 μm is more preferred.
<黏著劑層> <Adhesive layer>
以下針對前述附黏著劑層之光學薄膜中之黏著劑層進行說明。該黏著劑層係由下述黏著劑組成物所形成,該黏著劑組成物含有(甲基)丙烯酸系聚合物(A)作為基底聚合物,該(甲基)丙烯酸系聚合物(A)包含80質量%以上之單體(a)作為單官能性單體單元,該單體(a)選自具碳數1~4烷基之(甲基)丙烯酸烷基酯、(甲基)丙烯酸烷氧基烷基酯、含氟單體及丙烯腈中之至少1種,且作為單體單元含有20質量%以上之丙烯酸正丁酯作為單體單元、或含有70質量%以上之(甲基)丙烯酸烷氧基烷基酯。前述單官能性單體單元係構成(甲基)丙烯酸系聚合物(A)且具有1個(甲基)丙烯醯基、乙烯基等不飽和雙鍵之化合物的單元。前述(甲基)丙烯酸系聚合物(A)包含含有前述(甲基)丙烯酸烷基酯(a)之單體成分的部分聚合物及/或由前述單體成分所得之(甲基)丙烯酸系聚合物。另,(甲基)丙烯酸酯係指丙烯酸酯及/或甲基丙烯酸酯,本發明之(甲基)亦為同義。 The adhesive layer in the optical film with the adhesive layer is described below. The adhesive layer is formed by the following adhesive composition, which contains a (meth)acrylic polymer (A) as a base polymer, and the (meth)acrylic polymer (A) contains 80% by mass or more of a monomer (a) as a monofunctional monomer unit, and the monomer (a) is selected from at least one of a (meth)acrylic acid alkyl ester having an alkyl group of 1 to 4 carbon atoms, a (meth)acrylic acid alkoxyalkyl ester, a fluorine-containing monomer, and acrylonitrile, and contains 20% by mass or more of n-butyl acrylate as a monomer unit, or contains 70% by mass or more of a (meth)acrylic acid alkoxyalkyl ester. The aforementioned monofunctional monomer unit is a unit of a compound having one unsaturated double bond such as a (meth)acrylic acid group or a vinyl group, which constitutes a (meth)acrylic acid polymer (A). The aforementioned (meth)acrylic acid polymer (A) includes a partial polymer of a monomer component containing the aforementioned (meth)acrylic acid alkyl ester (a) and/or a (meth)acrylic acid polymer obtained from the aforementioned monomer component. In addition, (meth)acrylic acid ester refers to acrylate and/or methacrylate, and (meth) in the present invention is also synonymous.
前述(甲基)丙烯酸系聚合物(A)的主骨架由單體(a)所形成,該單體(a)選自前述具碳數1~4烷基之(甲 基)丙烯酸烷基酯、(甲基)丙烯酸烷氧基烷基酯、含氟單體及丙烯腈中之至少1種。作為前述單體單元,前述單體(a)之質量比率在構成(甲基)丙烯酸系聚合物(A)的總構成單體(單官能性單體100質量%,以下相同)之質量比率中,為80質量%以上,藉由使用所述比率之(甲基)丙烯酸系聚合物(A),可抑制前述黏著劑層因油脂或乳油成分而剝落。 The main skeleton of the aforementioned (meth)acrylic polymer (A) is formed by a monomer (a), and the monomer (a) is selected from at least one of the aforementioned (meth)acrylic acid alkyl esters having an alkyl group with 1 to 4 carbon atoms, (meth)acrylic acid alkoxyalkyl esters, fluorinated monomers, and acrylonitrile. As the aforementioned monomer unit, the mass ratio of the aforementioned monomer (a) in the mass ratio of the total constituent monomers (monofunctional monomers 100 mass%, the same below) constituting the (meth)acrylic polymer (A) is 80 mass% or more. By using the (meth)acrylic polymer (A) of the aforementioned ratio, the aforementioned adhesive layer can be inhibited from peeling off due to oil or emulsifiable concentrate components.
前述具碳數1~4烷基之(甲基)丙烯酸烷基酯中之烷基可舉例如直鏈狀或支鏈狀烷基,例如可舉甲基、乙基、丙基、異丙基、正丁基、異丁基、三級丁基等。 The alkyl group in the aforementioned (meth)acrylic acid alkyl ester having an alkyl group with 1 to 4 carbon atoms may be a linear or branched alkyl group, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tertiary butyl group, etc.
前述具碳數1~4烷基之(甲基)丙烯酸烷基酯宜為具碳數4烷基之(甲基)丙烯酸烷基酯,且尤宜為丙烯酸正丁酯。丙烯酸正丁酯係構成(甲基)丙烯酸系聚合物(A)之必需的單體單元,可僅以丙烯酸正丁酯構成前述單體(a)。作為單體單元,丙烯酸正丁酯之質量比率在構成(甲基)丙烯酸系聚合物(A)的總構成單體(單官能性單體100質量%)之質量比率中,為20質量%以上,藉由使用所述比率之(甲基)丙烯酸系聚合物(A),可抑制前述黏著劑層因油脂或乳油成分而剝落。丙烯酸正丁酯的前述質量比率可使用30質量%以上,可使用40質量%以上,可使用50質量%以上可使用,且可使用60質量%以上,更可使用70質量%以上,並可使用80質量%以上,且使用90質量%以上更佳。 The aforementioned (meth)acrylic acid alkyl ester having an alkyl group with 1 to 4 carbon atoms is preferably an (meth)acrylic acid alkyl ester having an alkyl group with 4 carbon atoms, and is particularly preferably n-butyl acrylate. n-butyl acrylate is an essential monomer unit constituting the (meth)acrylic polymer (A), and the aforementioned monomer (a) may be constituted by n-butyl acrylate alone. As a monomer unit, the mass ratio of n-butyl acrylate in the mass ratio of the total constituent monomers constituting the (meth)acrylic polymer (A) (monofunctional monomer 100 mass %) is 20 mass % or more. By using the (meth)acrylic polymer (A) having such a ratio, it is possible to suppress the aforementioned adhesive layer from being peeled off by oil or emulsifiable concentrate components. The mass ratio of n-butyl acrylate can be 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, and preferably 90% or more.
上述(甲基)丙烯酸烷氧基烷基酯並無特別限定,前述烷氧基烷基宜為合計碳數3~25烷氧基烷基。例如上述(甲基)丙烯酸烷氧基烷基酯可舉2-甲氧基乙基(甲基) 丙烯酸酯、2-乙氧基乙基(甲基)丙烯酸酯、3-甲氧基丙基(甲基)丙烯酸酯、3-乙氧基丙基(甲基)丙烯酸酯、4-甲氧基丁基(甲基)丙烯酸酯、乙氧基丁基(甲基)丙烯酸酯等,其他還可舉甲氧基三乙二醇(甲基)丙烯酸酯等烷氧基聚伸烷基二醇等,市售物可舉甲氧基聚乙二醇(甲基)丙烯酸酯(大阪有機化學工業公司製bisma MPE400A)等。 The above-mentioned alkoxyalkyl (meth)acrylate is not particularly limited, and the above-mentioned alkoxyalkyl is preferably an alkoxyalkyl having a total carbon number of 3 to 25. For example, the above-mentioned alkoxyalkyl (meth)acrylate can include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, etc. Other examples include alkoxypolyalkylene glycols such as methoxytriethylene glycol (meth)acrylate, and commercially available products include methoxypolyethylene glycol (meth)acrylate (bisma MPE400A manufactured by Osaka Organic Chemical Industries, Ltd.).
上述含氟單體並無特別限定,可舉具(甲基)丙烯醯基、乙烯基等自由基聚合性碳-碳雙鍵且具有至少1個經氟原子取代之碳數3~10烷基者。例如,氟單體可舉例如2,2,2-三氟乙基丙烯酸酯、2-(全氟己基)乙基丙烯酸酯、2,2,3,3,3-五氟丙基丙烯酸酯、2-(全氟丁基)乙基丙烯酸酯、3-全氟丁基-2-羥丙基丙烯酸酯、3-全氟己基-2-羥丙基丙烯酸酯、3-(全氟-3-甲基丁基)-2-羥丙基丙烯酸酯、1H,1H,3H-四氟丙基丙烯酸酯、1H,1H,5H-八氟戊基丙烯酸酯、1H,1H,7H-十二氟庚基丙烯酸酯、1H-1-(三氟甲基)三氟乙基丙烯酸酯、1H,1H,3H-六氟丁基丙烯酸酯、1,2,2,2-四氟-1-(三氟甲基)乙基丙烯酸酯等。此外,上述含氟單體中,具羥基者不包含於後述含羥基單體中。 The fluorine-containing monomer is not particularly limited, and examples thereof include a monomer having a free radical polymerizable carbon-carbon double bond such as a (meth)acryl group or a vinyl group and having at least one fluorine-substituted alkyl group having 3 to 10 carbon atoms. For example, the fluorine monomer may include 2,2,2-trifluoroethyl acrylate, 2-(perfluorohexyl)ethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-(perfluorobutyl)ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 1H,1H,3H-tetrafluoropropyl acrylate, 1H,1H,5H-octafluoropentyl acrylate, 1H,1H,7H-dodecafluoroheptyl acrylate, 1H-1-(trifluoromethyl)trifluoroethyl acrylate, 1H,1H,3H-hexafluorobutyl acrylate, 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl acrylate, and the like. In addition, among the above-mentioned fluorine-containing monomers, those having a hydroxyl group are not included in the hydroxyl-containing monomers described below.
又,前述單體(a)係使用選自具碳數1~4烷基之(甲基)丙烯酸烷基酯、(甲基)丙烯酸烷氧基烷基酯、含氟單體及丙烯腈中之至少1種,但前述單體(a)可全部由前述具碳數1~4烷基之(甲基)丙烯酸烷基酯構成(態樣(1))。為該態樣(1)時,作為前述單體單元宜含有30質量%以上之丙烯酸正丁酯。該態樣(1)由加熱及確保濕熱耐久性之觀點來 看為佳。 Furthermore, the monomer (a) is at least one selected from (meth) acrylate alkyl esters having an alkyl group with 1 to 4 carbon atoms, (meth) acrylate alkoxyalkyl esters, fluorinated monomers, and acrylonitrile, but the monomer (a) may be entirely composed of the (meth) acrylate alkyl esters having an alkyl group with 1 to 4 carbon atoms (aspect (1)). In the aspect (1), it is preferred that the monomer unit contains 30% by mass or more of n-butyl acrylate. The aspect (1) is preferred from the viewpoint of heating and ensuring wet-heat durability.
以上述單體(a)使用全部為前述具碳數1~4烷基之(甲基)丙烯酸烷基酯之態樣(1)來說,可採用例如將前述單體(a)全部僅由丙烯酸正丁酯形成之態樣(10)。為該態樣(10)時,作為前述單體單元宜含有70質量%以上之丙烯酸正丁酯。此時,丙烯酸正丁酯之前述單體單元雖會依共聚單體、交聯劑等種類而異,但可以80質量%以上、90質量%以上作使用,並可以95質量%以上作使用。該態樣(10)由加熱及確保濕熱耐久性之觀點來看為佳。 For example, in the embodiment (1) in which the monomer (a) is entirely composed of the aforementioned (meth) alkyl esters having an alkyl group with 1 to 4 carbon atoms, the embodiment (10) in which the aforementioned monomer (a) is entirely composed of n-butyl acrylate can be adopted. In the embodiment (10), the aforementioned monomer unit preferably contains 70% by mass or more of n-butyl acrylate. At this time, the aforementioned monomer unit of n-butyl acrylate may vary depending on the type of copolymer monomer, crosslinking agent, etc., but it can be used at 80% by mass or more, 90% by mass or more, and even 95% by mass or more. The embodiment (10) is preferred from the viewpoint of heating and ensuring wet-heat durability.
又,以上述單體(a)使用全部為前述具碳數1~4烷基之(甲基)丙烯酸烷基酯之態樣(1)來說,可採用例如除丙烯酸正丁酯外,還併用除丙烯酸正丁酯外之前述具碳數1~4烷基之(甲基)丙烯酸烷基酯之態樣(11)。除丙烯酸正丁酯外之前述具碳數1~4烷基之(甲基)丙烯酸烷基酯宜為具碳數1~3烷基之(甲基)丙烯酸烷基酯與丙烯酸三級丁酯。具碳數1~3烷基之(甲基)丙烯酸烷基酯宜為丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯等具碳數1~2烷基之(甲基)丙烯酸烷基酯。即,併用丙烯酸正丁酯與除丙烯酸正丁酯外之前述單體(a)的態樣(11)中,上述單體(a)宜使用具碳數1~3烷基之(甲基)丙烯酸烷基酯或丙烯酸三級丁酯、及丙烯酸正丁酯。該態樣(11)由耐油性及加工性、處理性、耐裂痕性之觀點來看為佳。 In the embodiment (1) in which all the monomers (a) are the aforementioned (meth)acrylic acid alkyl esters having an alkyl group with 1 to 4 carbon atoms, for example, the embodiment (11) in which the aforementioned (meth)acrylic acid alkyl esters having an alkyl group with 1 to 4 carbon atoms other than n-butyl acrylate are used in combination may be used. The aforementioned (meth)acrylic acid alkyl esters having an alkyl group with 1 to 4 carbon atoms other than n-butyl acrylate are preferably (meth)acrylic acid alkyl esters having an alkyl group with 1 to 3 carbon atoms and tertiary butyl acrylate. The (meth)acrylic acid alkyl esters having an alkyl group with 1 to 3 carbon atoms are preferably (meth)acrylic acid alkyl esters having an alkyl group with 1 to 2 carbon atoms such as methyl acrylate, methyl methacrylate, and ethyl acrylate. That is, in the embodiment (11) in which n-butyl acrylate and the aforementioned monomers (a) other than n-butyl acrylate are used in combination, the aforementioned monomers (a) are preferably (meth)acrylic acid alkyl esters having an alkyl group with 1 to 3 carbon atoms or tertiary butyl acrylate, and n-butyl acrylate. This aspect (11) is better from the perspectives of oil resistance, processability, handling, and crack resistance.
為前述併用系統的態樣(11)時,前述具碳數1~3烷基之(甲基)丙烯酸烷基酯的前述質量比率宜設為 4~60質量%,且宜設為4~50質量%,更佳設為10~40質量%;另一方面,丙烯酸正丁酯的前述質量比率宜設為30質量%以上,且宜設為30~96質量%,更佳設為40~90質量%,且宜調整成合計80質量%以上。 In the case of the aforementioned combined system (11), the aforementioned mass ratio of the aforementioned (meth)acrylic acid alkyl ester having an alkyl group with 1 to 3 carbon atoms is preferably set to 4 to 60 mass %, preferably 4 to 50 mass %, and more preferably 10 to 40 mass %; on the other hand, the aforementioned mass ratio of n-butyl acrylate is preferably set to 30 mass % or more, preferably 30 to 96 mass %, more preferably 40 to 90 mass %, and preferably adjusted to a total of 80 mass % or more.
並且,上述併用系統的態樣(11)中,在前述具碳數1~4烷基之(甲基)丙烯酸烷基酯(惟,除丙烯酸正丁酯外)使用丙烯酸烷基酯之態樣(11A)時,前述丙烯酸烷基酯的前述質量比率宜設為15~60質量%,且宜設為15~45質量%,更佳設為20~40質量%;另一方面,丙烯酸正丁酯的前述質量比率宜設為30質量%以上,且宜設為40~85質量%,更佳設為40~75質量%,且宜調整成合計80質量%以上。該態樣(11A)由耐油性及加工性、處理性、耐裂痕性之觀點來看為佳。 Furthermore, in the embodiment (11) of the combined system, when the aforementioned (meth) acrylic acid alkyl ester (except for n-butyl acrylate) is used as the acrylic acid alkyl ester (11A), the aforementioned mass ratio of the acrylic acid alkyl ester is preferably set to 15-60 mass%, preferably 15-45 mass%, and more preferably 20-40 mass%; on the other hand, the aforementioned mass ratio of n-butyl acrylate is preferably set to 30 mass% or more, preferably 40-85 mass%, more preferably 40-75 mass%, and preferably adjusted to a total of 80 mass% or more. This embodiment (11A) is preferred from the viewpoints of oil resistance, processability, handling, and crack resistance.
並且,上述併用系統的態樣(11)中,在前述具碳數1~4烷基之(甲基)丙烯酸烷基酯(惟,除丙烯酸正丁酯外)使用甲基丙烯酸烷基酯之態樣(11B)時,前述甲基丙烯酸烷基酯的前述質量比率宜設為5~15質量%,且宜設為5~10質量%;另一方面,丙烯酸正丁酯的前述質量比率宜設為70質量%以上,且宜設為70~90質量%,且宜調整成合計80質量%以上。該態樣(11B)由加工性或處理性、耐裂痕性之觀點來看為佳。 Furthermore, in the embodiment (11) of the combined system, when the aforementioned (meth)acrylic acid alkyl ester (except for n-butyl acrylate) is used as methacrylic acid alkyl ester (11B), the aforementioned mass ratio of the aforementioned methacrylic acid alkyl ester is preferably set to 5-15 mass%, and preferably to 5-10 mass%; on the other hand, the aforementioned mass ratio of n-butyl acrylate is preferably set to 70 mass% or more, and preferably to 70-90 mass%, and preferably adjusted to a total of 80 mass% or more. This embodiment (11B) is preferred from the viewpoint of processability or handling, and crack resistance.
又,上述單體(a)可採用例如併用前述具碳數1~4烷基之(甲基)丙烯酸烷基酯及前述含氟單體之態樣(21)。為前述併用系統之態樣(21)時,前述具碳數1~4烷基 之(甲基)丙烯酸烷基酯的前述質量比率宜設為30質量%以上,且宜設為30~55質量%,而含氟單體宜設為25質量%以上,且宜設為25~50質量%,並宜調整成合計80質量%以上,且丙烯酸正丁酯宜調整成30質量%以上,更宜調整成30~55質量%。該態樣(21)由耐油性之觀點來看為佳。 Furthermore, the monomer (a) may be, for example, a state (21) in which the aforementioned (meth)acrylic acid alkyl ester having an alkyl group with 1 to 4 carbon atoms and the aforementioned fluorine-containing monomer are used in combination. In the state (21) of the aforementioned combined system, the aforementioned mass ratio of the aforementioned (meth)acrylic acid alkyl ester having an alkyl group with 1 to 4 carbon atoms is preferably set to 30 mass% or more, and preferably to 30 to 55 mass%, and the fluorine-containing monomer is preferably set to 25 mass% or more, and preferably to 25 to 50 mass%, and preferably adjusted to a total of 80 mass% or more, and n-butyl acrylate is preferably adjusted to 30 mass% or more, and more preferably adjusted to 30 to 55 mass%. This state (21) is preferred from the viewpoint of oil resistance.
又,上述單體(a)可採用例如併用前述具碳數1~4烷基之(甲基)丙烯酸烷基酯及丙烯腈之態樣(22)。為前述併用系統之態樣(22)時,前述具碳數1~4烷基之(甲基)丙烯酸烷基酯的前述質量比率宜設為70質量%以上,且宜設為70~85質量%,而丙烯腈宜設為5質量%以上,且宜設為10~20質量%,並且宜調整成合計80質量%以上,且丙烯酸正丁酯宜調整成70質量%以上,且宜調整成70~85質量%。該態樣(22)由加熱耐久性之觀點來看為佳。 Furthermore, the monomer (a) may be, for example, a combination of the aforementioned (meth)acrylic acid alkyl ester having an alkyl group with 1 to 4 carbon atoms and acrylonitrile (22). In the combination system (22), the mass ratio of the aforementioned (meth)acrylic acid alkyl ester having an alkyl group with 1 to 4 carbon atoms is preferably set to 70 mass% or more, and preferably to 70 to 85 mass%, and acrylonitrile is preferably set to 5 mass% or more, and preferably to 10 to 20 mass%, and preferably adjusted to a total of 80 mass% or more, and n-butyl acrylate is preferably adjusted to 70 mass% or more, and preferably adjusted to 70 to 85 mass%. This aspect (22) is preferred from the viewpoint of heat durability.
又,上述單體(a)可採用例如使用70質量%以上之前述(甲基)丙烯酸烷氧基烷基酯之態樣(23)。為前述態樣(23)時,可使用80質量%以上、且90質量%以上、並且100質量%之(甲基)丙烯酸烷氧基烷基酯。又,態樣(23)中可併用前述具碳數1~4烷基之(甲基)丙烯酸烷基酯。前述具碳數1~4烷基之(甲基)丙烯酸烷基酯的前述質量比率宜設為20質量%以上,前述(甲基)丙烯酸烷氧基烷基酯宜設為70質量%以上,且宜設為70~99質量%,並且宜調整成合計80質量%以上,且丙烯酸正丁酯宜調整成20質量%以上。該態樣(23)由高黏著力、耐油性之觀點來看為佳。 Furthermore, the monomer (a) may adopt, for example, the embodiment (23) using 70% by mass or more of the aforementioned (meth) alkoxyalkyl ester. In the aforementioned embodiment (23), 80% by mass or more, 90% by mass or more, and 100% by mass of the aforementioned (meth) alkoxyalkyl ester may be used. Furthermore, the aforementioned (meth) alkyl ester having an alkyl group with 1 to 4 carbon atoms may be used in combination in embodiment (23). The aforementioned mass ratio of the aforementioned (meth) alkyl ester having an alkyl group with 1 to 4 carbon atoms is preferably set to 20% by mass or more, the aforementioned (meth) alkoxyalkyl ester is preferably set to 70% by mass or more, and is preferably set to 70 to 99% by mass, and is preferably adjusted to a total of 80% by mass or more, and n-butyl acrylate is preferably adjusted to 20% by mass or more. This embodiment (23) is preferred from the viewpoint of high adhesion and oil resistance.
此外,上述併用系統之態樣(21)乃至(23)中, 在丙烯酸正丁酯或前述(甲基)丙烯酸烷氧基烷基酯滿足前述質量比率之範圍內,前述具碳數1~4烷基之(甲基)丙烯酸烷基酯可併用丙烯酸正丁酯以外之單體。尤其,上述態樣(21)中,前述具碳數1~4烷基之(甲基)丙烯酸烷基酯除丙烯酸正丁酯外,可適宜採用使用前述具碳數1~3烷基之丙烯酸烷基酯之態樣。 In addition, in the above-mentioned combined system aspects (21) to (23), within the range where n-butyl acrylate or the aforementioned alkoxyalkyl (meth)acrylate satisfies the aforementioned mass ratio, the aforementioned (meth)acrylate alkyl ester having an alkyl group with 1 to 4 carbon atoms may be used in combination with a monomer other than n-butyl acrylate. In particular, in the above-mentioned aspect (21), the aforementioned (meth)acrylate alkyl ester having an alkyl group with 1 to 4 carbon atoms may be used in addition to n-butyl acrylate, in addition to the aforementioned alkyl acrylate alkyl ester having an alkyl group with 1 to 3 carbon atoms.
此外,為了改善接著性及耐熱性,除前述單體(a)之單體單元外,可於(甲基)丙烯酸系聚合物(A)中,藉由共聚來導入1種以上具有具(甲基)丙烯醯基或乙烯基等不飽和雙鍵之聚合性官能基的共聚單體。前述共聚單體質量比率為20質量%以下。 In addition, in order to improve adhesion and heat resistance, in addition to the monomer units of the aforementioned monomer (a), one or more copolymerizable monomers having unsaturated double bonds such as (meth)acrylic acid or vinyl groups can be introduced into the (meth)acrylic polymer (A) by copolymerization. The mass ratio of the aforementioned copolymerizable monomer is 20% by mass or less.
惟,具碳數5以上烷基之(甲基)丙烯酸烷基酯的聚合比率一多,由抑制前述黏著劑的剝落之觀點來看不佳,故具碳數5以上烷基之(甲基)丙烯酸烷基酯的聚合比率為20質量%以下,宜為15質量%以下,且宜為10質量%以下,以5質量%以下為佳,3質量%以下更佳,又以1質量%以下為佳,而不使用最佳。 However, a higher polymerization ratio of the alkyl (meth)acrylate having an alkyl group with more than 5 carbon atoms is not good from the viewpoint of suppressing the peeling of the aforementioned adhesive. Therefore, the polymerization ratio of the alkyl (meth)acrylate having an alkyl group with more than 5 carbon atoms is 20% by mass or less, preferably 15% by mass or less, and preferably 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, and it is best not to use it.
前述共聚單體例如可使用含芳香環(甲基)丙烯酸酯。含芳香環(甲基)丙烯酸酯係一於其結構中含有芳香環結構且含有(甲基)丙烯醯基之化合物。作為芳香環,可舉如苯環、萘環或聯苯環。 The aforementioned copolymer monomer may be, for example, an aromatic ring-containing (meth)acrylate. An aromatic ring-containing (meth)acrylate is a compound containing an aromatic ring structure and a (meth)acryloyl group in its structure. Examples of the aromatic ring include a benzene ring, a naphthalene ring, or a biphenyl ring.
含芳香環(甲基)丙烯酸酯的具體例可舉例如(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸鄰苯基苯酚酯、(甲基)丙烯酸苯氧酯、(甲基)丙烯酸苯氧乙酯、 (甲基)丙烯酸苯氧丙酯、苯氧基二乙二醇(甲基)丙烯酸酯、環氧乙烷改質壬苯酚(甲基)丙烯酸酯、環氧乙烷改質甲酚(甲基)丙烯酸酯、苯酚環氧乙烷改質(甲基)丙烯酸酯、2-羥-3-苯氧丙基(甲基)丙烯酸酯、甲氧基苄基(甲基)丙烯酸酯、氯苄基(甲基)丙烯酸酯、(甲基)丙烯酸甲苯酚酯、(甲基)丙烯酸聚苯乙烯酯等具有苯環之物;羥乙基化β-萘酚丙烯酸酯、(甲基)丙烯酸2-萘酚乙酯、丙烯酸2-萘氧乙酯、2-(4-甲氧基-1-萘氧基)乙基(甲基)丙烯酸酯等具有萘環之物;(甲基)丙烯酸聯苯酯等具有聯苯環者。 Specific examples of aromatic ring-containing (meth)acrylates include benzyl (meth)acrylate, phenyl (meth)acrylate, o-phenylphenol (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide-modified nonylphenol (meth)acrylate, ethylene oxide-modified cresol (meth)acrylate, phenol ethylene oxide-modified (meth)acrylate, 2-hydroxy- 3-phenoxypropyl (meth)acrylate, methoxybenzyl (meth)acrylate, chlorobenzyl (meth)acrylate, cresol (meth)acrylate, polystyrene (meth)acrylate and the like having a benzene ring; hydroxyethylated β-naphthol acrylate, 2-naphthol ethyl (meth)acrylate, 2-naphthyloxyethyl acrylate, 2-(4-methoxy-1-naphthyloxy)ethyl (meth)acrylate and the like having a naphthyl ring; biphenyl (meth)acrylate and the like having a biphenyl ring.
由黏著特性及耐久性之觀點,前述含芳香環(甲基)丙烯酸酯宜為(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧乙酯,且尤為(甲基)丙烯酸苯氧乙酯。 From the viewpoint of adhesion and durability, the aforementioned aromatic ring-containing (meth)acrylate is preferably benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and especially phenoxyethyl (meth)acrylate.
含芳香環(甲基)丙烯酸酯的前述質量比率為20質量%以下,宜為3~18質量%,且宜為5~16質量%,10~14質量%更佳。含芳香環(甲基)丙烯酸酯的質量比率為3質量%以上時,由抑制顯示不均來看為佳。 The aforementioned mass ratio of the aromatic ring-containing (meth)acrylate is less than 20 mass %, preferably 3 to 18 mass %, preferably 5 to 16 mass %, and more preferably 10 to 14 mass %. When the mass ratio of the aromatic ring-containing (meth)acrylate is 3 mass % or more, it is better from the perspective of suppressing display unevenness.
又,前述共聚單體可舉例如含羥基單體、含羧基單體、含醯胺基單體等含官能基單體。 Furthermore, the aforementioned copolymer monomers may include functional group-containing monomers such as hydroxyl group-containing monomers, carboxyl group-containing monomers, and amide group-containing monomers.
含羥基單體係一於其結構中含有羥基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含羥基單體的具體例可舉例如(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸12-羥月桂酯等(甲基)丙烯酸羥基烷基 酯或(4-羥甲基環己基)-甲基丙烯酸酯等。由耐久性之觀點,前述含羥基單體中宜為(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸4-羥丁酯,尤以(甲基)丙烯酸4-羥丁酯為佳。 A hydroxyl-containing monomer is a compound containing a hydroxyl group in its structure and a polymerizable unsaturated double bond such as a (meth)acryloyl group or a vinyl group. Specific examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and other hydroxyalkyl (meth)acrylates or (4-hydroxymethylcyclohexyl)-methacrylate. From the perspective of durability, the aforementioned hydroxyl-containing monomers are preferably 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate is particularly preferred.
含羧基單體係一於其結構中含有羧基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含羧基單體之具體例可舉例如(甲基)丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、伊康酸、馬來酸、延胡索酸、巴豆酸等。從共聚性、價格及黏著特性的觀點來看,前述含羧基單體中以丙烯酸為宜。 A carboxyl group-containing monomer is a compound containing a carboxyl group and a polymerizable unsaturated double bond such as a (meth)acrylic acid group or a vinyl group in its structure. Specific examples of carboxyl group-containing monomers include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. Among the above carboxyl group-containing monomers, acrylic acid is preferred from the viewpoints of copolymerizability, price, and adhesive properties.
含羥基單體、含羧基單體在黏著劑組成物含有交聯劑時會成為其與交聯劑的反應點。由於含羥基單體、含羧基單體在分子間與交聯劑之反應性佳,故為了提升所獲得之黏著劑層的凝集性及耐熱性,宜使用該等單體。 When the adhesive composition contains a crosslinking agent, hydroxyl-containing monomers and carboxyl-containing monomers will become reaction points with the crosslinking agent. Since hydroxyl-containing monomers and carboxyl-containing monomers have good intermolecular reactivity with the crosslinking agent, it is advisable to use these monomers in order to enhance the cohesion and heat resistance of the obtained adhesive layer.
含羥基單體的前述質量比率宜為3質量%以下,且宜為0.01~3質量%,0.1~2質量%更佳,且更佳為0.2~2質量%。由交聯黏著劑層之觀點、耐久性或黏著特性之觀點來看,含羥基單體的質量比率設為0.01質量%以上為佳。另一方面,大於3質量%時,由耐久性之觀點來看不佳。 The mass ratio of the hydroxyl-containing monomer is preferably less than 3 mass%, preferably 0.01 to 3 mass%, more preferably 0.1 to 2 mass%, and more preferably 0.2 to 2 mass%. From the perspective of the crosslinking adhesive layer, durability or adhesive properties, the mass ratio of the hydroxyl-containing monomer is preferably set to 0.01 mass% or more. On the other hand, when it is greater than 3 mass%, it is not good from the perspective of durability.
含羧基單體的前述質量比率宜為10質量%以下,且宜為0.01~8質量%,0.05~6質量%更佳,又以0.1~5質量%更佳。將含羧基單體的質量比率設為0.01質量%以上由耐久性之觀點來看為佳。 The mass ratio of the carboxyl group-containing monomer is preferably less than 10 mass %, and preferably 0.01 to 8 mass %, more preferably 0.05 to 6 mass %, and even more preferably 0.1 to 5 mass %. It is better to set the mass ratio of the carboxyl group-containing monomer to 0.01 mass % or more from the perspective of durability.
含醯胺基單體係一於其結構中含有醯胺基 且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含醯胺基單體之具體例可舉(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基-N-丙烷(甲基)丙烯醯胺、胺甲基(甲基)丙烯醯胺、胺乙基(甲基)丙烯醯胺、巰甲基(甲基)丙烯醯胺、巰乙基(甲基)丙烯醯胺等丙烯醯胺系單體;N-(甲基)丙烯醯基嗎福林、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯啶等N-丙烯醯基雜環單體;N-乙烯基吡咯啶酮、N-乙烯基-ε-己內醯胺等含N-乙烯基內醯胺系單體等。含醯胺基單體在可抑制歷時性的(尤其在加濕環境下的)表面電阻值的上升或滿足耐久性來看為佳。尤其,含醯胺基單體中尤宜為含N-乙烯基內醯胺系單體。 An amide-containing monomer is a compound containing an amide group in its structure and containing a polymerizable unsaturated double bond such as a (meth)acrylamide group or a vinyl group. Specific examples of amide-containing monomers include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropylacrylamide, N-methyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxymethyl-N-propane(meth)acrylamide, aminomethyl(meth)acrylamide, Acrylamide monomers such as (methyl)acrylamide, aminoethyl (meth)acrylamide, methyl (meth)acrylamide, ethyl (meth)acrylamide; N-acryl heterocyclic monomers such as N-(meth)acrylaminophenothrin, N-(meth)acrylpiperidine, N-(meth)acrylpyrrolidine; N-vinyl lactam-containing monomers such as N-vinylpyrrolidone and N-vinyl-ε-caprolactam. Amide-containing monomers are preferred in terms of suppressing the increase in surface resistance over time (especially in a humidified environment) or satisfying durability. In particular, among the amide-containing monomers, N-vinyl lactam-containing monomers are particularly preferred.
含醯胺基單體的前述質量比率一大,有對光學薄膜之投錨性降低之傾向,故前述質量比率宜為10質量%以下,且以5質量%以下更佳。由抑制歷時性的(尤其在加濕環境下的)表面電阻值的上升之觀點來看,宜為0.1質量%以上。前述質量比率宜為0.3質量%以上,且0.5質量%以上更佳。 A large mass ratio of the amide-containing monomer tends to reduce the anchoring property of the optical film, so the mass ratio should be less than 10 mass%, and preferably less than 5 mass%. From the perspective of suppressing the increase in surface resistance over time (especially in a humidified environment), it should be more than 0.1 mass%. The mass ratio should be more than 0.3 mass%, and more preferably more than 0.5 mass%.
上述以外之其他共聚單體之具體例可舉馬來酸酐、伊康酸酐等含酸酐基單體;丙烯酸的己內酯加成物;烯丙基磺酸、2-(甲基)丙烯醯胺基-2-甲基丙磺酸、(甲基)丙烯醯胺基丙磺酸、磺丙基(甲基)丙烯酸酯等含磺酸基 單體;2-羥乙基丙烯醯基磷酸酯等含磷酸基單體等。 Specific examples of other copolymer monomers other than the above include monomers containing anhydride groups such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; monomers containing sulfonic acid groups such as allyl sulfonic acid, 2-(methyl)acrylamide-2-methylpropanesulfonic acid, (methyl)acrylamidepropanesulfonic acid, sulfopropyl (methyl)acrylate; monomers containing phosphate groups such as 2-hydroxyethylacryl phosphate, etc.
又,以改質為目的的單體之例還可列舉(甲基)丙烯酸胺乙酯、N,N-二甲基胺乙基(甲基)丙烯酸酯、三級丁基胺乙基(甲基)丙烯酸酯等(甲基)丙烯酸烷基胺基烷基酯;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯;N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺或N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體;N-環己基馬來醯亞胺或N-異丙基馬來醯亞胺、N-月桂基馬來醯亞胺或N-苯基馬來醯亞胺等之馬來醯亞胺系單體;N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等伊康醯亞胺系單體等。 Examples of monomers for the purpose of modification include alkylaminoalkyl (meth)acrylates such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and tertiary butylaminoethyl (meth)acrylate; alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; N-(meth)acryloyloxymethylenesuccinimide or N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyloxymethylenesuccinimide; ) Succinimide monomers such as acrylyl-8-oxyoctamethylene succinimide; maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, or N-phenylmaleimide; iconimide monomers such as N-methyliconimide, N-ethyliconimide, N-butyliconimide, N-octyliconimide, N-2-ethylhexyliconimide, N-cyclohexyliconimide, and N-lauryliconimide.
並且,改質單體也可使用乙酸乙烯酯、丙酸乙烯酯等乙烯基系單體;(甲基)丙烯酸環氧丙酯等含環氧基(甲基)丙烯酸酯;(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯等二醇系(甲基)丙烯酸酯;(甲基)丙烯酸四氫糠酯、聚矽氧(甲基)丙烯酸酯等(甲基)丙烯酸酯單體等。更可列舉異戊二烯、丁二烯、異丁烯、乙烯基醚等。 Furthermore, the modified monomers may also include vinyl monomers such as vinyl acetate and vinyl propionate; epoxy (meth)acrylates such as glycidyl (meth)acrylate; glycol (meth)acrylates such as polyethylene glycol (meth)acrylate and polypropylene glycol (meth)acrylate; (meth)acrylate monomers such as tetrahydrofurfuryl (meth)acrylate and polysiloxane (meth)acrylate, etc. Isoprene, butadiene, isobutylene, vinyl ether, etc. may also be used.
並且,上述以外之可共聚單體尚可舉如含有矽原子之矽烷系單體等。作為矽烷系單體,可列舉例如3-丙烯醯氧丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、4-乙烯基丁基三甲氧基矽烷、4-乙烯基 丁基三乙氧基矽烷、8-乙烯基辛基三甲氧基矽烷、8-乙烯基辛基三乙氧基矽烷、10-甲基丙烯醯氧癸基三甲氧基矽烷、10-丙烯醯氧癸基三甲氧基矽烷、10-甲基丙烯醯氧癸基三乙氧基矽烷、10-丙烯醯氧癸基三乙氧基矽烷等。 In addition, copolymerizable monomers other than the above-mentioned monomers include silane monomers containing silicon atoms. Examples of silane monomers include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinyl butyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-acryloxydecyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, 10-acryloxydecyltriethoxysilane, etc.
在前述(甲基)丙烯酸系聚合物(A)之總構成單體(單官能性單體100質量%)的質量比率中,(甲基)丙烯酸系聚合物(A)中前述其他共聚單體的比率宜為0~10質量%左右,且宜為0~7質量%左右,更宜為0~5質量%左右。 In the mass ratio of the total constituent monomers (monofunctional monomers 100 mass %) of the aforementioned (meth)acrylic polymer (A), the ratio of the aforementioned other copolymerized monomers in the (meth)acrylic polymer (A) is preferably about 0 to 10 mass %, and preferably about 0 to 7 mass %, and more preferably about 0 to 5 mass %.
又,作為共聚單體,也可使用三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚A二環氧丙基醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯等(甲基)丙烯酸與多元醇之酯化物等的具有2個以上(甲基)丙烯醯基、乙烯基等不飽和雙鍵之多官能性單體,或在聚酯、環氧、胺甲酸酯等的骨架上附加2個以上(甲基)丙烯醯基、乙烯基等不飽和雙鍵作為與單體成分相同的官能基的聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、胺甲酸酯(甲基)丙烯酸酯等。 As the copolymer monomer, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, trihydroxymethylenepropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate may also be used. ester, caprolactone-modified dipentatriol hexa(meth)acrylate and polyol esters such as (meth)acrylate and polyols having two or more (meth)acrylic acid groups, vinyl groups and other unsaturated double bonds, or polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, etc., with two or more (meth)acrylic acid groups, vinyl groups and other unsaturated double bonds added to the backbone of polyester, epoxy, urethane, etc. as the same functional group as the monomer component.
以前述共聚單體來說,使用上述多官能性單體等時,多官能性單體會作為交聯成分發揮功能。上述多官能性單體之使用量會依其分子量或官能基數等而異,不 過相對於單官能性單體之合計100質量份,宜在1質量份以下作使用,且以0.5質量份以下更較佳。而下限值並無特別限定,惟以0質量份以上為佳,0.01質量份以上較佳。藉由多官能性單體之使用量在前述範圍內,可提升接著力。 For the aforementioned copolymer monomers, when the aforementioned multifunctional monomers are used, the multifunctional monomers will function as crosslinking components. The amount of the aforementioned multifunctional monomers used will vary depending on their molecular weight or functional groups, but relative to 100 parts by mass of the total monofunctional monomers, it is preferably used in an amount of less than 1 part by mass, and preferably less than 0.5 parts by mass. The lower limit value is not particularly limited, but preferably more than 0 parts by mass, and more preferably more than 0.01 parts by mass. By using the amount of the multifunctional monomers within the aforementioned range, the bonding strength can be improved.
本發明之(甲基)丙烯酸系聚合物(A)通常重量平均分子量宜為100萬~250萬。若考慮耐久性尤其是耐熱性,重量平均分子量宜為120萬~200萬。以耐熱性觀點來看,重量平均分子量如果在100萬以上為宜。又,重量平均分子量若大於250萬,有黏著劑容易變硬的傾向,而易發生剝落。另,顯示分子量分布之重量平均分子量(Mw)/數量平均分子量(Mn)宜為1.8以上且10以下,較宜為1.8~7,更宜為1.8~5。分子量分布(Mw/Mn)若大於10,由耐久性觀點來看不宜。此外,重量平均分子量、分子量分布(Mw/Mn)是依照GPC(凝膠滲透層析法)來測定且以聚苯乙烯換算所算出之值而求得。 The (meth)acrylic polymer (A) of the present invention generally has a weight average molecular weight of 1 million to 2.5 million. Considering durability, especially heat resistance, the weight average molecular weight is preferably 1.2 million to 2 million. From the perspective of heat resistance, it is preferable that the weight average molecular weight is above 1 million. Moreover, if the weight average molecular weight is greater than 2.5 million, the adhesive tends to harden and peeling occurs easily. In addition, the weight average molecular weight (Mw)/number average molecular weight (Mn) showing the molecular weight distribution is preferably greater than 1.8 and less than 10, preferably 1.8 to 7, and more preferably 1.8 to 5. If the molecular weight distribution (Mw/Mn) is greater than 10, it is not preferable from the perspective of durability. In addition, the weight average molecular weight and molecular weight distribution (Mw/Mn) are measured by GPC (gel permeation chromatography) and calculated using polystyrene conversion.
所述(甲基)丙烯酸系聚合物(A)的製造,可適當選擇溶液聚合、塊狀聚合、乳化聚合、放射線(UV)聚合等各種自由基聚合等之公知的製造方法。又,所得(甲基)丙烯酸系聚合物(A)可為無規共聚物、嵌段共聚物、接枝共聚物等任一者。 The (meth)acrylic polymer (A) can be produced by appropriately selecting various known production methods such as solution polymerization, block polymerization, emulsion polymerization, radiation (UV) polymerization, and other free radical polymerization methods. In addition, the obtained (meth)acrylic polymer (A) can be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
此外,溶液聚合中,聚合溶劑可使用例如乙酸乙酯、甲苯等。作為具體之溶液聚合例,反應可於氮等非活性氣體氣流下添加聚合引發劑,且一般係於50~70℃左右、5~30小時左右之反應條件下進行。 In addition, in solution polymerization, the polymerization solvent may be ethyl acetate, toluene, etc. As a specific example of solution polymerization, the reaction may be carried out under a flow of an inert gas such as nitrogen, with the addition of a polymerization initiator, and is generally carried out under reaction conditions of about 50-70°C and about 5-30 hours.
自由基聚合所使用之聚合引發劑、鏈轉移劑、乳化劑等可無特別限定地適當選擇來使用。此外,(甲基)丙烯酸系聚合物(A)之重量平均分子量可藉由聚合引發劑、鏈轉移劑的使用量及反應條件來控制,並可因應其等之種類來適當調整其使用量。 The polymerization initiator, chain transfer agent, emulsifier, etc. used in the free radical polymerization can be appropriately selected and used without particular limitation. In addition, the weight average molecular weight of the (meth)acrylic polymer (A) can be controlled by the amount of the polymerization initiator and chain transfer agent used and the reaction conditions, and the amount used can be appropriately adjusted according to the type of the initiator and chain transfer agent.
又,用以形成本發明之黏著劑層的黏著劑組成物含有矽烷耦合劑(B)作為添加劑。藉由組合前述矽烷耦合劑(B)與含有80質量%以上之上述具碳數1~4烷基之(甲基)丙烯酸烷基酯(a)作為單體單元的(甲基)丙烯酸系聚合物(A)來使用,可抑制黏著劑層因油脂或乳油成分而剝落。 In addition, the adhesive composition used to form the adhesive layer of the present invention contains a silane coupling agent (B) as an additive. By combining the aforementioned silane coupling agent (B) with a (meth)acrylic polymer (A) containing 80% by mass or more of the aforementioned (meth)acrylic acid alkyl ester (a) having a carbon number of 1 to 4 alkyl group as a monomer unit, the adhesive layer can be prevented from peeling off due to oil or emulsifiable concentrate components.
前述矽烷耦合劑(B)宜使用選自含環氧基之矽烷耦合劑(b1)及含巰基之矽烷耦合劑(b2)中之至少1種。 The aforementioned silane coupling agent (B) is preferably at least one selected from epoxy-containing silane coupling agents (b1) and butyl-containing silane coupling agents (b2).
前述含環氧基之矽烷耦合劑(b1)可舉例如3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等低分子型(非寡聚物型)含環氧基之矽烷耦合劑,或信越化學工業公司製X-41-1053、X-41-1056、X-41-1059A、X-24-9590、KR-516等寡聚物型含環氧基之矽烷耦合劑。由抑制黏著劑層因油脂或乳油成分而剝落之效果大來看,前述含環氧基之矽烷耦合劑(b1)宜為低分子型(非寡聚物型)含環氧基之矽烷耦合劑。 Examples of the epoxy-containing silane coupling agent (b1) include low molecular weight (non-oligomer type) epoxy-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or oligomer type epoxy-containing silane coupling agents such as X-41-1053, X-41-1056, X-41-1059A, X-24-9590, and KR-516 manufactured by Shin-Etsu Chemical Co., Ltd. In view of the great effect of inhibiting the peeling of the adhesive layer due to oil or emulsion components, the aforementioned epoxy-containing silane coupling agent (b1) is preferably a low molecular weight (non-oligomer type) epoxy-containing silane coupling agent.
又,前述含巰基之矽烷耦合劑(b2)可舉3-巰丙基三甲氧基矽烷、3-巰丙基甲基二甲氧基矽烷、3-巰丙 基三乙氧基矽烷、3-巰丙基甲基二乙氧基矽烷、β-巰基甲基苯基乙基三甲氧基矽烷、巰基甲基三甲氧基矽烷、6-巰基己基三甲氧基矽烷、10-巰基癸基三甲氧基矽烷等低分子型(非寡聚物型)含巰基之矽烷耦合劑,或信越化學公司製X-41-1805、X-41-1810、X-41-1818等。由抑制黏著劑層因油脂或乳油成分而剝落之效果大來看,前述含巰基之矽烷耦合劑(b2)宜為寡聚物型含巰基之矽烷耦合劑。 In addition, the aforementioned silane coupling agent containing a silane group (b2) may include low molecular weight (non-oligomer type) silane coupling agents containing a silane group such as 3-butyltrimethoxysilane, 3-butylmethyldimethoxysilane, 3-butyltriethoxysilane, 3-butylmethyldiethoxysilane, β-butylmethylphenylethyltrimethoxysilane, butylmethyltrimethoxysilane, 6-butylhexyltrimethoxysilane, 10-butyldecyltrimethoxysilane, or X-41-1805, X-41-1810, X-41-1818 manufactured by Shin-Etsu Chemical Co., Ltd. In view of the great effect of inhibiting the peeling of the adhesive layer due to oil or emulsion components, the aforementioned silane coupling agent containing silane groups (b2) is preferably an oligomer type silane coupling agent containing silane groups.
又,上述以外之低分子型矽烷耦合劑(B)可舉例如綜研化學公司製A100等含乙醯乙醯基之矽烷耦合劑;3-胺丙基三甲氧基矽烷、N-2-(胺乙基)-3-胺丙基甲基二甲氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基亞丁基)丙胺、N-苯基-γ-胺丙基三甲氧基矽烷等含胺基之矽烷耦合劑;3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷等含(甲基)丙烯醯基之矽烷耦合劑;3-異氰酸酯基丙基三乙氧基矽烷等含異氰酸酯基之矽烷耦合劑等。又,上述以外之寡聚物型矽烷耦合劑可舉例如信越化學公司製KR-213等。 In addition, examples of the low molecular weight silane coupling agent (B) other than the above include silane coupling agents containing acetoacetyl groups such as A100 manufactured by Soken Chemical Co., Ltd.; silane coupling agents containing amino groups such as 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, and N-phenyl-γ-aminopropyltrimethoxysilane; silane coupling agents containing (meth)acryl groups such as 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; silane coupling agents containing isocyanate groups such as 3-isocyanatepropyltriethoxysilane, etc. In addition, oligomer-type silane coupling agents other than those mentioned above include KR-213 manufactured by Shin-Etsu Chemical Co., Ltd.
該等於分子內具有多個烷氧矽基之矽烷耦合劑由於不易揮發且具有多個烷氧矽基,因此可有效提升耐久性而較為理想。尤其是在附黏著劑之光學薄膜的被黏體為較玻璃更不易與烷氧矽基反應的透明導電層(例如ITO等)時,耐久性仍佳。此外,所謂寡聚物型係指單體為二聚物以上且低於100聚物左右的聚合物,而寡聚物型矽烷耦合劑之重量平均分子量宜為300~30000左右。 Such silane coupling agents with multiple alkoxysilane groups in the molecule are less volatile and have multiple alkoxysilane groups, so they can effectively improve durability and are more ideal. Especially when the adherend of the optical film with the adhesive is a transparent conductive layer (such as ITO, etc.) that is less likely to react with alkoxysilane groups than glass, the durability is still good. In addition, the so-called oligomer type refers to a polymer whose monomer is a dimer or more and less than about 100 polymers, and the weight average molecular weight of the oligomer type silane coupling agent is preferably about 300~30000.
前述矽烷耦合劑(B)可分別單獨使用,亦可將2種以上混合來使用,但整體含量相對於前述(甲基)丙烯酸系聚合物(A)100質量份,宜為0.01~5質量份,較宜為0.02~3質量份,更宜為0.05~1質量份,並且以0.1~0.8質量份為佳。此外,如上述,前述矽烷耦合劑(B)宜使用選自含環氧基之矽烷耦合劑(b1)及含巰基之矽烷耦合劑(b2)中之至少1種,而併用該等矽烷耦合劑(b1)、(b2)與其他矽烷耦合劑時,相對於前述(甲基)丙烯酸系聚合物(A)100質量份,其他矽烷耦合劑可以3質量份以下且與前述矽烷耦合劑(B)相同量以下來使用。 The silane coupling agent (B) may be used alone or in combination of two or more thereof. The total content of the silane coupling agent (B) is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, more preferably 0.05 to 1 part by mass, and most preferably 0.1 to 0.8 parts by mass, based on 100 parts by mass of the (meth)acrylic polymer (A). In addition, as mentioned above, the aforementioned silane coupling agent (B) is preferably at least one selected from epoxy-containing silane coupling agents (b1) and butyl-containing silane coupling agents (b2), and when the silane coupling agents (b1), (b2) and other silane coupling agents are used together, the other silane coupling agents can be used in an amount of 3 parts by mass or less and the same amount as the aforementioned silane coupling agent (B) relative to 100 parts by mass of the aforementioned (meth)acrylic polymer (A).
本發明之黏著劑組成物可含有交聯劑(C)。作為交聯劑(C),可使用有機系交聯劑或多官能性金屬螯合物。有機系交聯劑可舉出如異氰酸酯系交聯劑、過氧化物系交聯劑、環氧系交聯劑、亞胺系交聯劑等。多官能性金屬螯合物是多價金屬與有機化合物共價鍵結或配位鍵結之物。多價金屬原子可列舉Al、Cr、Zr、Co、Cu、Fe、Ni、V、Zn、In、Ca、Mg、Mn、Y、Ce、Sr、Ba、Mo、La、Sn、Ti等。有機化合物中可共價鍵結或配位鍵結之原子可舉如氧原子等,有機化合物則可舉烷基酯、醇化合物、羧酸化合物、醚化合物、酮化合物等。 The adhesive composition of the present invention may contain a crosslinking agent (C). As the crosslinking agent (C), an organic crosslinking agent or a multifunctional metal chelate may be used. Examples of organic crosslinking agents include isocyanate crosslinking agents, peroxide crosslinking agents, epoxy crosslinking agents, and imine crosslinking agents. Multifunctional metal chelates are covalently bonded or coordinately bonded polyvalent metals and organic compounds. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. Atoms that can form covalent bonds or coordinate bonds in organic compounds include oxygen atoms, etc., and organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, ketone compounds, etc.
前述交聯劑(C)宜為異氰酸酯系交聯劑。異氰酸酯系交聯劑可使用具有至少2個異氰酸酯基之化合物。例如,一般會使用胺甲酸酯化反應所用之公知的脂肪族聚異氰酸酯、脂環族聚異氰酸酯、芳香族聚異氰酸酯等。 The aforementioned crosslinking agent (C) is preferably an isocyanate crosslinking agent. Isocyanate crosslinking agents can use compounds having at least two isocyanate groups. For example, well-known aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, etc. used in urethanization reactions are generally used.
相對於(甲基)丙烯酸系聚合物(A)100質量份,前述交聯劑(C)之使用量宜為3質量份以下,且較宜為0.01~3質量份,更宜為0.02~2質量份,又更宜為0.03~1質量份。另,交聯劑(C)低於0.01質量份時,黏著劑恐交聯不足而無法滿足耐久性或黏著特性;另一方面,若多過3質量份,黏著劑會變得太硬而有耐久性降低之傾向。 The amount of the crosslinking agent (C) used relative to 100 parts by weight of the (meth)acrylic polymer (A) is preferably 3 parts by weight or less, and preferably 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, and even more preferably 0.03 to 1 part by weight. In addition, when the crosslinking agent (C) is less than 0.01 parts by weight, the adhesive may not be sufficiently crosslinked and may not satisfy the durability or adhesive properties; on the other hand, if it is more than 3 parts by weight, the adhesive may become too hard and tend to have reduced durability.
並且,本發明之黏著劑組成物中可含有其他公知之添加劑,舉例而言可因應使用用途適當添加抗靜電劑、著色劑、顏料等粉體,染料、界面活性劑、塑化劑、增黏劑、表面潤滑劑、調平劑、軟化劑、抗氧化劑、抗老化劑、光穩定劑、紫外線吸收劑、聚合抑制劑、無機或有機填充劑、金屬粉、粒狀、箔狀物等。又,亦可在可控制的範圍內採用添加還原劑的氧化還原系。該等添加劑相對於(甲基)丙烯酸系聚合物(A)100質量份宜在5質量份以下、較宜在3質量份以下且更宜在1質量份以下的範圍使用。 Furthermore, the adhesive composition of the present invention may contain other known additives, for example, antistatic agents, colorants, pigments and other powders, dyes, surfactants, plasticizers, thickeners, surface lubricants, levelers, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, granular, foil-like materials, etc. may be appropriately added according to the application. In addition, a redox system with a reducing agent added may also be used within a controllable range. Such additives are preferably used in an amount of less than 5 parts by mass, more preferably less than 3 parts by mass, and more preferably less than 1 part by mass relative to 100 parts by mass of the (meth)acrylic polymer (A).
另一方面,本發明之黏著劑組成物中不含有具聚醚骨架且於至少1末端具反應性矽基之聚醚化合物。前述具反應性矽基之聚醚化合物可舉例如日本特開第2010-275522號公報中所揭示者。前述具反應性矽基之聚醚化合物就可提升重工性之觀點來看較佳,但由抑制黏著劑層因油脂或乳油成分而剝落之觀點來看不佳。使用前述具反應性矽基之聚醚化合物時,即便使用前述矽烷耦合劑(B),仍無法抑制前述黏著劑層之剝落。 On the other hand, the adhesive composition of the present invention does not contain a polyether compound having a polyether skeleton and a reactive silyl group at at least one end. The aforementioned polyether compound having a reactive silyl group can be exemplified by the one disclosed in Japanese Patent Publication No. 2010-275522. The aforementioned polyether compound having a reactive silyl group is better from the perspective of improving the workability, but is not good from the perspective of inhibiting the peeling of the adhesive layer due to oil or emulsion components. When the aforementioned polyether compound having a reactive silyl group is used, even if the aforementioned silane coupling agent (B) is used, the peeling of the aforementioned adhesive layer cannot be inhibited.
本發明之黏著劑層可以貼合於光學薄膜(含有至少1片偏光薄膜)之附黏著劑層之光學薄膜之形式來使用。該附黏著劑層之光學薄膜可藉由於光學薄膜之至少單面以前述黏著劑組成物形成黏著劑層而獲得。 The adhesive layer of the present invention can be used in the form of an optical film with an adhesive layer attached to an optical film (including at least one polarizing film). The optical film with an adhesive layer can be obtained by forming an adhesive layer on at least one side of the optical film with the aforementioned adhesive composition.
形成前述黏著劑層的方法可藉由例如以下方法來製作:將前述黏著劑組成物塗佈於經剝離處理過的分離件等,並乾燥去除聚合溶劑等形成黏著劑層後轉印到光學薄膜(偏光薄膜)之方法;或者將前述黏著劑組成物塗佈於光學薄膜(偏光薄膜)後,乾燥去除聚合溶劑等以在光學薄膜形成黏著劑層的方法。另,於塗佈黏著劑時可適當另外添加聚合溶劑以外之一種以上溶劑。 The method for forming the aforementioned adhesive layer can be prepared by, for example, the following method: applying the aforementioned adhesive composition to a separation piece that has been subjected to a peeling treatment, and drying to remove the polymerization solvent, etc. to form an adhesive layer, and then transferring it to an optical film (polarizing film); or applying the aforementioned adhesive composition to an optical film (polarizing film), and then drying to remove the polymerization solvent, etc. to form an adhesive layer on the optical film. In addition, when applying the adhesive, one or more solvents other than the polymerization solvent may be appropriately added.
前述黏著劑層之厚度並無特別限制,惟若較薄,則其與影像顯示部之密著性會降低,或有加熱收縮時容易發生剝落之傾向,另一方面,若較厚,則油脂或乳油成分會容易被黏著劑層吸收,而造成容易發生剝落,因此例如宜為10~30μm左右,且15~20μm更佳。 There is no particular restriction on the thickness of the adhesive layer. However, if it is thinner, its adhesion to the image display part will be reduced, or it may be prone to peeling off when heated and shrunk. On the other hand, if it is thicker, the oil or emulsion components will be easily absorbed by the adhesive layer, causing it to peel off easily. Therefore, for example, it is preferably about 10~30μm, and 15~20μm is more preferred.
前述黏著劑層通常油酸膨潤度為100質量%以上,油酸膨潤度愈小,由油酸造成之影響愈小。根據本發明附黏著劑層之光學薄膜,在黏著劑層之油酸膨潤度大於130%時、以及為140%以上時、進而為150%以上時,可將油脂或乳油成分對黏著劑層之影響抑制得較小。又,在黏著劑層之油酸膨潤度大於130%時,可縮小黏著劑層吸收油脂或乳油成分後對其他光學構件之影響。另一方面,若黏著劑層之油酸膨潤度變大時,則油脂或乳油成分對黏 著劑層之影響亦會變大,因此油酸膨潤度宜為190%以下,且宜為180%以下。 The aforementioned adhesive layer usually has an oleic acid swelling degree of 100 mass % or more. The smaller the oleic acid swelling degree, the smaller the influence caused by the oleic acid. According to the optical film with an adhesive layer of the present invention, when the oleic acid swelling degree of the adhesive layer is greater than 130%, or greater than 140%, or further greater than 150%, the influence of the grease or emulsifiable concentrate component on the adhesive layer can be suppressed to a smaller extent. In addition, when the oleic acid swelling degree of the adhesive layer is greater than 130%, the influence of the grease or emulsifiable concentrate component absorbed by the adhesive layer on other optical components can be reduced. On the other hand, if the oleic acid swelling degree of the adhesive layer increases, the influence of the fat or emulsion component on the adhesive layer will also increase, so the oleic acid swelling degree should be below 190%, and preferably below 180%.
<影像顯示部> <Image display section>
影像顯示部係形成上述附黏著劑層之光學薄膜之光學薄膜(含有至少1片偏光薄膜)以及部分影像顯示裝置者,影像顯示裝置可舉液晶顯示裝置、有機EL(電致發光)顯示裝置、PDP(電漿顯示器面板)、電子紙等。 The image display part is an optical film (including at least one polarizing film) of the optical film forming the above-mentioned adhesive layer and a part of the image display device. The image display device can be a liquid crystal display device, an organic EL (electroluminescent) display device, a PDP (plasma display panel), an electronic paper, etc.
前述影像顯示部可舉例如液晶顯示裝置所用液晶單元。液晶單元可使用例如TN型或STN型、π型、VA型、IPS型等任意類型之液晶單元。 The aforementioned image display unit can be, for example, a liquid crystal unit used in a liquid crystal display device. The liquid crystal unit can be any type of liquid crystal unit such as TN type, STN type, π type, VA type, IPS type, etc.
<影像顯示面板> <Image display panel>
形成影像顯示面板時,除前述光學薄膜外,還可因應各配置處之適性積層其他光學薄膜來使用。例如,在液晶顯示面板中,係於相對於液晶單元之視辨側為相反之側至少配置偏光薄膜,而未對該偏光薄膜特別限制。又,前述其他光學薄膜可舉例如可為反射板或反透射板、相位差薄膜(包含1/2或1/4等的波長板)、視角補償薄膜、增亮薄膜等可用於形成液晶顯示裝置等之光學層者。該等可使用1層或2層以上。 When forming an image display panel, in addition to the aforementioned optical films, other optical films can also be used in accordance with the suitability of each configuration location. For example, in a liquid crystal display panel, at least a polarizing film is configured on the side opposite to the viewing side of the liquid crystal unit, and there is no particular restriction on the polarizing film. In addition, the aforementioned other optical films can be, for example, reflective plates or anti-transmission plates, phase difference films (including 1/2 or 1/4 wavelength plates), viewing angle compensation films, brightness enhancement films, etc., which can be used to form optical layers of liquid crystal display devices, etc. These can be used in one layer or two layers or more.
<影像顯示裝置> <Image display device>
本發明之液晶顯示裝置等各種影像顯示裝置的形成可依循習知來進行。藉由適當組裝視需要之照明系統等構成零件並組入驅動電路等來形成。一般而言,液晶顯示裝置係以下述方式形成:將液晶單元(玻璃基板/液晶層/玻璃 基板之構成)與配置在其兩側之偏光薄膜及因應需求的照明系統等構成零件適當組裝,再組入驅動電路等。於視辨側係配置前述光學薄膜,而另一側係配置其他偏光薄膜。又,液晶顯示裝置中可形成諸如於照明系統中使用背光件或反射板者等適當之液晶顯示裝置。並且,形成液晶顯示裝置時,可以將例如擴散板、防眩層、抗反射膜、保護板、稜鏡陣列、透鏡陣列片材、光擴散板、背光件等適當的零件在適當位置配置1層或2層以上。 The formation of various image display devices such as the liquid crystal display device of the present invention can be carried out according to the prior art. It is formed by appropriately assembling the components of the lighting system and the like as required and incorporating the drive circuit and the like. Generally speaking, a liquid crystal display device is formed in the following manner: the liquid crystal unit (glass substrate/liquid crystal layer/glass substrate structure) and the polarizing film arranged on both sides thereof and the components of the lighting system and the like as required are appropriately assembled, and then the drive circuit and the like are incorporated. The aforementioned optical film is arranged on the visual side, and other polarizing films are arranged on the other side. In addition, a suitable liquid crystal display device such as one using a backlight or a reflector in the lighting system can be formed in the liquid crystal display device. Furthermore, when forming a liquid crystal display device, appropriate parts such as a diffusion plate, an anti-glare layer, an anti-reflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, etc. can be arranged in one or more layers at appropriate positions.
實施例 Implementation example
以下,以製造例、實施例來具體說明本發明,惟本發明不受該等實施例限定。至於,各例中之份及%皆為重量基準。以下,未特別規定之室溫放置條件皆為23℃且65%RH。 The present invention is specifically described below using manufacturing examples and embodiments, but the present invention is not limited to these embodiments. As for the parts and % in each example, they are all based on weight. Below, the room temperature conditions not specifically specified are all 23°C and 65%RH.
<測定(甲基)丙烯酸系聚合物(A)之重量平均分子量> <Determination of the weight average molecular weight of (meth)acrylic acid polymer (A)>
(甲基)丙烯酸系聚合物之重量平均分子量(Mw)是利用GPC(凝膠滲透層析法)來測定。針對Mw/Mn亦同樣進行測定。 The weight average molecular weight (Mw) of (meth)acrylic acid polymers is measured by GPC (gel permeation chromatography). Mw/Mn is also measured in the same way.
‧分析裝置:Tosoh(東曹)公司製,HLC-8120GPC ‧Analysis device: HLC-8120GPC manufactured by Tosoh Corporation
‧管柱:Tosoh公司製,G7000HXL+GMHXL+GMHXL ‧Column: Made by Tosoh, G7000H XL +GMH XL +GMH XL
‧管柱尺寸:各7.8mmφ×30cm計90cm ‧Column size: 7.8mmφ×30cm each, totaling 90cm
‧管柱溫度:40℃ ‧Column temperature: 40℃
‧流量:0.8mL/min ‧Flow rate: 0.8mL/min
‧注入量:100μL ‧Injection volume: 100μL
‧溶析液:四氫呋喃 ‧Solvent: Tetrahydrofuran
‧檢測器:示差折射計(RI) ‧Detector: Differential refractometer (RI)
‧標準試料:聚苯乙烯 ‧Standard sample: polystyrene
<調製光學薄膜> <Adjusting optical films>
依下述方式調製實施例、比較例及參考例所用光學薄膜A乃至D。 The optical films A to D used in the embodiments, comparative examples and reference examples are prepared in the following manner.
(製作薄型偏光件) (Making thin polarizers)
對吸水率0.75%、Tg75℃之非晶質異酞酸共聚聚對苯二甲酸乙二酯(IPA共聚PET)薄膜(厚度:100μm)基材的單面施行電暈處理,並在該電暈處理面上於25℃下塗佈以9:1之比含有聚乙烯醇(聚合度4200,皂化度99.2莫耳%)及乙醯乙醯基改質PVA(聚合度1200,乙醯乙醯基改質度4.6%,皂化度99.0莫耳%以上,日本合成化學工業公司製,商品名「Gohsefimer Z200」)的水溶液並乾燥,形成厚度11μm的PVA系樹脂層,而製作出積層體。 A single side of an amorphous isophthalic acid copolymer polyethylene terephthalate (IPA copolymer PET) film substrate (thickness: 100μm) with a water absorption rate of 0.75% and a Tg of 75℃ was subjected to a corona treatment, and an aqueous solution containing polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetyl acetyl modified PVA (polymerization degree 1200, acetyl acetyl modification degree 4.6%, saponification degree 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gohsefimer Z200") in a ratio of 9:1 was applied to the corona treated surface at 25℃ and dried to form a PVA resin layer with a thickness of 11μm, thereby producing a laminate.
將所得積層體在120℃之烘箱內於周速相異的輥件間沿縱方向(長邊方向)進行自由端單軸延伸2.0倍(空中輔助延伸處理)。 The obtained laminate was subjected to free-end uniaxial stretching 2.0 times in the longitudinal direction (long side direction) between rollers with different peripheral speeds in an oven at 120°C (in-air assisted stretching treatment).
接著,使積層體浸漬於液溫30℃的不溶解浴(相對於水100份摻混4份之硼酸而得的硼酸水溶液)中30秒(不溶解處理)。 Next, the laminate was immersed in an insolubilizing bath (boric acid aqueous solution obtained by mixing 4 parts of boric acid with 100 parts of water) at a liquid temperature of 30°C for 30 seconds (insolubilizing treatment).
接著,一邊使其浸漬於液溫30℃的染色浴中一邊調整碘濃度、浸漬時間以使偏光板成為預定之透射率。本實施例係使其浸漬於相對於100份的水摻混0.2份的碘、1.0份 的碘化鉀所得之碘水溶液中60秒(染色處理)。 Next, while immersing it in a dyeing bath at a temperature of 30°C, the iodine concentration and immersion time are adjusted so that the polarizing plate has a predetermined transmittance. In this embodiment, it is immersed in an iodine aqueous solution obtained by mixing 0.2 parts of iodine and 1.0 parts of potassium iodide with respect to 100 parts of water for 60 seconds (dyeing treatment).
接著,使其浸漬於液溫30℃的交聯浴(相對於水100份摻混3份的碘化鉀並摻混3份的硼酸而得之硼酸水溶液)中30秒(交聯處理)。 Then, immerse it in a crosslinking bath (boric acid aqueous solution obtained by mixing 3 parts of potassium iodide and 3 parts of boric acid with 100 parts of water) at a liquid temperature of 30°C for 30 seconds (crosslinking treatment).
其後,一邊使積層體浸漬於液溫70℃之硼酸水溶液(相對於100份的水摻混4份硼酸並摻混5份碘化鉀所得之水溶液),一邊於不同周速之輥件間沿縱方向(長邊方向)進行單軸延伸以使總延伸倍率達5.5倍(水中延伸)。 Afterwards, the laminate was immersed in a boric acid aqueous solution at a temperature of 70°C (an aqueous solution obtained by mixing 4 parts of boric acid and 5 parts of potassium iodide with 100 parts of water), while being uniaxially stretched in the longitudinal direction (long side direction) between rollers of different peripheral speeds to achieve a total stretching ratio of 5.5 times (stretching in water).
之後,使積層體浸漬於液溫30℃的洗淨浴(相對於水100份,摻混4份的碘化鉀而得之水溶液)中(洗淨處理)。 Afterwards, the laminate was immersed in a cleaning bath (an aqueous solution obtained by mixing 4 parts of potassium iodide with 100 parts of water) at a liquid temperature of 30°C (cleaning treatment).
以上述方式獲得了包含厚度5μm之偏光件的光學薄膜積層體。 In the above manner, an optical thin film laminate including a polarizer with a thickness of 5μm was obtained.
(透明保護薄膜) (Transparent protective film)
丙烯酸薄膜1:對厚度40μm之具有內酯環結構的(甲基)丙烯酸樹脂薄膜之易接著處理面施行電暈處理後來使用。 Acrylic film 1: The easily bondable surface of a 40μm thick (meth) acrylic resin film with a lactone ring structure was subjected to corona treatment before use.
TAC薄膜:將厚度40μm之三醋酸纖維素薄膜進行皂化處理後來使用。 TAC film: Use 40μm thick cellulose triacetate film after saponification.
COP薄膜1:使用厚度13μm的環烯烴系樹脂薄膜(商品名:ZF14-013,日本ZEON(股)製)。 COP film 1: Use a 13μm thick cycloolefin resin film (trade name: ZF14-013, manufactured by ZEON Co., Ltd., Japan).
COP薄膜2:使用厚度25μm的環烯烴系系樹脂薄膜(商品名:ZF14-013,日本ZEON(股)製)。 COP film 2: Use a 25μm thick cycloolefin resin film (trade name: ZF14-013, manufactured by ZEON Co., Ltd., Japan).
上述透明保護薄膜皆顯示「在光學上為各向同性」,面內相位差Re(550)為0nm~10nm,且厚度方向之相位差 Rth(550)為-10nm~+10nm。 The above transparent protective films all show "optical isotropy", with an in-plane phase difference Re(550) of 0nm~10nm, and a thickness direction phase difference Rth(550) of -10nm~+10nm.
(製作應用於透明保護薄膜之接著劑) (Manufacturing adhesive for transparent protective film)
將N-羥乙基丙烯醯胺10份、丙烯醯基嗎福林30份、1,9-壬二醇二丙烯酸酯45份、(甲基)丙烯酸單體聚合而成的丙烯酸系寡聚物(ARUFONUP1190,東亞合成公司製)10份、光聚合起始劑(IRGACURE 907,BASF公司製)3份、聚合起始劑(KAYACURE DETX-S,日本化藥公司製)2份混合,而調製出紫外線硬化型接著劑。 10 parts of N-hydroxyethylacrylamide, 30 parts of acrylamide, 45 parts of 1,9-nonanediol diacrylate, 10 parts of an acrylic oligomer obtained by polymerizing (meth)acrylic acid monomers (ARUFONUP1190, manufactured by Toagosei Co., Ltd.), 3 parts of a photopolymerization initiator (IRGACURE 907, manufactured by BASF), and 2 parts of a polymerization initiator (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) were mixed to prepare a UV-curable adhesive.
(相位差薄膜) (Phase difference film)
第1相位差薄膜:使用厚度18μm之環狀烯烴系薄膜(折射率特性:nx>ny>nz,面內相位差:116nm)。 The first phase difference film: a cyclic olefin film with a thickness of 18μm (refractive index characteristics: nx>ny>nz, in-plane phase difference: 116nm).
第2相位差薄膜:使用厚度6μm之改質聚乙烯薄膜(折射率特性:nz>nx>ny,面內相位差:35nm)。 Second phase difference film: Use modified polyethylene film with a thickness of 6μm (refractive index characteristics: nz>nx>ny, in-plane phase difference: 35nm).
<單面保護偏光薄膜> <Single-sided protective polarizing film>
在上述光學薄膜積層體之偏光件表面上,一邊將上述紫外線硬化型接著劑a以使硬化後之接著劑層厚度成為1μm的方式進行塗佈,一邊貼合上述透明保護薄膜(厚度40μm:丙烯酸薄膜1或TAC薄膜)後,照射紫外線作為活性能量線使接著劑硬化。紫外線照射是使用充有鎵之金屬鹵素燈,照射裝置:Fusion UV Systems,Inc公司製的Light HAMMER10,燈泡:V燈泡,峰值照度:1600mW/cm2,累積照射量1000/mJ/cm2(波長380~440nm),紫外線照度則使用Solatell公司製的Sola-Check系統來測定。接著將非晶性PET基材剝離而製出使用有薄型偏光件之厚度46 μm的單面保護偏光薄膜。 On the surface of the polarizer of the optical film laminate, the UV curable adhesive a is applied so that the thickness of the cured adhesive layer becomes 1 μm, and the transparent protective film (thickness 40 μm: acrylic film 1 or TAC film) is attached, and then UV rays are irradiated as active energy rays to cure the adhesive. The UV irradiation is performed using a gallium-filled metal halogen lamp, irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., bulb: V bulb, peak illuminance: 1600 mW/cm 2 , cumulative irradiation dose 1000/mJ/cm 2 (wavelength 380~440nm), and the UV irradiance is measured using the Sola-Check system manufactured by Solatell. Then, the amorphous PET substrate was peeled off to produce a single-sided protective polarizing film with a thickness of 46 μm using a thin polarizer.
使用前述丙烯酸薄膜1之單面保護偏光薄膜1係供於調製下述附相位差薄膜之單面保護偏光薄膜。 The single-sided protected polarizing film 1 using the aforementioned acrylic film 1 is used to prepare the single-sided protected polarizing film with phase difference film described below.
使用前述TAC薄膜時,係直接作為單面保護偏光薄膜2使用。 When using the aforementioned TAC film, it is directly used as a single-sided protective polarizing film 2.
<附相位差薄膜之單面保護偏光薄膜> <Single-sided protective polarizing film with phase difference film>
於前述單面保護偏光薄膜1之薄型偏光件側依序貼合第1相位差薄膜、第2相位差薄膜,而獲得厚度72μm之附相位差薄膜之單面保護偏光薄膜。貼合係與上述相同,使用紫外線硬化型接著劑a而形成厚度1μm之接著劑層。此外,係貼合成第1相位差薄膜之慢軸相對於偏光件之吸收軸呈0。,而第2相位差薄膜之慢軸相對於偏光件之吸收軸呈90°之角度。 The first phase difference film and the second phase difference film are sequentially bonded to the thin polarizer side of the aforementioned single-sided protective polarizing film 1 to obtain a single-sided protective polarizing film with a phase difference film thickness of 72 μm. The bonding is the same as above, using a UV curing adhesive a to form an adhesive layer with a thickness of 1 μm. In addition, the first phase difference film is bonded so that the slow axis is 0° relative to the absorption axis of the polarizer, and the slow axis of the second phase difference film is 90° relative to the absorption axis of the polarizer.
<製作雙面保護偏光薄膜> <Production of double-sided protective polarizing film>
在上述光學薄膜積層體之偏光件表面上,一邊將上述紫外線硬化型接著劑a以使硬化後之接著劑層厚度成為1μm的方式進行塗佈,一邊貼合上述COP薄膜1(厚度25μm)後,照射紫外線作為活性能量線使接著劑硬化。紫外線照射是使用充有鎵之金屬鹵素燈,照射裝置:Fusion UV Systems,Inc公司製的Light HAMMER10,燈泡:V燈泡,峰值照度:1600mW/cm2,累積照射量1000/mJ/cm2(波長380~440nm),紫外線照度則使用Solatell公司製的Sola-Check系統來測定。接著,剝離非晶性PET基材,並於其剝離面利用上述接著劑貼合上述COP薄膜2(厚度13μm)後, 同樣使其硬化,而製作出使用有薄型偏光件的厚度45μm之雙面保護偏光薄膜。 On the surface of the polarizer of the optical film laminate, the UV curable adhesive a was applied so that the thickness of the cured adhesive layer was 1 μm, and the COP film 1 (thickness 25 μm) was attached, and then UV rays were irradiated as active energy rays to cure the adhesive. The UV irradiation was performed using a gallium-filled metal halogen lamp, the irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., the bulb: V bulb, the peak illuminance: 1600 mW/cm 2 , the cumulative irradiation amount 1000/mJ/cm 2 (wavelength 380~440nm), and the UV irradiance was measured using the Sola-Check system manufactured by Solatell. Next, the amorphous PET substrate was peeled off, and the COP film 2 (thickness 13 μm) was bonded to the peeled surface using the adhesive, and then cured in the same manner to produce a double-sided protected polarizing film with a thickness of 45 μm using a thin polarizer.
<製作附表面處理層之薄膜:ARTAC:厚度44μm> <Production of thin film with surface treatment layer: ARTAC: thickness 44μm>
對厚度40μm的三醋酸纖維素薄膜進行濺鍍而形成膜厚4μm的抗反射層。 A 40μm thick cellulose triacetate film is sputtered to form an anti-reflection layer with a thickness of 4μm.
<製作附表面處理層之薄膜:ARTAC:厚度84μm> <Production of thin film with surface treatment layer: ARTAC: thickness 84μm>
對厚度80μm的三醋酸纖維素薄膜進行濺鍍而形成膜厚4μm的抗反射層。 A cellulose triacetate film with a thickness of 80 μm is sputtered to form an anti-reflection layer with a thickness of 4 μm.
<製作附表面處理層之薄膜:LCTAC(厚度42μm)> <Production of a film with a surface treatment layer: LCTAC (thickness 42μm)>
對厚度40μm的三醋酸纖維素薄膜進行塗佈而形成膜厚2μm的液晶相位差層。 A 40μm thick cellulose triacetate film is coated to form a 2μm thick liquid crystal phase difference layer.
<調製黏著劑層A> <Preparing adhesive layer A>
(調製丙烯酸系聚合物) (Preparation of acrylic polymer)
將含有丙烯酸正丁酯100份及丙烯酸5份之單體混合物饋入具備攪拌葉片、溫度計、氮氣導入管、冷卻器的4口燒瓶中。並相對於前述單體混合物(固體成分)100份,將作為聚合引發劑之2,2’-偶氮雙異丁腈0.1份與乙酸乙酯100份一起饋入,一邊緩慢攪拌一邊導入氮氣進行氮取代後,將燒瓶內的液溫保持在55℃附近,進行8小時聚合反應,調製出重量平均分子量(Mw)160萬之丙烯酸系聚合物之溶液。 A monomer mixture containing 100 parts of n-butyl acrylate and 5 parts of acrylic acid was fed into a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler. 0.1 parts of 2,2'-azobisisobutyronitrile as a polymerization initiator and 100 parts of ethyl acetate were fed to 100 parts of the above-mentioned monomer mixture (solid component), and nitrogen was introduced while slowly stirring to replace the nitrogen. The liquid temperature in the flask was maintained at around 55°C, and the polymerization reaction was carried out for 8 hours to prepare a solution of an acrylic polymer with a weight average molecular weight (Mw) of 1.6 million.
(調製黏著劑組成物) (Preparation of adhesive composition)
相對於上述所得之丙烯酸系聚合物之溶液的固體成分100份,摻混異氰酸酯系交聯劑(Tosoh公司製Coronate L,三羥甲丙烷二異氰酸甲苯酯)0.45份,而調製出丙烯酸系黏著劑組成物之溶液。 0.45 parts of isocyanate crosslinking agent (Coronate L, trihydroxymethylpropane diisocyanate toluene ester, manufactured by Tosoh) was mixed with 100 parts of the solid content of the acrylic polymer solution obtained above to prepare a solution of acrylic adhesive composition.
(形成黏著劑層) (Forming adhesive layer)
接著,以使乾燥後的黏著劑層的厚度成為23μm或12μm,將上述丙烯酸系黏著劑組成物之溶液塗佈於經聚矽氧系剝離劑處理過之聚對苯二甲酸乙二酯薄膜(分離薄膜:三菱化學聚酯薄膜(股)製,MRF38)的單面上,並以155℃乾燥1分鐘,而於分離薄膜表面形成黏著劑層A。 Next, the solution of the acrylic adhesive composition was applied to one side of a polyethylene terephthalate film (separation film: MRF38 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) treated with a silicone release agent so that the thickness of the adhesive layer after drying was 23 μm or 12 μm, and dried at 155°C for 1 minute to form an adhesive layer A on the surface of the separation film.
將上述偏光薄膜、附表面處理層之薄膜以下述構成積層而調製出光學薄膜A乃至F。前述積層係於附表面處理層之薄膜的三醋酸纖維素薄膜側透過黏著劑層A貼合來進行。前述附相位差薄膜之單面保護偏光薄膜之積層係於丙烯酸薄膜1側貼合黏著劑層A。前述單面保護偏光薄膜2之積層係於TAC薄膜側貼合黏著劑層A。前述雙面保護偏光薄膜之積層係於COP薄膜2側貼合黏著劑層A。 The polarizing film and the film with the surface treatment layer are laminated in the following configuration to prepare optical films A to F. The lamination is performed by laminating the triacetate cellulose film side of the film with the surface treatment layer through the adhesive layer A. The lamination of the single-sided protected polarizing film with the phase difference film is performed by laminating the adhesive layer A on the acrylic film 1 side. The lamination of the single-sided protected polarizing film 2 is performed by laminating the adhesive layer A on the TAC film side. The lamination of the double-sided protected polarizing film is performed by laminating the adhesive layer A on the COP film 2 side.
光學薄膜A(合計厚度128μm):ARTAC(厚度44μm)/黏著劑層A(厚度12μm)/附相位差薄膜之單面保護偏光薄膜(厚度72μm)。 Optical film A (total thickness 128μm): ARTAC (thickness 44μm)/adhesive layer A (thickness 12μm)/single-sided protected polarizing film with phase difference film (thickness 72μm).
光學薄膜B(合計厚度179μm):ARTAC(厚度84μm)/黏著劑層A(厚度23μm)/附相位差薄膜之單面保護偏光薄膜(厚度72μm)。 Optical film B (total thickness 179μm): ARTAC (thickness 84μm)/adhesive layer A (thickness 23μm)/single-sided protected polarizing film with phase difference film (thickness 72μm).
光學薄膜C(合計厚度244μm):ARTAC(厚度84μm)/黏著劑層A(厚度23μm)/LCTAC(厚度42μm)/黏著劑層A(厚度23μm)/附相位差薄膜之單面保護偏光薄膜(厚度72μm)。 Optical film C (total thickness 244μm): ARTAC (thickness 84μm)/adhesive layer A (thickness 23μm)/LCTAC (thickness 42μm)/adhesive layer A (thickness 23μm)/single-sided protected polarizing film with phase difference film (thickness 72μm).
光學薄膜D(合計厚度72μm):附相位差薄膜之單面保護偏光薄膜(厚度72μm)。 Optical film D (total thickness 72μm): single-sided protected polarizing film with phase difference film (thickness 72μm).
光學薄膜E(合計厚度217μm):ARTAC(厚度84μm)/黏著劑層A(厚度23μm)/LCTAC(厚度42μm)/黏著劑層A(厚度23μm)/雙面保護偏光薄膜(厚度45μm)。 Optical film E (total thickness 217μm): ARTAC (thickness 84μm)/adhesive layer A (thickness 23μm)/LCTAC (thickness 42μm)/adhesive layer A (thickness 23μm)/double-sided protected polarizing film (thickness 45μm).
光學薄膜F(合計厚度244μm):ARTAC(厚度84μm)/黏著劑層A(厚度23μm)/LCTAC(厚度42μm)/黏著劑層A(厚度23μm)/單面保護偏光薄膜2(厚度72μm)。 Optical film F (total thickness 244μm): ARTAC (thickness 84μm)/adhesive layer A (thickness 23μm)/LCTAC (thickness 42μm)/adhesive layer A (thickness 23μm)/single-sided protected polarizing film 2 (thickness 72μm).
實施例1 Implementation Example 1
(調製丙烯酸系聚合物) (Preparation of acrylic polymer)
於具備攪拌葉片、溫度計、氮氣導入管、冷卻器之四口燒瓶中饋入含有丙烯酸正丁酯81.9份、丙烯酸苄酯13.2份、丙烯酸4-羥丁酯0.1份、丙烯酸4.8份的單體混合物。並相對於前述單體混合物(固體成分)100份,將作為聚合引發劑之2,2’-偶氮雙異丁腈0.1份與乙酸乙酯100份一起饋入,一邊緩慢攪拌一邊導入氮氣進行氮取代後,將燒瓶內的液溫保持在55℃附近,進行8小時聚合反應,調製出重量平均分子量(Mw)160萬之丙烯酸系聚合物之溶液。 A monomer mixture containing 81.9 parts of n-butyl acrylate, 13.2 parts of benzyl acrylate, 0.1 parts of 4-hydroxybutyl acrylate, and 4.8 parts of acrylic acid was added to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler. 0.1 parts of 2,2'-azobisisobutyronitrile as a polymerization initiator and 100 parts of ethyl acetate were added to 100 parts of the above-mentioned monomer mixture (solid component). After nitrogen substitution was performed while slowly stirring, the liquid temperature in the flask was maintained at around 55°C, and the polymerization reaction was carried out for 8 hours to prepare a solution of an acrylic polymer with a weight average molecular weight (Mw) of 1.6 million.
(調製黏著劑組成物) (Preparation of adhesive composition)
相對於上述所得之丙烯酸系聚合物之溶液的固體成 分100份,摻混寡聚物型含巰基之矽烷耦合劑(信越化學工業公司製X-41-1810)0.2部、異氰酸酯系交聯劑(Tosoh公司製Coronate L,三羥甲丙烷二異氰酸甲苯酯)0.45份,而調製出丙烯酸系黏著劑組成物之溶液。 0.2 parts of oligomeric silane coupling agent (X-41-1810 manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.45 parts of isocyanate crosslinking agent (Coronate L manufactured by Tosoh Co., Ltd., toluene trihydroxymethyl propane diisocyanate) were mixed with 100 parts of the solid content of the acrylic polymer solution obtained above to prepare a solution of an acrylic adhesive composition.
(形成黏著劑層) (Forming adhesive layer)
接著,以使乾燥後的黏著劑層的厚度成為20μm,將上述丙烯酸系黏著劑組成物之溶液塗佈於經聚矽氧系剝離劑處理過之聚對苯二甲酸乙二酯薄膜(分離薄膜:三菱化學聚酯薄膜(股)製,MRF38)的單面上,並以155℃乾燥1分鐘,而於分離薄膜表面形成黏著劑層B。 Next, the solution of the acrylic adhesive composition was applied to one side of a polyethylene terephthalate film (separation film: MRF38 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) treated with a silicone release agent so that the thickness of the adhesive layer after drying was 20 μm, and dried at 155°C for 1 minute to form an adhesive layer B on the surface of the separation film.
(調製附黏著劑層之光學薄膜及製作影像顯示面板) (Preparing optical films with adhesive layers and manufacturing image display panels)
準備影像顯示部(包含對角15吋尺寸之液晶單元:厚度300μm)。 Prepare the image display unit (including a 15-inch diagonal liquid crystal unit: 300μm thickness).
於前述調製出之光學薄膜A的附相位差薄膜之單面保護偏光薄膜側貼合上述調製出之黏著劑層B,而調製出附黏著劑層之光學薄膜(短邊、長邊皆較前述液晶單元短4mm的偏光薄膜)。從該附黏著劑層之光學薄膜剝離分離薄膜後,於前述影像顯示部之視辨側透過該黏著劑層B用貼合機貼合前述光學薄膜A(第2相位差薄膜側),而製出影像顯示面板(液晶顯示面板)。接著,於50℃、0.5MPa下進行15分鐘高壓釜處理,使上述光學薄膜A完全密著於影像顯示部。然後,將所得影像顯示面板進行雷射裁切成形成15吋尺寸。 The above-prepared adhesive layer B is laminated to the single-sided protective polarizing film side of the phase difference film of the above-prepared optical film A, and an optical film with an adhesive layer (a polarizing film with short and long sides 4 mm shorter than the above-mentioned liquid crystal unit) is prepared. After peeling off the separation film from the optical film with an adhesive layer, the above-mentioned optical film A (the second phase difference film side) is laminated to the visual side of the above-mentioned image display part through the adhesive layer B using a laminating machine to produce an image display panel (liquid crystal display panel). Then, an autoclave treatment is performed at 50°C and 0.5MPa for 15 minutes to make the above-mentioned optical film A completely adhere to the image display part. Then, the obtained image display panel is laser cut into a 15-inch size.
(製作附邊框之影像顯示面板) (Create an image display panel with a border)
準備按前述影像顯示面板(15吋尺寸)之外緣加工而成的寬度1mm、高度5mm之橡膠成形物(保持部的總寬度1.5mm,凸部有6處,如圖4之處,其中1邊從兩邊側起算彈性中間層為5cm)作為彈性中間層。 Prepare a rubber molded product with a width of 1mm and a height of 5mm processed according to the outer edge of the aforementioned image display panel (15-inch size) (the total width of the retaining part is 1.5mm, there are 6 convex parts, such as the part in Figure 4, and one side of the elastic middle layer is 5cm from both sides) as the elastic middle layer.
又,準備按上述影像顯示面板(15吋尺寸)成形的寬度1mm、高度3mm之施有金屬調濺鍍的樹脂板(框)作為外側邊框(已與可嵌入面板的凹型框體框一體化者)。 In addition, a resin plate (frame) with a width of 1mm and a height of 3mm and metal splash-coated is prepared as an outer frame (integrated with a concave frame that can be embedded in the panel) according to the above-mentioned image display panel (15-inch size).
將前述彈性中間層安裝至前述外部邊框已一體化的框體,接著組入前述影像顯示面板(設間隙為1mm以下),而製作出於前述影像顯示裝置之端面外側全部依序安裝有前述彈性中間層、外側邊框而成之如圖2(圖2A、圖2B)所示結構的附邊框之影像顯示面板。所得附邊框之影像顯示面板中,彈性中間層係設成較前述影像顯示面板(光學薄膜A)之視辨側的最表面突出1mm。前述彈性中間層為與前述影像顯示面板之端面接觸之結構。前述外側邊框係藉由接著劑固定於前述彈性中間層。 The elastic middle layer is mounted to the frame body integrated with the outer frame, and then the image display panel is assembled (the gap is set to be less than 1 mm), and the image display panel with a frame is manufactured, in which the elastic middle layer and the outer frame are installed in sequence on the outer side of the end surface of the image display device, as shown in FIG2 (FIG. 2A, FIG2B). In the obtained image display panel with a frame, the elastic middle layer is set to protrude 1 mm from the outermost surface of the visual side of the image display panel (optical film A). The elastic middle layer is a structure that contacts the end surface of the image display panel. The outer frame is fixed to the elastic middle layer by an adhesive.
實施例2~32及比較例1~8 Implementation Examples 2 to 32 and Comparative Examples 1 to 8
於實施例1中,將調製丙烯酸系聚合物所用單體混合物之組成或比率、調製黏著劑組成物所用之矽烷耦合劑的種類或摻混量、交聯劑的種類或摻混量、或形成之黏著劑層的厚度變更成如表1所示,除此之外依與實施例1相同方式而形成黏著劑層B。又,使用上述所得黏著劑層B並使用表1所示光學薄膜A乃至F,依與實施例1相同方式調製附黏 著劑層之光學薄膜後,製出影像顯示面板。又,依與實施例1相同方式而製出附邊框之影像顯示面板。 In Example 1, the composition or ratio of the monomer mixture used to prepare the acrylic polymer, the type or blending amount of the silane coupling agent used to prepare the adhesive composition, the type or blending amount of the crosslinking agent, or the thickness of the formed adhesive layer are changed to those shown in Table 1. Otherwise, the adhesive layer B is formed in the same manner as in Example 1. Furthermore, using the adhesive layer B obtained above and the optical films A to F shown in Table 1, an optical film with an adhesive layer is prepared in the same manner as in Example 1 to produce an image display panel. Furthermore, an image display panel with a frame is produced in the same manner as in Example 1.
此外,使用光學薄膜E時,係於雙面保護偏光薄膜側貼合黏著劑層B而調製出附黏著劑層之光學薄膜,而使用光學薄膜F時,係於單面保護偏光薄膜2側貼合黏著劑層B而調製出附黏著劑層之光學薄膜。 In addition, when using optical film E, adhesive layer B is attached to the sides of the double-sided protective polarizing film to prepare an optical film with an adhesive layer, and when using optical film F, adhesive layer B is attached to the two sides of the single-sided protective polarizing film to prepare an optical film with an adhesive layer.
惟,實施例30係製作圖3(圖3A、圖3B)所示結構之附邊框之影像顯示面板。在該附邊框之影像顯示面板中,係準備按上述影像顯示面板(15吋尺寸)成形的寬20mm、高2mm之施有金屬調濺鍍的樹脂板(框)作為內側邊框而組合完成。彈性中間層係設成與前述影像顯示面板之端面有15mm間隙。外側邊框、前述彈性中間層係使用可確保前述間隙之大小者。前述外側邊框係藉由接著劑固定於前述彈性中間層。前述內部邊框係藉由接著劑固定於前述影像顯示面板之最表面的端部、前述彈性中間層。 However, in Example 30, an image display panel with a frame having a structure shown in FIG. 3 (FIG. 3A, FIG. 3B) is manufactured. In the image display panel with a frame, a resin plate (frame) with a width of 20 mm and a height of 2 mm and a metal splash coating is prepared according to the above-mentioned image display panel (15-inch size) as an inner frame and assembled. The elastic middle layer is set to have a gap of 15 mm with the end face of the above-mentioned image display panel. The outer frame and the above-mentioned elastic middle layer are used to ensure the size of the above-mentioned gap. The above-mentioned outer frame is fixed to the above-mentioned elastic middle layer by an adhesive. The above-mentioned inner frame is fixed to the end of the outermost surface of the above-mentioned image display panel and the above-mentioned elastic middle layer by an adhesive.
此外,比較例3之黏著劑層的形成所用黏著劑組成物係依下述方法調製。 In addition, the adhesive composition used to form the adhesive layer of Comparative Example 3 is prepared according to the following method.
於由丙烯酸2-乙基己酯(2EHA)67份、丙烯酸2-羥乙酯(HEA)15份及N-乙烯基-2-吡咯啶酮(NVP)18份所構成之單體混合物中,作為光聚合引發劑摻混1-羥環己基苯基酮(商品名:IRGACURE184,BASF公司製)0.050份、2,2-二甲氧基-1,2-二苯基乙-1-酮(商品名:IRGACURE651,BASF公司製)0.050份之後,照射紫外線直到黏度(計測條件:BH黏度計5號轉子,10rpm,測定溫度30℃)達約20Pa ‧s為止,而製得上述單體成分的一部分已聚合的預聚物組成物(聚合率:9%)。接著,於該預聚物組成物中添加己二醇二丙烯酸酯(HDDA)0.09份並混合而獲得黏著劑組成物。於剝離薄膜(商品名「MRF#38」,三菱樹脂(股)製)之經剝離處理過之面上,以使厚度成為20μm之方式塗佈上述黏著劑組成物,而形成黏著劑組成物層。然後,貼合另一黏著劑組成物層之表面與剝離薄膜(「MRN#38」、三菱樹脂(股)製)之經剝離處理過之面,並以照度:4mW/cm2、光量:1200mJ/cm2之條件進行紫外線照射,使光硬化而形成黏著劑層,製出黏著片。 A monomer mixture consisting of 67 parts of 2-ethylhexyl acrylate (2EHA), 15 parts of 2-hydroxyethyl acrylate (HEA) and 18 parts of N-vinyl-2-pyrrolidone (NVP) was mixed with 0.050 parts of 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184, manufactured by BASF) and 0.050 parts of 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: IRGACURE 651, manufactured by BASF) as a photopolymerization initiator, and then irradiated with ultraviolet light until the viscosity (measurement conditions: BH viscometer No. 5 rotor, 10 rpm, measurement temperature 30°C) reached about 20 Pa ‧ s, thereby obtaining a prepolymer composition (polymerization rate: 9%) in which part of the above monomer components were polymerized. Next, 0.09 parts of hexanediol diacrylate (HDDA) was added to the prepolymer composition and mixed to obtain an adhesive composition. The adhesive composition was applied to the peeling-treated surface of a release film (trade name "MRF#38", manufactured by Mitsubishi Resin Co., Ltd.) in a manner to a thickness of 20 μm to form an adhesive composition layer. Then, the surface of another adhesive composition layer was attached to the peeling-treated surface of a release film ("MRN#38", manufactured by Mitsubishi Resin Co., Ltd.), and ultraviolet rays were irradiated under the conditions of illumination: 4 mW/cm 2 and light quantity: 1200 mJ/cm 2 to cure the light and form an adhesive layer to produce an adhesive sheet.
參考例1(製作蓋玻璃.附邊框之影像顯示面板) Reference Example 1 (Making a cover glass and image display panel with a frame)
使用與實施例1調製出之影像顯示面板相同之影像顯示面板,而製出圖5所示結構之附邊框之影像顯示面板。 Using the same image display panel as that prepared in Example 1, an image display panel with a frame having the structure shown in FIG5 is prepared.
外側邊框係準備與實施例1所用之物相同之物。 The outer frame is prepared in the same manner as that used in Example 1.
蓋玻璃係準備按前述影像顯示面板(15吋尺寸)成形之厚度1500μm的強化玻璃。 The cover glass is a 1500μm thick tempered glass prepared to be formed according to the aforementioned image display panel (15-inch size).
於前述影像顯示面板之端面外側全部安裝前述外側邊框而組裝。前述外側邊框係藉由接著劑固定於前述影像顯示面板。前述蓋玻璃係藉由黏著劑層(日東電工公司製LUCIACS CS9864)貼合。 The aforementioned outer frame is installed on the outer side of the end surface of the aforementioned image display panel for assembly. The aforementioned outer frame is fixed to the aforementioned image display panel by an adhesive. The aforementioned cover glass is bonded by an adhesive layer (LUCIACS CS9864 manufactured by Nitto Denko Corporation).
對在上述實施例、比較例及參考例所得附黏著劑層之光學薄膜及附邊框之影像顯示面板進行以下評估。將評估結果列於表1。 The optical film with adhesive layer and the image display panel with frame obtained in the above-mentioned embodiment, comparative example and reference example were evaluated as follows. The evaluation results are listed in Table 1.
<加濕時之藥品試驗> <Drug testing when moistened>
於所得附邊框之影像顯示面板的彈性中間層(在參考例中為外側邊框)之內側(全部)使用2mL滴管滴下下述藥品10mL。 Use a 2mL dropper to drop 10mL of the following medicine on the inner side (entire) of the elastic middle layer (outer side frame in the reference example) of the obtained framed image display panel.
油酸:和光純藥公司製之油酸(1級,含有65%)。 Oleic acid: Oleic acid manufactured by Wako Pure Chemical Industries, Ltd. (grade 1, containing 65%).
凡士林保濕乳:聯合利華公司製之UJ身體乳液COAB(含有水63%、甘油26%) Vaseline moisturizing lotion: Unilever's UJ body lotion COAB (containing 63% water and 26% glycerin)
防曬乳:EDGEWELL PERSONAL CARE Banana Boat Sunscreen Lotion SPF 30。 Sunscreen: EDGEWELL PERSONAL CARE Banana Boat Sunscreen Lotion SPF 30.
滴下藥品後,將附邊框之影像顯示面板在65℃ 90%RH之條件下保存72小時後,放置於常溫(23℃)下。然後,從附邊框之影像顯示面板取出附黏著劑層之光學薄膜,以肉眼觀察外觀並依下述基準評估黏著劑層B之剝落。 After dripping the drug, the image display panel with the frame was stored at 65℃ 90%RH for 72 hours and then placed at room temperature (23℃). Then, the optical film with the adhesive layer was removed from the image display panel with the frame, and the appearance was observed with the naked eye and the peeling of the adhesive layer B was evaluated according to the following criteria.
(評估基準) (Evaluation criteria)
◎:無剝落。 ◎: No peeling.
○:無剝落,端部因膠膨潤而膨脹。 ○: No peeling, the end is swollen due to rubber expansion.
△:0.5mm以下之微小的剝落。 △: Minor peeling below 0.5mm.
NG:有剝落(剝落:mm亦記載於表1)。 NG: There is peeling (peeling: mm is also recorded in Table 1).
<測定油酸膨潤度> <Determination of oleic acid swelling>
將各例所用之形成於分離薄膜表面的黏著劑層B裁切成20mm×40mm後做成試樣並測定其質量(W1)。接著,將前述試樣於60℃、濕度90%之條件下浸漬於油酸中24小時後,將試樣從油酸取出,並以乙醇洗淨試樣表面後,以110℃乾燥3小時。測定乾燥後之試樣的質量(W3),使用下述 式(2)算出丙烯酸黏著劑之油酸膨潤率。試樣之分離薄膜的質量(W2)係另外測定。 The adhesive layer B formed on the surface of the separation film used in each example was cut into 20mm×40mm and made into a sample and its mass (W1) was measured. Then, the sample was immersed in oleic acid at 60℃ and 90% humidity for 24 hours, the sample was taken out of the oleic acid, and the sample surface was washed with ethanol and dried at 110℃ for 3 hours. The mass of the dried sample (W3) was measured, and the oleic acid swelling rate of the acrylic adhesive was calculated using the following formula (2). The mass (W2) of the separation film of the sample was measured separately.
膨潤率(%)={(W3-W2)/(W1-W2)}×100 Swelling rate (%) = {(W3-W2)/(W1-W2)}×100
<耐裂痕性> <Crack resistance>
與前述<加濕時之藥品試驗>相同地,於附邊框之影像顯示面板的彈性中間層(在參考例中為外側邊框)之內側(全部)使用2mL滴管滴下油酸10mL。滴下藥品後,將附邊框之影像顯示面板在65℃ 90%RH之條件下保存72小時後,放置於常溫(23℃)下。 Similar to the above-mentioned <Drug Test in Humidification>, 10 mL of oleic acid was dripped on the inner side (entire) of the elastic middle layer (outer frame in the reference example) of the framed image display panel using a 2 mL dropper. After dripping the drug, the framed image display panel was stored at 65°C 90%RH for 72 hours and then placed at room temperature (23°C).
之後,從附邊框之影像顯示面板取出附黏著劑層之光學薄膜,並將該附黏著劑層之光學薄膜的黏著劑層設置於下側後,從上側以顯微鏡(10倍)用肉眼觀察於偏光薄膜的透明保護薄膜有無產生裂痕(是否有龜裂而看起來較白)。 Afterwards, the optical film with adhesive layer was taken out from the image display panel with border frame, and the adhesive layer of the optical film with adhesive layer was set on the lower side. Then, the transparent protective film of the polarizing film was observed from the upper side with a microscope (10 times) and naked eyes to see if there were any cracks (whether there were turtle cracks and it looked whiter).
此外,比較例8(使用雙面保護偏光薄膜之例)中,係以肉眼觀察取出之附黏著劑層之光學薄膜的側面。從側面觀看時,偏光件兩面的透明保護薄膜只要有其中一者有裂痕,即評估為有裂痕。 In addition, in Comparative Example 8 (the example of using a double-sided protective polarizing film), the side of the optical film with the adhesive layer removed was observed with the naked eye. When viewed from the side, if one of the transparent protective films on both sides of the polarizing element has a crack, it is evaluated as having a crack.
表1中表示如下:MA:丙烯酸甲酯、EA:丙烯酸乙酯、BA:丙烯酸正丁酯、MMA:甲基丙烯酸甲酯、2EHA:丙烯酸2-乙基己酯、Viscoat 3F:2,2,2-三氟乙基丙烯酸酯、BzA:丙烯酸苄酯、4HBA:丙烯酸4-羥丁酯、HEA:丙烯酸2-羥乙酯、NVP:N-乙烯基吡咯啶酮、AA:丙烯酸、MEA:丙烯酸甲氧乙酯、SAT10:Kaneka公司製之SAT10、KBM403:信越化學工業公司製的KBM-403、KBM573:信越化學工業公司製的KBM-573、A100:綜研化學公司製之A100(含乙醯乙醯基之矽烷耦合劑)、X-41-1810:信越化學工業公司製的寡聚物型含巰基之矽烷偶合劑、X-41-1056:信越化學工業公司製的寡聚物型含環氧基之矽烷耦合劑、C/HX:異氰酸酯系交聯劑(Tosoh公司製CORONATE HX,六亞甲基二異氰酸酯的三聚異氰酸酯物)、 TETRAD C:環氧系交聯劑(三菱瓦斯化學公司製TETRAD C/1,3-雙(N,N-環氧丙基胺基甲基)環己烷)、C/L:異氰酸酯系交聯劑(Tosoh公司製之CORONATE L,三羥甲丙烷二異氰酸甲苯酯)、D160N:異氰酸酯交聯劑(三井化學公司製的Takenate D160N,三羥甲丙烷六亞甲基二異氰酸酯) Table 1 shows the following: MA: methyl acrylate, EA: ethyl acrylate, BA: n-butyl acrylate, MMA: methyl methacrylate, 2EHA: 2-ethylhexyl acrylate, Viscoat 3F: 2,2,2-trifluoroethyl acrylate, BzA: benzyl acrylate, 4HBA: 4-hydroxybutyl acrylate, HEA: 2-hydroxyethyl acrylate, NVP: N-vinylpyrrolidone, AA: acrylic acid, MEA: methoxyethyl acrylate, SAT10: SAT10 manufactured by Kaneka, KBM403: KBM-403 manufactured by Shin-Etsu Chemical, KBM573: KBM-573 manufactured by Soken Chemical Co., Ltd., A100: A100 manufactured by Soken Chemical Co., Ltd. (silane coupling agent containing acetyl groups), X-41-1810: oligomeric silane coupling agent containing hydroxyl groups manufactured by Shin-Etsu Chemical Co., Ltd., X-41-1056: oligomeric silane coupling agent containing epoxy groups manufactured by Shin-Etsu Chemical Co., Ltd., C/HX: isocyanate crosslinking agent (CORONATE manufactured by Tosoh Corporation) HX, isocyanurate of hexamethylene diisocyanate), TETRAD C: epoxy crosslinking agent (TETRAD C/1,3-bis(N,N-epoxypropylaminomethyl)cyclohexane manufactured by Mitsubishi Gas Chemical Co., Ltd.), C/L: isocyanate crosslinking agent (CORONATE L manufactured by Tosoh Co., Ltd., toluene trihydroxymethylpropane diisocyanate), D160N: isocyanate crosslinking agent (Takenate D160N manufactured by Mitsui Chemicals Co., Ltd., hexamethylene diisocyanate)
HDDA:己二醇二丙烯酸酯。 HDDA: Hexanediol diacrylate.
A:影像顯示面板 A: Image display panel
1:影像顯示部 1: Image display unit
2:光學薄膜(包含偏光薄膜) 2: Optical films (including polarizing films)
3:黏著劑層(影像顯示部側) 3: Adhesive layer (image display side)
4:彈性中間層 4: Elastic middle layer
5:外部邊框 5: External border
41:保持部 41:Maintenance Department
a:最表面 a: The most superficial
t:距離 t: distance
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JP6014781B1 (en) * | 2016-03-02 | 2016-10-25 | 積水化学工業株式会社 | Adhesive tape and adhesive tape for fixing electronic device parts |
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JP7343316B2 (en) | 2023-09-12 |
CN113196365B (en) | 2023-06-13 |
KR20210103479A (en) | 2021-08-23 |
JP2020098321A (en) | 2020-06-25 |
JP2020098320A (en) | 2020-06-25 |
TW202024277A (en) | 2020-07-01 |
JP7440993B2 (en) | 2024-02-29 |
CN113196365A (en) | 2021-07-30 |
CN113168789A (en) | 2021-07-23 |
TWI840412B (en) | 2024-05-01 |
TW202033712A (en) | 2020-09-16 |
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KR20210104050A (en) | 2021-08-24 |
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