TWI763932B - Manufacturing method of laminated body with protective film and laminated body with protective film - Google Patents
Manufacturing method of laminated body with protective film and laminated body with protective filmInfo
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- TWI763932B TWI763932B TW107134447A TW107134447A TWI763932B TW I763932 B TWI763932 B TW I763932B TW 107134447 A TW107134447 A TW 107134447A TW 107134447 A TW107134447 A TW 107134447A TW I763932 B TWI763932 B TW I763932B
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- protective film
- resin layer
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- resin
- film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
Abstract
根據本發明之一態樣，提供一種附保護膜之積層體10之製造方法，其具備以下步驟：準備積層體20，該積層體20具備第1基材21、及設置於作為第1基材21的一面之第1面21A側且膜厚方向D的剖面之壓痕硬度為100 MPa以上之第1樹脂層22；於作為第2基材31之一面之第1面31A側塗佈含有游離輻射聚合性化合物之第2樹脂層用組成物，使其乾燥而形成塗膜35；以第1樹脂層22與塗膜35接觸之方式使積層體20與塗膜34接觸；以及於使積層體20與塗膜35接觸之狀態下，藉由對塗膜35照射游離輻射而使塗膜35硬化，形成可剝離之保護膜30，該保護膜30具備第2基材31、及位於較第2基材31靠第1樹脂層22側且由塗膜35之硬化物構成，並且膜厚方向D的剖面之壓痕硬度為100 MPa以上之第2樹脂層32。According to an aspect of the present invention, there is provided a method for producing a layered body 10 with a protective film, which includes the steps of preparing a layered body 20 including a first base material 21 and providing a first base material as the first base material. A first resin layer 22 having an indentation hardness of 100 MPa or more on the first surface 21A side of one side of the first surface of the second substrate 31 and a cross section in the film thickness direction D; The composition for the second resin layer of the radiation polymerizable compound is dried to form the coating film 35; the layered body 20 and the coating film 34 are brought into contact with the first resin layer 22 and the coating film 35; 20 In a state in contact with the coating film 35, the coating film 35 is hardened by irradiating the coating film 35 with ionizing radiation to form a peelable protective film 30, the protective film 30 having a second substrate 31, The base material 31 is on the side of the first resin layer 22 and is composed of a cured product of the coating film 35, and the indentation hardness of the cross section in the film thickness direction D is 100 MPa or more of the second resin layer 32.
Description
本發明係關於一種附保護膜之積層體之製造方法及附保護膜之積層體。The present invention relates to a method for producing a laminate with a protective film and a laminate with a protective film.
先前以來，已知有智慧型手機或平板終端等圖像顯示裝置，圖像顯示裝置多數情況下使用具有基材及設置於基材之一面側之硬塗層之積層體。Conventionally, image display apparatuses such as smart phones and tablet terminals are known, and the image display apparatuses often use a laminate having a base material and a hard coat layer provided on one surface side of the base material.
於硬塗層之表面，為了防止於搬送時或其後之加工時產生損傷而貼附有具有黏著層之保護膜（例如參照專利文獻1）。該保護膜於進行搬送或加工等後被剝離而組入至圖像顯示裝置。 [先前技術文獻] [專利文獻]A protective film having an adhesive layer is attached to the surface of the hard coat layer in order to prevent damage during transportation or subsequent processing (for example, refer to Patent Document 1). This protective film is peeled off after carrying out conveyance, processing, etc., and is incorporated in an image display device. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本特開2016-60117號公報[Patent Document 1] Japanese Patent Laid-Open No. 2016-60117
[發明所欲解決之課題][The problem to be solved by the invention]
具有硬塗層之積層體亦有被用於感測器（例如圖像顯示裝置用途之感測器或車載用途之感測器（例如包含把手或片材等人所觸摸之部分之感測器））之情況。該感測器亦有需要可摺疊、可捲曲等可撓性之情形。於此種感測器所使用之積層體中，由於保護膜係臨近前貼附，故而作為附保護膜之積層體要求薄型化或兩面具有多種功能。Laminates with a hard coat layer are also used in sensors (such as sensors for image display devices or sensors for in-vehicle use (such as sensors including handles or sheets) that are touched by people. )) situation. The sensor also needs to be flexible such as foldable and rollable. In the laminated body used for this kind of sensor, since the protective film is attached in the near front, the laminated body with the protective film is required to be thinned or have multiple functions on both sides.
先前對於進行熱加工步驟之附保護膜之積層體，亦要求加工步驟前後之防捲曲性，因此例如藉由對附保護膜之積層體之正面及背面使用相同之膜厚或相同之樹脂材料而解決防捲曲性。Previously, for a laminate with a protective film subjected to a thermal processing step, anti-curling properties before and after the processing step were also required. Therefore, for example, by using the same film thickness or the same resin material for the front and back of the laminate with a protective film. Addresses curl resistance.
然而，目前亦有要求附保護膜之積層體之正面與背面具有不同功能之情況，使用不同之樹脂材料、或成為不同之膜厚之情況逐漸增加。However, at present, the front and back surfaces of the laminate with the protective film are required to have different functions, and the use of different resin materials or the use of different film thicknesses is gradually increasing.
又，為了將保護膜經剝離之積層體不僅應用於圖像顯示裝置以外之用途，且亦應用於圖像顯示裝置之用途，而要求無白濁感之透明性。Moreover, in order to apply the laminated body from which the protective film was peeled off not only to the use of an image display apparatus, but also to the use of an image display apparatus, the transparency which does not become cloudy is requested|required.
進而，對於保護膜，為了保護積層體而要求特定之硬度，並且要求於積層體之加工製程前後之物性變化較小。然而，目前之保護膜由於具有黏著層，故而有於保護膜之表面無法獲得特定之硬度，且於加工製程中積層體之物性發生變化之問題。Furthermore, the protective film is required to have a specific hardness in order to protect the layered body, and it is required that the change in physical properties before and after the processing of the layered body is small. However, since the current protective film has an adhesive layer, a specific hardness cannot be obtained on the surface of the protective film, and the physical properties of the laminate change during processing.
本發明係考慮此種方面而完成者，其目的在於提供一種具有特定之剖面硬度或表面硬度，且於加工製程前後之物性變化較小的附保護膜之積層體之製造方法及附保護膜之積層體。 [解決課題之技術手段]The present invention has been made in consideration of such an aspect, and an object of the present invention is to provide a method for producing a laminated body with a protective film, which has a specific cross-sectional hardness or surface hardness, and has a small change in physical properties before and after processing, and a method for producing a layered product with a protective film. Laminated body. [Technical means to solve the problem]
本發明包含以下之發明。 [1]一種附保護膜之積層體之製造方法，其具備以下步驟：準備積層體，該積層體具備第1基材、及設置於上述第1基材的一面側且膜厚方向的剖面之壓痕硬度為100 MPa以上之第1樹脂層；於第2基材之一面側塗佈含有游離輻射聚合性化合物之第2樹脂層用組成物，使其乾燥而形成塗膜；以上述第1樹脂層與上述塗膜接觸之方式使上述積層體與上述塗膜接觸；於使上述積層體與上述塗膜接觸之狀態下，藉由對上述塗膜照射游離輻射而使上述塗膜硬化，形成可剝離之保護膜，該保護膜具備上述第2基材、及位於較上述第2基材靠上述第1樹脂層側且由上述塗膜之硬化物構成並且膜厚方向的剖面之壓痕硬度為100 MPa以上之第2樹脂層。The present invention includes the following inventions. [1] A method for producing a layered product with a protective film, comprising the steps of preparing a layered product including a first base material and a cross section of a film thickness direction provided on one surface side of the first base material. A first resin layer with an indentation hardness of 100 MPa or more; a composition for a second resin layer containing an ionizing radiation polymerizable compound is coated on one surface side of the second substrate, and dried to form a coating film; with the above-mentioned first The above-mentioned laminated body is brought into contact with the above-mentioned coating film in such a manner that the resin layer is in contact with the above-mentioned coating film; in a state where the above-mentioned laminated body is in contact with the above-mentioned coating film, the above-mentioned coating film is cured by irradiating the above-mentioned coating film with ionizing radiation to form A peelable protective film comprising the second base material and the indentation hardness of the cross section in the film thickness direction which is located on the side of the first resin layer with respect to the second base material and is composed of the cured product of the coating film. It is a 2nd resin layer of 100 MPa or more.
[2]如上述[1]所記載之附保護膜之積層體之製造方法，其中，上述第2樹脂層之上述壓痕硬度小於上述第1樹脂層之壓痕硬度。[2] The method for producing a laminate with a protective film according to the above [1], wherein the indentation hardness of the second resin layer is smaller than the indentation hardness of the first resin layer.
[3]如上述[1]或[2]所記載之附保護膜之積層體之製造方法，其中，上述游離輻射聚合性化合物包含非環氧烷（alkylene oxide）改質之游離輻射聚合性化合物與環氧烷改質之游離輻射聚合性化合物。[3] The method for producing a laminate with a protective film according to the above [1] or [2], wherein the ionizing radiation polymerizable compound includes a non-alkylene oxide-modified ionizing radiation polymerizable compound Ionizing radiation polymerizable compounds modified with alkylene oxides.
[4]如上述[1]至[3]中任一項所記載之附保護膜之積層體之製造方法，其中，上述第2樹脂層用組成物含有聚矽氧系化合物。[4] The method for producing a laminate with a protective film according to any one of the above [1] to [3], wherein the composition for the second resin layer contains a polysiloxane-based compound.
[5]一種附保護膜之積層體，其具備：具備第1基材及設置於上述第1基材的一面側之第1樹脂層之積層體、與可剝離地密接於上述積層體之保護膜；且上述保護膜具備：第2基材、及位於較上述第2基材靠上述第1樹脂層側且密接於上述第1樹脂層之第2樹脂層；上述第1樹脂層之膜厚方向的剖面及上述第2樹脂層之膜厚方向的剖面之壓痕硬度分別為100 MPa以上。[5] A laminate with a protective film, comprising: a laminate including a first base material and a first resin layer provided on one surface side of the first base material, and a protection releasably adhered to the laminate film; and the protective film includes: a second base material, and a second resin layer located on the side of the first resin layer relative to the second base material and in close contact with the first resin layer; the film thickness of the first resin layer The indentation hardness of the cross section in the direction and the cross section in the film thickness direction of the second resin layer is 100 MPa or more, respectively.
[6]如上述[5]所記載之附保護膜之積層體，其中，上述第2樹脂層之上述壓痕硬度小於上述第1樹脂層之壓痕硬度。[6] The protective film-attached laminate according to the above [5], wherein the indentation hardness of the second resin layer is smaller than the indentation hardness of the first resin layer.
[7]如上述[5]或[6]所記載之附保護膜之積層體，其中，上述保護膜由上述第2基材與上述第2樹脂層構成。[7] The protective film-attached laminate according to the above [5] or [6], wherein the protective film is composed of the second base material and the second resin layer.
[8]如上述[5]至[7]中任一項所記載之附保護膜之積層體，其中，上述積層體進而具備第1功能層，該第1功能層設置於上述第1樹脂層之與上述第1基材側之面為相反側之面側，上述第1功能層包含透光性樹脂及配置於上述透光性樹脂中之多個導電性纖維，上述積層體之存在上述第1功能層之區域之光漫反射率為0.5%以下。[8] The laminated body with a protective film according to any one of the above [5] to [7], wherein the laminated body further includes a first functional layer provided on the first resin layer The surface on the opposite side to the first base material side, the first functional layer includes a translucent resin and a plurality of conductive fibers arranged in the translucent resin, and the layered product has the first functional layer. 1. The light diffuse reflectance in the region of the functional layer is 0.5% or less.
[9]如上述[5]至[8]所記載之附保護膜之積層體，其中，上述保護膜進而具備第2功能層，該第2功能層設置於上述第2基材與上述第2樹脂層之間、或設置於上述第2基材之與上述第2樹脂層側之第1面為相反側之第2面。[9] The protective film-attached laminate according to the above [5] to [8], wherein the protective film further includes a second functional layer provided on the second substrate and the second functional layer. Between the resin layers, or the second surface provided on the opposite side to the first surface on the side of the second resin layer of the second base material.
[10]如上述[5]至[9]中任一項所記載之附保護膜之積層體，其中，上述第2樹脂層之膜厚為1 μm以上且10 μm以下。[10] The laminate with a protective film according to any one of the above [5] to [9], wherein the film thickness of the second resin layer is 1 μm or more and 10 μm or less.
[11]如上述[5]至[10]中任一項所記載之附保護膜之積層體，其中，於剝離了上述保護膜之狀態下之上述第2樹脂層的表面之鉛筆硬度為H以上。[11] The protective film-attached laminate according to any one of the above [5] to [10], wherein the pencil hardness of the surface of the second resin layer in a state where the protective film is peeled off is H above.
[12]如上述[5]至[11]中任一項所記載之附保護膜之積層體，其中，於將上述附保護膜之積層體於150℃之環境下加熱1小時之前後，分別測定加熱前之上述積層體與上述保護膜之剝離強度及加熱後之上述積層體與上述保護膜之剝離強度時，上述加熱後之上述剝離強度相對於上述加熱前之上述剝離強度的上升率為100%以下。[12] The laminated body with a protective film according to any one of the above [5] to [11], before and after heating the above-mentioned laminated body with a protective film in an environment of 150° C. for 1 hour, respectively When the peel strength of the laminate and the protective film before heating and the peel strength of the laminate and the protective film after heating were measured, the increase rate of the peel strength after the heating relative to the peel strength before the heating was measured. 100% or less.
[13]如上述[5]至[12]中任一項所記載之附保護膜之積層體，其中，將上述附保護膜之積層體於150℃之環境下加熱1小時後之上述積層體與上述保護膜之剝離強度為200 mN/25 mm以下。[13] The laminated body with a protective film according to any one of the above [5] to [12], wherein the laminated body with a protective film is heated in an environment of 150° C. for 1 hour. The peel strength with the above protective film is 200 mN/25 mm or less.
[14]如上述[5]至[13]中任一項所記載之附保護膜之積層體，其中，將上述附保護膜之積層體於150℃之環境下加熱1小時，加熱後將上述保護膜剝離時上述第2樹脂層之表面之對水的接觸角為70°以上且95°以下。[14] The laminated body with a protective film according to any one of the above [5] to [13], wherein the laminated body with a protective film is heated in an environment of 150° C. for 1 hour, and after heating, the above-mentioned laminated body is heated at 150° C. The contact angle with respect to water of the surface of the said 2nd resin layer at the time of peeling of a protective film is 70 degrees or more and 95 degrees or less.
[15]如上述[5]至[14]中任一項所記載之附保護膜之積層體，其中，上述第2樹脂層係包含非環氧烷改質之游離輻射聚合性化合物與環氧烷改質之游離輻射聚合性化合物的第2樹脂用組成物之硬化物。[15] The protective film-attached laminate according to any one of the above [5] to [14], wherein the second resin layer comprises a non-alkylene oxide-modified ionizing radiation polymerizable compound and an epoxy The cured product of the second resin composition of the alkane-modified ion radiation polymerizable compound.
[16]如上述[5]至[15]中任一項所記載之附保護膜之積層體，其中，上述第2樹脂層含有聚矽氧系化合物。[16] The protective film-attached laminate according to any one of the above [5] to [15], wherein the second resin layer contains a polysiloxane-based compound.
[17]一種附保護膜之積層體，其具備：積層體，其具備第1基材及設置於上述第1基材之一面側之第1樹脂層；以及保護膜，其可剝離地密接於上述積層體；且上述保護膜具備第2基材、及位於較上述第2基材靠上述第1樹脂層側且密接於上述第1樹脂層之第2樹脂層；且於剝離了上述保護膜之狀態下之上述第2樹脂層的表面之鉛筆硬度為H以上。[17] A laminate with a protective film, comprising: a laminate including a first base material and a first resin layer provided on one surface side of the first base material; and a protective film releasably adhered to the above-mentioned laminated body; and the above-mentioned protective film includes a second base material and a second resin layer located on the side of the above-mentioned second base material and on the side of the above-mentioned first resin layer and in close contact with the above-mentioned first resin layer; and after the above-mentioned protective film is peeled off The pencil hardness of the surface of the said 2nd resin layer in this state is H or more.
[18]一種附保護膜之積層體，其具備：積層體，其具備第1基材及設置於上述第1基材之一面側之第1樹脂層；以及保護膜，其可剝離地密接於上述積層體；且上述保護膜具備第2基材、及位於較上述第2基材靠上述第1樹脂層側且密接於上述第1樹脂層之第2樹脂層；於將上述附保護膜之積層體於150℃之環境下加熱1小時之前後，分別測定加熱前之上述積層體與上述保護膜之剝離強度及加熱後之上述積層體與上述保護膜之剝離強度時，上述加熱後之上述剝離強度相對於上述加熱前之上述剝離強度的上升率為100%以下。[18] A laminate with a protective film comprising: a laminate including a first base material and a first resin layer provided on one surface side of the first base material; and a protective film releasably adhered to the above-mentioned laminated body; and the above-mentioned protective film includes a second base material, and a second resin layer located on the side of the above-mentioned first resin layer relative to the above-mentioned second base material and in close contact with the above-mentioned first resin layer; Before and after the laminate was heated at 150°C for 1 hour, the peel strength of the laminate and the protective film before heating and the peel strength of the laminate and the protective film after heating were measured, respectively. The rate of increase of the peel strength with respect to the peel strength before the heating was 100% or less.
[19]一種附保護膜之積層體，其具備：積層體，其具備第1基材及設置於上述第1基材之一面側之第1樹脂層；以及保護膜，其可剝離地密接於上述積層體；且上述保護膜具備第2基材、及位於較上述第2基材靠上述第1樹脂層側且密接於上述第1樹脂層之第2樹脂層；且將上述附保護膜之積層體於150℃之環境下加熱1小時後之上述積層體與上述保護膜之剝離強度為200 mN/25 mm以下。[19] A laminate with a protective film comprising: a laminate including a first base material and a first resin layer provided on one surface side of the first base material; and a protective film releasably adhered to the above-mentioned laminate; and the above-mentioned protective film includes a second base material, and a second resin layer located on the side of the above-mentioned second base material on the side of the above-mentioned first resin layer and in close contact with the above-mentioned first resin layer; and the above-mentioned protective film is attached. The peel strength of the laminate and the protective film after the laminate was heated in an environment of 150° C. for 1 hour was 200 mN/25 mm or less.
[20]一種附保護膜之積層體，其具備：積層體，其具備第1基材及設置於上述第1基材之一面側之第1樹脂層；以及保護膜，其可剝離地密接於上述積層體；上述保護膜具備第2基材、及位於較上述第2基材靠上述第1樹脂層側且密接於上述第1樹脂層之第2樹脂層；且將上述附保護膜之積層體於150℃之環境下加熱1小時，加熱後將上述保護膜剝離時上述第2樹脂層之表面之對水的接觸角為70°以上且95°以下。[20] A laminate with a protective film, comprising: a laminate including a first base material and a first resin layer provided on one surface side of the first base material; and a protective film releasably adhered to The above-mentioned laminated body; the above-mentioned protective film includes a second base material and a second resin layer located on the side of the above-mentioned second base material on the side of the above-mentioned first resin layer and in close contact with the above-mentioned first resin layer; and the above-mentioned laminated layer with the protective film The body was heated in an environment of 150°C for 1 hour, and when the protective film was peeled off after heating, the contact angle to water of the surface of the second resin layer was 70° or more and 95° or less.
[21]一種附保護膜之積層體，其具備：積層體，其具備第1基材及設置於上述第1基材之一面側之第1樹脂層；以及保護膜，其可剝離地密接於上述積層體；且上述保護膜具備第2基材、及位於較上述第2基材靠上述第1樹脂層側且密接於上述第1樹脂層之第2樹脂層；且上述第2樹脂層係包含非環氧烷改質之游離輻射聚合性化合物與環氧烷改質之游離輻射聚合性化合物的第2樹脂用組成物之硬化物。 [發明之效果][21] A laminate with a protective film, comprising: a laminate including a first base material and a first resin layer provided on one surface side of the first base material; and a protective film releasably adhered to the above-mentioned laminate; and the above-mentioned protective film includes a second base material, and a second resin layer located on the side of the first resin layer relative to the second base material and in close contact with the first resin layer; and the second resin layer is a A cured product of a second resin composition comprising a non-alkylene oxide-modified ion radiation polymerizable compound and an alkylene oxide-modified ion radiation polymerizable compound. [Effect of invention]
根據本發明，可提供一種具有特定之剖面硬度或表面硬度，且於加工製程前後之物性變化較小的附保護膜之積層體。According to the present invention, it is possible to provide a layered body with a protective film which has a specific cross-sectional hardness or surface hardness and has a small change in physical properties before and after processing.
以下，參照圖式對本發明之實施形態之積層體、觸控面板、及圖像顯示裝置進行說明。圖1係本實施形態之附保護膜之積層體之概略構成圖，圖2係圖1所示之附保護膜之積層體之局部放大圖。圖3及圖4係實施形態之另一附保護膜之積層體之概略構成圖，圖5係圖4之附保護膜之積層體之示意性俯視圖。圖6及圖7係實施形態之另一附保護膜之積層體之概略構成圖。圖8（A）～圖8（C）及圖9（A）～圖9（C）係示意性地表示本實施形態之附保護膜之積層體的製造步驟之圖。Hereinafter, a laminated body, a touch panel, and an image display device according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic configuration diagram of the laminated body with a protective film according to the present embodiment, and FIG. 2 is a partial enlarged view of the laminated body with a protective film shown in FIG. 1 . 3 and 4 are schematic configuration diagrams of another laminate with a protective film according to the embodiment, and FIG. 5 is a schematic plan view of the laminate with a protective film in FIG. 4 . FIG. 6 and FIG. 7 are schematic structural diagrams of another laminated body with a protective film according to the embodiment. FIGS. 8(A) to 8(C) and FIGS. 9(A) to 9(C) are diagrams schematically showing the production steps of the laminate with the protective film of the present embodiment.
＜＜＜＜附保護膜之積層體＞＞＞＞
圖1所示之附保護膜之積層體10具備：積層體20，其具備第1基材21及設置於作為第1基材21的一面之第1面21A側之第1樹脂層22；以及保護膜30，其可剝離地密接於積層體20之第1樹脂層22。積層體20除具備第1基材21及第1樹脂層22以外，進而具備設置於第1基材21之與第1面21A為相反側之面即第2面21B側的第1功能層23。本說明書中之「功能層」係指於積層體中意圖發揮某些功能之層。具體而言，例如作為積層體中之第1功能層，可列舉：導電層、易接著層、折射率調整層、彈性、伸長率等物理特性調整層、穿透吸收光波長調整層、顏料/染料著色層、紫外線防止層等。功能層不僅可為單層，亦可為積層有2層以上者。於功能層為積層有2層以上者之情形時，各層所具有之功能可相同亦可不同。於本實施形態中，對第1功能層23為導電層之情形進行說明。＜＜＜＜Laminated body with protective film＞＞＞＞
The laminated
附保護膜之積層體10之厚度較佳為25 μm以上且500 μm以下。若附保護膜之積層體10之厚度為25 μm以上，則附保護膜之積層體10之搬送時或加工時之操作性變得良好，又，若為500 μm以下，則就薄型化之觀點而言良好，又，可容易地捲取。附保護膜之積層體10之厚度之下限更佳為50 μm以上，上限更佳為300 μm以下、200 μm以下、160 μm以下（數值越小越佳）。附保護膜之積層體10之厚度可藉由使用厚度測定裝置（產品名「Digimatic Indicator IDF-130」，Mitutoyo股份有限公司製造）測定任意10個部位之厚度，並算出其算術平均值而求出。It is preferable that the thickness of the
於將附保護膜之積層體10於150℃之環境下加熱1小時之前後，加熱後之積層體20與保護膜30之剝離強度相對於加熱前之積層體20與保護膜30之剝離強度的上升率較佳為100%以下。如下所述，若對附保護膜之積層體進行加熱，則有積層體與保護膜之剝離強度較加熱前上升之傾向，若上述上升率為100%以下，則即便於將附保護膜之積層體10進行加熱之情形時，亦可容易地剝離保護膜30。上述上升率依序進而較佳為80%以下、60%以下、50%以下、40%以下（數值越小越佳）。再者，上升率亦可為負。加熱前之積層體20與保護膜30之剝離強度及加熱後之積層體20與保護膜30之剝離強度係分別使用拉伸試驗機（產品名「Tensilon萬能材料試驗機RTF-1150-H」，A＆D股份有限公司製造），藉由以下之測定方法所測得之值。於測定剝離強度時，首先，於縱12.5 cm×橫5 cm×厚度1.1 mm之玻璃板貼附雙面膠帶（寺岡股份有限公司製作所 No.751B）。另一方面，將附保護膜之積層體切成縱15 cm×橫2.5 cm之大小，將第1基材側貼附於玻璃板上之雙面膠帶，保持於拉伸試驗機之一對治具。繼而，使貼附於玻璃板之附保護膜之積層體保持於拉伸試驗機之一對治具。於使附保護膜之積層體保持於治具時，以人手預先使保護膜自積層體略微剝離，製作出起點，使保護膜保持於其中一治具，使玻璃板及積層體保持於另一治具。繼而，於該狀態下，於剝離速度300 mm/分鐘、剝離距離50 mm、剝離角度180°之條件下剝離保護膜，測定此時之積層體與保護膜之剝離強度。再者，剝離強度設為進行3次測定所獲得之值之算術平均值。加熱後之保護膜之剝離強度相對於加熱前之保護膜之剝離強度之上升率係於將上述上升率設為A（%），將加熱前之保護膜之剝離強度設為B（mN/25 mm），將加熱後之剝離強度設為C（mN/25 mm）時，根據以下之式算出。再者，於不切成上述樣品之大小之情形時，例如可將縱向長度設為8 cm左右。
A＝（C－B）/B×100Before and after heating the
將附保護膜之積層體10於150℃之環境下加熱1小時前之積層體20與保護膜30之剝離強度較佳為200 mN/25 mm以下。若該剝離強度為200 mN/25 mm以下，則可於加熱前容易地剝離保護膜30。又，將附保護膜之積層體10於150℃之環境下加熱1小時後之積層體20與保護膜30之剝離強度較佳為200 mN/25 mm以下。若該剝離強度為200 mN/25 mm以下，則即便於加熱後，亦可容易地剝離保護膜30。關於加熱前之上述剝離強度及加熱後之上述剝離強度之下限，就使保護膜30密接於積層體20而有效地保護第1樹脂層22之觀點而言，較佳為10 mN/25 mm以上。加熱前之上述剝離強度及加熱後之上述剝離強度之上限依序進而較佳為150 mN/25 mm以下、120 mN/25 mm以下、110 mN/25 mm以下、105 mN/25 mm以下（數值越小越佳）。The peel strength of the laminate 20 and the
將附保護膜之積層體10於150℃之環境下加熱1小時，此時加熱後之附保護膜的積層體10之MD方向及TD方向的加熱收縮率分別較佳為0.8%以下。此處，所謂MD方向係指於為長方形型顯示器之情形時與短軸平行之方向，所謂TD方向係指與長軸平行之方向。於為正方形之情形時，選擇4邊中之任意1邊，將與該邊平行之方向稱為MD，將與該邊垂直之方向稱為TD。進而，於為不定形之情形時，切成適當之正方形（例如可為50 cm見方、40 cm見方、30 cm見方、20 cm見方、10 cm見方、5 cm見方等大小之正方形），係指如上所述之方向。再者，於製造步驟所使用之輥形態之膜中，MD為Machine Direction：機械軸方向（膜流動之行進方向），TD為Transverse Direction：橫寬方向。若附保護膜之積層體10的MD方向及TD方向的加熱收縮率分別為0.8%以下，則於加熱附保護膜之積層體10之情形時，即便將第1功能層23圖案化，亦可使第1功能層23之尺寸變化變小。上述MD方向及TD方向的加熱收縮率分別依序進而較佳為0.6%以下、0.5%以下（數值越小越佳）。加熱收縮率設為以如下方式測定。首先，將附保護膜之積層體以MD方向成為縱向、TD方向成為橫向之方式切成縱8 cm×橫8 cm之大小。對於所切出之附保護膜之積層體，利用圖像尺寸測定器（IM-6120：Keyence股份有限公司製造）測定加熱前之縱向及橫向之長度。繼而，將該切出之附保護膜之積層體於150℃之環境下加熱1小時，利用上述圖像尺寸測定器測定加熱後之附保護膜之積層體之縱向及橫向之長度，基於以下之式算出MD方向及TD方向的加熱收縮率。於以下之式中，DMD
為MD方向之加熱收縮率（%），DTD
為TD方向之加熱收縮率（%），EMD
為加熱前之附保護膜之積層體之MD方向之長度（cm），ETD
為加熱前之附保護膜之積層體之TD方向之長度（cm），FMD
為加熱後之附保護膜之積層體之MD方向之長度（cm），FTD
為加熱後之附保護膜之積層體之TD方向之長度（cm）。再者，於無法將附保護膜之積層體切成上述大小之情形時，亦可將附保護膜之積層體適當切成作為可操作之大小的縱2 cm×橫2 cm以上之大小。
DMD
＝（FMD
－EMD
）/EMD
×100
DTD
＝（FTD
－ETD
）/ETD
×100The
將附保護膜之積層體10於150℃之環境下加熱1小時，此時加熱後之附保護膜之積層體10之捲曲量較佳為±10 mm以下。若捲曲量為±10 mm以下，則可容易地操作附保護膜之積層體10。捲曲量設為以如下方式測定。首先，將附保護膜之積層體切成縱34 cm×橫34 cm之大小。繼而，將該切出之附保護膜之積層體於150℃之環境下加熱1小時，將加熱後之附保護膜之積層體置於平坦之台上。繼而，分別測定附保護膜之積層體之四角與台之距離，以將其進行平均所得之值作為捲曲量。再者，於以保護膜成為下側之方式放置於台之情形時，將附保護膜之積層體之上表面捲曲成凹狀之情形設為正（+），將附保護膜之積層體之上表面捲曲成凸狀之情形設為負（-）。捲曲量依序進而較佳為±9 mm以下、±8 mm以下、±7 mm以下、±5 mm以下（數值越小越佳）。再者，於無法將附保護膜之積層體切成上述大小之情形時，亦可將附保護膜之積層體適當切成能夠充分進行捲曲測定之大小即縱5 cm×橫5 cm以上之大小。The
於將附保護膜之積層體10於150℃之環境下加熱1小時之前後，於測定附保護膜之積層體10之霧度值（全霧度值）時，自加熱後之附保護膜之積層體10之霧度值減去加熱前之附保護膜之積層體10之霧度值所得之值即霧度變化量較佳為5%以內。若霧度變化量為5%以內，則可獲得即便於加熱後亦具有良好之透明性之附保護膜之積層體10。此種霧度變化量可藉由在下述第2基材31之與第2樹脂層32側之第1面31A為相反側之第2面31B設置低聚物析出抑制層而達成。附保護膜之積層體10之霧度值係依據JIS K7136：2000，使用測霧計（產品名「HM-150」，村上色彩技術研究所股份有限公司製造），於切成縱10 cm×橫10 cm之大小後，於無捲曲或褶皺且無指紋或灰塵等之狀態下以積層體成為非光源側之方式設置，對1片附保護膜之積層體測定3次，採用3次測定所獲得之值之算術平均值。附保護膜之積層體10目視之表面平坦，且第1功能層23等積層之層亦平坦，又，厚度之不均亦收斂於厚度之平均值之±10%之範圍內、較佳為±5%之範圍內。因此，認為藉由測定所切出之附保護膜之積層體之不同的3個部位之霧度值，可獲得大致附保護膜之積層體之面內整體之霧度值之平均值。再者，於無法將附保護膜之積層體切成上述大小之情形時，例如HM-150進行測定時之入口開口為20 mm
附保護膜之積層體10之正面10A之表面電阻值亦可低於附保護膜之積層體10之背面之表面電阻值。正面10A之表面電阻值可藉由與下述第1功能層23之表面電阻值相同之方式測定。又，背面10B之表面電阻值可使用表面電阻值測定器（產品名「Hiresta IP MCP-HT260」，三菱化學股份有限公司製造）進行測定。The surface resistance value of the
於將保護膜自附保護膜之積層體剝離時，有產生剝離帶電之虞。若產生剝離帶電，則有積層體中之第1功能層中之導電性纖維被切斷之虞。尤其導電性纖維有細線化之傾向，因此導電性纖維更容易切斷。因此，就抑制剝離保護膜30時之剝離帶電及導電性纖維之切斷之觀點而言，背面10B之表面電阻值較佳為1×1013
Ω/□以下。背面10B之此種表面電阻值可藉由使下述第2功能層33中含有抗靜電劑、或形成抗靜電層而達成。背面10B之表面電阻值更佳為1×1012
Ω/□以下、1×1011
Ω/□以下、1×1010
Ω/□以下（數值越小越佳）。When peeling a protective film from the laminated body with a protective film, there exists a possibility that peeling electrification may generate|occur|produce. When peeling electrification occurs, the conductive fibers in the first functional layer in the laminate may be cut. In particular, the conductive fibers tend to be thinned, and thus the conductive fibers are more easily cut. Therefore, the surface resistance value of the
附保護膜之積層體可切割為所需之大小，亦可為輥狀。於將附保護膜之積層體切割為所需之大小之情形時，附保護膜之積層體之大小並無特別限制，可根據圖像顯示裝置之顯示面之大小而適當決定。具體而言，附保護膜之積層體之大小例如亦可成為5英吋以上且500英吋以下。本說明書中之所謂「英吋」，於附保護膜之積層體為四邊形狀之情形時係指對角線之長度，於為圓形狀之情形時係指直徑，於為橢圓形狀之情形時係指短徑與長徑之和之平均值。此處，於附保護膜之積層體為四邊形狀之情形時，若作為圖像顯示裝置之顯示畫面無問題，則求出上述英吋時之附保護膜之積層體之縱橫比並無特別限定。例如可列舉縱：橫＝1：1、4：3、16：10、16：9、2：1等。但是，尤其於富有圖案性之車載用途或數位標牌中，此種縱橫比並無限定。又，於附保護膜之積層體10之大小較大之情形時，設為自任意之位置（於較端部靠中央部附近）切成A5大小（148 mm×210 mm）後，切成各測定項目之大小。The laminated body with the protective film can be cut into the desired size, and can also be in the form of a roll. When cutting the laminated body with the protective film into a desired size, the size of the laminated body with the protective film is not particularly limited, and can be appropriately determined according to the size of the display surface of the image display device. Specifically, the size of the laminate with the protective film may be, for example, 5 inches or more and 500 inches or less. The term "inch" in this specification refers to the length of the diagonal line when the laminate with the protective film is quadrilateral, the diameter when it is a circle, and the diameter when it is an ellipse. Refers to the average of the sum of the short and long diameters. Here, in the case where the laminate with the protective film has a quadrangular shape, the aspect ratio of the laminate with the protective film in the above-mentioned inch is not particularly limited as long as there is no problem as a display screen of an image display device. . For example, vertical:horizontal=1:1, 4:3, 16:10, 16:9, 2:1, and the like. However, especially in patterned automotive applications or digital signage, such an aspect ratio is not limited. In addition, when the size of the
＜＜＜積層體＞＞＞
積層體20之厚度較佳為25 μm以上且500 μm以下。若積層體20之厚度為25 μm以上，則操作性變得良好，又，若為100 μm以下，則就薄型化之觀點而言良好。附保護膜之積層體10之厚度之下限更佳為40 μm以上，上限更佳為250 μm以下、100 μm以下、70 μm以下（數值越小越佳）。積層體20之厚度可藉由使用厚度測定裝置（產品名「Digimatic Indicator IDF-130」，Mitutoyo股份有限公司製造）測定任意10個部位之厚度，並算出其算術平均值而求出。＜＜＜Laminated body＞＞＞
The thickness of the
積層體20較佳為於剝離了保護膜30之狀態下，霧度值（總霧度值）成為5%以下。若積層體20之霧度值為5%以下，則可獲得充分之光學性能。積層體20之霧度值係藉由與附保護膜之積層體10之霧度值相同之方法而測定。積層體20之霧度值較佳為1.5%以下，最佳為1.2%以下。但是，於電阻極低之情形時，具體而言於為10 Ω/□以下之情形時，霧度值較佳為2%以下，最佳為1.5%以下。再者，即便於圖案化後或成為感測器後，亦可測定出霧度變化量，若切成22 mm見方以上所測得之結果本身為5%以下，則霧度變化量亦可謂5%以內。The
積層體20較佳為於剝離了保護膜30之狀態下，總光線穿透率為80%以上。若積層體20之總光線穿透率為80%以上，則可獲得充分之光學性能。總光線穿透率係依據JIS K7361-1：1997，使用測霧計（產品名「HM-150」，村上色彩技術研究所股份有限公司製造），於切成縱5 cm×橫10 cm之大小後，於無捲曲或褶皺且無指紋或灰塵等之狀態下，以第1樹脂層成為非光源側之方式設置，對1片積層體測定3次，採用3次測定所獲得之值之算術平均值。積層體20目視之表面平坦，且第1功能層23等積層之層亦平坦，又，厚度之不均收斂於厚度之平均值之±10%之範圍內，較佳為收斂於±5%之範圍內。因此，認為藉由測定所切出之積層體之不同的3個部位之總光線穿透率，可獲得大致之積層體之面內整體之總光線穿透率之平均值。再者，於無法將積層體切成上述大小之情形時，例如HM-150進行測定時之入口開口為20 mm
積層體20如下所述具有包含導電性纖維25之作為導電層之第1功能層23。尤其若使用金屬奈米線作為導電性纖維，則會因金屬奈米線而產生光散射，容易產生導電部看上去發白而***之現象（乳濁）。又，由於金屬奈米線尤其容易因來自LED之光而發生反射，故而若使用LED作為光源，則有乳濁之問題變得顯著之傾向，業界謀求進一步之乳濁之解決。再者，針對上述乳濁之問題，亦對使金屬奈米線之纖維直徑變細進行研究，但若使金屬奈米線之纖維直徑變細，則雖然霧度值降低，但乳濁之問題依然殘留。霧度值與乳濁係不同之事物，即便使霧度值降低，亦未解決乳濁。就抑制此種乳濁之問題之觀點而言，於積層體20中，存在第1功能層23之區域之光漫反射率（Specular Component Exclude：SCE）較佳為成為0.5%以下。所謂「光漫反射率」係指除正反射光以外之光之反射率。再者，設為除正反射光以外之原因在於，由於正反射光較大地受到與空氣界面之折射率差之影響，故而正反射率與乳濁並無相關關係。上述光漫反射率較佳為成為0.4%以下、0.35%以下、0.3%以下（數值越小越佳）。The
於測定上述光漫反射率時，首先於切成10 cm×10 cm之大小之導電性膜無捲曲或褶皺且無指紋或灰塵等之狀態下，將積層體、黏著膜、及黑色板依序貼合。積層體係以成為較黑色板更上側且第1功能層成為上側之方式配置。繼而，自第1功能層側使用分光測色計（產品名「CM-600d」，Konica Minolta股份有限公司，測定口
作為使積層體20之存在第1功能層23之區域的光漫反射率為0.5%以下之方法，並無特別限定，例如可列舉：於第1功能層23中除了含有透光性樹脂24及導電性纖維25以外，亦含有下述至少一部分表面呈現出較導電性纖維25暗之顏色之表面暗色系纖維。It does not specifically limit as a method of making the light diffuse reflectance of the area|region where the 1st
積層體20之黃度指數（YI）較佳為15以下。若積層體20之YI為15以下，則可抑制積層體20之黃色調，可應用於要求透明性之用途。黃度指數（YI）係將切成50 mm×100 mm之大小之積層體以第1功能層側成為光源側之方式配置於分光光度計（產品名「UV-3100PC」，島津製作所股份有限公司製造，光源：鎢絲燈及氘燈）內，於該狀態下測定積層體之波長300 nm～780 nm之穿透率，由該穿透率並依照JIS Z8722：2009所記載之運算式而計算出色度三刺激值X、Y、Z，由三刺激值X、Y、Z並依照ASTM D1925：1962所記載之運算式而算出。積層體20之黃度指數（YI）之上限更佳為10以下、7以下、3以下（數值越小越佳）。上述黃度指數（YI）係對1片積層體測定3次，設為進行3次測定所獲得之值之算術平均值。再者，於UV-3100PC中，黃度指數係藉由在連接於UV-3100PC之顯視器上讀取上述穿透率之測定資料，於計算項目中選中「YI」之項目而算出。波長300 nm～780 nm之穿透率之測定設為藉由如下方式求出，即，於以下之條件下，於波長300 nm～780 nm分別於前後1 nm之間測定最低5點量之穿透率，算出其平均值。又，若於分光穿透率之光譜中出現起伏，則亦可以δ5.0 nm進行平滑化處理。再者，於不切成上述大小之情形時，只要為3 cm見方以上即可。
（測定條件）
・波長區域：300 nm～780 nm
・掃描速度：高速
・狹縫寬度：2.0
・取樣間隔：自動（0.5 nm間隔）
・照明：C
・光源：D2及WI
・視野：2°
・光源切換波長：360 nm
・S/R切換：標準
・檢測器：PM
・自動歸零：於基準線之掃描後於550 nm實施The yellowness index (YI) of the
積層體20之用途並無特別限定，例如亦可用於使用光學膜或具備透明導電層之導電性膜之各種用途（例如感測器用途）。又，積層體20適於圖像顯示裝置（包含智慧型手機、平板終端、可攜帶式終端、個人電腦、電視機、數位標牌、公共資訊顯示器（PID）、車載顯示器等）用途或車載（包含電車或車輛建造用機械等所有車）用途。於使用積層體20作為車載用途之感測器之情形時，可列舉例如配置於把手或片材等人所觸摸之部分之感測器。又，積層體20亦適於需要可摺疊、可捲曲等可撓性之用途。進而，亦可用於住宅或車（包含電車或車輛建造用機械等所有車）中所使用之電氣化製品或窗。尤其是積層體20可適宜地用於重視透明性之部分。又，積層體不僅就透明性等技術性觀點而言較佳，而且亦可適宜地用於要求設計性或圖案性之電氣化製品。作為積層體20之具體用途，例如可列舉：除霜器、天線、太陽電池、影音系統、揚聲器、電扇、電子黑板或半導體用載膜等。積層體20之使用時之形狀係視用途而適當設計，因此並無特別限定，例如亦可成為曲面狀。The application of the
如上所述，積層體20具備第1基材21及設置於第1基材21之第1面21A側之第1樹脂層22。As described above, the
＜＜第1基材＞＞
作為第1基材21，並無特別限定，例如可列舉由樹脂所構成之基材。作為此種樹脂，例如可列舉：聚烯烴系樹脂、聚碳酸酯系樹脂、聚丙烯酸酯系樹脂、聚酯系樹脂、芳香族聚醚酮系樹脂、聚醚碸系樹脂、乙醯纖維素系樹脂、聚醯亞胺系樹脂、聚醯胺醯亞胺系樹脂、聚醯胺系樹脂、或將該等樹脂混合2種以上而成之混合物等。再者，第1基材亦可為玻璃基材。<<First base material>>
Although it does not specifically limit as
於獲得可摺疊之積層體作為積層體20之情形時，作為構成第1基材21之樹脂，就摺疊性良好之方面而言，較佳為使用聚醯亞胺系樹脂、聚醯胺醯亞胺系樹脂、聚醯胺系樹脂、聚酯系樹脂、或該等之混合物。又，於該等中，就不僅具有優異之摺疊性，而且亦具有優異之硬度及透明性，又，耐熱性亦優異，藉由進行煅燒亦可賦予更優異之硬度及透明性之方面而言，較佳為聚醯亞胺系樹脂、聚醯胺系樹脂、或該等之混合物。When a foldable laminate is obtained as the laminate 20, as the resin constituting the
作為聚烯烴系樹脂，例如可列舉聚乙烯、聚丙烯、環狀聚烯烴基材等。作為環狀聚烯烴系樹脂，例如可列舉具有降莰烯骨架者。As a polyolefin resin, polyethylene, a polypropylene, a cyclic polyolefin base material, etc. are mentioned, for example. As a cyclic polyolefin resin, what has a norbornene skeleton is mentioned, for example.
作為聚碳酸酯系樹脂，例如可列舉：以雙酚類（雙酚A等）作為基底之芳香族聚碳酸酯、二乙二醇雙烯丙基碳酸酯等脂肪族聚碳酸酯等。Examples of polycarbonate-based resins include aromatic polycarbonates based on bisphenols (bisphenol A, etc.), and aliphatic polycarbonates such as diethylene glycol bisallyl carbonate.
作為聚丙烯酸酯系樹脂，例如可列舉：聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸乙酯、(甲基)丙烯酸甲酯-(甲基)丙烯酸丁酯共聚物等。As a polyacrylate resin, a polymethyl (meth)acrylate, a polyethyl (meth)acrylate, a methyl (meth)acrylate-butyl (meth)acrylate copolymer etc. are mentioned, for example.
作為聚酯系樹脂，例如可列舉聚對苯二甲酸乙二酯（PET）、聚對苯二甲酸丙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯（PEN）之至少1種。Examples of polyester-based resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate (PEN). At least 1 species.
作為芳香族聚醚酮系樹脂，例如可列舉聚醚醚酮（PEEK）等。As an aromatic polyether ketone-type resin, polyether ether ketone (PEEK) etc. are mentioned, for example.
作為乙醯纖維素系樹脂，例如可列舉三乙醯纖維素（TAC）、二乙醯纖維素。三乙醯纖維素係能夠於可見光區域380～780 nm使平均光穿透率為50%以上之樹脂。三乙醯纖維素之平均光穿透率較佳為70%以上，進而較佳為85%以上。Examples of the acetyl cellulose-based resin include triacetyl cellulose (TAC) and diacetyl cellulose. Triacetyl cellulose is a resin that can achieve an average light transmittance of more than 50% in the visible light region of 380-780 nm. The average light transmittance of triacetate cellulose is preferably 70% or more, more preferably 85% or more.
再者，作為三乙醯纖維素，除了純粹之三乙醯纖維素以外，亦可為如乙酸丙酸纖維素、乙酸丁酸纖維素之亦併用作為與纖維素形成酯之脂肪酸之乙酸以外之成分所得者。又，於該等三乙醯纖維素系樹脂中，亦可視需要添加二乙醯纖維素等其他纖維素低級脂肪酸酯、或塑化劑、紫外線吸收劑、易滑劑等各種添加劑。Furthermore, as triacetate cellulose, in addition to pure triacetate cellulose, for example, cellulose acetate propionate, cellulose acetate butyrate, and acetic acid, which is used in combination as a fatty acid that forms an ester with cellulose, may also be used. Ingredient Gainer. In addition, other cellulose lower fatty acid esters such as diacetyl cellulose, or various additives such as plasticizers, ultraviolet absorbers, and slip agents may be added to these triacetylcellulose-based resins as necessary.
聚醯亞胺系樹脂亦可為脂肪族聚醯亞胺系樹脂，較佳為含有芳香族環之芳香族系聚醯亞胺樹脂。芳香族系聚醯亞胺樹脂係於四羧酸成分及二胺成分之至少一者中含有芳香族環者。The polyimide-based resin may be an aliphatic polyimide-based resin, preferably an aromatic-based polyimide resin containing an aromatic ring. The aromatic polyimide resin contains an aromatic ring in at least one of a tetracarboxylic acid component and a diamine component.
聚醯亞胺系樹脂亦可於其一部分中含有聚醯胺結構。作為可含有之聚醯胺結構，例如可列舉：如1,2,4-苯三甲酸酐之含有三羧酸殘基之聚醯胺醯亞胺結構、或如對苯二甲酸之含有二羧酸殘基之聚醯胺結構。聚醯胺系樹脂之概念不僅包含脂肪族聚醯胺，而且亦包含芳香族聚醯胺（芳醯胺）。The polyimide-based resin may contain a polyimide structure in a part thereof. Examples of the polyamide structure that can be contained include a polyamide imide structure containing a tricarboxylic acid residue such as 1,2,4-benzenetricarboxylic acid anhydride, or a dicarboxylic acid containing structure such as terephthalic acid. Polyamide structure of residues. The concept of polyamide resin includes not only aliphatic polyamide but also aromatic polyamide (aramide).
第1基材21之厚度並無特別限定，可設為3 μm以上且500 μm以下，就操作性等觀點而言，第1基材21之厚度之下限依序較佳為10 μm以上、20 μm以上（數值越大越佳）。就薄膜化之觀點而言，第1基材21之厚度之上限依序較佳為250 μm以下、100 μm以下、80 μm以下、60 μm以下、40 μm以下（數值越小越佳）。第1基材21之厚度設為自使用掃描式電子顯微鏡（SEM）所拍攝之第1基材21之剖面照片隨機測定10個部位之厚度，以所測得之厚度之平均值之形式求出者。The thickness of the
於第1基材21之表面，為了提高接著性，亦可對表面實施電暈放電處理、氧化處理等物理處理。又，第1基材21亦可於至少一面側具有用以提高與其他層之接著性、防止捲取時之貼附、及/或抑制形成其他層之塗佈液之收縮的基底層。但是，於本說明書中，存在於第1基材之至少一面側且接觸第1基材之基底層設為構成第1基材之一部分，而不包含於第1樹脂層者。The surface of the
基底層例如含有固著劑或底塗劑。作為固著劑或底塗劑，例如可使用聚胺酯（polyurethane）樹脂、聚酯樹脂、聚氯乙烯系樹脂、聚乙酸乙烯酯系樹脂、氯乙烯-乙酸乙烯酯共聚物、丙烯酸系樹脂、聚乙烯醇系樹脂、聚乙烯醇縮醛樹脂、乙烯與乙酸乙烯酯或丙烯酸等之共聚物、乙烯與苯乙烯及/或丁二烯等之共聚物、烯烴樹脂等熱塑性樹脂及/或其改質樹脂等。The base layer contains, for example, a fixing agent or a primer. As the fixing agent or the primer, for example, polyurethane resin, polyester resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, polyethylene can be used Alcohol-based resins, polyvinyl acetal resins, copolymers of ethylene and vinyl acetate or acrylic acid, copolymers of ethylene and styrene and/or butadiene, thermoplastic resins such as olefin resins, and/or modified resins thereof Wait.
如上所述，為了防止捲取時之貼附，基底層亦可含有易滑劑等粒子。作為粒子，可列舉二氧化矽（silica）粒子等。As described above, in order to prevent sticking during winding, the base layer may contain particles such as slip agents. As a particle, a silica particle etc. are mentioned.
＜＜第1樹脂層＞＞
第1樹脂層22配置於第1基材21之第1面21A側。本說明書中之「第1樹脂層」係指主要由樹脂構成之層，除樹脂以外，亦可含有粒子或添加劑。又，本說明書中之「第1樹脂層」設為單層。本實施形態中之第1樹脂層22為硬塗層。本說明書中之「硬塗層」係指接下來說明之壓痕硬度為100 MPa以上之層。<<1st resin layer>>
The
第1樹脂層22之膜厚方向D之剖面之壓痕硬度成為100 MPa以上。第1樹脂層22之壓痕硬度之下限較佳為200 MPa以上，就彎曲時不易產生龜裂且可容易地操作之方面而言，上限較佳為1000 MPa以下，更佳為800 MPa以下。本說明書中之「壓痕硬度」係指由壓頭之自負載至卸載為止之荷重-位移曲線所求出之值。上述壓痕硬度（HIT
）之測定係使用HYSITRON（海思創）公司製造之「TI950 TriboIndenter」對測定樣品進行。具體而言，首先，將附保護膜之積層體切成縱1 cm×橫1 cm之大小，將所獲得之附保護膜之積層體放入至聚矽氧系包埋板中，使環氧系樹脂流入，利用樹脂包埋附保護膜之積層體整體。其後，將包埋樹脂於65℃放置12小時以上而使其硬化。其後，使用超薄切片機（產品名「超薄切片機EM UC7」，Leica Microsystems股份有限公司製造），將進給厚度設定為100 nm，製作超薄切片。將切出超薄切片後之剩餘之塊體作為測定樣品。繼而，將測定樣品以測定樣品之藉由將上述切片切出所獲得之剖面相對於載玻片之表面大致垂直之方式經由接著樹脂（產品名「Aronalpha（註冊商標）一般用」，東亞合成股份有限公司製造）固定於市售之載玻片（產品名「載玻片(切放型) 1-9645-11」，AS ONE股份有限公司製造）。具體而言，於上述載玻片之中央部滴加上述接著樹脂。此時，不將接著樹脂進行塗佈擴散，又，為了不使接著樹脂自測定樣品溢出，滴加設為1滴。使測定樣品以測定樣品之藉由將上述切片切出所獲得之剖面相對於載玻片之表面大致垂直之方式接觸載玻片，於載玻片與測定樣品之間將接著樹脂進行擠壓擴散而暫時接著。繼而，於該狀態下，在室溫放置12小時，藉由接著將測定樣品固定於載玻片。再者，固定方法為任意，只要測定用樣品不移動即可。繼而，於測定樣品之剖面中，找到平坦之部位，於該平坦之部位，以於位移基準之測定中最大壓入位移成為100 nm之方式，將三角錐（Berkovich）壓頭（三角錐，BRUKER公司製造之TI-0039）以速度10 nm/秒歷時10秒自位移0 nm施加負載至位移100 nm並同時垂直地壓入至第1樹脂層22。此處，為了避免第1基材或第2樹脂層之影響及避免第1樹脂層之側緣之影響，三角錐壓頭設為壓入至自第1基材或第2樹脂層與樹脂層之界面向樹脂層之中央側分別離開500 nm、自第1樹脂層之兩側端分別向第1樹脂層之中央側離開500 nm的第1樹脂層之部分內。其後，於位移100 nm時保持5秒後，以10秒自位移100 nm卸載至位移0 nm。繼而，連續地測定與此時之壓入荷重F（N）對應之壓入深度h（nm），製作荷重-位移曲線。根據所製作之荷重-位移曲線，如下述數式（1）所示，由將最大壓入荷重Fmax
（N）除以壓頭與第1樹脂層22接觸之接觸投影面積Ap
（mm2
）所得之值而求出壓痕硬度（HIT
）。壓痕硬度（HIT
）設為測定10個部位所獲得之值之算術平均值。Ap
係使用標準試樣之熔融石英，藉由Oliver-Pharr法修正壓頭前端曲率後之接觸投影面積。
HIT
＝Fmax
/Ap
（1）The indentation hardness of the cross section in the film thickness direction D of the
第1樹脂層22如上所述作為硬塗層發揮功能，因此於剝離了保護膜30之狀態下，第1樹脂層22之表面較佳為於JIS K5600-5-4：1999所規定之鉛筆硬度試驗為H以上。藉由使第1樹脂層22之表面之鉛筆硬度為H，積層體20變硬，可提高耐久性。再者，就防止積層體20之捲曲之觀點而言，第1樹脂層22之表面之鉛筆硬度之上限較佳為設為4H左右。於鉛筆硬度試驗中，將附保護膜之積層體10切成縱5 cm×橫10 cm之大小，剝離保護膜30，利用Nichiban股份有限公司製造之Cellotape（註冊商標）將剝離了保護膜30之積層體以第1樹脂層22成為上側且無彎折或褶皺之方式固定於玻璃板上，於對鉛筆施加750 g之荷重並且將刮痕速度設為1 mm/秒之狀態下進行。第1樹脂層22之表面之鉛筆硬度設為於鉛筆硬度試驗中未於第1樹脂層22之表面產生損傷之最高硬度。再者，於測定鉛筆硬度時，使用多根硬度不同之鉛筆進行，每1根鉛筆進行5次鉛筆硬度試驗，於5次中4次以上未對第1樹脂層22之表面造成損傷之情形時，判斷該硬度之鉛筆未對第1樹脂層22之表面造成損傷。上述損傷係指於螢光燈下對進行鉛筆硬度試驗之積層體20之表面進行穿透觀察而被視認到者。As the
於未加熱附保護膜之積層體10之狀態下，剝離保護膜30時之第1樹脂層22之表面之水的接觸角（以下有時亦將該接觸角稱為「初期接觸角」）較佳為70°以上且95°以下。若初期接觸角為70°以上且95°以下，則可容易地剝離保護膜30。又，將附保護膜之積層體10於150℃之環境下加熱1小時，於加熱後剝離保護膜30時之第1樹脂層22之表面之對水的接觸角（以下有時亦將該接觸角稱為「加熱後接觸角」）較佳為70°以上且95°以下。若加熱後接觸角為70°以上且95°以下，則即便於加熱附保護膜之積層體10之情形時，亦可容易地剝離保護膜30。第1樹脂層22之表面之對水的初期接觸角及加熱後接觸角係依照JIS R3257：1999所記載之靜滴法，使用顯微鏡式接觸角計（產品名「DropMaster300」，協和界面科學股份有限公司製造）進行測定。具體而言，將附保護膜之積層體10切成縱5 cm×橫10 cm之大小，於在所切出之附保護膜之積層體10中剝離了保護膜30之狀態下，將1 μL之水滴加至第1樹脂層22之表面，對於剛滴加後之接觸角進行10點測定。繼而，將其等之算術平均值作為第1樹脂層22之表面之接觸角。The contact angle of water on the surface of the
第1樹脂層22之膜厚較佳為0.5 μm以上且15 μm以下。若第1樹脂層22之膜厚為0.5 μm以上，則可獲得所需之硬度，又，若第1樹脂層22之膜厚為15 μm以下，則可實現薄型化。就抑制第1樹脂層22之破裂之觀點而言，第1樹脂層22之膜厚之下限更佳為12 μm以下。又，就實現第1樹脂層22之薄膜化，且另一方面抑制捲曲之產生之觀點而言，第1樹脂層22之上限更佳為10 μm以下。The film thickness of the
第1樹脂層之膜厚係使用掃描穿透式電子顯微鏡（STEM）、或穿透式電子顯微鏡（TEM）拍攝第1樹脂層之剖面，於該剖面之圖像中測定10個部位之第1樹脂層之膜厚，採用該10個部位之膜厚之算術平均值。具體而言，首先，由附保護膜之積層體製作剖面觀察用樣品。詳細而言，將切成2 mm×5 mm之附保護膜之積層體放入至聚矽氧系包埋板中，使環氧系樹脂流入，利用樹脂包埋附保護膜之積層體整體。其後，將包埋樹脂於65℃放置12小時以上而使其硬化。其後，使用超薄切片機（產品名「超薄切片機 EM UC7」，Leica Microsystems股份有限公司製造），將進給厚度設定為100 nm，製作超薄切片。利用附膠棉膜之篩目（150目）採取所製作之超薄切片，設為STEM用樣品。再者，若於該樣品未獲得導通，則有難以看到藉由STEM所獲得之觀察圖像之情形，因此較佳為濺鍍Pt-Pd20秒左右。濺鍍時間可適當調整，由於10秒較少且100秒過多，故而所濺鍍之金屬會成為粒子狀之異物圖像，因此必須注意。其後，使用掃描穿透式電子顯微鏡（STEM）（產品名「S-4800（TYPE2）」，Hitachi High-Technologies股份有限公司製造），拍攝STEM用樣品之剖面照片。於該剖面照片之拍攝時，將檢測器設為「TE」、將加速電壓設為「30 kV」、將發射電流設為「10 μA」而進行STEM觀察。關於倍率，同時調節焦距來辨別各層或觀察對比度及亮度，並於5000倍～20萬倍適當調節。較佳之倍率為1萬倍～10萬倍，進而較佳之倍率為1萬倍～5萬倍，最佳之倍率為2.5萬倍～5萬倍。再者，於拍攝剖面照片時，亦可進而將光圈設為「射柱偵測光圈3」，將物鏡光圈設為「3」，又，將W.D.設為「8 mm」。於測定第1樹脂層之膜厚時，於進行剖面觀察時，重要的是能夠盡量明確地觀察到第1樹脂層與其他層（第1基材或包埋樹脂等）之界面對比度。假設因對比度不足而難以觀察到該界面之情形時，若實施四氧化鋨、四氧化釕、磷鎢酸等染色處理，則變得容易觀察到有機層間之界面，因此亦可進行染色處理。又，界面之對比度有於高倍率時更難以辨別之情形。於此情形時，亦同時於低倍率觀察。例如於2.5萬倍與5萬倍、或5萬倍與10萬倍等高低兩種倍率進行觀察，於兩倍率求出上述算術平均值，進而將其平均值作為第1樹脂層之膜厚之值。The film thickness of the first resin layer is obtained by photographing a cross-section of the first resin layer with a scanning transmission electron microscope (STEM) or a transmission electron microscope (TEM), and measuring the first of 10 positions in the image of the cross-section. For the film thickness of the resin layer, the arithmetic mean of the film thicknesses of the 10 locations was used. Specifically, first, a sample for cross-section observation is produced from the laminate with a protective film. Specifically, the protective film-attached laminate cut into 2 mm×5 mm was placed in a silicone-based embedding plate, and an epoxy-based resin was poured to embed the entire protective film-attached laminate with the resin. Then, the embedding resin was left to stand at 65° C. for 12 hours or more to be hardened. Then, using an ultramicrotome (product name "Ultramicrotome EM UC7", manufactured by Leica Microsystems Co., Ltd.), the feed thickness was set to 100 nm to prepare ultrathin sections. The produced ultra-thin sections were collected using a mesh (150 mesh) with a colloidal cotton film, and were set as samples for STEM. Furthermore, if conduction is not obtained in the sample, it may be difficult to see the observation image obtained by STEM, so it is preferable to sputter Pt-Pd for about 20 seconds. The sputtering time can be adjusted appropriately. Since 10 seconds is too short and 100 seconds is too long, the sputtered metal will become a particle-like foreign matter image, so it is necessary to pay attention. Then, using a scanning transmission electron microscope (STEM) (product name "S-4800 (TYPE2)", manufactured by Hitachi High-Technologies Co., Ltd.), a cross-sectional photograph of the sample for STEM was taken. At the time of taking this cross-sectional photograph, STEM observation was performed with the detector set to "TE", the acceleration voltage set to "30 kV", and the emission current set to "10 μA". Regarding the magnification, adjust the focal length at the same time to distinguish each layer or observe the contrast and brightness, and adjust it appropriately from 5,000 times to 200,000 times. The preferred magnification is 10,000 to 100,000 times, the further preferred magnification is 10,000 to 50,000 times, and the best magnification is 25,000 to 50,000 times. Furthermore, when taking a cross-sectional photo, the aperture can be further set to "column detection aperture 3", the objective lens aperture can be set to "3", and the W.D. can be set to "8 mm". When measuring the film thickness of the first resin layer, it is important to observe the interface contrast between the first resin layer and other layers (first base material, embedding resin, etc.) as clearly as possible when observing the cross-section. If it is difficult to observe the interface due to insufficient contrast, if dyeing treatment such as osmium tetroxide, ruthenium tetroxide, phosphotungstic acid, etc. is performed, the interface between the organic layers can be easily observed, so dyeing treatment can also be performed. In addition, the contrast of the interface is more difficult to distinguish at high magnification. In this case, it is also observed at low magnification at the same time. For example, observation is performed at two magnifications, such as 25,000 times and 50,000 times, or 50,000 times and 100,000 times, and the arithmetic average value is obtained at the double rate, and the average value is used as the difference between the film thickness of the first resin layer. value.
第1樹脂層22可至少由樹脂構成。再者，第1樹脂層22除了包含樹脂以外，亦可包含無機粒子、有機粒子及調平劑等添加劑之至少任一者。第1樹脂層22較佳為除包含樹脂以外，亦包含作為添加劑之聚矽氧系化合物或氟系化合物。The
＜樹脂＞
作為第1樹脂層22中之樹脂，可列舉含有聚合性化合物之聚合物（硬化物、交聯物）者。樹脂除包含聚合性化合物之聚合物以外，亦可包含溶劑乾燥型樹脂。作為聚合性化合物，可列舉游離輻射聚合性化合物及/或熱聚合性化合物。＜Resin＞
As resin in the
游離輻射聚合性化合物係於1分子中具有至少一個游離輻射聚合性官能基之化合物。本說明書中之「游離輻射聚合性官能基」係指可藉由游離輻射照射進行聚合反應之官能基。作為游離輻射聚合性官能基，例如可列舉：(甲基)丙烯醯基、乙烯基、烯丙基等乙烯性不飽和基。再者，「(甲基)丙烯醯基」係指包含「丙烯醯基」及「甲基丙烯醯基」之兩者之含義。又，作為使游離輻射聚合性化合物聚合時所照射之游離輻射，可列舉可見光線、紫外線、X射線、電子束、α射線、β射線、及γ射線。The ionizing radiation polymerizable compound is a compound having at least one ionizing radiation polymerizable functional group in one molecule. The "free radiation polymerizable functional group" in this specification refers to a functional group that can undergo a polymerization reaction by ion radiation irradiation. Examples of free radiation polymerizable functional groups include ethylenically unsaturated groups such as (meth)acryloyl groups, vinyl groups, and allyl groups. In addition, "(meth)acryloyl group" means the meaning including both of "acryloyl group" and "methacryloyl group". Moreover, visible rays, ultraviolet rays, X rays, electron beams, alpha rays, beta rays, and gamma rays are exemplified as ionizing radiation to be irradiated when polymerizing the ionizing radiation polymerizable compound.
作為游離輻射聚合性化合物，可列舉游離輻射聚合性單體、游離輻射聚合性低聚物、或游離輻射聚合性預聚物，可將該等適當調整而使用。作為游離輻射聚合性化合物，較佳為游離輻射聚合性單體與游離輻射聚合性低聚物或游離輻射聚合性預聚物之組合。Examples of the ionizing radiation polymerizable compound include ionizing radiation polymerizable monomers, ionizing radiation polymerizable oligomers, or ionizing radiation polymerizable prepolymers, and these can be appropriately adjusted and used. The ionizing radiation polymerizable compound is preferably a combination of ionizing radiation polymerizable monomer and ionizing radiation polymerizable oligomer or ionizing radiation polymerizable prepolymer.
作為游離輻射聚合性單體，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-乙基己酯等含有羥基之單體、或乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、四亞甲基二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、新戊四醇二(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、二新戊四醇四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、甘油(甲基)丙烯酸酯等(甲基)丙烯酸酯類。Examples of the ionized radiation polymerizable monomers include monohydroxy groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. body, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, neotaerythritol di(meth)acrylate Acrylates, Neotaerythritol Tri(meth)acrylate, Neotaerythritol Tetra(meth)acrylate, Dipionaerythritol Tetra(meth)acrylate, Dipionaerythritol Hex(meth)acrylate (Meth)acrylates such as acrylates and glycerol (meth)acrylates.
作為游離輻射聚合性低聚物，較佳為2官能以上之多官能低聚物，較佳為游離輻射聚合性官能基為3個（3官能）以上之多官能低聚物。作為上述多官能低聚物，例如可列舉：聚酯(甲基)丙烯酸酯、(甲基)丙烯酸胺酯、聚酯-(甲基)丙烯酸胺酯、聚醚(甲基)丙烯酸酯、多元醇(甲基)丙烯酸酯、三聚氰胺(甲基)丙烯酸酯、異氰尿酸酯（isocyanurate）(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等。The ionizing radiation polymerizable oligomer is preferably a polyfunctional oligomer having two or more functionalities, and more preferably a polyfunctional oligomer having three (trifunctional) or more ionizing radiation polymerizable functional groups. As said polyfunctional oligomer, polyester (meth)acrylate, (meth)acrylate urethane, polyester-(meth)acrylate, polyether (meth)acrylate, polyether (meth)acrylate, polyether (meth)acrylate, Alcohol (meth)acrylate, melamine (meth)acrylate, isocyanurate (meth)acrylate, epoxy (meth)acrylate, and the like.
游離輻射聚合性預聚物例如亦可具有1萬之重量平均分子量。作為游離輻射聚合性預聚物之重量平均分子量，較佳為1萬以上且8萬以下，更佳為1萬以上且4萬以下。於重量平均分子量超過8萬之情形時，由於黏度較高，故而塗佈適性降低，有所獲得之第1樹脂層之外觀劣化之虞。作為多官能預聚物，可列舉：(甲基)丙烯酸胺酯、異氰尿酸酯(甲基)丙烯酸酯、聚酯-(甲基)丙烯酸胺酯、環氧(甲基)丙烯酸酯等。The free radiation polymerizable prepolymer may have, for example, a weight average molecular weight of 10,000. The weight average molecular weight of the ionizing radiation polymerizable prepolymer is preferably 10,000 or more and 80,000 or less, and more preferably 10,000 or more and 40,000 or less. When the weight average molecular weight exceeds 80,000, since the viscosity is high, the coating suitability is lowered, and the appearance of the obtained first resin layer may be deteriorated. Examples of the polyfunctional prepolymer include urethane (meth)acrylate, isocyanurate (meth)acrylate, polyester-urethane (meth)acrylate, epoxy (meth)acrylate, and the like. .
熱聚合性化合物係於1分子中具有至少1個熱聚合性官能基者。本說明書中之「熱聚合性官能基」係指可藉由加熱而於相同之官能基彼此之間或與其他官能基之間進行聚合反應之官能基。作為熱聚合性官能基，可列舉：羥基、羧基、異氰酸基、胺基、環狀醚基、巰基等。The thermally polymerizable compound has at least one thermally polymerizable functional group in one molecule. The "thermally polymerizable functional group" in this specification refers to a functional group that can undergo a polymerization reaction between the same functional groups or with other functional groups by heating. As a thermally polymerizable functional group, a hydroxyl group, a carboxyl group, an isocyanate group, an amine group, a cyclic ether group, a mercapto group, etc. are mentioned.
作為熱聚合性化合物，並無特別限定，例如可列舉環氧化合物、多元醇化合物、異氰酸酯化合物、三聚氰胺化合物、脲化合物、酚化合物等。Although it does not specifically limit as a thermopolymerizable compound, For example, an epoxy compound, a polyol compound, an isocyanate compound, a melamine compound, a urea compound, a phenol compound, etc. are mentioned.
溶劑乾燥型樹脂係如熱塑性樹脂等，於塗佈時僅使為了調整固形物成分而添加之溶劑乾燥便成為被膜之樹脂。於添加溶劑乾燥型樹脂之情形時，可於形成第1樹脂層22時有效地防止塗液之塗佈面之被膜缺陷。作為溶劑乾燥型樹脂，並無特別限定，一般而言可使用熱塑性樹脂。Solvent-drying resins are thermoplastic resins, etc., and only the solvent added to adjust the solid content during coating is dried to become the resin of the film. In the case of adding a solvent drying type resin, film defects on the coating surface of the coating liquid can be effectively prevented when the
作為熱塑性樹脂，例如可列舉：苯乙烯系樹脂、(甲基)丙烯酸系樹脂、乙酸乙烯酯系樹脂、乙烯醚系樹脂、含鹵素之樹脂、脂環式烯烴系樹脂、聚碳酸酯系樹脂、聚酯系樹脂、聚醯胺系樹脂、纖維素衍生物、聚矽氧系樹脂及橡膠或彈性體等。Examples of thermoplastic resins include styrene-based resins, (meth)acrylic-based resins, vinyl acetate-based resins, vinyl ether-based resins, halogen-containing resins, alicyclic olefin-based resins, polycarbonate-based resins, Polyester-based resin, polyamide-based resin, cellulose derivatives, polysiloxane-based resin, rubber or elastomer, etc.
熱塑性樹脂較佳為非晶性且可溶於有機溶劑（尤其是能夠溶解多種聚合物或硬化性化合物之共用溶劑）。尤其就透明性或耐候性之觀點而言，較佳為苯乙烯系樹脂、(甲基)丙烯酸系樹脂、脂環式烯烴系樹脂、聚酯系樹脂、纖維素衍生物（纖維素酯類等）等。The thermoplastic resin is preferably amorphous and soluble in organic solvents (especially a common solvent capable of dissolving various polymers or hardening compounds). In particular, from the viewpoint of transparency and weather resistance, styrene-based resins, (meth)acrylic-based resins, alicyclic olefin-based resins, polyester-based resins, cellulose derivatives (cellulose esters, etc.) are preferred. )Wait.
＜無機粒子＞
無機粒子係用以提高第1樹脂層22之機械強度或鉛筆強度之成分，主要由無機物構成之粒子。無機粒子亦可含有有機成分，但較佳為僅由無機物構成。無機粒子亦可為藉由有機成分進行表面處理者。作為無機粒子，例如可列舉：二氧化矽（SiO2
）粒子、氧化鋁粒子、二氧化鈦粒子、氧化錫粒子、摻銻氧化錫（簡稱：ATO）粒子、氧化鋅粒子等無機氧化物粒子。於該等中，就進一步提高硬度之觀點而言，較佳為二氧化矽粒子。作為二氧化矽粒子，可列舉球形二氧化矽粒子或異形二氧化矽粒子，於該等中，較佳為異形二氧化矽粒子。本說明書中之「球形粒子」係指例如真球狀、橢圓球狀等之粒子，「異形粒子」係指馬鈴薯狀之於表面具有無規之凹凸之形狀之粒子。上述異形粒子由於其表面積與球狀粒子相比較大，故而藉由含有此種異形粒子，與上述聚合性化合物等之接觸面積變大，可使第1樹脂層22之表面硬度更優異。第1樹脂層22中所含之二氧化矽粒子是否為異形二氧化矽粒子可藉由利用穿透式電子顯微鏡（TEM）或掃描穿透式電子顯微鏡（STEM）對第1樹脂層22之剖面進行觀察而確認。於使用球形二氧化矽粒子之情形時，球形二氧化矽粒子之粒徑越小，則第1樹脂層之硬度變得越高。相對於此，即便異形二氧化矽粒子不如市售之最小粒徑之球形二氧化矽粒子般小，亦可達成與該球形二氧化矽同等之硬度。<Inorganic particles> Inorganic particles are components for improving the mechanical strength or pencil strength of the
異形二氧化矽粒子之平均一次粒徑較佳為1 nm以上且100 nm以下。即便異形二氧化矽粒子之平均一次粒徑為該範圍，亦可達成與平均一次粒徑為1 nm以上且45 nm以下之球形二氧化矽同等之硬度。異形二氧化矽粒子之平均一次粒徑係使用穿透式電子顯微鏡（TEM）或掃描穿透式電子顯微鏡（STEM）對第1功能層之剖面進行拍攝，由所拍攝之第1樹脂層之剖面之圖像測定粒子外周之2點間距離之最大值（長徑）與最小值（短徑），並進行平均而求出粒徑，採用20個粒子之粒徑之算術平均值。又，球形二氧化矽粒子之平均粒徑係使用穿透式電子顯微鏡（TEM）或掃描穿透式電子顯微鏡（STEM）於倍率1萬倍～10萬倍拍攝粒子之剖面之圖像，由該圖像測定20個粒子之粒徑，採用20個粒子之粒徑之算術平均值。於使用掃描穿透式電子顯微鏡（STEM）（產品名「S-4800（TYPE2）」，Hitachi High-Technologies股份有限公司製造）進行剖面照片之拍攝時，將檢測器（選擇信號）設為「TE」、加速電壓設為「30 kV」、發射電流設為「10 μA」而進行觀察。其他藉由STEM所獲得之剖面照片之拍攝條件可參照下述條件。The average primary particle size of the irregular-shaped silica particles is preferably 1 nm or more and 100 nm or less. Even if the average primary particle size of the irregular-shaped silica particles is in this range, the hardness equivalent to that of spherical silica with an average primary particle size of 1 nm or more and 45 nm or less can be achieved. The average primary particle size of the irregular-shaped silica particles is obtained by photographing the cross-section of the first functional layer using a transmission electron microscope (TEM) or scanning transmission electron microscope (STEM). The maximum value (long axis) and the minimum value (short axis) of the distance between two points on the outer periphery of the particles are measured on the image, and the average value is obtained to obtain the particle diameter, and the arithmetic mean of the particle diameters of 20 particles is used. In addition, the average particle size of spherical silica particles is obtained by using a transmission electron microscope (TEM) or scanning transmission electron microscope (STEM) at a magnification of 10,000 times to 100,000 times to take images of the cross-section of the particles. The particle diameters of 20 particles were measured by image, and the arithmetic mean of the particle diameters of the 20 particles was used. When taking a cross-sectional photograph using a scanning transmission electron microscope (STEM) (product name "S-4800 (TYPE2)", manufactured by Hitachi High-Technologies Co., Ltd.), set the detector (selection signal) to "TE". ”, the acceleration voltage was set to “30 kV”, and the emission current was set to “10 μA” for observation. For the shooting conditions of other cross-sectional photos obtained by STEM, refer to the following conditions.
第1樹脂層22中之無機粒子之含量較佳為20質量%以上且70質量%以下。若無機粒子之含量為20質量%以上，則可確保充分之硬度，又，若無機粒子之含量為70質量%以下，則填充率不會過度上升，因此無機粒子與樹脂成分之密接性良好，可抑制第1樹脂層之硬度降低。The content of the inorganic particles in the
作為無機粒子，較佳為使用表面具有游離輻射聚合性官能基之無機粒子（反應性無機粒子）。此種表面具有游離輻射聚合性官能基之無機粒子可藉由利用矽烷偶合劑等對無機粒子進行表面處理而製成。作為利用矽烷偶合劑對無機粒子之表面進行處理之方法，可列舉對無機粒子噴霧矽烷偶合劑之乾式法、或於使無機粒子分散至溶劑後添加矽烷偶合劑使其進行反應之濕式法等。As the inorganic particles, inorganic particles (reactive inorganic particles) having a free radiation polymerizable functional group on the surface are preferably used. Such inorganic particles having a free radiation polymerizable functional group on the surface can be produced by surface-treating the inorganic particles with a silane coupling agent or the like. As a method of treating the surface of the inorganic particles with a silane coupling agent, a dry method in which a silane coupling agent is sprayed on the inorganic particles, a wet method in which a silane coupling agent is added and reacted after dispersing the inorganic particles in a solvent, etc. .
＜有機粒子＞
有機粒子亦為用以提高第1樹脂層22之機械強度或鉛筆強度之成分，主要由有機物構成之粒子。有機粒子亦可含有無機成分，但較佳為僅由有機物構成。作為有機粒子，例如可列舉塑膠珠粒。作為塑膠珠粒，作為具體例，可列舉：聚苯乙烯珠粒、三聚氰胺樹脂珠粒、丙烯酸系珠粒、丙烯酸系-苯乙烯珠粒、聚矽氧珠粒、苯并胍胺（benzoguanamine）珠粒、苯并胍胺-甲醛縮合珠粒、聚碳酸酯珠粒、聚乙烯珠粒等。＜Organic particles＞
The organic particles are also components for improving the mechanical strength or pencil strength of the
＜聚矽氧系化合物＞
聚矽氧系化合物係用以使第1樹脂層22相對於第2樹脂層32容易剝離之成分。藉由第1樹脂層22含有聚矽氧系化合物，聚矽氧系化合物於第1樹脂層22之與第2樹脂層32之界面附近偏存，因此可於第1樹脂層22與第2樹脂層32之間之界面容易地剝離保護膜30。＜Polysiloxane compound＞
The polysiloxane-based compound is a component for making the
聚矽氧系化合物亦可為具有聚合性官能基者。於使用具有聚合性官能基之聚矽氧系化合物作為聚矽氧系化合物之情形時，聚矽氧系化合物於第2樹脂層32層中以與樹脂鍵結之狀態存在。The polysiloxane-based compound may also have a polymerizable functional group. When a polysiloxane-based compound having a polymerizable functional group is used as the polysiloxane-based compound, the polysiloxane-based compound exists in the
作為聚矽氧系化合物，並無特別限定，可列舉：二甲基聚矽氧烷、甲基苯基聚矽氧烷、甲基氫聚矽氧烷等直鏈聚矽氧或改質聚矽氧。The polysiloxane-based compound is not particularly limited, and examples thereof include linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydropolysiloxane, or modified polysiloxanes. oxygen.
作為改質聚矽氧，例如可列舉：(甲基)丙烯醯基改質聚矽氧等乙烯性不飽和基改質聚矽氧、胺基改質聚矽氧、醯胺改質聚矽氧、環氧基改質聚矽氧、羧基改質聚矽氧、醇改質聚矽氧、甲醇改質聚矽氧、巰基改質聚矽氧等。Examples of the modified polysiloxane include ethylenically unsaturated group-modified polysiloxane such as (meth)acryloyl group-modified polysiloxane, amine group-modified polysiloxane, and amide-modified polysiloxane. , Epoxy modified polysiloxane, carboxyl modified polysiloxane, alcohol modified polysiloxane, methanol modified polysiloxane, mercapto modified polysiloxane, etc.
聚矽氧系化合物之含量較佳為相對於游離輻射聚合性化合物100質量份為0.05質量份以上且1質量份以下。若聚矽氧系化合物之含量為0.05質量份以上，則可於第1樹脂層22與第2樹脂層32之界面容易地剝離保護膜30，又，若聚矽氧系化合物之含量為1質量份以下，則可於第1樹脂層22與第2樹脂層32之界面確保所需之密接性。The content of the polysiloxane-based compound is preferably 0.05 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the ionizing radiation polymerizable compound. If the content of the polysiloxane-based compound is 0.05 parts by mass or more, the
作為聚矽氧系化合物之市售品，例如可列舉：Seikabeam 10-28（大日精化工業股份有限公司製造）或BYK-313、BYK-322、BYK-331、BYK-333、BYK-345、BYK-377、BYK-378、BYK-UV3500、BYK-UV3510（均為BYK-Chemie Japan股份有限公司製造）等。Examples of commercially available polysiloxane compounds include Seikabeam 10-28 (manufactured by Dainissei Chemical Co., Ltd.), BYK-313, BYK-322, BYK-331, BYK-333, BYK-345, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510 (all manufactured by BYK-Chemie Japan Co., Ltd.), etc.
＜氟系化合物＞
氟系化合物係用以使第1樹脂層22相對於第2樹脂層32容易剝離之成分。藉由第1樹脂層22含有氟系化合物，氟系化合物於第1樹脂層22之與第2樹脂層32之界面附近偏存，因此可於第1樹脂層22與第2樹脂層32之間之界面容易地剝離保護膜30。<Fluorine compound>
The fluorine-based compound is a component for making the
氟系化合物亦可為具有聚合性官能基者。於使用具有聚合性官能基之氟化合物作為氟系化合物之情形時，氟系化合物係於第2樹脂層32層中以與樹脂鍵結之狀態存在。The fluorine-based compound may also have a polymerizable functional group. When a fluorine compound having a polymerizable functional group is used as the fluorine compound, the fluorine compound is present in the
氟系化合物之含量較佳為相對於游離輻射聚合性化合物100質量份為0.05質量份以上且1質量份以下。若氟系化合物之含量為0.05質量份以上，則可於第1樹脂層22與第2樹脂層32之界面容易地剝離保護膜30，又，若氟系化合物之含量為1質量份以下，則可於第1樹脂層22與第2樹脂層32之界面確保所需之密接性。The content of the fluorine-based compound is preferably 0.05 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the ionizing radiation polymerizable compound. When the content of the fluorine-based compound is 0.05 parts by mass or more, the
作為氟系化合物之市售品，例如可列舉：F-568、F-556、F-554、F-553（均為DIC股份有限公司製造）等。As a commercial item of a fluorine type compound, F-568, F-556, F-554, F-553 (all are manufactured by DIC Co., Ltd.) etc. are mentioned, for example.
＜＜第1功能層＞＞
第1功能層23設置於第1基材21之第2面21B側，第1功能層23之表面23A成為附保護膜之積層體10之正面10A。第1功能層23係作為導電層發揮功能者。第1功能層23係由未圖案化之狀態之膜，所謂固體膜構成。第1功能層亦可經圖案化，由多個導電部與位於導電部間之非導電部構成。＜＜The first functional layer＞＞
The 1st
如圖2所示，第1功能層23包含透光性樹脂24、及配置於透光性樹脂24中之導電性纖維25。又，就抑制乳濁之觀點而言，第1功能層23亦可進而包含異種纖維（未圖示）。第1功能層23係包含導電性纖維25之層，於難以確認第1功能層23之界面之情形時，亦可進行藉由濺鍍法於第1功能層23之表面形成Pt-Pd、Pt或Au等金屬層等電子顯微鏡觀察中通常使用之預處理。又，若實施四氧化鋨、四氧化釕、磷鎢酸等染色處理，則容易觀察到有機層間之界面，因此亦可於利用樹脂包埋附保護膜之積層體後進行染色處理。又，本說明書中之「透光性」係指使光穿透之性質。又，「透光性」無需一定透明，亦可為半透明。又，本說明書中之「導電性纖維」係指具有導電性且具有長度與粗度（例如直徑）相比充分長之形狀者，例如長度大致為粗度之5倍以上者包含於導電性纖維。As shown in FIG. 2 , the first
第1功能層23可自第1功能層23之表面23A電性導通。第1功能層23是否可自第1功能層23之表面23A電性導通可藉由測定第1功能層23之表面電阻值而判斷。第1功能層之表面電阻值之測定方法於下文敘述，故而此處省略說明。若第1功能層之表面電阻值之算術平均值未達1 MΩ/□，則可判斷自第1功能層之表面獲得電性導通。The first
第1功能層23之表面電阻值成為200 Ω/□以下。若第1功能層23之表面電阻值超過200 Ω/□，則尤其於觸控面板用途中有產生響應速度變慢等異常之虞。第1功能層23之表面電阻值係第1功能層23之表面23A之表面電阻值。表面電阻值可使用依據JIS K7194：1994（導電性塑膠之利用四探針法之電阻率試驗方法）之接觸式電阻計（產品名「Loresta AX MCP-T370型」，Mitsubishi Chemical Analytech股份有限公司製造，端子形狀：ASP）及非破壞式（渦電流法）之電阻計（產品名「EC-80P」，Napson股份有限公司製造，＜URL:https://www.napson.co.jp/wp/wp-content/uploads/2016/08/Napson_EC80P_ leaflet_160614.pdf＞）之任一者進行測定，就可不因第1功能層之膜厚而準確地測定之方面而言，較佳為使用非破壞式電阻計進行測定。非破壞式電阻計之探針僅與樣品簡易接觸即可測定，不會對樣品造成損傷，可於任意場所進行測定。就該含義而言，有時亦稱為非接觸式。藉由非破壞式電阻計進行之第1功能層之表面電阻值之測定設為，將切成80 mm×50 mm之大小之附保護膜之積層體以第1功能層側成為上表面的方式配置於平坦之玻璃板上，使探針與第1功能層接觸而進行。於使用EC-80P測定表面電阻值之情形時，選擇SW2，選擇模式M-H之片材電阻測定Ω/□。又，可根據測定範圍而容易地替換探針類型，於本實施形態中使用測定範圍為10～1000 Ω/□範圍之探針、0.5～10 Ω/□範圍之探針。再者，亦可利用EC-80P-PN（Napson股份有限公司製造）代替EC-80P而同樣地測定，於該機種之情形時，P/N選擇P即可。又，利用接觸式電阻計之第1功能層之表面電阻值之測定設為藉由如下方式進行，即，將切成80 mm×50 mm之大小之附保護膜之積層體以第1功能層側成為上表面的方式配置於平坦之玻璃板上，將ASP端子配置於第1功能層之中心，將所有電極接腳均勻地壓抵於第1功能層。於利用接觸式電阻計測定表面電阻值時，選擇測定片材電阻之模式即Ω/□。其後，若按下開始按鈕並保持，則顯示測定結果。無論電阻計之種類如何，表面電阻值之測定均設為於23℃及相對濕度55%之環境下進行。又，於測定表面電阻值時，不論電阻計之種類，於水平之桌上配置附保護膜之積層體，於均勻之平面狀態下進行測定，於附保護膜之積層體無法維持捲曲等平面狀態之情形時，於利用膠帶等將附保護膜之積層體貼附於玻璃板之狀態下進行。測定部位係設為第1功能層之中心部之3個部位，表面電阻值係設為3個部位之表面電阻值之算術平均值。此處，若全部依照JIS K7194：1994，則測定點為1點、5點、或9點，實際上，若將附保護膜之積層體切成80 mm×50 mm之大小，如JIS K7194：1994之圖5所示般測定，則有測定值變得不穩定之情形。因此，關於測定點，與JIS K7194：1994不同，設為於第1功能層之中央部3個部位進行測定。例如於JIS K7194：1994之圖5之1號位置、1號與7號之間之位置（較佳為接近於1號之位置）、及1號與9號之間之位置（較佳為接近於1號之位置）進行測定。較理想為於樣品之中心附近測定表面電阻值亦報告於井阪 大智、其他1人、“利用四探針法之導電性薄膜之電阻率測定”2008年度電子資訊通信學會東京分部學生研究發表會＜URL:https://www.ieice.org/tokyo/gakusei/kenkyuu/14/pdf/120.pdf＞中。第1功能層23之表面電阻值之下限依序較佳為1 Ω/□以上、5 Ω/□以上、10 Ω/□以上（數值越大越佳），又，第1功能層23之表面電阻值之上限依序進而較佳為100 Ω/□以下、70 Ω/□以下、60 Ω/□以下、50 Ω/□以下（數值越小越佳）。The surface resistance value of the first
第1功能層23之膜厚較佳為未達300 nm。再者，若第1功能層23之膜厚為300 nm以上，則相應地，透光性樹脂24之膜厚變得過厚，因此所有導電性纖維埋入至透光性樹脂中，由此一部分導電性纖維不再露出於第1功能層之表面，有自第1功能層之表面無法獲得電性導通之虞。第1功能層之膜厚變得越大，則導電性纖維彼此重疊之部分越增加，因此可達成1 Ω/□以上且10 Ω/□以下之低表面電阻值，但若導電性纖維過度重疊，則亦有難以維持低霧度值之情形。因此，膜厚較佳為300 nm以下。再者，只要可維持低表面電阻值，則第1功能層為薄膜時就光學特性、薄膜化之觀點而言較佳。就實現薄型化之觀點及獲得低霧度值等良好之光學特性之觀點而言，第1功能層23之膜厚之上限依序進而較佳為145 nm、140 nm以下、120 nm以下、110 nm以下、80 nm以下、50 nm以下（數值越小越佳）。又，第1功能層23之膜厚之下限較佳為10 nm以上。若第1功能層之膜厚未達10 nm，則相應地，透光性樹脂24之膜厚變得過薄，因此有產生導電性纖維自第1功能層之脫離、第1功能層之耐久性之劣化、耐擦傷性降低之虞。又，為了不產生導電性纖維容易切斷等不穩定性，較佳為導電性纖維之纖維直徑為一定程度之大小。作為導電性纖維可穩定地維持形態之纖維直徑，考慮為10 nm以上或15 nm以上。另一方面，為了獲得穩定之電性導通，較理想為導電性纖維以重疊2根以上之方式接觸，因此第1功能層23之膜厚之下限更佳為20 nm以上或30 nm以上。The film thickness of the first
第1功能層23之膜厚可藉由與第1樹脂層22之膜厚相同之方法進行測定。於測定第1功能層之膜厚時，於進行剖面觀察時，重要的是能夠盡可能明確地觀察到第1功能層與其他層（第1樹脂層或包埋樹脂等）之界面對比度。假設因對比度不足而難以觀察到該界面之情形時，亦可進行藉由濺鍍法於第1功能層之表面形成Pt或Au等金屬層等電子顯微鏡觀察中通常使用之預處理。又，若實施四氧化鋨、四氧化釕、磷鎢酸等染色處理，則容易觀察到有機層間之界面，因此亦可進行染色處理。又，界面之對比度有於高倍率時更難以辨別之情形。於此情形時，亦同時於低倍率進行觀察。例如於2.5萬倍與5萬倍、或5萬倍與10萬倍等高低兩種倍率進行觀察，於兩倍率求出上述算術平均值，進而將其平均值作為第1功能層之膜厚之值。The film thickness of the first
＜透光性樹脂＞
透光性樹脂24係為了防止導電性纖維25自第1功能層23之脫離且提高第1功能層23之耐久性或耐擦傷性而覆蓋導電性纖維25者，係以自第1功能層23之表面23A可獲得電性導通之程度覆蓋導電性纖維25者。具體而言，如上所述，若一部分導電性纖維未於第1功能層之表面露出，則有自第1功能層之表面無法獲得電性導通之虞，因此透光性樹脂24較佳為以一部分導電性纖維25自第1功能層23之表面23A露出之方式覆蓋導電性纖維25。為了以一部分導電性纖維25於第1功能層23之表面23A露出之方式利用透光性樹脂24覆蓋導電性纖維25，例如只要調整透光性樹脂24之膜厚即可。即，若透光性樹脂之膜厚過厚，則所有導電性纖維均埋入至透光性樹脂中，由此一部分導電性纖維不再於第1功能層之表面露出，有自第1功能層之表面無法獲得電性導通之虞。又，若透光性樹脂之膜厚過薄，則有產生導電性纖維自第1功能層之脫離、第1功能層之耐久性之劣化、耐擦傷性降低之虞。因此，必須將透光性樹脂之膜厚調節為適度之厚度。＜Translucent resin＞
The light-transmitting
就上述觀點而言，透光性樹脂24之膜厚較佳為未達300 nm。透光性樹脂24之膜厚設為藉由與第1功能層23之膜厚相同之方法測定者。透光性樹脂24之膜厚之上限依序進而較佳為145 nm以下、140 nm以下、120 nm、110 nm以下、80 nm以下、50 nm以下（數值越小越佳）。又，透光性樹脂24之膜厚之下限較佳為10 nm以上。From the above viewpoint, the film thickness of the
若透光性樹脂24為具有透光性之樹脂，則無特別限定，作為透光性樹脂，可列舉聚合性化合物之聚合物或熱塑性樹脂等。作為聚合性化合物，可列舉與於第1樹脂層22之欄中所說明之聚合性化合物相同者，故而此處省略說明。The
＜導電性纖維＞
導電性纖維25較佳為以多根存在於第1功能層23中。導電性纖維25可自第1功能層23之表面23A電性導通，因此於第1功能層23之厚度方向導電性纖維25彼此接觸。＜Conductive fiber＞
The
一部分導電性纖維25較佳為於第1功能層23之表面23A露出。再者，只要以導電性纖維25固定於第1功能層23之程度露出導電性纖維25之一部分即可，導電性纖維25自第1功能層23之表面23A突出之情形亦包含於導電性纖維25於第1功能層23之表面23A露出之情形。若一部分導電性纖維未於第1功能層之表面露出，則有自第1功能層之表面無法獲得電性導通之虞，因此若藉由上述測定方法而自第1功能層23之表面23A獲得電性導通，則可判斷一部分導電性纖維25於第1功能層23之表面23A露出。本說明書中之所謂「露出」，亦包含導電性纖維經一些樹脂塗佈之狀態。導電性纖維自身亦可不於表面伸出。藉由使導電性纖維經一些樹脂塗佈，塗膜物性提高，因此較為良好。所謂其塗佈材料，考慮製造含有導電性纖維之分散液之情形時之聚合物分散劑、藉由使該分散液進而分散至其他黏合劑內而形成之黏合劑樹脂等。此種樹脂塗佈係指於可獲得如上所述之導通之程度上極薄者。Part of the
導電性纖維25之平均纖維直徑較佳為200 nm以下。若導電性纖維25之平均纖維直徑為200 nm以下，則積層體之霧度值不會過高，又，透光性能充分。就第1功能層23之導電性或防止斷線之觀點而言，導電性纖維25之平均纖維直徑之下限依序進而較佳為5 nm以上、7 nm以上、10 nm以上、15 nm以上（就防止斷線之觀點而言，數值越大越佳），導電性纖維25之平均纖維直徑之上限更佳為180 nm以下、30 nm以下、28 nm以下、25 nm以下、20 nm以下、15 μm以下（就防止乳濁之觀點而言，數值越小越佳）。若考慮防止乳濁與導電性、防止斷線，則例如較佳為使用具有7 nm以上且15 nm以下之平均纖維直徑之導電性纖維。就大量生產性之方面而言，較佳為大於15 nm且為25 nm以下。The average fiber diameter of the
導電性纖維25之平均纖維直徑係例如使用穿透式電子顯微鏡（TEM）（產品名「H-7650」，Hitachi High-Technologies股份有限公司製造），於10萬倍～20萬倍拍攝50張，藉由TEM附屬之軟體於拍攝畫面上實測100根導電性纖維之纖維直徑，以其算術平均值之形式求出。於使用上述H-7650測定纖維直徑時，將加速電壓設為「100 kV」，將發射電流設為「10 μA」，將聚焦透鏡光圈設為「1」，將物鏡光圈設為「0」，將觀察模式設為「HC」，將Spot設為「2」。又，藉由掃描穿透式電子顯微鏡（STEM）（產品名「S-4800（TYPE2）」，Hitachi High-Technologies股份有限公司製造），亦可測得導電性纖維之纖維直徑。於使用STEM之情形時，於10萬倍～20萬倍拍攝50張，藉由STEM附屬之軟體於拍攝畫面上實測100根導電性纖維之纖維直徑，以其算術平均值之形式求出導電性纖維之纖維直徑。於使用上述S-4800（TYPE2）測定纖維直徑時，將信號選擇設為「TE」，將加速電壓設為「30 kV」，將發射電流設為「10 μA」，將探針電流設為「Norm」，將焦點模式設為「UHR」，將聚光透鏡1設為「5.0」，將W.D.設為「8 mm」，將Tilt設為「0°」。The average fiber diameter of the
於測定導電性纖維25之平均纖維直徑時，使用藉由以下之方法所製作之測定用樣品。此處，由於TEM測定為高倍率，故而重要的是以導電性纖維盡可能不重疊之方式使導電性纖維分散液之濃度盡可能降低。具體而言，較佳為對於導電性纖維分散液，對應於組成物之分散介質利用水或醇將導電性纖維之濃度稀釋至0.05質量%以下，或將固形物成分稀釋至0.2質量%以下。進而，將該稀釋之導電性纖維分散液於TEM或STEM觀察用之附碳支持膜之柵網上滴加1滴，於室溫使其乾燥，於上述條件下進行觀察，作為觀察圖像資料。基於此求出算術平均值。作為附碳支持膜之柵網，較佳為Cu柵型號「#10-1012 彈性碳ELS-C10 STEM Cu100P柵規格」，又，就耐電子束照射量且電子束穿透率較塑膠支持膜良好而言，較佳為適於高倍率且耐有機溶劑者。又，於滴加時，若僅為柵網，則過於微小而難以滴加，因此於載玻片上載置柵網而滴加即可。When measuring the average fiber diameter of the
上述纖維直徑可基於照片進行實測而求出，又，亦可基於圖像資料進行二值化處理而算出。於進行實測之情形時，亦可印刷照片並適當放大。此時，導電性纖維之黑度之濃度較其他成分更濃地映入。測定點係將輪廓外側作為起點、終點而測定。導電性纖維之濃度設為以導電性纖維之質量相對於導電性纖維分散液之總質量之比率求出者，又，固形物成分設為藉由分散介質以外之成分（導電性纖維、樹脂成分、其他添加劑）之質量相對於導電性纖維分散液之總質量之比率而求出者。除上述方法以外，亦可藉由上述TEM、STEM觀察而對成為30～70 Ω/□之電阻值之實際之導電層進行實測。於此情形時，並非自金屬纖維纏結之部分，而自相對稀疏之部分實測10根，能夠以所獲得之平均值之形式求出。The said fiber diameter can be calculated|required by actual measurement based on a photograph, and can also be calculated by performing a binarization process based on image data. In the case of actual measurement, photos can also be printed and appropriately enlarged. At this time, the density of the blackness of the conductive fiber is reflected more densely than other components. The measurement points are measured with the outside of the contour as the start point and the end point. The concentration of the conductive fibers is determined by the ratio of the mass of the conductive fibers to the total mass of the conductive fiber dispersion, and the solid content is determined by components other than the dispersion medium (conductive fibers, resin components) , other additives) to the ratio of the total mass of the conductive fiber dispersion. In addition to the above-mentioned method, an actual conductive layer having a resistance value of 30 to 70 Ω/□ can be measured by the above-mentioned TEM and STEM observation. In this case, 10 pieces are actually measured from the relatively sparse part, not from the tangled part of the metal fibers, and can be obtained as an average value obtained.
導電性纖維25之平均纖維長度較佳為1 μm以上。若導電性纖維25之平均纖維長度為1 μm以上，則可形成具有充分之導電性能之第1功能層，可抑制霧度值之上升或透光性能之降低。導電性纖維25之平均纖維長度之上限亦可設為500 μm以下、300 μm以下、40 μm以下、35 μm以下、30 μm以下、20 μm以下、15 μm以下，又，導電性纖維25之平均纖維長度之下限亦可設為3 μm以上、5 μm以上、7 μm以上、或10 μm以上。例如，作為導電性纖維25，可較佳地使用具有10 μm以上且30 μm以下之平均纖維長度之導電性纖維。The average fiber length of the
導電性纖維25之平均纖維長度係例如使用掃描式電子顯微鏡（SEM）（產品名「S-4800（TYPE2）」，Hitachi High-Technologies股份有限公司製造）之SEM功能，於500～2000萬倍拍攝10張，藉由附屬軟體於拍攝畫面上測定100根導電性纖維之纖維長度，以該100根導電性纖維之纖維長度之算術平均值之形式求出。於使用上述S-4800（TYPE2）測定纖維長度時，使用傾斜45°之試樣台，將信號選擇設為「SE」，將加速電壓設為「3 kV」，將發射電流設為「10 μA～20 μA」，將SE檢測器設為「混合」，將探針電流設為「Norm」，將焦點模式設為「UHR」，將聚光透鏡1設為「5.0」，將W.D.設為「8 mm」，將Tilt設為「30°」。再者，於SEM觀察時，由於不使用TE檢測器，故而必須於SEM觀察前卸除TE檢測器。上述S-4800可選擇STEM功能與SEM功能，於測定上述纖維長度時設為使用SEM功能。The average fiber length of the
於測定導電性纖維25之平均纖維長度時，使用藉由以下之方法所製作之測定用樣品。首先，將導電性纖維分散液以塗佈量成為10 mg/m2
之方式塗佈於B5大小之厚度50 μm之聚對苯二甲酸乙二酯（PET）膜之未處理面，使分散介質乾燥而於PET膜表面配置導電性纖維，從而製作導電性膜。自該導電性膜之中央部切出10 mm×10 mm之大小。繼而，使用銀膠將該切出之導電性膜相對於台面平坦地貼附於具有45°傾斜之SEM試樣台（型號「728-45」，日新EM股份有限公司製造，傾斜型試樣台45°，
上述纖維長度可基於照片進行實測而求出，又，亦可基於圖像資料進行二值化處理而算出。於基於照片進行實測之情形時，藉由與上述相同之方法而進行。The above-mentioned fiber length may be obtained by actual measurement based on a photograph, or may be calculated by performing a binarization process based on image data. In the case of carrying out the actual measurement based on the photograph, it is carried out by the same method as above.
作為導電性纖維25，較佳為選自由導電性碳纖維、金屬奈米線等金屬纖維、金屬被覆有機纖維、金屬被覆無機纖維、及奈米碳管所構成之群中之至少1種纖維。The
作為上述導電性碳纖維，例如可列舉氣相生長法碳纖維（VGCF）、奈米碳管、線杯、線壁等。該等導電性碳纖維可使用1種或2種以上。Examples of the conductive carbon fibers include vapor-grown carbon fibers (VGCF), carbon nanotubes, bobbins, and wire walls. One or more of these conductive carbon fibers can be used.
作為上述金屬纖維之金屬元素之具體例，可列舉不鏽鋼、Ag、Cu、Au、Al、Rh、Ir、Co、Zn、Ni、In、Fe、Pd、Pt、Sn、Ti等。此種金屬纖維可使用1種或2種以上。金屬纖維較佳為纖維直徑為200 nm以下及纖維長度為1 μm以上之金屬奈米線。As a specific example of the metal element of the said metal fiber, stainless steel, Ag, Cu, Au, Al, Rh, Ir, Co, Zn, Ni, In, Fe, Pd, Pt, Sn, Ti etc. are mentioned. One type or two or more types of such metal fibers can be used. The metal fibers are preferably metal nanowires with a fiber diameter of 200 nm or less and a fiber length of 1 μm or more.
上述金屬纖維例如可藉由使不鏽鋼、鐵、金、銀、鋁、鎳、鈦等較細且較長地伸長之拉線法或切削法而獲得。The above-mentioned metal fibers can be obtained by, for example, a wire drawing method or a cutting method in which stainless steel, iron, gold, silver, aluminum, nickel, titanium, etc. are elongated thin and long.
又，於使用銀奈米線作為金屬纖維之情形時，銀奈米線可於多元醇（例如乙二醇）及聚(乙烯吡咯啶酮)之存在下藉由銀鹽（例如硝酸銀）之液相還原而合成。均勻大小之銀奈米線之大量生產例如可依據Xia, Y.et al., Chem. Mater. (2002), 14, 4736-4745及Xia, Y.et al., Nanoletters(2003)3(7), 955-960所記載之方法而獲得。Also, in the case of using silver nanowires as metal fibers, silver nanowires can be prepared by a solution of silver salts (eg, silver nitrate) in the presence of polyols (eg, ethylene glycol) and poly(vinylpyrrolidone) Synthesized by phase reduction. Mass production of silver nanowires of uniform size can be carried out according to, for example, Xia, Y. et al., Chem. Mater. (2002), 14, 4736-4745 and Xia, Y. et al., Nanoletters (2003) 3 (7 ), obtained by the method described in 955-960.
金屬奈米線之製造手段並無特別限制，例如可使用液相法或氣相法等公知手段。又，具體之製造方法亦無特別限制，可使用公知之製造方法。例如作為Ag奈米線之製造方法，可參考Adv. Mater., 2002, 14 , 833～837；Chem.Mater., 2002, 14, 4736～4745等，作為Au奈米線之製造方法，可參考日本特開2006-233252號公報等，作為Cu奈米線之製造方法，可參考日本特開2002-266007號公報等，作為Co奈米線之製造方法，可參考日本特開2004-149871號公報等。The manufacturing method of the metal nanowire is not particularly limited, and for example, a known method such as a liquid phase method or a gas phase method can be used. In addition, the specific manufacturing method is not specifically limited, either, and a well-known manufacturing method can be used. For example, for the production method of Ag nanowires, refer to Adv. Mater., 2002, 14, 833-837; Chem.Mater., 2002, 14, 4736-4745, etc. For the production method of Au nanowires, refer to Japanese Patent Application Laid-Open No. 2006-233252, etc., as a method for producing Cu nanowires, reference can be made to Japanese Patent Application Laid-Open No. 2002-266007, etc., as a method for producing Co nanowires, reference can be made to Japanese Patent Application Laid-Open No. 2004-149871 Wait.
作為上述金屬被覆有機纖維，例如可列舉於丙烯酸系纖維塗佈有金、銀、鋁、鎳、鈦等或使用多種該等金屬之合金的纖維等。此種金屬被覆合成纖維可使用1種或2種以上。Examples of the metal-coated organic fibers include acrylic fibers coated with gold, silver, aluminum, nickel, titanium, etc., or fibers using alloys of a plurality of these metals. One type or two or more types of such metal-coated synthetic fibers can be used.
＜異種纖維＞
異種纖維係與導電性纖維25不同種類之纖維。於第1功能層23是否存在異種纖維可藉由如下方式判斷，即，藉由使用掃描式電子顯微鏡（SEM）（產品名「S-4800（TYPE2）」，Hitachi High-Technologies股份有限公司製造）於倍率5萬倍對異種纖維進行觀察而確認是否為纖維狀，且藉由能量分散型X射線分析裝置（EDX：上述SEM附屬之EDAX公司製造之Genesis2000）判斷是否檢測到與構成導電性纖維之元素不同之元素。EDX之測定條件係將加速電壓設為「15 kV」，將發射電流設為「20 μA」，將W.D.設為「15 mm」。表面暗色系纖維16為異種纖維之一種，因此表面暗色系纖維之纖維直徑或纖維長度等亦適用於異種纖維。＜Exotic fiber＞
The dissimilar fibers are fibers of a different type from the
（表面暗色系纖維）
表面暗色系纖維係表面之至少一部分呈現出較導電性纖維25暗之顏色之纖維。暗色系纖維之表面之至少一部分是否呈現出較導電性纖維25暗之顏色例如可藉由在含有用以形成第1功能層之表面暗色系纖維之分散液之狀態下，觀察該分散液之色調與含有導電性纖維之分散液之色調，或藉由自含有表面暗色系纖維之分散液取出表面暗色系纖維，並將表面暗色系纖維之色調與導電性纖維之色調進行比較而判斷。又，於表面暗色系纖維由金屬構成之情形時，亦可藉由以下之方法而判斷暗色系纖維之表面之至少一部分是否呈現出較導電性纖維25暗之顏色。首先，藉由使用掃描式電子顯微鏡（SEM）（產品名「S-4800（TYPE2）」，Hitachi High-Technologies公司製造）於倍率5萬倍對暗色系纖維進行觀察，確認是否為纖維狀。繼而，藉由能量分散型X射線分析裝置（EDX）確認是否自導電部檢測到與導電性纖維不同之金屬。於檢測到與導電性纖維不同之金屬之情形時，由已知資訊獲得該金屬之纖維狀態下之色調。繼而，藉由將由已知資訊獲得之色調與導電性纖維之色調進行比較，判斷暗色系纖維是否呈現出較導電性纖維暗之顏色。本說明書中之所謂「暗色」係指能夠使導電部之光漫反射率降低之黑色、灰色、褐色等低亮度之顏色。(Dark-colored fibers on the surface)
The surface-dark-colored fibers are fibers whose surface is darker than that of the
表面暗色系纖維較佳為整個表面呈現暗色，但並非必須整個表面呈現暗色。即，表面暗色系纖維亦可具有局部不呈現暗色之部分。但是，就使上述光漫反射率（SCE）為0.5%以下之觀點而言，表面暗色系纖維16較佳為存在呈現出某種程度以上之暗色之部分（以下將該部分稱為「暗色部」）。例如於表面暗色系纖維之暗色部較表面暗色系纖維之其他部分變粗之情形時，使用掃描式電子顯微鏡（SEM）（產品名「S-4800（TYPE2）」，Hitachi High-Technologies公司製造）於倍率5萬倍對表面暗色系纖維進行觀察時，若較其他部分變粗之部分之長度（暗色部之長度）以1.5 μm以上存在，則可確實地使光漫反射率為0.5%以下。再者，表面暗色系纖維在使用上述掃描式電子顯微鏡（SEM）於倍率5萬倍觀察時，即便暗色部之長度未達1.5 μm，亦有可藉由導電性纖維25與表面暗色系纖維之摻合比率而使光漫反射率為0.5%以下之情形，但於暗色部由塗膜構成之情形時，有塗佈時暗色部自纖維脫落之情況，容易成為缺陷。The surface dark-colored fibers preferably have a dark color on the entire surface, but do not necessarily have a dark color on the entire surface. That is, the dark-colored fibers on the surface may have a portion that does not appear dark locally. However, from the viewpoint of setting the above-mentioned diffuse reflectance (SCE) to be 0.5% or less, the dark-colored fibers 16 on the surface preferably have a portion exhibiting a dark color to a certain degree or more (hereinafter, this portion is referred to as a "dark portion"). ”). For example, when the dark part of the surface dark-colored fiber is thicker than the other parts of the surface dark-colored fiber, a scanning electron microscope (SEM) (product name "S-4800 (TYPE2)", manufactured by Hitachi High-Technologies Co., Ltd.) is used. When the surface dark-colored fibers are observed at a magnification of 50,000 times, if the length of the part thicker than the other parts (the length of the dark part) is 1.5 μm or more, the light diffuse reflectance can be reliably reduced to 0.5% or less. Furthermore, when the surface dark-colored fibers are observed at a magnification of 50,000 using the above-mentioned scanning electron microscope (SEM), even if the length of the dark-colored part is less than 1.5 μm, the
表面暗色系纖維25之平均纖維直徑較佳為30 nm以下。若表面暗色系纖維之平均纖維直徑為30 nm以下，則可抑制積層體20之霧度值之上升，又，透光性能變得充分。就靜電對策之觀點而言，表面暗色系纖維之平均纖維直徑之下限較佳為5 nm以上、7 nm以上、10 nm（就防止斷線之觀點而言，數值越大越佳）。又，表面暗色系纖維之平均纖維直徑之上限較佳為28 nm以下、25 nm以下、20 nm以下（就乳濁之觀點而言，數值越小越佳）。表面暗色系纖維之平均纖維直徑設為藉由與導電性纖維25之平均纖維直徑相同之方法測定。The average fiber diameter of the surface dark-
表面暗色系纖維之平均纖維長度較佳為10 μm以上且20 μm以下。若表面暗色系纖維之平均纖維長度為10 μm以上，則亦無招致由凝聚所致之霧度值得上升或透光性能的降低之虞。又，若表面暗色系纖維之平均纖維長度為20 μm以下，則可不堵塞於過濾器而進行塗佈。再者，表面暗色系纖維之平均纖維長度之下限亦可設為5 μm以上、7 μm以上、或10 μm以上，表面暗色系纖維之平均纖維長度之上限亦可設為40 μm以下、35 μm以下、或30 μm以下。The average fiber length of the surface dark-colored fibers is preferably 10 μm or more and 20 μm or less. If the average fiber length of the dark-colored fibers on the surface is 10 μm or more, there is no possibility that the haze value due to aggregation will increase or the light transmission performance will decrease. In addition, if the average fiber length of the dark-colored fibers on the surface is 20 μm or less, the coating can be performed without clogging the filter. Furthermore, the lower limit of the average fiber length of the surface dark-colored fibers can also be set to 5 μm or more, 7 μm or more, or 10 μm or more, and the upper limit of the average fiber length of the surface dark-colored fibers can also be set to 40 μm or less, 35 μm or less than 30 μm.
第1功能層23之導電性係藉由導電性纖維25而獲得，因此表面暗色系纖維本身亦可未必具有導電性，但為了抑制第1功能層23之導電性之降低，表面暗色系纖維較佳為導電性纖維。The conductivity of the first
關於第1功能層23中之表面暗色系纖維之含量，若上述光漫反射率（SCE）為成為0.5%以下之量，則無特別限定，導電性纖維25與表面暗色系纖維之重量比率較佳為97：3～30：70。若上述比率為該範圍，則可於導電部中獲得導電性，並且可進一步抑制乳濁。The content of the surface dark-colored fibers in the first
作為表面暗色系纖維，可列舉於纖維材之表面具有藉由黑化處理等暗色化處理所形成之暗色系皮膜的形成有暗色部之纖維或纖維材本身呈現出暗色之暗色系纖維。作為暗色化處理，例如可列舉塗裝、鍍覆、表面處理等。作為表面處理，例如可列舉化學處理或陽極氧化等。Examples of the dark-colored fibers on the surface include fibers with dark-colored portions formed on the surface of the fiber material having a dark-colored film formed by darkening treatment such as blackening, or dark-colored fibers in which the fiber material itself exhibits dark color. Examples of the darkening treatment include painting, plating, surface treatment, and the like. As surface treatment, chemical treatment, anodization, etc. are mentioned, for example.
於藉由鍍覆使纖維材之表面暗色化之情形時，亦可藉由電解鍍覆及無電解鍍覆之任一者形成暗色系皮膜。When the surface of the fiber material is darkened by plating, a dark-colored film may be formed by either electrolytic plating or electroless plating.
化學處理係藉由化學品或其溶液改變金屬表面之組成之處理，例如有氧化處理、磷酸鹽化處理、硫化處理等。於纖維材由金屬構成之情形時，根據纖維材之材質選擇使用如使金屬物呈現出黑色之化學處理。例如於纖維材之材質為銅之情形時，將纖維材浸漬於含有亞氯酸鈉及氫氧化鉀之水溶液、或含有多硫化銻之水溶液、含有亞氯酸鈉及磷酸鈉、氫氧化鈉之水溶液、含有過硫酸鉀及氫氧化鈉之水溶液等中即可。再者，呈現出黑色之暗色部之形成深度可藉由調節化學處理之溶液之組成、溫度、浸漬時間等條件而調整。Chemical treatment refers to the treatment of changing the composition of the metal surface by chemicals or their solutions, such as oxidation treatment, phosphating treatment, vulcanization treatment, etc. When the fiber material is made of metal, a chemical treatment such as blackening of the metal material is selected and used according to the material of the fiber material. For example, when the material of the fiber material is copper, the fiber material is immersed in an aqueous solution containing sodium chlorite and potassium hydroxide, or an aqueous solution containing antimony polysulfide, or an aqueous solution containing sodium chlorite, sodium phosphate, and sodium hydroxide. An aqueous solution, an aqueous solution containing potassium persulfate and sodium hydroxide, etc. may be used. Furthermore, the formation depth of the dark part showing black can be adjusted by adjusting the composition, temperature, immersion time and other conditions of the chemical treatment solution.
（形成有暗色部之纖維）
形成有暗色部之纖維係於纖維材之表面具有藉由黑化處理等暗色化處理所形成之暗色系皮膜的纖維。作為纖維材，就上述原因而言，亦可不為導電性纖維，但較佳為導電性纖維。於纖維材為導電性纖維之情形時，纖維材亦可不由與導電性纖維25相同之導電性材料構成，亦可由與導電性纖維25相同之材料構成。(fibers with dark parts formed)
The fiber in which the dark part is formed is a fiber having a dark-colored film formed by darkening treatment such as blackening treatment on the surface of the fiber material. Although the fiber material may not be a conductive fiber for the above-mentioned reasons, it is preferably a conductive fiber. When the fiber material is a conductive fiber, the fiber material may not be made of the same conductive material as the
暗色系皮膜較佳為無機皮膜。於暗色系皮膜為無機皮膜之情形時，作為構成暗色皮膜之無機材料，例如可列舉金屬、金屬氧化物或金屬硫化物之金屬化合物等。作為金屬，可列舉銅、鈷、鎳、鋅、鉬、錫、鉻、或該等之合金等，於該等中，較佳為銅、鈷、鎳、或該等之合金等。又，作為金屬化合物，可列舉該等金屬之化合物或氯化碲等。鈷、鎳、及氯化碲於皮膜呈現出黑色。The dark-colored film is preferably an inorganic film. When the dark-colored film is an inorganic film, examples of the inorganic material constituting the dark-colored film include metals, metal compounds of metal oxides, and metal sulfides. Examples of the metal include copper, cobalt, nickel, zinc, molybdenum, tin, chromium, or alloys thereof, and among these, copper, cobalt, nickel, or alloys thereof are preferred. Moreover, as a metal compound, the compound of these metals, tellurium chloride, etc. are mentioned. Cobalt, nickel, and tellurium chloride appear black in the film.
暗色系皮膜之膜厚較佳為10 nm以上且140 nm以下。若暗色系皮膜之膜厚為10 nm以上，則可確實地使纖維成為暗色，又，若為140 nm以下，則亦可確保優異之光學特性。暗色系皮膜之膜厚之下限更佳為30 nm以上，暗色系皮膜之膜厚之上限更佳為100 nm以下。The thickness of the dark-colored film is preferably 10 nm or more and 140 nm or less. When the film thickness of the dark-colored film is 10 nm or more, the fibers can be reliably made dark, and when the thickness is 140 nm or less, excellent optical properties can be ensured. The lower limit of the film thickness of the dark-colored film is more preferably 30 nm or more, and the upper limit of the film thickness of the dark-colored film is more preferably 100 nm or less.
（暗色系纖維） 暗色系纖維係由纖維材構成者。若纖維材本身呈現出暗色，則暗色系纖維並無特別限定，例如可列舉導電性纖維。作為導電性纖維，可列舉金屬纖維、金屬氧化物纖維、奈米碳管纖維等。作為構成金屬纖維之金屬，可列舉銅、鈷、鎳、或該等之合金（例如銅鎳）等。再者，鈷本身為銀色，但鈷纖維顯示黑色，又，鎳纖維呈現出黑色。作為奈米碳管纖維，可列舉多層、單層、或人字型奈米碳管。(dark fiber) Dark-colored fibers are composed of fiber materials. The dark-colored fibers are not particularly limited as long as the fiber material itself exhibits a dark color, and examples thereof include conductive fibers. Examples of the conductive fibers include metal fibers, metal oxide fibers, carbon nanotube fibers, and the like. As a metal which comprises a metal fiber, copper, cobalt, nickel, or these alloys (for example, copper-nickel) etc. are mentioned. Furthermore, cobalt itself is silver, but cobalt fibers appear black, and nickel fibers appear black. As carbon nanotube fibers, multilayer, single-layer, or chevron-shaped carbon nanotubes can be mentioned.
亦可並非使表面暗色系纖維含有於第1功能層23中，而於第1功能層23上設置含有表面暗色系纖維之其他第1功能層。若使表面暗色系纖維含有於含有導電性纖維之第1功能層中，則表面暗色系纖維會阻礙導電性纖維彼此之接觸，有電阻值上升之虞，藉由使表面暗色系纖維含有於與含有導電性纖維25之第1功能層23不同之第1功能層中，可抑制因表面暗色系纖維所致之導電性纖維25彼此之接觸之阻礙，藉此可抑制乳濁並且實現低電阻值。Instead of containing the surface dark-colored fibers in the first
＜＜＜保護膜＞＞＞
若將保護膜30暫時自積層體20剝離，則無法再次貼附於積層體20。就該含義而言，與黏著膜不同。＜＜＜Protective film＞＞＞
Once the
保護膜30具備第2基材31、及位於較第2基材31靠第1樹脂層22側且密接於第1樹脂層22之第2樹脂層32。保護膜30於第2基材31之與第2樹脂層32側之第1面31A為相反側之第2面31B進而具備第2功能層33。保護膜30若具備第2基材31及第2樹脂層32，則亦可不具備第2功能層33。關於附保護膜之積層體，若加熱附保護膜之積層體，則有自第2基材析出低聚物成分，霧度值上升，而失去透明性之情況。另一方面，於附保護膜之積層體中，若剝離保護膜，則積層體之第1功能層帶電，第1功能層中所含之導電性纖維變得容易斷線。因此，作為第2功能層33，較佳為具有抑制第2基材31中之低聚物之析出之低聚物析出抑制功能及抑制剝離帶電等之抗靜電功能之至少任一者之層。本實施形態中，對第2功能層33為低聚物析出抑制層之情形進行說明。The
保護膜30之厚度並無特別限定，較佳為25 μm以上且500 μm以下。若保護膜30之厚度為25 μm以上，則可容易地操作，又，若為500 μm以下，則可薄型化。就抑制加熱後之捲曲之觀點而言，保護膜30之厚度之下限更佳為30 μm以上、38 μm以上、50 μm以上（數值越大越佳）。保護膜30之厚度之上限更佳為250 μm以下、188 μm以下、125 μm以下（數值越小越佳）。保護膜30之厚度設為自使用掃描式電子顯微鏡（SEM）所拍攝之保護膜30之剖面照片隨機測定10個部位之厚度，以所測得之厚度之平均值之形式所求出者。The thickness of the
＜＜第2基材＞＞
作為第2基材31，並無特別限定，例如亦可為與第1基材21相同者。<<Second base material>>
It does not specifically limit as the
＜＜第2樹脂層＞＞
第1樹脂層22配置於第1基材21之第1面21A側。本說明書中之「第2樹脂層」係指主要由樹脂構成之層，除樹脂以外亦可含有粒子或添加劑。又，本說明書中之「第2樹脂層」係設為單層者。本實施形態中之第2樹脂層32為硬塗層。<<Second resin layer>>
The
第2樹脂層32之膜厚方向D之剖面之壓痕硬度成為100 MPa以上。第2樹脂層32之壓痕硬度之下限較佳為200 MPa以上、250 MPa以上、300 MPa以上（數值越大越佳），就彎曲時不易產生龜裂，且可容易地操作之方面而言，上限更佳為1000 MPa以下、800 MPa以下、700 MPa以下。第2樹脂層32之壓痕硬度可藉由與第1樹脂層22之壓痕硬度相同之方法進行測定。The indentation hardness of the cross section in the film thickness direction D of the
第2樹脂層32之壓痕硬度較佳為小於第1樹脂層22之壓痕硬度。藉由使第2樹脂層32之壓痕硬度小於第1樹脂層22之壓痕硬度，第2樹脂層32可容易地追隨第1樹脂層22，即便為於積層體20附有保護膜30之狀態，亦容易彎曲。第2樹脂層32之壓痕硬度與第1樹脂層22之壓痕硬度之差（第2樹脂層32之壓痕硬度－第1樹脂層22之壓痕硬度）較佳為100 MPa以上且800 MPa以下。若該差為100 MPa以上，則可抑制保護膜30之***或破裂，又，若該差為800 MPa以下，則可抑制剝離保護膜30時之破裂，可撓性優異。該差之下限更佳為200 MPa以上（數值越大越佳），上限更佳為600 MPa以下且500 MPa以下（數值越小越佳）。於貼合步驟中，於第2樹脂層為剛性之情形時，由於追隨性不足，故而產生破裂。此時，亦有破裂亦傳遞至鄰接於該第2樹脂層之第1樹脂層之情形。然而，如本發明所示，藉由如上述般使第2樹脂層32之可撓性變得良好，可實施良好之後續步驟。The indentation hardness of the
第2樹脂層32如上所述作為硬塗層發揮功能，因此於剝離了保護膜30之狀態下，第2樹脂層32之表面較佳為於JIS K5600-5-4：1999所規定之鉛筆硬度試驗為H以上。藉由使第2樹脂層32之表面之鉛筆硬度為H，保護膜30變硬，可提高耐久性或操作性。再者，就防止附保護膜之積層體10之捲曲之觀點而言，第2樹脂層32之表面之鉛筆硬度之上限較佳為4H左右。第2樹脂層32之表面之鉛筆硬度設為藉由與第1樹脂層22之表面之鉛筆硬度相同之方法測定者。As the
於未對附保護膜之積層體10加熱之狀態下，剝離保護膜30時之第2樹脂層32之表面之水接觸角（以下有時亦將該接觸角稱為「初期接觸角」）較佳為70°以上且95°以下。若初期接觸角為70°以上且95°以下，則可容易地剝離保護膜30。又，將附保護膜之積層體10於150℃之環境下加熱1小時，加熱後剝離保護膜30時之第2樹脂層32之表面之對水的接觸角（以下有時亦將該接觸角稱為「加熱後接觸角」）較佳為75°以上且90°以下。若加熱後接觸角為75°以上且90°以下，則即便於加熱附保護膜之積層體10之情形時，亦可容易地剝離保護膜30。第2樹脂層32之表面之對水的初期接觸角及加熱後接觸角設為藉由與第1樹脂層22之表面之對水的初期接觸角及加熱後接觸角相同之方法測定。In the state where the laminate 10 with the protective film is not heated, the water contact angle of the surface of the
第2樹脂層32之膜厚較佳為厚於第1樹脂層22之膜厚。藉由使第2樹脂層32之膜厚厚於第1樹脂層22之膜厚，可同時實現第1樹脂層22之良好之彎曲性與第2樹脂層32之缺陷（貼合步驟容易產生之氣泡或異物等）個數之降低。第2樹脂層32之膜厚與第1樹脂層22之膜厚之差（第2樹脂層32之膜厚－第1樹脂層22之膜厚）較佳為1 μm以上且10 μm以下。若該差為1 μm以上，則可減少第2樹脂層32之缺陷，又，若為10 μm以下，則於將第1樹脂層22彎曲時不易產生龜裂。該差之下限更佳為3 μm以上、5 μm以上（數值越大越佳），上限更佳為8 μm以下、6 μm以下（數值越小越佳）。The film thickness of the
第2樹脂層32之膜厚較佳為1 μm以上且10 μm以下。若第2樹脂層32之膜厚為1 μm以上，則可獲得所需之硬度，又，若第2樹脂層32之膜厚為10 μm以下，則於彎曲時不易產生龜裂，又，可容易地操作。第2樹脂層32之膜厚設為藉由與第1樹脂層22之膜厚相同之方法測定者。就抑制第2樹脂層32之破裂之觀點而言，第2樹脂層32之膜厚之下限更佳為3 μm以上、4 μm以上、5 μm以上（數值越大越佳）。又，就實現第2樹脂層32之薄膜化，且另一方面抑制捲曲之產生之觀點而言，第2樹脂層32之上限更佳為9 μm以下、8 μm以下、7 μm以下（數值越小越佳）。The film thickness of the
第2樹脂層32可至少由樹脂構成。再者，第2樹脂層32較佳為除含有樹脂以外，亦含有聚矽氧系化合物、氟系化合物、抗靜電劑作為添加劑。再者，於第2功能層33為抗靜電層之情形時，第2樹脂層32亦可不含抗靜電劑。The
＜樹脂＞
作為第2樹脂層32中之樹脂，可列舉含有游離輻射聚合性化合物之聚合物（硬化物、交聯物）者。作為游離輻射聚合性化合物，作為游離輻射聚合性化合物，較佳為包含非環氧烷改質之游離輻射聚合性化合物與環氧烷改質之游離輻射聚合性化合物。環氧烷改質之游離輻射聚合性化合物具有降低與第1樹脂層22之密接性之性質，因此藉由使用環氧烷改質之游離輻射聚合性化合物，可確保對於第1樹脂層22之所需之密接性，並且可調整第2樹脂層32之對第1樹脂層22之密接性。＜Resin＞
As the resin in the
（非環氧烷改質之游離輻射聚合性化合物）
非環氧烷改質之游離輻射聚合性化合物係未經環氧烷改質之化合物。本說明書中之「非環氧烷改質」係指於游離輻射聚合性化合物中不具有環氧乙烷（-CH2
-CH2
-O-）、環氧丙烷（-CH2
-CH2
-CH2
-O-）等環氧烷之結構。作為非環氧烷改質之游離輻射聚合性化合物，並無特別限定，可列舉於第1樹脂層22之樹脂之欄中所列舉之游離輻射聚合性化合物。(Non-alkylene oxide-modified ionizing radiation polymerizable compounds) Non-alkylene oxide-modified ionizing radiation polymerizable compounds are compounds that have not been modified with alkylene oxides. The term "non-alkylene oxide modified" in this specification refers to the absence of ethylene oxide (-CH 2 -CH 2 -O-) or propylene oxide (-CH 2 -CH 2 -) in the ionized radiation polymerizable compound. CH 2 -O-) and other alkylene oxide structures. It does not specifically limit as a non-alkylene oxide-modified ionizing radiation polymerizable compound, The ionizing radiation polymerizable compound listed in the column of resin of the
（環氧烷改質之游離輻射聚合性化合物）
環氧烷改質之游離輻射聚合性化合物係經環氧烷改質之化合物。本說明書中之「環氧烷改質」係指於游離輻射聚合性化合物中具有環氧乙烷（-CH2
-CH2
-O-）、環氧丙烷（-CH2
-CH2
-CH2
-O-）等環氧烷之結構。作為環氧烷，就保護膜30之剝離力之觀點而言，較佳為碳數2～4個之環氧烷（環氧乙烷、環氧丙烷、環氧丁烷），尤佳為碳數2～3個之環氧烷（環氧乙烷、環氧丙烷），進而較佳為碳數2個之環氧烷（環氧乙烷）。(Ionizing radiation polymerizable compound modified by alkylene oxide) The ionizing radiation polymerizable compound modified by alkylene oxide is a compound modified by alkylene oxide. The term "modified alkylene oxide" in this specification refers to a compound having ethylene oxide (-CH 2 -CH 2 -O-), propylene oxide (-CH 2 -CH 2 -CH 2 ) in the ionized radiation polymerizable compound. -O-) and other alkylene oxide structures. As the alkylene oxide, from the viewpoint of the peeling force of the
環氧烷改質之游離輻射聚合性化合物之含量較佳為相對於非環氧烷改質之游離輻射聚合性化合物100質量份為30質量份以上且90質量份以下。若環氧烷改質之游離輻射聚合性化合物之含量為30質量份以上，則可於第1樹脂層22與第2樹脂層32之間之界面容易地進行剝離，又，若環氧烷改質之游離輻射聚合性化合物之含量為90質量份以下，則可確保所需之密接性。The content of the alkylene oxide-modified ion radiation polymerizable compound is preferably 30 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the non-alkylene oxide-modified ion radiation polymerizable compound. If the content of the alkylene oxide-modified ionized radiation polymerizable compound is 30 parts by mass or more, peeling can be easily performed at the interface between the
作為環氧烷改質之游離輻射化合物，並無特別限定，可列舉於第1樹脂層22之樹脂之欄中所列舉之游離輻射聚合性化合物經環氧烷改質之化合物。於該等中，就保護膜30之剝離力之觀點而言，較佳為環氧乙烷改質二新戊四醇六(甲基)丙烯酸酯、環氧丙烷改質二新戊四醇六(甲基)丙烯酸酯等。The alkylene oxide-modified ionizing radiation compound is not particularly limited, and the ionizing radiation polymerizable compounds listed in the column of the resin of the
＜聚矽氧系化合物＞
聚矽氧系化合物係用以使第2樹脂層32相對於第1樹脂層22容易剝離之成分。藉由第2樹脂層32含有聚矽氧系化合物，聚矽氧系化合物於第1樹脂層22之與第2樹脂層32之界面附近偏存，因此可於第1樹脂層22與第2樹脂層32之間之界面容易地剝離保護膜30。＜Polysiloxane compound＞
The polysiloxane-based compound is a component for making the
聚矽氧系化合物亦可為具有聚合性官能基者。於使用具有聚合性官能基之聚矽氧系化合物作為聚矽氧系化合物之情形時，聚矽氧系化合物係於第2樹脂層32層中以與樹脂鍵結之狀態存在。The polysiloxane-based compound may also have a polymerizable functional group. When a polysiloxane-based compound having a polymerizable functional group is used as the polysiloxane-based compound, the polysiloxane-based compound exists in a state of being bonded to the resin in the
作為聚矽氧系化合物，並無特別限定，可使用與於第1樹脂層22之欄中所說明之聚矽氧系化合物相同者。It does not specifically limit as a polysiloxane type compound, The thing similar to the polysiloxane type compound demonstrated in the column of the
聚矽氧系化合物之含量較佳為相對於游離輻射聚合性化合物100質量份為0.05質量份以上且1質量份以下。若聚矽氧系化合物之含量為0.05質量份以上，則可於第1樹脂層22與第2樹脂層32之界面容易地剝離保護膜30，又，若聚矽氧系化合物之含量為1質量份以下，則可於第1樹脂層22與第2樹脂層32之界面確保所需之密接性。The content of the polysiloxane-based compound is preferably 0.05 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the ionizing radiation polymerizable compound. If the content of the polysiloxane-based compound is 0.05 parts by mass or more, the
＜氟系化合物＞
氟系化合物係用以使第2樹脂層32相對於第1樹脂層22容易剝離之成分。藉由第2樹脂層32含有氟系化合物，氟系化合物於第1樹脂層22之與第2樹脂層32之界面附近偏存，因此可於第1樹脂層22與第2樹脂層32之間之界面容易地剝離保護膜30。<Fluorine compound>
The fluorine-based compound is a component for easily peeling the
氟系化合物亦可為具有聚合性官能基者。於使用具有聚合性官能基之氟系化合物作為氟系化合物之情形時，氟系化合物係於第2樹脂層32層中以與樹脂鍵結之狀態存在。The fluorine-based compound may also have a polymerizable functional group. When a fluorine-based compound having a polymerizable functional group is used as the fluorine-based compound, the fluorine-based compound is present in the
作為氟系化合物，並無特別限定，可使用與於第1樹脂層22之欄中所說明之氟系化合物相同者。It does not specifically limit as a fluorine type compound, The thing similar to the fluorine type compound demonstrated in the column of the
氟系化合物之含量較佳為相對於游離輻射聚合性化合物100質量份為0.05質量份以上且1質量份以下。若氟系化合物之含量為0.05質量份以上，則可於第1樹脂層22與第2樹脂層32之界面容易地剝離保護膜30，又，若氟系化合物之含量為1質量份以下，則可於第1樹脂層22與第2樹脂層32之界面確保所需之密接性。The content of the fluorine-based compound is preferably 0.05 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the ionizing radiation polymerizable compound. When the content of the fluorine-based compound is 0.05 parts by mass or more, the
＜抗靜電劑＞ 作為抗靜電劑，並無特別限定，例如可使用四級銨鹽等離子傳導型抗靜電劑或導電性聚合物等電子傳導型抗靜電劑。＜Antistatic agent＞ Although it does not specifically limit as an antistatic agent, For example, an ion-conductive type antistatic agent, such as a quaternary ammonium salt, or an electron-conductive type antistatic agent, such as a conductive polymer, can be used.
＜＜第2功能層＞＞
第2功能層33之表面33A成為附保護膜之積層體10之背面10B。第2功能層33如上所述係具有低聚物析出抑制功能之低聚物析出抑制層。藉由設置作為低聚物析出抑制層之第2功能層33，可抑制低聚物成分自第2基材31之析出，因此可抑制附保護膜之積層體10之霧度值之上升，可確保透明性。＜＜Second functional layer＞＞
The surface 33A of the 2nd
第2功能層33並無特別限定，可由樹脂構成。作為構成第2功能層33之樹脂，例如可使用與構成第1樹脂層22之樹脂相同之樹脂。又，於第2功能層33為抗靜電層之情形時，第2功能層33包含樹脂與抗靜電劑。作為抗靜電劑，可使用與於第2樹脂層32之欄中所說明之抗靜電劑相同之抗靜電劑。The second
第2功能層33之膜厚較佳為0.5 μm以上且10 μm以下。若第2功能層33之膜厚為0.5 μm以上，則可進一步抑制低聚物自第2基材31之析出，又，若為10 μm以下，則可抑制捲曲之產生。第2功能層33之膜厚可藉由與第1功能層23之膜厚相同之方法進行測定。The film thickness of the second
＜＜＜其他附保護膜之積層體＞＞＞
附保護膜之積層體10於第1基材21之與第1面21A為相反側之面即第2面21B具備第1功能層23，但亦可為如圖3所示般，於第1基材21之第2面21B不具備第1功能層之附保護膜之積層體40。附保護膜之積層體40除了具備於第1基材21之第2面21B不具備第1功能層的積層體50以外，與附保護膜之積層體10相同，故而此處省略說明。＜＜＜Other laminates with protective film＞＞＞
The
附保護膜之積層體10具備未經圖案化之固體膜之第1功能層23，亦可為如圖4及圖5所示般，具備第1功能層71經圖案化之積層體70之附保護膜之積層體60。第1功能層71設置於第1基材21之與第1面21A為相反側之面即第2面21B側。第1功能層71具有藉由圖案化而具有特定之形狀之導電部72及非導電部73。第1功能層71及導電部72之膜厚與第1功能層23之膜厚相同。The laminate 10 with the protective film includes the first
＜＜導電部＞＞
導電部72係顯示導電性之部分，與第1功能層23同樣地由透光性樹脂24與導電性纖維25構成。導電部72例如係作為投影型靜電電容方式之觸控面板之X方向之電極發揮功能者，如圖5所示，具備沿X方向延伸之多個感測器部72A及連結於各感測器部72A之端子部（未圖示）。各感測器部72A設置於作為可檢測觸控位置之區域的矩形狀之有效區域內，端子部設置於鄰接於有效區域且自四側呈周狀包圍有效區域之區域即無效區域內。＜＜Conductive part＞＞
The
各感測器部72A具有呈直線狀延伸之線部72B及自線部72B膨出之膨出部72C。於圖5中，線部72B沿與感測器部72A之排列方向交叉之方向呈直線狀延伸。膨出部72C係自線部72B膨出之部分。因此，各感測器部72A之寬度於設置有膨出部72C之部分變粗。於本實施形態中，膨出部72C具有俯視呈大致正方形狀之外輪廓。再者，膨出部72C並不限於俯視呈大致正方形狀，亦可為菱形狀、或條狀。Each
＜＜非導電部＞＞
非導電部73係位於導電部72間且不顯示導電性之部分。非導電部73實質上不含導電性纖維25。本說明書中之「實質上」係指即便於因金屬離子自導電部之遷移而使金屬離子析出至非導電部側之情形時，只要為未產生導電部間之電性短路之程度，則亦可含有若干導電性纖維。非導電部73較佳為完全不含導電性纖維25。再者，藉由利用雷射光（例如紅外線雷射）使導電性纖維25昇華，或藉由利用光蝕刻法之濕式蝕刻將導電性纖維25自非導電部73去除時，有殘留構成導電性纖維25之導電性材料之虞，由於該導電性材料並非纖維狀，故而不視為導電性纖維。＜＜Non-conductive portion＞＞
The
關於非導電部73之膜厚，由於非導電部73與導電部72一體地設置，故而無論於在第1基材上設置有基底層之情形時，抑或未設置基底層之情形時，均較佳為未達300 nm。本說明書中之「非導電部之膜厚」係指直接積層於積層有藉由剖面觀察判斷為包含導電性纖維之導電部之層的基盤部分（第1基材、基底層等）之部分。非導電部73之膜厚設為藉由與第1功能層23之膜厚相同之方法測定者。非導電部73之膜厚之上限依序進而較佳為145 nm以下、140 nm以下、120 nm、110 nm以下、80 nm以下、50 nm以下（數值越小越佳）。又，非導電部73之膜厚之下限較佳為10 nm以上。非導電部73之膜厚設為藉由與第1功能層23之膜厚相同之方法測定者。As for the film thickness of the
非導電部73係由透光性樹脂24構成。再者，非導電部73亦可具有空腔部，該空腔部係藉由使導電性纖維25昇華而形成，且不存在導電性纖維。於此情形時，於形成非導電部73時因導電性纖維25昇華而穿破應作為非導電部73之區域而釋出至外部，因此非導電部73之表面變得粗面化。非導電部73之透光性樹脂24係與第1功能層23之透光性樹脂24相同，故而此處省略說明。The
附保護膜之積層體10於第2基材31之第2面31B具備第2功能層33，如圖6所示，亦可為不具備第2功能層33之附保護膜之積層體80。附保護膜之積層體80除具備不具備第2功能層之保護膜90以外，與附保護膜之積層體10相同，故而此處省略說明。The
附保護膜之積層體10於第2基材31之第2面31B具備第2功能層33，如圖7所示，亦可為於第2基材31與第2樹脂層32之間具備第2功能層111之附保護膜之積層體100。附保護膜之積層體100除具備於第2基材31與第2樹脂層32之間具備第2功能層111的保護膜110以外，與附保護膜之積層體10相同，故而此處省略說明。The
＜＜附保護膜之積層體之製造方法＞＞
附保護膜之積層體10例如可藉由以下方式製作。首先，如圖8（A）所示，準備積層體20，該積層體20具備：第1基材21；第1樹脂層22，其設置於第1基材21之第1面21A側，且膜厚方向的剖面之壓痕硬度為100 MPa以上；及第1功能層23，其設置於第1基材21之第2面21B側。<<Manufacturing method of laminated body with protective film>>
The
積層體20例如可藉由以下方式獲得。具體而言，首先，於第1基材21之第1面21A塗佈第1樹脂層用組成物，使其乾燥而形成第1樹脂層用組成物之塗膜。The
第1樹脂層用組成物含有聚合性化合物，此外，亦可視需要添加上述粒子、上述聚矽氧系化合物、溶劑、聚合起始劑。進而，於第1樹脂層用組成物中，依照提高第1樹脂層之硬度、抑制硬化收縮、或控制折射率等目的，亦可添加先前公知之分散劑、界面活性劑、矽烷偶合劑、固著劑、防著色劑、著色劑（顏料、染料）、消泡劑、難燃劑、紫外線吸收劑、接著賦予劑、聚合抑制劑、抗氧化劑、表面改質劑、易滑劑等。The composition for a 1st resin layer contains a polymerizable compound, and the said particle|grain, the said polysiloxane type compound, a solvent, and a polymerization initiator may be added as needed. Further, in the composition for the first resin layer, for the purpose of increasing the hardness of the first resin layer, suppressing curing shrinkage, or controlling the refractive index, a conventionally known dispersant, surfactant, silane coupling agent, solid Adhesives, anti-coloring agents, coloring agents (pigments, dyes), defoaming agents, flame retardants, ultraviolet absorbers, adhesion agents, polymerization inhibitors, antioxidants, surface modifiers, slip agents, etc.
＜溶劑＞ 作為溶劑，例如可列舉：醇類（甲醇、乙醇、丙醇、異丙醇、正丁醇、二級丁醇、三級丁醇、苄醇、PGME、乙二醇等）、酮類（丙酮、甲基乙基酮（MEK）、環己酮、甲基異丁基酮、二丙酮醇、環庚酮、二乙基酮等）、醚類（1,4-二口咢烷、二口咢口柬、二異丙醚二口咢烷、四氫呋喃等）、脂肪族烴類（己烷等）、脂環式烴類（環己烷等）、芳香族烴類（甲苯、二甲苯等）、鹵化碳類（二氯甲烷、二氯乙烷等）、酯類（甲酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乳酸乙酯等）、賽珞蘇類（甲基賽珞蘇、乙基賽珞蘇、丁基賽珞蘇等）、乙酸賽珞蘇類、亞碸類（二甲基亞碸等）、醯胺類（二甲基甲醯胺、二甲基乙醯胺等）、或該等之混合物。＜Solvent＞ Examples of the solvent include alcohols (methanol, ethanol, propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, benzyl alcohol, PGME, ethylene glycol, etc.), ketones (acetone , methyl ethyl ketone (MEK), cyclohexanone, methyl isobutyl ketone, diacetone alcohol, cycloheptanone, diethyl ketone, etc.), ethers (1,4-diethyl ketone, diethyl ketone, etc.) encapsulation, diisopropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.) , halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl lactate, etc.), selenium ( Methyl selenium, ethyl selenium, butyl selenium, etc.), acetate selenium, sulfites (dimethyl sulfoxide, etc.), amides (dimethylformamide, dimethyl sulfoxide, etc.) methylacetamide, etc.), or a mixture of these.
＜聚合起始劑＞ 聚合起始劑係藉由光或熱而分解而產生自由基或離子種，從而使聚合性化合物之聚合（交聯）開始或進行之成分。第1樹脂層用組成物所使用之聚合起始劑可列舉：光聚合起始劑（例如光自由基聚合起始劑、光陽離子聚合起始劑、光陰離子聚合起始劑）或熱聚合起始劑（例如熱自由基聚合起始劑、熱陽離子聚合起始劑、熱陰離子聚合起始劑）、或該等之混合物。<Polymerization initiator> The polymerization initiator is a component that decomposes by light or heat to generate radicals or ionic species, thereby starting or progressing the polymerization (crosslinking) of the polymerizable compound. Examples of the polymerization initiator used in the composition for the first resin layer include photopolymerization initiators (eg, photoradical polymerization initiators, photocationic polymerization initiators, and photoanionic polymerization initiators) or thermal polymerization initiators. Initiators (eg, thermal radical polymerization initiators, thermal cationic polymerization initiators, thermal anionic polymerization initiators), or mixtures of these.
第1樹脂層用組成物中之聚合起始劑之含量較佳為相對於聚合性化合物100質量份為0.5質量份以上且10.0質量份以下。藉由將聚合起始劑之含量設為該範圍內，可充分地保持硬塗性能且可抑制硬化阻礙。The content of the polymerization initiator in the composition for the first resin layer is preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the polymerizable compound. By setting the content of the polymerization initiator to be within this range, hard coating performance can be sufficiently maintained and hardening inhibition can be suppressed.
作為塗佈第1樹脂層用組成物之方法，可列舉旋轉塗佈、浸漬法、噴霧法、斜板式（slide）塗佈法、棒式塗佈法、輥塗法、凹版法、模嘴（die）塗佈法等公知之塗佈方法。Examples of methods for applying the composition for the first resin layer include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure, and die ( A known coating method such as die) coating method.
繼而，藉由對塗膜照射紫外線等游離輻射或進行加熱，使聚合性化合物聚合（交聯），使塗膜硬化而形成第1樹脂層22。Next, by irradiating or heating the coating film with ionizing radiation such as ultraviolet rays, the polymerizable compound is polymerized (crosslinked), the coating film is cured, and the
於使用紫外線作為使第1樹脂層用組成物硬化時之游離輻射之情形時，可利用自超高壓水銀燈、高壓水銀燈、低壓水銀燈、碳弧、氙弧、金屬鹵化物燈等發出之紫外線等。又，作為紫外線之波長，可使用190～380 nm之波長區域。作為電子束源之具體例，可列舉柯克勞夫-沃耳吞（Cockcroft-Walton）型、凡德格拉夫（Van de Graaff）型、共振變壓器型、絕緣芯變壓器型、或直線型、高頻高壓（dynamitron）型、高頻型等各種電子束加速器。In the case of using ultraviolet rays as ionizing radiation for curing the composition for the first resin layer, ultraviolet rays emitted from ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, metal halide lamps, etc. can be used. Moreover, as a wavelength of an ultraviolet-ray, the wavelength range of 190-380 nm can be used. As a specific example of the electron beam source, a Cockcroft-Walton type, a Van de Graaff type, a resonance transformer type, an insulated core transformer type, or a linear type, a high Various electron beam accelerators such as high frequency high voltage (dynamitron) type and high frequency type.
於在第1基材21之第1面21A上形成第1樹脂層22後，於第1基材21之第2面21B塗佈含有導電性纖維25及有機系分散介質之導電性纖維分散液，使其乾燥而於第2面21B配置多個導電性纖維25。有機系分散介質亦可含有未達10質量%之水。再者，導電性纖維分散液除含有導電性纖維25及有機系分散介質以外，亦可含有熱塑性樹脂或由聚合性化合物所構成之樹脂成分。但是，若導電性纖維分散液中之樹脂成分之含量過多，則樹脂成分進入至導電性纖維間，第1功能層之導通劣化，因此必須調節樹脂成分之含量。本說明書中之「樹脂成分」之概念除包含樹脂（但是，不包含用以防止覆蓋導電性纖維之導電性纖維彼此之自熔接或與環境中之物質之反應等之於導電性纖維合成時形成於導電性纖維周邊之構成有機保護層之樹脂（例如聚乙烯吡咯啶酮等））以外，亦包含如聚合性化合物般聚合而可成為樹脂之成分。又，導電性纖維分散液中之樹脂成分係於形成第1功能層23後構成透光性樹脂24之一部分者。After the
作為有機系分散介質，並無特別限定，較佳為親水性有機系分散介質。作為有機系分散介質，例如可列舉：己烷等飽和烴類；甲苯、二甲苯等芳香族烴類；甲醇、乙醇、丙醇、丁醇等醇類；丙酮、甲基乙基酮（MEK）、甲基異丁基酮、二異丁基酮等酮類；乙酸乙酯、乙酸丁酯等酯類；四氫呋喃、二口咢烷、二乙基醚等醚類；N,N-二甲基甲醯胺、N-甲基吡咯啶酮（NMP）、N,N-二甲基乙醯胺等醯胺類；氯化乙烯、氯苯等鹵代烴等。於該等中，就導電性纖維分散液之穩定性之觀點而言，較佳為醇類。The organic dispersion medium is not particularly limited, but a hydrophilic organic dispersion medium is preferred. Examples of the organic dispersion medium include saturated hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, propanol, and butanol; acetone and methyl ethyl ketone (MEK) , methyl isobutyl ketone, diisobutyl ketone and other ketones; ethyl acetate, butyl acetate and other esters; tetrahydrofuran, dioxane, diethyl ether and other ethers; N,N-dimethyl ether Carboxamides, N-methylpyrrolidone (NMP), N,N-dimethylacetamide and other amides; chlorinated ethylene, chlorobenzene and other halogenated hydrocarbons, etc. Among these, alcohols are preferable from the viewpoint of the stability of the conductive fiber dispersion liquid.
作為導電性纖維分散液中可含有之熱塑性樹脂，可列舉：丙烯酸系樹脂；聚對苯二甲酸乙二酯等聚酯系樹脂；聚苯乙烯、聚乙烯基甲苯、聚乙烯基二甲苯、聚醯亞胺、聚醯胺、聚醯胺醯亞胺等芳香族系樹脂；聚胺酯系樹脂；環氧系樹脂；聚烯烴系樹脂；丙烯腈-丁二烯-苯乙烯共聚物（ABS）；纖維素系樹脂；聚氯乙烯系樹脂；聚乙酸酯系樹脂；聚降莰烯系樹脂；合成橡膠；氟系樹脂等。Examples of thermoplastic resins that can be contained in the conductive fiber dispersion include: acrylic resins; polyester resins such as polyethylene terephthalate; polystyrene, polyvinyltoluene, polyvinylxylene, polyvinyl Aromatic resins such as amide, polyamide, and polyamide amide; polyurethane resin; epoxy resin; polyolefin resin; acrylonitrile-butadiene-styrene copolymer (ABS); fiber Polyvinyl chloride resin; Polyacetate resin; Polynorbornene resin; Synthetic rubber; Fluorine resin, etc.
作為導電性纖維分散液中可含有之聚合性化合物，可列舉與於第1樹脂層22之欄中所說明之聚合性化合物相同者，故而此處省略說明。As the polymerizable compound that can be contained in the conductive fiber dispersion liquid, the same ones as those described in the column of the
於在第1基材21上配置多個導電性纖維25後，塗佈含有聚合性化合物及溶劑之透光性樹脂用組成物，使其乾燥而形成透光性樹脂用組成物之塗膜。透光性樹脂用組成物含有聚合性化合物及溶劑，此外，亦可視需要添加聚合起始劑。After arranging a plurality of
繼而，藉由對塗膜照射紫外線等游離輻射使聚合性化合物聚合（交聯）而使塗膜硬化，形成透光性樹脂24，從而形成第1功能層23。藉此，形成積層體20。Next, the polymerizable compound is polymerized (cross-linked) by irradiating the coating film with ionizing radiation such as ultraviolet rays, the coating film is cured, the
另一方面，如圖8（B）所示，於第2基材31之第2面31B塗佈第1功能層用組成物，使其乾燥而形成第2功能層用組成物之塗膜34。繼而，如圖8（C）所示，藉由對塗膜34照射紫外線等游離輻或進行加熱使聚合性化合物聚合（交聯），而使塗膜34硬化，從而形成第2功能層33。On the other hand, as shown in FIG. 8(B) , the composition for the first functional layer is coated on the
繼而，如圖9（A）所示，於第2基材31之面31A塗佈第2樹脂層用組成物，使其乾燥而形成第2樹脂層用組成物之塗膜35。塗膜35之乾燥例如可於40℃以上且150℃以下之溫度進行。再者，於塗膜35之乾燥時亦可不進行加熱。Next, as shown in FIG.9(A), the composition for 2nd resin layers is apply|coated to the
第2樹脂層用組成物包含游離輻射聚合性化合物，較佳為進而包含聚矽氧系化合物。游離輻射聚合性化合物較佳為非環氧烷改質之游離輻射聚合性化合物與環氧烷改質之游離輻射聚合性化合物之混合物。此外，第2樹脂層用組成物亦可視需要包含溶劑、聚合起始劑。The composition for the second resin layer contains an ionizing radiation polymerizable compound, and preferably further contains a polysiloxane-based compound. The ionizing radiation polymerizable compound is preferably a mixture of a non-alkylene oxide-modified ionizing radiation polymerizable compound and an alkylene oxide-modified ionizing radiation polymerizable compound. Moreover, the composition for 2nd resin layers may contain a solvent and a polymerization initiator as needed.
於形成塗膜35後，如圖9（B）所示，以第1樹脂層22與塗膜35接觸之方式使積層體20與塗膜35接觸。繼而，如圖9（C）所示，於使積層體20與塗膜35接觸之狀態下，藉由對塗膜35照射游離輻射而使塗膜35硬化。藉此，形成第2樹脂層32，並且可獲得具有密接於積層體20之可剝離的保護膜30之附保護膜的積層體10。After the
於獲得附保護膜之積層體60之情形時，若於將保護膜貼附於積層體之狀態下使第1功能層圖案化，則可於第1功能層形成導電部及非導電部。圖案化例如可藉由利用雷射光使一部分導電性纖維昇華、或藉由利用光蝕刻法之濕式蝕刻將一部分導電性纖維去除而進行。When the
再者，於上述中，準備具有第1功能層23之積層體20，使保護膜30密接於積層體20，所準備之積層體具備第1基材及第1樹脂層即可，於使保護膜密接於積層體後，亦可於積層體形成第1功能層。Furthermore, in the above, the
＜＜＜附保護膜之積層體之使用方法＞＞＞
附保護膜之積層體10、40、60、80、100例如可以如下方式使用。例如，亦可首先對附保護膜之積層體10、40、60、80、100進行搬送步驟及加工步驟之至少任一步驟，其後進行剝離保護膜30、90、110之剝離步驟。＜＜＜How to use the laminated body with protective film＞＞＞
The
作為加工步驟，並無特別限定，可列舉圖案化步驟及/或金屬配線形成步驟。圖案化步驟係將第1功能層圖案化為特定之形狀之步驟，金屬配線形成步驟係於經圖案化之第1功能層形成金屬配線之步驟。例如於使用附保護膜之積層體10之情形時，藉由與附保護膜之積層體50相同之方法將第1功能層23圖案化為特定之形狀，而形成導電部及非導電部。其後，於經圖案化之第1功能層形成金屬配線。又，於使用附保護膜之積層體40之情形時，由於第1功能層經圖案化，故而於第1功能層形成金屬配線。Although it does not specifically limit as a processing process, A patterning process and/or a metal wiring formation process are mentioned. The patterning step is a step of patterning the first functional layer into a specific shape, and the metal wiring forming step is a step of forming a metal wiring on the patterned first functional layer. For example, when using the
於金屬配線步驟中，例如亦可將如金屬膠之導電性膠以與導電部接觸之方式進行網版印刷，繼而將藉由網版印刷所形成之特定形狀之導電性膠層加熱至150℃左右而獲得金屬配線。又，亦可將具有感光性之導電性膠以與導電部接觸之方式進行塗佈而獲得導電性膠層，藉由光蝕刻技術將導電性膠層圖案化為特定之形狀，將經圖案化為特定之形狀之導電性膠層加熱至150℃左右而獲得金屬配線。In the metal wiring step, for example, conductive paste such as metal paste can also be screen-printed in contact with the conductive portion, and then the conductive paste layer with a specific shape formed by screen printing is heated to about 150°C. And obtain metal wiring. In addition, it is also possible to apply a photosensitive conductive adhesive in contact with the conductive part to obtain a conductive adhesive layer, and pattern the conductive adhesive layer into a specific shape by photolithography technology. Metal wiring is obtained by heating the conductive adhesive layer of a specific shape to about 150°C.
導電性膠較佳為含有選自金、銀、銅、鈀、白金、鋁、鎳之群中之至少1種之膠，於該等中，就獲得低電阻值之觀點而言，較佳為銀膠。The conductive paste is preferably a paste containing at least one selected from the group consisting of gold, silver, copper, palladium, platinum, aluminum, and nickel, and among these, from the viewpoint of obtaining a low resistance value, preferably Silver glue.
根據本實施形態，使具有壓痕硬度為100 MPa以上之第2樹脂層32之保護膜30可剝離地密接於壓痕硬度為100 MPa以上之第1樹脂層22，因此與具有黏著層之保護膜不同，可獲得特定之剖面硬度或表面硬度，且可減小加工製程前後之積層體20、50、70之物性變化。再者，於如黏著層之過於柔軟之層中，即便欲測定壓痕硬度亦無法測定。According to the present embodiment, since the
又，藉由使第2樹脂層32之上述壓痕硬度小於第1樹脂層22，保護膜30側變得富有可撓性。結果為，於對多樣之形態之對象物之貼合步驟中，可良好地防止因保護膜30側之物性起因而於具備第1樹脂層22之積層體10產生龜裂等缺陷。Moreover, by making the said indentation hardness of the
進而，於第2樹脂層之上述壓痕硬度小於第1樹脂層之情形時，有於加熱步驟前後容易於單側發生捲曲、或剝離強度發生變化之情形。於本實施形態中，亦可藉由特意對第2樹脂層32與第1樹脂層22之膜厚設定差而良好地維持加熱步驟前後之捲曲、剝離強度。Furthermore, when the said indentation hardness of a 2nd resin layer is smaller than a 1st resin layer, it may become easy to curl on one side before and after a heating process, or the peeling strength may change. In this embodiment, the curl and peeling strength before and after the heating step can also be well maintained by deliberately setting a difference between the film thicknesses of the
於如金屬配線形成步驟之後續步驟中，若有對附保護膜之積層體加熱之情況，則有保護膜之剝離強度較加熱前上升之傾向。尤其，於使用具有黏著層之保護膜作為保護膜之情形時，加熱後之保護膜之剝離強度較加熱前之剝離強度上升數倍。相對於此，於本實施形態中，由於使用具有壓痕硬度為100 MPa以上之第2樹脂層32之保護膜，故而與具有黏著層之保護膜相比，可抑制加熱後之保護膜30的剝離強度相對於加熱前之保護膜30的剝離強度之上升。In the subsequent steps such as the metal wiring forming step, if the laminated body with the protective film is heated, the peel strength of the protective film tends to be higher than before heating. In particular, when a protective film with an adhesive layer is used as the protective film, the peel strength of the protective film after heating is several times higher than that before heating. On the other hand, in the present embodiment, since the protective film having the
本發明者等人針對乳濁之問題反覆努力研究，結果發現，若使導電層之光漫反射率降低至0.5%，則可抑制乳濁。根據本實施形態，由於積層體20之存在第1功能層23之區域之光漫反射率（SCE）成為0.5%以下，故而可抑制乳濁。The inventors of the present invention have repeatedly studied the problem of opacity, and found that opacification can be suppressed by reducing the light diffuse reflectance of the conductive layer to 0.5%. According to this embodiment, since the light diffuse reflectance (SCE) of the area|region where the 1st
導電性纖維尤其容易因來自LED之光而產生反射，因此若對使用LED元件作為光源之LED圖像顯示裝置使用含有導電性纖維之導電性膜，則容易產生乳濁，於積層體20中可抑制乳濁，因此積層體20可適宜地用於LED圖像顯示裝置。In particular, conductive fibers are likely to be reflected by light from LEDs. Therefore, if a conductive film containing conductive fibers is used for an LED image display device using an LED element as a light source, opacity is likely to occur, and the
本實施形態之附保護膜之積層體之用途並無特別限定，本實施形態之附保護膜之積層體10、40、60、80、100例如能夠於剝離了保護膜30、90、110之積層體20、50、70之狀態下組入至圖像顯示裝置而使用。圖10係本實施形態之圖像顯示裝置之概略構成圖，圖11係本實施形態之觸控面板之示意性俯視圖。再者，於以下之圖像顯示裝置中，例示使用積層體70之例。又，於圖10及圖11中，標註有與圖1相同之符號之構件係與圖1所示之構件相同者，因此省略說明。The use of the laminate with protective film of the present embodiment is not particularly limited, and the laminate with
＜＜＜圖像顯示裝置＞＞＞
如圖10所示，圖像顯示裝置120主要具備：顯示面板130，其用以顯示圖像；背光裝置140，其配置於顯示面板130之背面側；觸控面板150，其配置於較顯示面板130靠觀察者側；及透光性接著層160，其介置於顯示面板130與觸控面板150之間。於本實施形態中，由於顯示面板130為液晶顯示面板，故而圖像顯示裝置120具備背光裝置140，但視顯示面板（顯示元件）之種類，亦可不具備背光裝置140。＜＜＜Image display device＞＞＞
As shown in FIG. 10 , the
＜＜顯示面板＞＞
如圖10所示，顯示面板130具有如下構造，即，自背光裝置140側朝向觀察者側，依序積層有三乙醯纖維素膜（TAC膜）或環烯烴聚合物膜等保護膜131、偏光元件132、保護膜133、透光性黏著層134、顯示元件135、透光性黏著層136、保護膜137、偏光元件138、保護膜139。顯示面板130只要具備顯示元件135即可，亦可不具備保護膜131等。＜＜Display panel＞＞
As shown in FIG. 10 , the
顯示元件135為液晶顯示元件。但是，顯示元件135並不限於液晶顯示元件，例如亦可為使用有機發光二極體（OLED）、無機發光二極體、及/或量子點發光二極體（QLED）之顯示元件。液晶顯示元件係於2片玻璃基材間配置有液晶層、配向膜、電極層、彩色濾光片等而成者。The
＜＜背光裝置＞＞
背光裝置140係自顯示面板130之背面側對顯示面板130照明者。作為背光裝置140，可使用公知之背光裝置，又，背光裝置140可為邊緣照明型或正下方型背光裝置之任一者。＜＜Backlight＞＞
The
＜＜觸控面板＞＞
觸控面板150具備：導電性膜170；積層體70，其配置於較導電性膜170靠觀察者側；覆蓋玻璃等透光性覆蓋構件151，其配置於較積層體70靠觀察者側；透光性黏著層152，其介置於積層體70與導電性膜170之間；及透光性黏著層153，其介置於積層體70與透光性覆蓋構件151之間。＜＜Touch Panel＞＞
The
＜導電性膜＞
導電性膜170成為與積層體70相同之結構。即，如圖10所示，導電性膜170具備：第1基材171；第1樹脂層172，其設置於第1基材171之一面側；及導電層173，其設置於第1基材171之與一面為相反側之面即另一面側。第1基材171係與第1基材21相同者，第1樹脂層172係與第1樹脂層22相同者，故而此處省略說明。＜Conductive film＞
The
導電層173成為與第1功能層71相同之結構，具備多個透光性之導電部174及位於導電部134間之透光性之非導電部175。The
（導電部及非導電部）
導電部174成為與導電部72相同之結構。即，導電部174係由透光性樹脂及配置於透光性樹脂中之導電性纖維構成。非導電部175係由透光性樹脂構成，實質上不含導電性纖維。(Conductive part and non-conductive part)
The
導電部174係作為投影型靜電電容方式之觸控面板之Y方向之電極發揮功能者，如圖11所示，具備多個感測器部174A及連結於各感測器部174A之端子部（未圖示）。感測器部174A成為與感測器部72A相同之構造，但於Y方向延伸。The
＜透光性黏著層＞
透光性黏著層134、136例如可列舉如OCA（Optical Clear Adhesive）之黏著片材。亦可使用透光性接著層代替透光性黏著層134、136。<Translucent adhesive layer>
The light-transmitting
＜＜透光性接著層＞＞
透光性接著層160介置於顯示面板130與觸控面板150之間，且接著於顯示面板130與觸控面板150之兩者。藉此，將顯示面板130與觸控面板150固定。透光性接著層160例如由如OCR（Optically Clear Resin）之含有聚合性化合物之液狀硬化性接著層用組成物之硬化物構成。<<Translucent Adhesive Layer>>
The light-transmitting
透光性接著層160之膜厚較佳為10 μm以上且50 μm以下。若透光性接著層160之膜厚為10 μm以上，則不會過薄，因此不易產生異物之嚙入或階差追隨不足等異常，又，若透光性接著層160之膜厚為150 μm以下，則可實現製造成本之降低。透光性接著層160之膜厚可藉由與第1基材21之厚度相同之方法進行測定。亦可使用透光性黏著層代替透光性接著層160。
[實施例]The film thickness of the light-transmitting
為了詳細地說明本發明，以下列舉實施例進行說明，但本發明並不限定於該等記載。In order to demonstrate this invention in detail, an Example is given and demonstrated below, but this invention is not limited to these descriptions.
＜硬塗層用組成物之製備＞ 以成為下述所示之組成之方式摻合各成分，獲得硬塗層用組成物。 （硬塗層用組成物1） ・新戊四醇三丙烯酸酯與新戊四醇四丙烯酸酯之混合物（產品名「KAYARAD PET-30」，日本化藥股份有限公司製造）：25質量份 ・聚合起始劑（產品名「Irgacure（註冊商標）184」，BASF JAPAN公司製造）：4質量份 ・聚矽氧系化合物（產品名「Seikabeam 10-28（MB）」，大日精化工業股份有限公司製造）：0.1質量份 ・甲基異丁基酮（MIBK）：100質量份<Preparation of composition for hard coating> Each component was blended so that it might become the composition shown below, and the composition for hard-coat layers was obtained. (Composition 1 for hard coating) ・Mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 25 parts by mass ・Polymerization initiator (product name "Irgacure (registered trademark) 184", manufactured by BASF JAPAN): 4 parts by mass ・Polysiloxane-based compound (product name "Seikabeam 10-28 (MB)", manufactured by Dainisei Chemical Industry Co., Ltd.): 0.1 part by mass ・Methyl isobutyl ketone (MIBK): 100 parts by mass
（硬塗層用組成物2） ・環氧乙烷改質雙酚A二丙烯酸酯（產品名「BPE-20」，第一工業製藥股份有限公司製造，2官能）：25質量份 ・新戊四醇三丙烯酸酯與新戊四醇四丙烯酸酯之混合物（產品名「KAYARAD PET-30」，日本化藥股份有限公司製造）：25質量份 ・聚合起始劑（產品名「Irgacure（註冊商標）184」，BASF JAPAN公司製造）：4質量份 ・聚矽氧系化合物（產品名「Seikabeam 10-28（MB）」，大日精化工業股份有限公司製造）：0.1質量份 ・甲基異丁基酮（MIBK）：100質量份(Composition 2 for hard coating) ・Ethylene oxide-modified bisphenol A diacrylate (product name "BPE-20", manufactured by Daiichi Kogyo Co., Ltd., bifunctional): 25 parts by mass ・Mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 25 parts by mass ・Polymerization initiator (product name "Irgacure (registered trademark) 184", manufactured by BASF JAPAN): 4 parts by mass ・Polysiloxane-based compound (product name "Seikabeam 10-28 (MB)", manufactured by Dainisei Chemical Industry Co., Ltd.): 0.1 part by mass ・Methyl isobutyl ketone (MIBK): 100 parts by mass
（硬塗層用組成物3） ・環氧乙烷改質雙酚A二丙烯酸酯（產品名「BPE-20」，第一工業製藥股份有限公司製造，2官能）：25質量份 ・新戊四醇三丙烯酸酯與新戊四醇四丙烯酸酯之混合物（產品名「KAYARAD PET-30」，日本化藥股份有限公司製造）：10質量份 ・丙烯酸胺酯預聚物（產品名「UN-350」，根上工業股份有限公司製造，重量平均分子量12500，2官能）：15質量份 ・聚合起始劑（產品名「Irgacure（註冊商標）184」，BASF JAPAN公司製造）：4質量份 ・聚矽氧系化合物劑（產品名「Seikabeam 10-28（MB）」，大日精化工業股份有限公司製造）：0.1質量份 ・甲基異丁基酮（MIBK）：50質量份(Composition 3 for hard coating) ・Ethylene oxide-modified bisphenol A diacrylate (product name "BPE-20", manufactured by Daiichi Kogyo Co., Ltd., bifunctional): 25 parts by mass ・Mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 10 parts by mass ・Urethane acrylate prepolymer (product name "UN-350", manufactured by Negami Kogyo Co., Ltd., weight average molecular weight 12,500, bifunctional): 15 parts by mass ・Polymerization initiator (product name "Irgacure (registered trademark) 184", manufactured by BASF JAPAN): 4 parts by mass ・Polysiloxane-based compound agent (product name "Seikabeam 10-28 (MB)", manufactured by Dainisei Chemical Industry Co., Ltd.): 0.1 part by mass ・Methyl isobutyl ketone (MIBK): 50 parts by mass
（硬塗層用組成物4） ・環氧乙烷改質雙酚A二丙烯酸酯（產品名「BPE-20」，第一工業製藥股份有限公司製造，2官能）：50質量份 ・聚合起始劑（產品名「Irgacure（註冊商標）184」，BASF JAPAN公司製造）：4質量份 ・聚矽氧系化合物（產品名「Seikabeam 10-28（MB）」，大日精化工業股份有限公司製造）：0.1質量份 ・甲基異丁基酮（MIBK）：100質量份(Composition 4 for hard coating) ・Ethylene oxide modified bisphenol A diacrylate (product name "BPE-20", manufactured by Daiichi Kogyo Co., Ltd., bifunctional): 50 parts by mass ・Polymerization initiator (product name "Irgacure (registered trademark) 184", manufactured by BASF JAPAN): 4 parts by mass ・Polysiloxane-based compound (product name "Seikabeam 10-28 (MB)", manufactured by Dainisei Chemical Industry Co., Ltd.): 0.1 part by mass ・Methyl isobutyl ketone (MIBK): 100 parts by mass
（硬塗層用組成物5） ・環氧乙烷改質雙酚A二丙烯酸酯（產品名「BPE-20」，第一工業製藥股份有限公司製造，2官能）：35質量份 ・新戊四醇三丙烯酸酯與新戊四醇四丙烯酸酯之混合物（產品名「KAYARAD PET-30」，日本化藥股份有限公司製造）：15質量份 ・聚合起始劑（產品名「Irgacure（註冊商標）184」，BASF JAPAN公司製造）：4質量份 ・聚矽氧系化合物（產品名「Seikabeam 10-28（MB）」，大日精化工業股份有限公司製造）：0.1質量份 ・甲基異丁基酮（MIBK）：100質量份(Composition 5 for hard coating) ・Ethylene oxide-modified bisphenol A diacrylate (product name "BPE-20", manufactured by Daiichi Kogyo Co., Ltd., bifunctional): 35 parts by mass ・Mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 15 parts by mass ・Polymerization initiator (product name "Irgacure (registered trademark) 184", manufactured by BASF JAPAN): 4 parts by mass ・Polysiloxane-based compound (product name "Seikabeam 10-28 (MB)", manufactured by Dainisei Chemical Industry Co., Ltd.): 0.1 part by mass ・Methyl isobutyl ketone (MIBK): 100 parts by mass
（硬塗層用組成物6） ・環氧乙烷改質雙酚A二丙烯酸酯（產品名「BPE-20」，第一工業製藥股份有限公司製造，2官能）：25質量份 ・新戊四醇三丙烯酸酯與新戊四醇四丙烯酸酯之混合物（產品名「KAYARAD PET-30」，日本化藥股份有限公司製造）：25質量份 ・聚合起始劑（產品名「Irgacure（註冊商標）184」，BASF JAPAN公司製造）：4質量份 ・氟系化合物（產品名「F-477」，DIC股份有限公司製造）：0.1質量份 ・甲基異丁基酮（MIBK）：50質量份(Composition 6 for hard coating) ・Ethylene oxide-modified bisphenol A diacrylate (product name "BPE-20", manufactured by Daiichi Kogyo Co., Ltd., bifunctional): 25 parts by mass ・Mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 25 parts by mass ・Polymerization initiator (product name "Irgacure (registered trademark) 184", manufactured by BASF JAPAN): 4 parts by mass ・Fluorine-based compound (product name "F-477", manufactured by DIC Co., Ltd.): 0.1 part by mass ・Methyl isobutyl ketone (MIBK): 50 parts by mass
（硬塗層用組成物7）
・環氧乙烷改質雙酚A二丙烯酸酯（產品名「BPE-20」，第一工業製藥股份有限公司製造，2官能）：10質量份
・新戊四醇三丙烯酸酯與新戊四醇四丙烯酸酯之混合物（產品名「KAYARAD PET-30」，日本化藥股份有限公司製造）：25質量份
・抗靜電硬塗劑（產品名「Yupimer H-6500」，Mitsubishi Chemical股份有限公司製造）：15質量份
・聚合起始劑（產品名「Irgacure（註冊商標）184」，BASF JAPAN公司製造）：4質量份
・聚矽氧系化合物（產品名「Seikabeam 10-28（MB）」，大日精化工業股份有限公司製造）：0.1質量份
・甲基異丁基酮（MIBK）：100質量份(
（硬塗層用組成物8） ・新戊四醇三丙烯酸酯與新戊四醇四丙烯酸酯之混合物（產品名「KAYARAD PET-30」，日本化藥股份有限公司製造）：50質量份 ・聚合起始劑（產品名「Irgacure（註冊商標）184」，BASF JAPAN公司製造）：4質量份 ・聚矽氧系化合物（產品名「Seikabeam 10-28（MB）」，大日精化工業股份有限公司製造）：0.1質量份 ・甲基異丁基酮（MIBK）：50質量份(Composition 8 for hard coating) ・Mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 50 parts by mass ・Polymerization initiator (product name "Irgacure (registered trademark) 184", manufactured by BASF JAPAN): 4 parts by mass ・Polysiloxane-based compound (product name "Seikabeam 10-28 (MB)", manufactured by Dainisei Chemical Industry Co., Ltd.): 0.1 part by mass ・Methyl isobutyl ketone (MIBK): 50 parts by mass
（硬塗層用組成物9） ・環氧乙烷改質雙酚A二丙烯酸酯（產品名「BPE-20」，第一工業製藥股份有限公司製造，2官能）：25質量份 ・新戊四醇三丙烯酸酯與新戊四醇四丙烯酸酯之混合物（產品名「KAYARAD PET-30」，日本化藥股份有限公司製造）：25質量份 ・聚合起始劑（產品名「Irgacure（註冊商標）184」，BASF JAPAN公司製造）：4質量份 ・甲基異丁基酮（MIBK）：100質量份(Composition 9 for hard coating) ・Ethylene oxide-modified bisphenol A diacrylate (product name "BPE-20", manufactured by Daiichi Kogyo Co., Ltd., bifunctional): 25 parts by mass ・Mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate (product name "KAYARAD PET-30", manufactured by Nippon Kayaku Co., Ltd.): 25 parts by mass ・Polymerization initiator (product name "Irgacure (registered trademark) 184", manufactured by BASF JAPAN): 4 parts by mass ・Methyl isobutyl ketone (MIBK): 100 parts by mass
＜低聚物析出抑制層用組成物之製備＞ 以成為下述所示之組成之方式摻合各成分，獲得低聚物析出抑制層用組成物。 （低聚物析出抑制層用組成物1） ・甲苯二異氰酸酯（產品名「Coronate T-80」，Tosoh股份有限公司製造）：100質量份 ・丙烯酸多元醇（產品名「6KW-700」，Taisei Fine Chemical股份有限公司製造）：20質量份<Preparation of composition for oligomer precipitation suppression layer> Each component was blended so that it might become the composition shown below, and the composition for oligomer deposition suppression layers was obtained. (Composition 1 for Oligomer Precipitation Suppression Layer) ・Toluene diisocyanate (product name "Coronate T-80", manufactured by Tosoh Co., Ltd.): 100 parts by mass ・Acrylic polyol (product name "6KW-700", manufactured by Taisei Fine Chemical Co., Ltd.): 20 parts by mass
＜抗靜電層用組成物之製備＞ 以成為下述所示之組成之方式摻合各成分，獲得抗靜電層用組成物。 （抗靜電層用組成物1） ・甲苯二異氰酸酯（產品名「Coronate T-80」，Tosoh股份有限公司製造）：100質量份 ・丙烯酸多元醇（產品名「6KW-700」，Taisei Fine Chemical股份有限公司製造）：20質量份 ・聚(3,4-乙二氧基噻吩)/聚苯乙烯磺酸（PEDOT/PSS，抗靜電劑，荒川化學工業股份有限公司製造）：0.2質量份<Preparation of composition for antistatic layer> Each component was blended so that it might become the composition shown below, and the composition for antistatic layers was obtained. (Composition 1 for antistatic layer) ・Toluene diisocyanate (product name "Coronate T-80", manufactured by Tosoh Co., Ltd.): 100 parts by mass ・Acrylic polyol (product name "6KW-700", manufactured by Taisei Fine Chemical Co., Ltd.): 20 parts by mass ・Poly(3,4-ethylenedioxythiophene)/polystyrenesulfonic acid (PEDOT/PSS, antistatic agent, manufactured by Arakawa Chemical Industry Co., Ltd.): 0.2 parts by mass
＜銀奈米線分散液之製備＞ （銀奈米線分散液1） 使用乙二醇（EG）作為還原劑，使用聚乙烯吡咯啶酮（PVP：平均分子量130萬，Sigma-Aldrich公司製造）作為有機保護劑，將下述所示之核形成步驟與粒子生長步驟分離而進行粒子形成，製備銀奈米線分散液1。<Preparation of silver nanowire dispersion> (Silver Nanowire Dispersion Liquid 1) Using ethylene glycol (EG) as a reducing agent and polyvinylpyrrolidone (PVP: average molecular weight: 1.3 million, manufactured by Sigma-Aldrich) as an organic protective agent, the nucleation step and the particle growth step shown below were separated Then, particle formation was performed to prepare a silver nanowire dispersion liquid 1 .
1.核形成步驟
於反應容器內攪拌保持為160℃之EG液100 mL，並同時於一定流量歷時1分鐘添加硝酸銀之EG溶液（硝酸銀濃度：1.0莫耳/L）2.0 mL。其後，於160℃保持10分鐘，並同時使銀離子還原而形成銀之核粒子。確認到反應液呈現出源於奈米大小之銀微粒子之表面電漿子吸收的黃色，銀離子被還原而形成銀之微粒子（核粒子）。繼而，於一定流量歷時10分鐘添加PVP之EG溶液（PVP濃度：3.0×10-1
莫耳/L）10.0 mL。1.
2.粒子生長步驟 將結束上述核形成步驟後之含有核粒子之反應液進行攪拌並保持為160℃，使用雙噴法於一定流量歷時120分鐘添加硝酸銀之EG溶液（硝酸銀濃度：1.0×10-1 莫耳/L）100 mL與PVP之EG溶液（PVP濃度：3.0×10-1 莫耳/L）100 mL。於該粒子生長步驟中，每30分鐘採取反應液並利用電子顯微鏡進行確認，結果核形成步驟中所形成之核粒子隨時間經過而以線狀之形態生長，未觀察到粒子生長步驟中之新的微粒子之生成。2. In the particle growth step, the reaction solution containing the nucleus particles after the above-mentioned nucleus formation step was stirred and kept at 160°C, and the EG solution of silver nitrate (silver nitrate concentration: 1.0×10 − 1 mol/L) 100 mL and EG solution of PVP (PVP concentration: 3.0×10 -1 mol/L) 100 mL. In the particle growth step, the reaction solution was collected every 30 minutes and confirmed with an electron microscope. As a result, the nucleus particles formed in the nucleus formation step grew in a linear form over time, and no new particles were observed in the particle growth step. the generation of microparticles.
3.脫鹽水洗步驟 於將結束粒子生長步驟之反應液冷卻至室溫後，使用區分分子量0.2 μm之超濾膜實施脫鹽水洗處理，並且將溶劑替換為乙醇。最後，將液量濃縮至100 mL。最後，以銀奈米線濃度成為0.1質量%之方式利用乙醇稀釋，獲得銀奈米線分散液1。3. Demineralized water washing step After the reaction solution after the particle growth step was cooled to room temperature, desalted water washing was performed using an ultrafiltration membrane with a molecular weight of 0.2 μm, and the solvent was replaced with ethanol. Finally, the liquid volume was concentrated to 100 mL. Finally, the silver nanowire dispersion liquid 1 was obtained by diluting with ethanol so that the silver nanowire concentration became 0.1 mass %.
測定銀奈米線分散液1中之銀奈米線之平均纖維直徑及平均纖維長度，結果銀奈米線之平均纖維直徑為30 nm，平均纖維長度為15 μm。銀奈米線之平均纖維直徑係使用穿透式電子顯微鏡（TEM）（產品名「H-7650」，Hitachi High-Technologies股份有限公司製造），於10萬倍～20萬倍拍攝50張，藉由TEM附屬之軟體於拍攝畫面上實測100根導電性纖維之纖維直徑，以其算術平均值之形式求出。於測定上述纖維直徑時，將加速電壓設為「100 kV」，將發射電流設為「10 μA」，將聚焦透鏡光圈設為「1」，將物鏡光圈設為「0」，將觀察模式設為「HC」，將Spot設為「2」。又，銀奈米線之纖維長度係使用掃描式電子顯微鏡（SEM）（產品名「S-4800（TYPE2）」，Hitachi High-Technologies股份有限公司製造），於500～2000萬倍測定100根銀奈米線之纖維長度，以該100根銀奈米線之纖維長度之算術平均值之形式求出。於測定上述纖維長度時，將信號選擇設為「SE」，將加速電壓設為「3 kV」，將發射電流設為「10 μA」，將SE檢測器設為「混合」。銀奈米線之平均纖維長度係使用掃描式電子顯微鏡（SEM）（產品名「S-4800（TYPE2）」，Hitachi High-Technologies股份有限公司製造）之SEM功能，於500～2000萬倍拍攝10張，藉由附屬軟體於拍攝畫面上測定100根銀奈米線之纖維長度，以該100根銀奈米線之纖維長度之算術平均值之形式求出。於測定上述纖維長度時，使用45°傾斜之試樣台，將信號選擇設為「SE」，將加速電壓設為「3 kV」，將發射電流設為「10 μA～20 μA」，將SE檢測器設為「混合」，將探針電流設為「Norm」，將焦點模式設為「UHR」，將聚光透鏡1設為「5.0」，將W.D.設為「8 mm」，將Tilt設為「30°」。再者，將TE檢測器預先卸除。於測定銀奈米線之纖維直徑時，使用藉由以下之方法所製作之測定用樣品。首先，對於銀奈米線分散液1，對應於組成物之分散介質而利用乙醇將銀奈米線之濃度稀釋至0.05質量%以下。進而，將該經稀釋之銀奈米線分散液1於TEM或STEM觀察用之附碳支持膜之柵網（Cu柵型號「#10-1012 彈性碳ELS-C10 STEM Cu100P柵規格」）上滴加1滴，於室溫使其乾燥，於上述條件下進行觀察，作為觀察圖像資料。基於此求出算術平均值。於測定銀奈米線之纖維長度時，使用藉由以下之方法所製作之測定用樣品。首先，將銀奈米線分散液1以塗佈量成為10 mg/m2
的方式塗佈於B5大小之厚度50 μm的聚對苯二甲酸乙二酯（PET）膜之未處理面，使分散介質乾燥而於PET膜表面配置導電性纖維，製作導電性膜。自該導電性膜之中央部切出10 mm×10 mm之大小。繼而，使用銀漿將該切出之導電性膜相對於台面平坦地貼附於具有45°傾斜之SEM試樣台（型號「728-45」，日新EM股份有限公司製造，傾斜型試樣台45°，
（銀奈米線分散液2） 首先，將甲醛次硫酸鈉二水合物（雕白粉）122 g與數量平均分子量為40000之聚乙烯基吡咯啶酮12.5 g溶解於少量純水中，於該水溶液中進而添加純水，使總容量為500 mL。繼而，於該水溶液中添加2-二乙基胺基乙醇72 g，製備水溶液A。另一方面，將氯化鎳（NiCl2 ・6H2 O）95 g溶解於少量純水中，於該水溶液中進而添加純水而總容量為500 mL，調製水溶液B。(Silver Nanowire Dispersion Liquid 2) First, 122 g of sodium formaldehyde sulfoxylate dihydrate (diamond powder) and 12.5 g of polyvinylpyrrolidone with a number average molecular weight of 40,000 were dissolved in a small amount of pure water, and dissolved in the aqueous solution. Then, pure water was added to make the total volume 500 mL. Next, 72 g of 2-diethylaminoethanol was added to this aqueous solution, and an aqueous solution A was prepared. On the other hand, an aqueous solution B was prepared by dissolving 95 g of nickel chloride (NiCl 2 6H 2 O) in a small amount of pure water, and adding pure water to the aqueous solution so that the total volume was 500 mL.
繼而，將水溶液A攪拌並同時加熱至60℃，於該60℃之水溶液A中慢慢地添加水溶液B，進而於60℃攪拌2小時並保持，獲得黑色之膠體分散液。利用超濾膜將該膠體分散液洗淨至濾液之導電率成為133 μS/cm，獲得固形物成分之分散液。Then, the aqueous solution A was heated to 60°C while stirring, and the aqueous solution B was slowly added to the aqueous solution A at 60°C, and further stirred at 60°C for 2 hours and maintained to obtain a black colloidal dispersion. The colloidal dispersion was washed with an ultrafiltration membrane until the conductivity of the filtrate became 133 μS/cm, and a dispersion of solid content was obtained.
藉由X射線繞射（XRD）測定所獲得之固形物成分之結晶結構，結果確認到固形物成分為具有面心立方（face-centered cubic structure）之結晶結構之鎳奈米線。The crystal structure of the obtained solid content was measured by X-ray diffraction (XRD), and as a result, it was confirmed that the solid content was nickel nanowires having a face-centered cubic structure.
測定所獲得之鎳奈米線分散液中之銀奈米線之平均纖維直徑及平均纖維長度，結果鎳奈米線之平均纖維直徑為80 nm，平均纖維長度為2.4 μm。又，鎳奈米線分散液呈現出黑色，又，自鎳奈米線分散液取出鎳奈米線並進行觀察，結果鎳奈米線呈現出黑色。The average fiber diameter and average fiber length of the silver nanowires in the obtained nickel nanowire dispersion were measured. As a result, the average fiber diameter of the nickel nanowires was 80 nm and the average fiber length was 2.4 μm. In addition, the nickel nanowire dispersion liquid appeared black, and when the nickel nanowires were taken out from the nickel nanowire dispersion liquid and observed, the nickel nanowires appeared black.
繼而，將所獲得之鎳奈米線分散液以銀奈米線與鎳奈米線之重量比成為90：10之方式添加至銀奈米線分散液1中，獲得分散有銀奈米線與鎳奈米線之銀奈米線分散液2。Then, the obtained nickel nanowire dispersion liquid was added to the silver nanowire dispersion liquid 1 in such a way that the weight ratio of silver nanowires and nickel nanowires was 90:10, to obtain the dispersion liquid of silver nanowires and nickel nanowires. Silver nanowire dispersion of nickel nanowires 2.
（銀奈米線分散液3） 首先，獲得銀奈米線分散液1，並且另外獲得銀奈米線分散液1之製造過程中所形成之濃縮物。繼而，於處理溫度25℃之條件下，將該濃縮物於作為金屬黑化處理液之二氧化碲0.25重量%（以碲濃度計0.2重量%）、鹽酸0.45重量%、硫酸20重量%之水溶液中浸漬30秒，於濃縮物之表面形成含有氯化碲（TeCl2 ）之皮膜。(Silver Nanowire Dispersion Liquid 3) First, a silver nanowire dispersion liquid 1 was obtained, and a concentrate formed during the manufacturing process of the silver nanowire dispersion liquid 1 was additionally obtained. Then, under the condition of a treatment temperature of 25°C, the concentrate was dissolved in an aqueous solution of 0.25% by weight of tellurium dioxide (0.2% by weight in terms of tellurium concentration), 0.45% by weight of hydrochloric acid, and 20% by weight of sulfuric acid as a metal blackening treatment solution. Immerse in the medium for 30 seconds to form a film containing tellurium chloride (TeCl 2 ) on the surface of the concentrate.
於取出所獲得之具有皮膜之濃縮物後，添加500 g之純水，進行10分鐘攪拌，使該濃縮物分散後，進而添加10倍量之丙酮，於進一步攪拌後進行24小時靜置。於靜置後，重新觀察到濃縮物與上清液，因此利用移液管小心地將上清液部分去除。為了獲得良好之導電性，過量之有機保護劑為無用者，因此視需要將該洗淨操作進行1～20次左右，將具有作為固形物成分之皮膜之銀奈米線充分地洗淨。After taking out the obtained concentrate with a film, 500 g of pure water was added, and the mixture was stirred for 10 minutes to disperse the concentrate. Then, 10 times the amount of acetone was added, and after further stirring, the mixture was allowed to stand for 24 hours. After standing, the concentrate and the supernatant were re-observed, so the supernatant was partially removed with a pipette. In order to obtain good electrical conductivity, an excessive amount of the organic protective agent is useless. Therefore, this cleaning operation is performed about 1 to 20 times as necessary to sufficiently clean the silver nanowires having a film as a solid content.
對上述洗淨後之具有皮膜之銀奈米線添加異丙醇而獲得形成有皮膜之銀奈米線分散液。測定形成有皮膜之銀奈米線分散液中之形成有皮膜之銀奈米線的平均纖維直徑及平均纖維長度，結果銀奈米線之平均纖維直徑為25 nm，平均纖維長度為15 μm。又，形成有皮膜之銀奈米線分散液呈現出黑色，又，自形成有皮膜之銀奈米線分散液取出形成有皮膜之銀奈米線並進行觀察，結果形成有皮膜之銀奈米線之表面呈現出黑色。Isopropanol was added to the washed silver nanowires with a film to obtain a film-formed silver nanowire dispersion. The average fiber diameter and average fiber length of the film-formed silver nanowires in the film-formed silver nanowire dispersion liquid were measured. As a result, the average fiber diameter of the silver nanowires was 25 nm and the average fiber length was 15 μm. Furthermore, the film-formed silver nanowire dispersion was black, and the film-formed silver nanowires were taken out from the film-formed silver nanowire dispersion and observed, and as a result, a film-formed silver nanowire was formed. The surface of the line appears black.
於獲得形成有皮膜之銀奈米線分散液後，將形成有皮膜之銀奈米線分散液以銀奈米線與形成有皮膜之銀奈米線之重量比成為90：10之方式添加至銀奈米線分散液1中，而獲得銀奈米線分散液3。After obtaining the film-formed silver nanowire dispersion liquid, the film-formed silver nanowire dispersion liquid was added to the mixture in such a way that the weight ratio of the silver nanowires and the film-formed silver nanowires became 90:10. In the silver nanowire dispersion liquid 1, the silver nanowire dispersion liquid 3 was obtained.
＜透光性樹脂用組成物之製備＞ 以成為下述所示之組成之方式摻合各成分，而獲得透光性樹脂用組成物1。 （透光性樹脂用組成物1） ・新戊四醇三丙烯酸酯與新戊四醇四丙烯酸酯之混合物（產品名「KAYARAD-PET-30」，日本化藥股份有限公司製造）：5質量份 ・聚合起始劑（產品名「Irgacure184」，BASF JAPAN公司製造）：0.25質量份 ・甲基乙基酮（MEK）：70質量份 ・環己酮：24.75質量份<Preparation of composition for translucent resin> Each component was blended so that it might become the composition shown below, and the composition 1 for translucent resins was obtained. (Translucent resin composition 1) ・Mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate (product name "KAYARAD-PET-30", manufactured by Nippon Kayaku Co., Ltd.): 5 parts by mass ・Polymerization initiator (product name "Irgacure184", manufactured by BASF JAPAN): 0.25 parts by mass ・Methyl ethyl ketone (MEK): 70 parts by mass ・Cyclohexanone: 24.75 parts by mass
＜實施例1＞ 首先，準備作為第1基材之於單面具有基底層之厚度50 μm之第1聚對苯二甲酸乙二酯（PET）基材（產品名「Cosmoshine A4100」，東洋紡股份有限公司製造），於第1PET基材之單面塗佈硬塗層組成物1而形成塗膜。繼而，對於所形成之塗膜，以0.5 m/s之流速使50℃之乾燥空氣流通15秒後，進而以10 m/s之流速使70℃之乾燥空氣流通30秒而使其乾燥，藉此使塗膜中之溶劑蒸發，以累計光量成為100 mJ/cm2 之方式照射紫外線而使塗膜硬化，藉此形成作為第1樹脂層之膜厚1 μm之第1硬塗層。<Example 1> First, a first polyethylene terephthalate (PET) substrate (product name "Cosmoshine A4100", manufactured by Toyobo Co., Ltd.) having a base layer on one side and a thickness of 50 μm was prepared as a first substrate. Co., Ltd.), the hard coating composition 1 was applied to one side of the first PET substrate to form a coating film. Next, for the formed coating film, drying air at 50°C was circulated at a flow rate of 0.5 m/s for 15 seconds, and then drying air at 70°C was circulated at a flow rate of 10 m/s for 30 seconds to be dried. This evaporates the solvent in the coating film, irradiates ultraviolet rays so that the cumulative light intensity becomes 100 mJ/cm 2 to harden the coating film, thereby forming a first hard coat layer with a thickness of 1 μm as the first resin layer.
於形成第1硬塗層後，於第1PET基材之與形成有硬塗層之面為相反側之未處理面上以成為10 mg/m2 的方式塗佈銀奈米線分散液1。繼而，對於所塗佈之銀奈米線分散液1，以0.5 m/s之流速使50℃之乾燥空氣流通15秒後，進而以10 m/s之流速使70℃之乾燥空氣流通30秒，從而使銀奈米線分散液1中之分散介質蒸發，藉此於聚對苯二甲酸乙二酯膜之表面配置多個銀奈米線。After the formation of the first hard coat layer, the silver nanowire dispersion liquid 1 was applied on the untreated surface of the first PET substrate on the opposite side to the surface on which the hard coat layer was formed so as to be 10 mg/m 2 . Next, for the coated silver nanowire dispersion 1, drying air at 50°C was circulated at a flow rate of 0.5 m/s for 15 seconds, and then drying air at 70°C was circulated at a flow rate of 10 m/s for 30 seconds. , so that the dispersion medium in the silver nanowire dispersion liquid 1 is evaporated, thereby disposing a plurality of silver nanowires on the surface of the polyethylene terephthalate film.
繼而，以覆蓋銀奈米線之方式塗佈上述透光性樹脂用組成物1，形成塗膜。繼而，對於所形成之塗膜，以0.5 m/s之流速使50℃之乾燥空氣流通15秒後，進而以10 m/s之流速使70℃之乾燥空氣流通30秒而使其乾燥，藉此使塗膜中之溶劑蒸發，以累計光量成為100 mJ/cm2 之方式照射紫外線而使塗膜硬化，藉此形成膜厚為100 nm之透光性樹脂，獲得由透光性樹脂及配置於透光性樹脂中之銀奈米線所構成之導電層。藉此，獲得依序具備第1硬塗層、第1PET基材、及導電層之積層體。Next, the above-mentioned composition 1 for a translucent resin was applied so as to cover the silver nanowires to form a coating film. Next, for the formed coating film, drying air at 50°C was circulated at a flow rate of 0.5 m/s for 15 seconds, and then drying air at 70°C was circulated at a flow rate of 10 m/s for 30 seconds to be dried. This evaporates the solvent in the coating film, irradiates ultraviolet rays so that the cumulative light intensity becomes 100 mJ/cm 2 to harden the coating film, thereby forming a light-transmitting resin with a film thickness of 100 nm. A conductive layer formed by silver nanowires in a light-transmitting resin. Thereby, the laminated body provided with a 1st hard-coat layer, a 1st PET base material, and a conductive layer in this order was obtained.
另一方面，於作為第2基材之厚度100 μm之第2聚對苯二甲酸乙二酯（PET）基材（產品名「Cosmoshine A4300」，東洋紡股份有限公司製造）之一面即第2面塗佈低聚物析出抑制層用組成物1。繼而，將所形成之塗膜加熱至180℃而使塗膜硬化，藉此形成膜厚500 nm之低聚物析出抑制層。其後，於第2PET基材之與低聚物析出抑制層之面為相反側之面即第1面塗佈硬塗層用組成物2，形成塗膜。繼而，對於所形成之塗膜，以10 m/s之流速使70℃之乾燥空氣流通30秒而使其乾燥，藉此使塗膜中之溶劑蒸發。On the other hand, as the second base material, one side of a second polyethylene terephthalate (PET) base material (product name "Cosmoshine A4300", manufactured by Toyobo Co., Ltd.) with a thickness of 100 μm is the second side. Composition 1 for an oligomer deposition inhibiting layer was applied. Next, the formed coating film was heated to 180° C. to harden the coating film, thereby forming an oligomer deposition inhibiting layer with a film thickness of 500 nm. Then, the composition 2 for hard-coat layers was apply|coated to the 1st surface which is the surface opposite to the surface of the oligomer deposition-inhibiting layer of a 2nd PET base material, and a coating film was formed. Then, about the formed coating film, the solvent in the coating film was evaporated by circulating dry air at 70° C. for 30 seconds at a flow rate of 10 m/s for drying.
繼而，以第1硬塗層與經乾燥之塗膜接觸之方式使上述積層體接觸，於該狀態下，以累計光量成為100 mJ/cm2 之方式照射紫外線而使塗膜硬化。藉此，獲得由第2PET基材及與第1硬塗層密接之作為第2樹脂層之膜厚6 μm之第2硬塗層所構成的保護膜，並且獲得附保護膜之積層體。Next, the above-mentioned layered body was brought into contact so that the first hard coat layer was in contact with the dried coating film, and in this state, ultraviolet rays were irradiated so that the cumulative light amount became 100 mJ/cm 2 to harden the coating film. Thereby, the protective film which consists of the 2nd PET base material and the 2nd hard-coat layer with a film thickness of 6 micrometers as a 2nd resin layer adhering to the 1st hard-coat layer was obtained, and the laminated body with a protective film was obtained.
上述第1硬塗層等之膜厚係分別自使用掃描穿透式電子顯微鏡（STEM）所拍攝之導電部之剖面照片隨機測定10個部位之厚度，設為所測得之10個部位之厚度之算術平均值。具體之剖面照片之拍攝係藉由以下之方法進行。首先，由附保護膜之積層體製作剖面觀察用樣品。詳細而言，將切成2 mm×5 mm之附保護膜之積層體放入至聚矽氧系包埋板中，使環氧系樹脂流入，利用樹脂包埋附保護膜之積層體整體。其後，將包埋樹脂於65℃放置12小時以上而使其硬化。其後，使用超薄切片機（產品名「超薄切片機 EM UC7」，Leica Microsystems股份有限公司製造），將進給厚度設定為100 nm，製作超薄切片。利用附膠棉膜之篩目（150）採取所製作之超薄切片，設為STEM用樣品。其後，使用掃描穿透式電子顯微鏡（STEM）（產品名「S-4800（TYPE2）」，Hitachi High-Technologies股份有限公司製造）拍攝STEM用樣品之剖面照片。於拍攝該剖面照片時，將檢測器設為「TE」，將加速電壓設為30 kV，將發射電流設為「10 μA」。關於倍率，調節焦距來辨別各層或觀察對比度及亮度，並同時於5000倍～20萬倍適當調節。較佳之倍率為1萬倍～5萬倍，進而較佳為2.5萬倍～4萬倍。若過度提昇倍率，則層界面之像素變粗而變得難以辨別，因此於膜厚測定中較良好的是不過度提昇倍率。再者，於拍攝剖面照片時，進而將光圈設為「射柱偵測光圈3」，將物鏡光圈設為「3」，又，將W.D.設為「8 mm」。不僅實施例1，以下之實施例及比較例之第1硬塗層等之膜厚均藉由該方法進行測定。The thicknesses of the above-mentioned first hard coat layer etc. were measured at 10 locations at random from cross-sectional photographs of the conductive portion taken with a scanning transmission electron microscope (STEM), and set as the measured thicknesses at 10 locations. The arithmetic mean of . The photographing of a specific cross-sectional photograph was performed by the following method. First, a sample for cross-section observation was produced from the laminate with the protective film. Specifically, the protective film-attached laminate cut into 2 mm×5 mm was placed in a silicone-based embedding plate, and an epoxy-based resin was poured to embed the entire protective film-attached laminate with the resin. Then, the embedding resin was left to stand at 65° C. for 12 hours or more to be hardened. Then, using an ultramicrotome (product name "Ultramicrotome EM UC7", manufactured by Leica Microsystems Co., Ltd.), the feed thickness was set to 100 nm to prepare ultrathin sections. The produced ultra-thin sections were collected using a mesh (150) with a colloidal cotton film, and were used as samples for STEM. Then, the cross-sectional photograph of the sample for STEM was taken using a scanning transmission electron microscope (STEM) (product name "S-4800 (TYPE2)", manufactured by Hitachi High-Technologies Co., Ltd.). When taking this cross-sectional photograph, the detector was set to "TE", the acceleration voltage was set to 30 kV, and the emission current was set to "10 μA". Regarding the magnification, adjust the focal length to distinguish each layer or observe the contrast and brightness, and at the same time adjust it appropriately from 5000 times to 200,000 times. The preferred magnification is 10,000 to 50,000 times, and more preferably 25,000 to 40,000 times. If the magnification is increased too much, the pixels at the layer interface become thicker and it becomes difficult to distinguish, so it is preferable not to increase the magnification too much in the film thickness measurement. Furthermore, when taking a cross-sectional photo, the aperture was further set to "column detection aperture 3", the objective lens aperture was set to "3", and the W.D. was set to "8 mm". Not only Example 1, but also the film thicknesses of the first hard coat layers in the following Examples and Comparative Examples were measured by this method.
＜實施例2＞ 於實施例2中，使用硬塗層用組成物3代替硬塗層用組成物2而形成第2硬塗層，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。<Example 2> In Example 2, a laminate with a protective film was obtained in the same manner as in Example 1, except that the composition 3 for a hard coat layer was used instead of the composition 2 for a hard coat layer to form the second hard coat layer. .
＜實施例3＞ 於實施例3中，使用硬塗層用組成物4代替硬塗層用組成物2而形成第2硬塗層，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。<Example 3> In Example 3, a layered product with a protective film was obtained in the same manner as in Example 1, except that the composition 4 for a hard coat layer was used instead of the composition 2 for a hard coat layer to form the second hard coat layer. .
＜實施例4＞ 於實施例4中，使用硬塗層用組成物5代替硬塗層用組成物2而形成第2硬塗層，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。<Example 4> In Example 4, a layered product with a protective film was obtained in the same manner as in Example 1, except that the composition 5 for a hard coat layer was used instead of the composition 2 for a hard coat layer to form the second hard coat layer .
＜實施例5＞ 於實施例5中，使用硬塗層用組成物6代替硬塗層用組成物2而形成第2硬塗層，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。<Example 5> In Example 5, a layered product with a protective film was obtained in the same manner as in Example 1, except that the composition 6 for a hard coat layer was used instead of the composition 2 for a hard coat layer to form the second hard coat layer .
＜實施例6＞
於實施例6中，使用硬塗層用組成物7代替硬塗層用組成物2而形成第2硬塗層，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。<Example 6>
In Example 6, a layered product with a protective film was obtained in the same manner as in Example 1, except that the
＜實施例7＞ 於實施例7中，不於第2PET基材之與第2硬塗層側之面為相反側之面設置低聚物析出抑制層，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。<Example 7> In Example 7, except that the oligomer precipitation suppressing layer was not provided on the surface of the second PET base material on the opposite side to the second hard coat layer side, the same procedure as in Example 1 was carried out to obtain the oligomer deposition inhibiting layer. A laminate of protective films.
＜實施例8＞ 於實施例8中，於第2PET基材之與第1面為相反側之第2面進而具備抗靜電層代替低聚物析出抑制層，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。於抗靜電層之形成中，首先，於第2PET基材之第2面塗佈抗靜電層用組成物1。繼而，將所形成之塗膜加熱至180℃而使塗膜硬化，藉此形成膜厚200 nm之抗靜電層。<Example 8> In Example 8, it was obtained in the same manner as in Example 1, except that the second surface of the second PET base material on the opposite side to the first surface was further provided with an antistatic layer instead of the oligomer deposition suppressing layer. Laminate with protective film. In the formation of the antistatic layer, first, the composition 1 for an antistatic layer was coated on the second surface of the second PET substrate. Next, the formed coating film was heated to 180° C. to harden the coating film, thereby forming an antistatic layer with a film thickness of 200 nm.
＜實施例9＞ 於實施例9中，使用銀奈米線分散液2代替銀奈米線分散液1而形成導電層，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。<Example 9> In Example 9, except that the silver nanowire dispersion 2 was used instead of the silver nanowire dispersion 1 to form the conductive layer, a laminate with a protective film was obtained in the same manner as in Example 1.
＜實施例10＞ 於實施例10中，使用銀奈米線分散液3代替銀奈米線分散液1而形成導電層，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。<Example 10> In Example 10, except that the silver nanowire dispersion 3 was used instead of the silver nanowire dispersion 1 to form the conductive layer, a laminate with a protective film was obtained in the same manner as in Example 1.
＜比較例1＞ 於比較例1中，使用由PET基材與設置於PET基材之單面之黏著層所構成的保護膜（產品名「CP170u」，日東電工股份有限公司製造）代替保護膜，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。再者，保護膜係以黏著層密接於第1硬塗層之方式配置。<Comparative Example 1> In Comparative Example 1, a protective film (product name "CP170u", manufactured by Nitto Denko Co., Ltd.) composed of a PET base material and an adhesive layer provided on one side of the PET base material was used instead of the protective film. In the same manner as in Example 1, a protective film-attached laminate was obtained. In addition, a protective film is arrange|positioned so that an adhesive layer may be in close contact with the 1st hard-coat layer.
＜比較例2＞ 於比較例2中，使用由PET基材與設置於PET基材之單面之黏著層所構成的保護膜（產品名「SAT TM40125TG」，SUN A.KAKEN股份有限公司製造）代替保護膜，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。再者，保護膜係以黏著層密接於第1硬塗層之方式配置。<Comparative Example 2> In Comparative Example 2, a protective film (product name "SAT TM40125TG", manufactured by Sun A.KAKEN Co., Ltd.) composed of a PET substrate and an adhesive layer provided on one side of the PET substrate was used instead of the protective film, except Except for this, a laminate with a protective film was obtained in the same manner as in Example 1. In addition, a protective film is arrange|positioned so that an adhesive layer may be in close contact with the 1st hard-coat layer.
＜比較例3＞ 於比較例3中，使用硬塗層用組成物8代替硬塗層用組成物2而形成第2硬塗層，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。<Comparative Example 3> In Comparative Example 3, a laminate with a protective film was obtained in the same manner as in Example 1, except that the composition 8 for a hard coat layer was used instead of the composition 2 for a hard coat layer to form the second hard coat layer .
＜比較例4＞ 於比較例4中，使用硬塗層用組成物9代替硬塗層用組成物2而形成第2硬塗層，除此以外，藉由與實施例1相同之方式獲得附保護膜之積層體。<Comparative Example 4> In Comparative Example 4, a laminate with a protective film was obtained in the same manner as in Example 1, except that the composition 9 for a hard coat layer was used instead of the composition 2 for a hard coat layer to form the second hard coat layer .
＜壓痕硬度測定＞ 於實施例1～6及比較例3、4之附保護膜之積層體中，作為剖面硬度，測定第1硬塗層及第2硬塗層之各者之膜厚方向的剖面之壓痕硬度，又，於比較例1、2之附保護膜之積層體中，測定第1硬塗層及黏著層之各者之膜厚方向的剖面之壓痕硬度。具體而言，首先，將切成縱1 cm×橫1 cm之大小之附保護膜之積層體放入至聚矽氧系包埋板中，使環氧系樹脂流入，利用樹脂包埋附保護膜之積層體整體。其後，將包埋樹脂於65℃放置12小時以上而使其硬化。其後，使用超薄切片機（產品名「超薄切片機 EM UC7」，Leica Microsystems股份有限公司製造），將進給厚度設定為100 nm，製作超薄切片。繼而，將切出超薄切片之剩餘之塊體作為測定樣品。繼而，經由接著樹脂（產品名「Aronalpha（註冊商標）一般用」，東亞合成股份有限公司製造），將測定樣品以測定樣品之藉由將上述切片切出所獲得的剖面相對於載玻片之表面大致垂直之方式，固定於市售之載玻片（產品名「載玻片(切放型) 1-9645-11」，AS ONE股份有限公司製造）。具體而言，於上述載玻片之中央部滴加上述接著樹脂。此時，不將接著樹脂進行塗佈擴散，又，為了不使接著樹脂自測定樣品溢出，滴加設為1滴。使測定樣品以測定樣品之藉由將上述切片切出所獲得之剖面相對於載玻片之表面大致垂直之方式與載玻片接觸，於載玻片與測定樣品之間將接著樹脂擠壓擴散而暫時接著。繼而，於該狀態下，於室溫放置12小時，藉由接著將測定樣品固定於載玻片。繼而，於測定樣品之剖面中，找到平坦之部位，於該平坦之部位，使用HYSITRON（海思創）公司製造之「TI950 TriboIndenter」，以於位移基準之測定中最大壓入位移成為100 nm之方式，將三角錐型壓頭以速度10 nm/秒，歷時10秒自位移0 nm施加負載至位移100 nm，並同時壓入至各層中，其後於100 nm時保持5秒後，以10秒自位移100 nm卸載至位移0 nm。繼而，連續地測定與此時之壓入荷重F（N）對應之壓入深度h（nm），製作荷重-位移曲線。根據所製作之荷重-位移曲線，藉由如上述數式（1）所示將最大壓入荷重Fmax （N）除以壓頭與各層接觸之接觸投影面積Ap （mm2 ）所獲得之值而求出壓痕硬度HIT 。壓痕硬度設為測定10個部位所獲得之值之算術平均值。再者，Ap 係設為使用標準試樣之熔融石英，藉由Oliver-Pharr法修正壓頭先端曲率後之接觸投影面積。<Measurement of Indentation Hardness> In the laminates with protective films of Examples 1 to 6 and Comparative Examples 3 and 4, the film thickness direction of each of the first hard coat layer and the second hard coat layer was measured as the cross-sectional hardness. The indentation hardness of the cross-section was measured, and the indentation hardness of the cross-section in the film thickness direction of each of the first hard coat layer and the adhesive layer was measured in the laminates with protective films of Comparative Examples 1 and 2. Specifically, first, a layered body with a protective film cut into a size of 1 cm in length x 1 cm in width is placed in a polysiloxane-based embedding plate, and an epoxy-based resin is poured into it, and the protective film is embedded with the resin. The entire laminate of films. Then, the embedding resin was left to stand at 65° C. for 12 hours or more to be hardened. Then, using an ultramicrotome (product name "Ultramicrotome EM UC7", manufactured by Leica Microsystems Co., Ltd.), the feed thickness was set to 100 nm, and an ultrathin section was produced. Next, the remaining block from which the ultrathin section was cut was used as a measurement sample. Then, through the adhesive resin (product name "Aronalpha (registered trademark) for general use", manufactured by Toagosei Co., Ltd.), the measurement sample was measured so that the cross section of the measurement sample obtained by cutting out the above-mentioned section was relative to the surface of the glass slide. In a substantially vertical manner, it was fixed on a commercially available glass slide (product name "Slide glass (cut-and-place type) 1-9645-11", manufactured by AS ONE Co., Ltd.). Specifically, the said adhesive resin was dripped at the center part of the said glass slide. At this time, the adhesive resin was not applied and spread, and it was added dropwise to one drop so as not to overflow the adhesive resin from the measurement sample. The measurement sample is brought into contact with the glass slide in such a manner that the cross section of the measurement sample obtained by cutting the above-mentioned section is substantially perpendicular to the surface of the glass slide, and the resin is squeezed and diffused between the glass slide and the measurement sample. Continue for now. Then, in this state, it was left to stand at room temperature for 12 hours, and then the measurement sample was fixed to a glass slide. Then, find a flat part in the cross section of the measurement sample, and use the "TI950 TriboIndenter" manufactured by HYSITRON in the flat part, so that the maximum indentation displacement in the measurement of the displacement reference becomes 100 nm. In this way, the triangular pyramid-shaped indenter was loaded at a speed of 10 nm/s, applied a load from a displacement of 0 nm to a displacement of 100 nm for 10 seconds, and pressed into each layer at the same time. Seconds unload from a displacement of 100 nm to a displacement of 0 nm. Next, the indentation depth h (nm) corresponding to the indentation load F(N) at this time was continuously measured, and a load-displacement curve was prepared. According to the produced load-displacement curve, it is obtained by dividing the maximum pressing load F max (N) by the contact projected area Ap (mm 2 ) of the indenter in contact with each layer as shown in the above equation (1). The value of the indentation hardness H IT was obtained. The indentation hardness was set as the arithmetic mean of the values obtained by measuring 10 locations. In addition, Ap is set as the contact projection area after correcting the curvature of the tip of the indenter by the Oliver-Pharr method using fused silica of a standard sample.
＜剝離強度測定＞
於實施例及比較例之附保護膜之積層體中，在將附保護膜之積層體於150℃之環境下加熱1小時之前後，測定加熱前之積層體與保護膜之剝離強度及加熱後之積層體與保護膜之剝離強度，求出加熱後之剝離強度相對於加熱前之剝離強度之上升率。加熱前之積層體與保護膜之剝離強度及加熱後之積層體與保護膜之剝離強度係分別使用拉伸試驗機（產品名「Tensilon萬能材料試驗機RTF-1150-H」，A＆D股份有限公司製造），藉由以下之測定方法進行測定。首先，於縱12.5 cm×橫5 cm×厚度1.1 mm之玻璃板貼附雙面膠帶（寺岡製作所股份有限公司 No.751B）。另一方面，將加熱前之附保護膜之積層體切成縱15 cm×橫2.5 cm之大小，將第1PET側貼附於玻璃板上之雙面膠帶，使其保持於拉伸試驗機之一對治具。於使附保護膜之積層體保持於治具時，以人手預先將保護膜自積層體略微剝離，製作出起點，使保護膜保持於其中一治具並且使玻璃板及積層體保持於另一治具。繼而，於該狀態下，於剝離速度300 mm/分鐘、剝離距離50 mm、剝離角度180°之條件下，測定剝離保護膜時之剝離強度。另一方面，另外將加熱前之附保護膜之積層體切成縱15 cm×橫2.5 cm之大小，對將該切出之附保護膜之積層體於150℃加熱1小時。繼而，於加熱後之附保護膜之積層體中，於與上述相同之條件剝離保護膜，測定此時之剝離強度。關於加熱後之剝離強度相對於加熱前之剝離強度之上升率，若將上述上升率設為A（%），將加熱前之剝離強度設為B（mN/25 mm），將加熱後之剝離強度設為C（mN/25 mm），則藉由以下之式而算出。
A＝（C－B）/B×100<Peel strength measurement>
In the laminates with protective films of Examples and Comparative Examples, before and after heating the laminates with protective films in an environment of 150° C. for 1 hour, the peel strengths of the laminates before heating and the protective films and after heating were measured. The peeling strength of the laminated body and the protective film was calculated|required, and the increase rate of the peeling strength after heating with respect to the peeling strength before heating was calculated|required. The peel strength of the laminate and the protective film before heating and the peel strength of the laminate and the protective film after heating were measured using a tensile testing machine (product name "Tensilon Universal Tester RTF-1150-H", A&D Co., Ltd. production), and measured by the following measurement method. First, a double-sided tape (Teraoka Manufacturing Co., Ltd. No. 751B) was attached to a glass plate of 12.5 cm in height x 5 cm in width x 1.1 mm in thickness. On the other hand, the laminated body with the protective film before heating was cut into a size of 15 cm in length x 2.5 cm in width, and the first PET side was attached to the double-sided tape on the glass plate, and it was held in the tensile tester. A pair of jigs. When holding the laminated body with the protective film on the jig, the protective film is slightly peeled off from the laminated body by hand to make a starting point. Jig. Next, in this state, under the conditions of peeling speed 300 mm/min, peeling
＜接觸角測定＞ 在將實施例1～10之附保護膜之積層體於150℃之環境下加熱1小時之前後，分別測定剝離保護膜時之第1硬塗層之表面及第2樹脂層之表面之對水的接觸角。又，在將比較例1、2之附保護膜之積層體於150℃之環境下加熱1小時之前後，分別測定剝離保護膜時之第1硬塗層之表面之對水的接觸角。再者，於比較例3、4之附保護膜之積層體中，無法測定剝離保護膜時之第1硬塗層之表面及第2樹脂層之表面之對水的接觸角，原因在於，無法自比較例3、4之附保護膜之積層體剝離保護膜。對水的接觸角係依照JIS R3257：1999所記載之靜滴法，使用顯微鏡式接觸角計（產品名「DropMaster300」，協和界面科學股份有限公司製造）進行測定。第1硬塗層之表面之對水的接觸角係將附保護膜之積層體切成縱5 cm×橫10 cm之大小，於剝離了保護膜之狀態下，將1 μL之水滴加至第1硬塗層之表面，並10點測定剛滴加後之接觸角，將其等之算術平均值作為第1硬塗層之表面之接觸角。又，第2硬塗層之表面之對水的接觸角亦藉由與第1硬塗層之表面之對水的接觸角相同之方式求出。<Contact angle measurement> Before and after heating the laminates with the protective film of Examples 1 to 10 at 150° C. for 1 hour, the water resistance of the surface of the first hard coat layer and the surface of the second resin layer when the protective film was peeled off was measured, respectively. contact angle. Moreover, before and after heating the laminated body with the protective film of Comparative Examples 1 and 2 in the environment of 150 degreeC for 1 hour, the contact angle with respect to water of the surface of the 1st hard-coat layer when peeling the protective film was measured, respectively. Furthermore, in the laminates with protective films of Comparative Examples 3 and 4, the contact angles to water of the surface of the first hard coat layer and the surface of the second resin layer when the protective film was peeled off could not be measured because the The protective film was peeled off from the laminated body with the protective film of Comparative Examples 3 and 4. The contact angle with respect to water was measured according to the static drop method described in JIS R3257:1999 using a microscope-type contact angle meter (product name "DropMaster300", manufactured by Kyowa Interface Science Co., Ltd.). The contact angle of the surface of the first hard coat layer with water is to cut the laminated body with the protective film into a size of 5 cm in length x 10 cm in width, and in the state where the protective film is peeled off, 1 μL of water is added dropwise to the first layer. 1 The surface of the hard coat layer, and the contact angle immediately after the dropwise addition was measured at 10 points, and the arithmetic mean value thereof was taken as the contact angle of the surface of the first hard coat layer. In addition, the contact angle with respect to water of the surface of the 2nd hard-coat layer was calculated|required by the same method as the contact angle with respect to water of the surface of the 1st hard-coat layer.
＜鉛筆硬度測定＞ 於實施例1～10及比較例1、2之附保護膜之積層體中，剝離保護膜，測定第1硬塗層之表面之鉛筆硬度作為表面硬度。又，於實施例1～6中，測定所剝離之保護膜之第2硬塗層之表面之鉛筆硬度，於比較例1、2中，測定所剝離之保護膜之黏著層之表面之鉛筆硬度。於測定第1硬塗層之表面之鉛筆硬度之鉛筆硬度試驗中，將未進行加熱之附保護膜之積層體切成縱5 cm×橫5 cm之大小，剝離保護膜，利用Nichiban股份有限公司製造之Cellotape（註冊商標）將保護膜經剝離之積層體以第1硬塗層成為上側且無彎折或褶皺之方式固定於玻璃板上，於對鉛筆施加750 g之荷重，並且將刮痕速度設為1 mm/秒之狀態下進行。第1硬塗層之表面之鉛筆硬度設為於鉛筆硬度試驗中未於第1硬塗層之表面產生損傷之最高硬度。再者，於測定鉛筆硬度時，使用多根硬度不同之鉛筆進行，每1根鉛筆進行5次鉛筆硬度試驗，於5次中4次以上未對第1硬塗層之表面造成損傷之情形時，判斷該硬度之鉛筆未對第1硬塗層之表面造成損傷。上述損傷係指於螢光燈下對進行鉛筆硬度試驗之積層體之表面進行穿透觀察而視認到者。又，第2硬塗層及黏著層之表面之鉛筆硬度亦藉由與第1硬塗層之鉛筆硬度相同之方式進行測定。<Pencil hardness measurement> In the laminated bodies with protective films of Examples 1 to 10 and Comparative Examples 1 and 2, the protective films were peeled off, and the pencil hardness of the surface of the first hard coat layer was measured as the surface hardness. Furthermore, in Examples 1 to 6, the pencil hardness of the surface of the second hard coat layer of the peeled protective film was measured, and in Comparative Examples 1 and 2, the pencil hardness of the surface of the adhesive layer of the peeled protective film was measured. . In the pencil hardness test for measuring the pencil hardness of the surface of the first hard coat layer, the unheated laminate with the protective film was cut into a size of 5 cm in length x 5 cm in width, and the protective film was peeled off using Nichiban Co., Ltd. The cellotape (registered trademark) manufactured by the company fixes the layered product with the peeled protective film on a glass plate with the first hard coat layer on the upper side without bending or wrinkling, and applies a load of 750 g to the pencil, and scratches The speed is set to 1 mm/sec. The pencil hardness of the surface of the 1st hard-coat layer was the highest hardness which did not generate|occur|produce damage on the surface of the 1st hard-coat layer in the pencil hardness test. Furthermore, when measuring the pencil hardness, use a plurality of pencils with different hardnesses, and conduct 5 pencil hardness tests for each pencil, and the surface of the first hard coat layer is not damaged in 4 or more of the 5 times. , it was judged that the pencil with this hardness did not cause damage to the surface of the first hard coat layer. The above-mentioned damage refers to what is visually recognized by penetrating observation of the surface of the layered product subjected to the pencil hardness test under a fluorescent lamp. Moreover, the pencil hardness of the surface of a 2nd hard-coat layer and an adhesive layer was also measured by the same method as the pencil hardness of a 1st hard-coat layer.
＜霧度變化量測定＞ 於實施例及比較例之附保護膜之積層體中，在將附保護膜之積層體於150℃加熱1小時之前後，分別測定霧度值（總霧度值），求出自加熱後之霧度值減去加熱前之霧度值所獲得之值即霧度變化量（%）。霧度值係依據JIS K7136：2000，使用測霧計（產品名「HM-150」，村上色彩技術研究所股份有限公司製造）進行測定。霧度值係切成縱5 cm×橫10 cm之大小後，於無捲曲或褶皺且無指紋或灰塵等之狀態下以導電部側成為非光源側之方式設置，對附保護膜之1片積層體測定3次，採用進行3次測定所獲得之值之算術平均值。<Measurement of change in haze> In the laminates with protective films of Examples and Comparative Examples, before and after heating the laminates with protective films at 150° C. for 1 hour, the haze values (total haze values) were measured, respectively, and the values after heating were obtained. The value obtained by subtracting the haze value before heating from the haze value is the haze change amount (%). The haze value was measured according to JIS K7136:2000 using a haze meter (product name "HM-150", manufactured by Murakami Color Institute Co., Ltd.). The haze value is cut into a size of 5 cm in length x 10 cm in width, and in a state where there is no curling or wrinkling and no fingerprints or dust, etc., the side of the conductive part is set so that the side of the non-light source is attached to a piece of protective film. The layered body was measured three times, and the arithmetic mean of the values obtained by performing the three measurements was used.
＜加熱收縮率測定＞ 於實施例及比較例之附保護膜之積層體中，將附保護膜之積層體於150℃加熱1小時，測定加熱後之附保護膜的積層體之MD方向及TD方向的加熱收縮率。具體而言，首先，將附保護膜之積層體以MD方向成為縱向、TD方向成為橫向之方式切成縱8 cm×橫8 cm之大小。利用圖像尺寸測定器（IM-6120：Keyence股份有限公司製造）對所切出之附保護膜之積層體測定加熱前之縱向及橫向之長度。繼而，將該切出之附保護膜之積層體於150℃之環境下加熱1小時，利用上述圖像尺寸測定器測定加熱後之附保護膜之積層體之縱向及橫向的長度，基於以下之式算出MD方向及TD方向的加熱收縮率。於以下之式中，DMD 為MD方向之加熱收縮率（%），DTD 為TD方向之加熱收縮率（%），EMD 為加熱前之附保護膜之積層體之MD方向之長度（cm），ETD 為加熱前之附保護膜之積層體之TD方向之長度（cm），FMD 為加熱後之附保護膜之積層體之MD方向之長度（cm），FTD 為加熱後之附保護膜之積層體之TD方向之長度（cm）。 DMD ＝（FMD －EMD ）/EMD ×100 DTD ＝（FTD －ETD ）/ETD×100<Measurement of heat shrinkage ratio> Among the laminates with protective films of Examples and Comparative Examples, the laminates with protective films were heated at 150° C. for 1 hour, and the MD direction and TD of the laminates with protective films after heating were measured. Heat shrinkage in the direction. Specifically, first, the protective film-attached laminate was cut into a size of 8 cm in length×8 cm in width so that the MD direction became the vertical direction and the TD direction became the horizontal direction. The lengths in the longitudinal direction and the transverse direction before heating were measured for the layered body with the protective film that was cut out using an image sizer (IM-6120: manufactured by Keyence Co., Ltd.). Next, the cut-out laminate with protective film was heated at 150° C. for 1 hour, and the lengths in the longitudinal and transverse directions of the laminate with protective film after heating were measured using the above-mentioned image sizer, based on the following The formula calculates the heat shrinkage in the MD direction and the TD direction. In the following formula, D MD is the heating shrinkage rate (%) in the MD direction, D TD is the heating shrinkage rate (%) in the TD direction, and E MD is the MD direction length of the laminate with the protective film before heating ( cm), E TD is the length in the TD direction of the laminate with the protective film before heating (cm), F MD is the length in the MD direction of the laminate with the protective film after heating (cm), and F TD is the after heating The length (cm) in the TD direction of the laminate with the protective film. D MD = (F MD - E MD )/E MD ×100 D TD = (F TD -E TD )/ETD × 100
＜加熱捲曲量測定＞ 於實施例及比較例之附保護膜之積層體中，將附保護膜之積層體於150℃加熱1小時，測定加熱後之附保護膜之積層體之捲曲量。具體而言，首先，將附保護膜之積層體切成縱34 cm×橫34 cm之大小。繼而，將該切出之附保護膜之積層體於150℃之環境下加熱1小時，將加熱後之附保護膜之積層體放置於平坦之台上。繼而，分別測定附保護膜之積層體之四邊與台之距離，以將其進行平均所得之值作為捲曲量。再者，於以保護膜成為下側之方式放置於台之情形時，將附保護膜之積層體之上表面捲曲成凹狀之情形設為正（+），將附保護膜之積層體之上表面捲曲成凸狀之情形設為負（-）。<Measurement of heat curl amount> In the laminates with protective films of Examples and Comparative Examples, the laminates with protective films were heated at 150° C. for 1 hour, and the curling amount of the laminates with protective films after heating was measured. Specifically, first, the protective film-attached laminate was cut into a size of 34 cm in length x 34 cm in width. Next, this cut-out laminate with protective film was heated in an environment of 150° C. for 1 hour, and the heated laminate with protective film was placed on a flat table. Then, the distance between the four sides of the laminated body with the protective film and the table was measured, and the value obtained by averaging them was used as the curl amount. Furthermore, in the case where the protective film is placed on the table so that the lower side is placed, the upper surface of the laminated body with the protective film is curled into a concave shape as positive (+). The case where the upper surface was curled into a convex shape was set as negative (-).
＜表面電阻值測定＞ 於實施例及比較例之附保護膜之積層體中，測定正面及背面之表面電阻值。附保護膜之積層體之正面的表面電阻值之測定係使用依據JIS K7194：1994（導電性塑膠之利用四探針法之電阻率試驗方法）之接觸式電阻計（產品名「Loresta AX MCP-T370型」，Mitsubishi Chemical Analytech股份有限公司製造，端子形狀：ASP探針）而進行。具體而言，藉由如下方式進行，即，將切成80 mm×50 mm之大小之附保護膜的積層體以導電層側成為上表面，且附保護膜的積層體成為均勻之平面狀態之方式配置於平坦的玻璃板上，將ASP探針配置於導電層之中心，將所有的電極接腳均勻地壓抵於導電層。於利用接觸式電阻計之測定時，選擇作為測定片材電阻之模式之Ω/□。其後，按下開始按鈕並保持，獲得測定結果。附保護膜之積層體之背面之表面電阻值之測定係使用表面電阻值測定器（產品名「Hiresta IP MCP-HT260」，三菱化學股份有限公司製造）於施加電壓500 V進行。表面電阻值之測定部位係設為附保護膜之積層體之表面或背面的中心部之3個部位，表面電阻值設為3個部位之表面電阻值之算術平均值。無論電阻計之種類如何，表面電阻值之測定均於23℃及相對濕度55%之環境下進行。<Measurement of surface resistance value> In the laminated bodies with protective films of Examples and Comparative Examples, the surface resistance values of the front and back surfaces were measured. The surface resistance value of the front surface of the laminated body with the protective film was measured using a contact resistance meter (product name "Loresta AX MCP- T370 type", manufactured by Mitsubishi Chemical Analytech Co., Ltd., terminal shape: ASP probe). Specifically, it is performed by cutting the laminated body with a protective film into a size of 80 mm×50 mm so that the conductive layer side becomes the upper surface, and the laminated body with a protective film is in a uniform planar state. The method is arranged on a flat glass plate, the ASP probe is arranged in the center of the conductive layer, and all the electrode pins are evenly pressed against the conductive layer. In the measurement using a contact resistance meter, Ω/□ was selected as a mode for measuring sheet resistance. After that, the start button is pressed and held to obtain the measurement result. The surface resistance value of the back surface of the laminated body with a protective film was measured using a surface resistance value measuring device (product name "Hiresta IP MCP-HT260", manufactured by Mitsubishi Chemical Co., Ltd.) at an applied voltage of 500 V. The measurement site of the surface resistance value was set to 3 sites in the center part of the front or back of the laminated body with the protective film, and the surface resistance value was set to the arithmetic mean of the surface resistance values of the 3 sites. Regardless of the type of resistance meter, the measurement of surface resistance is carried out in an environment of 23°C and a relative humidity of 55%.
＜剝離帶電壓評價＞ 於實施例之附保護膜之積層體中，測定剝離保護膜時之剝離帶電壓並進行評價。具體而言，首先使切成縱15 cm×橫2.5 cm之大小之附保護膜之積層體保持於拉伸試驗機（產品名「Tensilon萬能材料試驗機RTF-1150-H」，A＆D股份有限公司製造）之一對治具。於使附保護膜之積層體保持於治具時，以人手預先將保護膜自積層體略微剝離，製作出起點，使保護膜保持於其中一治具並且使積層體保持於另一治具。於該狀態下，於剝離速度300 mm/分鐘、剝離距離50 mm、剝離角度180°之條件下剝離保護膜。繼而，使用配置於距離積層體之表面之中央為高度100 mm的位置之電位測定機（型號「KSD-0103」，春日電機公司製造），測定積層體之表面之剝離帶電壓。測定係於23℃、相對濕度55%之環境下進行。 ○：帶電壓為10 kv以下。 △：帶電壓超過10 kv且為50 kv以下。 ×：帶電壓超過50 kv。<Evaluation of peeling charge voltage> In the laminated body with a protective film of an Example, the peeling electric voltage at the time of peeling a protective film was measured and evaluated. Specifically, first, the protective film-attached laminate cut into a size of 15 cm in length x 2.5 cm in width was held in a tensile testing machine (product name "Tensilon Universal Material Testing Machine RTF-1150-H", A&D Co., Ltd. manufacturing) one pair of jigs. When holding the laminated body with the protective film on the jig, the protective film is slightly peeled off from the laminated body by hand to make a starting point, and the protective film is held in one of the jigs and the laminated body is held in the other jig. In this state, the protective film was peeled off under the conditions of a peeling speed of 300 mm/min, a peeling distance of 50 mm, and a peeling angle of 180°. Next, using a potential measuring machine (model "KSD-0103", manufactured by Kasuga Electric Co., Ltd.) disposed at a height of 100 mm from the center of the surface of the laminated body, the peeling charge voltage on the surface of the laminated body was measured. The measurement was carried out in an environment of 23°C and a relative humidity of 55%. ○: The charging voltage is 10 kV or less. △: The charging voltage exceeds 10 kV and is 50 kV or less. ×: The charging voltage exceeds 50 kV.
＜光漫反射率（SCE）測定＞ 於實施例之積層體中，測定存在導電層之區域之光漫反射率。具體而言，首先，將保護膜導電性膜切成10 cm×10 cm之大小，剝離保護膜。另一方面，準備大小10 cm×10 cm之黏著膜（商品名「Panaclean」，Panac股份有限公司製造，折射率1.49）及大小10 cm×10 cm之黑色壓克力板（商品名「Comoglas」，Kuraray股份有限公司，DFA2CG 502K（黑）系，厚度2 mm，總光線穿透率0%，折射率1.49）。繼而，依序積層黑色壓克力板、黏著膜、及切成上述大小且剝離了保護膜之積層體。再者，以積層體成為較黑色壓克力板更上側，且導電層成為較聚對苯二甲酸乙二酯膜更上側之方式配置。繼而，使用分光測色計（產品名「CM-600d」，Konica Minolta股份有限公司，測定口φ11 mm），於以下之測定條件下，自積層體之導電層側測定光漫反射率。光漫反射率係對1片積層體測定3次，設為進行3次測定所獲得之值之算術平均值。於測定光漫反射率時，於在積層體之中央部載有CM-600d之狀態下按下測定按鈕進行測定。 （測定條件） ・主光源：D65 ・光源2：無 ・視野：2度 ・表色系：Yxy ・色差式：ΔE﹡ ab<Measurement of diffuse light reflectance (SCE)> In the laminates of Examples, the diffuse light reflectance of the region where the conductive layer exists was measured. Specifically, first, the protective film conductive film was cut into a size of 10 cm×10 cm, and the protective film was peeled off. On the other hand, an adhesive film (trade name "Panaclean", manufactured by Panac Co., Ltd., refractive index 1.49) with a size of 10 cm × 10 cm and a black acrylic sheet (trade name "Comoglas" with a size of 10 cm × 10 cm) were prepared. , Kuraray Co., Ltd., DFA2CG 502K (black) series, thickness 2 mm, total light transmittance 0%, refractive index 1.49). Next, a black acrylic plate, an adhesive film, and a layered body cut into the above-mentioned size and peeled off the protective film were laminated in this order. In addition, it arrange|positions so that a laminated body may become an upper side rather than a black acrylic sheet, and a conductive layer may become an upper side rather than a polyethylene terephthalate film. Next, using a spectrophotometer (product name "CM-600d", Konica Minolta Co., Ltd., measuring port φ11 mm), the light diffuse reflectance was measured from the conductive layer side of the laminate under the following measurement conditions. The light diffuse reflectance was measured 3 times with respect to 1 sheet of laminated body, and it was set as the arithmetic mean value of the values obtained by performing the measurement 3 times. When measuring the light diffuse reflectance, the measurement button was pressed in the state which carried CM-600d in the center part of a laminated body. (Measurement conditions) ・Main light source: D65 ・Light source 2: None ・Field of view: 2 degrees ・Color system: Yxy ・Color difference formula: ΔE ﹡ ab
＜乳濁評價＞ 於實施例之積層體中，觀察外觀，確認於導電層之表面是否產生乳濁。評價基準如以下所述。 ◎：未確認到乳濁。 ○：確認到少許乳濁，但為實際使用中無問題之等級。 △：確認到某種程度之乳濁。 ×：明確地確認到乳濁。＜Evaluation of opacity＞ In the laminated body of the Example, the external appearance was observed, and it was confirmed whether opacity was generated on the surface of the conductive layer. The evaluation criteria are as follows. ⊚: No opacity was recognized. ○: A little opacity was observed, but it was a level that did not cause any problems in actual use. △: Some degree of opacity is recognized. ×: Opacity was clearly observed.
以下將結果示於表1及表2。
[表1]
[表2]
[表3]
於比較例1、2之附保護膜之積層體中，黏著層之壓痕硬度未達100 MPa，因此無法獲得特定之鉛筆硬度，又，於加熱前後，剝離強度或接觸角上升。又，於比較例3、4之附保護膜之積層體中，第1硬塗層與第2硬塗層牢固地結合，因此無法剝離保護膜。相對於此，於實施例1～10之附保護膜之積層體中，可剝離保護膜，且第1硬塗層及第2硬塗層之壓痕硬度分別為100 MPa以上，因此可獲得特定之鉛筆硬度，又，可較比較例1、2抑制加熱前後之剝離強度或接觸角之上升。再者，所謂鉛筆硬度試驗係指鉛筆芯之直徑較大，以其直徑整體對樣品面施加負重之試驗，因此對硬度產生影響至相當之深度。有硬度結果亦因樹脂層之膜厚或基底之素材而發生變化之情況，有無法判斷純粹之樹脂層本身之硬度之情形。因此，於本發明中，為了盡可能消除厚度之影響，較佳為使用能夠測定局部硬度之壓痕硬度之測定，且藉由測定剖面之硬度而非表面之硬度，而以樹脂層本身之硬度解決課題。In the laminates with protective films of Comparative Examples 1 and 2, the indentation hardness of the adhesive layer was less than 100 MPa, so the specific pencil hardness could not be obtained, and the peel strength or contact angle increased before and after heating. Moreover, in the laminated body with a protective film of the comparative examples 3 and 4, since the 1st hard-coat layer and the 2nd hard-coat layer were firmly bonded, the protective film could not be peeled off. On the other hand, in the laminates with protective film of Examples 1 to 10, the protective film can be peeled off, and the indentation hardness of the first hard coat layer and the second hard coat layer are respectively 100 MPa or more, so specific Moreover, compared with Comparative Examples 1 and 2, the peel strength and the contact angle increase before and after heating can be suppressed. Furthermore, the so-called pencil hardness test refers to a test in which the diameter of the pencil lead is relatively large, and the entire diameter of the lead exerts a load on the sample surface, thus affecting the hardness to a considerable depth. In some cases, the hardness results also vary depending on the film thickness of the resin layer or the material of the substrate, and in some cases, the hardness of the pure resin layer itself cannot be judged. Therefore, in the present invention, in order to eliminate the influence of thickness as much as possible, it is preferable to use the measurement of indentation hardness that can measure the local hardness, and to measure the hardness of the cross section instead of the hardness of the surface, and use the hardness of the resin layer itself. solve the problem.
於實施例6、8之附保護膜之積層體中，由於具備含有抗靜電劑之第2硬塗層或抗靜電層，故而剝離保護膜時之帶電壓小於實施例1～5、7、9、10之附保護膜之積層體。又，於實施例9、10之積層體中，由於導電層含有鎳奈米線或形成有皮膜之銀奈米線，故而光漫反射率低於實施例1～8之積層體。又，如表3所示，光漫反射率與乳濁存在相關關係，具體而言，確認到若光漫反射率為0.5%以下，則乳濁得到抑制。In the laminates with protective film of Examples 6 and 8, since the second hard coat layer or antistatic layer containing an antistatic agent is provided, the charging voltage when the protective film is peeled off is lower than that of Examples 1 to 5, 7 and 9. , 10 of the laminated body with protective film. In addition, in the laminates of Examples 9 and 10, since the conductive layer contains nickel nanowires or silver nanowires formed with a film, the light diffuse reflectance is lower than that of the laminates of Examples 1 to 8. In addition, as shown in Table 3, there is a correlation between the light diffuse reflectance and opacity, and specifically, it was confirmed that opacity is suppressed when the light diffuse reflectance is 0.5% or less.
10、40、60、80、100‧‧‧附保護膜之積層體
10A‧‧‧正面
10B‧‧‧背面
20、50、70‧‧‧積層體
21、171‧‧‧第1基材
21A、31A‧‧‧第1面
21B、31B‧‧‧第2面
22、172‧‧‧第1樹脂層
23、71‧‧‧第1功能層
23A‧‧‧表面
24‧‧‧透光性樹脂
25‧‧‧導電性纖維
30、90、110、131、133、137、139‧‧‧保護膜
31‧‧‧第2基材
32‧‧‧第2樹脂層
33、111‧‧‧第2功能層
34、35‧‧‧塗膜
72、174‧‧‧導電部
72A、174A‧‧‧感測器部
72B‧‧‧線部
72C‧‧‧膨出部
73、175‧‧‧非導電部
120‧‧‧圖像顯示裝置
130‧‧‧顯示面板
134、136、152、153‧‧‧透光性黏著層
135‧‧‧顯示元件
132、138‧‧‧偏光元件
140‧‧‧背光裝置
150‧‧‧觸控面板
151‧‧‧透光性覆蓋構件
160‧‧‧透光性接著層
170‧‧‧導電性膜
173‧‧‧導電層
D‧‧‧膜厚方向10, 40, 60, 80, 100‧‧‧Laminated body with
圖1係實施形態之附保護膜之積層體之概略構成圖。 圖2係圖1所示之附保護膜之積層體之局部放大圖。 圖3係實施形態之另一附保護膜之積層體之概略構成圖。 圖4係實施形態之另一附保護膜之積層體之概略構成圖。 圖5係圖4之附保護膜之積層體之示意性俯視圖。 圖6係實施形態之另一附保護膜之積層體之概略構成圖。 圖7係實施形態之另一附保護膜之積層體之概略構成圖。 圖8（A）～圖8（C）係示意性地表示實施形態之附保護膜之積層體的製造步驟之圖。 圖9（A）～圖9（C）係示意性地表示實施形態之附保護膜之積層體的製造步驟之圖。 圖10係實施形態之圖像顯示裝置之概略構成圖。 圖11係實施形態之觸控面板之示意性俯視圖。FIG. 1 is a schematic configuration diagram of a laminate with a protective film according to an embodiment. FIG. 2 is a partial enlarged view of the laminate with the protective film shown in FIG. 1 . FIG. 3 is a schematic configuration diagram of another protective film-attached laminate according to the embodiment. Fig. 4 is a schematic configuration diagram of another protective film-attached laminate according to the embodiment. FIG. 5 is a schematic plan view of the laminate with protective film of FIG. 4 . FIG. 6 is a schematic configuration diagram of another protective film-attached laminate according to the embodiment. FIG. 7 is a schematic configuration diagram of another laminated body with a protective film according to the embodiment. FIGS. 8(A) to 8(C) are diagrams schematically showing the production steps of the laminate with the protective film according to the embodiment. FIGS. 9(A) to 9(C) are diagrams schematically showing the production steps of the laminate with the protective film according to the embodiment. FIG. 10 is a schematic configuration diagram of an image display device according to an embodiment. FIG. 11 is a schematic plan view of the touch panel of the embodiment.
10‧‧‧附保護膜之積層體 10‧‧‧Laminated body with protective film
10A‧‧‧正面 10A‧‧‧Front
10B‧‧‧背面 10B‧‧‧Back
20‧‧‧積層體 20‧‧‧Laminate
21‧‧‧第1基材 21‧‧‧First Substrate
21A‧‧‧第1面 21A‧‧‧Side 1
21B‧‧‧第2面 21B‧‧‧Side 2
22‧‧‧第1樹脂層 22‧‧‧First resin layer
23‧‧‧第1功能層 23‧‧‧First functional layer
23A‧‧‧表面 23A‧‧‧Surface
30‧‧‧保護膜 30‧‧‧Protective film
31‧‧‧第2基材 31‧‧‧Second substrate
31A‧‧‧第1面 31A‧‧‧Side 1
31B‧‧‧第2面 31B‧‧‧Side 2
32‧‧‧第2樹脂層 32‧‧‧Second resin layer
33‧‧‧第2功能層 33‧‧‧Second functional layer
D‧‧‧膜厚方向 D‧‧‧film thickness direction
Claims (14)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017191666 | 2017-09-29 | ||
| JPJP2017-191666 | 2017-09-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201919908A TW201919908A (en) | 2019-06-01 |
| TWI763932B true TWI763932B (en) | 2022-05-11 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW107134447A TWI763932B (en) | 2017-09-29 | 2018-09-28 | Manufacturing method of laminated body with protective film and laminated body with protective film |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7400470B2 (en) |
| TW (1) | TWI763932B (en) |
| WO (1) | WO2019066079A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019172423A1 (en) * | 2018-03-09 | 2019-09-12 | 大日本印刷株式会社 | Electroconductive film, sensor, touch panel, and image display device |
| JP6732161B1 (en) * | 2019-06-20 | 2020-07-29 | 昭和電工株式会社 | Transparent conductive film laminate and processing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010017991A (en) * | 2008-07-14 | 2010-01-28 | Toppan Printing Co Ltd | Hard coat film |
| JP2012077141A (en) * | 2010-09-30 | 2012-04-19 | Lintec Corp | Hard coat layer surface-forming film, process for producing optical member with hard coat layer and optical member with hard coat layer |
| TW201612001A (en) * | 2014-07-29 | 2016-04-01 | Dainippon Printing Co Ltd | Laminated body, conductive laminated body, and touch panel |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI537358B (en) | 2011-07-15 | 2016-06-11 | Denka Company Ltd | And a translucent hard substrate laminating apparatus |
| JP5660152B2 (en) | 2013-03-19 | 2015-01-28 | 株式会社麗光 | Hard coat transfer film with adjustable peel strength and method for producing the same |
| US20150169089A1 (en) | 2013-12-12 | 2015-06-18 | Pedco, LLC | Surface Protection Film and Method of Making a Protection Film for a Touch Screen |
-
2018
- 2018-09-28 JP JP2019545205A patent/JP7400470B2/en active Active
- 2018-09-28 TW TW107134447A patent/TWI763932B/en active
- 2018-09-28 WO PCT/JP2018/036602 patent/WO2019066079A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010017991A (en) * | 2008-07-14 | 2010-01-28 | Toppan Printing Co Ltd | Hard coat film |
| JP2012077141A (en) * | 2010-09-30 | 2012-04-19 | Lintec Corp | Hard coat layer surface-forming film, process for producing optical member with hard coat layer and optical member with hard coat layer |
| TW201612001A (en) * | 2014-07-29 | 2016-04-01 | Dainippon Printing Co Ltd | Laminated body, conductive laminated body, and touch panel |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019066079A1 (en) | 2019-04-04 |
| TW201919908A (en) | 2019-06-01 |
| JP7400470B2 (en) | 2023-12-19 |
| JPWO2019066079A1 (en) | 2020-10-22 |
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