TWI676551B - Laminate film - Google Patents

Laminate film Download PDF

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Publication number
TWI676551B
TWI676551B TW104109472A TW104109472A TWI676551B TW I676551 B TWI676551 B TW I676551B TW 104109472 A TW104109472 A TW 104109472A TW 104109472 A TW104109472 A TW 104109472A TW I676551 B TWI676551 B TW I676551B
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Taiwan
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particles
film
resin
laminated film
coating
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TW104109472A
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Chinese (zh)
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TW201540499A (en
Inventor
前川茂俊
Shigetoshi Maekawa
內田裕仁
Hirohito Uchida
田中照也
Teruya Tanaka
仲村博門
Hirokado Nakamura
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日商東麗股份有限公司
Toray Industries, Inc.
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0226—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures having particles on the surface
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0033—Means for improving the coupling-out of light from the light guide
    • G02B6/005—Means for improving the coupling-out of light from the light guide provided by one optical element, or plurality thereof, placed on the light output side of the light guide
    • G02B6/0051—Diffusing sheet or layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • G02F1/133602—Direct backlight
    • G02F1/133605—Direct backlight including specially adapted reflectors

Abstract

本發明為一種積層薄膜，其特徵為：於薄膜的至少一側的表面上設置包含由樹脂(A)構成之數量平均粒徑為4μm以上的粒子(a)之塗布層，數量平均粒徑0.1μm以上1μm以下的粒子(b)附著在粒子(a)的表面上。 The present invention is a laminated film, characterized in that a coating layer containing particles (a) having a number average particle size of 4 μm or more made of resin (A) is provided on the surface of at least one side of the film, and the number average particle size is 0.1 Particles (b) of 1 μm or more and 1 μm or less adhere to the surface of the particles (a).

本發明提供：即便液晶電視內的溫度變成高溫，與以往相比會發生因導光板的翹曲造成對反射板的加重及因導光板的熱膨脹及收縮造成之導光板與反射板的摩擦，也能夠防止因密接造成的亮度不均、導光板及反射板的損傷之積層反射薄膜、光學片。 The present invention provides that even if the temperature in a liquid crystal television becomes high, compared with the past, the light guide plate is warped due to the warpage of the light guide plate and the light guide plate is caused by the thermal expansion and contraction of the light guide plate and the friction caused by the thermal expansion and contraction of the light guide plate. Laminated reflective films and optical sheets that can prevent uneven brightness due to adhesion and damage to light guide plates and reflective plates.

Description

積層薄膜 Laminated film

本發明係關於設置有含有粒子的塗布層之積層薄膜以及使用該積層薄膜之背光單元。 The present invention relates to a laminated film provided with a coating layer containing particles and a backlight unit using the laminated film.

液晶顯示器中使用照射液晶胞的背光。以往，根據液晶顯示器的種類，而在較小的液晶監視器中採用側光式的背光，反之，在較大的液晶電視中採用直下型的背光。就此等的背光用反射薄膜而言，一般可使用因氣泡而形成的多孔性白色薄膜(專利文獻1)。 A liquid crystal display uses a backlight that illuminates a liquid crystal cell. In the past, depending on the type of liquid crystal display, a side-light type backlight was used in a smaller liquid crystal monitor, whereas a direct-type backlight was used in a larger liquid crystal television. As such a reflective film for a backlight, a porous white film formed by bubbles is generally used (Patent Document 1).

又，為防止因從冷陰極管所發射的紫外線造成之薄膜的黃變，亦提出一種積層紫外線吸收層的白色薄膜(專利文獻2、3)。 In addition, in order to prevent yellowing of a thin film due to ultraviolet rays emitted from a cold cathode tube, a white film laminated with an ultraviolet absorbing layer has also been proposed (Patent Documents 2 and 3).

再者，就特別適合與附加稜鏡形狀的導光板一起使用者而言，亦開發出將含有軟質微粒的層積層成基材片層而成之反射薄膜(專利文獻4、5)。 Furthermore, for users who are particularly suitable for use with a light guide plate with a cymbal shape, a reflective film formed by laminating a layer containing soft particles into a substrate sheet has also been developed (Patent Documents 4 and 5).

依據液晶電視的薄型化，液晶電視中亦採用側光式背光，同時正積極進行關於側光式背光的開發。再者，為了降低耗電量以及無水銀化，而採用發光二極體(以下簡稱為LED)作為光源。 Due to the thinness of LCD TVs, edge-lit backlights are also used in LCD TVs, and development of edge-lit backlights is being actively pursued. Furthermore, in order to reduce power consumption and non-mercury, a light emitting diode (hereinafter referred to as LED) is used as a light source.

在液晶電視中，與筆記型電腦或桌上型電腦 顯示器不同，其被要求高亮度，必須配置許多的LED。因此，必須製成使用熱傳導係數高的鋁的殼體，進行散熱措施(measures for the heat radiation)。然而，在採用鋁的情況下，機械強度容易下降。因此，必須藉由例如壓深成型在殼體上形成凹凸。 In an LCD TV, with a laptop or desktop computer Different displays, which are required to have high brightness, must be equipped with many LEDs. Therefore, it is necessary to make a case using aluminum having a high thermal conductivity coefficient and perform measures for the heat radiation. However, when aluminum is used, the mechanical strength is liable to decrease. Therefore, it is necessary to form unevenness on the case by, for example, deep drawing.

再者，側光型的背光中必須要有導光板作為光學構件。關於導光板，在以往的筆記型電腦或桌上型電腦顯示器中，到25吋型左右的尺寸已相當足夠，但液晶電視需要30~100吋型。因此，開發出主要對壓克力板施予點印刷而成之具有凸狀部的導光板、具有使用雷射加工或UV轉印法之凹狀部之導光板等。 Furthermore, a side-light type backlight requires a light guide plate as an optical member. Regarding the light guide plate, in the conventional notebook computer or desktop computer monitor, the size to about 25 inches is quite enough, but the LCD TV needs 30 to 100 inches. Therefore, light guide plates having convex portions, and light guide plates having concave portions using a laser process or a UV transfer method have been developed, mainly by applying dot printing to acrylic plates.

於是，為了防止對導光板的刮痕或密接，已開發出：該反射板於與導光板相接的面上調整軟質微粒的平均粒徑或埋藏率來抑制微粒的脫落並抑制因密接產生的白點缺陷的發生之反射薄膜、或藉由控制薄膜的緩衝率(cushion factor)來抑制亮度不均及白點缺陷的產生之反射薄膜、將含有2種不同硬度的微粒的層積層成基材片狀而成之反射薄膜(專利文獻6、7、8)。 Therefore, in order to prevent scratches or adhesion to the light guide plate, it has been developed that the reflecting plate adjusts the average particle diameter or burial rate of the soft particles on the surface that is in contact with the light guide plate to suppress the fall of the particles and suppress the occurrence of the particles caused by the adhesion. Reflective film that causes white point defects, or reflective film that controls the occurrence of uneven brightness and white point defects by controlling the cushioning factor of the film, and laminates containing two particles of different hardnesses as a substrate Sheet-shaped reflective film (Patent Documents 6, 7, and 8).

另一方面，藉由將使光擴散的擴散片或控制光的行進方向之棱鏡片等的光學片配置在導光板與液晶面板之間，而使來自導光板的光出光的效率提升，並且達成改善亮度不均。此等光學片亦為了與導光板鄰接，而開發出在與導光板鄰接的面上施加微粒塗布(beads coat)，防止對導光板的刮痕或密接之技術(專利文獻9、10)。 On the other hand, by arranging optical sheets such as a diffusion sheet that diffuses light or a prism sheet that controls the traveling direction of the light between the light guide plate and the liquid crystal panel, the efficiency of light emission from the light guide plate is improved and achieved Improve uneven brightness. In order to adjoin these light guide plates, these optical sheets have been developed with a technique of applying a beads coat on a surface adjacent to the light guide plate to prevent scratches or adhesion to the light guide plate (Patent Documents 9 and 10).

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開平8-262208號公報 [Patent Document 1] Japanese Unexamined Patent Publication No. 8-262208

[專利文獻2]日本特開2001-166295號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2001-166295

[專利文獻3]日本特開2002-90515號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2002-90515

[專利文獻4]日本特開2003-92018號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2003-92018

[專利文獻5]日本特表2008-512719號公報 [Patent Document 5] Japanese Patent Publication No. 2008-512719

[專利文獻6]日本特開2009-244509號公報 [Patent Document 6] Japanese Patent Laid-Open No. 2009-244509

[專利文獻7]國際公開第2011/105294號 [Patent Document 7] International Publication No. 2011/105294

[專利文獻8]日本特開2012-242489號公報 [Patent Document 8] Japanese Patent Application Publication No. 2012-242489

[專利文獻9]日本特開2008-262147號公報 [Patent Document 9] Japanese Patent Laid-Open No. 2008-262147

[專利文獻10]日本特開2007-86730號公報 [Patent Document 10] Japanese Patent Laid-Open No. 2007-86730

近年來，為了節省成本而使用利用熱傳導率低的鋼板或樹脂而成的殼體，因此殼體內的溫度會上升，導光板會重複收縮和膨脹而導光板會翹曲，會有一部分與反射板或光學片強烈地相互摩擦的狀況發生。 In recent years, in order to save costs, a housing made of steel or resin with low thermal conductivity is used. Therefore, the temperature in the housing will rise, the light guide plate will repeatedly shrink and expand, and the light guide plate will warp. Or, the optical sheet rubs strongly against each other.

因此，反射板及光學片中可列舉出以下的課題點。 Therefore, the following problems can be cited in the reflection plate and the optical sheet.

(1)導光板與反射板及光學片未均一地密接而發生亮度不均之問題。 (1) The light guide plate, the reflection plate, and the optical sheet are not uniformly adhered to each other, causing a problem of uneven brightness.

(2)導光板與反射板及光學片密接，因導光板的熱膨脹、收縮而在反射板及光學片上產生皺摺，而發生亮度 不均之問題 (2) The light guide plate is in close contact with the reflective plate and the optical sheet. The thermal expansion and contraction of the light guide plate causes wrinkles on the reflective plate and the optical sheet, resulting in brightness. The problem of unevenness

(3)刮傷導光板表面及/或削掉反射板表面或光學片的微粒，而發生亮度不均之問題 (3) The surface of the light guide plate is scratched and / or particles on the surface of the reflective plate or the optical sheet are scraped off, causing uneven brightness.

本發明提供一種即便液晶電視內的溫度變得比以往還要高溫，且與以往相比，會發生因導光板的翹曲造成對反射板或光學片的加重或摩擦，還是能夠防止因密接造成的亮度不均、導光板及反射板或光學片的損傷。 The invention provides that even if the temperature in a liquid crystal television becomes higher than in the past, and compared with the past, the reflection plate or the optical sheet may be aggravated or rubbed due to the warpage of the light guide plate, it is still possible to prevent Uneven brightness, damage to the light guide plate and reflective plate or optical sheet.

為了解決該課題，本發明之積層薄膜具有以下的構成。 In order to solve this problem, the laminated film of this invention has the following structures.

(1)一種積層薄膜，其特徵為：於薄膜的至少一側的表面上設置包含由樹脂(A)構成之數量平均粒徑為4μm以上的粒子(a)之塗布層，數量平均粒徑0.1μm以上1μm以下的粒子(b)附著在粒子(a)的表面上。 (1) A laminated film characterized in that a coating layer containing particles (a) having a number average particle diameter of 4 μm or more made of resin (A) is provided on a surface of at least one side of the film, and the number average particle diameter is 0.1 Particles (b) of 1 μm or more and 1 μm or less adhere to the surface of the particles (a).

(2)如前述記載之積層薄膜，其特徵為：於白色薄膜的至少一側的表面上設置包含由樹脂(A)構成之數量平均粒徑為4μm以上的粒子(a)之塗布層，數量平均粒徑為0.1μm以上1μm以下的粒子(b)附著在粒子(a)的表面上。 (2) The laminated film as described above, characterized in that: a coating layer containing particles (a) having a number average particle diameter of 4 μm or more made of resin (A) is provided on the surface of at least one side of the white film, and the number is Particles (b) having an average particle diameter of 0.1 μm or more and 1 μm or less adhere to the surface of the particles (a).

(3)如(1)記載之積層薄膜，其特徵在於：前述薄膜為透明，前述薄膜的全光線穿透率為60%以上。 (3) The laminated film according to (1), wherein the film is transparent, and the total light transmittance of the film is 60% or more.

(4)如(1)或(3)記載之積層薄膜，其特徵為平均10個以上的粒子(b)附著在1個粒子(a)的表面。 (4) The laminated film according to (1) or (3), characterized in that an average of 10 or more particles (b) adhere to the surface of one particle (a).

(5)如(1)至(4)中任一項記載之積層薄膜，其中粒子(a)係由聚酯樹脂構成。 (5) The laminated film according to any one of (1) to (4), wherein the particles (a) are composed of a polyester resin.

(6)如(1)至(5)中任一項記載之積層薄膜，其中粒子 (b)是由不同於樹脂(A)的樹脂(B)構成。 (6) The laminated film according to any one of (1) to (5), wherein the particles are (b) is made of resin (B) different from resin (A).

(7)如(1)至(5)中任一項記載之積層薄膜，其中粒子(b)為無機粒子。 (7) The laminated film according to any one of (1) to (5), wherein the particles (b) are inorganic particles.

(8)如(1)至(7)中任一項記載之積層薄膜，其中塗布層的厚度小於1μm。 (8) The laminated film according to any one of (1) to (7), wherein the thickness of the coating layer is less than 1 μm.

(9)如(1)至(7)中任一項記載之積層薄膜，其中塗布層的厚度小於0.5μm。 (9) The laminated film according to any one of (1) to (7), wherein the thickness of the coating layer is less than 0.5 μm.

(10)如(1)至(9)中任一項記載之積層薄膜，其中粒子(a)的數量平均粒徑為4μm以上60μm以下。 (10) The laminated film according to any one of (1) to (9), wherein the number average particle diameter of the particles (a) is 4 μm or more and 60 μm or less.

(11)如(1)至(10)中任一項記載之積層薄膜，其中粒子(b)的數量平均粒徑為100nm以上800nm以下。 (11) The laminated film according to any one of (1) to (10), wherein the number average particle diameter of the particles (b) is 100 nm to 800 nm.

(12)如(1)、(2)或(4)至(11)中任一項記載之積層薄膜，其為邊緣型背光單元用的反射板。 (12) The laminated film according to any one of (1), (2), or (4) to (11), which is a reflective plate for an edge type backlight unit.

(13)一種邊緣型背光單元，其係使用如(1)至(11)中任一項記載之積層薄膜而成之邊緣型背光單元。 (13) An edge type backlight unit, which is an edge type backlight unit using the laminated film according to any one of (1) to (11).

若根據本發明之積層薄膜，則可防止關於反射板、光學片之前述(1)導光板與反射板及光學片未均一地密接而發生亮度不均之問題；(2)導光板與反射板及光學片密接，因導光板的熱膨脹、收縮而在反射板及光學片上產生皺摺，而發生亮度不均之問題；(3)刮傷導光板表面及/或削掉反射板表面或光學片的微粒，而發生亮度不均之問題。 According to the laminated film of the present invention, the aforementioned (1) the problem that the light guide plate and the reflective plate and the optical sheet are not uniformly adhered to each other and the uneven brightness occurs can be prevented; (2) the light guide plate and the reflective plate And the optical sheet are in close contact, and the problem of uneven brightness occurs due to wrinkles on the reflective plate and the optical sheet due to thermal expansion and contraction of the light guide plate; (3) scratching the surface of the light guide plate and / or cutting off the surface of the reflective plate or the optical sheet Particles, and the problem of uneven brightness occurs.

11‧‧‧附著於粒子12的表面上的粒子 11‧‧‧ Particles attached to the surface of particle 12

12‧‧‧粒子 12‧‧‧ particles

13‧‧‧黏結劑樹脂 13‧‧‧Binder Resin

第1圖為積層薄膜表面的粒子的掃描式電子顯微鏡(SEM)照片。 FIG. 1 is a scanning electron microscope (SEM) photograph of particles on the surface of a laminated film.

[實施發明之形態] [Form of Implementing Invention]

本發明之積層薄膜為一種積層薄膜，其特徵為：於薄膜的至少一側的表面上設置包含由樹脂(A)構成之數量平均粒徑為4μm以上的粒子(a)之塗布層，數量平均粒徑0.1μm以上1μm以下的粒子(b)附著在粒子(a)的表面上。 The laminated film of the present invention is a laminated film characterized in that a coating layer containing particles (a) having a number average particle diameter of 4 μm or more made of resin (A) is provided on the surface of at least one side of the film, and the number is averaged. Particles (b) having a particle diameter of 0.1 μm or more and 1 μm or less adhere to the surface of the particles (a).

(1.1)積層薄膜的塗布層 (1.1) Coating layer of laminated film

本發明之塗布層中含有的粒子是由附著有粒子(b)之粒子(a)構成。藉由使粒徑小的粒子(b)附著在粒子(a)的表面，而不會有因導光板的熱膨脹、收縮導致在反射板或光學片上產生皺摺而發生亮度不均之情況。又，不會有因導光板與反射板或光學片互相摩擦而刮傷導光板表面、及/或削掉反射板或光學片表面的微粒，因而發生亮度不均之情況。具有這些效果的機構的詳細情況尚不清楚，但認為這是因為在導光板與反射板或光學片壓接並施加剪切力時，藉由在粒子(a)的表面設置小粒徑的粒子(b)，摩擦應力會下降，粒子(a)不會黏附在導光板上，在導光板與反射板或光學片之間不會產生大的摩擦力。 The particles contained in the coating layer of the present invention are composed of particles (a) to which the particles (b) are attached. By adhering the particles (b) having a small particle diameter to the surface of the particles (a), there is no possibility of uneven brightness due to wrinkles on the reflection plate or optical sheet due to thermal expansion and contraction of the light guide plate. In addition, the light guide plate and the reflective plate or the optical sheet are rubbed against each other to scratch the surface of the light guide plate and / or to remove particles on the surface of the reflective plate or the optical sheet, thereby causing uneven brightness. The details of the mechanism having these effects are unknown, but it is thought that this is because when the light guide plate is pressed against the reflection plate or the optical sheet and a shear force is applied, a particle having a small particle diameter is provided on the surface of the particle (a). (b) The frictional stress will decrease, and the particles (a) will not adhere to the light guide plate, and no large frictional force will be generated between the light guide plate and the reflective plate or the optical sheet.

就使粒子(b)附著在粒子(a)的表面之方法而言，較佳可例示例如：利用TECHNO SYSTEMS股份有限公司發行的「分散‧凝集的闡明與應用技術」所記載的異質絮凝(heteroflocculation)法之方法。具體來說，可列 舉：在當塗液中含有根據pH而ζ電位改變之SiO2所例示之無機粒子及/或有機粒子時調整塗液的pH，以無機粒子及/或有機粒子的ζ電位的符號為不同的方式來調整pH，使小粒徑的粒子附著在大粒徑的粒子的周圍之方法。此時，因粒子的粒徑或表面狀態而為非常有限的pH範圍之情況多，而且藉由有機粒子與無機粒子的組合亦會有無進行異質絮凝的條件的情況。就較佳的無機物而言，可列舉SiO2、TiO2、γ-Al2O3或ZnO等金屬氧化物。在有機粒子與有機粒子的組合之情況下，任一個的ζ電位均是相同符號之情況多，為了進行異質絮凝，而如化學工業協會編「最近的化學工程 特殊粉體技術」所記載，藉由使粒子與粒子的表面電位的差變大，就能夠得到異質絮凝體。尤其是粒子(a)與粒子(b)的ζ電位差係以20mV以上為佳，更佳為30mV以上，再更佳為40mV以上。各個粒子的ζ電位係以粒子(a)為-30mV以上-20mV以下且粒子(b)的ζ電位為-120mV以上60mV以下之組合為佳。就使粒子的ζ電位在上述範圍之方法而言，有藉由調整構成粒子的樹脂的末端COOH基、酚性OH基和末端NH2基的量而能夠達成之情況。具體來說，有藉由在粒子的表面上具有此等末端基而能夠使負的ζ電位變大的情況。又，亦可使用陰離子性界面活性劑。又，就變小的方法而言，有藉由吸附而使有機離子或錯離子吸附、使陽離子性界面活性劑吸附、形成鹽等，因而能夠使ζ電位差變小之情況。 As a method for attaching the particles (b) to the surface of the particles (a), a preferable example is the use of heteroflocculation described in "Explanation and Application Technology of Dispersion and Agglutination" issued by TECHNO SYSTEMS Co., Ltd. ) Method of law. Specifically, when the coating liquid contains inorganic particles and / or organic particles exemplified by SiO 2 whose zeta potential changes according to pH, the pH of the coating liquid can be adjusted, and the zeta potential of the inorganic particles and / or organic particles can be adjusted. The symbol of is a method of adjusting the pH in a different way so that particles with a small particle diameter adhere to the particles with a large particle diameter. At this time, there are many cases where the pH range is very limited due to the particle size or surface state of the particles, and there is a case where the conditions of heterogeneous flocculation are not performed by a combination of organic particles and inorganic particles. Preferable inorganic substances include metal oxides such as SiO 2 , TiO 2 , γ-Al 2 O 3 and ZnO. In the case of a combination of organic particles and organic particles, the zeta potential of any one of them is often the same symbol. In order to perform heterogeneous flocculation, as described in "Recent Chemical Engineering Special Powder Technology" edited by the Chemical Industry Association, borrow By increasing the difference in the surface potential between the particles and the particles, a heterogeneous floc can be obtained. In particular, the zeta potential difference between the particles (a) and (b) is preferably 20 mV or more, more preferably 30 mV or more, and even more preferably 40 mV or more. The zeta potential of each particle is preferably a combination of the particle (a) being -30 mV or more and -20 mV or less and the particle (b) having a zeta potential of -120 mV or more and 60 mV or less. The method of making the zeta potential of the particles within the above range may be achieved by adjusting the amounts of the terminal COOH group, phenolic OH group, and terminal NH 2 group of the resin constituting the particle. Specifically, a negative zeta potential may be increased by having such terminal groups on the surface of a particle. Moreover, an anionic surfactant can also be used. In addition, as a method for reducing the size, there may be a case where the zeta potential difference can be made small because the organic ion or the counter ion is adsorbed by adsorption, the cationic surfactant is adsorbed, and a salt is formed.

附著在每1個粒子(a)的表面上的粒子(b)的數量係以平均10個以上為佳，更佳為50個以上，最佳為100 個以上。藉由具有10個以上，而導光板與粒子(a)的接觸面積會下降，能夠使傷痕減少。上限推測為500個以下。表面的粒子被覆率若過多，則會變得跟只有粒子(b)的巨大粒子一樣，結果會與導光板相黏，產生傷痕或脫落，因而不佳。為了使附著在每1個粒子(a)的表面上的粒子(b)的數量為10個以上，例如可藉由使粒子(a)與粒子(b)的ζ電位差為20mV以上來調整。又，為了為500個以下，能夠藉由調節粒子(b)的摻合量來調整。本發明所稱的附著的粒子的個數是指以SEM觀察表面時的1個粒子(a)的表面上所附著的粒子(b)的個數。 The number of particles (b) adhering to the surface of each particle (a) is preferably 10 or more on average, more preferably 50 or more, and most preferably 100 More than. By having 10 or more, the contact area of a light-guide plate and a particle (a) will fall, and a flaw can be reduced. The upper limit is estimated to be 500 or less. If the particle coverage on the surface is too large, it will become the same as a giant particle with only particles (b). As a result, it will stick to the light guide plate and cause scratches or peeling, which is not good. In order to make the number of particles (b) attached to the surface of each particle (a) to be 10 or more, for example, the zeta potential difference between particles (a) and (b) can be adjusted by 20 mV or more. The number of particles (b) can be adjusted to be 500 or less. The number of particles adhered in the present invention refers to the number of particles (b) adhered to the surface of one particle (a) when the surface is observed by SEM.

(1.2)粒子(a) (1.2) Particles (a)

粒子(a)是由樹脂(A)構成。樹脂(A)的種類沒有特殊的限定，但可列舉聚甲基丙烯酸甲酯丙烯酸酯樹脂、丙烯酸苯乙烯系樹脂、聚甲基丙烯酸甲酯樹脂、聚甲基丙烯酸丁酯樹脂、聚矽氧系樹脂、聚苯乙烯系樹脂、聚碳酸酯樹脂、苯并胍胺系樹脂、三聚氰胺系樹脂、聚烯烴系樹脂、聚酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、或聚氟乙烯系樹脂及此等的交聯物等。 The particles (a) are composed of a resin (A). The type of the resin (A) is not particularly limited, but examples thereof include polymethyl methacrylate acrylate resin, acrylic styrene-based resin, polymethyl methacrylate resin, polybutyl methacrylate resin, and polysiloxane Resin, polystyrene resin, polycarbonate resin, benzoguanamine resin, melamine resin, polyolefin resin, polyester resin, polyamide resin, polyimide resin, or polyfluoride Vinyl-based resins and these cross-linked products.

在本發明中，尤其是從易於控制樹脂的彈性、與黏結劑的親和性良好之觀點來看，較佳為丙烯酸系樹脂、耐綸系樹脂、聚酯系樹脂。 In the present invention, acrylic resins, nylon-based resins, and polyester-based resins are particularly preferred from the viewpoint of easy control of the elasticity of the resin and good affinity with the binder.

特佳為熱塑性聚酯系樹脂。就較佳的聚酯而言，從易於控制樹脂的彈性來看，以聚對苯二甲酸乙二酯或聚對苯二甲酸丁二酯等芳香族聚酯或聚酯彈性體為佳。就聚酯彈性體的具體例而言，有各種的商品名、例 如：DuPont公司製的「HYTREL」(註冊商標)、Ticona公司製的「RITEFLEX」(註冊商標)及DSM公司製的「ARNITEL」(註冊商標)等，由許多公司進行販售。 Particularly preferred is a thermoplastic polyester resin. As for the preferable polyester, from the viewpoint of easily controlling the elasticity of the resin, an aromatic polyester or polyester elastomer such as polyethylene terephthalate or polybutylene terephthalate is preferred. Specific examples of the polyester elastomer include various trade names and examples. For example, "HYTREL" (registered trademark) made by DuPont, "RITEFLEX" (registered trademark) made by Ticona, and "ARNITEL" (registered trademark) made by DSM are sold by many companies.

構成粒子(a)的樹脂(A)係以其彎曲彈性率為500MPa以上3000MPa以下為佳，更佳為1000MPa以上2700MPa以下。本發明中的彎曲彈性率是指依照ASTM-D790-98所測定的值。此時的測定係將樹脂(A)在90℃下熱風乾燥3小時以上，使用射出成形機(日精樹脂工業製NEX-1000)將乾燥後的顆粒在圓筒溫度240℃、模具溫度50℃的成形條件下成形而得到127×12.7×6.4mm的彎曲試片，將所得到的127×12.7×6.4mm的彎曲試片作為測定樣品來使用。彎曲彈性率若比上述範圍小，則塗布在白色薄膜上作為反射板而安裝至液晶顯示器時會有白點產生的情況。彎曲彈性率若比上述範圍大，則導光板與反射板相互摩擦時會有在導光板產生傷痕的情況。為了將熱塑性樹脂的彎曲彈性率調整成上述範圍內，可列舉例如：使長鏈的聚烷二醇與芳香族聚酯共聚合。又，在DuPont公司製的「HYTREL」(註冊商標)中，HYTREL 7247或HYTREL 8238具有上述範圍內的彎曲彈性率，因此能夠使用該產品。 The resin (A) constituting the particles (a) preferably has a flexural modulus of 500 MPa to 3000 MPa, and more preferably 1000 MPa to 2700 MPa. The flexural modulus in the present invention is a value measured in accordance with ASTM-D790-98. The measurement at this time was performed by drying the resin (A) with hot air at 90 ° C for 3 hours or more, and using an injection molding machine (NEX-1000, manufactured by Nissei Plastics Industries) to dry the pellets at a cylinder temperature of 240 ° C and a mold temperature of 50 ° C It was molded under the molding conditions to obtain a bending test piece of 127 × 12.7 × 6.4 mm, and the obtained bending test piece of 127 × 12.7 × 6.4 mm was used as a measurement sample. If the bending elastic modulus is smaller than the above range, white spots may be generated when the white film is coated on a white film as a reflection plate and mounted on a liquid crystal display. If the bending elastic modulus is larger than the above range, a scratch may occur in the light guide plate when the light guide plate and the reflective plate are rubbed against each other. To adjust the flexural modulus of the thermoplastic resin to fall within the above range, for example, a long-chain polyalkanediol and an aromatic polyester are copolymerized. Moreover, in "HYTREL" (registered trademark) manufactured by DuPont, since HYTREL 7247 or HYTREL 8238 has a bending elastic modulus within the above range, this product can be used.

就製造粒子(a)的方法而言，可列舉使其加熱熔融後從噴嘴噴灑噴霧而得到球狀粒子的方法(日本特公平2-12975號公報)；使其溶解於加熱溶媒後冷卻析出而得到球狀粒子的方法(日本特開昭51-79158號公報)；藉由將經加熱熔融的樹脂強制分散在不互溶且已加熱 的聚矽氧烷中而得到球狀粒子的方法(日本特開2001-213970號公報)；藉由使高分子溶液相分離且使乳液形成並添加不良溶媒而得到微粒子的方法(國際公開第2009/142231號)等作為能夠適當使用的方法。從易於控制粒徑、易於使粒徑分布指數減小、起因於因熔融造成的熱劣化之粒子的黃變不易產生之觀點來看，較佳使用：藉由使高分子溶液相分離且使乳液形成並添加不良溶媒而得到微粒子的手法。 The method for producing the particles (a) includes a method of obtaining spherical particles by spraying and spraying from a nozzle after heating and melting (Japanese Patent Publication No. 2-12975); cooling and precipitating after dissolving in a heating medium; Method for obtaining spherical particles (Japanese Patent Laid-Open No. 51-79158); by forcibly dispersing a resin melted by heating in an immiscible and heated state Method for obtaining spherical particles in polysiloxane (Japanese Patent Application Laid-Open No. 2001-213970); method for obtaining fine particles by phase separation of a polymer solution, forming an emulsion, and adding a poor solvent (International Publication No. 2009 / 142231), etc. as a method that can be appropriately used. From the viewpoint of easy control of the particle diameter, easy reduction of the particle size distribution index, and less yellowing of particles due to thermal degradation due to melting, it is preferably used: by phase separation of the polymer solution and emulsion A method of forming and adding a poor solvent to obtain fine particles.

粒子(a)的數量平均粒徑為4μm以上，較佳為6μm以上，更佳為8μm以上。上限較佳為60μm以下，更佳為20μm以下，再更佳為15μm以下。若小於4μm，則塗布在反射薄膜上並安裝至液晶顯示器時會有白點產生的情況，而且還有比60μm大的粒子會脫落的情況。就將粒徑調整成上述範圍之方法而言，可使用周知的方法。具體來說，可列舉日本特開2001-213970號公報、國際公開第2009/142231號中記載之方法。 The number average particle diameter of the particles (a) is 4 μm or more, preferably 6 μm or more, and more preferably 8 μm or more. The upper limit is preferably 60 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. If it is less than 4 μm, white spots may be generated when the film is coated on a reflective film and mounted on a liquid crystal display, and particles larger than 60 μm may fall off. As a method for adjusting the particle diameter to the above range, a known method can be used. Specifically, the methods described in Japanese Patent Application Laid-Open No. 2001-213970 and International Publication No. 2009/142231 can be cited.

本發明之由樹脂(A)構成的粒子(a)係以其粒徑分布指數為1~3為佳，更佳為1~2，最佳為1~1.5。藉由粒徑分布指數在上述範圍內，於將反射板壓在導光板上的狀況下，僅有一部分粒徑大的粒子會與導光板密接以及粒子變形，藉此而能夠防止白點容易產生。又，在粒徑分布指數比上述範圍大的情況(即，含有粗大粒子的情況)下，於塗布步驟中例如會有引起後述的繞線棒(Meyer bar)的粒子堵塞、塗布條紋(coating stripe)產生的情況等，從塗布外觀的觀點來看為不佳的情況。就使粒 徑分布指數在上述範圍內之方法而言，係以在使高分子相分離並使乳液形成之方法中，實施乳液形成及微粒子化步驟的溫度在100℃以上為佳。上限為溶解、相分離的溫度，不過只要能夠得到所期望的微粒子，則沒有特殊的限制，但通常為100℃~300℃的範圍，較佳為100℃~280℃，更佳為120℃~260℃，再更佳為120℃~240℃，特佳為120℃~220℃，最佳為120℃~200℃的範圍。 The particles (a) made of the resin (A) according to the present invention preferably have a particle size distribution index of 1 to 3, more preferably 1 to 2, and most preferably 1 to 1.5. When the particle size distribution index is within the above range, only a part of particles having a large particle size will be in close contact with the light guide plate and deform the particles under the condition that the reflecting plate is pressed against the light guide plate, thereby preventing white spots from easily occurring. . When the particle size distribution index is larger than the above range (that is, when coarse particles are contained), the coating step may cause, for example, clogging of particles of a later-mentioned Meyer bar and coating stripe. ) And the like are not good from the viewpoint of coating appearance. Make grain In the method in which the diameter distribution index is within the above range, in the method of separating a polymer phase and forming an emulsion, it is preferable that the temperature for carrying out the steps of forming the emulsion and the micronization step is 100 ° C or higher. The upper limit is the temperature for dissolution and phase separation, but there is no particular limitation as long as the desired fine particles can be obtained, but it is usually in the range of 100 ° C to 300 ° C, preferably 100 ° C to 280 ° C, more preferably 120 ° C 260 ° C, more preferably 120 ° C to 240 ° C, particularly preferably 120 ° C to 220 ° C, and most preferably 120 ° C to 200 ° C.

還有，本發明中所稱的粒徑分布指數是指將粒子(a)的體積平均粒徑(Dv)除以數量平均粒徑(Dn)而成的值。 The particle size distribution index referred to in the present invention is a value obtained by dividing the volume average particle diameter (Dv) of the particles (a) by the number average particle diameter (Dn).

(1.3)粒子(b) (1.3) Particles (b)

粒子(b)係以由與構成粒子(a)的樹脂(A)不同的樹脂(B)構成為佳。若樹脂(B)與樹脂(A)相同，則會有粒子(b)無法附著在粒子(a)的表面上的情況而不佳。若樹脂(B)的種類為與樹脂(A)不同的組合，則沒有特殊的限定，但可列舉聚甲基丙烯酸甲酯丙烯酸酯樹脂、丙烯酸苯乙烯系樹脂、聚甲基丙烯酸甲酯樹脂、聚甲基丙烯酸丁酯樹脂、聚矽氧系樹脂、聚苯乙烯系樹脂、聚碳酸酯樹脂、苯并胍胺系樹脂、三聚氰胺系樹脂、聚烯烴系樹脂、聚酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、或聚氟乙烯系樹脂及此等的交聯物等。 The particles (b) are preferably composed of a resin (B) different from the resin (A) constituting the particles (a). If the resin (B) is the same as the resin (A), the particles (b) may not adhere to the surface of the particles (a), which is not preferable. If the type of the resin (B) is a combination different from the resin (A), there is no particular limitation, but examples include polymethyl methacrylate acrylate resin, acrylic styrene resin, polymethyl methacrylate resin, Polybutyl methacrylate resin, polysiloxane resin, polystyrene resin, polycarbonate resin, benzoguanamine resin, melamine resin, polyolefin resin, polyester resin, polyamide resin Resins, polyimide-based resins, or polyvinyl fluoride-based resins, and these cross-linked products.

在本發明中，係以選定根據塗布液的pH而ζ電位的變化與粒子(a)不同之樹脂為佳。樹脂(A)為聚酯樹脂時，能夠較佳地選定聚苯乙烯樹脂或耐綸樹脂等作為樹脂(B)。 In the present invention, it is preferable to select a resin having a change in zeta potential different from that of the particles (a) according to the pH of the coating liquid. When the resin (A) is a polyester resin, a polystyrene resin, a nylon resin, or the like can be preferably selected as the resin (B).

粒子(b)亦可為無機粒子，藉由為無機粒子，根據塗布液的pH調整而能夠在粒子(a)的表面附著粒子(b)的情形多而可較佳地使用。無機粒子的種類並沒有限定，但為了易於根據pH而進行ζ電位的控制，較佳使用金屬氧化物。就無機粒子的具體例而言，可較佳地列舉矽石粒子、氧化鋁、二氧化鈦等。 The particle (b) may be an inorganic particle, and since the particle (b) is an inorganic particle, the particle (b) can be attached to the surface of the particle (a) depending on the pH adjustment of the coating liquid, and it can be preferably used. The type of the inorganic particles is not limited, but in order to easily control the zeta potential according to pH, a metal oxide is preferably used. Specific examples of the inorganic particles include silica particles, alumina, and titanium dioxide.

粒子(b)的數量平均粒徑為0.1μm以上1μm以下，較佳為100nm以上800nm以下，最佳為200nm以上500nm以下。若超過1μm，則有不會附著在粒子(a)的表面之情況而不佳。又，若小於100nm，則有變得比存在於粒子(a)表面的塗布膜的厚度還小的情況，並且有變得無法在粒子(a)的表面形成突起之情況，因而不佳。就上述範圍的數量平均粒徑之有機粒子的具體例而言，有各種的商品，例如：總研化學公司製的圓球狀聚苯乙烯乳膠粒子「DYNOSPHERES」、日本觸媒公司製交聯聚甲基丙烯酸甲酯粒子「Epostar(註冊商標)MX」、積水化成品公司製丙烯酸系的次微米微粒子「Techpolymer(註冊商標)」等，由許多公司進行販售，可使用此等。又，就無機粒子的具體例而言，可列舉觸媒化成工業公司製矽石粒子「Spherical Slurry」或日本觸媒公司製矽石粒子「Seahoster(註冊商標)」等，能夠使用此等。 The number average particle diameter of the particles (b) is 0.1 μm or more and 1 μm or less, preferably 100 nm or more and 800 nm or less, and most preferably 200 nm or more and 500 nm or less. When it exceeds 1 micrometer, it may not be adhering to the surface of a particle (a), and it is unpreferable. Moreover, if it is less than 100 nm, it may become smaller than the thickness of the coating film which exists on the surface of particle (a), and it may become impossible to form a protrusion on the surface of particle (a), and it is unpreferable. Specific examples of the organic particles having the number-average particle diameter in the above range include various products, for example, spherical polystyrene latex particles "DYNOSPHERES" manufactured by Soken Chemical Co., Ltd., and cross-linked polymer manufactured by Japan Catalyst Corporation. Methyl methacrylate particles "Epostar (registered trademark) MX", acrylic submicron microparticles "Techpolymer (registered trademark)" manufactured by Sekisui Chemicals Co., Ltd., and the like are sold by many companies and can be used. Specific examples of the inorganic particles include silica particles "Spherical Slurry" manufactured by Catalytic Chemical Industries, Ltd., and silica particles "Seahoster (registered trademark)" manufactured by Nihon Catalytic Corporation, and these can be used.

(1.4)黏結劑樹脂 (1.4) Binder resin

黏結劑樹脂係包含水溶性樹脂，而且使用水系的塗布液進行塗布對環境的影響少，因而較佳。此處所稱的水溶性樹脂是表示一種含有選自磺酸基、羧酸基、羥基 及該等的鹽中之至少1種的官能基之樹脂。水溶性樹脂較佳為將具有磺酸基、磺酸鹽基、羧酸基、羧酸鹽基等官能基之單體共聚合而成之樹脂，更佳為將具有羧酸基及/或羧酸基鹽的單體共聚合而成之樹脂。藉由其為水溶性，其與基材薄膜及粒子(a)的親和性佳，能夠形成有機粒子(a)脫落少的塗布層。又，藉由黏結劑樹脂為水溶性樹脂，能夠作成使黏結劑樹脂及粒子溶解或分散於水之塗液狀態來使用。當然亦可將使黏結劑樹脂與粒子預先分別溶解或分散於水而成者任意地混合來使用。又，由於藉由使用利用水而成的塗液，能夠在線上塗布(in-line coating)法中進行塗布，因此從節省成本的觀點來看，亦為較佳。將具有上述官能基的單體與黏結劑樹脂共聚合之方法係能夠採取周知的方法。水溶性樹脂係以由選自包含聚酯樹脂、丙烯酸樹脂、聚胺基甲酸酯樹脂之群組中的至少一種所形成為佳，以聚酯樹脂或丙烯酸樹脂為更佳。黏結劑樹脂係與基材薄膜的密接性佳而且為透明而較佳，上述樹脂能夠符合這些特性。就此等水溶性樹脂而言，能夠取得DIC(股)製的製品名「WATERSOL」(註冊商標)或高松油脂(股)的「PESRESIN」等。 The binder resin is preferably a water-soluble resin, and the application using a water-based coating liquid has less environmental impact. The water-soluble resin referred to here means that it contains a kind selected from sulfonic acid group, carboxylic acid group, and hydroxyl group. And at least one kind of functional resin among the salts. The water-soluble resin is preferably a resin obtained by copolymerizing a monomer having functional groups such as a sulfonic acid group, a sulfonic acid salt group, a carboxylic acid group, and a carboxylic acid salt group, and more preferably a resin having a carboxylic acid group and / or a carboxylic acid group. A resin obtained by copolymerizing monomers of an acidic salt. Since it is water-soluble, it has good affinity with the base film and the particles (a), and can form a coating layer with a small amount of organic particles (a) falling off. In addition, since the binder resin is a water-soluble resin, it can be used in a coating liquid state in which the binder resin and particles are dissolved or dispersed in water. Of course, the binder resin and the particles may be arbitrarily mixed and used by dissolving or dispersing them in water in advance. In addition, since it is possible to perform coating by an in-line coating method by using a coating liquid made of water, it is also preferable from the viewpoint of cost saving. As a method for copolymerizing a monomer having the above-mentioned functional group and a binder resin, a known method can be adopted. The water-soluble resin is preferably formed of at least one selected from the group consisting of a polyester resin, an acrylic resin, and a polyurethane resin, and more preferably a polyester resin or an acrylic resin. The adhesive resin is excellent in adhesiveness with the base film and is transparent and preferable. The above resin can meet these characteristics. As for these water-soluble resins, a product name "WATERSOL" (registered trademark) made by DIC (stock), "PESRESIN" of Takamatsu grease (stock) can be obtained.

又，形成塗布層的黏結劑樹脂中，能夠在不阻礙發明效果的範圍內添加各種添加劑。就添加劑而言，可使用例如：抗氧化劑、交聯劑、螢光增白劑、抗靜電劑、偶合劑等。 Moreover, various additives can be added to the binder resin which forms a coating layer within the range which does not inhibit the effect of invention. As the additives, for example, antioxidants, crosslinking agents, fluorescent whitening agents, antistatic agents, coupling agents, and the like can be used.

例如，藉由在塗布層中添加交聯劑，能夠使對基材薄膜的密接性進一步提升，同時亦能夠進一步減 少有機粒子的脫落。就交聯劑而言，可列舉例如：異氰酸酯交聯劑、聚矽氧交聯劑、聚烯烴交聯劑等。又，塗布層中的交聯劑的含量較佳為5重量%以下，更佳為0.1~4重量%，再者最佳為0.5~3重量%的範圍內。若交聯劑的含量在該較佳範圍內，則會充分地得到其效果，而且在設置塗布層後亦可防止薄膜捲曲。 For example, by adding a crosslinking agent to the coating layer, the adhesion to the substrate film can be further improved, and at the same time, it can be further reduced. Less shedding of organic particles. Examples of the crosslinking agent include an isocyanate crosslinking agent, a polysiloxane crosslinking agent, and a polyolefin crosslinking agent. The content of the crosslinking agent in the coating layer is preferably 5% by weight or less, more preferably 0.1 to 4% by weight, and still more preferably within the range of 0.5 to 3% by weight. When the content of the cross-linking agent is within the preferable range, the effect can be sufficiently obtained, and the film can be prevented from curling even after the coating layer is provided.

又，藉由添加抗靜電劑，能夠防止灰塵等異物朝薄膜附著。就抗靜電劑而言，可列舉例如：界面活性劑、離子系導電性聚合物、電子傳導性聚合物、導電性金屬氧化物、金屬類等，但不限定於此等。又，就界面活性劑、離子系導電性聚合物而言，具體來說可列舉如下述者。 In addition, by adding an antistatic agent, foreign matter such as dust can be prevented from adhering to the film. Examples of the antistatic agent include, but are not limited to, surfactants, ionic conductive polymers, electron conductive polymers, conductive metal oxides, and metals. Specific examples of the surfactant and the ionic conductive polymer include the following.

就界面活性劑而言，可列舉磺酸鹽化化合物、N-醯基胺基酸或其鹽、烷基醚羧酸鹽等陰離子界面活性劑；脂肪族胺鹽、脂肪族4級銨鹽等陽離子界面活性劑；羧基甜菜鹼、咪唑啉甜菜鹼(imidazolinium betaine)、胺基羧酸鹽等兩性界面活性劑等。其中，較佳適用磺酸鹽化化合物，具體來說，可適用十二烷基苯磺酸鈉、硬脂基苯磺酸鈉、辛基苯磺酸鈉、十二烷基苯磺酸鉀、十二烷基苯磺酸鋰、辛基萘磺酸鋰、氧基萘磺酸鈉、十二烷基萘磺酸鈉、十二烷基萘磺酸鉀、丁基磺酸鈉、戊基磺酸鈉、己基磺酸鈉、庚基磺酸鈉、辛基磺酸鈉、壬基磺酸鈉、癸基磺酸鈉、十一烷基磺酸鈉、十二烷基磺酸鈉、十三烷基磺酸鈉、十四烷基磺酸鈉、十四烷基磺酸鈉、十五烷基磺酸鈉、十六烷基磺酸鈉、十七烷基磺酸 鈉、十八烷基磺酸鈉、癸基磺酸鉀、十二烷基磺酸鉀、十八烷基磺酸鉀等。 Examples of the surfactant include anionic surfactants such as sulfonate compounds, N-fluorenylamino acids or their salts, and alkyl ether carboxylates; aliphatic amine salts, and aliphatic quaternary ammonium salts. Cationic surfactants; amphoteric surfactants such as carboxybetaine, imidazolinium betaine, and amine carboxylate. Among them, sulfonated compounds are preferably used, and specifically, sodium dodecylbenzenesulfonate, sodium stearylbenzenesulfonate, sodium octylbenzenesulfonate, potassium dodecylbenzenesulfonate, Lithium dodecylbenzenesulfonate, lithium octylnaphthalenesulfonate, sodium oxynaphthalenesulfonate, sodium dodecylnaphthalenesulfonate, potassium dodecylnaphthalenesulfonate, sodium butylsulfonate, pentylsulfonate Sodium, sodium hexylsulfonate, sodium heptylsulfonate, sodium octylsulfonate, sodium nonylsulfonate, sodium decylsulfonate, sodium undecylsulfonate, sodium dodecylsulfonate, thirteen Sodium alkylsulfonate, sodium tetradecylsulfonate, sodium tetradecylsulfonate, sodium pentadecylsulfonate, sodium cetylsulfonate, heptadecylsulfonic acid Sodium, sodium octadecylsulfonate, potassium decylsulfonate, potassium dodecylsulfonate, potassium octadecylsulfonate, and the like.

就離子系導電性聚合物而言，可列舉聚苯乙烯磺酸及其鹼金屬鹽、銨鹽等的聚苯乙烯磺酸鹽類；以烷基磷酸酯鹽或烷基醚磷酸酯鹽所代表之磷酸鹽系低分子化合物為單體所共聚合而成之磷酸高分子化合物、具有離子性官能基的聚丙烯酸酯等。 Examples of the ionic conductive polymer include polystyrene sulfonic acid, polystyrene sulfonates such as alkali metal salts, ammonium salts, and the like; represented by alkyl phosphate salts or alkyl ether phosphate salts The phosphate-based low-molecular compound is a phosphate polymer compound copolymerized by monomers, a polyacrylate having an ionic functional group, and the like.

塗布層的塗布厚度(d；自未含有粒子(a)的部分之基材薄膜表面到塗布層表面的距離)較佳為小於1μm，更佳為小於500nm，再更佳為小於400nm。藉由使塗布厚度在上述範圍內，不僅能夠減少黏結劑樹脂的使用量，更可以進行使用線上塗布法的塗布，而能夠大幅降低成本。又，當塗布厚度在1μm以上時，有塗布不均等的塗布外觀明顯變差的情況而不佳。塗布厚度的下限係以50nm為佳。塗布厚度若小於50nm，則有有機粒子脫落的情況。就塗布層的塗布厚度的測定方法而言，切割包含粒子的截面，以SEM或穿透式電子顯微鏡(TEM)進行觀察，而能夠求得其塗布層的塗布厚度。就使塗布層的塗布厚度在上述範圍內之方法而言，可列舉例如：藉由調整塗液的黏結劑樹脂濃度與塗液的塗敷厚度來達成之方法等。 The coating thickness of the coating layer (d; the distance from the surface of the substrate film to the surface of the coating layer of the portion not containing particles (a)) is preferably less than 1 μm, more preferably less than 500 nm, and even more preferably less than 400 nm. By setting the coating thickness within the above range, not only the amount of the binder resin used can be reduced, but also coating by the in-line coating method can be performed, and the cost can be significantly reduced. When the coating thickness is 1 μm or more, the coating appearance may be significantly deteriorated due to uneven coating. The lower limit of the coating thickness is preferably 50 nm. If the coating thickness is less than 50 nm, the organic particles may fall off. In the method for measuring the coating thickness of a coating layer, the cross section including particles is cut and observed with a SEM or a transmission electron microscope (TEM), and the coating thickness of the coating layer can be determined. The method of making the coating thickness of the coating layer into the above range includes, for example, a method achieved by adjusting the concentration of the binder resin of the coating liquid and the coating thickness of the coating liquid.

塗布層表面的表面粗糙度(SRz；三維十點平均粗糙度)係以5μm以上60μm以下為佳，更佳為10μm以上30μm以下。若小於5μm，則將塗布在白色薄膜上而成之積層薄膜作為反射板而組裝在液晶顯示器時會有白點產 生的情況，又若比60μm大，則有粒子脫落的情況。就以包含在上述範圍內之方式調整表面粗糙度的方法而言，例如可列舉調整有機粒子的粒徑及塗液的黏結劑樹脂濃度與塗液的塗敷厚度之方法等。 The surface roughness (SRz; three-dimensional ten-point average roughness) of the surface of the coating layer is preferably 5 μm or more and 60 μm or less, and more preferably 10 μm or more and 30 μm or less. If it is less than 5 μm, a white film will be produced when the laminated film formed by coating on a white film is used as a reflection plate when assembled on a liquid crystal display. If it is larger than 60 μm, particles may fall off. The method of adjusting the surface roughness so as to include the above range includes, for example, a method of adjusting the particle diameter of the organic particles, the binder resin concentration of the coating liquid, and the coating thickness of the coating liquid.

粒子(a)及粒子(b)係以使用黏結劑樹脂來被覆為佳。能夠藉由使用黏結劑樹脂來被覆粒子，而難以脫落。藉由以周知的方法來改善粒子的濕潤性，而能夠使用黏結劑樹脂被覆粒子。又，針對被覆狀態，係能夠透過粒子截面的SEM或是TEM來確認。此時，藉由使用釕染色等而能夠更明確地確認。 The particles (a) and (b) are preferably coated with a binder resin. The particles can be coated with a binder resin to make it difficult to fall off. By improving the wettability of the particles by a known method, the particles can be coated with a binder resin. The coating state can be confirmed by SEM or TEM of the particle cross section. In this case, it can be confirmed more clearly by using ruthenium dyeing or the like.

本發明之積層薄膜係以塗布層表面上的有機粒子的粒子密度為5個/mm2以上100000個/mm2以下為佳，較佳為400個/mm2以上100000個/mm2以下，更佳為1000個/mm2以上100000個/mm2以下。使用粒子密度為上述數值範圍內之積層薄膜作為液晶顯示器的反射板或是光擴散薄膜來使用時，能夠得到適度的光擴散性。就使塗布層表面的粒子密度在上述的數值範圍內之方法而言，係能夠藉由調整塗液中的粒子量、塗布膜厚度、製膜中進行塗布時之塗布後的延伸步驟之延伸倍率而達成。 Laminated thin-film of the present invention to particle density of the organic particles on the surface of the coating layer is 5 / mm 2 or more and 100,000 / mm 2 preferably less, preferably 400 / mm 2 100 000 or more / less 2 mm, more It is preferably 1,000 pieces / mm 2 or more and 100,000 pieces / mm 2 or less. When a laminated film having a particle density within the above-mentioned numerical range is used as a reflection plate or a light diffusion film of a liquid crystal display, a moderate light diffusivity can be obtained. The method for making the particle density on the surface of the coating layer within the above-mentioned numerical range is an adjustment of the amount of particles in the coating liquid, the thickness of the coating film, and the stretching ratio of the stretching step after coating during coating. And reach.

本發明之積層薄膜的第二態樣為一種積層薄膜，其特徵為：於白色薄膜的至少一側的表面上設置包含由樹脂(A)構成之數量平均粒徑為4μm以上的粒子(a)之塗布層，數量平均粒徑0.1μm以上1μm以下的粒子(b)附著在粒子(a)的表面上；第三態樣為一種積層薄膜，其特徵在於前述薄膜為透明，前述薄膜的全光線穿透率為 60%以上。 A second aspect of the laminated film of the present invention is a laminated film characterized in that particles (a) containing a number of particles having an average particle diameter of 4 μm or more made of resin (A) are provided on at least one surface of a white film. In the coating layer, particles (b) having a number average particle diameter of 0.1 μm or more and 1 μm or less adhere to the surface of the particle (a); a third aspect is a laminated film characterized in that the film is transparent and the light of the film is full light Penetration rate Above 60%.

本發明之積層薄膜之薄膜為白色薄膜或透明薄膜。 The laminated film of the present invention is a white film or a transparent film.

(2.1)白色薄膜的構成 (2.1) Composition of white film

關於構成本發明之第二態樣之積層薄膜的白色薄膜，在作為液晶顯示器用背光或照明用途的反射板使用時，可見光反射率越高越好。反射率係以80%以上為佳，更佳為90%以上，再更佳為95%以上。因此，較佳使用在內部含有氣泡及/或不互溶的粒子之薄膜。此等的白色薄膜並未受到限定，但較佳使用多孔性的未延伸或經雙軸延伸的聚烯烴薄膜、或多孔性的未延伸或經雙軸延伸的聚酯薄膜等白色薄膜。尤其是從成形性或生產性的觀點來看，較佳使用白色聚酯薄膜。就白色聚烯烴薄膜及白色聚酯薄膜而言，可列舉日本特開平4-239540號公報、日本特開平8-262208號公報、日本特開2002-90515號公報、日本特開2002-138150號公報或日本特開2004-330727號公報所揭示的白色薄膜。 Regarding the white film constituting the laminated film of the second aspect of the present invention, the higher the visible light reflectance, the better it is when it is used as a reflector for a backlight of a liquid crystal display or a lighting application. The reflectance is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more. Therefore, a film containing bubbles and / or immiscible particles inside is preferably used. These white films are not limited, but white films such as porous unstretched or biaxially stretched polyolefin films, or porous unstretched or biaxially stretched polyester films are preferably used. In particular, from the viewpoint of moldability and productivity, a white polyester film is preferably used. Examples of the white polyolefin film and the white polyester film include Japanese Patent Laid-Open No. 4-239540, Japanese Patent Laid-Open No. 8-262208, Japanese Patent Laid-Open No. 2002-90515, and Japanese Patent Laid-Open No. 2002-138150. Or the white film disclosed in Japanese Patent Application Laid-Open No. 2004-330727.

就構成白色薄膜的可塑性樹脂而言，可列舉例如：聚對苯二甲酸乙二酯或聚對萘二甲酸乙二酯等聚酯、聚丙烯或環狀聚烯烴等聚烯烴、聚苯乙烯、丙烯酸樹脂等。從成形性或生產性的觀點來看，較佳使用聚酯。 Examples of the plastic resin constituting the white film include polyesters such as polyethylene terephthalate and polyethylene terephthalate, polyolefins such as polypropylene and cyclic polyolefins, polystyrene, Acrylic resin, etc. From the viewpoint of moldability or productivity, polyester is preferably used.

又，就不互溶的粒子而言，可列舉例如：包含氧化鈦、硫酸鋇、二氧化矽或碳酸鈣等之無機粒子；丙烯酸粒子、耐綸粒子、聚苯乙烯粒子或聚矽氧粒子等有機粒子。又，構成白色薄膜的熱塑性樹脂亦能夠使用 不互溶的樹脂，在擠壓機之中使不互溶的樹脂分散而使用。就不互溶的樹脂而言，構成白色薄膜的熱塑性樹脂為聚酯時，可列舉聚丙烯、聚甲基戊烯或環狀聚烯烴等烯烴樹脂或聚苯乙烯樹脂等。 Examples of immiscible particles include inorganic particles including titanium oxide, barium sulfate, silicon dioxide, and calcium carbonate; organic particles such as acrylic particles, nylon particles, polystyrene particles, and polysiloxane particles; particle. Also, a thermoplastic resin constituting a white film can be used. The immiscible resin is used by dispersing the immiscible resin in an extruder. In the case of immiscible resins, when the thermoplastic resin constituting the white film is a polyester, olefin resins such as polypropylene, polymethylpentene, and cyclic polyolefins, or polystyrene resins can be mentioned.

白色薄膜可為單層薄膜，亦可為積層薄膜。 The white film may be a single-layer film or a laminated film.

只要根據使用的用途要求的特性適當地選擇白色薄膜的厚度即可，並沒有特別的限定。在液晶TV用途中，從薄膜的剛性的觀點來看，較佳使用250μm以上600μm以下。又，在液晶監視器用途中，較佳使用188μm以上300μm以下。 The thickness of the white film may be appropriately selected according to the characteristics required for the intended use, and is not particularly limited. In the liquid crystal TV application, from the viewpoint of the rigidity of the film, it is preferable to use from 250 μm to 600 μm. For liquid crystal monitor applications, it is preferable to use 188 μm to 300 μm.

本案之積層薄膜之設置含有粒子(a)及粒子(b)的塗布層的面係以與上述白色薄膜的導光板相接的一側的面為佳。 The surface of the multilayer film of the present case in which the coating layer containing the particles (a) and (b) is provided is preferably the surface on the side that is in contact with the light guide plate of the white film.

(2.2)透明薄膜的構成 (2.2) Composition of transparent film

構成本發明之積層薄膜的透明薄膜是指全光線穿透率60%以上的薄膜。液晶顯示器用背光中作為擴散片使用時，全光線穿透率較佳為70%以上，更佳為90%以上。因此，較佳使用內部含有不互溶的粒子之內部擴散薄膜或是於基材薄膜表面設置含有微粒的擴散層而成之擴散薄膜。就於表面設置擴散層而成之擴散薄膜而言，可列舉日本特開2007-86730號公報所揭示的擴散薄膜。 The transparent film constituting the laminated film of the present invention refers to a film having a total light transmittance of 60% or more. When used as a diffusion sheet in a backlight for a liquid crystal display, the total light transmittance is preferably 70% or more, and more preferably 90% or more. Therefore, it is preferable to use an internal diffusion film containing immiscible particles inside or a diffusion film provided with a diffusion layer containing fine particles on the surface of the base film. Examples of the diffusion film in which a diffusion layer is provided on the surface include a diffusion film disclosed in Japanese Patent Application Laid-Open No. 2007-86730.

就構成透明薄膜的可塑性樹脂而言，可列舉例如：聚對苯二甲酸乙二酯或聚對萘二甲酸乙二酯等聚酯、聚丙烯或環狀聚烯烴等聚烯烴、聚苯乙烯、丙烯酸樹脂等。從成形性或生產性的觀點來看，較佳使用聚酯。 Examples of the plastic resin constituting the transparent film include polyesters such as polyethylene terephthalate and polyethylene terephthalate, polyolefins such as polypropylene and cyclic polyolefins, polystyrene, Acrylic resin, etc. From the viewpoint of moldability or productivity, polyester is preferably used.

只要根據使用的用途要求的特性適當地選擇透明薄膜的厚度即可，並沒有特別的限定。在液晶TV用途中，從薄膜的剛性的觀點來看，較佳使用50μm以上150μm以下。又，在液晶監視器用途中，較佳使用30μm以上100μm以下。 The thickness of the transparent film may be appropriately selected according to the characteristics required for the intended use, and is not particularly limited. In the liquid crystal TV application, from the viewpoint of the rigidity of the film, it is preferable to use 50 μm or more and 150 μm or less. For liquid crystal monitor applications, 30 μm to 100 μm is preferably used.

本案之積層薄膜之設置含有粒子(a)及粒子(b)的塗布層的面係以與上述透明薄膜的導光板相接的一側的面為佳。透明薄膜為擴散薄膜時，係以與設置有擴散層的面為不同的面為佳；透明薄膜為棱鏡片時，係以與稜鏡面為不同的面為佳。 It is preferable that the surface of the multilayer film of this case where the coating layer containing particles (a) and particles (b) is provided is the surface on the side that is in contact with the light guide plate of the transparent film. When the transparent film is a diffusion film, it is preferable to use a surface different from the surface on which the diffusion layer is provided; when the transparent film is a prism sheet, it is preferable to use a surface different from the concrete surface.

(3)製造方法 (3) Manufacturing method

本發明之第二態樣之於白色薄膜的至少一側的表面形成塗布層時，例如會將含有聚酯樹脂與不互溶成分的混合物視需要地進行充分的真空乾燥，並供給至具有擠壓機(主擠壓機)之製膜裝置之經加熱的擠壓機。不互溶成分的添加係可使用事先均勻地熔融混練並使其摻合所製作的母粒(master chip)，或亦可直接供給至混練擠壓機等。使用事先均勻地將含有聚酯樹脂與不互溶成分的混合物熔融混練而成之母粒，由於能促進不互溶成分的分散因而較佳。 In the second aspect of the present invention, when a coating layer is formed on the surface of at least one side of a white film, for example, a mixture containing a polyester resin and an immiscible component is vacuum-dried as needed and supplied to a substrate having extrusion The heated extruder of the film making device of the machine (main extruder). The immiscible ingredient may be added by using a master chip prepared by uniformly melting and kneading in advance, or may be directly supplied to a kneading extruder or the like. It is preferable to use a master batch prepared by melt-kneading a mixture containing a polyester resin and an immiscible component in advance, since it can promote dispersion of the immiscible component.

又，在熔融擠壓之際，係以使用篩目40μm以下的過濾器過濾後，導入至T字模噴嘴內，藉由擠壓成形得到熔融片為佳。將此熔融片在已冷卻成表面溫度10℃以上60℃以下的滾筒上藉由靜電而密接冷卻固化，製作未延伸薄膜。 In the case of melt extrusion, it is preferably filtered through a filter having a mesh size of 40 μm or less, and then introduced into a T-shaped nozzle, and a melt sheet is preferably obtained by extrusion molding. This molten sheet was closely cooled and solidified by static electricity on a roller cooled to a surface temperature of 10 ° C. to 60 ° C. to produce an unstretched film.

藉由按照後述的線上塗布法對此未延伸薄膜進行延伸及熱處理，而能夠得到於表面上具有塗布層的積層薄膜。 The unstretched film is stretched and heat-treated in accordance with the on-line coating method described later, and a laminated film having a coating layer on the surface can be obtained.

又，本發明之第三態樣之於透明薄膜的至少一側的表面形成塗布層時，例如會視需要地對聚酯樹脂進行充分的真空乾燥，並供給至具有擠壓機(主擠壓機)之製膜裝置之經加熱的擠壓機。 In addition, in a third aspect of the present invention, when a coating layer is formed on at least one surface of a transparent film, for example, a polyester resin is sufficiently vacuum-dried, if necessary, and supplied to an extruder (main extrusion). Machine), a heated extruder of the film making device.

又，在熔融擠壓之際，係以使用篩目40μm以下的過濾器過濾後，導入至T字模噴嘴內，藉由擠壓成形得到熔融片為佳。將此熔融片在已冷卻成表面溫度10℃以上60℃以下的滾筒上藉由靜電而密接冷卻固化，製作未延伸薄膜。 In the case of melt extrusion, it is preferably filtered through a filter having a mesh size of 40 μm or less, and then introduced into a T-shaped nozzle, and a melt sheet is preferably obtained by extrusion molding. This molten sheet was closely cooled and solidified by static electricity on a roller cooled to a surface temperature of 10 ° C. to 60 ° C. to produce an unstretched film.

藉由按照後述的線上塗布法對此未延伸薄膜進行延伸及熱處理，而能夠得到於表面上具有塗布層的積層薄膜。 The unstretched film is stretched and heat-treated in accordance with the on-line coating method described later, and a laminated film having a coating layer on the surface can be obtained.

在所得到的積層薄膜的一側的表面上設置光擴散層時，係以將多數的有機聚合物微粒子以黏結劑分散固定來形成為佳。就前述有機聚合物微粒子而言，較佳為由交聯型的丙烯酸樹脂及甲基丙烯酸樹脂、聚乙烯、聚丙烯、聚苯乙烯、聚矽氧樹脂、三聚氰胺樹脂等有機聚合物所製作的粒子，特佳為交聯型的丙烯酸樹脂或甲基丙烯酸樹脂(PMMA樹脂)。前述有機聚合物微粒子的質量平均粒徑較佳為1~100μm，更佳為1~25μm。就前述光擴散層的黏結劑而言，較佳為有機聚合物黏結劑，就該有機聚合物黏結劑而言，可列舉例如：含有丙烯酸 酯及甲基丙烯酸酯之至少任一種作為單體的一成分之均聚物或共聚物，特佳為(甲基)丙烯酸樹脂。較佳為藉由在上述積層薄膜上塗布將有機聚合物黏結劑與有機聚合物微粒子添加混合在適當的溶劑中調製而成之塗布液並乾燥來形成。 When a light-diffusion layer is provided on the surface of one side of the obtained laminated film, it is preferable to form and disperse and fix many organic polymer fine particles with a binder. The organic polymer fine particles are preferably particles made of an organic polymer such as a crosslinked acrylic resin and a methacrylic resin, polyethylene, polypropylene, polystyrene, polysiloxane, and melamine resin. Particularly preferred is a crosslinked acrylic resin or methacrylic resin (PMMA resin). The mass average particle diameter of the organic polymer fine particles is preferably 1 to 100 μm, and more preferably 1 to 25 μm. The adhesive for the light diffusion layer is preferably an organic polymer adhesive, and examples of the organic polymer adhesive include acrylic acid A homopolymer or copolymer of at least one of an ester and a methacrylate as a single component of the monomer is particularly preferably a (meth) acrylic resin. It is preferably formed by applying a coating solution prepared by adding and mixing an organic polymer binder and organic polymer fine particles in an appropriate solvent on the laminated film, and then drying.

前述有機聚合物微粒子的含量相對於前述黏結劑100質量份，較佳為100~500質量份，更佳為200~400質量份。 The content of the organic polymer fine particles is preferably 100 to 500 parts by mass, and more preferably 200 to 400 parts by mass based on 100 parts by mass of the binder.

從塗布後容易乾燥的觀點來看，溶媒較佳為沸點150℃以下的有機溶媒，特佳為環己酮、1,4-二

Figure TWI676551B_D0001
烷、乙二醇單甲基醚乙酸酯。亦可在上述列舉的有機溶媒中混合後再與醇類等的其它有機溶媒混合，從通用性的觀點來看，較佳使用甲基乙基酮。 From the viewpoint of easy drying after coating, the solvent is preferably an organic solvent having a boiling point of 150 ° C or lower, and particularly preferred are cyclohexanone, 1,4-bis
Figure TWI676551B_D0001
Alkane, ethylene glycol monomethyl ether acetate. The organic solvents listed above may be mixed with other organic solvents such as alcohols, and methyl ethyl ketone is preferably used from the viewpoint of versatility.

對前述積層薄膜的塗布係能夠使用旋轉塗布機、輥塗布機、棒塗布機、簾幕式塗布機等周知的塗布手段來進行。乾燥步驟中的溫度係以90~130℃為佳，較佳為100~120℃。時間係以10秒鐘~5分鐘為佳，更佳為1~2分鐘。 The coating of the laminated film can be performed using a known coating means such as a spin coater, a roll coater, a bar coater, and a curtain coater. The temperature in the drying step is preferably 90 to 130 ° C, and more preferably 100 to 120 ° C. The time is preferably 10 seconds to 5 minutes, and more preferably 1 to 2 minutes.

在本案之第一、第二及第三態樣中，積層薄膜上設置包含由樹脂(A)構成之數量平均粒徑為4μm以上的粒子(a)之塗布層，在粒子(a)的表面上附著有數量平均粒徑0.1μm以上1μm以下的粒子(b)。就形成塗布層的方法而言，除了將塗液塗布於雙軸延伸後的基材薄膜之方法(離線塗布(off-line coating)法)之外，還有於塗液的塗布後延伸薄膜並進行熱處理之方法(線上塗布法)。從塗布 層與基材薄膜的密接性及節省成本的觀點來看，較佳為線上塗布法。就線上塗布法而言，可列舉將塗液塗布在未延伸薄膜表面後往雙軸方向延伸之方法、或是將塗液塗布在單軸延伸薄膜表面後進一步往與前一個單軸延伸方向交叉的方向(例如為與單軸延伸方向正交的方向)延伸之方法等，但以後者為佳。 In the first, second, and third aspects of the present case, a coating layer containing particles (a) having a number average particle diameter of 4 μm or more made of resin (A) is provided on the laminated film, and the surface of the particles (a) is provided. Particles (b) having a number average particle diameter of 0.1 μm to 1 μm are attached to the particles. As a method for forming a coating layer, in addition to a method (off-line coating method) in which a coating liquid is applied to a substrate film after biaxial stretching, there is also a method in which the film is extended after the coating liquid is applied. Method for performing heat treatment (on-line coating method). From coating From the viewpoint of the adhesiveness between the layer and the base film and the cost saving, the in-line coating method is preferred. As for the online coating method, a method of applying a coating liquid on the surface of an unstretched film and extending in a biaxial direction may be mentioned, or a coating liquid may be coated on the surface of a uniaxially stretched film and further intersect with the previous uniaxially extending direction. The method (e.g., a direction orthogonal to the uniaxial extension direction) is preferably extended, but the latter is preferred.

後者之將塗布劑塗布在單軸延伸薄膜表面後進一步往與前一個單軸延伸方向交叉的方向延伸之方法，具體來說係以如後所述地進行為佳。首先，將熱塑性樹脂原料供給至擠壓裝置，在熱塑性樹脂的熔點以上的溫度下進行熔融擠壓而從狹縫狀的模頭作為熔融片擠壓至旋轉冷卻滾筒上，在旋轉冷卻滾筒表面上以成為玻璃轉移溫度以下的溫度的方式進行急冷固化，得到非晶狀態的未延伸片。在此情況下，為了使薄片的平面性提升，係以提高薄片與旋轉冷卻滾筒的密接性為佳，較佳採用靜電施加密接法。 The latter method of applying a coating agent on the surface of a uniaxially stretched film and then extending it in a direction that intersects with the previous uniaxially extending direction is specifically performed as described below. First, a thermoplastic resin raw material is supplied to an extrusion device, and melt-extruded at a temperature above the melting point of the thermoplastic resin, and extruded from a slit-shaped die as a molten sheet onto a rotary cooling drum, and on the surface of the rotary cooling drum. It quenched and solidified so that it might become temperature below glass transition temperature, and obtained the unstretched sheet of an amorphous state. In this case, in order to improve the flatness of the sheet, it is better to improve the adhesion between the sheet and the rotary cooling drum, and it is preferable to adopt an electrostatic application adhesion method.

接著，將上述的未延伸片往縱軸方向延伸。延伸溫度通常為(構成基材薄膜的熱塑性樹脂的玻璃轉移溫度-5℃)~(構成基材薄膜的熱塑性樹脂的玻璃轉移溫度+25℃)的範圍，延伸倍率通常為3~6倍的範圍。延伸能夠在一階段或兩階段以上下進行。接著，在薄膜的至少一側的表面上塗布塗液。就塗液的塗布方法而言，可使用例如：繞線棒塗布機、反轉輥塗布機、凹版塗布機、桿塗布機、氣刮刀塗布機(air doctor coater)或此等以外的塗布裝置。塗布層可僅形成在薄膜的單面上，亦 可形成在雙面上。僅形成在單面上時，在其相反面上亦能夠視需要地形成與上述塗布層不同的塗布層而賦予其它特性。還有，為了改良對塗液的薄膜之塗布性和黏著性，亦可在塗布前對薄膜施加化學處理或放電處理。 Next, the unstretched sheet is extended in the longitudinal axis direction. The elongation temperature is usually in the range of (glass transition temperature of the thermoplastic resin constituting the base film-5 ° C) to (the glass transition temperature of the thermoplastic resin constituting the base film + 25 ° C), and the elongation ratio is generally in the range of 3 to 6 times. . Extension can be performed in one or more stages. Next, a coating liquid is applied on the surface of at least one side of the film. As the coating liquid coating method, for example, a wire rod coater, a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, or other coating devices can be used. The coating layer can be formed only on one side of the film, or Can be formed on both sides. When formed on only one surface, a coating layer different from the above-mentioned coating layer can be optionally formed on the opposite surface to impart other characteristics. In addition, in order to improve the applicability and adhesion of the thin film to the coating liquid, chemical treatment or discharge treatment may be applied to the thin film before coating.

已塗布的薄膜於拉幅機的預熱區域預熱至90~150℃的溫度範圍並進行適度的乾燥後，往橫軸方向(與縱軸方向正交的方向)延伸。延伸溫度通常在(構成基材薄膜的熱塑性樹脂的玻璃轉移溫度-5℃)~(構成基材薄膜的熱塑性樹脂的玻璃轉移溫度+40℃)的範圍，延伸倍率通常為3~6倍，較佳為3.2~4.5倍的範圍。還有，亦可在上述的預熱之前暫時將薄膜冷卻至玻璃轉移點以下。 The coated film is preheated to a temperature range of 90 to 150 ° C. in a preheating area of the tenter, and is appropriately dried, and then extends in a horizontal axis direction (a direction orthogonal to the vertical axis direction). The elongation temperature is usually in the range of (glass transition temperature of the thermoplastic resin constituting the base film-5 ° C) to (glass transition temperature of the thermoplastic resin constituting the base film + 40 ° C), and the elongation ratio is generally 3 to 6 times. The range is preferably 3.2 to 4.5 times. In addition, the film may be temporarily cooled below the glass transition point before the preheating.

接著，在20%以內的伸長、收縮或固定長度下進行1秒鐘~5分鐘的熱處理。此時，尤其是為了使縱軸方向及/或橫軸方向的熱收縮率在適當的範圍內，亦可在熱處理步驟內或熱處理後往縱軸方向及/或橫軸方向進行通常為10%以內、較佳為5%以內的鬆弛處理。熱處理溫度會隨著延伸條件而不同，但通常為180~250℃，較佳為190~230℃的範圍。熱處理溫度超過250℃時，會有薄膜的配向變差的傾向，而且亦有一部分的塗布層發生熱分解的情況。另一方面，熱處理溫度小於180℃時，會有薄膜的熱收縮率過大之情況。 Next, heat treatment is performed for 1 second to 5 minutes at an elongation, contraction, or fixed length of less than 20%. In this case, in particular, in order to make the thermal shrinkage rate in the vertical axis direction and / or horizontal axis direction within an appropriate range, it is also possible to carry out the heat treatment step or the heat treatment in the vertical axis direction and / or the horizontal axis direction, usually at 10%. Less than 5%, preferably less than 5%. The heat treatment temperature varies depending on the elongation conditions, but is usually in the range of 180 to 250 ° C, preferably in the range of 190 to 230 ° C. When the heat treatment temperature exceeds 250 ° C., the alignment of the thin film tends to deteriorate, and a part of the coating layer may be thermally decomposed. On the other hand, when the heat treatment temperature is lower than 180 ° C, the thermal shrinkage of the film may be too large.

塗布液的調整方法係可列舉：使黏結劑樹脂、粒子依序溶解或分散於水中之方法、或是將使黏結劑樹脂與粒子預先分別溶解及分散於水中而成者任意地混合之方法。塗布液包含黏結劑樹脂、粒子及水，為了減 少塗布條紋，係以將水相對於塗布液的含量調整成50重量%以上為佳。 The method for adjusting the coating liquid may be a method of sequentially dissolving or dispersing the binder resin and particles in water, or a method of arbitrarily mixing the binder resin and the particles by dissolving and dispersing them in water separately in advance. The coating liquid contains a binder resin, particles, and water. The less streaks are applied, and the content of water relative to the coating liquid is preferably adjusted to 50% by weight or more.

(4)測定/評定方法 (4) Measurement / evaluation method

(4.1)表面粗糙度(SRz)的測定方法 (4.1) Method for measuring surface roughness (SRz)

依據JIS-B-0601(2001)實施測定，就測定儀器而言，係使用小坂研究所製的表面粗糙度測定儀(型號：SE3500)，測定條件係如下所述。 The measurement was performed in accordance with JIS-B-0601 (2001). As a measuring instrument, a surface roughness measuring instrument (model: SE3500) manufactured by Kosaka Research Institute was used, and the measurement conditions were as follows.

‧進給速度：0.1mm/s ‧Feeding speed: 0.1mm / s

‧X節距：1.00μm ‧X pitch: 1.00μm

‧Y節距：5.0μm ‧Y pitch: 5.0μm

‧Z測定倍率：20000 ‧Z measurement magnification: 20000

‧低域截止：0.25mm。 ‧Low domain cutoff: 0.25mm.

(4.2)塗布層的厚度(d)的測定方法及有機粒子的塗膜內被覆狀態的評定方法 (4.2) Method for measuring the thickness (d) of the coating layer and method for evaluating the coating state in the coating film of the organic particles

將積層薄膜以薄片切片機在截面方向切出70~100nm的厚度的切片，以四氧化釕進行染色。由使用穿透式電子顯微鏡「TEM2010」(日本電子(股)製)將經染色的切片擴大500~10,000倍進行觀察拍攝之截面照片，測量求得沒有有機粒子的部分之塗布層的厚度。於隨機選出的10處進行測量，將其平均值定為塗布層的厚度。 The laminated film was cut into a slice with a thickness of 70 to 100 nm in a cross-sectional direction by a slicer, and dyed with ruthenium tetraoxide. The thickness of the coating layer in the portion without organic particles was measured by measuring a cross-section photograph taken by expanding a stained section by 500 to 10,000 times using a transmission electron microscope "TEM2010" (manufactured by Japan Electronics Corporation). Measurement was performed at 10 randomly selected locations, and the average value was determined as the thickness of the coating layer.

又，藉由所得到的截面照片確認有機粒子的塗膜內被覆狀態，如下述地進行判定。 Moreover, the coating state in the coating film of the organic particle was confirmed from the obtained cross-sectional photograph, and it determined as follows.

塗膜被覆粒子表面積的全部之情況：A The entire situation of the surface area of the coating film particles: A

因粒子表面積的塗膜造成之被覆為8成以上且小於10成之情況：B Cases where the coating is 80% or more and less than 10% due to the coating of the particle surface area: B

因粒子表面積的塗膜造成之被覆為4成以上且小於8成之情況：C Cases where the coating due to the particle surface area is 40% or more and less than 80%: C

因粒子表面積的塗膜造成之被覆小於4成之情況：D。 Case where the coating is less than 40% due to the coating film of the particle surface area: D.

(4.3)塗布層中的粒子的數量平均粒徑R、粒徑分布指數的測定方法 (4.3) Method for measuring number average particle diameter R and particle size distribution index of particles in coating layer

以掃描式電子顯微鏡(日本電子公司製掃描式電子顯微鏡JSM-6301NF)觀察設置在積層薄膜表面上之塗布層的粒子，測定粒徑。還有，在粒子不是圓形的情況下，測定長徑作為其粒徑。又，數量平均粒徑R(Dn)及體積平均粒徑(Dv)係由針對隨機選出的100個粒子進行測定而得到之上述粒徑的值求得。 The particles of the coating layer provided on the surface of the laminated film were observed with a scanning electron microscope (scanning electron microscope JSM-6301NF manufactured by Japan Electronics Corporation), and the particle diameter was measured. When the particles are not circular, the major axis is measured as the particle diameter. The number-average particle diameter R (Dn) and the volume-average particle diameter (Dv) were obtained from the values of the particle diameters obtained by measuring 100 randomly selected particles.

按照下述計算式(1)，計算粒徑分布指數(PDI)。 The particle size distribution index (PDI) was calculated according to the following calculation formula (1).

PDI=Dv/Dn‧‧‧(1) PDI = Dv / Dn‧‧‧ (1)

還有，Dn：數量平均粒徑、Dv：體積平均粒徑、PDI：粒徑分布指數。 In addition, Dn: number average particle diameter, Dv: volume average particle diameter, and PDI: particle size distribution index.

(4.4)附著於粒子(a)的粒子(b)的個數 (4.4) Number of particles (b) attached to particles (a)

以掃描式電子顯微鏡(日本電子公司製掃描式電子顯微鏡JSM-6301NF)觀察設置於積層薄膜的表面之塗布層的粒子，計算附著於粒子(a)的粒子(b)的個數。對每20個粒子(a)計算附著的粒子(b)的個數，將每1個粒子(a)的平均附著數量定為附著於粒子(a)的粒子(b)的個數。 The particles of the coating layer provided on the surface of the laminated film were observed with a scanning electron microscope (scanning electron microscope JSM-6301NF manufactured by Japan Electronics Corporation), and the number of particles (b) adhering to the particles (a) was counted. The number of particles (b) to be attached is calculated for every 20 particles (a), and the average number of particles (a) to be attached to each particle is set to the number of particles (b) to be attached to the particles (a).

(4.5)顯示器白點的評定方法 (4.5) Evaluation method of display white point

將積層薄膜組裝至AUO公司製LED顯示器(T240HW01)的背光單元中，以畫面成為水平的方式進行設置，並點燈。針對以規定重量的砝碼按住畫面中央時 的狀態，以下述的基準進行評定。此時，在將白色薄膜作成基材的積層薄膜之情況下作為反射板進行測定，在將透明薄膜作成基材的積層薄膜的情況下組裝至導光板與光學片之間後進行測定。 The laminated film was assembled into a backlight unit of an LED display (T240HW01) made by AUO, and the screen was set so that the screen became horizontal and turned on. When holding the center of the screen with a weight of a predetermined weight The state of the battery was evaluated on the basis of the following criteria. At this time, when a white film is used as a laminated film of a substrate, the measurement is performed as a reflection plate, and when a transparent film is used as a laminated film of a substrate, measurement is performed after being assembled between a light guide plate and an optical sheet.

沒有砝碼而產生白點的情況：F Case of white spots without weights: F

在0.5kg的砝碼下產生白點的情況：E Case of white spot under 0.5kg weight: E

在1.0kg的砝碼下產生白點的情況：D Case of white spot under 1.0kg weight: D

在1.5kg的砝碼下產生白點的情況：C Case of white spot under 1.5kg weight: C

在2.0kg的砝碼下產生白點的情況：B Case of white spot under 2.0kg weight: B

在2.0kg的砝碼下未產生白點的情況：A In the case of no white spots under a weight of 2.0kg: A

還有，使用的背光為側光型背光，具有導光板及光源(LED)，光源位在導光板的邊緣部。在此白點評定方法中，可明確區分出未產生白點的情況與產生白點的情況。 In addition, the backlight used is an edge-light type backlight, which includes a light guide plate and a light source (LED), and the light source is located at an edge portion of the light guide plate. In this white evaluation method, a case where a white spot is not generated can be clearly distinguished from a case where a white spot is generated.

(4.6)有機粒子的粒子密度的測定方法 (4.6) Method for measuring particle density of organic particles

以掃描式電子顯微鏡(日本電子公司製掃描式電子顯微鏡JSM-6301NF)觀察積層薄膜的表面，在250μm×400μm的10視野下計算粒子的個數，將該數量N定為有機粒子的粒子密度(個/mm2)。還有，此時附著於粒子(a)的粒子(b)並未計算個數。 The surface of the laminated film was observed with a scanning electron microscope (scanning electron microscope JSM-6301NF made by Japan Electronics Co., Ltd.), and the number of particles was counted under a field of view of 250 μm × 400 μm. The number N was determined as the particle density of the organic particles ( / Mm 2 ). In this case, the number of particles (b) attached to the particles (a) was not counted.

(4.7)導光板刮削及反射薄膜上的粒子脫落的評定 (4.7) Evaluation of light guide plate scraping and particle shedding on reflective film

在分解40吋液晶電視(Samsung公司製、PAVVUN40B7000WF)而得到的導光板上，以與積層薄膜的凸部接觸的方式使其積層後，在200gf/cm2(0.0196MPa)、100gf/cm2(0.0098MPa)及50gf/cm2(0.0049MPa)的負重下 將反射片試料以1m/min的線速度提高，以肉眼確認於前述導光板的表面上產生的刮痕的程度並如所下述地進行評定。以各個負重對同一個樣品實施3次，以目視進行判定。 The light guide plate obtained by disassembling a 40-inch liquid crystal television (Samsung, PAVVUN40B7000WF) was laminated so as to be in contact with the convex portion of the laminated film, and then was laminated at 200 gf / cm 2 (0.0196 MPa), 100 gf / cm 2 ( 0.0098 MPa) and 50 gf / cm 2 (0.0049 MPa), the reflection sheet sample was increased at a linear speed of 1 m / min, and the degree of scratches generated on the surface of the light guide plate was visually confirmed, and as described below. Assess. The same sample was performed three times with each load, and judged visually.

A級：在任何的負重下皆未觀察到傷痕。 Grade A: No scar was observed under any load.

B級：在200gf/cm2的負重下觀察到傷痕，但在100gf/cm2的負重下、50gf/cm2的負重下未觀察到傷痕。 Class B: scratches observed under load 200gf / cm 2, but the load 100gf / cm 2 is, 50gf / cm No scratches observed under the load 2.

C級：在200gf/cm2、100gf/cm2的負重下觀察到傷痕，但在50gf/cm2的負重下未觀察到傷痕。 Class C: In 200gf / cm 2, 100gf / cm 2 of scar is observed under load, but in 50gf / cm 2 load was not observed injuries.

D級：在50gf/cm2的負重下觀察到傷痕。 Grade D: A scar was observed under a load of 50 gf / cm 2 .

又，亦於反射薄膜確認有機粒子的脫落。 In addition, the peeling of the organic particles was also confirmed on the reflective film.

A級：在任何的負重下皆未觀察到粒子脫落。 Grade A: No particle shedding was observed under any load.

B級：在200gf/cm2的負重下觀察到粒子脫落，但在100gf/cm2的負重下、50gf/cm2的負重下未觀察到粒子脫落。 Class B: observed under load 200gf / cm 2 to particle shedding, but in the load 100gf / cm 2 is, 50gf / cm particle shedding was not observed under the load 2.

C級：在200gf/cm2、100gf/cm2的負重下觀察到粒子脫落，但在50gf/cm2的負重下未觀察到粒子脫落。 Class C: In 200gf / cm 2, 100gf / cm 2 the load applied to the particle shedding was observed, but at 50gf / cm 2 load was not observed particle shedding.

D級：在50gf/cm2的負重下觀察到粒子脫落。 Grade D: Particle shedding was observed under a load of 50 gf / cm 2 .

(4.8)積層薄膜的反射率 (4.8) Reflectivity of laminated film

於分光光度計U-3410(日立製作所(股))中安裝有φ60積分球130-0632(日立製作所(股))(內表面為硫酸鋇製)及10°傾斜間隔件的狀態下求得560nm的光反射率。還有，光反射率係將從積層薄膜的塗布面一側測量求得的值作為該白色薄膜的反射率。標準白色板係使用Hitachi Instruments Service(股)製的構件編號210-0740(氧化鋁) 。測定5個樣品，將其平均定為反射率。 560 nm was obtained with a spectrophotometer U-3410 (Hitachi Seisakusho Co., Ltd.) with a φ60 integrating sphere 130-0632 (Hitachi Seisakusho Co., Ltd.) (inner surface made of barium sulfate) and a 10 ° inclined spacer. Light reflectance. The light reflectance is a value obtained by measuring the coating film side of the laminated film as the reflectance of the white film. The standard white board is made of Hitachi Instruments Service (stock) part number 210-0740 (alumina) . Five samples were measured and the average was determined as the reflectance.

(4.9)積層薄膜的全光線穿透率 (4.9) Full light transmittance of laminated film

依據JIS K7361-1997，使用霧度計(NDH7000、日本電色工業股份有限公司製)進行測定。此時，將塗布面設置在光源側，進行測定。測定5個樣品，將其平均定為全光線穿透率。 The measurement was performed in accordance with JIS K7361-1997 using a haze meter (NDH7000, manufactured by Nippon Denshoku Industries Co., Ltd.). At this time, the coating surface was placed on the light source side, and measurement was performed. Five samples were measured and averaged as the total light transmittance.

[實施例] [Example]

以下藉由實施例等更具體說明發明，但本發明並未受到其限定。 Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto.

[原料] [raw material]

(1)作為基材薄膜的白色薄膜、透明薄膜用樹脂 (1) Resin for white film and transparent film as base film

‧PET(聚對苯二甲酸乙二酯)樹脂 ‧PET (polyethylene terephthalate) resin

使用作為酸成分之對苯二甲酸、作為二醇成分之乙二醇，對所得到的聚酯粒以銻原子換算計成為300ppm的方式添加三氧化銻(聚合觸媒)，進行聚縮合反應，得到極限黏度0.63dl/g的聚對苯二甲酸乙二酯粒(PET)樹脂。所得到的PET樹脂的玻璃轉移溫度為80℃。 Using terephthalic acid as an acid component and ethylene glycol as a diol component, antimony trioxide (polymerization catalyst) was added to the obtained polyester particles so that the amount of antimony atoms was 300 ppm, and a polycondensation reaction was performed. A polyethylene terephthalate (PET) resin having an limiting viscosity of 0.63 dl / g was obtained. The glass transition temperature of the obtained PET resin was 80 ° C.

‧環狀烯烴共聚物樹脂 ‧Cyclic olefin copolymer resin

使用玻璃轉移溫度為178℃、MVR(260℃/2.16kg)為4.5ml/10min之環狀烯烴樹脂「TOPAS」(註冊商標、Polyplastics公司製)作為不互溶成分。 As the immiscible component, a cyclic olefin resin "TOPAS" (registered trademark, manufactured by Polyplastics) having a glass transition temperature of 178 ° C and an MVR (260 ° C / 2.16kg) of 4.5 ml / 10min was used.

(2)用於形成塗布層的塗液 (2) Coating liquid for forming a coating layer

‧聚酯系黏結劑樹脂(材料A) ‧Polyester based binder resin (Material A)

以蒸餾水稀釋PESRESIN A-215E(高松油脂(股)製、30重量%溶液)，調製25重量%溶液。 PESRESIN A-215E (manufactured by Takamatsu Oil & Fat Co., Ltd., 30% by weight solution) was diluted with distilled water to prepare a 25% by weight solution.

‧界面活性劑(材料B) ‧Surfactant (Material B)

使用「Novec」(註冊商標)FC-4430(菱江化學(股)製、5重量%溶液)。 "Novec" (registered trademark) FC-4430 (manufactured by Ryoe Chemical Co., Ltd., 5% by weight solution) was used.

‧交聯劑(材料C) ‧Crosslinking agent (Material C)

「Epocros」WS-500(日本觸媒公司製) `` Epocros '' WS-500 (manufactured by Japan Catalyst Corporation)

‧有機粒子(材料D-1) ‧Organic particles (Material D-1)

使用總研化學公司製的粒徑0.05μm的圓球聚苯乙烯粒子的固體成分濃度1%的水分散體「DYNOSPHERES」。 An aqueous dispersion "DYNOSPHERES" having a solid content concentration of 1% of spherical polystyrene particles having a particle diameter of 0.05 µm manufactured by Soken Chemical Co., Ltd. was used.

‧有機粒子(材料D-2) ‧Organic particles (Material D-2)

使用總研化學公司製的粒徑0.3μm的圓球聚苯乙烯粒子的固體成分濃度1%的水分散體「DYNOSPHERES」。 An aqueous dispersion "DYNOSPHERES" having a solid content concentration of 1% of spherical polystyrene particles having a particle diameter of 0.3 µm manufactured by Soken Chemical Co., Ltd. was used.

‧有機粒子(材料D-3) ‧Organic particles (Material D-3)

使用總研化學公司製的粒徑0.6μm的圓球聚苯乙烯粒子的固體成分濃度1%的水分散體「DYNOSPHERES」。 An aqueous dispersion "DYNOSPHERES" having a solid content concentration of 1% of spherical polystyrene particles having a particle diameter of 0.6 µm manufactured by Soken Chemical Co., Ltd. was used.

‧有機粒子(材料D-4) ‧Organic particles (Material D-4)

使用總研化學公司製的粒徑0.9μm的圓球聚苯乙烯粒子的固體成分濃度1%的水分散體「DYNOSPHERES」。 An aqueous dispersion "DYNOSPHERES" having a solid content concentration of 1% of spherical polystyrene particles having a particle diameter of 0.9 µm manufactured by Soken Chemical Co., Ltd. was used.

‧有機粒子(材料D-5) ‧Organic particles (Material D-5)

使用總研化學公司製的粒徑1.2μm的圓球聚苯乙烯粒子的固體成分濃度1%的水分散體「DYNOSPHERES」。 An aqueous dispersion "DYNOSPHERES" having a solid content concentration of 1% of spherical polystyrene particles having a particle diameter of 1.2 µm manufactured by Soken Chemical Co., Ltd. was used.

‧有機粒子(材料D-6) ‧Organic particles (Material D-6)

使用總研化學公司製的粒徑0.2μm的圓球聚苯乙烯粒子的固體成分濃度1%的水分散體「DYNOSPHERES」。 An aqueous dispersion "DYNOSPHERES" having a solid content concentration of 1% of spherical polystyrene particles having a particle diameter of 0.2 µm manufactured by Soken Chemical Co., Ltd. was used.

‧無機粒子(材料E) ‧Inorganic particles (Material E)

使用將數量平均粒徑0.3μm的矽石粒子與蒸餾水混 合而成之10重量%溶液的水分散體。 Use silica particles with a number average particle size of 0.3 μm and distilled water A 10% by weight aqueous dispersion of the solution.

‧有機粒子(材料F-1) ‧Organic particles (Material F-1)

在1000ml的耐壓玻璃高壓釜(耐壓硝子工業(股)製、hyper Gras Star TEM-V1000N)中，加入33.25g的聚醚酯(「HYTREL」(註冊商標)8238、DuPont股份有限公司製、重量平均分子量27,000、彎曲彈性率1100MPa)、299.25g的N-甲基-2-吡咯啶酮、17.5g的聚乙烯醇(和光純藥工業股份有限公司製、PVA-1500、重量平均分子量29,000：藉由以甲醇進行的洗淨而將醋酸鈉含量降低至0.05質量%而成者)，進行氮取代後，加熱至180℃，進行攪拌4小時直到聚合物溶解。之後，將作為不良溶媒之350g的離子交換水經由液體輸送泵，以2.92g/分鐘的速度滴下。結束輸入所有量的水後，在攪拌的狀態下使其降溫，將所得到的懸浮液過濾，加入700g的離子交換水進行再成漿洗淨(reslurry washing)，使過濾出的物質在80℃下真空乾燥10小時，得到28.3g的白色固體。以掃描式電子顯微鏡觀察所得到的粉體，結果為圓球狀的微粒子，且為數量平均粒徑12.0μm、體積平均粒徑14.7μm、粒徑分布指數1.23的聚醚酯微粒子。該聚醚酯的熔點為224℃，該聚醚酯的降溫結晶化溫度為161℃。將所得到的粒子與蒸餾水混合，製成40質量%的水分散液，將其作為材料F-1。 In a 1000 ml pressure-resistant glass autoclave (manufactured by Pressure-resistant Glass Industrial Co., Ltd., hyper Gras Star TEM-V1000N), 33.25 g of a polyether ester ("HYTREL" (registered trademark) 8238, manufactured by DuPont Co., Ltd., Weight average molecular weight 27,000, flexural modulus 1100 MPa), 299.25 g of N-methyl-2-pyrrolidone, 17.5 g of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., PVA-1500, weight average molecular weight 29,000: (By reducing the sodium acetate content to 0.05% by mass by washing with methanol), after nitrogen substitution, heating to 180 ° C., and stirring for 4 hours until the polymer is dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped at a rate of 2.92 g / min through a liquid transfer pump. After inputting all the amount of water, the temperature was lowered while stirring, and the obtained suspension was filtered, and 700 g of ion-exchanged water was added for reslurry washing, and the filtered material was allowed to cool at 80 ° C. Drying under vacuum for 10 hours gave 28.3 g of a white solid. Observation of the obtained powder with a scanning electron microscope revealed that it was spherical fine particles, and polyetherester fine particles having a number average particle diameter of 12.0 μm, a volume average particle diameter of 14.7 μm, and a particle size distribution index of 1.23. The melting point of the polyether ester was 224 ° C, and the temperature-lowering crystallization temperature of the polyether ester was 161 ° C. The obtained particles were mixed with distilled water to prepare a 40% by mass aqueous dispersion, and this was used as a material F-1.

‧有機粒子(材料F-2) ‧Organic particles (Material F-2)

除了調整聚醚酯的量以外，係以與有機粒子(材料F)同樣的條件，得到數量平均粒徑3.0μm的聚醚酯微粒子。將所得到的粒子與蒸餾水混合，製成40質量%的水分散 液。 Except that the amount of polyether ester was adjusted, polyether ester fine particles having a number average particle diameter of 3.0 μm were obtained under the same conditions as the organic particles (material F). The obtained particles were mixed with distilled water to make a 40% by mass water dispersion. liquid.

‧有機粒子(材料F-3) ‧Organic particles (Material F-3)

除了調整聚醚酯的量以外，係以與有機粒子(材料F)同樣的條件，得到數量平均粒徑5.0μm的聚醚酯微粒子。將所得到的粒子與蒸餾水混合，製成40質量%的水分散液。 Except that the amount of the polyether ester was adjusted, polyether ester fine particles having a number average particle diameter of 5.0 μm were obtained under the same conditions as the organic particles (material F). The obtained particles were mixed with distilled water to prepare a 40% by mass aqueous dispersion.

‧有機粒子(材料F-4) ‧Organic particles (material F-4)

除了調整聚醚酯的量以外，係以與有機粒子(材料F)同樣的條件，得到數量平均粒徑20.0μm的聚醚酯微粒子。將所得到的粒子與蒸餾水混合，製成40質量%的水分散液。 Except that the amount of the polyether ester was adjusted, polyether ester fine particles having a number average particle diameter of 20.0 μm were obtained under the same conditions as the organic particles (material F). The obtained particles were mixed with distilled water to prepare a 40% by mass aqueous dispersion.

[實施例1] [Example 1]

(1)塗液的調製 (1) Preparation of coating liquid

將下述材料以1)至5)的順序調配塗液的原料，使用萬能攪拌機攪拌10分鐘，調製塗液。使用0.1當量的鹽酸，將已調整的塗布液調整成pH6.5。 The following materials were prepared in the order of 1) to 5), and the raw materials of the coating liquid were prepared, and they were stirred for 10 minutes using a universal mixer to prepare a coating liquid. The adjusted coating liquid was adjusted to pH 6.5 using 0.1 equivalent of hydrochloric acid.

1)蒸餾水：33.3重量份 1) Distilled water: 33.3 parts by weight

2)材料A：17.1重量份 2) Material A: 17.1 parts by weight

3)材料B：0.6重量份 3) Material B: 0.6 parts by weight

4)材料C：4.0重量份 4) Material C: 4.0 parts by weight

5)材料D-2：30.0重量份 5) Material D-2: 30.0 parts by weight

6)材料F：15.0重量份 6) Material F: 15.0 parts by weight

(2)製膜 (2) Film making

在180℃的溫度下將80重量份的PET與20重量份的環狀烯烴共聚物樹脂之混合物真空乾燥3小時後，供給至 擠壓機A，在280℃的溫度下進行熔融擠壓。又，在180℃的溫度下將100重量份的PET真空乾燥3小時後，供給至擠壓機B，在280℃的溫度下進行熔融擠壓。以將分別來自各個擠壓機A、B的樹脂往厚度方向以B/A/B的順序進行積層的方式合併後，導入T字模噴嘴。 A mixture of 80 parts by weight of PET and 20 parts by weight of a cyclic olefin copolymer resin was vacuum-dried at 180 ° C for 3 hours, and then supplied to Extruder A performs melt extrusion at a temperature of 280 ° C. In addition, 100 parts by weight of PET was vacuum-dried at 180 ° C for 3 hours, and then supplied to extruder B, and melt-extruded at 280 ° C. The resins from the extruder A and B were laminated in the order of B / A / B in the thickness direction, and then introduced into a T-shaped nozzle.

接著，自T字模噴嘴內擠壓成片狀，形成熔融積層片，以靜電施加法使該熔融積層片在表面溫度保持在25℃的滾筒上密接冷卻固化而得到未延伸積層薄膜。此時，將與滾筒接觸的薄膜面定為背面，將與空氣接觸的面定為「表」面。然後，將該未延伸積層薄膜以加熱至80℃的溫度的輥(預熱輥)群預熱後，利用輥的圓周速率差往縱軸方向進行3.5倍延伸，以25℃的溫度的輥群冷卻，得到單軸延伸薄膜。 Next, it was extruded into a sheet shape from a T-die nozzle to form a molten laminated sheet, and the molten laminated sheet was tightly cooled and solidified on a roller kept at a surface temperature of 25 ° C. by an electrostatic application method to obtain an unstretched laminated film. In this case, the surface of the film that is in contact with the drum is defined as the back surface, and the surface that is in contact with air is defined as the "surface" surface. Then, the unstretched laminated film is preheated with a group of rolls (preheating rolls) heated to a temperature of 80 ° C, and then stretched 3.5 times in the direction of the vertical axis by using the circumferential speed difference of the rolls, and the group of rolls at a temperature of 25 ° C Cooled to obtain a uniaxially stretched film.

再接著，在空氣中對單軸延伸薄膜的「表」面施加電暈放電處理，以使用繞線棒的棒塗布方式將上述塗布層形成塗液塗布在該處理面上。 Then, a corona discharge treatment was applied to the "surface" surface of the uniaxially stretched film in air, and the coating layer-forming coating liquid was applied on the treated surface by a bar coating method using a wire rod.

一面以夾具夾持上述塗布有塗布層形成塗液的單軸延伸薄膜的兩端，一面導入至拉幅機內的100℃的預熱區域進行乾燥後，接著連續在100℃的加熱區域中往垂直於縱軸方向的方向(橫軸方向)延伸3.5倍。再接著，在拉幅機內的熱處理區域中施加190℃的熱處理，再於190℃下往6%橫軸方向進行鬆弛處理後，接著均一地緩慢冷卻後進行捲取，得到於厚度188μm的薄膜上設置有厚度200nm的塗布層之白色積層薄膜。B層的膜後為10μm。將塗液組成、所得到的積層薄膜的物性的評定結果示於表1、表2。 The two ends of the uniaxially stretched film coated with the coating layer-forming coating liquid are clamped by a jig while being introduced into a preheating area at 100 ° C in a tenter and dried, and then continuously heated in a heating area at 100 ° C. The direction (horizontal axis direction) perpendicular to the longitudinal axis direction extends 3.5 times. Next, a heat treatment at 190 ° C was applied to the heat treatment area in the tenter, and then a relaxation treatment was performed at 190 ° C in the 6% horizontal axis direction, followed by uniformly slow cooling, and then coiling to obtain a film having a thickness of 188 μm. A white laminated film with a coating layer having a thickness of 200 nm was provided thereon. The thickness of the layer B was 10 μm. Table 1 and Table 2 show the evaluation results of the coating composition and the physical properties of the obtained laminated film.

第1圖顯示以SEM觀察本實施例中所得到的積層薄膜的塗布層所含的有機粒子之結果。其為有機粒子(材料D)附著在有機粒子(材料F)的表面上之狀態。 FIG. 1 shows the results of observing the organic particles contained in the coating layer of the laminated film obtained in this example by SEM. This is a state where the organic particles (material D) are attached to the surface of the organic particles (material F).

[實施例2~11] [Examples 2 to 11]

除了將塗布層形成塗液的組成設為表1所示的條件、將塗布層的厚度設為表2所示的條件以外，係以與實施例1相同的條件進行製膜，得到厚度188μm的積層的白色薄膜。將薄膜的各種特性示於表2。塗布外觀皆良好，而且粒子的脫落也都很少。 Except that the composition of the coating layer-forming coating liquid was set to the conditions shown in Table 1 and the thickness of the coating layer was set to the conditions shown in Table 2, a film was formed under the same conditions as in Example 1 to obtain a film having a thickness of 188 μm. Laminated white film. Table 2 shows various characteristics of the film. The coating appearance was good, and the shedding of particles was very small.

[實施例12] [Example 12]

在180℃的溫度下將PET真空乾燥3小時後，供給至擠壓機A，在280℃的溫度下進行熔融擠壓。將來自擠壓機A的熔融樹脂導入T字模噴嘴。 After PET was vacuum-dried at 180 ° C for 3 hours, it was supplied to extruder A and melt-extruded at 280 ° C. The molten resin from the extruder A was introduced into a T-die nozzle.

接著，自T字模噴嘴內擠壓成片狀，形成熔融PET片，以靜電施加法使該熔融PET片在表面溫度保持在25℃的滾筒上密接冷卻固化而得到未延伸PET薄膜。此時，將與滾筒接觸的薄膜面定為背面，將與空氣接觸的面定為「表」面。然後，將該未延伸PET薄膜以加熱至80℃的溫度的輥(預熱輥)群預熱後，利用輥的圓周速率差往縱軸方向進行3.5倍延伸，以25℃的溫度的輥群冷卻，得到單軸延伸薄膜。 Next, it was extruded into a sheet shape from a T-die nozzle to form a molten PET sheet, and the molten PET sheet was tightly cooled and solidified on a roller kept at a surface temperature of 25 ° C by an electrostatic application method to obtain an unstretched PET film. In this case, the surface of the film that is in contact with the drum is defined as the back surface, and the surface that is in contact with air is defined as the "surface" surface. Then, the unstretched PET film is preheated with a group of rolls (preheating rolls) heated to a temperature of 80 ° C, and then stretched 3.5 times in the direction of the vertical axis by using the circumferential speed difference of the rolls, and the group of rolls at a temperature of 25 ° C Cooled to obtain a uniaxially stretched film.

再接著，在空氣中對單軸延伸薄膜的「表」面施加電暈放電處理，以使用繞線棒的棒塗布方式將表1所示的塗布層形成塗液塗布在該處理面上。 Next, a corona discharge treatment was applied to the "surface" surface of the uniaxially stretched film in air, and the coating layer forming coating solution shown in Table 1 was applied to the treated surface by a bar coating method using a wire rod.

一面以夾具夾持上述塗布有塗布層形成塗液 的單軸延伸薄膜的兩端，一面導入至拉幅機內的100℃的預熱區域進行乾燥後，接著連續在100℃的加熱區域中往垂直於縱軸方向的方向(橫軸方向)延伸3.5倍。再接著，在拉幅機內的熱處理區域中施加190℃的熱處理，再於190℃下往6%橫軸方向進行鬆弛處理後，接著均一地緩慢冷卻後進行捲取，得到於厚度188μm的薄膜上設置有厚度200nm的塗布層之積層薄膜。將塗液組成、所得到的積層薄膜的物性的評定結果示於表1、表2。 One side holds the above-mentioned coating layer with a jig to form a coating liquid. Both ends of the uniaxially stretched film are introduced into the preheating area at 100 ° C in the tenter and dried, and then continuously extended in the heating area at 100 ° C in a direction perpendicular to the vertical axis direction (horizontal axis direction). 3.5 times. Next, a heat treatment at 190 ° C was applied to the heat treatment area in the tenter, and then a relaxation treatment was performed at 190 ° C in the 6% horizontal axis direction, followed by uniformly slow cooling, and then coiling to obtain a film having a thickness of 188 μm. A laminated film having a coating layer having a thickness of 200 nm was provided thereon. Table 1 and Table 2 show the evaluation results of the coating composition and the physical properties of the obtained laminated film.

[比較例1] [Comparative Example 1]

除了將塗布層形成塗液的組成設為表1所示的條件、將塗布層的厚度設為表2所示的條件、不調整pH而維持在pH7.9以外，係以與實施例1相同的條件進行製膜，得到厚度188μm的積層白色薄膜。粒子(b)並未附著在粒子(a)上，在刮痕試驗中，於薄膜上發生粒子脫落。將薄膜的各種特性示於表2。從比較例1的薄膜有粒子脫落。 The composition was the same as in Example 1 except that the composition of the coating layer forming coating liquid was set to the conditions shown in Table 1, the thickness of the coating layer was set to the conditions shown in Table 2, and the pH was maintained at pH 7.9 without adjusting the pH. Film formation was performed under the conditions described above to obtain a laminated white film having a thickness of 188 μm. The particles (b) did not adhere to the particles (a), and in the scratch test, the particles fell off on the film. Table 2 shows various characteristics of the film. Particles came off from the film of Comparative Example 1.

[比較例2~4] [Comparative Examples 2 to 4]

除了將塗布層形成塗液的組成設為表1所示的條件、將塗布層的厚度設為表2所示的條件以外，係以與實施例1相同的條件進行製膜，得到厚度188μm的積層白色薄膜。將薄膜的各種特性示於表2。從比較例1的薄膜有粒子脫落。 Except that the composition of the coating layer-forming coating liquid was set to the conditions shown in Table 1 and the thickness of the coating layer was set to the conditions shown in Table 2, a film was formed under the same conditions as in Example 1 to obtain a film having a thickness of 188 μm. Laminated white film. Table 2 shows various characteristics of the film. Particles came off from the film of Comparative Example 1.

[產業上之可利用性] [Industrial availability]

本發明之薄膜係能夠適當地使用作為光反射板、光學片，尤其是能夠適當地使用作為背光用的光反射板，其中，能夠適當地使用作為側光型背光用的光反 射板。在此，側光型背光是指至少具有光源、導光板與反射板者，但亦可包含殼體等。還有，光源的種類並沒有特別的限定，但在使用CCFL或LED作為光源的情況下，能夠得到特別良好的效果。 The film of the present invention can be suitably used as a light reflecting plate and an optical sheet, and in particular can be suitably used as a light reflecting plate for a backlight. Among them, a light reflecting plate for an edge-light type backlight can be suitably used. Shooting board. Here, the edge-light type backlight refers to a person having at least a light source, a light guide plate, and a reflection plate, but may include a case and the like. The type of the light source is not particularly limited, but when CCFL or LED is used as the light source, a particularly good effect can be obtained.

Claims (12)

一種積層薄膜，其特徵為：於薄膜的至少一側的表面上設置包含由樹脂(A)構成之數量平均粒徑為6μm以上的粒子(a)之塗布層，而平均10個以上之數量平均粒徑0.1μm以上1μm以下的粒子(b)附著在1個粒子(a)的表面上。A laminated film characterized in that a coating layer containing particles (a) having a number average particle diameter of 6 μm or more made of resin (A) is provided on the surface of at least one side of the film, and an average of 10 or more Particles (b) having a particle diameter of 0.1 μm or more and 1 μm or less adhere to the surface of one particle (a). 如請求項1之積層薄膜，其中於白色薄膜的至少一側的表面上設置包含由樹脂(A)構成之數量平均粒徑為6μm以上的粒子(a)之塗布層，而平均10個以上之數量平均粒徑0.1μm以上1μm以下的粒子(b)附著在1個粒子(a)的表面上。For example, the laminated film of claim 1, wherein a coating layer containing particles (a) having a number average particle diameter of 6 μm or more made of resin (A) is provided on at least one surface of the white film, and an average of 10 Particles (b) having a number average particle diameter of 0.1 μm to 1 μm are attached to the surface of one particle (a). 如請求項1之積層薄膜，其中該薄膜為透明，該薄膜的全光線穿透率為60%以上。For example, the laminated film of claim 1, wherein the film is transparent, and the total light transmittance of the film is more than 60%. 如請求項1至3中任一項之積層薄膜，其中粒子(a)係由聚酯樹脂構成。The laminated film according to any one of claims 1 to 3, wherein the particles (a) are composed of a polyester resin. 如請求項4之積層薄膜，其中粒子(b)是由不同於樹脂(A)的樹脂(B)構成。The laminated film as claimed in claim 4, wherein the particles (b) are composed of a resin (B) different from the resin (A). 如請求項4之積層薄膜，其中粒子(b)為無機粒子。The laminated film as claimed in claim 4, wherein the particles (b) are inorganic particles. 如請求項1至3中任一項之積層薄膜，其中塗布層的厚度小於1μm。The laminated film according to any one of claims 1 to 3, wherein the thickness of the coating layer is less than 1 μm. 如請求項1至3中任一項之積層薄膜，其中塗布層的厚度小於0.5μm。The laminated film according to any one of claims 1 to 3, wherein the thickness of the coating layer is less than 0.5 μm. 如請求項1至3中任一項之積層薄膜，其中粒子(a)的數量平均粒徑為6μm以上60μm以下。The laminated film according to any one of claims 1 to 3, wherein the number average particle diameter of the particles (a) is 6 μm or more and 60 μm or less. 如請求項1至3中任一項之積層薄膜，其中粒子(b)的數量平均粒徑為100nm以上800nm以下。The laminated film according to any one of claims 1 to 3, wherein the number average particle diameter of the particles (b) is 100 nm to 800 nm. 如請求項1或2之積層薄膜，其為邊緣型背光單元用的反射板。The laminated film of claim 1 or 2 is a reflection plate for an edge type backlight unit. 一種邊緣型背光單元，其係使用如請求項1至11中任一項之積層薄膜而成之邊緣型背光單元。An edge type backlight unit is an edge type backlight unit formed by using a laminated film according to any one of claims 1 to 11.
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