TWI663061B - Laminated film and manufacturing method of laminated film - Google Patents

Abstract

本發明係一種積層薄膜，其係在支撐基材的至少一側之面上形成有包含A層與B層之表面層的積層薄膜，其特徵為：自支撐基材側起B層、A層依此順序相接，A層、B層、支撐基材之藉由微小硬度計所測定的25℃之儲存彈性模數(以下為E_A25、E_B25、E_C25)、120℃之儲存彈性模數(以下為E_A120、E_B120、E_C120)係滿足以下之條件，條件1 E_A25<E_B25≦E_C25；條件2 E_B120≦E_A120<E_C120；條件3 E_A25≦100MPa。 The present invention is a laminated film, which is formed on at least one side of a supporting substrate with a laminated film including a surface layer of A layer and B layer, and is characterized in that: layer B and layer A are from the supporting substrate side Connected in this order, the storage elastic modulus of layer A, layer B, and the supporting substrate measured at 25 ° C by a micro hardness tester (the following are E _A25 , E _B25 , and E _C25 ), and the storage elastic modulus at 120 ° C The numbers (the following are E _A120 , E _B120 , and E _C120 ) satisfy the following conditions: condition 1 E _A25 <E _B25 ≦ E _C25 ; condition 2 E _B120 ≦ E _A120 <E _C120 ; condition 3 E _A25 ≦ 100MPa.

本發明提供使耐擦傷性尤其反覆擦過耐性、與成型性並存之積層薄膜。 The present invention provides a laminated film which has abrasion resistance, particularly repeated rub resistance, and coexistence with moldability.

Description

積層薄膜、及積層薄膜之製造方法 Laminated film and manufacturing method of laminated film

本發明係關於使耐擦傷性尤其反覆擦過耐性、與成型性並存之積層薄膜。 The present invention relates to a laminated film which has abrasion resistance, particularly repeated rub resistance, and coexistence with moldability.

近年來，以彩色濾光片等之光學材料或平面顯示器、汽車車身的表面保護(損傷防止或防污性賦予等)為目的，而使用設有包含合成樹脂等的表面層之塑膠薄膜。 In recent years, a plastic film provided with a surface layer containing a synthetic resin or the like has been used for the purpose of protecting an optical material such as a color filter, a flat display, and the surface of a car body (such as preventing damage or imparting antifouling properties).

對於此等之表面層，在表面保護之觀點，係作為重要的特性而要求耐擦傷性。一般而言，係使用所謂的「硬塗材料」來賦予耐擦傷性，而該「硬塗材料」係使用非專利文獻1中記載之使包含有機矽烷系或多官能丙烯酸系等之各種預聚物、寡聚物等的塗料組成物，塗布-乾燥-熱或UV硬化而成的「高交聯密度材料」，或是使用進一步組合有各種表面修飾填料的「有機-無機混成材料」等，而提高了塗膜的表面硬度。 From the viewpoint of surface protection, these surface layers require scratch resistance as an important characteristic. Generally, a so-called "hard coating material" is used to impart abrasion resistance, and this "hard coating material" uses various prepolymers described in Non-Patent Document 1 to include an organic silane-based or polyfunctional acrylic system. Coating compositions such as polymers, oligomers, "high cross-link density materials" formed by coating-drying-heating or UV curing, or "organic-inorganic hybrid materials" using various surface-modified fillers, etc., The surface hardness of the coating film is improved.

另一方面，對於表面層，在表面保護之觀點，除了作為必要的特性而要求耐擦傷性之外，還因應用途而要求耐藥品性、耐油性、成型性等各式各樣的特性。特別是成型性係由於如只是使塗膜變硬，則對於變 形容易發生「龜裂」或「剝離」等，故要求難以損傷但柔軟之耐擦傷性與成型性的之並存。 On the other hand, from the standpoint of surface protection, the surface layer requires a variety of properties such as chemical resistance, oil resistance, and moldability depending on the application in addition to scratch resistance as required characteristics. In particular, moldability is because if the coating film is only hardened, The shape is prone to "cracking" or "peeling", so it is required to coexist with soft scratch resistance and moldability which are difficult to damage.

於硬塗材料中，作為使耐擦傷性與成型性並存之積層薄膜，專利文獻1中提案「一種積層薄膜，其係在基材薄膜的至少一面上設有硬塗層的積層薄膜，其特徵為：以超微小硬度計測定的硬塗層之表面硬度的最大值為0.05GPa以上4.0GPa以下，100℃環境下的破裂延伸度為15%以上且小於250%」。 In a hard-coating material, as a laminated film having both abrasion resistance and moldability, Patent Document 1 proposes "a laminated film, which is a laminated film in which a hard coat layer is provided on at least one side of a base film. The maximum value of the surface hardness of the hard coating layer measured by the ultra-micro hardness meter is 0.05 GPa or more and 4.0 GPa or less, and the elongation at break at 100 ° C is 15% or more and less than 250%. "

在另一方面，專利文獻2及3中提案使用所謂的「自我修復材料」之薄膜，其係藉由表面層的材料之彈性回復範圍的變形來修復在表面的損傷，達成耐擦傷性，再者，作為藉由使自我修復材料的伸長性提升而使成型性提升的材料，專利文獻4中提案「一種活性能量線硬化性塗布劑，其係包含由環氧樹脂、氧雜環丁烷樹脂、乙烯基醚樹脂所選出的至少1種樹脂(A)、與數量平均分子量為400以上的多元醇(B)、及活性能量線感應觸媒(C)之樹脂組成物，其特徵為：多元醇(B)係選自具有包含碳-碳鍵的主鏈之多元醇(B1)、聚碳酸酯多元醇(B2)、聚酯多元醇(B3)、聚醚多元醇(B4)的至少1種多元醇」。 On the other hand, Patent Documents 2 and 3 propose to use a so-called "self-healing material" film, which repairs the damage on the surface by deforming the elastic recovery range of the material of the surface layer to achieve scratch resistance, and then In addition, as a material that improves moldability by improving the elongation of self-healing materials, Patent Document 4 proposes "an active energy ray-curable coating agent comprising an epoxy resin and an oxetane resin. A resin composition of at least one resin (A) selected from vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray induction catalyst (C), which are characterized by: The alcohol (B) is at least 1 selected from the group consisting of a polyol (B1), a polycarbonate polyol (B2), a polyester polyol (B3), and a polyether polyol (B4) having a main chain including a carbon-carbon bond. Kind of polyol. "

又，就使自我修復材料之成型性提升的其他方法而言，作為著眼於積層構造的發明，專利文獻5中提案「一種附自我修復層的積層體，其係在樹脂基材的至少一側之面上，將應力緩和層與自我修復層以此順序積層之附自我修復層的積層體，其特徵為：該自我修復層係至少由軟質合成樹脂所構成，且接觸該自我修復 層的該應力緩和層之藉由奈米壓入(nano indentation)測定的硬度H係與自我修復層之藉由奈米壓入測定的硬度H同等或為低」。 As another method for improving the moldability of a self-healing material, as an invention focusing on a laminated structure, Patent Document 5 proposes "a laminated body with a self-healing layer, which is on at least one side of a resin substrate On the surface, a layered body with a self-healing layer laminated with a stress relaxation layer and a self-healing layer in this order is characterized in that the self-healing layer is composed of at least a soft synthetic resin and contacts the self-healing The hardness H of the layer of the stress relaxation layer measured by nano indentation is the same as or lower than the hardness H of the self-healing layer measured by nano indentation. "

[先前技術文獻] [Prior technical literature] [非專利文獻] [Non-patent literature]

[非專利文獻1]塑膠硬塗應用技術 股份有限公司CMC出版2004年 [Non-Patent Document 1] Plastic Hard Coating Application Technology Co., Ltd. CMC Publishing 2004

[專利文獻] [Patent Literature]

[專利文獻1]日本特開2009-184284號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2009-184284

[專利文獻2]國際公開第2011/136042號 [Patent Document 2] International Publication No. 2011/136042

[專利文獻3]日本特開平11-228905號公報 [Patent Document 3] Japanese Patent Application Laid-Open No. 11-228905

[專利文獻4]日本特開2007-284613號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2007-284613

[專利文獻5]日本特開2011-5766號公報 [Patent Document 5] Japanese Patent Laid-Open No. 2011-5766

然而，於前述表面層使用前述「硬塗材料」之成型體，雖然表面硬度極高，但常有在日常生活中損傷、損害外觀之事，經本發明者們針對此進行了調查，而得知「硬塗材料」雖然表面的硬度高，但若以柔軟的布等反覆擦過，則在表面發生微細的傷痕，而表面會白濁。 However, the molded article using the aforementioned "hard coating material" on the surface layer has extremely high surface hardness, but it is often damaged or damaged in daily life. The inventors have investigated this and learned that Although the "hard coating material" has a high surface hardness, if it is rubbed repeatedly with a soft cloth or the like, fine scratches occur on the surface and the surface becomes cloudy.

相對於此，經本發明者們針對專利文獻2、專利文獻3中提案的材料進行了確認，而得知在日常生 活中難以損傷，且即使反覆擦過也藉由自我修復機能而傷痕會恢復，係得到硬塗材料同等以上之耐擦傷性。 In contrast, the present inventors confirmed the materials proposed in Patent Document 2 and Patent Document 3, and learned that It is difficult to be damaged in life, and even if it is rubbed repeatedly, the scar will be restored by the self-repairing function, and the scratch resistance of the hard coating material is equal to or higher than that of the hard coating material.

然而，得知由於自我修復材料是柔軟的材料，而乍看似乎成型性優異，但若實際地進行成型，則在成型後立刻、或在成型後的保管時，於表面層，於表面層會有裂痕(破裂)，或以此作為起點而表面層剝離的情形。 However, I learned that since the self-healing material is a soft material, it seems that the moldability is excellent at first glance. However, if the molding is actually performed, it will be on the surface layer and on the surface layer immediately after molding or during storage after molding. There are cracks (cracks), or the surface layer is peeled off using this as a starting point.

又，專利文獻4、5中將使自我修復性與成型性並存作為課題之一而進行了提案，但經本發明者們進行了確認，任一者之效果皆在成型時的破裂或反覆擦過方面並不充分。又，專利文獻1至5中任一者皆未到達構想有關本發明之構造。因此，本發明之目的在於提供使耐擦傷性尤其反覆擦過耐性、與成型性並存之積層薄膜。 In addition, Patent Documents 4 and 5 propose coexistence of self-healing property and moldability as one of the problems. However, the inventors have confirmed that the effects of either are cracking or rubbing during molding. Not enough. In addition, none of Patent Documents 1 to 5 has reached the conception of the structure of the present invention. Therefore, an object of the present invention is to provide a laminated film which has abrasion resistance, particularly repeated rub resistance, and coexistence with moldability.

為了解決上述問題，本發明者們重複專心致力的研究的結果，完成了以下之發明。即，本發明係如以下。 In order to solve the above problems, the present inventors repeated the results of intensive studies, and completed the following inventions. That is, the present invention is as follows.

(1)一種積層薄膜，其係在支撐基材的至少一側之面上具有包含A層與B層的表面層之積層薄膜，其特徵為：自支撐基材側起B層、A層依此順序相接，A層、B層、支撐基材之藉由微小硬度計所測定的25℃之儲存彈性模數(以下為E_A25、E_B25、E_C25)、120℃之儲存彈性模數(以下為E_A120、E_B120、E_C120)係滿足以下之條件，條件1 E_A25<E_B25≦E_C25； 條件2 E_B120≦E_A120<E_C120；條件3 E_A25≦100MPa。 (1) A laminated film, which is a laminated film including a surface layer of A and B layers on at least one side of a supporting substrate, and is characterized in that the B layer and the A layer are formed from the supporting substrate side. This sequence is connected, the storage elastic modulus at 25 ° C (hereinafter E _A25 , E _B25 , E _C25 ) and the storage elastic modulus at 120 ° C measured by a micro hardness tester of layer A, layer B, and the supporting substrate. (The following are E _A120 , E _B120 , and E _C120 ) satisfy the following conditions, condition 1 E _A25 <E _B25 ≦ E _C25 ; condition 2 E _B120 ≦ E _A120 <E _C120 ; condition 3 E _A25 ≦ 100MPa.

(2)如(1)記載之積層薄膜，其中前述A層、B層、支撐基材係滿足以下之條件，條件4 0<E_C25-E_B25<5GPa；條件5 0<E_A120-E_B120<50MPa。 (2) The laminated film according to (1), wherein the above-mentioned layer A, layer B, and supporting substrate satisfy the following conditions, condition 40 <E _C25 -E _B25 <5GPa; condition 5 0 <E _A120 -E _B120 <50MPa.

(3)如(1)或(2)記載之積層薄膜，其中前述B層之玻璃轉移溫度(以下為Tg_B)係滿足以下之條件；條件6 60℃≦Tg_B≦130℃。 (3) The laminated film according to (1) or (2), wherein the glass transition temperature (hereinafter referred to as Tg _B ) of the layer _B satisfies the following conditions; condition 6 60 ° C ≦ Tg _B ≦ 130 ° C.

(4)如(1)至(3)中任一項記載之積層薄膜，其中前述B層之厚度(以下為T_B)係滿足以下之條件；條件7 0.1μm≦T_B≦5μm。 (4) The laminated film according to any one of (1) to (3), wherein the thickness of the B layer (hereinafter referred to as T _B ) satisfies the following conditions; Condition 7 0.1 μm ≦ T _B ≦ 5 μm.

(5)如(1)至(4)中任一項記載之積層薄膜，其中在前述表面層之垂直於基材的截面中，自表面層的表面起，在表面層厚度的10%之位置(以後當作位置1)、50%(以後當作位置2)、99%(以後當作位置3)的各位置之依據原子力顯微鏡的彈性模數E1、E2、E3係滿足以下之條件，條件8 E1≦E2<E3；條件9 E1≦100MPa；條件10 E3≧1GPa。 (5) The laminated film according to any one of (1) to (4), wherein the cross section of the surface layer perpendicular to the base material is 10% of the thickness of the surface layer from the surface of the surface layer. (Hereinafter referred to as position 1), 50% (hereinafter referred to as position 2), and 99% (hereinafter referred to as position 3). The elastic modulus of the atomic force microscope E1, E2, and E3 satisfy the following conditions. 8 E1 ≦ E2 <E3; condition 9 E1 ≦ 100MPa; condition 10 E3 ≧ 1GPa.

(6)一種積層薄膜之製造方法，其係如前述(1)至(5)中任一項記載的積層薄膜之製造方法，其特徵為：前述表面層係藉由將2種類以上的塗料組成物逐次地塗布於支撐基材上，乾燥、硬化而形成。 (6) A method for manufacturing a laminated film, which is the method for manufacturing a laminated film according to any one of (1) to (5), wherein the surface layer is composed of two or more kinds of coating materials. The material is sequentially applied to a support substrate, and is formed by drying and curing.

(7)一種積層薄膜之製造方法，其係如前述(1)至(5) 中任一項記載之積層薄膜之製造方法，其特徵為：前述表面層係藉由將2種類以上的塗料組成物同時地塗布於支撐基材上，乾燥、硬化而形成。 (7) A method for manufacturing a laminated film, which is as described in (1) to (5) above The method for producing a laminated film according to any one of the preceding claims, wherein the surface layer is formed by simultaneously coating two or more kinds of coating compositions on a supporting substrate, drying and curing.

如依照本發明，則可提供使耐擦傷性尤其反覆擦過耐性、與成型性並存之積層薄膜。 According to the present invention, it is possible to provide a laminated film having abrasion resistance, particularly repeated rub resistance, and coexistence with moldability.

1‧‧‧表面層中與B層接觸之層(A層) 1‧‧‧The layer in contact with layer B (layer A)

2‧‧‧與支撐基材接觸之層(B層) 2‧‧‧layer in contact with the supporting substrate (layer B)

3‧‧‧支撐基材(C層) 3‧‧‧ support substrate (C layer)

4‧‧‧包含A層與B層的表面層 4‧‧‧ Surface layer including layer A and layer B

5‧‧‧自表面層的表面起，表面層厚度的10%之位置(位置1) 5‧‧‧10% of the thickness of the surface layer from the surface of the surface layer (position 1)

6‧‧‧自表面層的表面起，表面層厚度的50%之位置(位置2) 6‧‧‧ from the surface of the surface layer, 50% of the thickness of the surface layer (position 2)

7‧‧‧自表面層的表面起，表面層厚度的99%之位置(位置3) 7‧‧‧ from the surface of the surface layer, 99% of the thickness of the surface layer (position 3)

8‧‧‧多層滑動模頭 8‧‧‧Multi-layer sliding die

9‧‧‧多層狹縫模頭 9‧‧‧Multi-layer Slot Die

10‧‧‧單層狹縫模頭 10‧‧‧Single-layer slit die

第1圖係顯示本發明之積層薄膜的構成之截面圖的一例。 Fig. 1 is an example of a cross-sectional view showing the structure of a laminated film of the present invention.

第2圖係顯示本發明之積層薄膜的構成之截面圖的一例。 Fig. 2 is an example of a cross-sectional view showing the structure of a laminated film of the present invention.

第3圖係顯示本發明中的表面層之形成方法的一例之截面圖。 Fig. 3 is a cross-sectional view showing an example of a method for forming a surface layer in the present invention.

第4圖係顯示本發明中的表面層之形成方法的一例之截面圖。 Fig. 4 is a cross-sectional view showing an example of a method for forming a surface layer in the present invention.

第5圖係顯示本發明中的表面層之形成方法的一例之截面圖。 Fig. 5 is a cross-sectional view showing an example of a method for forming a surface layer in the present invention.

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

為達成上述課題，本發明者們針對(1)實際使用環境下，自我修復材料較硬塗材料耐擦傷性優異的理由；(2)柔軟的自我修復材料在成型後立刻、或成型後的保管時，於表面層出現裂痕(破裂)、或以破裂作為起點而表面層剝離的理由，詳細地檢討而達成以下之考察。 In order to achieve the above-mentioned problems, the present inventors have pointed out (1) the reason why self-healing materials are more resistant to scratches than hard-coated materials in actual use environments; (2) the soft self-healing materials are stored immediately after molding, or after storage In this case, the reason for the occurrence of cracks (cracks) in the surface layer, or the peeling of the surface layer with the cracks as the starting point, was examined in detail to achieve the following examination.

首先，針對前述之(1)進行說明。對於塑膠表面之傷痕的形成，係受到「壓力」、「擦過者的硬度」、「擦過次數」之3個要素所影響。硬塗材料在實際使用環境傷痕會容易出現的理由，係起因於實際使用環境下的傷痕形成機構，即「實際使用環境下，擦過表面者的硬度低，但另一方面，接觸的次數非常多」。於硬塗材料，即使是在擦過者的硬度低、或擦過時的壓力低，且以1次的擦過並不在表面造成損傷的條件下，不至於在材料表面造成損傷的內部應變也會殘留，這會因「擦過次數」變多而被蓄積為應變。此結果，認為於硬度高、能彈性變形之應變範圍小的硬塗材料中，係超過應變的容許範圍而最後形成傷痕。另一方面，認為自我修復材料在實際使用環境中堅固，而對於反覆擦過為有效的原因，係因為材料的彈性回復範圍大，而即使在前述之條件下擦過，也可釋放應變，不形成傷痕。 First, (1) will be described. The formation of flaws on the plastic surface is affected by three factors: "pressure", "hardness of the wiper" and "number of wipes". The reason why hard coating materials are easy to appear in the actual use environment is due to the flaw formation mechanism in the actual use environment, that is, "the hardness of the person who rubs the surface is low in the actual use environment, but on the other hand, the number of contacts is very high ". For hard-coated materials, even if the hardness of the wiper is low, or the pressure during the brushing is low, and the surface does not cause damage to the surface with a single wipe, the internal strain that does not cause damage to the surface of the material will remain, This will accumulate strain as the number of "scratches" increases. As a result, it is considered that in a hard coating material having a high hardness and a small strain range capable of elastic deformation, a flaw is finally formed beyond the allowable range of the strain. On the other hand, the reason that self-healing materials are strong in actual use environment and effective for repeated rubbing is because the elastic recovery range of the material is large, and even if rubbing under the aforementioned conditions, strain can be released without forming scars. .

其次，針對前述之(2)進行說明。專利文獻2至3中記載之在表面層中使用藉由彈性回復而展現自我修復性的材料，在基材中使用一般的熱塑性樹脂之積層薄膜，由於表面層成為「熵彈性體=橡膠彈性體」，支撐基材成為「能量彈性體」，故亦可說是由對於熱之力學行為大不相同的材料所形成。由於若將如此的薄膜予以加熱、成型，則雖支撐基材會塑性變形而被固定化，但自我修復層會在彈性變形範圍中變形，故成為被支撐基材在伸長方向被拉伸之狀態，於表面層內發生殘留應力。而且，茲認為若是在後步驟，例如因射出成型而受到 進一步的加熱，或是使用環境中成為高的溫度，則會因表面層是熵彈性體的緣故，彈性模數會比成型時更上升，並於成型時的伸長為大之情況中達到斷裂極限，而發生破裂。 Next, (2) will be described. The materials described in Patent Documents 2 to 3 use a material that exhibits self-healing by elastic recovery in the surface layer, and a laminated film of a general thermoplastic resin in the base material. Since the surface layer becomes "entropy elastomer = rubber elastomer" ", The supporting substrate becomes an" energy elastomer ", so it can be said that it is formed of materials that have very different mechanical behaviors with respect to heat. If such a film is heated and molded, although the supporting substrate is plastically deformed and fixed, the self-healing layer is deformed in the elastic deformation range, so the supported substrate is stretched in the elongation direction. , Residual stress occurs in the surface layer. Furthermore, it is considered that if it is subjected to a later step, such as by injection molding, Further heating, or a high temperature in the use environment, will cause the elasticity of the surface layer to increase due to the entropy elastomer, and reach the breaking limit when the elongation during molding is large. , And rupture occurred.

因此，本發明者們發現具有以下構造的表面層之積層薄膜，其係作為積層薄膜之表面層，而一邊具有具有如前述之優異的耐擦傷性，尤其是實際使用環境下的反覆擦過耐性，一邊並存有充分的成型適應性。 Therefore, the present inventors have found that a laminated film having a surface layer having the following structure is used as a surface layer of the laminated film, and one side has the excellent abrasion resistance as described above, especially the repeated rub resistance under an actual use environment, One side has sufficient molding adaptability.

首先，本發明之積層薄膜係如第1圖所示，於支撐基材3的至少一側之面上，具有包含A層與B層的表面層，且自支撐基材側起B層、A層依此順序相接。 First, as shown in FIG. 1, the laminated film of the present invention has a surface layer including layer A and layer B on at least one side of the supporting substrate 3, and the layers B and A from the supporting substrate side The layers are connected in this order.

較佳為前述表面層中，自支撐基材側起第2層的層(第1圖中的1，即A層)、接觸支撐基材的層(第1圖中的2，即B層)、支撐基材(第1圖中的3，以下當作C層)之藉由微小硬度計所測定的25℃之儲存彈性模數(以下為E_A25、E_B25、E_C25)、120℃之儲存彈性模數(以下為E_A120、E_B120、E_C120)滿足以下之條件； 條件1 E_A25<E_B25≦E_C25 Among the aforementioned surface layers, the second layer (1 in FIG. 1, that is, layer A) and the layer that contacts the supporting substrate (2 in FIG. 1, that is, layer B) from the supporting substrate side are preferred. 2. The storage elastic modulus of the supporting substrate (3 in the first figure, hereinafter referred to as layer C) measured at 25 ° C (hereinafter _{referred to} as E _A25 , E _B25 , E _C25 ) and 120 ° C by a micro hardness tester. Storage modulus of elasticity (E _A120 , E _B120 , E _C120 below) meets the following conditions; Condition 1 E _A25 <E _B25 ≦ E _C25

條件2 E_B120≦E_A120<E_C120 Condition 2 E _B120 ≦ E _A120 <E _C120

條件3 E_A25≦100MPa。 Condition 3 E _A25 ≦ 100MPa.

此處，條件1係顯示在25℃的彈性模數，即將積層薄膜實際使用時的使用溫度之A層(表面層中接觸B層之層)、B層(表面層中接觸支撐基材之層)、C層(支撐基材)的儲存彈性模數之關係。意指C層係儲存彈性模數最高，而B層係儲存彈性模數比A層高且儲存彈性模數與 C層相同或比C層低，而A層係儲存彈性模數最低，更佳為E_A25<E_B25<E_C25。 Here, Condition 1 shows the elastic modulus at 25 ° C, that is, the layer A (the layer in contact with the layer B in the surface layer) and the layer B (the layer in contact with the supporting substrate in the surface layer) at the operating temperature at which the laminated film is actually used ), The relationship between storage elastic modulus of layer C (supporting substrate). Means that layer C has the highest storage elastic modulus, while layer B has a higher storage elastic modulus than layer A and has the same or lower storage elastic modulus than layer C, and layer A has the lowest storage elastic modulus, which is better. It is E _A25 <E _B25 <E _C25 .

藉由成為如此的構成，B層係成為具有充分的內聚力，而表面層對於C層具有充分的密接力，實際使用時即使反覆擦過也不易發生剝離，因而較佳。 By having such a structure, the B layer system has sufficient cohesion, and the surface layer has sufficient adhesion to the C layer, and it is not easy to peel off even after repeated rubbing in actual use, so it is preferable.

表面層只要是包含A層與B層，則亦可包含其他層。即，表面層之構成亦可如第3圖般以3層以上而構成，此情況之比A層更靠近表面側的層(當作Z層)之彈性模數係沒有特別的限定，但較佳為Z層係接近A層的彈性模數。此處，Z層亦可具有防污性、耐指紋性、耐染附性、抗反射性、防眩性、抗靜電性等其他的機能。 The surface layer may include other layers as long as it includes the A layer and the B layer. That is, the structure of the surface layer may be composed of three or more layers as shown in FIG. 3. In this case, the elastic modulus of the layer closer to the surface side than the A layer (referred to as the Z layer) is not particularly limited. Preferably, the Z layer is close to the elastic modulus of the A layer. Here, the Z layer may have other functions such as antifouling, fingerprint resistance, dyeing resistance, antireflection, antiglare, and antistatic properties.

前述之藉由微小硬度計所測定的儲存彈性模數，係表示製作積層薄膜的表面層之截面的超薄切片而藉由微小硬度計所測定之值。關於具體的測定方法、計算方法之詳細係如後述。 The aforementioned storage elastic modulus measured by a micro-hardness tester is a value measured by a micro-hardness tester which indicates an ultra-thin slice of the cross-section of the surface layer of a laminated film. The details of specific measurement methods and calculation methods will be described later.

此彈性模數之順序若相反地成為E_A25>E_B25>E_C25，則會因藉由表面層的彈性回復之應變釋放變得無法進行，而會有不耐反覆擦過之情況。又，若交換順序，即成為E_B25>E_A25>E_B25等，則會在層內形成應力集中部，而會有在其附近有發生剝離之情況。 If the order of this modulus of elasticity is E _A25 > E _B25 > E _{C25 on the} contrary, the strain release by the elastic recovery of the surface layer will not be able to be performed, and there may be cases of resistance to repeated rubbing. In addition, if the order is changed, that is, E _B25 > E _A25 > E _B25, etc., a stress concentration portion may be formed in the layer, and peeling may occur in the vicinity.

又，條件2係顯示在120℃的彈性模數，即在積層薄膜的成型溫度附近之A層、B層、C層的彈性模數之關係，意指B層係彈性模數最低或是與A層相同，而A層係彈性模數比C層還低，而C層係彈性模數最高。更佳為E_B120<E_A120<E_C120。 In addition, Condition 2 shows the elastic modulus at 120 ° C, that is, the relationship between the elastic modulus of the A layer, the B layer, and the C layer near the forming temperature of the laminated film, which means that the B layer system has the lowest elastic modulus or is related to The A layer is the same, and the elastic modulus of the A layer is lower than that of the C layer. The C layer has the highest elastic modulus. More preferably, it is E _B120 <E _A120 <E _C120 .

藉由使成為如此的構成，而在成型時B層的彈性模數會變得比A層還低，所以不會在A層殘存殘留應力，而即使於其後的步驟中之加熱、使用環境下的高溫中也不易發生破裂，故較佳。 With such a structure, the elastic modulus of the layer B becomes lower than that of the layer A during molding, so no residual stress will remain in the layer A, and even in the heating and use environment in the subsequent steps Cracking is not likely to occur at high temperatures, so it is preferred.

若交換此彈性模數的順序，即成為E_A120≦E_B120<E_C120，則因前述之機構，而殘留應力會在成型時蓄積，會有於其後的步驟中之加熱、使用環境下的高溫中發生破裂之情況。 If the order of this elastic modulus is exchanged, it becomes E _A120 ≦ E _B120 <E _C120 . Due to the aforementioned mechanism, residual stress will accumulate during molding, and it will be heated and used in the subsequent steps. Cracking occurs at high temperatures.

此處，條件3係顯示A層之在25℃的彈性模數(E_A25)之較佳範圍。E_A25之值較佳為100MPa以下，更佳為50MPa以下，特佳為20MPa以下。若E_A25之值超過100MPa，則會在反覆擦過時因彈性回復所致的應變之釋放有變不充分之情況。又，E_A之值小者雖然在達成本課題上沒有特別的障礙，但若成為1MPa以下則會有在表面發生黏著性之情況，從表面保護之觀點來看會有不實用之情況。 Here, Condition 3 shows a preferable range of the elastic modulus (E _A25 ) of the layer A at 25 ° C. The value of E _A25 is preferably 100 MPa or less, more preferably 50 MPa or less, and particularly preferably 20 MPa or less. If the value of E _A25 exceeds 100 MPa, the release of strain due to elastic recovery may be insufficient during repeated rubbing. In addition, although the value of E _A is small, there is no particular obstacle in achieving cost, but if it is 1 MPa or less, adhesion may occur on the surface, which may be impractical from the viewpoint of surface protection.

再者，較佳為滿足以下之條件4、條件5。 Furthermore, it is preferable to satisfy the following condition 4 and condition 5.

條件4 0<E_C25-E_B25<5GPa Condition 4 0 <E _C25 -E _B25 <5GPa

條件5 0<E_A120-E_B120<50MPa。 Condition 50 0 <E _A120 -E _B120 <50MPa.

此處，條件4係顯示在積層薄膜之實際使用環境下的溫度之B層與C層的較佳儲存彈性模數之差的範圍，更佳為100MPa<E_C25-E_B25<3GPa。 Here, Condition 4 shows the range of the difference in the preferred storage elastic modulus of the B layer and the C layer at the temperature under the actual use environment of the laminated film, more preferably 100 MPa <E _C25 -E _B25 <3GPa.

由於若E_C25-E_B25成為5GPa以上，則表面層之對於支撐基材的密接力會變不充分，故會有反覆擦過耐性降低之情況。若E_C25-E_B25成為零，則作為結果，由 於A層與B層的彈性模數差變大，而在A層與B層之層間界面的應力集中變大，會有因硬材料的擦過而傷痕容易殘留之情況。 When E _C25 -E _{B25 is} 5 GPa or more, the adhesion of the surface layer to the supporting substrate will be insufficient, so that repeated rub resistance may be reduced. If E _C25 -E _B25 becomes zero, as a result, since the difference in elastic modulus between the A layer and the B layer becomes larger, the stress concentration at the interface between the A layer and the B layer becomes larger, and there will be rubbing by hard materials In addition, the scars are likely to remain.

又，條件5係顯示在成型溫度之A層與B層的較佳儲存彈性模數之差的範圍，更佳為0<E_A120-E_B120<30MPa，尤佳為0<E_A120-E_B120<10MPa。 In addition, Condition 5 shows the range of the difference in the preferred storage elastic modulus of the A layer and the B layer at the molding temperature, more preferably 0 <E _A120 -E _B120 <30MPa, and even more preferably 0 <E _A120 -E _B120 <10MPa.

若E_A120-E_B120成為50MPa以上，則在成型過程中，表面層與支撐基材的密接力會變不充分，會有發生皺紋之情況。又，若E_B120那方變得比E_A120更大，則成型時在A層與B層之界面會發生殘留應力，會有容易發生破裂或剝離之情況。 If E _A120- E _{B120 is} 50 MPa or more, the adhesion between the surface layer and the supporting substrate becomes insufficient during the molding process, and wrinkles may occur. In addition, if the E _B120 side becomes larger than the E _A120 side, residual stress will occur at the interface between the A layer and the B layer during molding, and cracking or peeling may occur easily.

再者，較佳為前述表面層滿足以下之條件6。 The surface layer preferably satisfies the following condition 6.

條件6 60℃≦Tg_B≦130℃ Condition 6 60 ℃ ≦ Tg _B ≦ 130 ℃

此處，條件6係顯示在表面層之中與支撐基材接觸之層(B層)的玻璃轉移溫度之較佳範圍，較佳為60℃≦Tg_B≦100℃。 Here, Condition 6 shows a preferable range of the glass transition temperature of the layer (layer B) in contact with the supporting substrate among the surface layers, and is preferably 60 ° C ≦ Tg _B ≦ 100 ° C.

前述玻璃轉移溫度係表示自前述之藉由微小硬度計所測定的儲存彈性模數與損失彈性模數之比(損失正切)的溫度分散之極大值所求得之值。測定方法之詳細係如後述。 The glass transition temperature is a value obtained from the maximum value of the temperature dispersion of the ratio (loss tangent) of the storage elastic modulus to the loss elastic modulus measured by the micro hardness tester. The details of the measurement method are described later.

由於若B層之玻璃轉移溫度比60℃還更低，則表面層與支撐基材間的密接力降低，所以會有因室溫下的剝離、或硬材料所致的擦過而傷痕容易殘留之情況。又，在B層之玻璃轉移溫度比130℃還更高的情況，係會因條件而在成型時有容易發生破裂或剝離之情況。 If the glass transition temperature of layer B is lower than 60 ° C, the adhesion between the surface layer and the supporting substrate will be reduced, so there will be scratches that are likely to remain due to peeling at room temperature or rubbing caused by hard materials. Happening. In addition, when the glass transition temperature of the layer B is higher than 130 ° C, it is likely that cracking or peeling may occur during molding due to conditions.

再者，較佳為前述表面層滿足以下之條件7； 條件7 0.1μm≦T_B≦5μm。 The surface layer preferably satisfies the following Condition 7; Condition 7 0.1 μm ≦ T _B ≦ 5 μm.

此處，條件7係顯示在表面層中與支撐基材接觸之層(B層)的厚度(T_B)之較佳範圍，更佳為0.5μm≦T_B≦3μm。若B層之厚度比0.1μm更薄，則吸收成型時在表面層與支撐基材之間發生的殘留應力之能力會有稍微變弱之情況，若比5μm還更厚，則會有表面層與支撐基材之間的密接力稍微變弱之情況。 Here, Condition 7 shows a preferable range of the thickness (T _B ) of the layer (layer B) in contact with the supporting substrate in the surface layer, and more preferably 0.5 μm ≦ T _B ≦ 3 μm. If the thickness of the B layer is thinner than 0.1 μm, the ability to absorb the residual stress between the surface layer and the supporting substrate during molding may be slightly weakened. If it is thicker than 5 μm, there will be a surface layer The adhesion to the supporting substrate may be slightly weakened.

本發明之積層薄膜係如第2圖所示，在支撐基材的至少一側之面上，具有包含A層與B層的表面層之積層薄膜，較佳為在前述表面層之垂直於基材的截面中，自表面層的表面起，在表面層厚度的10%之位置(以後當作位置1；第2圖中的5之位置)、50%(以後當作位置2；第2圖中的6之位置)、99%(以後當作位置3；第2圖中的7之位置)的各位置之藉由原子力顯微鏡的彈性模數E1、E2、E3係滿足以下之條件8、條件9、條件10； 條件8 E1≦E2<E3 As shown in FIG. 2, the laminated film of the present invention is a laminated film having a surface layer including A layer and B layer on at least one side of a supporting substrate, preferably, the surface layer is perpendicular to the substrate In the cross section of the material, from the surface of the surface layer, at the position of 10% of the thickness of the surface layer (hereinafter referred to as position 1; position 5 in FIG. 2), 50% (hereinafter referred to as position 2; FIG. 2) The positions of 6 in the middle) and 99% (hereinafter referred to as position 3; position 7 in Fig. 2) of each position by the elastic modulus of the atomic force microscope E1, E2, E3 satisfy the following conditions 8. 9. Condition 10; Condition 8 E1 ≦ E2 <E3

條件9 E1≦100MPa Condition 9 E1 ≦ 100MPa

條件10 E3≧1GPa。 Condition 10 E3 ≧ 1GPa.

條件8係意圖以在表面層之厚度方向中，彈性模數自表面側朝向基材側變高為宜，較佳為E1≦E2<E3，更佳為E1<E2<E3。 Condition 8 is intended to increase the elastic modulus from the surface side toward the substrate side in the thickness direction of the surface layer, and it is preferably E1 ≦ E2 <E3, and more preferably E1 <E2 <E3.

由於若此順序係成為相反、即E1>E2>E3，則會變得在最表面無法進行彈性回復所致的應變釋放，所以會不耐反覆擦過，而且即使最表面係硬度高，也 會由於下部的彈性模數低，而應變變大，因而在高的壓力或硬度高的材料所致擦過之情況，會有耐擦傷性降低之情況。 If this sequence is reversed, that is, E1> E2> E3, the strain release caused by elastic recovery cannot be performed on the outermost surface, so it will not be resistant to repeated rubbing, and even if the outermost surface hardness is high, Because the lower modulus of elasticity is lower and the strain becomes larger, when the material is rubbed by a high pressure or a high hardness material, the abrasion resistance may be reduced.

條件9係顯示表面層的表面側之彈性模數(E1)的較佳範圍。E1之值較佳為100MPa以下，更佳為50MPa以下，特佳為20MPa以下。若E1之值超過100MPa，則會在反覆擦過時有彈性回復所致的應變之釋放變不充分之情況。又，E1之值小者雖然在達成本課題上沒有特別的障礙，但若為1MPa以下，則會有在表面發生黏著性之情況，會有從表面保護之觀點來看不實用之情況。 Condition 9 shows a preferable range of the elastic modulus (E1) of the surface side of the surface layer. The value of E1 is preferably 100 MPa or less, more preferably 50 MPa or less, and particularly preferably 20 MPa or less. If the value of E1 exceeds 100 MPa, the release of strain due to elastic recovery during repeated rubbing may become insufficient. In addition, although the value of E1 is small, there is no particular obstacle in achieving cost, but if it is 1 MPa or less, adhesion may occur on the surface, and it may not be practical from the viewpoint of surface protection.

條件10係顯示表面層的支撐基材側之彈性模數(E3)的較佳範圍。E3之值較佳為1GPa以上，更佳為2GPa以上，特佳為3GPa以上。若E3之值小於1GPa，則表面硬度會變不充分，會有對於硬材料所致擦過之耐久性變不充分之情況。針對耐擦傷性而言，E3之值愈高愈佳，但實用上從耐折性或加工性等之觀點來看，就作為積層薄膜上的表面層可使用之材料而言，100GPa左右為限度。 Condition 10 shows a preferable range of the elastic modulus (E3) of the support substrate side of the surface layer. The value of E3 is preferably 1 GPa or more, more preferably 2 GPa or more, and particularly preferably 3 GPa or more. If the value of E3 is less than 1 GPa, the surface hardness may be insufficient, and the durability against rubbing by a hard material may be insufficient. In terms of scratch resistance, the higher the value of E3, the better, but practically, from the viewpoint of folding resistance and processability, about 100 GPa is the limit for the materials that can be used as the surface layer on the laminated film. .

此處，針對表面層的儲存彈性模數、損失彈性模數及玻璃轉移溫度之測定進行敘述。此等之測定係可使用超微小硬度計(Hysitron公司製Tribo Indenter)來取得到模數映射影像[儲存彈性模數(E’)影像‧損失彈性模數(E”)影像]而進行。 Here, measurement of the storage elastic modulus, the loss elastic modulus, and the glass transition temperature of the surface layer will be described. These measurements can be performed using an ultra-micro hardness tester (Tribo Indenter manufactured by Hysitron Corporation) to obtain a modulus map image [storage elastic modulus (E ') image · loss elastic modulus (E ") image].

例如，將積層薄膜以電顯用環氧樹脂(日新EM公司製Quetol 812)包埋並使硬化後，以超薄切片機 (LEICA公司製Ultracut S)來製作積層薄膜的表面層之截面的超薄切片作為測定樣品，以以下的條件測定，並使用赫茲(Hertz)的接觸理論來算出彈性模數。 For example, the laminated film is embedded with an epoxy resin for display (Quetol 812 manufactured by Nisshin EM Co., Ltd.) and hardened, and then an ultra-thin microtome is used. (Ultracut S, manufactured by LEICA) was used to prepare an ultra-thin section of the cross section of the surface layer of the laminated film as a measurement sample, and the measurement was performed under the following conditions, and Hertz's contact theory was used to calculate the elastic modulus.

測定裝置：Hysitron公司製Tribo Indenter Measuring device: Tribo Indenter by Hysitron

使用壓頭：鑽石製Cubecorner壓頭(曲率半徑50nm) Indenter: Diamond Cubecorner indenter (curvature radius 50nm)

測定視野：約30mm見方 Measurement field of view: about 30mm square

測定頻率：200Hz Measurement frequency: 200Hz

測定環境：室溫‧大氣中 Measurement environment: room temperature, in the atmosphere

接觸荷重：0.3μN Contact load: 0.3μN

於以下說明藉由超微小硬度計的測定原理。 The measurement principle by the ultra-micro hardness tester will be described below.

已知將軸對稱壓頭壓入試料時的測定系之勁度(K)係以式(1)表示。 It is known that the stiffness (K) of the measurement system when the axisymmetric indenter is pressed into the sample is expressed by the formula (1).

此處，A為試料與壓頭接觸而形成之壓痕的投影面積，E^＊係壓頭系與試料系之複合彈性模數。 Here, A is the projected area of the indentation formed by the contact between the sample and the indenter, and E ^* is the composite elastic modulus of the indenter and the sample.

另一方面，茲認為：在壓頭接觸試料的最表面時，係將壓頭前端視為球狀，可採用有關球形與半無限平板之接觸的赫茲之接觸理論。於赫茲之接觸理論中，壓頭與試料接觸時的壓痕投影面之半徑a係以式(2)表示。 On the other hand, I believe that when the indenter contacts the outermost surface of the sample, the front end of the indenter is regarded as a spherical shape, and Hertz's contact theory regarding the contact between a sphere and a semi-infinite flat plate can be used. In Hertz's contact theory, the radius a of the indentation projection surface when the indenter is in contact with the sample is expressed by Equation (2).

此處，P為荷重，R為壓頭前端的曲率半徑。 Here, P is the load and R is the radius of curvature of the tip of the indenter.

因此，試料與壓頭接觸而形成之壓痕的投影面積A係以式(3)表示，可使用式(1)~式(3)而算出E^＊。 Therefore, the projected area A of the indentation formed by the contact between the sample and the indenter is expressed by Equation (3), and E ^* can be calculated using Equations (1) to (3).

所謂的模數映射(modulus mapping)，係基於上述赫茲之接觸理論，使壓頭接觸試料的最表面，於試驗中使壓頭微小振動，並作為時間之函數而取得對於振動之響應振幅、相位差，而求出K(測定系勁度)及D(試料阻尼)之方法。 The so-called modular mapping is based on the above-mentioned Hertzian contact theory. The indenter is brought into contact with the outermost surface of the sample, the indenter is slightly vibrated during the test, and the amplitude and phase of the response to vibration are obtained as a function of time. The difference is the method of determining K (measurement system stiffness) and D (sample damping).

若此振動為簡諧振子，則壓頭對試料的侵入方向之力的總和(檢測出荷重成分)F(t)係以式(4)表示。 If this vibration is a simple harmonic oscillator, the total (force component detected) F (t) of the force of the indenter in the intrusion direction of the sample is expressed by Equation (4).

此處，式(4)第1項表示來自壓頭軸的力(m：壓頭軸的質量)，式(4)第2項表示來自試料的黏性成分之力，式(4)第3項表示試料系的剛性，t表示時間。式(4)之F(t)係由於時間相關，而表示如式(5)。 Here, the first term of formula (4) represents the force from the indenter shaft (m: mass of the indenter shaft), the second term of formula (4) represents the force from the viscous component of the sample, and the third term of formula (4) The term represents the rigidity of the sample system, and t represents time. F (t) in formula (4) is expressed as formula (5) due to time correlation.

F(t)==F ₀ exp(iωt)…(式5) F ( t ) == F ₀ exp ( iωt ) ... (Eq. 5)

此處，F₀為常數，ω為角振動數。若將式(5)代入式(4)，將常微分方程式的特別解之式(6)代入，並解方程式，則可得到式(7)~(10)之關係式。 Here, F ₀ is a constant, and ω is an angular vibration number. If the equation (5) is substituted into the equation (4), the special solution of the ordinary differential equation (6) is substituted, and the equation is solved, the relational expressions of the equations (7) to (10) can be obtained.

此處，Φ為相位差。m係測定時已知，故在供試體之測定時，可藉由計測位移的振動振幅(h₀)、相位差(Φ)與激發振動振幅(F₀)，而由式(7)~式(10)算出K及D。 Here, Φ is a phase difference. The m system is known at the time of measurement. Therefore, when measuring the test body, the vibration amplitude (h ₀ ), phase difference (Φ), and excitation vibration amplitude (F ₀ ) of the displacement can be measured by the equation (7) ~ Equation (10) calculates K and D.

將E^＊視為儲存彈性模數(E’)，而彙總式(1)~式(10)，於測定系勁度之中，使用來自試料的 Ks(=K-mω²)，自式(11)算出儲存彈性模數。 E ^{* is} regarded as the storage elastic modulus (E '), and the formulas (1) to (10) are summarized. In the stiffness of the measurement system, Ks (= K-mω ² ) from the sample is used to express ( 11) Calculate the storage elastic modulus.

本發明中的損失彈性模數亦可與前述儲存彈性模數之測定同樣地測定，於前述式(8)中的測定系勁度之中，使用來自試料的Ks，自與式(11)合併而彙總的式(12)算出損失彈性模數。 The loss elastic modulus in the present invention can also be measured in the same manner as the measurement of the storage elastic modulus. Among the stiffness of the measurement system in the aforementioned formula (8), Ks from the sample is used, and it is combined with the formula (11). The aggregated formula (12) calculates the loss elastic modulus.

本發明中的玻璃轉移溫度亦可與前述儲存彈性模數之測定同樣地測定，自前面所算出的儲存彈性模數、損失彈性模數之比，求得損失正切(tanδ)，將所得之損失正切(tanδ)的峰值溫度當作玻璃轉移溫度(Tg)。 The glass transition temperature in the present invention can also be measured in the same manner as the measurement of the storage elastic modulus. From the ratio of the storage elastic modulus and the loss elastic modulus calculated previously, a loss tangent (tan δ) is obtained, and the obtained loss is calculated. The peak temperature of the tangent (tan δ) is taken as the glass transition temperature (Tg).

本發明中之藉由原子力顯微鏡的彈性模數測定，係藉由極微小部分的探針之壓縮試驗，由於是推壓力所致的變形程度，使用已知彈簧常數的懸臂，而測定表面層之厚度方向的各位置之截面中的彈性模數。具體而言係切斷積層薄膜，並藉由原子力顯微鏡來測定表面層之厚度方向的各位置之截面中的彈性模數。詳細係記載於實施例之項目，但可使用下述所示的原子力顯微鏡，使懸臂前端的探針接觸表面層之截面，自藉由最大2μN的壓入荷重而測定力曲線所求得的懸臂之撓曲量來 測定。詳細係如後述。 The elastic modulus measurement by the atomic force microscope in the present invention is a compression test of a very small portion of the probe. The degree of deformation caused by the pushing force is measured using a cantilever with a known spring constant to determine the surface layer. The modulus of elasticity in the cross section at each position in the thickness direction. Specifically, the laminated film was cut, and the elastic modulus in the cross section of each position in the thickness direction of the surface layer was measured by an atomic force microscope. The details are described in the examples. However, an atomic force microscope shown below can be used to bring the probe at the tip of the cantilever into contact with the cross section of the surface layer. The cantilever can be obtained by measuring the force curve with a maximum indentation load of 2 μN. Deflection Determination. The details are described later.

原子力顯微鏡：ASYLUM科技公司製MFP-3DSA-J Atomic force microscope: MFP-3DSA-J manufactured by ASYLUM Technology

懸臂：NANOSENSORS製之懸臂「R150-NCL-10(材質Si，彈簧常數48N/m，前端的曲率半徑150nm)。 Cantilever: Cantilever "R150-NCL-10 (Material Si, spring constant 48N / m, radius of curvature of the front end 150nm) made by NANOSENSORS".

以下，詳細說明本發明之實施形態。 Hereinafter, embodiments of the present invention will be described in detail.

[積層薄膜及表面層] [Laminated film and surface layer]

本發明之積層薄膜只要具有顯示前述物性的表面層，則可為平面狀態、或成型後的3次元形狀之任一者。此處，本發明中的「表面層」較佳為由至少2以上之層所形成。 The laminated film of the present invention may be in a planar state or a three-dimensional shape after molding as long as it has a surface layer exhibiting the aforementioned physical properties. Here, the "surface layer" in the present invention is preferably formed of at least two layers.

前述表面層全體之厚度係沒有特別的限定，但較佳為5μm以上200μm以下，更佳為10μm以上100μm以下。 The thickness of the entire surface layer is not particularly limited, but it is preferably 5 μm or more and 200 μm or less, and more preferably 10 μm or more and 100 μm or less.

作為前述之2以上之層，較佳為至少於前述表面層中具有與B層接觸之層(A層)、與支撐基材接觸之層(B層)，且A層、B層、支撐基材係滿足前述之關係。 As the above 2 or more layers, it is preferable that at least the aforementioned surface layer has a layer in contact with layer B (layer A), a layer in contact with support substrate (layer B), and layer A, layer B, and support substrate The material system satisfies the aforementioned relationship.

前述表面層係除了作為本發明之課題的耐擦傷性尤其反覆擦過耐性與成型性之並存以外，還可具有防污性、抗反射性、抗靜電性、導電性、熱線反射性、近紅外線吸收性、電磁波遮蔽性、易接著等其他的機能。 In addition to the abrasion resistance which is the subject of the present invention, the surface layer is a combination of rubbing resistance and moldability, it can also have antifouling properties, antireflective properties, antistatic properties, electrical conductivity, hot-line reflectivity, and near-infrared absorption. Properties, electromagnetic wave shielding, easy adhesion and other functions.

[支撐基材] [Support substrate]

構成本發明之積層薄膜所用的支撐基材之材料，可為熱塑性樹脂、熱硬化性樹脂之任一者，亦可為均聚樹 脂，也可為共聚合或2種類以上之摻合物。由於更佳為構成支撐基材的樹脂係成型性良好，所以以熱塑性樹脂為宜。 The material constituting the support substrate used in the laminated film of the present invention may be any of a thermoplastic resin and a thermosetting resin, or may be a homopolymer tree. The lipid may be a copolymer or a blend of two or more kinds. Since it is more preferable that the resin system constituting the supporting substrate has good moldability, a thermoplastic resin is preferred.

就熱塑性樹脂之例而言，可使用聚乙烯‧聚丙烯‧聚苯乙烯‧聚甲基戊烯等之聚烯烴樹脂、脂環族聚烯烴樹脂、尼龍6‧尼龍66等之聚醯胺樹脂、芳香族聚醯胺樹脂、聚酯樹脂、聚碳酸酯樹脂、聚芳酯樹脂、聚縮醛樹脂、聚苯硫樹脂、四氟乙烯樹脂‧三氟乙烯樹脂‧三氟氯乙烯樹脂‧四氟乙烯-6氟丙烯共聚物‧偏二氟乙烯樹脂等之氟樹脂、丙烯酸樹脂、甲基丙烯酸樹脂、聚縮醛樹脂、聚乙醇酸樹脂、聚乳酸樹脂等。熱塑性樹脂較佳為具備充分的延伸性與追隨性之樹脂。從強度‧耐熱性‧透明性之觀點來看，熱塑性樹脂尤其以聚酯樹脂或聚碳酸酯樹脂、甲基丙烯酸樹脂為宜，特佳為聚酯樹脂。 Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene; alicyclic polyolefin resins; polyamide resins such as nylon 6 and nylon 66; Aromatic polyamide resin, polyester resin, polycarbonate resin, polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene -6 Fluoropropylene copolymers, vinylidene fluoride resins and other fluorine resins, acrylic resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, etc. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. From the viewpoint of strength, heat resistance, and transparency, the thermoplastic resin is particularly preferably a polyester resin, a polycarbonate resin, or a methacrylic resin, and particularly preferably a polyester resin.

本發明中的聚酯樹脂，就是以酯鍵作為主鏈的主要結合鏈之高分子的總稱，係藉由酸成分及其酯與二醇成分之聚縮合而得。就具體例而言，可舉出聚對苯二甲酸乙二酯、聚對苯二甲酸丙二酯、聚2,6-萘二甲酸乙二酯、聚對苯二甲酸丁二酯等。又，亦可為於此等共聚合有作為酸成分或二醇成分的其他二羧酸及其酯或二醇成分者。於此等之中，在透明性、尺寸安定性、耐熱性等之點，特佳為聚對苯二甲酸乙二酯、聚2,6-萘二甲酸乙二酯。 The polyester resin in the present invention is a general term for a polymer having an ester bond as a main chain of a main chain, and is obtained by polycondensation of an acid component, an ester thereof, and a diol component. Specific examples include polyethylene terephthalate, polytrimethylene terephthalate, polyethylene 2,6-naphthalate, and polybutylene terephthalate. Moreover, it is also possible to co-polymerize other dicarboxylic acid and its ester or diol component as an acid component or a diol component. Among these, in terms of transparency, dimensional stability, heat resistance, etc., particularly preferred are polyethylene terephthalate and polyethylene 2,6-naphthalate.

又，於支撐基材中，亦可添加各種添加劑 ，例如抗氧化劑、抗靜電劑、結晶核劑、無機粒子、有機粒子、減黏劑、熱安定劑、滑劑、紅外線吸收劑、紫外線吸收劑、折射率調整用的摻雜劑等。支撐基材可為單層構成、積層構成之任一者。 Various additives can be added to the supporting substrate. For example, antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, dopants for refractive index adjustment, and the like. The supporting substrate may have any of a single-layer structure and a laminated structure.

於支撐基材之表面上，亦可在形成前述表面層之前實施各種的表面處理。就表面處理之例而言，可舉出藥品處理、機械性處理、電暈放電處理、火焰處理、紫外線照射處理、高頻處理、輝光放電處理、活性電漿處理、雷射處理、混酸處理及臭氧氧化處理。於此等之中，較佳為輝光放電處理、紫外線照射處理、電暈放電處理及火焰處理，更佳為輝光放電處理與紫外線處理。 Various types of surface treatments may be performed on the surface of the supporting substrate before forming the aforementioned surface layer. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and Ozone oxidation treatment. Among these, a glow discharge treatment, an ultraviolet irradiation treatment, a corona discharge treatment, and a flame treatment are preferable, and a glow discharge treatment and an ultraviolet treatment are more preferable.

又，於支撐基材之表面上，亦可預先設置與本發明之表面層不同的易接著層、抗靜電層、底塗層、紫外線吸收層等之機能性層，尤其以設置易接著層為宜。 In addition, on the surface of the supporting substrate, functional layers such as an easy-adhesion layer, an antistatic layer, an undercoat layer, and an ultraviolet absorbing layer that are different from the surface layer of the present invention may be provided in advance. should.

[塗料組成物] [Coating composition]

本發明之積層薄膜，係藉由在支撐基材上使用後述之積層薄膜的製造方法，將塗料組成物塗布、乾燥、硬化，而可形成具有能達成前述物性的構造之表面層。此處所謂的「塗料組成物」，就是指包含溶劑與溶質之液體，塗布於前述的支撐基材上，並藉由以乾燥步驟進行揮發溶劑、去除、硬化而能形成表面層之材料。此處，所謂的塗料組成物之「種類」，就是指只要構成塗料組成物的溶質之種類係一部分不同之液體。此溶質係包含 樹脂或是塗布製程內能形成彼等之材料(以後將此稱為前驅物)、粒子、及聚合起始劑、硬化劑、觸媒、均勻劑、紫外線吸收劑、抗氧化劑等之各種添加劑。 The laminated film of the present invention is a surface layer having a structure capable of achieving the aforementioned physical properties by applying, drying, and curing a coating composition by using a method for producing a laminated film described later on a supporting substrate. The "coating composition" as used herein refers to a material containing a solvent and a solute, which is coated on the aforementioned support substrate, and is capable of forming a surface layer by volatilizing the solvent, removing, and curing in a drying step. Here, the "kind" of a coating composition means a liquid in which the kind of the solute constituting the coating composition differs in part. This solute contains Resins or various additives (such as precursors), particles, and polymerization initiators, hardeners, catalysts, leveling agents, ultraviolet absorbers, antioxidants, etc. that can form them during the coating process.

本發明之積層薄膜係較佳為如前述，藉由使用至少2種類的塗料組成物(以下當作塗料組成物A、塗料組成物B)，在支撐基材上逐次地塗布、或同時塗布而形成。 As described above, the laminated film of the present invention is preferably applied sequentially or simultaneously on a supporting substrate by using at least two types of coating compositions (hereinafter referred to as coating composition A and coating composition B). form.

此處，塗料組成物A係包含適用於形成自表面層的支撐基材側起第2層，即前述的A層的樹脂或前驅物之液體，藉由在預先形成有B層的支撐基材上進行塗布、乾燥、硬化，或是在支撐基材上與B層之形成同時地進行塗布、乾燥、硬化而可形成A層。 Here, the coating composition A contains a liquid suitable for forming the second layer from the supporting substrate side of the surface layer, that is, the resin or precursor of the aforementioned layer A, and the supporting substrate on which the layer B is formed in advance is used. Coating, drying, and hardening can be performed on the substrate, or coating, drying, and hardening can be performed simultaneously with the formation of the layer B on the supporting substrate to form the layer A.

塗料組成物B係包含適用於形成表面層之與支撐基材接觸之層，即前述的B層的樹脂或前驅物之液體，藉由在支撐基材上進行塗布、乾燥、硬化，或是在表面側上與A層同時地進行塗布、乾燥、硬化而可形成B層。 The coating composition B includes a layer suitable for forming a surface layer in contact with a supporting substrate, that is, the resin or precursor liquid of the aforementioned layer B, by coating, drying, hardening, or The B layer can be formed by coating, drying, and curing on the surface side simultaneously with the A layer.

[塗料組成物A] [Coating composition A]

塗料組成物A係包含適用於構成表面層中之A層的材料或是可形成的前驅物之液體，較佳為包含以下(1)至(3)的鏈段之樹脂或前驅物作為溶質。 The coating composition A is a liquid containing a material suitable for constituting the layer A in the surface layer or a precursor that can be formed, and preferably a resin or precursor containing the following segments (1) to (3) as a solute.

(1)含有選自包含聚己內酯鏈段、聚碳酸酯鏈段及聚烷二醇鏈段之群組的至少一者之鏈段 (1) A segment containing at least one selected from the group consisting of a polycaprolactone segment, a polycarbonate segment, and a polyalkylene glycol segment

(2)胺基甲酸酯鍵 (2) Urethane bond

(3)含有選自包含氟化合物鏈段、聚矽氧烷鏈段及聚二甲基矽氧烷鏈段之群組的至少一者之鏈段。 (3) A segment containing at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment, and a polydimethylsiloxane segment.

關於此構成表面層之表面中的A層之樹脂所包含的各鏈段，可藉由TOF-SIMS、FT-IR等進行確認。 Each segment included in the resin constituting the A layer on the surface of the surface layer can be confirmed by TOF-SIMS, FT-IR, and the like.

又，塗料組成物A中所含有的前述(1)、(2)、(3)之質量份，較佳為(1)/(2)/(3)=95/5/1~50/50/15，更佳為(1)/(2)/(3)=90/10/1~60/40/10。以下，說明有關(1)、(2)、(3)之詳細。 The mass fractions of (1), (2), and (3) contained in the coating composition A are preferably (1) / (2) / (3) = 95/5/1 to 50/50. / 15, more preferably (1) / (2) / (3) = 90/10/1 ~ 60/40/10. Details of (1), (2), and (3) will be described below.

前述(1)聚己內酯鏈段、聚碳酸酯鏈段及聚烷二醇鏈段之詳細係如後述，但由於前述構成表面層之表面中的A層之樹脂係具有此等之鏈段，而可使表面層的自我修復性提升，且使反覆擦過性提升。 The details of the aforementioned (1) polycaprolactone segment, polycarbonate segment, and polyalkylene glycol segment are as described later, but since the resin constituting the A layer in the surface of the surface layer described above has such segments , Which can improve the self-healing ability of the surface layer, and improve repeated scrubbing.

有關前述胺基甲酸酯鍵之詳細係如後述，但由於前述構成表面層之表面中的A層之樹脂係具有此鍵，而可使表面層全體的強韌性提升。 The details of the urethane bond are described later, but since the resin of the A layer in the surface constituting the surface layer has the bond, the toughness of the entire surface layer can be improved.

有關前述氟聚醚鏈段之詳細係如後述，但藉由構成表面層之樹脂係含有此等，而可使顯示低表面能量的分子高密度地存在於最表面中，表面的反覆擦過性會提升。 The details of the aforementioned fluoropolyether segment are described later, but by including these in the resin system constituting the surface layer, molecules exhibiting low surface energy can be present on the outermost surface at a high density, and the surface's repetitive rubbing effect will be caused. Promotion.

[聚己內酯鏈段、聚碳酸酯鏈段、聚烷二醇鏈段] [Polycaprolactone segment, polycarbonate segment, polyalkylene glycol segment]

首先，聚己內酯鏈段就是指化學式1所示的鏈段。聚己內酯中亦包含如己內酯的重複單元為1(單體)、2(二聚物)、3(三聚物)者、或己內酯之重複單元到35為止的寡聚物。 First, the polycaprolactone segment refers to a segment represented by Chemical Formula 1. Polycaprolactone also includes oligomers in which the repeating units of caprolactone are 1 (monomer), 2 (dimer), 3 (trimer), or repeating units of caprolactone up to 35 .

n為1~35之整數。 n is an integer from 1 to 35.

含有聚己內酯鏈段的樹脂，係較佳為具有至少1個以上的氫氧基(羥基)者。氫氧基係較佳為在含有聚己內酯鏈段的樹脂之末端。 The resin containing a polycaprolactone segment is preferably one having at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the terminal of a resin containing a polycaprolactone segment.

就含有聚己內酯鏈段的樹脂而言，特佳為具有2~3官能的氫氧基之聚己內酯。具體而言，可使用化學式2所示的聚己內酯二醇， As for the resin containing a polycaprolactone segment, a polycaprolactone having a 2 to 3 functional hydroxyl group is particularly preferred. Specifically, a polycaprolactone diol represented by Chemical Formula 2 may be used,

此處，m+n為4~35之整數，m、n各自為1~34之整數，R係C₂H₄、C₂H₄OC₂H₄、C(CH₃)₃(CH₂)₂；或化學式3所示的聚己內酯三醇， Here, m + n is an integer from 4 to 35, m and n are each an integer from 1 to 34, and R is C ₂ H ₄ , C ₂ H ₄ OC ₂ H ₄ , and C (CH ₃ ) ₃ (CH ₂ ) ₂ ; or polycaprolactone triol represented by Chemical Formula 3,

此處，l+m+n為3~30之整數，l、m、n各 自為1~28之整數，R係CH₂CHCH₂、CH₃C(CH₂)₃、CH₃CH₂C(CH₂)₃ Here, l + m + n is an integer from 3 to 30, l, m, and n are each an integer from 1 to 28, and R is CH ₂ CHCH ₂ , CH ₃ C (CH ₂ ) ₃ , CH ₃ CH ₂ C ( CH ₂ ) ₃

等之聚己內酯多元醇；或化學式4所示的聚己內酯改性(甲基)丙烯酸羥基乙酯， And other polycaprolactone polyols; or polycaprolactone-modified (meth) acrylate hydroxyethyl esters shown in Chemical Formula 4,

此處，n為1~25之整數，R為H或CH₃等之活性能量線聚合性己內酯。作為其他的活性能量線聚合性己內酯之例，可舉出聚己內酯改性(甲基)丙烯酸羥基丙酯、聚己內酯改性(甲基)丙烯酸羥基丁酯等。 Here, n is an integer of 1 to 25, and R is an active energy ray polymerizable caprolactone such as H or CH ₃ . Examples of other active energy ray polymerizable caprolactones include polycaprolactone-modified hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxybutyl (meth) acrylate, and the like.

再者，於本發明，含有聚己內酯鏈段的樹脂係除了聚己內酯鏈段，還可含有(或是共聚合)其他的鏈段或單體。例如，亦可含有(或共聚合)包含後述的聚二甲基矽氧烷鏈段或聚矽氧烷鏈段、異氰酸酯化合物之化合物。 Furthermore, in the present invention, the resin containing a polycaprolactone segment may contain (or copolymerize) other segments or monomers in addition to the polycaprolactone segment. For example, it may contain (or copolymerize) a compound containing a polydimethylsiloxane segment or polysiloxane segment described later, and an isocyanate compound.

又，於本發明中，較佳為含有聚己內酯鏈段的樹脂中之聚己內酯鏈段的重量平均分子量為500~2,500，更佳的重量平均分子量為1,000~1,500。由於若聚己內酯鏈段的重量平均分子量為500~2,500，則自我修復性之效果會更展現，且反覆擦過性會更提升而較佳。 In the present invention, the weight average molecular weight of the polycaprolactone segment in the resin containing the polycaprolactone segment is preferably 500 to 2,500, and more preferably the weight average molecular weight is 1,000 to 1,500. If the weight-average molecular weight of the polycaprolactone segment is 500 to 2,500, the self-healing effect will be more exhibited, and the repetitive rubbing property will be more improved and better.

其次，聚烷二醇鏈段就是指化學式5所示的鏈段。於聚烷二醇中，亦包含如烷二醇之重複單元為2(二聚物)、3(三聚物)者，或烷二醇之重複單元到11為止的 寡聚物。 Next, the polyalkylene glycol segment is a segment represented by Chemical Formula 5. Polyalkylene glycols also include those in which the repeating unit of the alkanediol is 2 (dimer), 3 (trimer), or the repeating unit of the alkanediol up to 11 Oligomer.

n為2~4之整數，m為2~11之整數。 n is an integer from 2 to 4, and m is an integer from 2 to 11.

含有聚烷二醇鏈段的樹脂，較佳為具有至少1個以上的氫氧基(羥基)者。氫氧基較佳為在含有聚烷二醇鏈段的樹脂之末端。 The resin containing a polyalkylene glycol segment is preferably one having at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the terminal of a resin containing a polyalkylene glycol segment.

就含有聚烷二醇鏈段的樹脂而言，較佳為為了賦予彈性，而在末端具有丙烯酸酯基的聚烷二醇(甲基)丙烯酸酯。聚烷二醇(甲基)丙烯酸酯的丙烯酸酯官能基(或甲基丙烯酸酯官能基)數係沒有限定，但從硬化物的自我修復性之點來看，最佳為單官能。 The polyalkylene glycol segment-containing resin is preferably a polyalkylene glycol (meth) acrylate having an acrylate group at the terminal in order to impart elasticity. The number of acrylate functional groups (or methacrylate functional groups) of the polyalkylene glycol (meth) acrylate is not limited, but from the standpoint of the self-healing property of the cured product, it is preferably monofunctional.

就為了形成表面層而使用之塗料組成物中所含有的聚烷二醇(甲基)丙烯酸酯而言，可舉出聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、聚丁二醇(甲基)丙烯酸酯。各自為以下的化學式6、化學式7、化學式8所代表之構造。 Examples of the polyalkylene glycol (meth) acrylate contained in the coating composition used to form the surface layer include polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate. Polybutylene glycol (meth) acrylate. Each has the structure represented by the following Chemical Formula 6, Chemical Formula 7, and Chemical Formula 8.

聚乙二醇(甲基)丙烯酸酯： Polyethylene glycol (meth) acrylate:

聚丙二醇(甲基)丙烯酸酯： Polypropylene glycol (meth) acrylate:

聚丁二醇(甲基)丙烯酸酯： Polybutylene glycol (meth) acrylate:

化學式6、化學式7、化學式8中R為氫(H)或甲基(-CH₃)，m為2~11之整數。 In Chemical Formula 6, Chemical Formula 7, and Chemical Formula 8, R is hydrogen (H) or methyl (-CH ₃ ), and m is an integer from 2 to 11.

本發明中，較佳為使後述之含有異氰酸酯基的化合物與(聚)烷二醇(甲基)丙烯酸酯的氫氧基反應而作為胺基甲酸酯(甲基)丙烯酸酯用於表面層，藉此而構成表面層的樹脂可具有(2)胺基甲酸酯鍵及(3)(聚)烷二醇鏈段，而結果可使表面層的強韌性提升且同時使自我修復性提升而較佳。 In the present invention, it is preferred that an isocyanate group-containing compound to be described later be reacted with the hydroxyl group of (poly) alkanediol (meth) acrylate to be used as a urethane (meth) acrylate in the surface layer. In this way, the resin constituting the surface layer can have (2) urethane bonds and (3) (poly) alkanediol segments, and as a result, the toughness of the surface layer can be improved and at the same time, self-healing ability can be improved. And better.

於含有異氰酸酯基的化合物與聚烷二醇(甲基)丙烯酸酯的胺基甲酸酯化反應之際，就同時配合的(甲基)丙烯酸羥基烷酯而言，可例示(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯等。 When the isocyanate group-containing compound is urethanated with a polyalkylene glycol (meth) acrylate, the (meth) acrylic acid hydroxyalkyl (meth) acrylic acid may be exemplified as (meth) acrylic acid Hydroxyethyl ester, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like.

其次，聚碳酸酯鏈段就是指化學式9所示的鏈段。於聚碳酸酯中，亦包含如碳酸酯之重複單元為2(二聚物)、3(三聚物)者，或碳酸酯之重複單元到16為止的寡聚物。 Next, the polycarbonate segment refers to a segment represented by Chemical Formula 9. Polycarbonates also include oligomers in which the repeating units of carbonate are 2 (dimer), 3 (trimer), or repeating units of carbonate up to 16.

n為2~16之整數。 n is an integer from 2 to 16.

R₄係指碳數1~8為止的伸烷基或伸環烷基。 R _{4 is} an alkylene or cycloalkylene group having 1 to 8 carbon atoms.

含有聚碳酸酯鏈段的樹脂，較佳為具有至少1個以上的氫氧基(羥基)者。氫氧基較佳為在含有聚碳酸酯鏈段的樹脂之末端。 The polycarbonate segment-containing resin is preferably one having at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the terminal of a resin containing a polycarbonate segment.

就含有聚碳酸酯鏈段的樹脂而言，特佳為具有2官能的氫氧基之聚碳酸酯二醇。具體而言，係以化學式10表示。 As for the resin containing a polycarbonate segment, the polycarbonate diol which has a bifunctional hydroxyl group is especially preferable. Specifically, it is represented by Chemical Formula 10.

聚碳酸酯二醇：．．．化學式10 Polycarbonate diol :. ． ． Chemical formula 10

n為2~16之整數。R係指碳數1~8為止的伸烷基或伸環烷基。 n is an integer from 2 to 16. R means an alkylene group or a cycloalkylene group having 1 to 8 carbon atoms.

聚碳酸酯二醇係碳酸酯單元的重複數可為若干個，但由於若碳酸酯單元的重複數過大，則胺基甲酸酯(甲基)丙烯酸酯的硬化物之強度會降低，故重複數較佳為10以下。再者，聚碳酸酯二醇亦可為碳酸酯單元的重複數不同的2種以上之聚碳酸酯二醇的混合物。 The number of repetitions of the polycarbonate diol-based carbonate unit may be several, but if the number of repetitions of the carbonate unit is too large, the strength of the cured product of the urethane (meth) acrylate will be reduced, so the repetition is repeated. The number is preferably 10 or less. The polycarbonate diol may be a mixture of two or more polycarbonate diols having different carbonate unit repeat numbers.

聚碳酸酯二醇係較佳為數量平均分子量為500~10,000者，更佳為1,000~5,000者。若數量平均分子量小於500，則會有變得難以得到合適的柔軟性之情況 ，又，若數量平均分子量超過10,000，則會有耐熱性或耐溶劑性降低之情況，故前述程度者為合適。 The polycarbonate diol is preferably one having a number average molecular weight of 500 to 10,000, and more preferably 1,000 to 5,000. If the number average molecular weight is less than 500, it may become difficult to obtain suitable flexibility In addition, if the number average molecular weight exceeds 10,000, heat resistance or solvent resistance may be reduced, so the aforementioned degree is suitable.

又，就本發明所用之聚碳酸酯二醇而言，可適宜地例示UH-CARB、UD-CARB、UC-CARB(宇部興產股份有限公司)、PLACCEL CD-PL、PLACCEL CD-H(DAICEL化學工業股份有限公司)、KURARAY多元醇C系列(股份有限公司KURARAY)、Duranol系列(旭化成化學股份有限公司)等製品。此等聚碳酸酯二醇可單獨或組合二種類以上使用。 As the polycarbonate diol used in the present invention, UH-CARB, UD-CARB, UC-CARB (Ube Industrial Co., Ltd.), PLACCEL CD-PL, PLACCEL CD-H (DAICEL) can be suitably exemplified. Chemical Industry Co., Ltd.), KURARAY Polyol C Series (KURARAY Co., Ltd.), Duranol Series (Asahi Kasei Chemical Co., Ltd.) and other products. These polycarbonate diols can be used alone or in combination of two or more kinds.

再者，於本發明中，含有聚己內酯鏈段的樹脂，係除了聚己內酯鏈段，還可含有(或共聚合)其他的鏈段或單體。例如，可含有(或共聚合)包含後述的聚二甲基矽氧烷鏈段或聚矽氧烷鏈段、異氰酸酯化合物之化合物。 Moreover, in the present invention, the resin containing a polycaprolactone segment may contain (or copolymerize) other segments or monomers in addition to the polycaprolactone segment. For example, it may contain (or copolymerize) a compound containing a polydimethylsiloxane segment or a polysiloxane segment described later, and an isocyanate compound.

本發明中，較佳為使後述之含有異氰酸酯基的化合物與聚碳酸酯二醇之氫氧基反應，而作為胺基甲酸酯(甲基)丙烯酸酯使用於表面層之表面側，藉此而可使構成表面層的表面側之樹脂具有前述的(2)胺基甲酸酯鍵及(1)聚碳酸酯二醇鏈段，而結果可使表面層的強韌性提升並同時使自我修復性提升，可使反覆擦過性提升。 In the present invention, it is preferred that an isocyanate group-containing compound described later reacts with the hydroxyl group of polycarbonate diol, and is used as a urethane (meth) acrylate on the surface side of the surface layer, whereby The resin constituting the surface side of the surface layer can have the aforementioned (2) urethane bond and (1) polycarbonate diol segment, and as a result, the strength and toughness of the surface layer can be improved, and at the same time, self-healing can be improved. Sexual improvement, can make repeated sexual improvement.

[含有胺基甲酸酯鍵、異氰酸酯基的化合物]本發明中，「胺基甲酸酯鍵」就是指化學式11所示之鍵。 [Compound containing urethane bond and isocyanate group] In the present invention, the "urethane bond" means a bond represented by Chemical Formula 11.

由於前述構成表面層的表面側之樹脂具有此鍵，而可使表面層全體的強韌性提升。 Since the aforementioned resin constituting the surface side of the surface layer has this bond, the toughness of the entire surface layer can be improved.

塗料組成物A係包含市售的胺基甲酸酯改性樹脂，藉此而構成表面層的表面側之樹脂係成為可具有胺基甲酸酯鍵。又，於形成表面層的表面側之際，亦可將包含作為前驅物之含有異氰酸酯基的化合物與含有氫氧基的化合物之塗料組成物A塗布、乾燥、硬化，藉此使胺基甲酸酯鍵生成，而使表面層之表面側含有胺基甲酸酯鍵。 The coating composition A contains a commercially available urethane-modified resin, whereby the resin system constituting the surface side of the surface layer can have a urethane bond. In addition, when forming the surface side of the surface layer, the coating composition A containing an isocyanate group-containing compound and a hydroxyl group-containing compound as precursors may be coated, dried, and hardened to thereby form amino formic acid. An ester bond is formed, and the surface side of a surface layer contains a urethane bond.

本發明中，較佳為使異氰酸酯基與氫氧基反應來生成胺基甲酸酯鍵，藉此而在構成表面層的表面側之樹脂中導入胺基甲酸酯鍵。藉由使異氰酸酯基與氫氧基反應來生成胺基甲酸酯鍵，而使表面層的強韌性提升並同時使自我修復性提升，所以可使反覆擦過性提升。 In the present invention, it is preferable that an urethane bond is formed by reacting an isocyanate group with a hydroxyl group to introduce a urethane bond into a resin constituting the surface side of the surface layer. By reacting an isocyanate group with a hydroxyl group to form a urethane bond, the toughness of the surface layer is improved, and at the same time, the self-healing property is improved, so that the repeated rubbing property can be improved.

又，於具有前述之含有聚己內酯鏈段、聚碳酸酯鏈段、聚烷二醇鏈段的樹脂，或氫氧基之情況，亦可能藉著熱等而在此等樹脂與作為前驅物之含有異氰酸酯基的化合物之間使胺基甲酸酯鍵生成。 In addition, in the case of a resin having a polycaprolactone segment, a polycarbonate segment, a polyalkylene glycol segment, or a hydroxyl group, the resin may be used as a precursor by heat or the like. The urethane bond is formed between the isocyanate group-containing compounds.

若使用含有異氰酸酯基的化合物、與後述的具有氫氧基之含有聚矽氧烷鏈段的樹脂或含有具有氫氧基之聚二甲基矽氧烷鏈段的樹脂來形成表面層，則除了表面層的強韌性及自我修復性，還可提高表面的滑性 ，從反覆擦過性之觀點來看亦更佳。 If the surface layer is formed using a compound containing an isocyanate group, a resin containing a polysiloxane group having a hydroxyl group, or a resin containing a polydimethylsiloxane group having a hydroxyl group, described below, The toughness and self-healing properties of the surface layer can also improve the surface slip From the standpoint of repeated scrubbing, it is also better.

於本發明中，含有異氰酸酯基的化合物，就是指含有異氰酸酯基的樹脂，或含有氰酸酯基的單體或寡聚物。含有異氰酸酯基的化合物係可舉出例如：亞甲基雙-4-環己基異氰酸酯、甲苯二異氰酸酯的三羥甲基丙烷加成體、六亞甲基二異氰酸酯的三羥甲基丙烷加成體、異佛爾酮二異氰酸酯的三羥甲基丙烷加成體、甲苯二異氰酸酯的異三聚氰酸酯體、六亞甲基二異氰酸酯的異三聚氰酸酯體、六亞甲基異氰酸酯的縮二脲體等之(聚)異氰酸酯、及上述異氰酸酯的封端體等。 In the present invention, the compound containing an isocyanate group means a resin containing an isocyanate group, or a monomer or oligomer containing a cyanate group. Examples of the isocyanate group-containing compound system include methylenebis-4-cyclohexyl isocyanate, trimethylolpropane adduct of toluene diisocyanate, and trimethylolpropane adduct of hexamethylene diisocyanate. , Trimethylolpropane adduct of isophorone diisocyanate, isotricyanate of toluene diisocyanate, isotricyanate of hexamethylene diisocyanate, hexamethylene isocyanate (Poly) isocyanates such as biuret bodies, and blocked bodies of the aforementioned isocyanates.

於此等之含有異氰酸酯基的化合物之中，相較於脂環族或芳香族的異氰酸酯，脂肪族的異氰酸酯係自我修復性高而較佳。含有異氰酸酯基的化合物更佳為六亞甲基二異氰酸酯。又，含有異氰酸酯基的化合物，係具有異三聚氰酸酯環的異氰酸酯在耐熱性之點為特佳，最佳為六亞甲基二異氰酸酯的異三聚氰酸酯體。具有異三聚氰酸酯環的異氰酸酯會形成兼具自我修復性與耐熱特性的表面層。 Among these isocyanate group-containing compounds, aliphatic isocyanates are better in self-healing properties than alicyclic or aromatic isocyanates. The isocyanate group-containing compound is more preferably a hexamethylene diisocyanate. In addition, the isocyanate group-containing compound is an isocyanate having an isotricyanate ring, which is particularly preferable in terms of heat resistance, and is most preferably an isotricyanate body of hexamethylene diisocyanate. An isocyanate having an isotricyanate ring forms a surface layer having both self-healing properties and heat resistance properties.

[氟化合物鏈段、聚矽氧烷鏈段、聚二甲基矽氧烷鏈段] [Fluorine compound segment, polysiloxane segment, polydimethylsiloxane segment]

於本發明之積層薄膜中，較佳為構成表面層或是表面層的表面側之樹脂係具有鏈段，而該鏈段係包含選自包含氟化合物鏈段、聚矽氧烷鏈段及聚二甲基矽氧烷鏈段之群組的至少一者。 In the laminated film of the present invention, it is preferred that the resin constituting the surface layer or the surface side of the surface layer has a segment, and the segment system includes a segment selected from the group consisting of a fluorine compound segment, a polysiloxane segment, and a polymer At least one of the group of dimethylsiloxane segments.

再者，可將含有鏈段之樹脂、或是前驅物 的塗料組成物A，使用於形成表面層的塗料組成物之一，藉此而構成表面層的表面側之樹脂具有該等，其中該鏈段係含有選自包含氟化合物鏈段、聚矽氧烷鏈段及聚二甲基矽氧烷鏈段之群組的至少一者。 Furthermore, resins or precursors containing segments can be used. The coating composition A is one of the coating compositions used to form the surface layer, and the resin constituting the surface side of the surface layer has the following. The segment contains a component selected from the group consisting of a fluorine compound segment and polysiloxane. At least one of a group of an alkane segment and a polydimethylsiloxane segment.

以下，說明有關此等氟化合物鏈段、聚矽氧烷鏈段、聚二甲基矽氧烷鏈段。 Hereinafter, these fluorine compound segments, polysiloxane segments, and polydimethylsiloxane segments will be described.

首先，氟化合物鏈段係指包含選自包含氟烷基、氟氧基烷基、氟烯基、氟烷二基及氟氧基烷二基所組成之群組的至少一者之鏈段。 First, the fluorine compound segment refers to a segment including at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group.

此處，氟烷基、氟氧基烷基、氟烯基、氟烷二基、氟氧基烷二基，就是烷基、氧基烷基、烯基、烷二基、氧基烷二基所具有的氫之一部分、或是全部經取代成氟的取代基，任一者都是主要由氟原子與碳原子所構成之取代基，構造中可具有分支，亦可形成具有此等部位的構造所複數連結之二聚物、三聚物、寡聚物、聚合物構造。 Here, fluoroalkyl, fluorooxyalkyl, fluoroalkenyl, fluoroalkanediyl, and fluorooxyalkanediyl are alkyl, oxyalkyl, alkenyl, alkanediyl, and oxyalkanediyl. Part of or all of the hydrogen substituents are substituted with fluorine, each of which is a substituent mainly composed of a fluorine atom and a carbon atom, and may have branches in the structure, and may also have a Dimers, trimers, oligomers, and polymer structures connected by plural structures.

又，就前述氟化合物鏈段而言，較佳為氟聚醚鏈段，此係包含氟烷基、氧基氟烷基、氧基氟烷二基等之部位，更佳為化學式5、化學式6所代表之氟聚醚鏈段，係如已經敘述者。 The fluorine compound segment is preferably a fluoropolyether segment, which is a site containing a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, and the like, and more preferably Chemical Formula 5, Chemical Formula The fluoropolyether segment represented by 6 is as already described.

前述氟聚醚鏈段係包含氟烷基、氧基氟烷基、氧基氟烷二基等之鏈段，為化學式12、化學式13所代表之構造。 The aforementioned fluoropolyether segment is a segment including a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, and the like, and has a structure represented by Chemical Formula 12 and Chemical Formula 13.

此處，n1為1~3之整數，n2~n5為1或2之整數，k、m、p、s為0以上之整數，且p+s為1以上。較佳係n1為2以上，n2~n5為1或2之整數，更佳係n1為3，n2與n4為2，n3與n5為1或2之整數。 Here, n1 is an integer of 1 to 3, n2 to n5 are integers of 1 or 2, k, m, p, and s are integers of 0 or more, and p + s is 1 or more. Preferably, n1 is 2 or more, n2 to n5 are integers of 1 or 2, more preferably n1 is 3, n2 and n4 are 2, and n3 and n5 are integers of 1 or 2.

此氟聚醚鏈段之鏈長有較佳之範圍，碳數較佳為4以上12以下，更佳為4以上10以下，特佳為6以上8以下。碳數在3以下時由於表面能不充分降低，而會有撥油性降低之情況；在13以上時由於對溶劑的溶解性降低，而會有表面層的品位降低之情況。 The chain length of the fluoropolyether segment has a preferable range, and the number of carbons is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and particularly preferably 6 or more and 8 or less. When the carbon number is 3 or less, the surface energy may be insufficiently reduced, which may reduce the oil repellency. When the carbon number is 13 or more, the solubility of the solvent may be reduced, and the quality of the surface layer may be reduced.

此表面層中所含有的樹脂係包含氟化合物鏈段之情況下，較佳為前述的塗料組成物A包含以下的氟化合物D。此氟化合物D係化學式14所示的化合物。 When the resin system contained in this surface layer contains a fluorine compound segment, it is preferable that the aforementioned coating composition A contains the following fluorine compound D. This fluorine compound D is a compound represented by Chemical Formula 14.

R^f1-R₇-D¹ …化學式14 R ^f1 -R ₇ -D ¹ … Chemical formula 14

此處，R^f1表示氟化合物鏈段，R₇表示烷二基、烷三基及由彼等所衍生的酯構造、胺基甲酸酯構造、醚構造、三構造，D¹表示反應性部位。 Here, R ^f1 represents a fluorine compound segment, and R ₇ represents an alkanediyl group, an alkanetriyl group, and an ester structure, a urethane structure, an ether structure, Structure, D ¹ represents a reactive site.

此反應性部位係指因熱或光等之外部能量而與其他成分反應之部位。作為如此的反應性部位，從反應性之觀點來看，可舉出烷氧基矽烷基及烷氧基矽烷 基經水解的矽烷醇基、或羧基、氫氧基、環氧基、乙烯基、烯丙基、丙烯醯基、甲基丙烯醯基等。其中，從反應性、處理性之觀點來看，較佳為乙烯基、烯丙基、烷氧基矽烷基、矽烷基醚基或是矽烷醇基、或環氧基、丙烯醯(甲基丙烯醯)基。 The reactive site refers to a site that reacts with other components due to external energy such as heat or light. Examples of such reactive sites include alkoxysilyl and alkoxysilane from the viewpoint of reactivity. A hydrolyzed silanol group, or a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allyl group, an allyl group, a methacryl group, and the like. Among these, from the viewpoints of reactivity and handleability, vinyl, allyl, alkoxysilyl, silyl ether, or silanol groups, or epoxy groups, acrylic fluorene (methacrylic acid) are preferred.醯) based.

氟化合物D之一例為以下所示的化合物。可舉出：3,3-三氟丙基三甲氧基矽烷、3,3,3-三氟丙基三乙氧基矽烷、3,3,3-三氟丙基三異丙氧基矽烷、3,3,3-三氟丙基三氯矽烷、3,3,3-三氟丙基三異氰酸酯矽烷、2-全氟辛基三甲氧基矽烷、2-全氟辛基乙基三乙氧基矽烷、2-全氟辛基乙基三異丙氧基矽烷、2-全氟辛基乙基三氯矽烷、2-全氟辛基異氰酸酯矽烷、2,2,2-三氟乙基丙烯酸酯、2,2,3,3,3-五氟丙基丙烯酸酯、2-全氟丁基乙基丙烯酸酯、3-全氟丁基-2-羥基丙基丙烯酸酯、2-全氟己基乙基丙烯酸酯、3-全氟己基-2-羥基丙基丙烯酸酯、2-全氟辛基乙基丙烯酸酯、3-全氟辛基-2-羥基丙基丙烯酸酯、2-全氟癸基乙基丙烯酸酯、2-全氟-3-甲基丁基乙基丙烯酸酯、3-全氟-3-甲氧基丁基-2-羥基丙基丙烯酸酯、2-全氟-5-甲基己基乙基丙烯酸酯、3-全氟-5-甲基己基-2-羥基丙基丙烯酸酯、2-全氟-7-甲基辛基-2-羥基丙基丙烯酸酯、四氟丙基丙烯酸酯、八氟戊基丙烯酸酯、十二氟庚基丙烯酸酯、十六氟壬基丙烯酸酯、六氟丁基丙烯酸酯、2,2,2-三氟乙基甲基丙烯酸酯、2,2,3,3,3-五氟丙基甲基丙烯酸酯、2-全氟丁基乙基甲基丙烯酸酯、3-全氟丁基-2-羥基丙基甲基丙烯酸酯、2-全氟辛基乙基甲基丙烯酸酯、3- 全氟辛基-2-羥基丙基甲基丙烯酸酯、2-全氟癸基乙基甲基丙烯酸酯、2-全氟-3-甲基丁基乙基甲基丙烯酸酯、3-全氟-3-甲基丁基-2-羥基丙基甲基丙烯酸酯、2-全氟-5-甲基己基乙基甲基丙烯酸酯、3-全氟-5-甲基己基-2-羥基丙基甲基丙烯酸酯、2-全氟-7-甲基辛基乙基甲基丙烯酸酯、3-全氟-6-甲基辛基甲基丙烯酸酯、四氟丙基甲基丙烯酸酯、八氟戊基甲基丙烯酸酯、八氟戊基甲基丙烯酸酯、十二氟庚基甲基丙烯酸酯、十六氟壬基甲基丙烯酸酯、1-三氟甲基三氟乙基甲基丙烯酸酯、六氟丁基甲基丙烯酸酯、三丙烯醯基-十七氟壬烯基-季戊四醇等。 An example of the fluorine compound D is a compound shown below. Examples include: 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltriisopropoxysilane, 3,3,3-trifluoropropyltrichlorosilane, 3,3,3-trifluoropropyltriisocyanate silane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxy Silane, 2-perfluorooctylethyltriisopropoxysilane, 2-perfluorooctylethyltrichlorosilane, 2-perfluorooctylisocyanate silane, 2,2,2-trifluoroethylacrylic acid Ester, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutyl ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-perfluorohexyl Ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctyl ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecyl Ethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5- Methylhexyl ethyl acrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropane base Enoate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexafluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2 , 2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutyl ethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2- Perfluorooctyl ethyl methacrylate, 3- Perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro 3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl Methyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octa Fluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate Esters, hexafluorobutyl methacrylate, tripropenyl-heptafluorononenyl-pentaerythritol, and the like.

再者，氟化合物D亦可每1分子具有複數的氟聚醚部位。 The fluorine compound D may have a plurality of fluoropolyether sites per molecule.

就上述氟化合物D的市售之例而言，可舉出RS-75(DIC股份有限公司)、Optool DAC-HP(DAIKIN工業股份有限公司)、C10GACRY、C8HGOL(油脂製品股份有限公司)等，可利用此等之製品。 Examples of the commercially available fluorine compound D include RS-75 (DIC Corporation), Optool DAC-HP (DAIKIN Industries Co., Ltd.), C10GACRY, C8HGOL (Oil Products Corporation), etc., These products are available.

其次，敘述有關聚矽氧烷鏈段。於本發明中，聚矽氧烷鏈段就是指後述之化學式15所示的鏈段。 Next, the polysiloxane segment will be described. In the present invention, the polysiloxane segment refers to a segment represented by Chemical Formula 15 described later.

此處，聚矽氧烷中包含矽氧烷的重複單元為100左右之低分子量者(所謂的寡聚物)及矽氧烷的重複單元超過100之高分子量者(所謂的聚合物)的兩者。 Here, the polysiloxane contains a low-molecular-weight (so-called oligomer) having a repeating unit of about 100 and a high-molecular-weight (a so-called polymer) having a repeating unit of silica exceeding 100. By.

R₁、R₂係氫氧基或碳數1~8的烷基之任一者，於式中具有各自至少1個以上者，n為100~300之整數。 Each of R ₁ and R ₂ is a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, each of which has at least one or more in the formula, and n is an integer of 100 to 300.

前述聚矽氧烷鏈段、聚二甲基矽氧烷鏈段之詳細係如後述，但前述構成表面層的樹脂係由於具有此等之鏈段，而可提升耐熱性、耐候性，或提升因表面層的潤滑性所致的耐擦傷性。更佳為從潤滑性之方面係以包含後述之化學式16所示的聚二甲基矽氧烷鏈段較佳。 The details of the aforementioned polysiloxane segment and the polydimethylsiloxane segment are described later, but the resin constituting the surface layer can improve heat resistance, weather resistance, or improve due to the presence of these segments. Scratch resistance due to the lubricity of the surface layer. It is more preferable that it includes a polydimethylsiloxane segment represented by Chemical Formula 16 described later from the viewpoint of lubricity.

於本發明中，可將含有水解性矽烷基的矽烷化合物之部分水解物、有機矽溶膠或在該有機矽溶膠附加有具有自由基聚合物的水解性矽烷化合物之塗料組成物，作為含有聚矽氧烷鏈段的樹脂使用。 In the present invention, a partially hydrolyzed product of a hydrolyzable silane-containing silane compound, an organic silica sol, or a coating composition in which a hydrolyzable silane compound having a radical polymer is added to the organic silica sol can be used as the polysilicon-containing Resin resin is used.

含有聚矽氧烷鏈段的樹脂，係可例示四烷氧基矽烷、甲基三烷氧基矽烷、二甲基二烷氧基矽烷、γ-環氧丙氧基丙基三烷氧基矽烷、γ-環氧丙氧基丙基烷基二烷氧基矽烷、γ-甲基丙烯醯氧基丙基三烷氧基矽烷、γ-甲基丙烯醯氧基丙基烷基二烷氧基矽烷等之具有水解性矽烷基的矽烷化合物之完全或部分水解物或分散於有機溶劑中的有機矽溶膠、在有機矽溶膠之表面附加有水解性矽烷基的水解矽烷化合物者等。 Examples of the resin containing a polysiloxane segment are tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane Γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxy Complete or partial hydrolysates of hydrolyzable silane-based silane compounds, such as silanes, or organic silica sols dispersed in organic solvents, and hydrolyzed silane compounds having hydrolyzable silane groups added to the surface of the organosilica sols.

又，於本發明中，含有聚矽氧烷鏈段的樹脂，係除了聚矽氧烷鏈段，還可含有(共聚合)其他的鏈段等。例如，可含有(共聚合)具有聚己內酯鏈段、聚二甲基矽氧烷鏈段的單體成分。 In the present invention, the resin containing a polysiloxane segment may include (copolymerize) other segments in addition to the polysiloxane segment. For example, it may contain (copolymerize) a monomer component having a polycaprolactone segment and a polydimethylsiloxane segment.

當含有聚矽氧烷鏈段的樹脂為具有氫氧基 的共聚物時，若使用包含具有氫氧基之含有聚矽氧烷鏈段的樹脂(共聚物)與含有異氰酸酯基的化合物之塗料組成物來形成表面層，則可有效率地形成具有聚矽氧烷鏈段與胺基甲酸酯鍵之表面層。 When the resin containing a polysiloxane segment has a hydroxyl group In the case of a copolymer, if a surface layer is formed by using a coating composition containing a resin (copolymer) containing a polysiloxane group having a hydroxyl group and an isocyanate group-containing compound, a polysilicon having a high efficiency can be formed. Surface layer of oxane segment and urethane bond.

其次，敘述有關聚二甲基矽氧烷鏈段。於本發明中，所謂的聚二甲基矽氧烷鏈段，就是指化學式16所示的鏈段。於聚二甲基矽氧烷中，包含二甲基矽氧烷的重複單元為10~100之低分子量者(所謂的寡聚物)及二甲基矽氧烷的重複單元超過100之高分子量者(所謂的聚合物)的兩者。 Next, the polydimethylsiloxane segment will be described. In the present invention, the so-called polydimethylsiloxane segment refers to a segment represented by Chemical Formula 16. In polydimethylsiloxane, low molecular weight individuals (so-called oligomers) containing repeating units of dimethylsiloxane of 10 to 100 and high molecular weights having repeating units of dimethylsiloxane in excess of 100 Both (so-called polymers).

m為10~300之整數。 m is an integer from 10 to 300.

構成表面層的表面側之樹脂，若具有聚二甲基矽氧烷鏈段，則聚二甲基矽氧烷鏈段會配位於表面層之表面。藉於聚二甲基矽氧烷鏈段配位於表面層之表面，而表面層表面的潤滑性提升，可減低摩擦阻力。此結果，能夠使反覆擦過性提升。 If the resin constituting the surface side of the surface layer has a polydimethylsiloxane segment, the polydimethylsiloxane segment will be arranged on the surface of the surface layer. The polydimethylsiloxane segment is arranged on the surface of the surface layer, and the lubricity of the surface layer is improved, which can reduce the friction resistance. As a result, it is possible to improve the repetitive rubbing property.

於本發明中，作為含有聚二甲基矽氧烷鏈段的樹脂，較佳為使用在聚二甲基矽氧烷鏈段中共聚合有乙烯基單體之共聚物。 In the present invention, as the resin containing a polydimethylsiloxane segment, a copolymer in which a vinyl monomer is copolymerized in the polydimethylsiloxane segment is preferably used.

以使表面層的強韌性提升之目的，含有聚 二甲基矽氧烷鏈段的樹脂較佳為共聚合有具有與異氰酸酯基反應的氫氧基之單體等。 In order to improve the toughness of the surface layer, The resin of the dimethylsiloxane segment is preferably a monomer copolymerized with a hydroxyl group having a reaction with an isocyanate group, and the like.

當含有聚二甲基矽氧烷鏈段的樹脂為具有氫氧基的共聚物時，若使用包含具有氫氧基之含有聚二甲基矽氧烷鏈段的樹脂(共聚物)與含有異氰酸酯基的化合物之塗料組成物來形成表面層，則可有效率地形成具有聚二甲基矽氧烷鏈段與胺基甲酸酯鍵之表面層。 When the resin containing a polydimethylsiloxane segment is a copolymer having a hydroxyl group, if a resin containing a polydimethylsiloxane segment containing a hydroxyl group (copolymer) and an isocyanate-containing resin are used To form a surface layer by using a coating composition of a base-based compound, a surface layer having a polydimethylsiloxane segment and a urethane bond can be efficiently formed.

當含有聚二甲基矽氧烷鏈段的樹脂係與乙烯基單體之共聚物時，可為嵌段共聚物、接枝共聚物、無規共聚物之任一者。當含有聚二甲基矽氧烷鏈段的樹脂係與乙烯基單體之共聚物時，將此稱為聚二甲基矽氧烷系共聚物。聚二甲基矽氧烷系共聚物係可藉由活性聚合法、高分子起始劑法、高分子鏈轉移法等來製造，但若考慮生產性，則較佳為使用高分子起始劑法、高分子鏈轉移法。 When the copolymer of a resin based on a polydimethylsiloxane segment and a vinyl monomer is used, it may be any of a block copolymer, a graft copolymer, and a random copolymer. When a copolymer of a resin-based and vinyl monomer containing a polydimethylsiloxane segment is referred to as a polydimethylsiloxane-based copolymer. The polydimethylsiloxane copolymer can be produced by a living polymerization method, a polymer initiator method, a polymer chain transfer method, etc., but considering productivity, it is preferable to use a polymer initiator Method, polymer chain transfer method.

在使用高分子起始劑法時，可使用化學式17所示的高分子偶氮系自由基聚合起始劑，使與其他的乙烯基單體共聚合。又，亦可進行二階段的聚合，其係使過氧單體與具有不飽和基的聚二甲基矽氧烷在低溫下共聚合而合成在側鏈導入有過氧化物基的預聚物，並使該預聚物與乙烯基單體共聚合。 When the polymer initiator method is used, a polymer azo radical polymerization initiator represented by Chemical Formula 17 can be used to copolymerize with other vinyl monomers. It is also possible to carry out two-stage polymerization, which is a prepolymer in which a peroxide group is introduced into a side chain by copolymerizing a peroxy monomer and a polydimethylsiloxane having an unsaturated group at a low temperature. And copolymerize the prepolymer with a vinyl monomer.

m為10~300之整數，n為1~50之整數。 m is an integer from 10 to 300, and n is an integer from 1 to 50.

使用高分子鏈轉移法時，係例如可在化學式18所示的聚矽氧油上，附加HS-CH₂COOH或HS-CH₂CH₂COOH等而做成具有SH基的化合物後，利用SH基的鏈轉移而使該矽氧化合物與乙烯基單體共聚合，藉此合成嵌段共聚物。 When the chain transfer method using a polymer, for example based on polyethylene oxide of silicon oil represented by Chemical Formula 18, the additional HS-CH ₂ COOH or HS-CH ₂ CH ₂ COOH or the like made after the compound having SH group of the SH A block copolymer is synthesized by copolymerizing the siloxane compound with a vinyl monomer by chain transfer of a radical.

m為10~300之整數。 m is an integer from 10 to 300.

為了合成聚二甲基矽氧烷系接枝共聚物，係例如可使化學式19所示的化合物，即聚二甲基矽氧烷的甲基丙烯酸酯等與乙烯基單體共聚合，藉此而容易地得到接枝共聚物。 In order to synthesize a polydimethylsiloxane-based graft copolymer, for example, a compound represented by Chemical Formula 19, that is, a methacrylate of polydimethylsiloxane and the like can be copolymerized with a vinyl monomer, thereby Instead, a graft copolymer is easily obtained.

m為10~300之整數。 m is an integer from 10 to 300.

就與聚二甲基矽氧烷的共聚物所使用之乙烯基單體而言，係可舉出例如丙烯酸甲酯、丙烯酸乙酯 、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸辛酯、丙烯酸環己酯、丙烯酸四氫糠酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸十八酯、甲基丙烯酸月桂酯、甲基乙烯基醚、乙基乙烯基醚、正丙基乙烯基醚、苯乙烯、α-甲基苯乙烯、丙烯腈、甲基丙烯腈、醋酸乙烯酯、氯乙烯、偏二氯乙烯、氟乙烯、偏二氟乙烯、丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯、烯丙基環氧丙基醚、丙烯酸、甲基丙烯酸、伊康酸、巴豆酸、馬來酸、馬來酸酐、丙烯醯胺、甲基丙烯醯胺、N-羥甲基丙烯醯胺、N,N-二甲基丙烯醯胺、N,N-二甲基胺基乙基甲基丙烯酸酯、N,N-二乙基胺基乙基甲基丙烯酸酯、二乙醯基丙烯醯胺、丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯、甲基丙烯酸2-羥基丙酯、烯丙醇等。 Examples of the vinyl monomer used in the copolymer with polydimethylsiloxane include methyl acrylate and ethyl acrylate. , N-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Ester, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-formyl Styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, glycidyl acrylate, glycidyl methacrylate, allyl ring Oxypropyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-hydroxymethacrylamide, N, N-di Methacrylamide, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, diethylammonium acrylamide, 2-hydroxyacrylic acid Ethyl ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol .

又，聚二甲基矽氧烷系共聚物，較佳為在甲苯、二甲苯等的芳香族烴系溶劑、甲基乙基酮、甲基異丁基酮等的酮系溶劑、醋酸乙酯、醋酸丁酯等的酯系溶劑、乙醇、異丙醇等的醇系溶劑等單獨或是混合溶劑中，藉由溶液聚合法而製造 The polydimethylsiloxane copolymer is preferably an aromatic hydrocarbon solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, or ethyl acetate. Ester solvents such as butyl acetate, alcohol solvents such as ethanol, isopropanol, and the like, alone or in a mixed solvent, are produced by a solution polymerization method

視需要而併用苯甲醯過氧化物、偶氮雙異丁腈等之聚合起始劑。聚合反應較佳為在50~150℃進行3~12小時。 If necessary, a polymerization initiator such as benzamidine peroxide, azobisisobutyronitrile and the like is used in combination. The polymerization reaction is preferably performed at 50 to 150 ° C for 3 to 12 hours.

本發明中之聚二甲基矽氧烷系共聚物中的聚二甲基矽氧烷鏈段之量，於表面層的潤滑性或耐污染 性之點，係較佳在聚二甲基矽氧烷系共聚物的全部成分100質量%中為1~30質量%。又，聚二甲基矽氧烷鏈段的重量平均分子量較佳為1,000~30,000。 The amount of polydimethylsiloxane segments in the polydimethylsiloxane-based copolymer in the present invention, the lubricity or pollution resistance on the surface layer In terms of performance, it is preferably 1 to 30% by mass based on 100% by mass of all components of the polydimethylsiloxane copolymer. The weight average molecular weight of the polydimethylsiloxane segment is preferably 1,000 to 30,000.

於本發明中，作為為了形成表面層而使用的塗料組成物，當使用含有聚二甲基矽氧烷鏈段的樹脂時，除了聚二甲基矽氧烷鏈段，還可含有(共聚合)其他的鏈段等。例如，亦可含有(共聚合)聚己內酯鏈段或聚矽氧烷鏈段。 In the present invention, when a resin containing a polydimethylsiloxane segment is used as a coating composition for forming a surface layer, in addition to the polydimethylsiloxane segment, it may contain (copolymerization) ) Other links and so on. For example, it may contain (copolymerize) a polycaprolactone segment or a polysiloxane segment.

於為了形成表面層而使用的塗料組成物中，可使用聚己內酯鏈段與聚二甲基矽氧烷鏈段之共聚物、聚己內酯鏈段與聚矽氧烷鏈段之共聚物、聚己內酯鏈段與聚二甲基矽氧烷鏈段與聚矽氧烷鏈段之共聚物等。使用如此之塗料組成物所得之表面層，係成為可具有聚己內酯鏈段與聚二甲基矽氧烷鏈段及/或聚矽氧烷鏈段。 In the coating composition used to form the surface layer, a copolymer of a polycaprolactone segment and a polydimethylsiloxane segment, and a copolymerization of a polycaprolactone segment and a polysiloxane segment can be used. Polymer, polycaprolactone segment and copolymer of polydimethylsiloxane segment and polysiloxane segment. The surface layer obtained by using such a coating composition is capable of having a polycaprolactone segment and a polydimethylsiloxane segment and / or a polysiloxane segment.

於為了形成具有聚己內酯鏈段、聚矽氧烷鏈段及聚二甲基矽氧烷鏈段的表面層而使用的塗料組成物中，聚二甲基矽氧烷系共聚物、聚己內酯及聚矽氧烷之反應，係可在聚二甲基矽氧烷系共聚物合成時，適宜地添加聚己內酯鏈段及聚矽氧烷鏈段而進行共聚合。 In a coating composition used to form a surface layer having a polycaprolactone segment, a polysiloxane segment, and a polydimethylsiloxane segment, a polydimethylsiloxane copolymer, a polysiloxane The reaction between caprolactone and polysiloxane can be carried out by appropriately adding a polycaprolactone segment and a polysiloxane segment during the synthesis of the polydimethylsiloxane copolymer.

[塗料組成物B] [Coating composition B]

塗料組成物B係藉由在支撐基材上塗布、乾燥、硬化，而可形成表面硬度比A層還高的材料之液體，包含適合於形成B層的樹脂或前驅物。 The coating composition B is a liquid which can form a material having a surface hardness higher than that of the layer A by coating, drying, and hardening on a supporting substrate, and includes a resin or precursor suitable for forming the layer B.

塗料組成物B係可為熱硬化型樹脂、紫外線硬化型樹脂之任一者，也可為2種類以上的摻合物。 The coating composition B may be any one of a thermosetting resin and an ultraviolet curing resin, and may be a blend of two or more types.

本發明中的熱硬化型樹脂係包含含有氫氧基的樹脂與聚異氰酸酯化合物，作為含有氫氧基的樹脂，可舉出丙烯酸多元醇、聚醚多元醇、聚酯多元醇、聚烯烴系多元醇、聚碳酸酯多元醇、胺基甲酸酯多元醇等，此等係可為1種類或是2種類以上之摻合物。若含有氫氧基的樹脂之羥值為1~200mgKOH/g之範圍，則從成為塗膜時的耐久性、耐水解性、密接性之觀點來看較佳。羥值小於1mgKOH/g時，塗膜的硬化係幾乎不進行，會有耐久性或強度降低之情況。另一方面，羥值大於200mgKOH/g時，由於硬化收縮過大，會有使密接性降低之情況。 The thermosetting resin in the present invention contains a hydroxyl group-containing resin and a polyisocyanate compound. Examples of the hydroxyl group-containing resin include acrylic polyols, polyether polyols, polyester polyols, and polyolefin-based polyols. Alcohols, polycarbonate polyols, urethane polyols, etc. may be one type or a mixture of two or more types. When the hydroxyl group-containing resin has a hydroxyl value in the range of 1 to 200 mgKOH / g, it is preferable from the viewpoints of durability, hydrolysis resistance, and adhesiveness when it becomes a coating film. When the hydroxyl value is less than 1 mgKOH / g, hardening of the coating film hardly proceeds, and durability or strength may be reduced. On the other hand, when the hydroxyl value is more than 200 mgKOH / g, the curing shrinkage is too large, and the adhesion may be reduced.

本發明中之含有氫氧基的丙烯酸多元醇，係例如將丙烯酸酯或甲基丙烯酸酯作為成分聚合而得。如此的丙烯酸樹脂，係例如可將(甲基)丙烯酸酯作為成分，視需要共聚合(甲基)丙烯酸、伊康酸、馬來酸酐等之含有羧酸基的單體，藉此而容易地製造。就(甲基)丙烯酸酯而言，可舉出例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸甲基己酯、(甲基)丙烯酸環十二酯、(甲基)丙烯酸異酯等。就如此之含有氫氧基的丙烯酸多元醇而言，可舉出例如DIC股份有限公司；(商品名「Acrydic」(註冊商標)系列等)、大成精細化學股份有限公司；(商品名 「Acrit」(註冊商標)系列等)、日本觸媒股份有限公司；(商品名「Acryset」(註冊商標)系列等)、三井化學股份有限公司；(商品名「Takelac」(註冊商標)UA系列)等，可利用此等之製品。 The hydroxyl-containing acrylic polyol in the present invention is obtained by, for example, polymerizing acrylate or methacrylate as a component. Such an acrylic resin can be easily prepared by, for example, using a (meth) acrylate as a component and copolymerizing a carboxylic acid group-containing monomer such as (meth) acrylic acid, itaconic acid, and maleic anhydride as needed. Manufacturing. Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) ) Butyl acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethyl (meth) acrylate Hexyl ester, cyclohexyl (meth) acrylate, methylhexyl (meth) acrylate, cyclododecyl (meth) acrylate, isopropyl (meth) acrylate Esters, etc. Examples of such a hydroxyl group-containing acrylic polyol include DIC Corporation; (trade name "Acrydic" (registered trademark) series, etc.), Dacheng Fine Chemical Co., Ltd .; (trade name "Acrit" (Registered trademark) series, etc.), Japan Catalyst Co., Ltd .; (trade name "Acryset" (registered trademark) series, etc.), Mitsui Chemicals Co., Ltd .; (trade name "Takelac" (registered trademark) UA series), etc., These products are available.

就本發明中之含有氫氧基的聚醚多元醇而言，可舉出聚乙二醇或是三醇、聚丙二醇或是三醇、聚丁二醇或是三醇、聚四亞甲基二醇或是三醇，更且此等碳數不同的氧化烯化合物之加成聚合物或嵌段共聚物等。就如此之含有氫氧基的聚醚多元醇而言，可舉出旭硝子股份有限公司；(商品名「Excenol」(註冊商標)系列等)、三井化學股份有限公司；(商品名「Actcol」(註冊商標)系列等)，可利用此等之製品。 Examples of the polyether polyol containing a hydroxyl group in the present invention include polyethylene glycol or triol, polypropylene glycol or triol, polybutylene glycol or triol, and polytetramethylene. Diols or triols, and addition polymers or block copolymers of such alkylene oxide compounds having different carbon numbers. Examples of such a hydroxyl-containing polyether polyol include Asahi Glass Co., Ltd .; (trade name "Excenol" (registered trademark) series, etc.), Mitsui Chemicals Co., Ltd .; (trade name "Actcol" ( (Registered trademark) series, etc.), these products can be used.

就本發明中之含有氫氧基的聚酯多元醇而言，可舉出例如使乙二醇、丙二醇、丁二醇、戊二醇、己二醇、庚二醇、癸二醇、環己烷二甲醇等之脂肪族二醇、與例如琥珀酸、己二酸、癸二酸、富馬酸、辛二酸、壬二酸、1,10-十亞甲基二羧酸、環己烷二羧酸等之脂肪族二元酸作為必要原料成分而反應的脂肪族聚酯多元醇；或使乙二醇、丙二醇、丁二醇等之脂肪族二醇、與例如對苯二甲酸、間苯二甲酸、萘二羧酸等之芳香族二元酸作為必要原料成分而反應的芳香族聚酯多元醇。 Examples of the hydroxyl-containing polyester polyol in the present invention include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, decanediol, and cyclohexane. Aliphatic diols such as alkanedimethanol, and, for example, succinic acid, adipic acid, sebacic acid, fumaric acid, suberic acid, azelaic acid, 1,10-decamethylene dicarboxylic acid, cyclohexane An aliphatic polyester polyol in which an aliphatic dibasic acid such as a dicarboxylic acid is reacted as an essential raw material component; or an aliphatic diol such as ethylene glycol, propylene glycol, butylene glycol, and, for example, terephthalic acid, methane An aromatic polyester polyol in which an aromatic dibasic acid such as phthalic acid and naphthalenedicarboxylic acid reacts as an essential raw material component.

就如此之含有氫氧基的聚酯多元醇而言，可舉出DIC股份有限公司；(商品名「Polylite」(註冊商標)系列等)、股份有限公司KURARAY；(商品名「KURARAY多元醇」(註冊商標)系列等)、武田藥品工業 股份有限公司；(商品名「Takelac」(註冊商標)U系列)，可利用此等之製品。 Examples of such hydroxyl-containing polyester polyols include DIC Corporation; (trade name "Polylite" (registered trademark) series, etc.), KURARAY Corporation; (trade name "KURARAY Polyol") (Registered trademark) series, etc.), Takeda Pharmaceutical Industry Co., Ltd .; (brand name "Takelac" (registered trademark) U series), can use these products.

就本發明中之含有氫氧基的聚烯烴系多元醇而言，係丁二烯或異戊二烯等之碳數4至12個的二烯烴類之聚合物及共聚物、碳數4至12的二烯烴與碳數2至22的α-烯烴類之共聚物之中，含有氫氧基的化合物。作為使含有氫氧基的方法，並沒有特別的限制，但例如有使二烯單體與過氧化氫反應之方法。再者，亦可藉由將殘存的雙鍵進行氫鍵結，而飽和脂肪族化。就如此之含有氫氧基的聚烯烴系多元醇而言，可舉出日本曹達股份有限公司；(商品名「NISSO-PB」(註冊商標)G系列等)、出光興產股份有限公司；(商品名「Poly bd」(註冊商標)系列、「Epol」(註冊商標)系列等)，可利用此等之製品。 The hydroxyl-containing polyolefin polyol in the present invention is a diene-based polymer and copolymer having 4 to 12 carbons such as butadiene or isoprene, and 4 to 12 carbons. Among the copolymers of diene of 12 and α-olefins having 2 to 22 carbons, compounds containing a hydroxyl group. There is no particular limitation on the method for causing the hydroxyl group to be contained, but for example, there is a method for reacting a diene monomer with hydrogen peroxide. In addition, the remaining double bonds can be hydrogenated to saturate the aliphatic. Examples of such hydroxyl-containing polyolefin-based polyols include Japan's Soda Co., Ltd .; (trade name "NISSO-PB" (registered trademark) G series, etc.), Idemitsu Kosan Co., Ltd .; "Poly bd" (registered trademark) series, "Epol" (registered trademark) series, etc.) can be used.

就本發明中之含有氫氧基的聚碳酸酯多元醇而言，亦可使用例如僅用碳酸二烷酯與1,6-己二醇而得之聚碳酸酯多元醇，但於結晶性更低之點，較佳為作為二醇使用使1,6-己二醇、與1,4-丁二醇、1,5-戊二醇或1,4-環己烷二甲醇共聚合而得之聚碳酸酯多元醇。 As the polycarbonate polyol containing a hydroxyl group in the present invention, for example, a polycarbonate polyol obtained by using only a dialkyl carbonate and 1,6-hexanediol may be used, but the crystallinity is more crystalline. The lower point is preferably obtained by copolymerizing 1,6-hexanediol with 1,4-butanediol, 1,5-pentanediol, or 1,4-cyclohexanedimethanol as a diol. Polycarbonate polyols.

就如此之含有氫氧基的聚碳酸酯多元醇而言，可舉出共聚合聚碳酸酯多元醇之旭化成化學股份有限公司；(商品名「T5650J」、「T5652」、「T4671」、「T4672」等)、宇部興產股份有限公司；(商品名「ETERNACLL」(註冊商標)UM系列等)，可利用此等之製品。 Examples of such hydroxyl-containing polycarbonate polyols include Asahi Kasei Chemical Co., Ltd. which copolymerizes polycarbonate polyols; (trade names "T5650J", "T5652", "T4671", "T4672 ", Etc.), Ube Industrial Co., Ltd .; (trade name" ETERNACLL "(registered trademark) UM series, etc.), these products can be used.

本發明中之含有氫氧基的胺基甲酸酯多元 醇，係例如使聚異氰酸酯化合物與在1分子中含有至少2個氫氧基的化合物，以氫氧基對於異氰酸酯基成為過剩之方式的比率反應而可獲得。就彼時所使用的聚異氰酸酯化合物而言，可舉出六亞甲基二異氰酸酯、甲苯二異氰酸酯、間二甲苯二異氰酸酯、異佛爾酮二異氰酸酯等。又，就在1分子中含有至少2個氫氧基的化合物而言，可舉出多元醇類、聚酯二醇、聚乙二醇、聚丙二醇、聚碳酸酯二醇等。 Hydroxyl-containing urethane polyhydric in the present invention The alcohol is obtained, for example, by reacting a polyisocyanate compound with a compound containing at least two hydroxyl groups in one molecule in such a manner that the hydroxyl group becomes excessive with respect to the isocyanate group. Examples of the polyisocyanate compound used at that time include hexamethylene diisocyanate, toluene diisocyanate, m-xylene diisocyanate, isophorone diisocyanate, and the like. Examples of the compound containing at least two hydroxyl groups in one molecule include polyols, polyester diols, polyethylene glycols, polypropylene glycols, and polycarbonate diols.

就本發明中之熱硬化型樹脂所用的聚異氰酸酯化合物而言，係指含有異氰酸酯基的樹脂、或含有異氰酸酯基的單體或寡聚物。含有異氰酸酯基的化合物，可舉出例如亞甲基雙-4-環己基異氰酸酯、甲苯二異氰酸酯的三羥甲基丙烷加成體、六亞甲基二異氰酸酯的三羥甲基丙烷加成體、異佛爾酮二異氰酸酯的三羥甲基丙烷加成體、甲苯二異氰酸酯的異三聚氰酸酯體、六亞甲基二異氰酸酯的異三聚氰酸酯體、六亞甲基異氰酸酯的縮二脲體等之(聚)異氰酸酯、及上述異氰酸酯的封端體等。就如此之熱硬化型樹脂所用的聚異氰酸酯化合物而言，可舉出三井化學股份有限公司；(商品名「Takenate」(註冊商標)系列等)、日本聚胺基甲酸酯工業股份有限公司；(商品名「Coronate」(註冊商標)系列等)、旭化成化學股份有限公司；(商品名「Duranate」(註冊商標)系列等)、DIC股份有限公司；(商品名「Burnock」(註冊商標)系列等)，可利用此等之製品。 The polyisocyanate compound used for the thermosetting resin in the present invention refers to a resin containing an isocyanate group, or a monomer or oligomer containing an isocyanate group. Examples of the isocyanate group-containing compound include methylenebis-4-cyclohexyl isocyanate, trimethylolpropane adduct of toluene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, Trimethylolpropane adduct of isophorone diisocyanate, isotricyanate of toluene diisocyanate, isotricyanate of hexamethylene diisocyanate, condensation of hexamethylene isocyanate (Poly) isocyanates such as diurea bodies, and blocked bodies of the above-mentioned isocyanates. Examples of the polyisocyanate compound used in such thermosetting resins include Mitsui Chemicals Co., Ltd. (trade name "Takenate" (registered trademark) series, etc.), Japan Polyurethane Industry Co., Ltd .; (Brand name "Coronate" (registered trademark) series, etc.), Asahi Kasei Chemical Co., Ltd .; (brand name "Duranate" (registered trademark) series, etc.), DIC Corporation; (brand name "Burnock" (registered trademark) series Etc.), these products can be used.

就本發明中之紫外線硬化型樹脂而言，較 佳為多官能丙烯酸酯單體、寡聚物、烷氧基矽烷、烷氧基矽烷水解物、烷氧基矽烷寡聚物、胺基甲酸酯丙烯酸酯寡聚物等，更佳為多官能丙烯酸酯單體、寡聚物、胺基甲酸酯丙烯酸酯寡聚物。 As far as the ultraviolet curable resin in the present invention is concerned, Multifunctional acrylate monomer, oligomer, alkoxysilane, alkoxysilane hydrolysate, alkoxysilane oligomer, urethane acrylate oligomer, etc. Acrylate monomer, oligomer, urethane acrylate oligomer.

就多官能丙烯酸酯單體之例而言，可使用在1分子中具有2個以上的(甲基)丙烯醯氧基之多官能丙烯酸酯及其改性聚合物，作為具體例為季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三丙烯酸酯己烷亞甲基二異氰酸酯胺基甲酸酯聚合物等。此等之單體係可將1種或混合2種以上而使用。 As an example of the polyfunctional acrylate monomer, a polyfunctional acrylate having two or more (meth) acryloxy groups in one molecule and a modified polymer thereof can be used. As a specific example, pentaerythritol tris ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol pentaerythritol hexa (methyl) Group) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate hexanemethylene diisocyanate urethane polymer, and the like. These single systems can be used singly or in combination of two or more.

又，就市售的多官能丙烯酸系組成物而言，可舉出三菱縲縈股份有限公司；(商品名「Diabeam」(註冊商標)系列等)、日本合成化學工業股份有限公司；(商品名「SHIKOH」(註冊商標)系列等)、長瀨產業股份有限公司；(商品名「Denacol」(註冊商標)系列等)、新中村化學股份有限公司；(商品名「NK Ester」系列等)、DIC股份有限公司；(商品名「UNIDIC」(註冊商標)等)、東亞合成股份有限公司；(「Aronix」(註冊商標)系列等)、日油股份有限公司；(「Blemmer」(註冊商標)系列等)、日本化藥股份有限公司；(商品名「KAYARAD」(註冊商標)系列等)、共榮社化學股份有限公司；(商品名「Light Ester」系列等)等，可利用此等之製品。 Examples of commercially available polyfunctional acrylic compositions include Mitsubishi Electric Corporation; (trade name "Diabeam" (registered trademark) series, etc.), Japan Synthetic Chemical Industry Co., Ltd .; (trade name) "SHIKOH" (registered trademark) series, etc.), Nagase Industry Co., Ltd .; (brand name "Denacol" (registered trademark) series, etc.), Shin Nakamura Chemical Co., Ltd .; (brand name "NK Ester" series, etc.), DIC Corporation; (brand name "UNIDIC" (registered trademark), etc.), East Asia Synthetic Corporation; ("Aronix" (registered trademark) series, etc.), Japan Oil Corporation; ("Blemmer" (registered trademark) Series, etc.), Nippon Kayaku Co., Ltd .; (brand name "KAYARAD" (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd .; (brand name "Light Ester" series, etc.), etc., can use these product.

又，為了賦予前述特性，亦可使用丙烯酸聚合物。該丙烯酸聚合物更佳係不含不飽和基，重量平均分子量為5,000~200,000、玻璃轉移溫度為20~200℃。丙烯酸聚合物之玻璃轉移溫度小於20℃時，會有硬度降低之情況，且會有超過200℃時之延伸度不充分之情況。更佳的玻璃轉移溫度之範圍為50~150℃。 In order to impart the aforementioned characteristics, an acrylic polymer may be used. The acrylic polymer is more preferably unsaturated group-free, has a weight average molecular weight of 5,000 to 200,000, and a glass transition temperature of 20 to 200 ° C. When the glass transition temperature of the acrylic polymer is less than 20 ° C, the hardness may decrease, and the elongation beyond 200 ° C may be insufficient. A more preferred glass transition temperature is in the range of 50 to 150 ° C.

另外，前述丙烯酸聚合物係由於具有親水性官能基，而可賦予硬度。具體而言，可藉由使具有羧基的(甲基)丙烯酸、伊康酸、富馬酸、馬來酸等、或是具有氫氧基的2-(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯等之具有親水性官能基的不飽和單體與前述不飽和單體共聚合，而在丙烯酸聚合物中導入親水性官能基。 Moreover, the said acrylic polymer system can provide hardness because it has a hydrophilic functional group. Specifically, (meth) acrylic acid having a carboxyl group, itaconic acid, fumaric acid, maleic acid, or the like, or hydroxyethyl 2- (meth) acrylate having a hydroxyl group, An unsaturated monomer having a hydrophilic functional group such as hydroxypropyl acrylate is copolymerized with the unsaturated monomer, and a hydrophilic functional group is introduced into the acrylic polymer.

前述丙烯酸聚合物的重量平均分子量較佳為5,000~200,000。重量平均分子量小於5,000時，會有硬度變不充分之情況，重量平均分子量超過200,000時，會有包含塗布性的成型性或強韌性變不充分之情況。又，重量平均分子量係藉由聚合觸媒、鏈轉移劑的配合量及所使用的溶劑之類別而能夠調整。 The weight average molecular weight of the acrylic polymer is preferably 5,000 to 200,000. When the weight average molecular weight is less than 5,000, hardness may be insufficient, and when the weight average molecular weight exceeds 200,000, moldability including coating properties or toughness may be insufficient. The weight average molecular weight can be adjusted by the amount of the polymerization catalyst, the chain transfer agent, and the type of the solvent used.

前述丙烯酸聚合物含有比例，係較佳為塗料組成物B的總固體成分中1~50質量%，更佳為5~30質量%。由於藉由使成為1質量%以上，則延伸度係顯著提高，而使成為50質量%以下，則可維持硬度，所以較佳。 The content ratio of the acrylic polymer is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass of the total solid content of the coating composition B. Since the elongation is remarkably improved by setting it to 1% by mass or more, it is preferable to maintain the hardness by setting it to 50% by mass or less.

[溶劑] [Solvent]

前述塗料組成物A、塗料組成物B較佳為包含溶劑。就溶劑的種類數而言，較佳為1種類以上20種類以下，更 佳為1種類以上10種類以下，尤佳為1種類以上6種類以下。此處所謂的「溶劑」，就是指在塗布後的乾燥步驟中能夠幾乎使全量蒸發，自塗膜去除之在常溫、常壓下為液體之物質。 It is preferable that the said coating composition A and coating composition B contain a solvent. The number of types of the solvent is preferably from 1 to 20 and more It is preferably from 1 to 10 types, particularly preferably from 1 to 6 types. The "solvent" as used herein refers to a substance that can be evaporated from the coating film in the drying step after coating and is a liquid at normal temperature and pressure.

此處，溶劑的種類係由構成溶劑的分子構造所決定。即，即使相同的元素組成且官能基的種類與數目相同，結合關係相異者(結構異構物)、非前述結構異構物但在3次元空間內採取任何構形也無法完全地重疊者(立體異構物)，係看作為種類相異的溶劑。例如2-丙醇與正丙醇係看作為相異的溶劑。 Here, the type of the solvent is determined by the molecular structure constituting the solvent. That is, even if the same elemental composition and the same type and number of functional groups exist, those with different binding relationships (structural isomers) and those that are not the aforementioned structural isomers but cannot adopt any configuration in the three-dimensional space cannot completely overlap. (Stereoisomers) are considered to be solvents of different types. For example, 2-propanol and n-propanol are regarded as different solvents.

[其他的添加劑] [Other additives]

前述塗料組成物A與塗料組成物B較佳為包含聚合起始劑或硬化劑或觸媒。聚合起始劑及觸媒係為了促進表面層之硬化而使用。就聚合起始劑而言，較佳為可以使塗料組成物中所含有的成分開始或促進由陰離子、陽離子、自由基聚合反應等所致的聚合、縮合或交聯反應者。 It is preferable that the said coating composition A and coating composition B contain a polymerization initiator, a hardening agent, or a catalyst. A polymerization initiator and a catalyst are used in order to accelerate hardening of a surface layer. The polymerization initiator is preferably one capable of starting or promoting the polymerization, condensation, or crosslinking reaction caused by anions, cations, radical polymerization reactions, or the like, of the components contained in the coating composition.

聚合起始劑、硬化劑及觸媒係可使用各種之物。又，聚合起始劑、硬化劑及觸媒係可分別單獨使用，也可同時使用複數的聚合起始劑、硬化劑及觸媒。再者，亦可併用酸性觸媒或熱聚合起始劑。就酸性觸媒之例而言，可舉出鹽酸水溶液、甲酸、醋酸等。就熱聚合起始劑之例而言，可舉出過氧化物、偶氮化合物。另外，就光聚合起始劑之例而言，可舉出烷基苯酮系化合物、含硫系化合物、醯基膦氧化物系化合物、胺系化合 物等。 Various polymerization initiators, hardeners, and catalysts can be used. The polymerization initiator, curing agent, and catalyst may be used individually, or a plurality of polymerization initiators, curing agents, and catalysts may be used together. Furthermore, an acidic catalyst or a thermal polymerization initiator may be used in combination. Examples of the acidic catalyst include aqueous hydrochloric acid solution, formic acid, and acetic acid. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkyl phenone-based compounds, sulfur-containing compounds, fluorenylphosphine oxide-based compounds, and amine-based compounds. Things.

就光聚合起始劑而言，從硬化性之點來看，較佳為烷基苯酮系化合物。就烷基苯酮系化合物之具體例而言，可舉出1-羥基-環己基-苯基-酮、2,2-二甲氧基-1,2-二苯基乙-1-酮、2-甲基-1-(4-甲硫基苯基)-2-嗎啉代丙-1-酮、2-苄基-2-二甲基胺基-1-(4-苯基)-1-丁烷、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-(4-苯基)-1-丁烷、2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)-1-丁烷、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁烷、1-環己基-苯基酮、2-甲基-1-苯基丙-1-酮、1-[4-(2-乙氧基)-苯基]-2-羥基-2-甲基-1-丙-1-酮、雙(2-苯基-2-氧代乙酸)氧基雙乙烯、及此等之材料經高分子量化者等。 The photopolymerization initiator is preferably an alkyl phenone-based compound from the viewpoint of hardenability. Specific examples of the alkyl phenone-based compound include 1-hydroxy-cyclohexyl-phenyl-one, 2,2-dimethoxy-1,2-diphenylethyl-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-phenyl)- 1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- (4-phenyl) -1-butane, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -[4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropan-1-one, 1- [4- ( 2-ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, and the like Materials that have been quantified by polymers.

又，只要是不妨礙本發明的效果之範圍，則於為了形成表面層而使用的塗料組成物A、塗料組成物B中，亦可添加均平劑、紫外線吸收劑、滑劑、抗靜電劑等。藉此而表面層可含有均平劑、紫外線吸收劑、滑劑、抗靜電劑等。就均平劑之例而言，可舉出丙烯酸共聚物或矽氧系、氟系之均平劑。就紫外線吸收劑之具體例而言，可舉出二苯基酮系、苯并***系、草酸苯胺系、三系及受阻胺系之紫外線吸收劑。就抗靜電劑之例而言，可舉出鋰鹽、鈉鹽、鉀鹽、銣鹽、銫鹽、鎂鹽、鈣鹽等之金屬鹽。 Moreover, as long as it is in the range which does not inhibit the effect of the present invention, a leveling agent, an ultraviolet absorber, a slip agent, and an antistatic agent may be added to the coating composition A and the coating composition B used for forming the surface layer. Wait. Thereby, the surface layer may contain a leveling agent, an ultraviolet absorber, a slip agent, an antistatic agent, and the like. Examples of the leveling agent include acrylic copolymers, silicone-based, and fluorine-based leveling agents. Specific examples of the ultraviolet absorber include diphenyl ketone, benzotriazole, anilide oxalate, and triphenyl UV absorbing agent of series and hindered amine series. Examples of the antistatic agent include metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, and calcium salts.

[積層薄膜之製造方法] [Manufacturing method of laminated film]

本發明的積層薄膜之製造方法更佳為使用藉由將至少前述的塗料組成物A與塗料組成物B，逐次或同時地在 前述的支撐基材上塗布-乾燥-硬化而形成之製造方法。 The manufacturing method of the laminated film of the present invention is more preferably one in which at least the aforementioned coating composition A and coating composition B are sequentially or simultaneously applied. The manufacturing method of coating-drying-hardening on the aforementioned support substrate.

此處所謂的「逐次地塗布」，就是意圖在將1種類的塗料組成物塗布-乾燥-硬化後，接著將種類不同的塗料組成物塗布-乾燥-硬化，藉此而形成表面層者。藉由在本製造方法中適宜選擇所用的塗料組成物之種類、數目，而可控制表面層的表面側-基材側的彈性模數之大小或梯度、基材與表面層的彈性模數之大小，更藉由適宜選擇塗料組成物之種類、組成、乾燥條件、硬化條件，而可階段性或連續性地控制表面層內的彈性模數分布之形態。 The "sequential coating" herein is intended to form a surface layer by coating-drying-hardening one type of coating composition and then coating-drying-hardening different types of coating composition. By appropriately selecting the type and number of the coating composition used in this manufacturing method, the size or gradient of the elastic modulus of the surface side of the surface layer to the substrate side, and the elastic modulus of the substrate and the surface layer can be controlled. The size can also control the shape of the elastic modulus distribution in the surface layer stepwise or continuously by appropriately selecting the type, composition, drying conditions, and hardening conditions of the coating composition.

就另1個製造方法而言，係藉由將2種類以上的塗料組成物在支撐基材上「同時地」塗布、乾燥、硬化而形成之方法。塗料組成物之種類的數目只要是2種類以上，則沒有特別的規定。此處，所謂的「同時塗布」，就是意圖在塗布步驟中於支撐基材上，將2種類以上的液膜塗布後，乾燥、硬化。 The other manufacturing method is a method in which two or more kinds of coating compositions are coated, dried, and cured "simultaneously" on a supporting substrate. The number of types of coating composition is not particularly limited as long as it is two or more. Here, the "simultaneous coating" means that two or more types of liquid films are coated on the supporting substrate in the coating step, and then dried and hardened.

本製造方法中，塗布方法為將前述的塗料組成物逐次地塗布時，較佳為藉由以浸塗法、輥塗法、線棒塗布法、凹版塗布法或模頭塗布法(美國專利第2681294號說明書)等，塗布於支撐基材等上而形成表面層 In this manufacturing method, when the coating method is to apply the aforementioned coating composition one by one, it is preferable to use a dip coating method, a roll coating method, a bar coating method, a gravure coating method, or a die coating method (U.S. Patent No. No. 2681294), etc., and coated on a supporting substrate and the like to form a surface layer

又，將前述之2種類以上的塗料組成物同時塗布時，可為以塗布前的狀態依順序積層液膜後塗布之「多層滑動模頭塗布」(第3圖)，或於基材上同時地進行塗布與積層之「多層狹縫模頭塗布」(第4圖)，於支撐基材上形成 1層的液膜後，於未乾燥之狀態下使另1層積層之「濕疊濕(wet-on-wet)塗布」(第5圖)等之任一者。 In addition, when the two or more types of coating compositions described above are applied simultaneously, it may be a "multi-layer sliding die coating" (Figure 3), which is applied after the liquid film is sequentially laminated in the state before coating, or simultaneously on the substrate. "Multi-layer slit die coating" (Fig. 4) of coating and lamination is performed on the substrate and formed on a supporting substrate After one layer of the liquid film, any one of "wet-on-wet coating" (Fig. 5) and the like of the other layer is laminated in an undried state.

其次，將已塗布於支撐基材等上的液膜乾燥。較佳為除了自所得之積層薄膜中完全地去除溶劑，還於乾燥步驟中伴隨液膜的加熱。 Next, the liquid film which has been applied to a supporting substrate or the like is dried. In addition to completely removing the solvent from the obtained laminated film, it is preferable to accompany the heating of the liquid film in the drying step.

關於乾燥方法，可舉出傳熱乾燥(對於高熱物體的緊貼)、對流傳熱(熱風)、輻射傳熱(紅外線)、其他(微波、感應加熱)等。其中，於本發明之製造方法中，從必須精密地即使在寬度方向中亦使乾燥速度成為均勻來看，較佳為使用對流傳熱或輻射傳熱之方式。 Examples of the drying method include heat transfer drying (adherence to a hot object), convective heat transfer (hot air), radiant heat transfer (infrared), and other (microwave and induction heating). Among them, in the manufacturing method of the present invention, it is preferable to use a method of convective heat transfer or radiant heat transfer because the drying speed must be made uniform evenly in the width direction.

再者，亦可進行藉由照射熱或能量線之進一步的硬化操作(硬化步驟)。於硬化步驟中，使用塗料組成物A及塗料組成物B，而在以熱硬化的情況中，較佳為由室溫至200℃以下，從硬化反應的活性化能量之觀點來看，更佳為80℃以上200℃以下，尤佳為100℃以上200℃以下。 Further, a further hardening operation (hardening step) by irradiating heat or energy rays may be performed. In the hardening step, the coating composition A and the coating composition B are used. In the case of thermal curing, the temperature is preferably from room temperature to 200 ° C or lower. From the viewpoint of the activation energy of the curing reaction, it is more preferable. The temperature is 80 ° C to 200 ° C, and more preferably 100 ° C to 200 ° C.

又，藉由活性能量線而硬化時，從通用性之點來看，較佳為電子線(EB線)及/或紫外線(UV線)。另外，藉由紫外線而進行硬化時，從可防止氧阻礙來看，較佳為氧濃度係儘可能地低，更佳為在氮氣環境下(氮沖洗)進行硬化。氧濃度高時，最表面之硬化被阻礙，表面的硬化變得不充分，會有耐指紋性變不充分之情況。 In addition, in the case of hardening by active energy rays, in terms of versatility, electron rays (EB rays) and / or ultraviolet rays (UV rays) are preferred. In addition, when curing is performed by ultraviolet rays, it is preferred that the oxygen concentration be as low as possible from the viewpoint of preventing oxygen blocking, and it is more preferable that the curing is performed under a nitrogen atmosphere (nitrogen flushing). When the oxygen concentration is high, the hardening of the outermost surface is hindered, the hardening of the surface becomes insufficient, and the fingerprint resistance may become insufficient.

又，就照射紫外線時所用之紫外線燈的種類而言，可舉出例如放電燈方式、閃光方式、雷射方式、無電極燈方式等。用放電燈方式的高壓水銀燈使紫外 線硬化時，紫外線之照度以100~3,000mW/cm²，更佳為200~2,000mW/cm²，尤佳為300~1,500mW/cm²之條件來進行紫外線照射為宜為，紫外線之累積光量以100~3,000mJ/cm²，更佳為200~2,000mJ/cm²，尤佳為在300~1,500mJ/cm²之條件來進行紫外線照射為宜。此處，紫外線之照度就是每單位面積受到的照射強度，隨著燈輸出、發光光譜效率、發光燈泡的直徑、反射鏡的設計及與被照射物的光源距離而變化。然而，照度並不隨著搬送速率而變化。又，紫外線累積光量就是每單位面積受到的照射能量，為到達其表面之光子的總量。累積光量係反比於通過光源下的照射速度，且與照射次數和燈數成比例。 The types of ultraviolet lamps used when irradiating ultraviolet rays include, for example, a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. When the ultraviolet light is hardened by a high-pressure mercury lamp using a discharge lamp method, the ultraviolet light is irradiated under conditions of 100 to 3,000 mW / cm ² , more preferably 200 to 2,000 mW / cm ² , and particularly preferably 300 to 1,500 mW / cm ² . preferably is irradiated, the accumulated light quantity of ultraviolet at 100 ~ 3,000mJ / cm ^2, more preferably 200 ~ 2,000mJ / cm ^2, particularly preferably at 300 ~ 1,500mJ / cm ² of conditions appropriate to ultraviolet irradiation. Here, the illuminance of ultraviolet rays is the irradiation intensity per unit area, which varies with the lamp output, the spectral efficiency of light emission, the diameter of the light bulb, the design of the reflector, and the distance from the light source of the object to be irradiated. However, the illuminance does not change with the transfer rate. The cumulative amount of ultraviolet light is the irradiation energy received per unit area, which is the total amount of photons reaching the surface. The accumulated light amount is inversely proportional to the irradiation speed under the passing light source, and is proportional to the number of irradiations and the number of lamps.

[用途例] [Application example]

本發明之積層薄膜由於耐擦傷性優異，而可廣泛使用於例如電化製品或汽車的內裝構件、建築構件等。 Since the laminated film of the present invention is excellent in abrasion resistance, it can be widely used in, for example, electrochemical components, automobile interior components, and building components.

舉例來說，可適用於眼鏡‧太陽眼鏡、包裝盒、食品容器等之塑膠成型品、智慧型手機之殼體、觸控面板、鍵盤、電視‧空調機之遙控器等的家電製品、建築物、儀表板、行車導航器‧觸控面板、車內後視鏡等之車輛內裝品、及各種的印刷物之各自的表面等。 For example, it can be applied to plastic products such as glasses, sunglasses, packaging boxes, food containers, housings for smart phones, touch panels, keyboards, remote controls for televisions, air conditioners, and buildings. , Dashboard, driving navigator, touch panel, interior mirrors and other vehicle interior products, as well as various surfaces of various printed materials.

[實施例] [Example]

其次，基於實施例而說明本發明，惟本發明並非必定為此等所限定者。 Next, the present invention will be described based on examples, but the present invention is not necessarily limited to these.

<氟化合物D> <Fluorine compound D>

[氟化合物D1甲基乙基酮/甲基異丁基酮溶液] [Fluorine compound D1 methyl ethyl ketone / methyl isobutyl ketone solution]

作為氟化合物D1，使用包含氟聚醚部位的丙烯酸酯化合物(「Megafac」(註冊商標)RS-75 DIC股份有限公司製 固體成分濃度40質量%的甲基乙基酮/甲基異丁基酮溶液)。 As the fluorine compound D1, an acrylate compound containing a fluoropolyether moiety ("Megafac" (registered trademark) RS-75, manufactured by DIC Corporation, methyl ethyl ketone / methyl isobutyl ketone with a solid content concentration of 40% by mass, was used. Solution).

<聚矽氧烷化合物之合成> <Synthesis of Polysiloxane Compound>

[聚矽氧烷(a)] [Polysiloxane (a)]

於具備攪拌機、溫度計、冷凝器及氮氣導入管的500ml容量之燒瓶中，加入106質量份的乙醇、320質量份的四乙氧基矽烷、21質量份的去離子水及1質量份的1質量%鹽酸，在85℃保持2小時後，邊升溫邊回收乙醇，在180℃保持3小時。然後，冷卻而得到黏調的(聚)矽氧烷(a)。 In a 500 ml capacity flask equipped with a stirrer, thermometer, condenser, and nitrogen introduction tube, 106 parts by mass of ethanol, 320 parts by mass of tetraethoxysilane, 21 parts by mass of deionized water, and 1 part by mass of 1 part were added. % Hydrochloric acid, which was kept at 85 ° C for 2 hours, ethanol was recovered while the temperature was raised, and kept at 180 ° C for 3 hours. Then, it cooled, and the viscosity-adjusted (poly) siloxane (a) was obtained.

<聚二甲基矽氧烷化合物之合成> <Synthesis of Polydimethylsiloxane Compound>

[聚二甲基矽氧烷系嵌段共聚物(a)甲苯溶液] [Polydimethylsiloxane block copolymer (a) toluene solution]

使用與聚矽氧烷(a)之合成同樣的裝置，加入50質量份的甲苯及50質量份的甲基異丁基酮、20質量份的聚二甲基矽氧烷系高分子聚合起始劑(和光純藥股份有限公司製VPS-0501)、18質量份的甲基丙烯酸甲酯、38質量份的甲基丙烯酸丁酯、23質量份的甲基丙烯酸2-羥基乙酯、1重量份的甲基丙烯酸及0.5質量份的1-硫甘油，在180℃使反應8小時而得到聚二甲基矽氧烷系嵌段共聚物(a)的固體成分濃度50質量%之甲苯溶液。 Using the same apparatus as the synthesis of polysiloxane (a), 50 parts by mass of toluene, 50 parts by mass of methyl isobutyl ketone, and 20 parts by mass of polydimethylsiloxane-based polymer were added. Agent (VPS-0501 manufactured by Wako Pure Chemical Industries, Ltd.), 18 parts by mass of methyl methacrylate, 38 parts by mass of butyl methacrylate, 23 parts by mass of 2-hydroxyethyl methacrylate, and 1 part by weight The methacrylic acid and 0.5 parts by mass of 1-thioglycerin were reacted at 180 ° C. for 8 hours to obtain a toluene solution having a solid content concentration of 50% by mass of the polydimethylsiloxane block copolymer (a).

[聚二甲基矽氧烷化合物(b)] [Polydimethylsiloxane compound (b)]

作為聚二甲基矽氧烷化合物(b)，使用DAICEL CYTEC股份有限公司製EBECRYL350(2官能，聚矽氧丙烯酸酯)。 As the polydimethylsiloxane compound (b), EBECRYL350 (bifunctional, polysiloxane) manufactured by DAICEL CYTEC Co., Ltd. was used.

<胺基甲酸酯丙烯酸酯之合成> <Synthesis of Urethane Acrylate>

[胺基甲酸酯丙烯酸酯1之甲苯溶液] [Toluene solution of urethane acrylate 1]

混合50質量份的甲苯、50質量份的六亞甲基二異氰酸酯之異三聚氰酸酯改性類型(三井化學股份有限公司製「Takenate」(註冊商標)D-170N)、76質量份的聚己內酯改性丙烯酸羥基乙酯(DAICEL化學工業股份有限公司製Placcel FA5)、0.02質量份的月桂酸二丁錫及0.02質量份的氫醌單甲基醚，在70℃保持5小時。然後，添加79質量份的甲苯，得到固體成分濃度50質量%的胺基甲酸酯丙烯酸酯1之甲苯溶液。 50 parts by mass of toluene, 50 parts by mass of hexamethylene diisocyanate isotricyanate modified type ("Takenate" (registered trademark) D-170N manufactured by Mitsui Chemicals Co., Ltd.), and 76 parts by mass of Polycaprolactone-modified hydroxyethyl acrylate (Placcel FA5 manufactured by DAICEL Chemical Industry Co., Ltd.), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were kept at 70 ° C. for 5 hours. Then, 79 parts by mass of toluene was added to obtain a toluene solution of the urethane acrylate 1 having a solid content concentration of 50% by mass.

[胺基甲酸酯丙烯酸酯2之甲苯溶液] [Toluene solution of urethane acrylate 2]

混合100質量份的甲苯、50質量份的甲基-2,6-二異氰酸酯己酸酯及119質量份的聚碳酸酯二醇(DAICEL化學工業股份有限公司製Placcel CD-210HL)，升溫至40℃為止，保持8小時。然後，添加28質量份的丙烯酸2-羥基乙酯、5質量份的二季戊四醇六丙烯酸酯、0.02質量份的氫醌單甲基醚，在70℃保持30分鐘後，添加0.02質量份的月桂酸二丁錫，在80℃保持6小時。而且，最後添加97質量份的甲苯，得到固體成分濃度50質量%的胺基甲酸酯丙烯酸酯2之甲苯溶液。 100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate, and 119 parts by mass of polycarbonate diol (Placcel CD-210HL, manufactured by DAICEL Chemical Industry Co., Ltd.) were mixed, and the temperature was raised to 40. The temperature was maintained at 8 ° C for 8 hours. Then, 28 parts by mass of 2-hydroxyethyl acrylate, 5 parts by mass of dipentaerythritol hexaacrylate, and 0.02 parts by mass of hydroquinone monomethyl ether were added, and after maintaining at 70 ° C for 30 minutes, 0.02 parts by mass of lauric acid was added. Dibutyltin was held at 80 ° C for 6 hours. Then, 97 parts by mass of toluene was finally added to obtain a toluene solution of the urethane acrylate 2 having a solid content concentration of 50% by mass.

[胺基甲酸酯丙烯酸酯3之甲苯溶液] [Toluene solution of urethane acrylate 3]

加入50質量份的六亞甲基二異氰酸酯之異三聚氰酸酯改性體(三井化學股份有限公司製「Takenate」(註冊商標)D-170N，異氰酸酯基含量：20.9質量%)、53質量份的聚乙二醇單丙烯酸酯(日油股份有限公司製「Blemmer」( 註冊商標)AE-150(羥值：264(mgKOH/g))、0.02質量份的月桂酸二丁錫及0.02質量份的氫醌單甲基醚。然後，在70℃保持5小時而進行反應。反應結束後，於反應液中添加102質量份的甲基乙基酮(以下稱為MEK)，得到固體成分濃度50質量%的胺基甲酸酯丙烯酸酯3之甲苯溶液。 50 parts by mass of hexamethylene diisocyanate-modified isocyanurate ("Takenate" (registered trademark) D-170N, manufactured by Mitsui Chemicals Corporation, isocyanate group content: 20.9% by mass), 53% by mass Parts of polyethylene glycol monoacrylate ("Blemmer" manufactured by Nippon Oil Co., Ltd. Registered trademark) AE-150 (hydroxyl value: 264 (mgKOH / g)), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether. Thereafter, the reaction was carried out by keeping the temperature at 70 ° C for 5 hours. After the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction solution to obtain a toluene solution of the urethane acrylate 3 having a solid content concentration of 50% by mass.

[丙烯酸多元醇1] [Acrylic polyol 1]

作為丙烯酸多元醇1，使用含有氫氧基的丙烯酸多元醇(「Takelac」(註冊商標)UA-702三井化學股份有限公司製 固體成分濃度50質量%羥值：50mgKOH/g)。 As the acrylic polyol 1, a hydroxyl group-containing acrylic polyol ("Takelac" (registered trademark) UA-702 manufactured by Mitsui Chemicals Co., Ltd., solid content concentration 50% by mass hydroxyl value: 50mgKOH / g) was used.

[丙烯酸多元醇2] [Acrylic polyol 2]

作為丙烯酸多元醇2，使用含有氫氧基的丙烯酸多元醇(「Acrydic」(註冊商標)A-823 DIC股份有限公司製固體成分濃度50質量% 羥值30mgKOH/g)。 As the acrylic polyol 2, a hydroxyl group-containing acrylic polyol ("Acrydic" (registered trademark) A-823, manufactured by DIC Co., Ltd., having a solid content concentration of 50% by mass and a hydroxyl value of 30 mgKOH / g) was used.

[異氰酸酯化合物1] [Isocyanate compound 1]

作為異氰酸酯化合物，使用甲苯二異氰酸酯(「Coronate」(註冊商標)Coronate L日本聚胺基甲酸酯工業股份有限公司 固體成分濃度75質量% NCO含量13.5質量%)。 As the isocyanate compound, toluene diisocyanate ("Coronate" (registered trademark) Coronate L Japan Polyurethane Industry Co., Ltd. solid content concentration 75% by mass NCO content 13.5% by mass)) was used.

[多官能丙烯酸酯1] [Multifunctional acrylate 1]

作為多官能丙烯酸酯單體1，使用二季戊四醇六丙烯酸酯(「KAYARAD」DPHA日本化藥股份有限公司製，固體成分濃度100質量%)。 As the polyfunctional acrylate monomer 1, dipentaerythritol hexaacrylate ("KAYARAD" DPHA Nippon Kayaku Co., Ltd., solid content concentration 100% by mass) was used.

[多官能丙烯酸酯2] [Multifunctional acrylate 2]

作為多官能丙烯酸酯2，使用胺基甲酸酯丙烯酸酯寡聚物(「SHIKOH」(註冊商標)UV-3310B日本合成化學 工業股份有限公司製，固體成分濃度100質量%)。 As the polyfunctional acrylate 2, a urethane acrylate oligomer ("SHIKOH" (registered trademark) UV-3310B) was used. Industrial Co., Ltd., solid content concentration 100% by mass).

[多官能丙烯酸酯3] [Multifunctional acrylate 3]

作為多官能丙烯酸酯3，使用胺基甲酸酯丙烯酸酯寡聚物(「SHIKOH」(註冊商標)UV-1700B日本合成化學工業股份有限公司製，固體成分濃度100質量%)。 As the polyfunctional acrylate 3, a urethane acrylate oligomer ("SHIKOH" (registered trademark) UV-1700B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., with a solid content concentration of 100% by mass) was used.

[多官能丙烯酸酯4] [Multifunctional acrylate 4]

作為多官能丙烯酸酯4，使用胺基甲酸酯丙烯酸酯寡聚物(「SHIKOH」(註冊商標)UV-2750B日本合成化學工業股份有限公司製，固體成分濃度100質量%)。 As the polyfunctional acrylate 4, a urethane acrylate oligomer ("SHIKOH" (registered trademark) UV-2750B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration of 100% by mass) was used.

[丙烯酸聚合物1之合成] [Synthesis of acrylic polymer 1]

將24質量份的二月桂醯基過氧化物(Peroyl L日油股份有限公司製)加到495質量份的甲基乙基酮中，在70℃加溫30分鐘而使溶解，費4小時滴下混合有50質量份的甲基丙烯酸、90質量份的丙烯酸丁酯、100質量份的甲基丙烯酸甲酯及2.4質量份的4-甲基-2,4-二苯基戊烯-1(Nofmer MSD日油股份有限公司製)之溶液，攪拌聚合。然後，更在80℃進行2小時攪拌，得到含有親水性官能基的固體成分濃度35質量%之丙烯酸聚合物1的甲基乙基酮溶液(重量平均分子量6,000)。 24 parts by mass of dilauroyl peroxide (manufactured by Peroyl L Nippon Oil Co., Ltd.) was added to 495 parts by mass of methyl ethyl ketone, and the solution was dissolved by heating at 70 ° C for 30 minutes, and the solution was dripped over 4 hours. 50 parts by mass of methacrylic acid, 90 parts by mass of butyl acrylate, 100 parts by mass of methyl methacrylate, and 2.4 parts by mass of 4-methyl-2,4-diphenylpentene-1 (Nofmer MSD (Nippon Oil Co., Ltd.) solution, and stirred and polymerized. Then, it stirred at 80 degreeC for 2 hours, and obtained the methyl ethyl ketone solution (weight average molecular weight 6,000) of the acrylic polymer 1 containing the solid content concentration of the hydrophilic functional group of 35 mass%.

<塗料組成物A之調合> <Blend of Coating Composition A>

[塗料組成物A1] [Coating composition A1]

混合下述材料，使用甲基乙基酮稀釋，得到固體成分濃度40質量%的塗料組成物A1。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1 having a solid content concentration of 40% by mass.

‧氟化合物D1的固體成分濃度40質量%-甲基乙基酮/甲基異丁基酮溶液 3.8質量份 ‧Solid component concentration of fluorine compound D1 is 40% by mass-3.8 parts by mass of methyl ethyl ketone / methyl isobutyl ketone solution

(「Irgacure」(註冊商標)184 BASF日本股份有限公司)。 ("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[塗料組成物A2] [Coating composition A2]

混合下述材料，使用甲基乙基酮稀釋，得到固體成分濃度40質量%的塗料組成物A2。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A2 having a solid content concentration of 40% by mass.

(「Irgacure」(註冊商標)184 BASF日本股份有限公司)。 ("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[塗料組成物A3] [Coating composition A3]

混合下述材料，使用甲基乙基酮稀釋，得到固體成分濃度40質量%的塗料組成物A3。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A3 having a solid content concentration of 40% by mass.

(「Irgacure」(註冊商標)184 BASF日本股份有限公司)。 ("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[塗料組成物A4] [Coating composition A4]

混合下述材料，使用甲基乙基酮稀釋，得到固體成分濃度40質量%的塗料組成物A4。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 having a solid content concentration of 40% by mass.

(「Irgacure」(註冊商標)184 BASF日本股份有限公司)。 ("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[塗料組成物B1] [Coating composition B1]

混合下述材料，使用甲基乙基酮稀釋，得到固體成分濃度20質量%的塗料組成物B1。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B1 having a solid content concentration of 20% by mass.

(「Irgacure」(註冊商標)184 BASF日本股份有限公司)。 ("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[塗料組成物B2] [Coating composition B2]

混合下述材料，使用甲基乙基酮稀釋，得到固體成分濃度20質量%的塗料組成物B2。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B2 having a solid content concentration of 20% by mass.

[塗料組成物B3] [Coating composition B3]

混合下述材料，使用甲基乙基酮稀釋，得到固體成分濃度20質量%的塗料組成物B3。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B3 having a solid content concentration of 20% by mass.

[塗料組成物B4] [Coating composition B4]

混合下述材料，使用甲基乙基酮稀釋，得到固體成分濃度20質量%的塗料組成物B4。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B4 having a solid content concentration of 20% by mass.

(「Irgacure」(註冊商標)184 BASF日本股份有限公司)。 ("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[塗料組成物B5] [Coating composition B5]

混合下述材料，使用甲基乙基酮稀釋，得到固體成分濃度20質量%的塗料組成物B5。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B5 having a solid content concentration of 20% by mass.

(「Irgacure」(註冊商標)184 BASF日本股份有限公司)。 ("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[塗料組成物B6] [Coating composition B6]

混合下述材料，使用甲基乙基酮稀釋，得到固體成分濃度20質量%的塗料組成物B6。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B6 having a solid content concentration of 20% by mass.

(「Irgacure」(註冊商標)184 BASF日本股份有限公司)。 ("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

<積層薄膜之製造方法> <Manufacturing method of laminated film>

[積層薄膜之作成方法1] [Laminating film production method 1]

作為支撐基材(成為C層之層)，使用在PET樹脂薄膜上塗布有易接著性塗料的厚度100μm之「Lumirror」(註冊商標)U48(東麗股份有限公司製)。於支撐基材上，使用藉由狹縫模頭塗布機的連續塗布裝置，以乾燥後的表面層之厚度成為指定膜厚的方式來調整由狹縫之吐出流量，而塗布塗料組成物B，其次以下述之條件進行乾燥步 驟、硬化步驟，而在支撐基材上形成B層。 As a supporting substrate (the layer that becomes the C layer), "Lumirror" (registered trademark) U48 (manufactured by Toray Co., Ltd.) having a thickness of 100 µm and having an easily-adhesive coating applied to a PET resin film was used. Using a continuous coating device using a slit die coater on a supporting substrate, the coating composition B is applied so that the discharge flow rate from the slit is adjusted so that the thickness of the dried surface layer becomes a specified film thickness. Next, the drying step is performed under the following conditions And a hardening step to form a layer B on the supporting substrate.

「乾燥步驟」 "Drying step"

送風溫濕度：溫度：80℃ Supply air temperature and humidity: Temperature: 80 ℃

風速：塗布面側：5m/秒，反塗布面側：5m/秒 Wind speed: 5m / s on the coating side, 5m / s on the reverse coating side

風向：塗布面側：對於基材之面成平行，反塗布面側：對於基材之面成垂直 Wind direction: coating surface side: parallel to the substrate surface, reverse coating surface side: vertical to the substrate surface

滯留時間：2分鐘 Detention time: 2 minutes

「硬化步驟」 "Hardening step"

累積光量：120mJ/cm² Cumulative light quantity: 120mJ / cm ²

氧濃度：大氣環境。 Oxygen concentration: atmospheric environment.

再者，使用相同裝置，於上述所得之B層上 ，以乾燥後的表面層之厚度成為指定膜厚的方式，調整來自狹縫的吐出流量，塗布塗料組成物A，其次以下述之條件進行乾燥步驟、硬化步驟，得到積層薄膜。 Furthermore, using the same device, on the B layer obtained above The coating composition A was applied so that the discharge flow rate from the slit was adjusted so that the thickness of the surface layer after drying became a predetermined film thickness, and then a drying step and a curing step were performed under the following conditions to obtain a laminated film.

「乾燥步驟」 "Drying step"

送風溫濕度：溫度：80℃ Supply air temperature and humidity: Temperature: 80 ℃

風速：塗布面側：5m/秒，反塗布面側：5m/秒 Wind speed: 5m / s on the coating side, 5m / s on the reverse coating side

風向：塗布面側：對於基材之面成平行，反塗布面側：對於基材之面成垂直 Wind direction: coating surface side: parallel to the substrate surface, reverse coating surface side: vertical to the substrate surface

滯留時間：2分鐘 Detention time: 2 minutes

「硬化步驟」 "Hardening step"

累積光量：120mJ/cm² Cumulative light quantity: 120mJ / cm ²

氧濃度：200ppm(體積比率)以下。 Oxygen concentration: 200 ppm (volume ratio) or less.

[積層薄膜之作成方法2] [Laminated film production method 2]

作為支撐基材(成為C層之層)，使用在PET樹脂薄膜 上塗布有易接著性塗料的厚度100μm之「Lumirror」(註冊商標)U48(東麗股份有限公司製)。於支撐基材上，使用狹縫模頭塗布機的連續塗布裝置，以乾燥後的表面層之厚度成為指定膜厚的方式來調整由狹縫的吐出流量，而塗布塗料組成物B，其次以下述之條件進行乾燥步驟、硬化步驟，而在支撐基材上形成B層。 Used as a support substrate (to be the layer of layer C), used in PET resin film "Lumirror" (registered trademark) U48 (manufactured by Toray Industries, Ltd.) with a thickness of 100 µm coated with an easily-adhesive coating. On a supporting substrate, a continuous coating device using a slit die coater is used to apply the coating composition B by adjusting the discharge flow rate from the slit so that the thickness of the surface layer after drying becomes a specified film thickness, and the second or lower A drying step and a hardening step are performed under the conditions described above to form a layer B on the supporting substrate.

「乾燥步驟」 "Drying step"

送風溫濕度：溫度：80℃ Supply air temperature and humidity: Temperature: 80 ℃

風速：塗布面側：5m/秒、反塗布面側：5m/秒 Wind speed: coating surface side: 5m / s, reverse coating surface side: 5m / s

風向：塗布面側：對於基材之面成平行，反塗布面側：對於基材之面成垂直 Wind direction: coating surface side: parallel to the substrate surface, reverse coating surface side: vertical to the substrate surface

滯留時間：2分鐘 Detention time: 2 minutes

再者，使用相同裝置，於上述所得之B層上，以乾燥後的表面層之厚度成為指定膜厚的方式來調整由狹縫的吐出流量，而塗布塗料組成物A，其次以下述之條件進行乾燥步驟、硬化步驟，得到積層薄膜。 Furthermore, using the same device, on the layer B obtained above, the coating composition A was applied so that the discharge flow rate from the slit was adjusted so that the thickness of the surface layer after drying became the specified film thickness, followed by the following conditions A drying step and a hardening step are performed to obtain a laminated film.

「乾燥步驟」 "Drying step"

送風溫濕度：溫度：80℃ Supply air temperature and humidity: Temperature: 80 ℃

風速：塗布面側：5m/秒，反塗布面側：5m/秒 Wind speed: 5m / s on the coating side, 5m / s on the reverse coating side

風向：塗布面側：對於基材之面成平行，反塗布面側：對於基材之面成垂直 Wind direction: coating surface side: parallel to the substrate surface, reverse coating surface side: vertical to the substrate surface

滯留時間：2分鐘 Detention time: 2 minutes

「硬化步驟」 "Hardening step"

累積光量：120mJ/cm² Cumulative light quantity: 120mJ / cm ²

氧濃度：200ppm(體積比率)以下。 Oxygen concentration: 200 ppm (volume ratio) or less.

[積層薄膜之作成方法3] [Laminating film production method 3]

作為支撐基材(成為C層之層)，使用在PET樹脂薄膜上塗布有易接著性塗料的厚度100μm之「Lumirror」(註冊商標)U48(東麗股份有限公司製)。於支撐基材上，使用狹縫模頭塗布機的連續塗布裝置，以乾燥後的表面層之厚度成為指定膜厚的方式來調整由狹縫的吐出流量，而塗布塗料組成物A，其次以下述之條件進行乾燥步驟、硬化步驟，而在支撐基材上形成A層。 As a supporting substrate (the layer that becomes the C layer), "Lumirror" (registered trademark) U48 (manufactured by Toray Co., Ltd.) having a thickness of 100 µm and having an easily-adhesive coating applied to a PET resin film was used. On the supporting substrate, a continuous coating device using a slit die coater is used to adjust the discharge flow rate from the slit so that the thickness of the dried surface layer becomes a predetermined film thickness, and then coating composition A is applied, followed by the following A drying step and a hardening step are performed under the conditions described above to form an A layer on the supporting substrate.

「乾燥步驟」 "Drying step"

送風溫濕度：溫度：80℃ Supply air temperature and humidity: Temperature: 80 ℃

風速：塗布面側：5m/秒，反塗布面側：5m/秒 Wind speed: 5m / s on the coating side, 5m / s on the reverse coating side

風向：塗布面側：對於基材之面成平行，反塗布面側：對於基材之面成垂直 Wind direction: coating surface side: parallel to the substrate surface, reverse coating surface side: vertical to the substrate surface

滯留時間：2分鐘 Detention time: 2 minutes

「硬化步驟」 "Hardening step"

累積光量：120mJ/cm² Cumulative light quantity: 120mJ / cm ²

氧濃度：200ppm(體積比率)以下。 Oxygen concentration: 200 ppm (volume ratio) or less.

藉由以上之方法，作成實施例1~13、比較例1~2之積層薄膜。將對應於各實施例、比較例的上述積層薄膜之作成方法、所使用的塗料組成物、各層的膜厚記載於表1。 By the above methods, laminated films of Examples 1 to 13 and Comparative Examples 1 to 2 were prepared. Table 1 shows the methods for preparing the laminated films corresponding to the respective examples and comparative examples, the coating composition used, and the film thickness of each layer.

<積層薄膜之評價> <Evaluation of laminated film>

對於所製作的積層薄膜，實施以下所示的性能評價，於表2顯示所得之結果。除了特別事先指明之情況，測定係在各實施例、比較例中，針對1個樣品，改變位置進 行3次測定，使用其平均值。 The produced laminated film was subjected to performance evaluation shown below, and the results obtained are shown in Table 2. Except for the cases specified in advance, the measurement is performed in each of the examples and comparative examples by changing the position of one sample. Three measurements were performed, and the average value was used.

[儲存彈性模數、玻璃轉移溫度之測定] [Measurement of storage elastic modulus and glass transition temperature]

A.積層薄膜截面之確認 A. Confirmation of cross section of laminated film

用刀具切出積層薄膜，以電顯用環氧樹脂(日新EM公司製Quetol 812)包埋，在60℃的烘箱中費48小時使該環氧樹脂硬化後，以超薄切片機(LEICA公司製Ultracut S)，製作厚度約100nm的超薄切片。 The laminated film was cut out with a cutter, embedded in an epoxy resin (Quetol 812, manufactured by Nisshin EM Co., Ltd.), and the epoxy resin was cured in an oven at 60 ° C for 48 hours, and then an ultra-thin slicer (LEICA Ultracut S) manufactured by the company produces ultra-thin sections with a thickness of about 100 nm.

將所製作的超薄切片搭載於應研商事公司製100網目的Cu柵上，使用日立製透射型電子顯微鏡(TEM)H-7100FA，以100kV的加速電壓進行TEM觀察，進行積層薄膜截面之觀察，確認表面層與支撐基材之場所。 The prepared ultra-thin section was mounted on a Cu mesh of 100 mesh manufactured by Oken Corporation, and a transmission electron microscope (TEM) H-7100FA manufactured by Hitachi was used for TEM observation at an acceleration voltage of 100 kV to observe the cross-section of the laminated film. Check the surface layer and the place where the substrate is supported.

B.超微小硬度計之測定 B. Determination of ultra-micro hardness tester

將上述超薄切片當作樣品，使用超微小硬度計(Hysitron公司製Tribo Indenter)，取得表面層與支撐基材的模數映射影像，算出儲存彈性模數、損失彈性模數，自儲存彈性模數與損失彈性模數之比求得損失正切(tanδ)，將所得之損失正切(tanδ)的峰值溫度當作玻璃轉移溫度(Tg)。 Using the ultra-thin slice as a sample, an ultra-micro hardness tester (Tribo Indenter manufactured by Hysitron) was used to obtain the modulus mapping image of the surface layer and the supporting substrate, and the storage elastic modulus and the lost elastic modulus were calculated. The ratio of the modulus to the loss elastic modulus is used to obtain the loss tangent (tan δ), and the peak temperature of the obtained loss tangent (tan δ) is taken as the glass transition temperature (Tg).

測定條件係於下述表示。 The measurement conditions are shown below.

測定裝置：Hysitron公司製Tribo Indenter Measuring device: Tribo Indenter by Hysitron

使用壓頭：鑽石製Cubecorner壓頭(曲率半徑50nm) Indenter: Diamond Cubecorner indenter (curvature radius 50nm)

測定視野：約30mm見方 Measurement field of view: about 30mm square

測定頻率：10Hz Measurement frequency: 10Hz

測定環境：-20℃~120℃‧大氣中 Measurement environment: -20 ℃ ~ 120 ℃ ‧in air

接觸荷重：0.3μN。 Contact load: 0.3 μN.

[原子力顯微鏡的彈性模數之測定] [Measurement of Elastic Modulus of Atomic Force Microscope]

將實施例1~13、比較例1~2之積層薄膜，藉由冷凍切片法切出截面，將該截面當作測定面而固定於專用的樣品固定台，使用ASYLUM科技製的原子力顯微鏡(AFM)「MFP-3DSA-J」與NANOSENSORS製的懸臂「R150-NCL-10(材質Si，彈簧常數48N/m，前端的曲率半徑150nm)」，以Contact模式於表面層之厚度方向垂直地測定力曲線(懸臂的移動速度2μm/s，最大壓入荷重2μN)。 Sections of the laminated films of Examples 1 to 13 and Comparative Examples 1 to 2 were cut out by a freezing section method, and the sections were used as measurement surfaces and fixed to a dedicated sample holder. An AFM (AFM) ) "MFP-3DSA-J" and cantilever "R150-NCL-10 (material Si, spring constant 48N / m, radius of curvature 150nm at the front end)" made by NANOSENSORS, measured the force perpendicularly in the thickness direction of the surface layer in the Contact mode Curve (movement speed of cantilever 2 μm / s, maximum indentation load 2 μN).

根據上述測定方法，對於表面層之厚度方向，求得自表面層的表面起10%之位置(位置1)的彈性模數(E1)、50%之位置(位置2)的彈性模數(E2)、99%之位置(位置3)的彈性模數(E3)。具體而言，係將積層薄膜切斷，並測定表面層截面中的厚度方向之各位置的彈性模數。 According to the above measurement method, for the thickness direction of the surface layer, the elastic modulus (E1) at a position (position 1) of 10% from the surface of the surface layer and the elastic modulus (E2) at a position (position 2) of 50% are obtained. ), The elastic modulus (E3) at the 99% position (position 3). Specifically, the laminated film is cut, and the elastic modulus of each position in the thickness direction in the cross section of the surface layer is measured.

[破裂延伸度] [Rupture elongation]

將積層薄膜在長度方向及寬度方向中切出長度150mm×寬度10mm之矩形，當作樣品。使用拉伸試驗機(ORIENTEC製Tensilon UCT-100)，初期拉伸夾頭間距離設為50mm，拉伸速度設為10mm/分鐘，而進行拉伸試驗。此時的測定環境為23℃‧65RH%。在伸張之時，觀察伸張中的樣品，如以目視在樣品的任何位置看到破裂(龜裂)發生就停止(以停止時的延伸度成為5之整數的方式進行調整)。接下來所測定的樣品係自停止時的延伸度起，依順序採集以5%單位降低伸張延伸度的樣品，最終地進行到以目視而樣品的任何位置變得沒有破裂發生的延伸度為止。 A rectangular shape with a length of 150 mm and a width of 10 mm was cut out of the laminated film in the length direction and the width direction, and used as a sample. The tensile test was performed using a tensile tester (Tensilon UCT-100 manufactured by ORIENTEC), with an initial tension chuck distance of 50 mm and a tensile speed of 10 mm / min. The measurement environment at this time was 23 ° C · 65RH%. At the time of stretching, observe the sample during stretching, and stop visually if a crack (crack) occurs anywhere on the sample (adjust so that the elongation at the time of stopping becomes an integer of 5). The samples to be measured next were collected in order from the elongation at the time of the stoppage, and samples in which the elongation was reduced by 5% units were collected in order, and finally, the elongation at which no breakage occurred at any position of the sample was visually observed.

切出所採集的樣品之破裂部分的薄膜截面，以3,000倍的倍率於透射型電子顯微鏡觀察截面，將表面層的平均厚度之50%以上的破裂發生之情況當作有破裂(有表面層的破壞)，而在被視為有破裂的樣品之中，將具有最低延伸度的樣品之延伸度值當作破裂延伸度。 The film cross section of the fractured portion of the collected sample was cut out, and the cross section was observed with a transmission electron microscope at a magnification of 3,000 times, and the occurrence of cracking of more than 50% of the average thickness of the surface layer was regarded as cracking (there was damage to the surface layer ), And among the samples considered to be cracked, the elongation value of the sample with the lowest elongation is taken as the crack elongation.

然後，以自相同水準的不同位置所切出的3個樣品進行測定，並採用彼等之破裂延伸度的平均值。 Then, three samples cut from different positions of the same level were used for measurement, and the average value of their elongation at break was used.

[熱成型性] [Thermoformability]

使用真空成型機「FORMECH300X」(成光產業股份有限公司製)，使用遠紅外線加熱器，以薄膜表面溫度成為指定的溫度之方式，將所得之積層薄膜加熱1分鐘，使用圓柱狀的模具(底面直徑50mm)進行真空成型，形成積層薄膜。又，然後為了使硬化完全結束，使溫度成為180~200℃而繼續進行1分鐘加熱。將沿著模具而完成成型的狀態使用成型程度(深拉比：成型高度/底面直徑)，以以下之基準進行評價。 Using a vacuum forming machine "FORMECH300X" (manufactured by Singko Industries Co., Ltd.) and a far-infrared heater, the obtained laminated film was heated for 1 minute so that the film surface temperature became a predetermined temperature, and a cylindrical mold (bottom surface) was used. 50mm diameter) was vacuum formed to form a laminated film. Furthermore, in order to complete hardening completely, heating was continued for 1 minute so that temperature might become 180-200 degreeC. The degree of molding (deep drawing ratio: molding height / bottom surface diameter) was used in the state where the molding was completed along the mold, and the following criteria were used for evaluation.

A級：以深拉比1.0以上可成型。 Grade A: Formable with a deep draw ratio of 1.0 or more.

B級：以深拉比0.6以上且小於1.0可成型，但以1.0以上則無法成型。 Class B: Moldable at a deep draw ratio of 0.6 or more and less than 1.0, but cannot be molded at 1.0 or more.

C級：以深拉比0.3以上且小於0.6可成型，但以0.6以上則無法成型。 Class C: Moldable with a deep draw ratio of 0.3 or more and less than 0.6, but cannot be molded with 0.6 or more.

D級：僅深拉比小於0.3的曲面成型為可能，以0.3以上係無法成型。 Class D: Only curved surfaces with a deep draw ratio of less than 0.3 are possible, and molding cannot be performed with 0.3 or more.

E級：即使只稍微折彎，也發生薄膜破裂‧破裂。 Grade E: Even if it is only slightly bent, film cracking and rupture occur.

[表面層之藉由低硬度材料的反覆擦過耐性] [Surface layer's repeated rub resistance by low hardness material]

將積層薄膜放置在20℃的溫度下12小時後，於相同環境下在本光製作所製橡膠擦磨耗試驗機的前端(前端部面積1cm²)，安裝白絨坯布[600號 興和(股)製]，施加500g的荷重而在積層薄膜上5cm、5,000次來回，及施加1,000g荷重而在積層薄膜上5cm、200次來回摩擦，並進行下述的等級分類。再者，以自相同水準的不同位置所切出的3個樣品進行測定，進行下述的等級分類。採用已進行等級分類的3個樣品之值的平均值。 The laminated film was placed after 12 hours at temperature 20 ℃ is, in the same environment rubbing abrasion tester in the present light Seisakusho rubber tip end (the front end portion of the area of 1cm ^2), mounted Cashmere fabric [600 Kowa (Unit) manufactured ], A load of 500 g was applied to the laminated film at 5 cm and 5,000 strokes, and a load of 1,000 g was applied to the laminated film at 5 cm and 200 strokes, and the following classification was performed. In addition, measurement was performed on three samples cut from different positions of the same level, and the following classification was performed. The average of the values of the three samples that have been graded is used.

10點：無傷痕 10 points: No scars

7點：1~10條的傷痕 7 o'clock: 1 ~ 10 scars

4點：11~20條的傷痕 4 points: 11 ~ 20 scars

1點：試驗部分的表面層係全面剝離。 1 point: The surface layer of the test part was completely peeled.

[表面層之自我修復性] [Self-healing properties of surface layer]

於20℃的溫度下放置12小時後，在相同環境下對於表面層表面，於黃銅刷(TRUSCO製)施加下述之荷重而水平地刮劃5次後，依照下述之基準，目視判斷5分鐘放置後的傷痕之恢復狀態。再者，以自相同水準的不同位置所切出的3個樣品進行測定，採用彼等之平均值。 After standing at 20 ° C for 12 hours, the surface of the surface layer was scratched horizontally 5 times with a brass brush (manufactured by TRUSCO) under the same environment. The following load was applied, and then visually judged according to the following criteria Recovery of wounds after 5 minutes of standing. In addition, three samples cut from different positions of the same level were used for measurement, and their average values were used.

10點：以荷重1kg而傷痕不殘留 10 o'clock: 1kg load without scars

7點：以荷重1kg傷痕會殘留，但以700g則傷痕不殘留 7 o'clock: 1kg of scar will remain, but 700g will not remain.

4點：以荷重700g傷痕會殘留，但以500g則傷痕不殘留 4 points: The wounds will remain at 700g, but not at 500g

1點：以荷重500g而傷痕殘留。 1 point: A flaw remains at a load of 500 g.

[產業上之可利用性] [Industrial availability]

本發明之積層薄膜係可用於對於塑膠成型品、家電製品、建築物或車輛內裝品及各種的印刷物之各自的表面，賦予耐擦傷性尤其反覆擦過性與成型性並存之機能。 The laminated film of the present invention can be used to provide the functions of co-existence of scratch resistance and moldability to the respective surfaces of plastic molded products, home appliances, building or vehicle interior products, and various printed materials.

Claims (7)

一種積層薄膜，其係在支撐基材的至少一側之面上具有包含A層與B層的表面層之積層薄膜，其特徵為：自支撐基材側起B層、A層依此順序相接，A層、B層、支撐基材之藉由微小硬度計所測定的25℃之儲存彈性模數(以下為E_A25、E_B25、E_C25)、120℃之儲存彈性模數(以下為E_A120、E_B120、E_C120)係滿足以下之條件，條件1 E_A25<E_B25≦E_C25；條件2 E_B120≦E_A120<E_C120；條件3 E_A25≦100MPa。A laminated film is a laminated film comprising a surface layer of layers A and B on at least one side of a supporting substrate, and is characterized in that the layers B and A are phased in this order from the side of the supporting substrate. Then, the storage elastic modulus at 25 ° C (hereinafter A _E25 , E _B25 , E _C25 ) and the storage elastic modulus at 120 ° C (the following is E _A120 , E _B120 , and E _C120 ) satisfy the following conditions, condition 1 E _A25 <E _B25 ≦ E _C25 ; condition 2 E _B120 ≦ E _A120 <E _C120 ; condition 3 E _A25 ≦ 100MPa. 如請求項1之積層薄膜，其中該A層、B層、支撐基材係滿足以下之條件，條件4 0<E_C25-E_B25<5GPa；條件5 0<E_A120-E_B120<50MPa。For example, the laminated film of claim 1, wherein the A layer, the B layer, and the supporting substrate satisfy the following conditions, condition 40 <E _C25 -E _B25 <5GPa; condition 50 <E _A120 -E _B120 <50MPa. 如請求項1或2之積層薄膜，其中該B層之玻璃轉移溫度(以下為Tg_B)係滿足以下之條件，條件6 60℃≦Tg_B≦130℃。For example, the laminated film of claim 1 or 2, wherein the glass transition temperature (hereinafter Tg _B ) of the layer _B satisfies the following conditions, and the condition 6 is 60 ° C ≦ Tg _B ≦ 130 ° C. 如請求項1或2之積層薄膜，其中該B層之厚度(以下為T_B)係滿足以下之條件，條件7 0.1μm≦T_B≦5μm。For example, the laminated film of claim 1 or 2, wherein the thickness of the B layer (hereinafter referred to as T _B ) satisfies the following conditions, condition 7 0.1 μm ≦ T _B ≦ 5 μm. 如請求項1或2之積層薄膜，其中在該表面層之垂直於基材的截面中，自表面層的表面起，在表面層厚度的10%之位置(以後當作位置1)、50%(以後當作位置2)、99%(以後當作位置3)的各位置之依據原子力顯微鏡的彈性模數E1、E2、E3係滿足以下之條件，條件8 E1≦E2<E3；條件9 E1≦100MPa；條件10 E3≧1GPa。For example, the laminated film of claim 1 or 2, wherein in the cross section of the surface layer perpendicular to the substrate, from the surface of the surface layer, at the position of 10% of the thickness of the surface layer (hereinafter referred to as position 1), 50% (Hereinafter referred to as position 2) and 99% (hereinafter referred to as position 3). The elastic modulus of the atomic force microscope E1, E2, and E3 satisfy the following conditions, condition 8 E1 ≦ E2 <E3; condition 9 E1 ≦ 100MPa; condition 10 E3 ≧ 1GPa. 一種積層薄膜之製造方法，其係如請求項1至5中任一項之積層薄膜之製造方法，其特徵為：該表面層係藉由將2種類以上的塗料組成物逐次地塗布於支撐基材上，乾燥、硬化而形成。A method for manufacturing a laminated film, which is the method for manufacturing a laminated film according to any one of claims 1 to 5, characterized in that the surface layer is sequentially coated on a supporting substrate by applying two or more kinds of coating compositions. The material is formed by drying and hardening. 一種積層薄膜之製造方法，其係如請求項1至5中任一項之積層薄膜之製造方法，其特徵為：該表面層係藉由將2種類以上的塗料組成物同時地塗布於支撐基材上，乾燥、硬化而形成。A method for manufacturing a laminated film, which is the method for manufacturing a laminated film according to any one of claims 1 to 5, characterized in that the surface layer is coated with two or more kinds of coating compositions on a supporting substrate simultaneously. The material is formed by drying and hardening.