TWI762552B - Substrate protective film, member for preventing adhesion, and method for forming member for preventing adhesion - Google Patents

Abstract

An object of the present invention is to provide a substrate protective film that can reduce the adhesion of substances to the surface of the substrate more than the effect of reducing the adhesion of substances by electrostatic repulsion. The solution is to form a first layer (charge holding layer (3)) containing a charged substance and having electrostatic repulsion on the surface of the substrate (1), and forming a second layer that controls surface free energy on the surface of the first layer (Functional base layer (4) composed of functional groups having a functional group length of less than 1 nm and a low surface free energy of 50 mJ/m ² or less). By forming the substrate protective film (2) in this way, since the electrostatic repulsion on the surface of the substrate (1) can be maintained, the adhesion of substances caused by intermolecular forces can be reduced, and the effect of reducing the adhesion of substances by only the electrostatic repulsion can be reduced. to reduce the adhesion of substances to the surface of the substrate (1).

Description

Substrate protective film, member for preventing adhesion, and method for forming member for preventing adhesion

The present invention relates to a substrate protective film that can reduce the adhesion of substances to the surface of a substrate (such as a glass or resin substrate), and a member that prevents adhesion by forming this substrate protective film on the surface, its formation method.

[0002] As a technique for reducing the adhesion of substances (contaminants, etc.) to the surface of a substrate, there are techniques described in Proposed Patent Documents 1 and 2. In the techniques described in Patent Documents 1 and 2, the adhesion of substances is reduced by electrostatic repulsion by holding electric charges on the surface of the substrate. [Prior Art Document] [Patent Document] [0003] [Patent Document 1] Japanese Patent No. 4926176 [Patent Document 2] Japanese Patent No. 5624458

[Problems to be Solved by the Invention] [0004] As described in the above-mentioned Patent Documents 1 and 2, the adhesion of substances can be reduced by electrostatic repulsion by maintaining electric charges on the surface of the substrate, but the requirements are higher than Such a reduction in the adhesion of substances by electrostatic repulsion effectively reduces the adhesion of substances to the surface of the substrate. The present invention is completed in consideration of such current situation, hereby to provide a substrate protective film that can reduce the attachment of substances to the substrate surface higher than the substance adhesion reduction effect produced by electrostatic repulsion, and, provide a kind of substrate of this kind A protective film is formed on the surface to prevent adhesion, and the purpose is to form a method therefor. [Means for Solving the Problems] [0006] The base protective film of the present invention is a base protective film capable of reducing the adhesion of substances to the surface of the base, and is characterized by comprising a first layer containing a charged substance and having electrostatic repulsion, and a control surface The free-energy second layer is formed, the first layer is formed on the surface of the substrate, and the second layer is formed on the surface of the first layer. Moreover, the said 2nd layer is formed of the functional group with a low surface free energy of 50 mJ/m< ² > or less, and the thickness of this 2nd layer is less than 1 nm. [0007] According to the base protective film of the present invention, the adhesion of substances can be reduced by the electrostatic repulsion of the first layer formed on the base surface. Furthermore, since the second layer that controls the surface free energy is formed on the surface of the first layer, and the second layer is formed of functional groups with a low surface free energy of 50 mJ/m ² or less, the second layer is The thickness is adjusted to be less than 1 nm, so the second layer can reduce the surface free energy and reduce the adhesion of substances caused by intermolecular forces. In this way, since the electrostatic repulsion generated by the first layer on the surface of the substrate can be maintained, the adhesion of substances caused by intermolecular forces can be reduced, and the adhesion of substances to the substrate can be reduced more than the effect of reducing the adhesion of substances by only the electrostatic repulsion. surface attachment. [0008] The member for preventing adhesion of the present invention is characterized in that a substrate protective film having the above-mentioned characteristics is formed on the surface of a glass or resin substrate. According to such an adhesion preventing member, the adhesion of substances (contaminants, etc.) to the surface can be effectively reduced. [Effects of the Invention] [0009] According to the substrate protective film and the adhesion preventing member of the present invention, the adhesion of substances to the substrate surface can be reduced more than the substance adhesion reduction effect caused only by electrostatic repulsion.

[0037] ・電荷保持層形成 　　藉由刮刀法，在100mm×100mm之玻璃基板(浮法玻璃)的表面上，將上述電荷保持層形成用之溶液塗佈成形成後的厚度為100nm，於200℃使其硬化15分鐘，而於玻璃基板(基體)的表面上形成電荷保持層。 　　[0038] ・自組裝單分子膜形成(官能基層形成) 　　將形成有上述電荷保持層的玻璃基板、與自組裝單分子膜形成用之溶液：三甲氧基甲基矽烷0.5ml收容於密閉容器內，並將此密閉容器配置於真空加熱爐內。然後，在爐內壓力0.1kPa以下的減壓環境下於170℃加熱2小時，使甲基吸附於電荷保持層的表面上，而形成自組裝單分子膜(SAM)(參照圖1)。 　　[0039] 將此[實施例1]中所製作者，亦即在玻璃基板的表面上形成電荷保持層，並使甲基吸附於此電荷保持層的表面上而形成自組裝單分子膜(官能基層)者作為評定基板1。 　　[0040] [實施例2] 　　根據與[實施例1]相同的處理，在100mm×100mm之玻璃基板(浮法玻璃)的表面上形成電荷保持層。 　　[0041] 將形成有此電荷保持層的玻璃基板、與自組裝單分子膜形成用之溶液：己基三甲氧基矽烷0.5ml收容於密閉容器內，並將此密閉容器配置於真空加熱爐內。然後，在爐內壓力0.1kPa以下的減壓環境下於170℃加熱2小時，使己基吸附於電荷保持層的表面上，而形成自組裝單分子膜(SAM)(參照圖2)。 　　[0042] 將此[實施例2]中所製作者，亦即在玻璃基板的表面上形成電荷保持層，並使己基吸附於此電荷保持層的表面上而形成自組裝單分子膜(官能基層)者作為評定基板2。 　　[0043] [比較例1] 　　根據與[實施例1]相同的處理，在100mm×100mm之玻璃基板(浮法玻璃)的表面上形成電荷保持層。 　　[0044] 將此[比較例1]中所製作者，亦即在玻璃基板的表面上僅形成有電荷保持層者作為比較基板1。 　　[0045] [比較例2] 　　根據與[實施例1]相同的處理，在100mm×100mm之玻璃基板(浮法玻璃)的表面上形成電荷保持層。 　　[0046] 將形成有此電荷保持層的玻璃基板、與自組裝單分子膜形成用之溶液：十八基三甲氧基矽烷0.5ml收容於密閉容器內，並將此密閉容器配置於真空加熱爐內。然後，在爐內壓力0.1kPa以下的減壓環境下於170℃加熱2小時，使十八基吸附於電荷保持層的表面上，而形成自組裝單分子膜(SAM)(參照圖3)。 　　[0047] 將此[比較例2]中所製作者，亦即在玻璃基板的表面上形成電荷保持層，並使十八基吸附於此電荷保持層的表面上而形成自組裝單分子膜(官能基層)者作為比較基板2。 　　[0048] -表面自由能的評定- ＜接觸角測定＞ 　　作為接觸角測定所使用的溶媒，係準備水、二碘甲烷、正十六烷，並將此各溶媒，各以5μl對[實施例1]中所製作的評定基板1滴下，並測定各溶媒的接觸角。此接觸角測定係對評定基板1的5處進行，以此5處的平均作為各溶媒的接觸角。 　　[0049] ＜表面自由能的算出＞ 　　將上述接觸角測定中所得之各溶媒的接觸角θ代入由Young式與擴展Fowkes式所導出的下述式(1)，以所得3個算式為聯立方程式對其求解而求出γ_S ^d 、γ_S ^p 、及γ_S ^h ，並算出表面自由能(=γ_S ^d +γ_S ^p +γ_S ^h )。將其結果示於下述表2。 　　[0050]

[0051] 於此，(1)式中，γ_S ^d 、γ_S ^p 、γ_S ^h 係分別表示基板(官能基層、電荷保持層)的分散力成分、極性力成分、氫鍵力成分。 　　[0052] 又，γ_L 、γ_L ^d 、γ_L ^p 、γ_L ^h 係分別表示溶媒的表面自由能、分散力成分、極性力成分、氫鍵力成分。水、二碘甲烷、正十六烷之各溶媒的表面自由能γ_L 、分散力成分γ_L ^d 、極性力成分γ_L ^p 、氫鍵力成分γ_L ^h 為已知值。 　　[0053] 進而，對[實施例2]中所製作的評定基板2、[比較例1]中所製作的比較基板1、及[比較例2]中所製作的比較基板2之各基板，亦分別以與上述同樣的方法測定接觸角並算出表面自由能。將其各結果示於下述表2。 　　[0054] 又，下述表2中亦記載有自組裝單分子膜的厚度(官能基的厚度)。此外，就厚度而言，係以電荷保持層表面與自組裝單分子膜(官能基層)之間的長度作為厚度(參照圖1～圖3)。 　　[0055]

[0056] 由表2之結果，可確認表面吸附有甲基、己基之各官能基的評定基板1、2、及表面吸附有十八基(官能基)的比較基板2，與未吸附有官能基的比較基板1相比，可降低表面自由能。具體而言，可確認：就表面未吸附有官能基的比較基板1，其表面自由能為100mJ/m² 以上；相對於此，就表面吸附有官能基的評定基板1、2及比較基板2，可使表面自由能成為50mJ/m² 以下之較低的值。 　　[0057] -防污性能的評定- ＜粒子附著試驗＞ 　　對評定基板1、評定基板2、比較基板1、及比較基板2之各基板，使用假想為屋外污染的任意粒子，進行噴灑一定時間的粒子附著試驗。 　　[0058] ＜穿透率的變化率測定＞ 　　首先，就供測定穿透率的裝置參照圖4加以說明。 　　[0059] 此圖4所示裝置係具備：鹵素燈101；將此鹵素燈101的輸出光(鹵素光)聚集於試樣S(待測定穿透率之各基板)的聚光透鏡102；供檢測穿透試樣S的光的光檢測器103；及供輸入光檢測器103之輸出訊號的個人電腦104等。 　　[0060] 個人電腦104係基於光檢測器103之輸出訊號求取試樣S的鹵素光的穿透率(試樣S的穿透光強度/朝試樣S的入射光強度)。而且，個人電腦104係求取進行上述粒子附著試驗前之試樣S的穿透率、與進行粒子附著試驗後之試樣S的穿透率的差(穿透率的變化率)。 　　[0061] 然後，對此種裝置分別裝設評定基板1、評定基板2、比較基板1、及比較基板2之各基板的試樣S(粒子附著試驗前者與粒子附著試驗後者)，並針對此各基板測定上述粒子附著試驗前後之穿透率的變化率。將其結果示於下述表3。 　　[0062] 表3中，係設比較基板1之穿透率的變化率為100而表示評定基板1、2及比較基板2之各穿透率的變化率(%)。表3中，穿透率的變化率(粒子附著試驗前後之穿透率的變化率)愈小，表示物質(粒子)向基板表面的附著量愈低。此外，表3中亦記載自組裝單分子膜的厚度(官能基的厚度)。 　　[0063]

[0064] 由表3之結果，可確認評定基板1及評定基板2，即表面吸附有50mJ/m² 以下之低表面自由能的官能基(甲基、己基)，且此官能基層的厚度為未達1nm(0.19nm、0.89nm)的基板，比起未吸附有官能基的比較基板1穿透率的變化率較小，可提升防污性能(物質附著之減少效果)。 　　[0065] 又，如比較基板2，即使表面吸附有低表面自由能的官能基(十八基)，但此官能基層的厚度較厚(2.0nm)時，仍可確認比起未吸附有官能基的比較基板1(僅因靜電斥力而減少物質附著者)，穿透率的變化率較大，防污性能降低。 　　[0066] 由以上所述，藉由在電荷保持層的表面上附加官能基長度(厚度)未達1nm且為50mJ/m² 以下之低表面自由能的官能基，可謂可高於僅由靜電斥力所產生的物質附著減少效果地減少物質向基板(基體)表面的附著。研判這是因為，藉由在不喪失電荷保持層的靜電排斥機能下減少分子間力所引起的物質附著，可提升防污性能之故。 [產業上可利用性] 　　[0067] 本發明可有效地利用於可減少物質向基體的表面的附著之基體保護膜、及、此種基體保護膜形成於表面而成的防止附著之構件、與其形成方法。[Modes for Carrying Out the Invention] [0011] Hereinafter, embodiments of the present invention will be described based on the drawings. [0012] [Embodiment 1] FIG. 1 is a schematic diagram showing an example of the base protective film of the present invention. The base protective film 2 of this example is made up of a charge holding layer (the first layer) 3 with electrostatic repulsion, and a functional base layer (the second layer) 4 that controls the surface free energy. The charge holding layer 3 is formed on the surface of the (substrate) 1 , and the functional base layer 4 is formed on the surface of the charge holding layer 3 . [0014] The charge holding layer 3 is formed to contain a charged substance. The functional base layer 4 is a self-assembled monolayer (SAM) formed by methyl groups (functional groups with low surface free energy below 50 mJ/m ² ), and the thickness thereof is less than 1 nm. [0015] According to the base protective film 2 of this example, the adhesion of substances can be reduced by the electrostatic repulsion of the charge holding layer 3 formed on the surface of the base 1. Furthermore, on the surface of the charge holding layer 3, a functional base layer 4 composed of a functional group (methyl group) having a low surface free energy with a functional group length (thickness) of less than 1 nm and a surface free energy of 50 mJ/m ² or less is formed. , thus reducing the adhesion of substances caused by intermolecular forces. Thereby, since the electrostatic repulsion on the surface of the substrate 1 can be maintained, and the adhesion of substances due to intermolecular forces can be reduced, the substance adhesion reduction effect on the surface of the substrate 1 can be reduced more than the effect of reducing the adhesion of substances by only the electrostatic repulsion. attached. Moreover, as shown in Figure 1, on the surface of glass or resin base body 1, the base body protective film 2 formed by the charge holding layer 3 and the functional base layer 4 is formed, which is the "preventing adhesion" of the present invention. An example of "member" (member 10 for preventing adhesion). In addition, the functional base layer 4 is not limited to a self-assembled monolayer (SAM), and may be a layer (methyl group) formed by other formation methods (a method for forming a water-repellent group or a water-repellent/oil-repellent group to be described later). Floor). [0018] [Embodiment 2] FIG. 2 is a schematic diagram showing another example of the base protective film of the present invention. The base protective film 12 of this example has the following characteristics: on the surface of the charge holding layer (the 1st layer) 13 with electrostatic repulsion, there is formed a functional group by hexyl ( ^50mJ /m below the low surface free energy) The constituted functional base layer (SAM: second layer) 14; the other constitutions are the same as those of the above-mentioned [Embodiment 1]. In the base protective film 12 of this example, the electrostatic repulsion on the surface of the base 11 can also be maintained, while reducing the adhesion of substances caused by intermolecular forces, and can be higher than the adhesion of substances produced only by electrostatic repulsion. The adhesion of substances to the surface of the base body 11 is effectively reduced. Moreover, as shown in Figure 2, on the surface of the glass or resin base (substrate) 11, the base protective film 12 formed by the charge holding layer 13 and the functional base layer 14 is formed. Another example of "the member for preventing adhesion" (the member for preventing adhesion 20). In addition, the functional base layer 14 is not limited to the self-assembled monolayer (SAM), but may also be a layer (a base layer) formed by other formation methods (a method for forming a water-repellent group or a water-repellent/oil-repellent group to be described later). ). In the above embodiment, the functional base layer (4,14) formed by methyl or hexyl is formed on the surface of the charge holding layer (3,13), but the present invention is not limited to this, as long as it is functional For functional groups with a base length of less than 1 nm and a low surface free energy of 50 mJ/m ² or less, a functional base layer composed of other functional groups (refer to the hydrocarbon-based functional groups and fluoride-based functional groups described later) can also be formed. on the surface of the charge holding layer. [Charge Holding Layer] Next, the charge holding layer (3, 13) will be described. As the charged substance contained in the charge holding layer, any combination of conductors, dielectrics, or semiconductors can be used, and from the viewpoint of self-cleaning of the surface of the substrate, metal-doped titanium oxide, metal-doped titanium oxide, and metal-doped oxide are preferably used. silicon. The aforementioned metal is preferably at least one metal element selected from the group consisting of gold, silver, platinum, copper, zirconium, tin, manganese, nickel, cobalt, iron, zinc, alkali metals, and alkaline earth metals, and more Preferably, at least two kinds are used, and silver or tin, and copper or iron are more preferred. As titanium oxide, various oxides or peroxides such as TiO ₂ , TiO ₃ , TiO , TiO ₃ /nH ₂ O can be used; as silicon oxide, SiO ₂ , SiO ₃ , SiO, SiO ₃ /nH ₂ O can be used Various oxides or peroxides. [0026] The film thickness of the charge holding layer is not particularly limited, but is preferably in the range of 10 nm to 1 μm, more preferably in the range of 10 nm to 100 nm. [Functional base layer] Next, the functional base layer (4, 14) with low surface free energy will be described. First of all, the so-called reduction of surface free energy is equivalent to the meaning of water-repellent or water-repellent and oil-repellent on its surface. Moreover, in order to make the surface water-repellent or oil-repellent, it is necessary to form a water-repellent base or a water-repellent/oil-repellent base on the surface. In the present embodiment, the surface free energy is reduced by forming a water-repellent group or a water-repellent/oil-repellent group on the surface of the charge holding layer. [0029] As this water-repellent group, a hydrocarbon-based functional group can be mentioned. As hydrocarbon functional group, can enumerate alkyl group, alkylene group, phenyl group, benzyl group, phenethyl group, hydroxyphenyl group, chlorophenyl group, amine phenyl group, naphthyl group, anthracenyl group, pyrene group , thienyl, pyrrolyl, cyclohexyl, cyclohexenyl, cyclopentyl, cyclopentenyl, pyridyl, chloromethyl, methoxyethyl, hydroxyethyl, amine ethyl, cyano, mercaptopropyl , vinyl, acryloyloxyethyl, methacryloyloxyethyl, glycidoxypropyl, or acetoxyl, etc. [0031] Also, as the water/oil repellent group, a fluoride-based functional group can be mentioned. As the fluoride-based functional group, fluoroalkyl, fluoroalkylene, fluorophenyl, fluorobenzyl, fluorophenethyl, fluoronaphthyl, fluoroanthryl, fluoropyrene, fluorothiophene can be enumerated fluoropyrrolyl, fluorocyclohexyl, fluorocyclohexenyl, fluorocyclopentyl, fluorocyclopentenyl, fluoropyridyl, fluoromethoxyethyl, aminofluoroethyl, fluorovinyl, or fluoroethyl Aryloxy. As a method for forming the above water-repellent group or water-repellent/oil-repellent group (hydrocarbon-based functional group or fluoride-based functional group) on the surface of the charge holding layer, a self-assembled monolayer (SAM) can be used. ) chemical adsorption, evaporation by plasma CVD, formation by sol-gel method, coating of nanoparticles, method of using surface modifier, thin film formation by interlayer method, composite electroplating, electrophoresis, or etching treatment, etc. [Examples] [0034] Hereinafter, the examples of the present invention will be described together with the comparative examples. [Example 1] ・The solution for forming the charge holding layer First, as the solution for forming the charge holding layer, a product of Sustainable Titania Technology Co., Ltd. was used. Specifically, copper-doped anatase-type titanium peroxide, tin-doped anatase-type titanium peroxide, zirconium-doped anatase-type titanium peroxide, and potassium-doped polysilicate were mixed as shown in Table 1 below. The ratio (weight ratio) mixture was used as a solution for forming a charge holding layer. [0036]

・The charge holding layer is formed by the doctor blade method, on the surface of the glass substrate (float glass) of 100mm×100mm, the above-mentioned solution for forming the charge holding layer is applied to a thickness of 100nm after formation, and at 200 mm It was made to harden for 15 minutes, and a charge holding layer was formed on the surface of a glass substrate (base body).・Formation of self-assembled monomolecular film (functional base layer formation) The glass substrate on which the above-mentioned charge holding layer is formed, and the solution for forming the self-assembled monomolecular film: 0.5 ml of trimethoxymethylsilane are contained in a sealed container , and the airtight container is arranged in a vacuum heating furnace. Then, the furnace was heated at 170° C. for 2 hours under a reduced pressure atmosphere of 0.1 kPa or less in the furnace to adsorb methyl groups on the surface of the charge holding layer to form a self-assembled monolayer (SAM) (see FIG. 1 ). In this [Example 1], a charge holding layer is formed on the surface of a glass substrate, and methyl groups are adsorbed on the surface of the charge holding layer to form a self-assembled monolayer (functional Base layer) as the evaluation substrate 1. [Example 2] According to the same process as [Example 1], a charge holding layer was formed on the surface of a glass substrate (float glass) of 100 mm x 100 mm. [0041] The glass substrate on which the charge retention layer is formed, and the solution for forming a self-assembled monomolecular film: hexyltrimethoxysilane 0.5ml are contained in a sealed container, and the sealed container is placed in a vacuum heating furnace. Then, it was heated at 170° C. for 2 hours under a reduced pressure environment with a furnace pressure of 0.1 kPa or less, so that hexyl groups were adsorbed on the surface of the charge holding layer to form a self-assembled monolayer (SAM) (see FIG. 2 ). In this [Example 2], a charge-retaining layer is formed on the surface of a glass substrate, and hexyl groups are adsorbed on the surface of the charge-retaining layer to form a self-assembled monomolecular film (functional base layer). ) as the evaluation substrate 2. [Comparative Example 1] According to the same process as [Example 1], a charge holding layer was formed on the surface of a glass substrate (float glass) of 100 mm×100 mm. [0044] The one produced in this [Comparative Example 1], that is, the one having only the charge holding layer formed on the surface of the glass substrate, was used as the comparative substrate 1. [Comparative Example 2] According to the same treatment as in [Example 1], a charge holding layer was formed on the surface of a glass substrate (float glass) of 100 mm×100 mm. The glass substrate on which the charge holding layer is formed, and the solution for forming a self-assembled monomolecular film: 0.5 ml of octadecyltrimethoxysilane are contained in a sealed container, and the sealed container is arranged in a vacuum heating furnace Inside. Then, it was heated at 170° C. for 2 hours under a reduced pressure environment with a furnace pressure of 0.1 kPa or less, and the octadecyl group was adsorbed on the surface of the charge holding layer to form a self-assembled monolayer (SAM) (see FIG. 3 ). In this [Comparative Example 2], a charge holding layer was formed on the surface of the glass substrate, and the octadecyl group was adsorbed on the surface of the charge holding layer to form a self-assembled monomolecular film ( functional base layer) as the comparative substrate 2. -Evaluation of surface free energy- <Contact angle measurement> As the solvent used for the contact angle measurement, water, diiodomethane, and n-hexadecane were prepared, and 5 μl of each of these solvents were used for [Example The evaluation substrate 1 prepared in 1] was dropped, and the contact angle of each solvent was measured. This contact angle measurement was performed on 5 places of the evaluation substrate 1, and the average of the 5 places was used as the contact angle of each solvent. <Calculation of surface free energy> The contact angle θ of each solvent obtained in the above-mentioned contact angle measurement is substituted into the following formula (1) derived from the Young's formula and the extended Fowkes formula, and the obtained three formulas are combined as The equations are solved to obtain γ _S ^d , γ _Sp , and γ ^Sh , and the surface free energy ( ⁼ γ _S ^d +γ _Sp + ^{γ Sh )} _{is calculated} . The results are shown in Table 2 below. [0050]

Here, in the formula (1 ⁾ , γ _S ^d , γ _Sp , and γ ^Sh represent the dispersing force component, polar force component, and hydrogen bonding force component of the substrate (functional base layer, charge holding layer ₎ , respectively. Also, γ _L , γ _L ^d , γ _L ^p , and γ _L ^h represent the surface free energy, dispersing force component, polar force component, and hydrogen bonding force component of the solvent, respectively. The surface free energy γ _L , the dispersing force component γ _L ^d , the polar force component γ _L ^p , and the hydrogen bonding force component γ _L ^h of each solvent of water, diiodomethane, and n-hexadecane are known values. Furthermore, each of the evaluation substrates 2 produced in [Example 2], the comparative substrate 1 produced in [Comparative Example 1], and the comparative substrate 2 produced in [Comparative Example 2] were also tested. The contact angle was measured by the same method as the above, and the surface free energy was calculated. The respective results are shown in Table 2 below. [0054] Also, the thickness of the self-assembled monolayer (thickness of the functional group) is also recorded in the following Table 2. In addition, regarding the thickness, the length between the surface of the charge holding layer and the self-assembled monolayer (functional base layer) was used as the thickness (see FIGS. 1 to 3 ). [0055]

From the results in Table 2, it can be confirmed that the evaluation substrates 1 and 2 with each functional group of methyl group and hexyl group adsorbed on the surface, and the comparative substrate 2 with an octadecyl group (functional group) adsorbed on the surface are different from those without the functional group adsorbed on the surface. Compared with the base comparative substrate 1, the surface free energy can be reduced. Specifically, it was confirmed that the surface free energy of the comparative substrate 1 having no functional group adsorbed on the surface was 100 mJ/m ² or more, whereas the evaluation substrates 1 and 2 and the comparative substrate 2 having functional groups adsorbed on the surface were confirmed. , the surface free energy can be set to a low value of 50 mJ/m ² or less. -Evaluation of antifouling performance-<Particle adhesion test> Each substrate of evaluation substrate 1, evaluation substrate 2, comparative substrate 1, and comparative substrate 2 was sprayed for a certain period of time using arbitrary particles assumed to be outdoor pollution. Particle attachment test. [0058] <Measurement of the rate of change of the transmittance> First, an apparatus for measuring the transmittance will be described with reference to FIG. 4 . The device shown in this Fig. 4 is equipped with: halogen lamp 101; the output light (halogen light) of this halogen lamp 101 is gathered in the condenser lens 102 of sample S (each substrate of transmittance to be measured); A photodetector 103 for detecting light transmitted through the sample S; a personal computer 104 for inputting an output signal of the photodetector 103, and the like. [0060] The personal computer 104 obtains the transmittance of the halogen light of the sample S (transmitted light intensity of the sample S/incident light intensity to the sample S) based on the output signal of the photodetector 103. Then, the personal computer 104 obtains the difference between the penetration rate of the sample S before the particle adhesion test and the penetration rate of the sample S after the particle adhesion test (change rate of penetration rate). Then, the sample S of each substrate of the evaluation substrate 1, the evaluation substrate 2, the comparative substrate 1, and the comparative substrate 2 (the former of the particle adhesion test and the latter of the particle adhesion test) are respectively installed on this device, and for this For each substrate, the rate of change of the transmittance before and after the particle adhesion test was measured. The results are shown in Table 3 below. [0062] In Table 3, the rate of change of the transmittance of the comparative substrate 1 is assumed to be 100 to represent the rate of change (%) of the transmittances of the evaluation substrates 1, 2 and the comparative substrate 2. In Table 3, the smaller the change rate of the transmittance (the change rate of the transmittance before and after the particle adhesion test), the lower the adhesion amount of the substance (particle) to the substrate surface. In addition, Table 3 also describes the thickness of the self-assembled monolayer (thickness of functional groups). [0063]

From the results of Table 3, it can be confirmed that the evaluation substrate 1 and the evaluation substrate 2 are adsorbed on the surface with a functional group (methyl group, hexyl group) with low surface free energy below 50 ^mJ /m , and the thickness of this functional base layer is Substrates with less than 1 nm (0.19 nm, 0.89 nm) have a smaller change rate of transmittance than the comparative substrate 1 without functional groups adsorbed, and the antifouling performance (the effect of reducing substance adhesion) can be improved. In addition, as for the comparative substrate 2, even if a functional group (octadecyl) with low surface free energy is adsorbed on the surface, when the thickness of the functional base layer is thicker (2.0 nm), it can still be confirmed that the functional group is not adsorbed. The comparative substrate 1 of the base (the one in which the adhesion of substances was reduced only due to the electrostatic repulsion) had a large change rate of the transmittance, and the antifouling performance was lowered. From the above, by adding a functional group on the surface of the charge holding layer with a length (thickness) of less than ¹ nm and a low surface free energy of 50 mJ/m or less, it can be said that it can be said to be higher than that of static electricity alone. The substance adhesion reduction effect by the repulsive force reduces the adhesion of substances to the surface of the substrate (base). It is considered that this is because the antifouling performance can be improved by reducing the adhesion of substances caused by intermolecular forces without losing the electrostatic repulsion function of the charge holding layer. [Industrial Applicability] [0067] The present invention can be effectively used for a substrate protective film that can reduce the adhesion of substances to the surface of a substrate, and a member for preventing adhesion in which such a substrate protective film is formed on the surface, and forming method.

[0068] 1. 11‧‧‧Substrate 2, 12‧‧‧Substrate protective film 3, 13‧‧‧Charge holding layer 4, 14‧‧‧Functional base layer 10, 20‧‧‧Anti-adhering member

Fig. 1 is the schematic diagram showing an example of the base protective film of the present invention. Fig. 2 is a schematic view showing another example of the base protective film of the present invention. FIG. 3 is a schematic diagram showing the charge holding layer and self-assembled monolayer (SAM) formed in Comparative Example 2. FIG. Fig. 4 is a schematic configuration diagram showing an example of an apparatus for measuring transmittance.

1‧‧‧Substrate

2‧‧‧Substrate protective film

3‧‧‧Charge Holding Layer

4‧‧‧Functional base layer

10‧‧‧Components to prevent adhesion

Claims (7)

A base protective film, which is a base protective film that can reduce the adhesion of substances to the surface of the base, characterized in that it has electrostatic repulsion by doping an oxide containing at least one or more of Ti and Si with a metal. A first layer and a second layer that controls surface free energy, the first layer is formed on the surface of the substrate, the second layer is formed on the surface of the first layer, and the second layer is composed of 50 mJ The thickness of the second layer is less than 1 nm due to the formation of functional groups with a low surface free energy of not more than /m ² . The base protective film of claim 1, wherein the functional group is selected from methyl group or hexyl group belonging to the self-assembled monomolecular film. The base protective film of claim 1, wherein the functional group is selected from alkyl, alkylene, phenyl, benzyl, phenethyl, hydroxyphenyl, chlorophenyl, amine phenyl, naphthyl, anthracene base, pyrenyl, thienyl, pyrrolyl, cyclohexyl, cyclohexenyl, cyclopentyl, cyclopentenyl, pyridyl, chloromethyl, methoxyethyl, hydroxyethyl, amineethyl, cyano , mercaptopropyl, vinyl, acryloyloxyethyl, methacryloyloxyethyl, glycidoxypropyl, or hydrocarbon-based hydrophobic group constituted by acetyloxy. The base protective film of claim 1, wherein the functional group is selected from fluoroalkyl, fluoroalkyl, fluorophenyl, fluorobenzyl, fluorophenethyl, and fluoronaphthalene base, fluoroanthryl, fluoropyrene, fluorothienyl, fluoropyrrolyl, fluorocyclohexyl, fluorocyclohexenyl, fluorocyclopentyl, fluorocyclopentenyl, fluoropyridyl, fluoromethoxyethyl, amine The fluoride composed of fluoroethyl group, fluorovinyl group, or fluoroacetoxy group is a water-repellent oil-repellent group. The base protective film of claim 4, wherein the doping metal is selected from the group consisting of gold, silver, platinum, copper, zirconium, tin, manganese, nickel, cobalt, iron, zinc, alkali metals, and alkaline earth metals At least one metal element. A member for preventing adhesion, which is formed by forming the base protective film according to any one of Claims 1 to 5 on the surface of a glass or resin base. A method for forming a member for preventing adhesion, which is a method for forming a member for preventing adhesion formed by forming a base protective film as claimed in claim 6, wherein after forming a first layer on the surface of the base, on the surface of the first layer Above, by chemical adsorption of self-assembled monolayers (SAM), evaporation by plasma CVD, formation by sol-gel method, coating of nanoparticles, methods of using surface modifiers, and interlayers Legal thin-film formation, composite electroplating, electrophoresis, or etching can form a second layer with a thickness of less than 1 nm.

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