TWI643743B - Laminate film - Google Patents
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- TWI643743B TWI643743B TW104102454A TW104102454A TWI643743B TW I643743 B TWI643743 B TW I643743B TW 104102454 A TW104102454 A TW 104102454A TW 104102454 A TW104102454 A TW 104102454A TW I643743 B TWI643743 B TW I643743B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
一種積層薄膜,其係在支撐基材的至少一側具有表面層之積層薄膜,其特徵為滿足以下之條件1及條件2;條件1:剛體擺錘(rigid-body pendulum)試驗法之前述表面層在25℃的對數衰減率為0.1以上;條件2:前述表面層中所含有的樹脂包含以下之(1)至(4); A laminated film which is a laminated film having a surface layer on at least one side of a support substrate, which is characterized by satisfying the following conditions 1 and 2; Condition 1: the aforementioned surface of a rigid-body pendulum test method The logarithmic decay rate of the layer at 25 ° C is 0.1 or more; Condition 2: the resin contained in the surface layer comprises the following (1) to (4);
(1)聚己內酯鏈段 (1) Polycaprolactone segment
(2)胺基甲酸酯鍵 (2) urethane bond
(3)聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段 (3) Polyoxyalkylene segment and / or polydimethyl siloxane chain segment
(4)三環癸基鏈段。 (4) Tricyclic sulfhydryl chain segments.
本發明提供一種積層薄膜,其係除了成型材料所要求的成型性與因自我修復性所致的耐擦傷性之並存,還滿足密接耐久性、防污性。 The present invention provides a laminated film which is compatible with the moldability required for a molding material and the scratch resistance due to self-healing properties, and also satisfies the adhesion durability and the antifouling property.
Description
本發明關於一種積層薄膜,其係除了成型材料所要求的成型性與耐擦傷性之並存,密接耐久性與防污性亦優異。 The present invention relates to a laminated film which is excellent in adhesion durability and antifouling properties in addition to the moldability and scratch resistance required for a molding material.
於裝飾成型等之成型材料中,為了防止成型時的傷痕或防止成型後的物品使用過程中之傷痕,設置表面硬度化層。然而,表面硬度化層由於追隨成型的延伸性不足,而在成型時發生裂紋,或於極端的情況下薄膜斷裂,或表面硬度化層剝離,故一般採用在成型後形成表面硬度化層,以半硬化狀態成型後,以加熱或活性線照射等使完全硬化等之手段。然而,由於成型後的物品被3次元地加工,在後加工設置表面硬度化層係非常困難,而且以半硬化狀態成型時,有因成型條件而引起模具的髒污之情況。基於以上之點,期望能追隨成型的耐擦傷性材料,藉由本身的彈性恢復範圍之變形而能自我修復輕度的傷痕之「自我修復材料」係受到注目,而為專利文獻1及2所提案。 In the molding material such as decorative molding, a surface hardness layer is provided in order to prevent scratches during molding or to prevent scratches during use of the molded article. However, since the surface hardness layer is insufficient in the elongation of the follow-up molding, cracking occurs during molding, or in the extreme case, the film is broken, or the surface hardness layer is peeled off, it is generally used to form a surface hardness layer after molding. After molding in a semi-hardened state, it is completely hardened by heating or irradiation with an active wire. However, since the molded article is processed in three dimensions, it is extremely difficult to provide a surface hardness layer after the post-processing, and when it is molded in a semi-hardened state, there is a case where the mold is dirty due to the molding conditions. Based on the above, it is expected that the "self-healing material" which can follow the molded scratch-resistant material and which can repair the slight scratches by the deformation of the elastic recovery range is attracting attention, and is disclosed in Patent Documents 1 and 2. proposal.
另一方面,於智慧型手機殼體或平板PC殼體等,使用此等之成型體作為表面材料時,要求長期使用時的耐久性。尤其由於空氣中所存在的水分滲透至 成型材料內部,尤其攻撃成型材料之表面,因此有成型材料的表面被破壞,或發生表面層的剝離之問題。對於如此之問題,作為對於表面硬度化層賦予耐久性之技術,有提案專利文獻3之材料。又,作為形成兼顧對基材的密接強度與耐久性之層的技術,有提案專利文獻4之材料。 On the other hand, when such a molded body is used as a surface material in a smart phone case or a tablet PC case or the like, durability at the time of long-term use is required. Especially due to the penetration of moisture in the air to The inside of the molding material, especially the surface of the molding material, is destroyed, or the surface of the molding material is broken, or the surface layer is peeled off. In order to solve such a problem, there is a material of the patent document 3 proposed as a technique for imparting durability to the surface hardness layer. Moreover, as a technique for forming a layer that achieves both adhesion strength and durability to a substrate, a material of Patent Document 4 is proposed.
再者,於防污性之方面,牛仔褲或衣料或 含有染料的天然皮革、合成皮革若接觸由一般的軟質樹脂所構成之薄片,則有該等染料轉移至表面之問題,作為賦予對於此之耐性(以下,將此稱為抗染料轉移性)的方法,有提案專利文獻5之材料。 Furthermore, in terms of antifouling properties, jeans or clothing or When a natural leather or a synthetic leather containing a dye is in contact with a sheet composed of a general soft resin, there is a problem that the dye is transferred to the surface, and the resistance is imparted thereto (hereinafter, referred to as "dye transfer resistance"). The method has the material of the proposed patent document 5.
專利文獻1:國際公開第2011/136042號 Patent Document 1: International Publication No. 2011/136042
專利文獻2:日本特許第3926461號公報 Patent Document 2: Japanese Patent No. 3926461
專利文獻3:日本特開2013-166889號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2013-166889
專利文獻4:日本特開2012-233079號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2012-233079
專利文獻5:日本特開2008-62408號公報 Patent Document 5: Japanese Laid-Open Patent Publication No. 2008-62408
關於前述作為自我修復材料所提案的專利文獻1、專利文獻2之技術,本發明者們進行確認,結果雖然可確認成型性與自我修復性,但密接耐久性或防污性係大幅度地劣於硬塗材料。 The inventors of the present invention have confirmed the moldability and the self-healing property, but the adhesion durability or the antifouling property are greatly deteriorated. For hard coating materials.
又,關於前述專利文獻3之技術,本發明 者們進行確認,結果雖然可確認某種程度的密接耐久性之效果,但並非顯示成型性或自我修復性者。又,與前述專利文獻1及2的技術組合為不可能,無法兼具自我修復性。 Further, with regard to the technique of the aforementioned Patent Document 3, the present invention As a result, it was confirmed that although the effect of the adhesion durability was confirmed to some extent, it was not a moldability or self-healing property. Moreover, it is impossible to combine with the techniques of Patent Documents 1 and 2 described above, and it is not possible to have self-healing properties.
再者,關於前述專利文獻4之技術,雖然 在密接耐久性有效,但並非顯示成型性或自我修復性者,而且與前述專利文獻1至3之技術組合為不可能。 Furthermore, with regard to the technique of the aforementioned Patent Document 4, It is effective in the adhesion durability, but it does not exhibit moldability or self-healing property, and it is impossible to combine with the techniques of the aforementioned Patent Documents 1 to 3.
另外,前述專利文獻5中記載的手法係對 於抗染料轉移性有效,但並非顯示成型性或自我修復性者,而且與前述專利文獻1至4之技術組合為不可能,可知不與自我修復性並存。 Further, the method of the method described in the above Patent Document 5 is It is effective in resistance to dye transfer, but it does not exhibit moldability or self-healing property, and it is impossible to combine it with the techniques of the aforementioned Patent Documents 1 to 4, and it is understood that it does not coexist with self-healing property.
因此,本發明所欲解決的問題在於提供一 種積層薄膜,其係除了成型材料所要求的成型性與耐擦傷性之並存,還滿足密接耐久性、防污性。 Therefore, the problem to be solved by the present invention is to provide a The laminated film is in addition to the moldability and scratch resistance required for the molding material, and also satisfies the adhesion durability and the antifouling property.
為了解決上述問題,本發明者們重複專心致力的研究,結果完成以下之發明。即,本發明係如以下。 In order to solve the above problems, the inventors of the present invention repeated the intensive research and completed the following invention. 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具有表面層之積層薄膜,其特徵為滿足以下之條件1及條件2;條件1:剛體擺錘試驗法之前述表面層在25℃的對數衰減率為0.1以上;條件2:前述表面層中所含有的樹脂包含 以下之(1)至(4); <1> A laminated film which is a laminated film having a surface layer on at least one side of a support substrate, which is characterized by satisfying the following conditions 1 and 2; Condition 1: The aforementioned surface layer of the rigid body pendulum test method is 25 The logarithmic decay rate of °C is 0.1 or more; Condition 2: the resin contained in the surface layer contains (1) to (4) below;
(1)聚己內酯鏈段 (1) Polycaprolactone segment
(2)胺基甲酸酯鍵 (2) urethane bond
(3)聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段 (3) Polyoxyalkylene segment and / or polydimethyl siloxane chain segment
(4)三環癸基鏈段 (4) Tricyclic sulfhydryl segment
<2>如前述<1>記載之積層薄膜,其中於前述積層薄膜中,滿足以下之條件3;條件3:延伸-煮沸密接試驗法之前述表面層的密接指數為3以上。 <2> The laminated film according to the above <1>, wherein the laminated film satisfies the following condition 3; Condition 3: The adhesion index of the surface layer in the extension-boil adhesion test method is 3 or more.
<3>如前述<1>或<2>記載之積層薄膜,其中於前述積層薄膜中,滿足以下之條件4;條件4:剛體擺錘試驗法之前述表面層在100℃的相對儲存彈性模數係比在25℃的相對儲存彈性模數高。 <3> The laminated film according to the above <1> or <2>, wherein the laminated film satisfies the following condition 4; Condition 4: Relative storage elastic modulus of the surface layer of the rigid body pendulum test at 100 ° C The number system has a higher relative storage elastic modulus at 25 °C.
<4>如前述<1>至<3>中任一項記載之積層薄膜,其中於前述積層薄膜中,滿足以下之條件5至條件7;條件5:動態黏彈性法之前述表面層在25℃的儲存彈性模數為10MPa以上1,000MPa以下;條件6:動態黏彈性法之前述表面層在100℃的儲存彈性模數係比在25℃的儲存彈性模數高;條件7:動態黏彈性法之前述表面層在25℃的損失正切為0.15以上。 The laminated film according to any one of the above-mentioned <1> to <3> wherein the laminated film satisfies the following conditions 5 to 7; Condition 5: The surface layer of the dynamic viscoelastic method is 25 The storage elastic modulus of °C is 10 MPa or more and 1,000 MPa or less; Condition 6: The above-mentioned surface layer of the dynamic viscoelastic method has a storage elastic modulus at 100 ° C higher than the storage elastic modulus at 25 ° C; Condition 7: Dynamic viscoelasticity The loss of the surface layer of the above method at 25 ° C is 0.15 or more.
<5>如前述<1>至<4>中任一項記載之積層薄 膜,其中於前述積層薄膜中,滿足以下之條件8;條件8:拉伸試驗法之前述表面層在23℃的裂紋延伸度為20%以上。 <5> The laminated thin film according to any one of the above <1> to <4> The film in which the above-mentioned condition 8 is satisfied in the laminated film; Condition 8: The surface layer of the tensile test method has a crack elongation of at least 20% at 23 °C.
<6>如前述<1>至<5>中任一項記載之積層薄膜,其中於前述積層薄膜中,形成表面層的支撐基材係滿足以下之條件9;條件9:支撐基材的膨潤度指數為0.01以上。 The laminated film according to any one of the above-mentioned <1>, wherein the support substrate which forms the surface layer in the laminated film satisfies the following condition 9; Condition 9: swelling of the support substrate The degree index is 0.01 or more.
<7>如前述<1>至<6>中任一項記載之積層薄膜,其中於前述積層薄膜中,滿足以下之條件10;條件10:前述表面層中所含有的樹脂包含以下之(5);(5)氟化合物鏈段。 The laminated film according to any one of the above-mentioned <1>, wherein the laminated film satisfies the following condition 10; Condition 10: The resin contained in the surface layer contains the following (5) (5) a fluorine compound segment.
<8>如前述<1>至<7>中任一項記載之積層薄膜,其中於前述積層薄膜中,滿足以下之條件11;條件11:前述表面層中所含有的樹脂包含以下之(6);(6)聚碳酸酯鏈段。 The laminated film according to any one of the above-mentioned <1>, wherein the laminated film satisfies the following condition 11; Condition 11: the resin contained in the surface layer contains the following (6) (6) polycarbonate segment.
依照本發明,可得到能滿足成型性、自我修復性、密接耐久性、防污性之積層薄膜。 According to the present invention, a laminated film which satisfies moldability, self-healing property, adhesion durability, and antifouling property can be obtained.
1‧‧‧溫度(℃) 1‧‧‧ Temperature (°C)
2‧‧‧對數衰減率 2‧‧‧Logarithmic decay rate
3‧‧‧對數衰減率之溫度依賴性曲線 3‧‧‧ Temperature dependence curve of logarithmic decay rate
4‧‧‧溫度(℃) 4‧‧‧ Temperature (°C)
5‧‧‧儲存彈性模數(MPa) 5‧‧‧ Storage elastic modulus (MPa)
6‧‧‧儲存彈性模數之溫度依賴性曲線 6‧‧‧ Temperature dependence curve of storage elastic modulus
7‧‧‧溫度(℃) 7‧‧‧ Temperature (°C)
8‧‧‧損失彈性模數(MPa) 8‧‧‧ loss elastic modulus (MPa)
9‧‧‧損失彈性模數之溫度依賴性曲線 9‧‧‧ Temperature dependence curve of loss elastic modulus
10‧‧‧溫度(℃) 10‧‧‧ Temperature (°C)
11‧‧‧損失正切 11‧‧‧ loss tangent
12‧‧‧損失正切之溫度依賴性曲線 12‧‧‧The temperature dependence curve of the loss tangent
第1圖係剛體擺錘試驗法所得的對數衰減率數據之一例。 Fig. 1 is an example of logarithmic decay rate data obtained by the rigid body pendulum test method.
第2圖係動態黏彈性法所得的儲存彈性模數數據之一例。 Fig. 2 is an example of storage elastic modulus data obtained by the dynamic viscoelastic method.
第3圖係動態黏彈性法所得的損失彈性模數數據之一例。 Fig. 3 is an example of loss elastic modulus data obtained by the dynamic viscoelastic method.
第4圖係動態黏彈性法所得的損失正切數據之一例。 Fig. 4 is an example of the loss tangent data obtained by the dynamic viscoelastic method.
於說明本發明的實施形態之前,對於習知 技術之問題點,即成型性、自我修復性、密接耐久性與防污性之並存,以本發明者之觀點來考察。 Before describing the embodiments of the present invention, The technical problem points, that is, moldability, self-healing property, adhesion durability, and antifouling property, are examined from the viewpoint of the inventors.
首先,專利文獻1及專利文獻2中記載之 習知技術的自我修復性材料,無法與密接耐久性並存之理由,係因為於習知技術中為了使塗膜成為柔軟,藉由降低塗膜中的交聯結構之密度,而得到自我修復性或成型性。然而,副作用的效果,係空氣中的水分對塗膜的滲透量變多,長期使用條件下的塗膜之破壞,或塗膜自基材剝離等,密接耐久性係不充分。 First, it is described in Patent Document 1 and Patent Document 2. The reason why the self-healing material of the prior art cannot coexist with the adhesion durability is because the self-repairing property is obtained by reducing the density of the crosslinked structure in the coating film in order to make the coating film soft in the prior art. Or formability. However, the effect of side effects is that the amount of penetration of moisture in the air into the coating film is increased, the coating film under long-term use conditions is broken, or the coating film is peeled off from the substrate, and the adhesion durability is insufficient.
又,專利文獻3~5之技術,由於提高材料 表面的交聯密度,防止空氣中的水分之滲透量或染料的滲透,而顯示優異的密接耐久性或抗染料轉移性,但另一方面,不顯示成型性或自我修復性。再者,即使於專利文獻1或2的材料中組合專利文獻3或4之材料,也由於自我修復性與成型性及密接耐久性或防污性成為權衡之關係而無法並存。再者,於專利文獻4之技術中,由於材料的強度差,因此成型材料所要求的耐擦傷性係 不充分。 Moreover, the techniques of Patent Documents 3 to 5 are due to the improvement of materials. The crosslink density of the surface prevents the penetration of moisture in the air or the penetration of the dye, and exhibits excellent adhesion durability or dye transfer resistance, but on the other hand, it does not exhibit moldability or self-healing property. In addition, even if the material of Patent Document 3 or 4 is combined with the material of Patent Document 1 or 2, the self-healing property and the moldability, the adhesion durability, and the antifouling property are in a trade-off relationship. Furthermore, in the technique of Patent Document 4, the scratch resistance required for the molding material is poor due to the strength of the material. insufficient.
因此,本發明者們進行成型材料所要求的 成型性與因自我修復性所致的耐擦傷性之探討,而且作為表面層的力學特性,著眼於顯示黏彈性特性,即顯示彈性的性質之儲存彈性模數、顯示黏性的性質之損失彈性模數、將損失彈性模數除以儲存彈性模數而得之損失正切。又,亦著眼於具有與損失正切同等之意義的對數衰減率。 Therefore, the inventors required the molding materials to be required. Moldability and scratch resistance due to self-healing properties, and as a mechanical property of the surface layer, attention is paid to the display of viscoelastic properties, that is, the storage elastic modulus showing the property of elasticity, and the loss elasticity of the property showing viscosity Modulus, the loss tangent divided by the loss elastic modulus divided by the stored elastic modulus. Also, attention is paid to the logarithmic decay rate having the same meaning as the loss tangent.
於表面層受到來自外部的負荷時,其力學 的響應係依賴於前述的黏彈性特性。由於損失正切低的材料,即彈性的性質強之材料,係以力學的能量來儲存大部分的負荷,若負荷大,則超過能儲存的範圍之材料係毀壞。於如此的情況,則會在表面層發生傷痕等,耐擦傷性成為不充分。另一方面,損失正切高的材料,即黏性的性質強之材料,係將負荷作為損失能量,即作為熱能逸散的效果為大,所儲存之力學的能量為相對地小。因此,即使負荷大,低於能儲存的範圍之可能性也高,材料不易毀壞。結果,可抑制表面層的傷痕之發生等,耐擦傷性優異。 When the surface layer is subjected to external loads, its mechanics The response is dependent on the aforementioned viscoelastic properties. Due to the loss of the material with low tangent, that is, the material with strong elasticity, the mechanical energy is used to store most of the load. If the load is large, the material exceeding the range of storage can be destroyed. In such a case, scratches and the like occur on the surface layer, and the scratch resistance is insufficient. On the other hand, a material with a high tangent loss, that is, a material having a strong viscous property, has a load as a loss energy, that is, a heat dissipation effect is large, and a stored mechanical energy is relatively small. Therefore, even if the load is large, the possibility of being lower than the range in which it can be stored is high, and the material is not easily destroyed. As a result, it is possible to suppress the occurrence of scratches on the surface layer and the like, and it is excellent in scratch resistance.
又,由於藉由使儲存彈性模數成為一定的 範圍,前述損失正切的效果係進一步升高,若使前述表面層的儲存彈性模數與損失正切成為特定之範圍,則前述表面層的成型性與自我修復性係提高而較佳。 Moreover, by making the storage elastic modulus constant In the range, the effect of the loss tangent is further increased. When the storage elastic modulus and the loss tangent of the surface layer are in a specific range, the moldability and self-healing property of the surface layer are improved.
具體而言,較佳為使剛體擺錘試驗法之表 面層的對數衰減率成為特定之範圍,及/或使動態黏彈性 法之表面層的儲存彈性模數與損失正切成為特定之範圍。 Specifically, it is preferable to make the table of the rigid body pendulum test method The logarithmic decay rate of the top layer becomes a specific range and/or dynamic viscoelasticity The storage elastic modulus and loss tangent of the surface layer of the method become a specific range.
再者,對於積層薄膜的表面層之自我修復 性,著眼於表面層的黏彈性行為之溫度依賴性的理由,係根據以下的發現:於高溫的儲存彈性模數比某溫度的儲存彈性模數還高的自我修復材料中,隨著因加熱所致的表面層之儲存彈性模數的上升,自我修復性係升高。 Furthermore, self-healing of the surface layer of the laminated film Sexuality, the reason for focusing on the temperature dependence of the viscoelastic behavior of the surface layer, is based on the following findings: in self-healing materials where the storage elastic modulus at high temperatures is higher than the storage elastic modulus at a certain temperature, As a result of the increase in the storage elastic modulus of the surface layer, the self-healing system is elevated.
本發明者們進行上述現象之分析,結果發 現若在表面層發生擦傷,則該位移所伴隨發生的殘留應力與儲存彈性模數係有相關。即,查明表面層的儲存彈性模數若上升,則表面層內部的彈性力成為解放擦傷所伴隨的殘留應力之力,結果修復擦傷。 The inventors performed the analysis of the above phenomenon, and the result was If scratches occur in the surface layer, the residual stress associated with the displacement is related to the storage elastic modulus. In other words, when the storage elastic modulus of the surface layer is increased, the elastic force inside the surface layer becomes a force for liberating the residual stress accompanying the abrasion, and as a result, the abrasion is repaired.
於實際使用狀況設想此性質的利用時,由 於本發明之積層薄膜適用作為智慧型手機等的成型材料,當智慧型手機等的各種電子機器因在內部所發生的熱自殼體表面散熱而表面溫度上升時,自我修復材料亦連動地溫度上升,修復在室溫所發生的擦傷,因此可期待自我修復性升高。 When the use of this property is envisaged in actual use, The laminated film of the present invention is suitable as a molding material for a smart phone or the like, and when various electronic devices such as smart phones are cooled from the surface of the casing due to heat generated inside, the surface temperature of the self-healing material is also linked. Rise and repair the abrasions that occur at room temperature, so it is expected to increase self-healing.
具體而言,剛體擺錘試驗法之表面層在 100℃的相對儲存彈性模數,較佳為比在25℃的相對儲存彈性模數高。又,動態黏彈性法之表面層在100℃的儲存彈性模數較佳為比在25℃的儲存彈性模數高。 Specifically, the surface layer of the rigid body pendulum test method is The relative storage elastic modulus at 100 ° C is preferably higher than the relative storage elastic modulus at 25 ° C. Further, the storage elastic modulus of the surface layer of the dynamic viscoelastic method at 100 ° C is preferably higher than the storage elastic modulus at 25 ° C.
再者,本發明者們分析密接耐久性時,著 眼於滲入表面層的空氣中之水分。尤其發現於長期使用條件下,所滲入的水分係到達至表面層-支撐基材界面, 成為破壞界面之原因,表面層自支撐基材剝離。尤其自我修復材料由於表面層的交聯密度降低,認為侵入表面層的水分多。 Furthermore, the inventors analyzed the durability of the adhesion, The eye is the moisture in the air that penetrates into the surface layer. In particular, it has been found that under long-term use conditions, the infiltrated moisture reaches the surface layer-support substrate interface. The reason for the destruction of the interface is that the surface layer is peeled off from the support substrate. In particular, the self-healing material is considered to have a large amount of moisture intruding into the surface layer due to a decrease in the crosslinking density of the surface layer.
進行防止表面層-支撐基材界面的破壞之 方法的探討,最初提高表面層中的交聯結構之密度而密接耐久性升高,但如前述不與成型性或自我修復性並存。 Prevent damage to the surface layer-support substrate interface In the method, the density of the crosslinked structure in the surface layer is initially increased and the adhesion durability is increased, but as described above, it does not coexist with moldability or self-healing property.
因此,探討使成型性與自我修復性及密接 耐久性並存之方法,結果發現對於表面層中所含有的樹脂導入疏水性鏈段係有效。 Therefore, to explore the formability and self-healing and close The method of coexisting with durability found that it was effective to introduce a hydrophobic segment into the resin contained in the surface layer.
表面層中所含有的樹脂若包含疏水性鏈 段,則滲入表面層的空氣中之水分係減少。又,若著眼於所滲入的水分,則由於自表面層表面起至到達表面層-支撐基材界面為止重複接觸疏水鏈段,到達界面的水分量係進一步減少。因此,可抑制因所滲入的水分而造成的表面層-支撐基材界面之破壞,結果可提高密接耐久性。 The resin contained in the surface layer contains a hydrophobic chain In the segment, the moisture in the air that penetrates into the surface layer is reduced. Further, if attention is paid to the water to be infiltrated, the amount of water reaching the interface is further reduced by repeatedly contacting the hydrophobic segment from the surface of the surface layer to the interface of the surface layer-supporting substrate. Therefore, the destruction of the surface layer-supporting substrate interface due to the infiltrated moisture can be suppressed, and as a result, the adhesion durability can be improved.
又,重複地驗證前述效果,結果發現導入 來自脂環結構的疏水性鏈段係特別有效。脂環結構由於具有立體的結構,運動性相對地低於來自鏈狀結構的鏈段。因此,即使成型時或因來自外部的負荷而表面層遭受變形時,也由於可抑制表面層中的疏水性鏈段之分布狀態發生疏密,而可防止密接耐久性的降低。再者,由於此效果並不改變表面層的交聯結構密度,而不易因脂環結構而使成型性或自我修復性降低。 Again, the above effects are repeatedly verified, and the results are found to be imported. Hydrophobic segments from alicyclic structures are particularly effective. Since the alicyclic structure has a three-dimensional structure, the mobility is relatively lower than that of the chain from the chain structure. Therefore, even when the surface layer is deformed at the time of molding or due to a load from the outside, the distribution state of the hydrophobic segments in the surface layer can be suppressed from being dense, and the deterioration of the adhesion durability can be prevented. Further, since this effect does not change the crosslinked structure density of the surface layer, the moldability or self-healing property is not easily lowered due to the alicyclic structure.
具體而言,前述表面層中所含有的樹脂較 佳為包含三環癸基鏈段。 Specifically, the resin contained in the surface layer is more The best includes a tricyclic sulfhydryl segment.
再者,本發明者們分析染料轉移性時,著 眼染料之轉移程序。於是發現關於染料對表面層的轉移性,染料滲入的程序、染料固定的程序各自之區分係重要。 Furthermore, the inventors analyzed the dye transfer property, Eye dye transfer procedure. Thus, it has been found that the distinction between the dye transfer to the surface layer, the dye infiltration procedure, and the dye fixing procedure are important.
首先,關於染料滲入的程序,由於染料之 滲入中水係成為媒介,因此藉由防止水對於表面層的滲入,可抑制染料的滲入。藉由抑制染料之滲入,可減少後述之染料發生固定的機會,結果可提高抗染料轉移性。作為如此的方法,對於前述表面層中所含有的樹脂導入疏水性鏈段,尤其導入來自脂環結構的疏水性鏈段係有效。 First, the procedure for dye penetration, due to the dye The infiltration of the water system serves as a medium, so that the penetration of the dye can be suppressed by preventing the penetration of water into the surface layer. By suppressing the penetration of the dye, the chance of fixing the dye described later can be reduced, and as a result, the dye transfer resistance can be improved. As such a method, introduction of a hydrophobic segment into the resin contained in the surface layer, in particular, introduction of a hydrophobic segment derived from an alicyclic structure is effective.
具體而言,對於染料之滲入,前述表面層 中所含有的樹脂較佳為包含三環癸基鏈段。 Specifically, for the penetration of the dye, the aforementioned surface layer The resin contained in the resin preferably contains a tricyclic fluorenyl group.
其次,關於染料固定的程序,若表面層中 所含有的樹脂與染料之親和性高,則染料的固定機率變高。因此,藉由降低表面層中所含有的樹脂與染料之親和性,可抑制染料之固定,結果可提高抗染料轉移性。 作為如此的方法,對於前述表面層中所含有樹脂導入與染料的親和性低之鏈段係有效。 Second, the procedure for dye fixation, if in the surface layer When the affinity between the resin and the dye contained is high, the probability of fixing the dye becomes high. Therefore, by reducing the affinity of the resin contained in the surface layer and the dye, the fixation of the dye can be suppressed, and as a result, the dye transfer resistance can be improved. As such a method, it is effective to introduce a segment having a low affinity for a resin contained in the surface layer and a dye.
具體而言,前述表面層中所含有的樹脂較 佳為包含三環癸基鏈段、聚己內酯鏈段、聚碳酸酯鏈段。 Specifically, the resin contained in the surface layer is more Preferably, it comprises a tricyclic sulfhydryl segment, a polycaprolactone segment, and a polycarbonate segment.
再者,本發明者們著眼於成型時的負荷或 於長期使用條件下等在表面層-支撐基材之界面所發生的負荷。發現於成型時,會在表面層-支撐基材之界面發 生力學的負荷,即應力或變形,在表面層-支撐基材界面發生局部的密接破壞,此係使成型性降低之原因。又,發現於長期使用條件下,由於空氣中的水分滲入表面層,破壞表面層-支撐基材的界面,故表面層自支撐基材剝離,此係使密接耐久性降低之原因。因此,探討防止此等之表面層-支撐基材界面的密接破壞之方法,結果發現選擇具有與溶劑的親和性為一定以上之表面的支撐基材係有效。 Furthermore, the inventors focused on the load at the time of molding or The load occurring at the interface of the surface layer-supporting substrate under long-term use conditions. Found in the molding, will be at the interface of the surface layer - support substrate The mechanical load, that is, the stress or deformation, causes local adhesion failure at the interface of the surface layer-supporting substrate, which causes the formability to decrease. Further, it has been found that under long-term use conditions, since moisture in the air penetrates into the surface layer and breaks the interface between the surface layer and the support substrate, the surface layer is peeled off from the support substrate, which causes the adhesion durability to be lowered. Therefore, a method of preventing the adhesion of the surface layer-support substrate at the interface of the support layer was examined, and as a result, it was found that it is effective to select a support substrate having a surface having a certain affinity with a solvent or more.
支撐基材表面與溶劑的親和性若高,則於 支撐基材上形成表面層時,由於表面層之成分滲透至支撐基材上,可提高表面層-支撐基材界面之密接力。此係因為有效於抑制表面層-支撐基材界面的局部之密接破壞或抑制表面層自基材剝離,而可提高成型性或密接耐久性。具體而言,較佳為使支撐基材的膨潤度指數成為特定之範圍。 If the affinity of the surface of the support substrate with the solvent is high, then When the surface layer is formed on the support substrate, since the components of the surface layer penetrate into the support substrate, the adhesion of the surface layer-support substrate interface can be improved. This is because it is effective for suppressing local adhesion failure of the surface layer-supporting substrate interface or suppressing peeling of the surface layer from the substrate, thereby improving moldability or adhesion durability. Specifically, it is preferred that the swelling index of the support substrate be within a specific range.
以下,具體地敘述本發明之實施形態。 Hereinafter, embodiments of the present invention will be specifically described.
為了滿足上述課題,即成型性、自我修復性、密接耐久性及防污性,本發明之積層薄膜係在支撐基材的至少一側具有表面層之積層薄膜,其中較佳為滿足以下之條件1至條件3。 In order to satisfy the above problems, that is, moldability, self-healing property, adhesion durability, and antifouling property, the laminated film of the present invention is a laminated film having a surface layer on at least one side of a support substrate, and preferably satisfies the following conditions. 1 to 3.
條件1:剛體擺錘試驗法之前述表面層在25℃的對數衰減率為0.1以上。 Condition 1: The logarithmic decay rate of the aforementioned surface layer at 25 ° C in the rigid body pendulum test method was 0.1 or more.
條件2:前述表面層中所含有的樹脂包含以下之(1)至(4)。 Condition 2: The resin contained in the surface layer described above contains the following (1) to (4).
(1)聚己內酯鏈段 (1) Polycaprolactone segment
(2)胺基甲酸酯鍵 (2) urethane bond
(3)聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段 (3) Polyoxyalkylene segment and / or polydimethyl siloxane chain segment
(4)三環癸基鏈段 (4) Tricyclic sulfhydryl segment
再者,剛體擺錘試驗法係如後述。 Furthermore, the rigid body pendulum test method will be described later.
此處,所謂的樹脂係指包含高分子化合物的物質。 Here, the term "resin" means a substance containing a polymer compound.
從成型性與自我修復性之觀點來看,本發明之積層薄膜係於剛體擺錘試驗法中,前述表面層在25℃的對數衰減率較佳為0.1以上,更佳為0.2以上,特佳為0.4以上。對數衰減率表示在受到力學的負荷時之響應性,藉由使對數衰減率成為特定之值,可提高成型性及自我修復性。 From the viewpoint of moldability and self-healing property, the laminated film of the present invention is in the rigid body pendulum test method, and the logarithmic decay rate of the surface layer at 25 ° C is preferably 0.1 or more, more preferably 0.2 or more. It is 0.4 or more. The logarithmic decay rate indicates the responsiveness when subjected to a mechanical load, and by making the logarithmic decay rate a specific value, moldability and self-healing property can be improved.
對數衰減率若大,則由於前述來自外部的負荷作為熱能逸散的效果升高,成型性與自我修復性升高而較宜。對數衰減率愈大則該效果愈大,但由於自我修復材料具有交聯網絡而有極限,上限值判斷為1.0左右。另一方面,對數衰減率若小於0.1,則有因來自外部的負荷而破壞表面層,成型性及自我修復性降低之情況。 If the logarithmic decay rate is large, the effect of the above-described load from the outside as heat energy is increased, and the moldability and self-healing property are preferably improved. The larger the logarithmic decay rate, the greater the effect, but since the self-healing material has a crosslinked network and has a limit, the upper limit is judged to be about 1.0. On the other hand, when the logarithmic decay rate is less than 0.1, the surface layer may be damaged by external load, and moldability and self-healing property may be lowered.
為了使剛體擺錘試驗法之前述表面層在25℃的對數衰減率成為0.1以上,可藉由使前述表面層中所含有的樹脂滿足前述之條件2。 In order to make the logarithmic decay rate of the surface layer of the rigid body pendulum test method at 25 ° C 0.1 or more, the resin contained in the surface layer can satisfy the condition 2 described above.
前述(1)聚己內酯鏈段係指化學式1所示的鏈段,(2)胺基甲酸酯鍵係指化學式2所示的鍵結,(3)聚矽氧烷鏈段係指化學式3所示的鏈段,聚二甲基矽氧 烷鏈段係指化學式4所示的鏈段,(4)三環癸基鏈段係指化學式5所示的鏈段。此等之詳細係如後述。 The above (1) polycaprolactone segment means a segment represented by Chemical Formula 1, (2) a urethane bond refers to a bond represented by Chemical Formula 2, and (3) a polyoxyalkylene segment refers to a segment. Segment shown by Chemical Formula 3, polydimethyl oxime The alkyl segment means a segment represented by Chemical Formula 4, and the (4) tricyclodecyl segment refers to a segment represented by Chemical Formula 5. The details of these are as follows.
(n係1~35之整數);
(R1、R2係OH或碳數1~8的烷基之任一者,且式中分別具有至少1個以上,n係100~300之整數);
(m係10~300之整數);
(n係1至50之整數)。 (n is an integer from 1 to 50).
前述表面層中所含有的樹脂若具有(1)聚己內酯鏈段,則可提高所得之表面層的自我修復性而較佳。 When the resin contained in the surface layer has (1) a polycaprolactone segment, the surface layer obtained by self-repairability is preferably improved.
前述表面層中所含有的樹脂若具有(2)胺 基甲酸酯鍵,則可提高所得之表面層的強韌性,同時可提高自我修復性而較佳。 The resin contained in the surface layer has (2) an amine The urethane bond improves the toughness of the resulting surface layer while improving self-healing properties.
前述表面層中所含有的樹脂若具有(3)聚 矽氧烷鏈段及/或聚二甲基矽氧烷鏈段,則可提高所得之表面層的耐熱性、耐候性,或提高因表面層的潤滑性所致之耐擦傷性。 The resin contained in the surface layer has (3) poly The siloxane chain segment and/or the polydimethyl siloxane chain segment can improve the heat resistance and weather resistance of the obtained surface layer or improve the scratch resistance due to the lubricity of the surface layer.
前述表面層中所含有的樹脂若含有(4)三 環癸基鏈段,則可提高所得之表面層的成型性、密接耐久性、抗染料轉移性、塗膜之強韌性而較佳。 The resin contained in the surface layer contains (4) three The cyclodecyl group segment can improve the moldability, adhesion durability, dye transfer resistance, and toughness of the coating film of the obtained surface layer.
再者,從密接耐久性之觀點來看,於前述 積層薄膜中,較佳為滿足以下之條件3。 Furthermore, from the viewpoint of adhesion durability, the foregoing In the laminated film, it is preferred to satisfy the following condition 3.
條件3:延伸-煮沸密接試驗法之前述表面 層的密接指數為3以上。 Condition 3: The aforementioned surface of the extension-boil tight test method The adhesion index of the layer is 3 or more.
再者,延伸-煮沸密接試驗法係如後述。 Further, the extension-boil adhesion test method will be described later.
從密接耐久性之觀點來看,於延伸-煮沸 密接試驗法中,前述表面層的密接指數較佳為3以上,更佳為4以上,特佳為5。密接指數表示表面層與支撐 層的密接性,密接指數之高度表示密接性及密接耐久性之高度。 From the standpoint of adhesion durability, in extension-boil In the adhesion test method, the adhesion index of the surface layer is preferably 3 or more, more preferably 4 or more, and particularly preferably 5. The adhesion index indicates the surface layer and support The adhesion of the layer, the height of the adhesion index indicates the height of the adhesion and the durability of the adhesion.
密接指數若高,則尤其即使在長期使用條 件下,也可抑制表面層自支撐基材剝離,密接耐久性升高因而較佳。另一方面,密接指數若小於3,則尤其在長期使用條件下,表面層會自支撐基材剝離,有密接耐久性降低之情況。 If the adhesion index is high, especially in the long-term use Further, it is also possible to suppress the peeling of the surface layer from the support substrate, and it is preferable that the adhesion durability is increased. On the other hand, if the adhesion index is less than 3, the surface layer may be peeled off from the support substrate especially under long-term use conditions, and the adhesion durability may be lowered.
於延伸-煮沸密接試驗法中,為了使前述 表面層的密接指數成為3以上,可使前述表面層中所含有的樹脂滿足前述之條件2。 In the extension-boil tight test method, in order to The adhesion index of the surface layer is 3 or more, and the resin contained in the surface layer can satisfy the above condition 2.
再者,從自我修復性及成型性之觀點來 看,於前述積層薄膜中,較佳為滿足以下之條件4。 Furthermore, from the point of view of self-healing and formability It is preferable to satisfy the following condition 4 in the above laminated film.
條件4:剛體擺錘試驗法之前述表面層在 100℃的相對儲存彈性模數係比在25℃的相對儲存彈性模數高。 Condition 4: The aforementioned surface layer of the rigid body pendulum test method is The relative storage elastic modulus at 100 ° C is higher than the relative storage elastic modulus at 25 ° C.
再者,剛體擺錘試驗法係如後述。 Furthermore, the rigid body pendulum test method will be described later.
從自我修復性及成型性之觀點來看,剛體 擺錘試驗法之前述表面層在100℃的相對儲存彈性模數較佳為比在25℃的相對儲存彈性模數高。相對儲存彈性模數係表示在施加負荷時材料係可恢復何種程度,相對儲存彈性模數上升者表示自我修復性提高。 From the standpoint of self-healing and formability, rigid body The relative storage elastic modulus of the aforementioned surface layer of the pendulum test method at 100 ° C is preferably higher than the relative storage elastic modulus at 25 ° C. The relative storage elastic modulus indicates how much the material system can be restored when a load is applied, and the increase in the relative storage elastic modulus indicates an improvement in self-healing property.
前述表面層在100℃的相對儲存彈性模數 若比在25℃的相對儲存彈性模數高,則藉由前述效果而提高自我修復性。 Relative storage elastic modulus of the aforementioned surface layer at 100 ° C If the relative storage elastic modulus at 25 ° C is higher, the self-healing property is improved by the aforementioned effects.
為了使前述表面層在100℃的相對儲存彈性模數比 在25℃的相對儲存彈性模數高,可使表面層中所含有的樹脂滿足條件2。 In order to make the relative surface elastic modulus ratio of the aforementioned surface layer at 100 ° C The relative storage elastic modulus at 25 ° C is high, so that the resin contained in the surface layer can satisfy the condition 2.
再者,從自我修復性及成型性之觀點來 看,於前述積層薄膜中,較佳為滿足以下之條件5至條件7。 Furthermore, from the point of view of self-healing and formability It is preferable to satisfy the following conditions 5 to 7 in the above laminated film.
條件5:動態黏彈性法之前述表面層在 25℃的儲存彈性模數為10MPa以上1,000MPa以下。 Condition 5: The aforementioned surface layer of the dynamic viscoelastic method is The storage elastic modulus at 25 ° C is 10 MPa or more and 1,000 MPa or less.
條件6:動態黏彈性法之前述表面層在 100℃的儲存彈性模數係比在25℃的儲存彈性模數高。 Condition 6: The aforementioned surface layer of the dynamic viscoelastic method is The storage elastic modulus at 100 ° C is higher than the storage elastic modulus at 25 ° C.
條件7:動態黏彈性法之前述表面層在 25℃的損失正切為0.15以上。 Condition 7: The aforementioned surface layer of the dynamic viscoelastic method is The loss tangent at 25 ° C is 0.15 or more.
再者,動態黏彈性法係如後述。 Furthermore, the dynamic viscoelasticity method will be described later.
從自我修復性及成型性之觀點來看,於動 態黏彈性法中,前述表面層在25℃的儲存彈性模數較佳為10MPa以上1,000MPa以下,更佳為10MPa以上800MPa以下,特佳為150MPa以上500MPa以下。儲存彈性模數表示在受到力學的負荷時之彈性的響應性,藉由使儲存彈性模數成為特定之值,可提高成型性及自我修復性。 From the point of view of self-healing and formability, In the state viscoelasticity method, the storage elastic modulus of the surface layer at 25 ° C is preferably 10 MPa or more and 1,000 MPa or less, more preferably 10 MPa or more and 800 MPa or less, and particularly preferably 150 MPa or more and 500 MPa or less. The storage elastic modulus indicates the elasticity responsiveness under a mechanical load, and the storage modulus and self-healing property can be improved by making the storage elastic modulus a specific value.
儲存彈性模數若為某種程度地小,則由於 提高前述損失正切之效果,來自外部的負荷作為熱能逸散之效果升高,成型性與自我修復性升高而較佳。儲存彈性模數愈小則該效果愈大,但若過小則表面層的強韌性會降低,故下限值判斷為10MPa左右。另一方面,儲存彈性模數若比1,000MPa還大,則有因來自外部的負荷 而破壞表面層,成型性及自我修復性降低之情況。 If the storage elastic modulus is small to some extent, The effect of the aforementioned loss tangent is enhanced, and the effect from the external load as the heat energy dissipation is increased, and the moldability and self-healing property are improved. The smaller the storage elastic modulus is, the larger the effect is. However, if the storage layer is too small, the toughness of the surface layer is lowered, so the lower limit is determined to be about 10 MPa. On the other hand, if the storage elastic modulus is larger than 1,000 MPa, there is a load from the outside. The surface layer is destroyed, and the formability and self-healing property are lowered.
為了使動態黏彈性法之前述表面層在 25℃的儲存彈性模數成為10MPa以上1,000MPa以下,可使前述表面層中所含有的樹脂滿足前述之條件2。 In order to make the aforementioned surface layer of the dynamic viscoelastic method When the storage elastic modulus at 25 ° C is 10 MPa or more and 1,000 MPa or less, the resin contained in the surface layer can satisfy the above condition 2.
從自我修復性之觀點來看,動態黏彈性法 之前述表面層在100℃的儲存彈性模數較佳為比在25℃的儲存彈性模數高。儲存彈性模數表示在施加負荷時材料係可恢復何種程度,儲存彈性模數上升者表示自我修復性提高。 From the point of view of self-healing, dynamic viscoelastic method The storage elastic modulus of the aforementioned surface layer at 100 ° C is preferably higher than the storage elastic modulus at 25 ° C. The storage elastic modulus indicates how much the material system can be restored when a load is applied, and the rise in the storage elastic modulus indicates an improvement in self-healing property.
前述表面層在100℃的儲存彈性模數若比 在25℃的儲存彈性模數高,則藉由前述效果而提高自我修復性。為了使前述表面層在100℃的儲存彈性模數比在25℃的儲存彈性模數高,可使前述表面層中所含有的樹脂滿足前述之條件2。 The storage modulus of the aforementioned surface layer at 100 ° C When the storage elastic modulus at 25 ° C is high, the self-healing property is improved by the aforementioned effects. In order to make the storage elastic modulus of the surface layer at 100 ° C higher than the storage elastic modulus at 25 ° C, the resin contained in the surface layer described above can satisfy the aforementioned condition 2.
從成型性與自我修復性之觀點來看,本發 明之積層薄膜係於動態黏彈性法中,前述表面層在25℃的損失正切較佳為0.15以上,更佳為0.20以上,特佳為0.30以上。損失正切表示在受到力學的負荷時之響應性,藉由使損失正切成為特定之值,可提高成型性及自我修復性。 From the point of view of formability and self-repairability, this issue The laminated film of Ming is in the dynamic viscoelastic method, and the loss tangent of the surface layer at 25 ° C is preferably 0.15 or more, more preferably 0.20 or more, and particularly preferably 0.30 or more. The loss tangent indicates the responsiveness when subjected to a mechanical load, and the moldability and self-healing property can be improved by making the loss tangent a specific value.
損失正切若大,則前述來自外部的負荷作 為熱能逸散的效果升高,成型性與自我修復性升高而較佳。損失正切愈大則該效果愈大,但由於自我修復材料具有交聯網絡而有極限,上限值判斷為1.00左右。另一方面,損失正切若小於0.15,則有因來自外部的負荷而 破壞表面層,成型性及自我修復性降低之情況。 If the loss tangent is large, the aforementioned load from the outside is made. The effect of dissipating heat energy is increased, and the formability and self-healing property are improved. The larger the loss tangent is, the larger the effect is. However, since the self-healing material has a crosslinked network and has a limit, the upper limit value is judged to be about 1.00. On the other hand, if the loss tangent is less than 0.15, there is a load from the outside. Destroy the surface layer, and reduce the formability and self-healing properties.
為了使動態黏彈性法之前述表面層在 25℃的損失正切成為0.15以上,可使前述表面層中所含有的樹脂滿足前述之條件2。 In order to make the aforementioned surface layer of the dynamic viscoelastic method The loss tangent at 25 ° C is 0.15 or more, and the resin contained in the surface layer can satisfy the above condition 2.
再者,從成型性之觀點來看,於前述積層 薄膜中,較佳為滿足以下之條件8。 Furthermore, from the viewpoint of formability, the above laminate In the film, it is preferred to satisfy the following condition 8.
條件8:拉伸試驗法之前述表面層在23℃ 的裂紋延伸度為20%以上。 Condition 8: The aforementioned surface layer of the tensile test method is at 23 ° C The crack elongation is 20% or more.
再者,拉伸試驗法係如後述。 Further, the tensile test method will be described later.
從成型性之觀點來看,拉伸試驗法之前述 表面層在23℃的裂紋延伸度較佳為20%以上,更佳為30%,尤佳為40%以上。裂紋延伸度表示成型時的追隨性,裂紋延伸度之大小表示成型性之高度。 From the viewpoint of moldability, the aforementioned tensile test method The crack elongation of the surface layer at 23 ° C is preferably 20% or more, more preferably 30%, and particularly preferably 40% or more. The crack elongation indicates the followability at the time of molding, and the magnitude of the crack elongation indicates the height of the moldability.
在25℃的裂紋延伸度若大,則由於前述積 層薄膜可追隨所成型的物品之形狀,故成型性升高。在23℃的裂紋延伸度愈大愈佳,但由於表面層與支撐基材係在成型時的柔軟性有差異,故上限值判斷為500%左右。另一方面,在25℃的裂紋延伸度小於20%時,由於在成型加工時於表面層引入裂紋而成為成型不良,有成型性降低之情況。 If the crack elongation at 25 ° C is large, the above product The layer film can follow the shape of the formed article, so the moldability is increased. The larger the crack elongation at 23 ° C, the better, but the difference between the surface layer and the supporting substrate at the time of molding is different, so the upper limit is determined to be about 500%. On the other hand, when the crack elongation at 25 ° C is less than 20%, the film is introduced into the surface layer during the molding process to cause molding failure, and the moldability may be lowered.
為了使在25℃的裂紋延伸度成為20%以上,可使前述表面層中所含有的樹脂滿足前述之條件2。 In order to make the crack elongation at 25 ° C 20% or more, the resin contained in the surface layer described above can satisfy the above condition 2.
再者,從成型性及密接耐久性之觀點來看,於前述積層薄膜中,較佳為滿足以下之條件9。 Further, from the viewpoint of moldability and adhesion durability, it is preferable that the laminated film satisfies the following condition 9 as follows.
條件9:支撐基材的膨潤度指數為0.01以 上。 Condition 9: The swelling index of the support substrate is 0.01 on.
再者,膨潤度指數之測定方法係如後述。 In addition, the measuring method of the swelling degree index is mentioned later.
前述支撐基材的膨潤度指數較佳為0.01以上,更佳為0.05以上,尤佳為0.10以上。膨潤度指數表示與溶劑及塗料組成物的親和性,膨潤度指數的大小表示支撐基材與表面層的密接性之高度,即成型性或密接耐久性之高度。 The swelling index of the support substrate is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.10 or more. The swelling index indicates the affinity with the solvent and the coating composition, and the degree of the swelling index indicates the height of the adhesion between the supporting substrate and the surface layer, that is, the height of the moldability or the adhesion durability.
支撐基材的膨潤度指數若大,則由於表面層與支撐基材的密接性升高,而成型性或密接耐久性升高。膨潤度指數愈大愈佳,但太大時由於在表面層形成時會破壞支撐基材,故上限值判斷為10左右。另一方面,膨潤度指數若小於0.01,則有於因成型的變形時或因長期使用的經年劣化時,破壞表面層與支撐基材之界面,成型性或密接耐久性降低之情況。 When the swelling index of the support substrate is large, the adhesion between the surface layer and the support substrate is increased, and the moldability or the adhesion durability is increased. The larger the swelling index, the better, but when it is too large, the support substrate is destroyed when the surface layer is formed, so the upper limit is judged to be about 10. On the other hand, when the degree of swelling index is less than 0.01, the interface between the surface layer and the supporting substrate may be broken at the time of deformation due to molding or deterioration over a long period of use, and the moldability or the adhesion durability may be lowered.
為了使支撐基材的膨潤度指數成為0.01以上,可選擇具有特定的表面物性之支撐基材。 In order to make the swelling index of the support substrate 0.01 or more, a support substrate having specific surface physical properties may be selected.
再者,從防污性之觀點,於前述積層薄膜中,較佳為滿足以下之條件10。 Further, from the viewpoint of the antifouling property, it is preferable that the laminated film 10 satisfies the following condition 10.
條件10:表面層中所含有的樹脂包含以下之(5)。 Condition 10: The resin contained in the surface layer contains the following (5).
(5)氟化合物鏈段 (5) Fluorine compound segment
此處所謂的樹脂,就是指包含高分子化合物的物質,其範圍包含自聚合物起至寡聚物為止的範圍。 The term "resin" as used herein refers to a substance containing a polymer compound, and the range thereof ranges from the polymer to the oligomer.
前述(5)記載的氟化合物鏈段係指包含選自由氟烷基、氟氧基烷基、氟烯基、氟烷二基及氟氧基 烷二基所構成之群組的至少一者之鏈段,更佳為前述氟化合物鏈段係氟聚醚鏈段。前述氟聚醚鏈段係由氟烷基、氧基氟烷基、氧基氟烷二基等所構成之鏈段,係以化學式(6)、化學式(7)為代表之結構。 The fluorochemical segment described in the above (5) is selected from the group consisting of fluoroalkyl, fluoroalkyl, fluoroalkenyl, fluoroalkanediyl and fluoroalkoxy. The segment of at least one of the groups consisting of the alkanediyl groups is more preferably the fluorochemical segment-based fluoropolyether segment. The fluoropolyether segment is a segment composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group or the like, and is represented by a chemical formula (6) or a chemical formula (7).
(此處,n1係1~3之整數,n2~n5係1或2之整數,k、m、p、s係0以上之整數,且p+s為1以上。較佳為n1係2以上,n2~n5係1或2之整數,更佳為n1係3,n2與n4係2,n3與n5係1或2之整數)。 (here, n1 is an integer of 1 to 3, n2 to n5 are integers of 1 or 2, and 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 1 or 2 integers).
前述氟聚醚鏈段之詳細係如後述,構成表面層的樹脂係藉由包含此等,而使顯示低表面能的分子以高密度存在於最表面。 The details of the fluoropolyether segment will be described later, and the resin constituting the surface layer is such that the molecules exhibiting low surface energy are present on the outermost surface at a high density.
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。碳數為3以下時,由於表面能未充分降低而有撥油性降低之情況,13以上時,由於在溶劑中的溶解性降低,而有表面層的品位降低之情況。 The chain length of the fluoropolyether segment has a preferred range, carbon number It 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 oil repellency may be lowered because the surface energy is not sufficiently lowered, and when the solubility is 13 or more, the solubility of the solvent may be lowered, and the grade of the surface layer may be lowered.
前述表面層中所含有的樹脂若包含(5)氟 化合物鏈段,則可提高所得之表面層的密接耐久性、抗 染料轉移性而較佳。 The resin contained in the surface layer contains (5) fluorine The compound segment can improve the adhesion durability and resistance of the obtained surface layer. Dye transfer is preferred.
再者,從自我修復性及成型性之觀點來看,於前述積層薄膜中,較佳為滿足以下之條件11。 Further, from the viewpoint of self-healing property and moldability, it is preferable that the laminated film as described above satisfy the following condition 11.
條件11:表面層中所含有的樹脂包含以下之(6)。 Condition 11: The resin contained in the surface layer contains the following (6).
(6)聚碳酸酯鏈段 (6) polycarbonate segment
此處所謂的樹脂,就是指包含高分子化合物的物質,其範圍包含自聚合物起至寡聚物為止的範圍。 The term "resin" as used herein refers to a substance containing a polymer compound, and the range thereof ranges from the polymer to the oligomer.
前述(6)聚碳酸酯鏈段係指化學式8所示的鏈段。此等之詳細係如後述。 The above (6) polycarbonate segment means a segment represented by Chemical Formula 8. The details of these are as follows.
(n係2~16之整數;R3指碳數1至8為止的伸烷基或伸環烷基)。 (n is an integer of 2 to 16; R 3 is an alkylene group or a cycloalkyl group having 1 to 8 carbon atoms).
前述表面層中所含有的樹脂若具有(6)聚碳酸酯鏈段,則可提高所得之表面層的自我修復性及成型性而較佳。 When the resin contained in the surface layer has (6) a polycarbonate segment, the surface layer obtained by self-repairability and moldability can be preferably improved.
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]
本發明之積層薄膜係具有顯示特定之特性的表面層,可為平面狀(薄膜、薄片、板)。此處,所謂顯示特定之特性的表面層,就是意指能滿足前述之條件1及條件2的表面層。 The laminated film of the present invention has a surface layer exhibiting specific characteristics and can be planar (film, sheet, plate). Here, the surface layer which exhibits a specific characteristic means the surface layer which satisfies the conditions 1 and 2 mentioned above.
前述表面層係除本發明之課題的成型 性、自我修復性、密接耐久性、防污性,還可具有光澤性、耐指紋性、設計性、防反射、抗靜電、導電性、熱線反射、近紅外線吸收、電磁波遮蔽、易接著等之其它機能。 The surface layer is formed in addition to the subject of the present invention. Sex, self-healing, adhesion durability, anti-fouling, but also gloss, fingerprint resistance, design, anti-reflection, anti-static, electrical conductivity, hot wire reflection, near-infrared absorption, electromagnetic wave shielding, easy to follow, etc. Other functions.
前述表面層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,可按照前述其它機能來選擇其厚度。 The thickness of the aforementioned surface layer is not particularly limited, but It is preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less, and the thickness can be selected in accordance with the other functions described above.
[支撐基材] [support substrate]
構成本發明之積層薄膜所用的支撐基材之樹脂,可為熱塑性樹脂、熱硬化性樹脂之任一者,可為均聚樹脂,也可為共聚合或2種類以上之摻合物。構成支撐基材的樹脂,為了成型性良好,更佳為熱塑性樹脂。 The resin constituting the support substrate used for the laminated film of the present invention may be either a thermoplastic resin or a thermosetting resin, and may be a homopolymer resin or a copolymer or a blend of two or more types. The resin constituting the support substrate is preferably a thermoplastic resin for good moldability.
作為熱塑性樹脂之例,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,熱塑性樹脂特佳為聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂或甲基丙烯酸樹脂。 As an example of a thermoplastic resin, polyethylene can be used. Gather Propylene. Polystyrene. Polyolefin resin such as polymethylpentene, alicyclic polyolefin resin, nylon 6. Polyamide resin such as nylon 66, aromatic polyamide resin, polyester resin, polycarbonate resin, polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin. Trifluoroethylene resin. Chlorofluoroethylene resin. Tetrafluoroethylene-6 fluoropropylene copolymer. A fluororesin such as a vinylidene fluoride resin, an acrylic resin, a methacrylic resin, a polyacetal resin, a polyglycolic acid resin, or a polylactic acid resin. The thermoplastic resin is preferably a resin having sufficient elongation and followability. From strength. Heat resistance. From the viewpoint of transparency, the thermoplastic resin is particularly preferably a polyester resin, a polycarbonate resin, an acrylic resin or a methacrylic 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,藉由酸成分及其酯與二醇成分之聚縮合而得。作為具體例,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它二羧酸及其酯或二醇成分。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 based on an ester bond The general term for the polymer of the main chain of the chain is obtained by polycondensation of an acid component and an ester thereof with a diol component. Specific examples thereof include polyethylene terephthalate, polytrimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, and polybutylene terephthalate. Further, other dicarboxylic acids and esters or diol components which are acid components or diol components may be copolymerized therewith. Among these, in terms of transparency, dimensional stability, heat resistance and the like, polyethylene terephthalate or polyethylene-2,6-naphthalate is particularly preferred.
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、折射率調整用之摻雜劑等。支撐基材係可為單層構成、積層構成之任一者。 Moreover, various additions can be added to the support substrate. Agents such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducing agents, thermal stabilizers, slip agents, infrared absorbers, ultraviolet absorbers, dopants for refractive index adjustment, and the like. The support substrate may be either a single layer structure or a laminate structure.
於支撐基材之表面上,亦可在形成前述表 面層之前施予各種的表面處理。作為表面處理之例,可舉出藥品處理、機械處理、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。 On the surface of the support substrate, the aforementioned table may also be formed Various surface treatments are applied before the top layer. Examples of the surface treatment include pharmaceutical 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, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment, and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.
又,用於本發明之積層薄膜的支撐基材, 係如前述較佳為使用膨潤度指數為0.01以上之支撐基材(以下,支撐基材A)。若使用支撐基材A,則如前述地由於表面層與支撐基材之密接性升高,結果成型性或密接耐久性升高而較佳。 Moreover, the support substrate used in the laminated film of the present invention, As described above, it is preferred to use a support substrate having a degree of swelling index of 0.01 or more (hereinafter, support substrate A). When the support substrate A is used, the adhesion between the surface layer and the support substrate is increased as described above, and as a result, moldability or adhesion durability is improved.
作為用於本發明的支撐基材A,可合適地 例示「Cosmoshine」(註冊商標)A4300、A4100(東洋紡股份有限公司)、「Panlite」(註冊商標)PC-2151(帝人化成股份有限公司)等之製品。 As the support substrate A used in the present invention, suitably Products such as "Cosmoshine" (registered trademark) A4300, A4100 (Toyobo Co., Ltd.), "Panlite" (registered trademark) PC-2151 (Teijin Chemicals Co., Ltd.), and the like are exemplified.
[塗料組成物] [paint composition]
本發明之積層薄膜的製造方法係沒有特別的限定,但本發明之積層薄膜係可經過在前述支撐基材的至少一側塗布塗料組成物之步驟,視需要而經過乾燥之步驟或硬化之步驟而得。此塗料組成物較佳為包含含有前述之(1)聚己內酯鏈段、(2)胺基甲酸酯鍵、(3)聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段、(4)三環癸基鏈段之樹脂,或在塗布程序內可形成彼等之材料(以下稱為前驅物),藉由在後述的製造方法使用該塗料組成物,表面層中所含有的樹脂可具有此等之鏈段及鍵結。 The method for producing the laminated film of the present invention is not particularly limited, but the laminated film of the present invention may be subjected to a step of applying a coating composition on at least one side of the supporting substrate, and a drying step or a hardening step as necessary. And got it. Preferably, the coating composition comprises (1) a polycaprolactone segment, (2) a urethane bond, (3) a polyoxyalkylene segment, and/or a polydimethyl siloxane. a resin of a segment, (4) a tricyclic fluorenyl group, or a material (hereinafter referred to as a precursor) which can be formed in a coating process, which is used in a surface layer by a manufacturing method described later. The resin contained may have such segments and bonds.
再者,前述塗料組成物較佳為包含含有(5) 氟化合物鏈段的樹脂或前驅物。又,亦可包含含有(6)聚碳酸酯鏈段的樹脂或前驅物來代替含有(5)氟化合物鏈段的樹脂或前驅物,也可包含含有(5)氟化合物鏈段的樹脂或前驅物與含有(6)聚碳酸酯鏈段的樹脂或前驅物之兩者。 Furthermore, the coating composition preferably contains (5) A resin or precursor of a fluorochemical segment. Further, a resin or a precursor containing the (6) polycarbonate segment may be contained instead of the resin or precursor containing the (5) fluorochemical segment, or may contain a resin or precursor containing the (5) fluorochemical segment. Both the resin and the precursor containing the (6) polycarbonate segment.
又,於塗料組成物中,亦可包含後述的溶劑或其它成分。 Further, the coating composition may contain a solvent or other components described later.
[聚己內酯鏈段] [polycaprolactone segment]
於本發明之積層薄膜中,表面層中所含有的樹脂較佳為包含(1)聚己內酯鏈段。此處所謂的聚己內酯鏈段, 係指前述化學式1所示的鏈段。表面層中所含有的樹脂若包含(1)聚己內酯鏈段,則由於可提高表面層的自我修復性及成型性而較佳。 In the laminated film of the present invention, the resin contained in the surface layer preferably contains (1) a polycaprolactone segment. The so-called polycaprolactone segment here, It means the segment shown in the above Chemical Formula 1. When the resin contained in the surface layer contains the (1) polycaprolactone segment, it is preferable because the surface layer can be improved in self-healing property and moldability.
為了形成表面層而使用的塗料組成物,係藉由包含含有聚己內酯鏈段的樹脂或前驅物,而可使表面層中所含有的樹脂具有聚己內酯鏈段。 The coating composition used to form the surface layer can have a polycaprolactone segment in the resin contained in the surface layer by including a resin or a precursor containing a polycaprolactone segment.
含有聚己內酯鏈段的樹脂,較佳為具有至少1個以上的羥基(hydroxyl group)。羥基較佳為在含有聚己內酯鏈段的樹脂之末端。 The resin containing a polycaprolactone segment preferably has at least one or more hydroxyl groups. The hydroxyl group is preferably at the end of the resin containing the polycaprolactone segment.
作為含有聚己內酯鏈段的樹脂,特佳為具有2~3官能的羥基之聚己內酯。作為具有2~3官能的羥基之聚己內酯,具體而言可舉出化學式9所示的聚己內酯二醇、化學式10所示的聚己內酯三醇或化學式11所示的聚己內酯改性(甲基)丙烯酸羥乙酯。此處,化學式9所示的聚己內酯二醇及化學式10所示的聚己內酯三醇一般稱為聚己內酯多元醇。 As the resin containing a polycaprolactone segment, polycaprolactone having a hydroxy group having 2 to 3 functions is particularly preferred. Specific examples of the polycaprolactone having a hydroxy group having a 2-3 function include polycaprolactone diol represented by Chemical Formula 9, polycaprolactone triol represented by Chemical Formula 10, or polycondensation represented by Chemical Formula 11. Caprolactone modified hydroxyethyl (meth)acrylate. Here, the polycaprolactone diol represented by Chemical Formula 9 and the polycaprolactone triol represented by Chemical Formula 10 are generally referred to as polycaprolactone polyol.
化學式9所示的聚己內酯二醇係以下所表示。 The polycaprolactone diol represented by Chemical Formula 9 is represented by the following.
此處,m+n係4~35之整數,R4係C2H4、C2H4OC2H4、C(CH3)3或(CH2)2之任一者。 Here, m+n is an integer of 4 to 35, and R 4 is any one of C 2 H 4 , C 2 H 4 OC 2 H 4 , C(CH 3 ) 3 or (CH 2 ) 2 .
又,化學式10所示的聚己內酯三醇係以下所表示。 Further, the polycaprolactone triol represented by Chemical Formula 10 is represented by the following.
此處,l+m+n係3~30之整數,R5係 CH2CHCH2、CH3C(CH2)3或CH3CH2C(CH2)3之任一者。 Here, l+m+n is an integer of 3 to 30, and R 5 is any one of CH 2 CHCH 2 , CH 3 C(CH 2 ) 3 or CH 3 CH 2 C(CH 2 ) 3 .
再者,聚己內酯改性(甲基)丙烯酸羥乙酯係以下所表示。 Further, polycaprolactone-modified (hydroxy)ethyl methacrylate is represented by the following.
此處,n係1~25之整數,R6係H或CH3 之任一者。再者,於R6為H或CH3之任一者時,此等係稱為活性能量線聚合性己內酯。再者,所謂的(甲基)丙烯酸酯,就是表示甲基丙烯酸酯或丙烯酸酯。 Here, n is an integer of 1 to 25, and R 6 is either H or CH 3 . Further, when R 6 is either H or CH 3 , these are referred to as active energy ray-polymerizable caprolactone. Further, the so-called (meth) acrylate means methacrylate or acrylate.
此處所謂的活性能量線聚合性,就是藉由 紫外線(UV線)、電子線(EB線)等之活性能量線而進行交聯之性質,具有(甲基)丙烯酸酯基等之官能基的化合物係符合。作為其它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)丙烯酸羥丙酯、聚己內酯改性(甲基)丙烯酸羥丁酯等。 The so-called active energy ray polymerization is by A property of crosslinking with an active energy ray such as an ultraviolet ray (UV line) or an electron beam (EB line), and a compound having a functional group such as a (meth) acrylate group is compatible. Examples of the other active energy ray-polymerizable caprolactone include polycaprolactone-modified (hydroxy) methacrylate, polycaprolactone-modified (hydroxy) hydroxybutyl acrylate, and the like.
再者,於本發明中,含有聚己內酯鏈段的 樹脂,係除聚己內酯鏈段,還可含有(或共聚合)其它的鏈段或單體。例如,可含有(或共聚合)包含後述的三環癸基鏈段、聚二甲基矽氧烷鏈段或聚矽氧烷鏈段、聚碳酸酯鏈段、異氰酸酯化合物之化合物。 Furthermore, in the present invention, the polycaprolactone containing segment The resin, in addition to the polycaprolactone segment, may also contain (or copolymerize) other segments or monomers. For example, a compound containing a tricyclodecyl chain segment, a polydimethylsiloxane chain segment or a polyoxyalkylene segment, a polycarbonate segment, or an isocyanate compound to be described later may be contained (or copolymerized).
又,於本發明中,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較佳為500~2,500,重量平均分子量更佳為1,000~1,500。聚己內酯鏈段的重量平均分子量若為500~2,500,則由於進一步展現自我修復性之效果,而且耐擦傷性進一步升高而較佳。 Further, in the present invention, a tree containing a polycaprolactone segment The polycaprolactone segment in the fat preferably has a weight average molecular weight of 500 to 2,500 and a weight average molecular weight of preferably 1,000 to 1,500. When the weight average molecular weight of the polycaprolactone segment is 500 to 2,500, it is preferable because the effect of self-healing property is further exhibited and the scratch resistance is further increased.
即使對聚己內酯鏈段予以共聚合時、或另 行添加時,於形成表面層用的塗料組成物之全部固體成分100質量%中,聚己內酯鏈段之含量若為5~50質量%,則在自我修復性、設計性、成型性之點較佳。 Even when the polycaprolactone segments are copolymerized, or In the case of adding 100% by mass of the total solid content of the coating composition for forming the surface layer, the content of the polycaprolactone segment is 5 to 50% by mass, and the self-healing property, design property, and moldability are The point is better.
[胺基甲酸酯鍵] [urethane bond]
於本發明之積層薄膜中,表面層中所含有的樹脂較佳為包含(2)胺基甲酸酯鍵。此處所謂的胺基甲酸酯鍵,就是前述化學式2所示的鏈段。表面層中所含有的樹脂若包含(2)胺基甲酸酯鍵,則可提高表面層的強韌性,同時提高自我修復性而較佳。 In the laminated film of the present invention, the resin contained in the surface layer preferably contains (2) a urethane bond. Here, the urethane bond is a segment represented by the above Chemical Formula 2. When the resin contained in the surface layer contains (2) a urethane bond, the toughness of the surface layer can be improved and self-healing property can be improved.
為了形成表面層而使用的塗料組成物,係 藉由含有市售的胺基甲酸酯改性樹脂,而表面層中所含有的樹脂能具有胺基甲酸酯鍵。又,於形成表面層之際,藉由塗布一種塗料組成物,其包含作為前驅物之含有異 氰酸酯基的化合物與含有羥基的化合物,而在塗布步驟生成胺基甲酸酯鍵,亦可使表面層含有胺基甲酸酯鍵。 a coating composition used to form a surface layer The resin contained in the surface layer can have a urethane bond by containing a commercially available urethane-modified resin. Further, at the time of forming the surface layer, by coating a coating composition containing the difference as a precursor The cyanate group-containing compound and the hydroxyl group-containing compound form a urethane bond in the coating step, and the surface layer may also contain a urethane bond.
於本發明中,較佳為藉由使異氰酸酯基與 羥基反應來生成胺基甲酸酯鍵,而表面層中所含有的樹脂具有胺基甲酸酯鍵。藉由使異氰酸酯基與羥基反應來生成胺基甲酸酯鍵,可提高表面層的強韌性,同時提高自我修復性。 In the present invention, it is preferred to have an isocyanate group and The hydroxyl group reacts to form a urethane bond, and the resin contained in the surface layer has a urethane bond. By reacting an isocyanate group with a hydroxyl group to form a urethane bond, the toughness of the surface layer can be improved while improving self-healing properties.
又,當前述含有聚己內酯鏈段的樹脂或含 有三環癸基鏈段的樹脂或含有聚碳酸酯鏈段的樹脂、後述之含有聚矽氧烷鏈段的樹脂或含有聚二甲基矽氧烷鏈段的樹脂等具有羥基時,亦可因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生成胺基甲酸酯鍵。若使用含有異氰酸酯基的化合物與具有羥基之含有聚矽氧烷鏈段的樹脂或具有羥基之含有聚二甲基矽氧烷鏈段的樹脂來形成表面層,則由於可提高表面層的強韌性及彈性恢復性(自我修復性)及表面的滑性而較佳。 Further, when the above-mentioned resin containing polycaprolactone segments or contains When a resin having a tricyclic fluorenyl group segment, a resin containing a polycarbonate segment, a resin containing a polyoxyalkylene segment described later, or a resin containing a polydimethylsiloxane chain segment has a hydroxyl group, A urethane bond is formed between the resin and the isocyanate group-containing compound as a precursor due to heat or the like. When a surface layer is formed by using a compound containing an isocyanate group and a resin having a polyoxyalkylene segment having a hydroxyl group or a resin having a polydimethylsiloxane chain having a hydroxyl group, the surface layer can be improved in toughness. And elastic recovery (self-healing) and surface slipperiness are preferred.
於本發明中,所謂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,例如可舉出亞甲基雙-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 so-called isocyanate group-containing compound The substance refers to a resin containing an isocyanate group or a monomer or oligomer containing a cyanate group. Examples of the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, a trimethylolpropane adduct of toluene diisocyanate, and a trimethylolpropane adduct of hexamethylene diisocyanate. Trimethylolpropane adduct of isophorone diisocyanate, isomeric cyanurate of toluene diisocyanate, isomeric cyanurate of hexamethylene diisocyanate, hexamethylene isocyanate A polyisocyanate such as a diurea or a terminal block of the above isocyanate.
於此等之含有異氰酸酯基的化合物之 中,與脂環族或芳香族的異氰酸酯相比,脂肪族的異氰酸酯係自我修復性較高而較佳。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,係在耐熱性之點,特佳為具有異三聚氰酸酯環的異氰酸酯,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,係形成兼具自我修復性與耐熱特性的表面層。 Such isocyanate group-containing compounds Among them, aliphatic isocyanates are more self-healing than alicyclic or aromatic isocyanates, and are preferred. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. Further, the isocyanate group-containing compound is particularly preferably an isocyanate having an isomeric cyanate ring, and is preferably a hexamethylene diisocyanate isocyanurate. An isocyanate having an isomeric cyanate ring forms a surface layer having both self-healing properties and heat resistance properties.
[聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段] [Polyoxyalkylene segment and / or polydimethyl siloxane chain segment]
於本發明之積層薄膜中,表面層中所含有的樹脂較佳為包含(3)聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段。此處,聚矽氧烷鏈段係指前述化學式3所示的鏈段,聚二甲基矽氧烷鏈段係指前述化學式4所示的鏈段。表面層中所含有的樹脂若包含(3)聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段,則藉由聚二甲基矽氧烷鏈段配位於表面層中的最表面側,因表面層的潤滑性提高而具有使負荷逸散之效果,並且由於抑制在表面層發生的無法修復之擦傷的發生,可提高表面層的自我修復性而較佳。 In the laminated film of the present invention, the resin contained in the surface layer preferably contains (3) a polyoxyalkylene segment and/or a polydimethylsiloxane chain segment. Here, the polyoxyalkylene segment refers to the segment shown in the above Chemical Formula 3, and the polydimethylsiloxane chain segment refers to the segment shown in the above Chemical Formula 4. If the resin contained in the surface layer contains (3) a polyoxyalkylene segment and/or a polydimethylsiloxane chain, the polydimethylsiloxane chain is disposed in the surface layer. On the surface side, since the lubricity of the surface layer is improved, there is an effect of dissipating the load, and since the occurrence of scratches that cannot be repaired in the surface layer is suppressed, the self-healing property of the surface layer can be improved.
為了形成表面層而使用的塗料組成物,係藉由包含含有聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段的樹脂或前驅物,而可使表面層中所含有的樹脂具有聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段。 The coating composition used to form the surface layer can be made by containing a resin or a precursor containing a polyoxyalkylene segment and/or a polydimethylsiloxane chain segment. It has a polyoxyalkylene segment and/or a polydimethyloxyalkylene segment.
又,含有聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段的樹脂或前驅物較佳為包含反應性部位。此反應 性部位係指因熱或光等之外部能量而與其它成分反應之部位。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、羥基、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、矽烷基醚基或矽烷醇基、或環氧基、丙烯醯基、甲基丙烯醯基。 Further, the resin or precursor containing a polyoxyalkylene segment and/or a polydimethylsiloxane chain segment preferably contains a reactive site. This reaction A sexual site refers to a site that reacts with other components due to external energy such as heat or light. Examples of such a reactive site include a stanol group in which alkoxyalkylene group and alkoxyalkylene group are hydrolyzed, or a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allylic group, from the viewpoint of reactivity. Base, propylene sulfhydryl, methacryl fluorenyl and the like. Among them, from the viewpoint of reactivity and handleability, a vinyl group, an allyl group, an alkoxyalkyl group, a decyl ether group or a stanol group, or an epoxy group, an acryl group or a methacryl group is preferred.醯基.
以下,依序詳述聚矽氧烷鏈段與聚二甲基矽氧烷鏈段。 Hereinafter, the polyoxyalkylene segment and the polydimethyloxyalkylene segment are sequentially described in detail.
[聚矽氧烷鏈段] [polyoxyalkylene segment]
本發明中,所謂的聚矽氧烷鏈段,就是指前述化學式3所示的鏈段。 In the present invention, the term "polyoxyalkylene chain segment" means the segment shown in the above Chemical Formula 3.
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組成物,作為具有聚矽氧烷鏈段的化合物使用。 In the present invention, a hydrazine containing a hydrolyzable decyl group can be used. A partial hydrolyzate of an alkane compound, an organic cerium sol or a composition in which a hydrolyzable decane compound having a radical polymer is added to the organic cerium sol is used as a compound having a polyoxyalkylene segment.
具有聚矽氧烷鏈段的化合物,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。 a compound having a polyoxyalkylene segment, which can be exemplified by tetraalkane Oxydecane, methyltrialkoxydecane, dimethyldialkoxydecane, γ-glycidoxypropyltrialkoxydecane, γ-glycidoxypropylalkyldide Full or partial decane compound having a hydrolyzable decyl group such as decane, γ-methacryloxypropyltrialkoxy decane or γ-methacryloxypropylalkyl dialkoxy decane The hydrolyzate or an organic cerium sol dispersed in an organic solvent, or a hydrolyzed decane compound having a hydrolyzable decyl group added to the surface of the organic cerium sol.
又,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)其它的鏈段等。例如,可含有(共聚合)具有聚己內酯鏈段、三環癸基鏈段、聚碳酸酯鏈段、聚二甲基矽氧烷鏈段的單體成分。 Further, in the present invention, a tree containing a polyoxyalkylene segment The fat may contain (copolymerize) other segments or the like in addition to the polyoxyalkylene segment. For example, a monomer component having a polycaprolactone segment, a tricyclodecanyl segment, a polycarbonate segment, or a polydimethylsiloxane chain segment may be contained (copolymerized).
本發明中,作為含有聚矽氧烷鏈段的樹 脂,較佳為共聚合具有與異氰酸酯基反應的羥基之單體等。於含有聚矽氧烷鏈段的樹脂中,若具有與異氰酸酯基反應的羥基之單體等進行共聚合,則表面層的強韌性升高。 In the present invention, as a tree containing a polyoxyalkylene segment The lipid is preferably a monomer which copolymerizes a hydroxyl group which reacts with an isocyanate group. In the resin containing a polyoxyalkylene segment, when a monomer having a hydroxyl group reactive with an isocyanate group is copolymerized, the toughness of the surface layer is increased.
當含有聚矽氧烷鏈段的樹脂為具有羥基 的共聚物時,若使用一種包含含有具羥基的聚矽氧烷鏈段之樹脂(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,則可有效率地成為具有聚矽氧烷鏈段與胺基甲酸酯鍵之表面層。 When the resin containing a polyoxyalkylene segment has a hydroxyl group In the case of a copolymer, if a coating layer comprising a resin (copolymer) containing a polyoxyalkylene segment having a hydroxyl group and a compound containing an isocyanate group is used to form a surface layer, it is possible to efficiently form a polysiloxane. a surface layer of an alkane segment and a urethane bond.
[聚二甲基矽氧烷鏈段] [polydimethyl siloxane chain segment]
於本發明中,所謂的聚二甲基矽氧烷鏈段,就是指前述化學式4所示的鏈段。 In the present invention, the polydimethyl siloxane chain segment means the segment shown in the above Chemical Formula 4.
於本發明中,作為具有聚二甲基矽氧烷鏈 段的化合物,較佳為使用在聚二甲基矽氧烷鏈段共聚合有乙烯基單體之共聚物。 In the present invention, as having a polydimethyl siloxane chain The compound of the segment is preferably a copolymer obtained by copolymerizing a vinyl monomer in a polydimethylsiloxane chain segment.
當具有聚二甲基矽氧烷鏈段的化合物為 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。當聚二甲基矽氧烷鏈段的化合物為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。 When the compound having a polydimethyl siloxane chain segment is When it is a copolymer with a vinyl monomer, it may be any of a block copolymer, a graft copolymer, and a random copolymer. When the compound of the polydimethylsiloxane chain segment is a copolymer with a vinyl monomer, this is called a polydimethylsiloxane derivative.
作為具有聚二甲基矽氧烷鏈段的化合物 (聚二甲基矽氧烷系共聚物),合成聚二甲基矽氧烷系嵌段共聚物可藉由活性聚合法、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。 As a compound having a polydimethylsiloxane chain segment (Polydimethylsiloxane-based copolymer), the synthetic polydimethylsiloxane-based block copolymer can be produced by a living polymerization method, a polymer initiator method, a polymer chain transfer method, or the like, but When productivity is considered, it is preferable to use a polymer initiator method or a polymer chain transfer method.
使用高分子起始劑法時,具有聚二甲基矽 氧烷鏈段的化合物(聚二甲基矽氧烷系共聚物),係可使用化學式12所示的高分子偶氮系自由基聚合起始劑,使其與其它的乙烯基單體共聚合而得。 Polydimethyl hydrazine when using a polymer starter method The compound of the oxyalkylene chain (polydimethyl siloxane) is a polymer azo-based radical polymerization initiator represented by Chemical Formula 12, which is copolymerized with other vinyl monomers. And got it.
(m係10~300之整數,n係1~50之整數)。 (m is an integer from 10 to 300, and n is an integer from 1 to 50).
又,亦可進行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,合成在側鏈導入有過氧化物基的預聚物,使該預聚物與乙烯基單體共聚合之二階段的聚合。 Moreover, it is also possible to carry out the peroxymonomer and the unsaturated group. The polydimethylsiloxane is copolymerized at a low temperature to synthesize a two-stage polymerization in which a peroxide-based prepolymer is introduced into a side chain to copolymerize the prepolymer with a vinyl monomer.
使用高分子鏈轉移法時,具有聚二甲基矽 氧烷鏈段的化合物(聚二甲基矽氧烷系共聚物),例如係可在化學式13所示的聚矽氧油附加HS-CH2COOH或HS-CH2CH2COOH等而成為具有SH基的化合物後,利用SH基的鏈轉移,使該矽氧化合物與乙烯基單體共聚合而得。 When a polymer chain transfer method is used, a compound having a polydimethylsiloxane chain (polydimethylsiloxane) copolymer, for example, a polyfluorene oxide represented by Chemical Formula 13 may be added to the HS-CH. 2 COOH or HS-CH 2 CH 2 COOH or the like to form a compound having an SH group, and then obtained by copolymerization of the SH group with a vinyl monomer by chain transfer of the SH group.
(m係10~300之整數)。 (m is an integer from 10 to 300).
作為具有聚二甲基矽氧烷鏈段的化合物
(聚二甲基矽氧烷系共聚物),合成聚二甲基矽氧烷系接枝共聚物例如可藉由使化學式14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,而容易地獲得
(m係10~300之整數)。 (m is an integer from 10 to 300).
作為與具有聚二甲基矽氧烷鏈段的化合 物之共聚物所使用的乙烯基單體,例如可舉出丙烯酸甲酯、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、乙酸乙烯酯、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、甲基丙烯酸N,N-二甲基胺基乙酯、甲基丙烯酸N,N-二乙基胺基乙酯、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。 As a compound with a polydimethylsiloxane chain segment Examples of the vinyl monomer used for the copolymer of the copolymer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, and A. Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, octadecyl methacrylate, lauryl methacrylate, methyl Vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-methyl styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, Vinylidene fluoride, glycidyl acrylate, glycidyl methacrylate, allyl epoxypropyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, propylene Indoleamine, methacrylamide, N-methylol acrylamide, N,N-dimethyl decylamine, N,N-dimethylaminoethyl methacrylate, N,N methacrylate -diethylaminoethyl ester, diethyl propylene decylamine, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, olefin Propanol and the like.
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、乙酸乙酯、乙酸丁酯等的酯系溶劑、乙醇、異丙醇等的醇系溶劑等單獨或混合溶劑中,藉由溶液聚合法而製造。另外,較佳為視需要併用苯甲醯過氧化物、偶氮雙異丁基腈等之聚合起始劑。聚合反應較佳為在50~150℃進行3~12小時。 Further, the polydimethyl siloxane derivative is preferably in the form of An aromatic hydrocarbon solvent such as benzene or xylene; a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone; an ester solvent such as ethyl acetate or butyl acetate; or ethanol or isopropyl alcohol; The alcohol-based solvent or the like is produced by a solution polymerization method alone or in a mixed solvent. Further, it is preferred to use a polymerization initiator such as benzamidine peroxide or azobisisobutylcarbonitrile in combination. The polymerization reaction is preferably carried out at 50 to 150 ° C for 3 to 12 hours.
本發明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,較佳為在聚二甲基矽氧烷系共聚物的全部成分100質量%中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。 In the polydimethyl siloxane series copolymer of the present invention The amount of the polydimethylsiloxane chain segment is preferably from 1 to 30 mass in 100% by mass of all components of the polydimethylsiloxane derivative in terms of lubricity or stain resistance of the surface layer. %. Further, the polydimethylsiloxane chain segment preferably has a weight average molecular weight of 1,000 to 30,000.
即使對聚二甲基矽氧烷鏈段予以共聚合 時、或另行添加時,在為了形成表面層而使用的塗料組成物之全部成分100質量%中,二甲基矽氧烷鏈段若為1~20質量%,則於自我修復性、耐污染性、耐候性、耐熱性之點較佳。塗料組成物的全部成分100質量%不包 含未參與反應的溶劑。包含參與反應的單體成分。 Even if the polydimethylsiloxane chain is copolymerized In the case of 100% by mass of all the components of the coating composition used for forming the surface layer, the dimethyl siloxane chain segment is 1 to 20% by mass, and is self-healing and resistant to contamination. The point of properties, weather resistance and heat resistance is preferred. 100% by mass of the entire composition of the coating composition Contains solvents that are not involved in the reaction. Contains the monomer components involved in the reaction.
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)其它的鏈段等。例如,亦可含有(共聚合)聚己內酯鏈段、三環癸基鏈段、聚碳酸酯鏈段或聚矽氧烷鏈段。 In the present invention, used as a surface layer for forming The coating composition, when a resin containing a polydimethylsiloxane chain segment is used, may contain (copolymerization) other segments or the like in addition to the polydimethylsiloxane chain segment. For example, it is also possible to contain (copolymerization) a polycaprolactone segment, a tricyclodecanyl segment, a polycarbonate segment or a polyoxyalkylene segment.
為了形成表面層而使用的塗料組成物,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和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,係可能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。 a coating composition used to form a surface layer, Using a copolymer of a polycaprolactone segment and a polydimethyl siloxane chain, a copolymer of a polycaprolactone segment and a polyoxyalkylene segment, a polycaprolactone segment and a polydimethyl hydrazine a copolymer of an oxyalkylene segment and a polyoxyalkylene segment, and the like. The surface layer obtained by using such a coating composition may have a polycaprolactone segment and a polydimethylsiloxane chain segment and/or a polyoxyalkylene 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 order to form a polycaprolactone segment, polyoxyalkylene In the coating composition used for the surface layer of the segment and the polydimethylsiloxane chain segment, the reaction of the polydimethylsiloxane derivative, the polycaprolactone, and the polyoxyalkylene can be polymerized. When the dimethyloxane-based copolymer is synthesized, a polycaprolactone segment and a polyoxyalkylene segment are appropriately added to carry out copolymerization.
[三環癸基鏈段] [Tricyclic sulfhydryl segment]
於本發明之積層薄膜中,表面層中所含有的樹脂較佳為包含(4)三環癸基鏈段。此處,所謂的三環癸基鏈段,就是指前述化學式5所示的鏈段。表面層中所含有的樹脂若包含(4)三環癸基鏈段,則可提高表面層的防污性及密接耐久性而較佳。 In the laminated film of the present invention, the resin contained in the surface layer preferably contains a (4) tricyclononyl group segment. Here, the term "tricyclic fluorenyl group" means the segment shown in the above Chemical Formula 5. When the resin contained in the surface layer contains the (4) tricyclononyl group segment, the antifouling property and the adhesion durability of the surface layer can be improved.
為了形成表面層而使用的塗料組成物,係藉由包含含有三環癸基鏈段的樹脂或前驅物,而可使表面層中所 含有的樹脂具有三環癸基鏈段。 The coating composition used to form the surface layer can be made in the surface layer by including a resin or a precursor containing a tricyclononyl group segment. The resin contained has a tricyclic fluorenyl segment.
關於三環癸基鏈段之結構係如前述化學 式5所述,而對於前述塗料組成物較佳之含有三環癸基鏈段的樹脂或前驅物係化學式15所示的化合物。 The structure of the tricyclic fluorenyl group is as described above. The resin or precursor containing a tricyclononyl group segment is preferably a compound represented by the formula 15 in the above coating composition.
R7表示烷二基、烷三基、氧基烷二基、氧 基烷三基及由彼等所衍生的酯結構、胺基甲酸酯結構、醚結構、三結構之任一者,D1表示反應性部位。 R 7 represents an alkanediyl group, an alkanetriyl group, an oxyalkyldiyl group, an oxyalkylene group, and an ester structure derived therefrom, a urethane structure, an ether structure, and three In either of the structures, D 1 represents a reactive site.
該反應性部位係指因熱或光等之外部能 量而與其它成分反應之部位。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、羥基、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、矽烷基醚基或矽烷醇基、或環氧基、丙烯醯(甲基丙烯醯)基。 The reactive site refers to external energy due to heat or light. The amount of the part that reacts with other ingredients. Examples of such a reactive site include a stanol group in which alkoxyalkylene group and alkoxyalkylene group are hydrolyzed, or a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allylic group, from the viewpoint of reactivity. Base, propylene sulfhydryl, methacryl fluorenyl and the like. Among them, from the viewpoint of reactivity and handleability, a vinyl group, an allyl group, an alkoxyalkyl group, a decyl ether group or a stanol group, or an epoxy group or a propylene group (methacryl oxime) is preferred. )base.
更佳為R7係烷二基、胺基甲酸酯結構或 酯結構之任一者,D1係丙烯醯(甲基丙烯醯)基或羥基。 More preferably, it is any one of an R 7 -based alkanediyl group, a urethane structure or an ester structure, and D 1 is a propylene (methacryl oxime) group or a hydroxyl group.
作為對於前述之塗料組成物較佳之含有 三環癸基鏈段的樹脂或前驅物,以於前述化學式15中D1為丙烯醯(甲基丙烯醯)基,即具有三環癸基鏈段的(甲基)丙烯酸酯之市售材料之例而言,可舉出IRR214-K(Daicel -Allnex股份有限公司)、SR833S(Sartomer)、FA-513AS、FA-513M(日立化成股份有限公司)、A-DCP、DCP(新中村化學股份有限公司)、Light Acrylate DCP-A(共榮社化學股份有限公司)。 As a preferred resin or precursor containing a tricyclic fluorenyl group for the aforementioned coating composition, in the above Chemical Formula 15, D 1 is an acrylonitrile (methacryl oxime) group, that is, a tricyclic fluorenyl group Examples of commercially available materials of (meth) acrylate include IRR214-K (Daicel-Allnex Co., Ltd.), SR833S (Sartomer), FA-513AS, and FA-513M (Hitachi Kasei Co., Ltd.). A-DCP, DCP (Xinzhongcun Chemical Co., Ltd.), Light Acrylate DCP-A (Kyoeisha Chemical Co., Ltd.).
[氟化合物鏈段] [fluorochemical segment]
於本發明之積層薄膜中,表面層中所含有的樹脂較佳為包含(5)氟化合物鏈段。表面層中所含有的樹脂若包含(5)氟化合物鏈段,則可提高表面層的防污性及耐指紋性而較佳。 In the laminated film of the present invention, the resin contained in the surface layer preferably contains (5) a fluorine compound segment. When the resin contained in the surface layer contains the (5) fluorine compound segment, the antifouling property and the fingerprint resistance of the surface layer can be improved.
為了形成表面層而使用的塗料組成物,係 藉由包含含有氟化合物鏈段的樹脂或前驅物,而可使表面層中所含有的樹脂具有氟化合物鏈段。 a coating composition used to form a surface layer The resin contained in the surface layer can have a fluorine compound segment by including a resin or a precursor containing a fluorine compound segment.
氟化合物鏈段係指包含選自由氟烷基、氟 氧基烷基、氟烯基、氟烷二基及氟氧基烷二基所構成之群組的至少一者之鏈段。 Fluorine compound segment means comprising selected from fluoroalkyl, fluorine A segment of at least one of the group consisting of an oxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluoroaloxanediyl group.
此處,所謂的氟烷基、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全部經取代成氟的取代基,皆為主要由氟原子與碳原子所構成之取代基,結構中可具有分支,亦可形成具有此等部位的結構所複數連結之二聚物、三聚物、寡聚物、聚合物結構。 Here, the so-called fluoroalkyl, fluoroalkyl, fluoroolefin a fluoroalkanediyl group or a fluoroalkanediyl group, which is a substituent which is partially or wholly substituted with a fluorine of an alkyl group, an oxyalkyl group, an alkenyl group, an alkanediyl group or an oxyalkanediyl group. All of them are substituents mainly composed of a fluorine atom and a carbon atom, and may have a branch in the structure, and may also form a dimer, a trimer, an oligomer, a polymer structure in which a plurality of structures having such a structure are linked. .
又,作為前述氟化合物鏈段,較佳為氟聚 醚鏈段,此係由氟烷基、氧基氟烷基、氧基氟烷二基等所構成之部位,而更佳為以化學式(6)、化學式(7)為代表 的氟聚醚鏈段則已如上述。 Further, as the fluorine compound segment, fluoropolymer is preferred An ether segment, which is a moiety composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, etc., and more preferably represented by a chemical formula (6) or a chemical formula (7). The fluoropolyether segment is as described above.
以此表面層中所含有的樹脂包含氟化合 物鏈段而言,前述之塗料組成物較佳為包含以下之氟化合物。此氟化合物係化學式16所示的化合物。 The resin contained in the surface layer contains a fluoride compound In the case of the article segment, the aforementioned coating composition preferably contains the following fluorine compound. This fluorine compound is a compound represented by Chemical Formula 16.
R f1 -R B -D 1 ...化學式16 R f1 -R B -D 1 . . . Chemical formula 16
此處,Rf1表示氟化合物鏈段,R8表示烷二基、烷三基及由彼等所衍生的酯結構、胺基甲酸酯結構、醚結構、三結構,D1表示反應性部位。 Here, R f1 represents a fluorine compound segment, R 8 represents an alkanediyl group, an alkanetriyl group, and an ester structure derived therefrom, a urethane structure, an ether structure, and three 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它成分反應之部位。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、羥基、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、矽烷基醚基或矽烷醇基、或環氧基、丙烯醯(甲基丙烯醯)基。 This reactive site refers to a site that reacts with other components due to external energy such as heat or light. Examples of such a reactive site include a stanol group in which alkoxyalkylene group and alkoxyalkylene group are hydrolyzed, or a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allylic group, from the viewpoint of reactivity. Base, propylene sulfhydryl, methacryl fluorenyl and the like. Among them, from the viewpoint of reactivity and handleability, a vinyl group, an allyl group, an alkoxyalkyl group, a decyl ether group or a stanol group, or an epoxy group or a propylene group (methacryl oxime) is preferred. )base.
氟化合物之一例係以下所示的化合物。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、丙烯酸2,2,2-三氟乙酯、丙烯 酸2,2,3,3,3-五氟丙酯、丙烯酸2-全氟丁基乙酯、丙烯酸3-全氟丁基-2-羥基丙酯、丙烯酸2-全氟己基乙酯、丙烯酸3-全氟己基-2-羥基丙酯、丙烯酸2-全氟辛基乙酯、丙烯酸3-全氟辛基-2-羥基丙酯、丙烯酸2-全氟癸基乙酯、丙烯酸2-全氟-3-甲基丁基乙酯、丙烯酸3-全氟-3-甲氧基丁基-2-羥基丙酯、丙烯酸2-全氟-5-甲基己基乙酯、丙烯酸3-全氟-5-甲基己基-2-羥基丙酯、丙烯酸2-全氟-7-甲基辛基-2-羥基丙酯、丙烯酸四氟丙酯、丙烯酸八氟戊酯、丙烯酸十二氟庚酯、丙烯酸十六氟壬酯、丙烯酸六氟丁酯、甲基丙烯酸2,2,2-三氟乙酯、甲基丙烯酸2,2,3,3,3-五氟丙酯、甲基丙烯酸2-全氟丁基乙酯、甲基丙烯酸3-全氟丁基-2-羥基丙酯、甲基丙烯酸2-全氟辛基乙酯、甲基丙烯酸3-全氟辛基-2-羥基丙酯、甲基丙烯酸2-全氟癸基乙酯、甲基丙烯酸2-全氟-3-甲基丁基乙酯、甲基丙烯酸3-全氟-3-甲基丁基-2-羥基丙酯、甲基丙烯酸2-全氟-5-甲基己基乙酯、甲基丙烯酸3-全氟-5-甲基己基-2-羥基丙酯、甲基丙烯酸2-全氟-7-甲基辛基乙酯、甲基丙烯酸3-全氟-6-甲基辛酯、甲基丙烯酸四氟丙酯、甲基丙烯酸八氟戊酯、甲基丙烯酸八氟戊酯、甲基丙烯酸十二氟庚酯、甲基丙烯酸十六氟壬酯、甲基丙烯酸1-三氟甲基三氟乙酯、甲基丙烯酸六氟丁酯、三丙烯醯基-十七氟壬烯基-季戊四醇等。 One of the fluorine compounds is exemplified by the compounds shown below. 3,3-trifluoropropyltrimethoxydecane, 3,3,3-trifluoropropyltriethoxydecane, 3,3,3-trifluoropropyltriisopropoxydecane, 3,3, 3-trifluoropropyltrichloromethane, 3,3,3-trifluoropropyltriisocyanate decane, 2-perfluorooctyltrimethoxydecane, 2-perfluorooctylethyltriethoxydecane, 2 -Perfluorooctylethyltriisopropoxydecane, 2-perfluorooctylethyltrichlorodecane, 2-perfluorooctyl isocyanate decane, 2,2,2-trifluoroethyl acrylate, propylene Acid 2,2,3,3,3-pentafluoropropyl ester, 2-perfluorobutyl ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, acrylic acid 3-perfluorohexyl-2-hydroxypropyl ester, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecyl acrylate, 2-all of acrylic acid Fluoro-3-methylbutylethyl ester, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3-perfluoroacrylate -5-Methylhexyl-2-hydroxypropyl ester, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate , hexadecafluorodecyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, methacrylic acid 2 -Perfluorobutylethyl ester, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluorooctyl methacrylate, 3-perfluorooctyl-2-hydroxypropane methacrylate Ester, 2-perfluorodecyl methacrylate, 2-perfluoro-3-methylbutyl methacrylate, 3-perfluoro-3-methyl methacrylate Butyl-2-hydroxypropyl ester, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, methacrylic acid 2 -Perfluoro-7-methyloctylethyl ester, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate Ester, dodecafluoroheptyl methacrylate, hexadecafluorodecyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, tripropylene decyl-heptadecafluoro Decenyl-pentaerythritol and the like.
再者,氟化合物亦可每1分子具有複數的 氟聚醚部位。 Furthermore, the fluorine compound may have a plurality of molecules per molecule. Fluoropolyether site.
作為上述氟化合物的市售例,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,而可利用此等之製品。 As a commercially available example of the above fluorine compound, RS-75 (DIC stock) is exemplified. Ltd.), Optool DAC-HP (DAIKIN Industries Co., Ltd.), C10GACRY, C8HGOL (Oil Products Co., Ltd.), etc., and can use such products.
[聚碳酸酯鏈段] [polycarbonate segment]
於本發明之積層薄膜中,表面層中所含有的樹脂較佳為包含(6)聚碳酸酯鏈段。此處所謂的聚碳酸酯鏈段,就是指前述化學式8所示的鏈段。表面層中所含有的樹脂若含有(6)聚碳酸酯鏈段,則可提高表面層的強韌性及自我修復性而較佳。 In the laminated film of the present invention, the resin contained in the surface layer preferably contains (6) a polycarbonate segment. The polycarbonate segment referred to herein means the segment shown in the above Chemical Formula 8. When the resin contained in the surface layer contains (6) a polycarbonate segment, it is preferable to improve the toughness and self-healing property of the surface layer.
為了形成表面層而使用的塗料組成物,係藉由包含含有聚碳酸酯鏈段的樹脂或前驅物,而可使表面層中所含有的樹脂具有聚碳酸酯鏈段。 The coating composition used to form the surface layer can have a polycarbonate segment in the resin contained in the surface layer by including a resin or a precursor containing a polycarbonate segment.
含有聚碳酸酯鏈段的樹脂,較佳為具有至少1個以上的羥基(hydroxyl group)。羥基較佳為在含有聚碳酸酯鏈段的樹脂之末端。 The resin containing a polycarbonate segment preferably has at least one or more hydroxyl groups. The hydroxyl group is preferably at the end of the resin containing the polycarbonate segment.
作為含有聚碳酸酯鏈段的樹脂,特佳為具有2官能的羥基之聚碳酸酯二醇。具體而言為化學式(17)所示的聚碳酸酯二醇。 As the resin containing a polycarbonate segment, a polycarbonate diol having a bifunctional hydroxyl group is particularly preferred. Specifically, it is a polycarbonate diol represented by the chemical formula (17).
(R9係碳數1~8的烷基之任一者,n係1以上之整數)。 (R 9 is any one of alkyl groups having 1 to 8 carbon atoms, and n is an integer of 1 or more).
聚碳酸酯二醇係碳酸酯單元的重複數為多少皆可,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降低,故重複數n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 any, but if the number of repetitions of the carbonate unit is too large, the urethane (methyl) Since the strength of the cured acrylate is lowered, the number of repetitions n is preferably 10 or less. Further, the polycarbonate diol may be a mixture of two or more kinds of polycarbonate diols having different numbers of repeating carbonate units.
聚碳酸酯二醇係數量平均分子量較佳為 500~10,000,更佳為1,000~5,000。數量平均分子量若小於500,則有難以得到合適的柔軟性之情況,又數量平均分子量若超過10,000,則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 coefficient amount average molecular weight is preferably 500~10,000, more preferably 1,000~5,000. When the number average molecular weight is less than 500, it may be difficult to obtain appropriate flexibility, and if the number average molecular weight exceeds 10,000, heat resistance or solvent resistance may be lowered.
又,作為本發明所用之聚碳酸酯二醇,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(KURARAY股份有限公司)、Duranol系列(旭化成化學股份有限公司)等之製品。此等聚碳酸酯二醇係可單獨或組合二種類以上使用。 Further, as the polycarbonate diol used in the present invention, Suitably exemplified UH-CARB, UD-CARB, UC-CARB (Ube Industries Co., Ltd.), PLACCEL CD-PL, PLACCEL CD-H (DAICEL Chemical Industry Co., Ltd.), KURARAY Polyol C Series (KURARAY Limited Shares) Company), Duranol series (Asahi Kasei Chemical Co., Ltd.) and other products. These polycarbonate diols can be used singly or in combination of two or more kinds.
再者,於本發明中,含有聚碳酸酯鏈段的 樹脂或前驅物,係除了聚碳酸酯鏈段,還可含有(或共聚合)其它的鏈段或單體。例如,可含有(或共聚合)包含前述聚己內酯鏈段、三環癸基鏈段、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 polycarbonate segment is included The resin or precursor, in addition to the polycarbonate segment, may also contain (or copolymerize) other segments or monomers. For example, a compound containing the aforementioned polycaprolactone segment, tricyclodecyl segment, polydimethylsiloxane chain segment or polyoxyalkylene segment, or isocyanate compound may be contained (or copolymerized).
本發明中,較佳為藉由使前述含有異氰酸 酯基的化合物與聚碳酸酯二醇之羥基反應,作為胺基甲酸酯(甲基)丙烯酸酯使用於塗料組成物,而可使表面層具有(6)聚碳酸酯鏈段及(2)胺基甲酸酯鍵,結果可提高表面層的強韌性,同時提高自我修復性而較佳。 In the present invention, it is preferred that the aforementioned isocyanic acid is contained The ester group compound reacts with the hydroxyl group of the polycarbonate diol, and is used as a urethane (meth) acrylate for the coating composition, and the surface layer can have (6) a polycarbonate segment and (2) The urethane bond results in an increase in the toughness of the surface layer while improving self-healing properties.
[溶劑] [solvent]
前述塗料組成物亦可包含溶劑。溶劑的種類數較佳為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,特佳為1種類以上4種類以下。 The aforementioned coating composition may also contain a solvent. The number of the types of the solvent is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.
此處所謂的「溶劑」,就是指在塗布後的 乾燥步驟中可幾乎全量蒸發,在常溫、常壓下為液體之物質。 The term "solvent" as used herein refers to after coating. In the drying step, almost all of the evaporation can be carried out, and it is a liquid substance at normal temperature and normal pressure.
此處,溶劑的種類係由構成溶劑的分子結 構所決定。即,即使相同的元素組成且官能基的種類與數目為相同,結合關係相異者(結構異構物);以及雖然不是前述結構異構物,但在3次元空間內採取何種構形也無法緊密地重疊者(立體異構物),係作為種類相異的溶劑操作。例如2-丙醇與正丙醇係作為相異的溶劑操作。 Here, the type of solvent is a molecular knot constituting a solvent. The structure decided. That is, even if the same element composition and the type and number of functional groups are the same, the binding relationship is different (structural isomers); and although not the structural isomers described above, what configuration is adopted in the 3-dimensional space Those that cannot be closely overlapped (stereoisomers) are handled as solvents of different types. For example, 2-propanol and n-propanol are operated as dissimilar solvents.
再者,包含溶劑時,較佳為顯示以下特性 之溶劑。 Further, when a solvent is contained, it is preferred to exhibit the following characteristics Solvent.
條件1將以乙酸正丁酯為基準的相對 蒸發速度(ASTM D3539-87(2004))為最低之溶劑當作溶劑B時,溶劑B之相對蒸發速度為0.4以下。 Condition 1 will be based on n-butyl acetate relative When the evaporation rate (ASTM D3539-87 (2004)) is the lowest solvent as the solvent B, the relative evaporation rate of the solvent B is 0.4 or less.
此處,所謂以溶劑的乙酸正丁酯為基準之 相對蒸發速度,就是根據ASTM D3539-87(2004)所測定之蒸發速度。具體而言,係作為以在乾燥空氣下乙酸正丁酯蒸發90質量%時所需要的時間為基準之蒸發速度的相對值所定義之值。 Here, the reference is based on n-butyl acetate in a solvent. The relative evaporation rate is the evaporation rate measured according to ASTM D3539-87 (2004). Specifically, it is a value defined as a relative value of the evaporation rate based on the time required for evaporation of n-butyl acetate under dry air at 90% by mass.
前述溶劑的相對蒸發速度比0.4還大時, 由於前述聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段、及氟化合物鏈段之對於表面層中的最表面之配向所需要的時間變短,有發生所得之積層薄膜的自我修復性及防污性降低之情況。又,前述溶劑B的相對蒸發速度之下限,只要是在乾燥步驟中蒸發而可自塗膜去除之溶劑,則無問題,於一般的塗布步驟中,可為0.005以上。 When the relative evaporation rate of the aforementioned solvent is greater than 0.4, Since the time required for the alignment of the polyoxyalkylene segment and/or the polydimethylsiloxane chain segment and the fluorine compound segment with respect to the outermost surface in the surface layer is shortened, the resulting laminated film occurs. Reduced self-healing and anti-fouling properties. Further, the lower limit of the relative evaporation rate of the solvent B is not particularly limited as long as it is a solvent which can be removed from the coating film by evaporation in the drying step, and may be 0.005 or more in a general coating step.
作為溶劑B,有異丁酮(相對蒸發速度: 0.2)、異佛爾酮(相對蒸發速度:0.026)、二乙二醇單丁基醚(相對蒸發速度:0.004、)、二丙酮醇(相對蒸發速度:0.15)、油醇(相對蒸發速度:0.003)、乙二醇單乙基醚乙酸酯(相對蒸發速度:0.2)、壬基苯氧基乙醇(相對蒸發速度:0.25)、丙二醇單乙基醚(相對蒸發速度:0.1)、環己酮(相對蒸發速度:0.32)等。 As solvent B, there is isobutyrone (relative evaporation rate: 0.2), isophorone (relative evaporation rate: 0.026), diethylene glycol monobutyl ether (relative evaporation rate: 0.004,), diacetone alcohol (relative evaporation rate: 0.15), oleyl alcohol (relative evaporation rate: 0.003), ethylene glycol monoethyl ether acetate (relative evaporation rate: 0.2), nonylphenoxyethanol (relative evaporation rate: 0.25), propylene glycol monoethyl ether (relative evaporation rate: 0.1), cyclohexyl Ketone (relative evaporation rate: 0.32) and the like.
[塗料組成物中的其它成分] [Other ingredients in the coating composition]
又,前述塗料組成物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用於促進表面層之硬化。作為聚合起始劑,較佳為對於塗料組成物中所含有的成分,可開始或促進陰離子、陽離子、自由基聚合反應等所致的聚合、縮合或交聯反應者。 Further, the coating composition preferably contains a polymerization initiator or a hardener or a catalyst. The polymerization initiator and the catalyst are used to promote the hardening of the surface layer. As the polymerization initiator, it is preferred that the component contained in the coating composition can initiate or promote polymerization, condensation or crosslinking reaction due to anion, cation, radical polymerization or the like.
聚合起始劑、硬化劑及觸媒係可使用各種 者。又,聚合起始劑、硬化劑及觸媒係可各自單獨使用,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。作為酸性觸媒之例,可舉出鹽酸水溶液、甲酸、乙酸等。作為熱聚合起始劑之例,可舉出過氧化物、偶氮化合物。另外,作為 光聚合起始劑之例,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。還有,作為促進胺基甲酸酯鍵的形成反應之交聯觸媒之例,可舉出二月桂酸二丁錫、二乙基己酸二丁錫等。 Various polymerization initiators, hardeners and catalysts can be used. By. Further, the polymerization initiator, the curing agent, and the catalyst may be used singly or in combination with a plurality of polymerization initiators, hardeners, and catalysts. Further, an acid catalyst or a thermal polymerization initiator may be used in combination. Examples of the acidic catalyst include an aqueous hydrochloric acid solution, formic acid, acetic acid, and the like. Examples of the thermal polymerization initiator include a peroxide and an azo compound. In addition, as Examples of the photopolymerization initiator include an alkylphenone compound, a sulfur-containing compound, a mercaptophosphine oxide compound, and an amine compound. Further, examples of the crosslinking catalyst that promotes the formation reaction of the urethane bond include dibutyltin dilaurate and dibutyltin diethylhexanoate.
又,前述塗料組成物亦可包含烷氧基羥甲 基三聚氰胺等的三聚氰胺交聯劑、3-甲基-六氫苯二甲酸酐等的酸酐系交聯劑、二乙基胺基丙基胺等的胺系交聯劑等之其它交聯劑。 Further, the coating composition may also contain an alkoxyl group Other crosslinking agents such as a melamine crosslinking agent such as melamine, an acid anhydride crosslinking agent such as 3-methyl-hexahydrophthalic anhydride, or an amine crosslinking agent such as diethylaminopropylamine.
作為光聚合起始劑,從硬化性之點來看, 較佳為烷基苯酮系化合物。作為烷基苯酮系化合物之具體例,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。 As a photopolymerization initiator, from the viewpoint of hardenability, An alkylphenone-based compound is preferred. Specific examples of the alkylphenone compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and 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-di Methylamino-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)oxydiethylene, and the materials thereof Polymer quantifiers.
又,只要是不妨礙本發明的效果之範圍, 則於用於形成表面層的塗料組成物中,亦可添加均平劑、紫外線吸收劑、滑劑、抗靜電劑等。藉此,表面層可含有均平劑、紫外線吸收劑、滑劑、抗靜電劑等。作為均平劑之例,可舉出丙烯酸共聚物或矽氧系、氟系之 均平劑。作為紫外線吸收劑之具體例,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。作為抗靜電劑之例,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 does not impair the effect of the present invention, a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, or the like may be added to the coating composition for forming the surface layer. Thereby, the surface layer may contain a leveling agent, an ultraviolet absorber, a slip agent, an antistatic agent, or the like. Examples of the leveling agent include an acrylic copolymer, a fluorene-based, and a fluorine-based leveling agent. Specific examples of the ultraviolet absorber include diphenylketone, benzotriazole, oxalic acid, and And a hindered amine-based UV absorber. Examples of the antistatic agent include metal salts such as a lithium salt, a sodium salt, a potassium salt, a phosphonium salt, a phosphonium salt, a magnesium salt, and a calcium salt.
[積層薄膜之製造方法] [Manufacturing method of laminated film]
本發明之積層薄膜之表面上所形成的表面層,較佳為使用藉由將前述塗料組成物在前述支撐基材上塗布-乾燥-硬化而形成之製造方法。以下,將塗布之步驟記述為塗布步驟,將乾燥之步驟記述為乾燥步驟,將硬化之步驟記述為硬化步驟。 The surface layer formed on the surface of the laminated film of the present invention is preferably a production method formed by coating-drying-hardening the above-mentioned coating composition on the above-mentioned supporting substrate. Hereinafter, the step of coating is described as a coating step, the step of drying is described as a drying step, and the step of curing is described as a curing step.
於塗布步驟中,塗布塗料組成物之方法係 沒有特別的限定,但較佳為藉由浸塗法、輥塗法、線棒塗布法、凹版塗布法或模塗法(美國專利第2681294號說明書)等,將塗料組成物塗布於支撐基材上而形成表面層。再者,於此等塗布方式之中,凹版塗布法或模塗法係作為塗布方法更佳。 In the coating step, the method of applying the coating composition is There is no particular limitation, but it is preferred to apply the coating composition to the support substrate by dip coating, roll coating, wire bar coating, gravure coating or die coating (U.S. Patent No. 2,681,294). Form a surface layer. Further, among these coating methods, the gravure coating method or the die coating method is more preferable as the coating method.
於塗布步驟之後,藉由乾燥步驟來乾燥在 支撐基材之上所塗布的液膜。從自所得之積層薄膜中完全地去除溶劑之觀點來看,於乾燥步驟中較佳為伴隨液膜之加熱。 After the coating step, drying is performed by a drying step A liquid film coated on the support substrate. From the viewpoint of completely removing the solvent from the obtained laminated film, it is preferred to carry out heating with the liquid film in the drying step.
關於乾燥步驟的乾燥方法,可舉出傳熱乾 燥(緊貼於高熱物體)、對流傳熱(熱風)、輻射傳熱(紅外線)、其它(微波、感應加熱)等。其中,於本發明之製造方法中,從精密地在寬度方向中亦需要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。 Regarding the drying method of the drying step, heat transfer can be mentioned Dry (close to high heat objects), convective heat transfer (hot air), radiation heat transfer (infrared), other (microwave, induction heating), etc. Among them, in the production method of the present invention, it is preferable to use convection heat transfer or radiation heat transfer from the viewpoint of precisely making the drying speed uniform in the width direction.
乾燥步驟之乾燥過程一般分為(A)恒率乾 燥期間、(B)減率乾燥期間,前者係由於在液膜表面,溶劑分子對大氣中的擴散成為乾燥之速率限制,故乾燥速度係在此區間中固定,乾燥速度係被大氣中的被蒸發溶劑分壓、風速、溫度所支配,膜面溫度係由熱風溫度與大氣中的被蒸發溶劑分壓所決定之值而成為固定。後者係由於液膜中的溶劑之擴散成為速率限制,故乾燥速度在此區間中不顯示固定值而繼續降低,被液膜中的溶劑之擴散係數所支配,膜面溫度係上升。此處所謂的乾燥速度,就是表示每單位時間、單位面積的溶劑蒸發量,由g.m-2.s-1之次元所構成。 The drying process in the drying step is generally divided into (A) constant rate drying period, (B) decrement drying period, the former is due to the rate of drying of the solvent molecules in the atmosphere on the surface of the liquid film, so the drying speed is The interval is fixed, and the drying speed is governed by the partial pressure of the evaporating solvent in the atmosphere, the wind speed, and the temperature. The film surface temperature is fixed by the value determined by the hot air temperature and the partial pressure of the evaporated solvent in the atmosphere. In the latter case, since the diffusion of the solvent in the liquid film is rate-limiting, the drying rate does not show a fixed value in this section and continues to decrease, and is controlled by the diffusion coefficient of the solvent in the liquid film, and the film surface temperature rises. The so-called drying speed here means the amount of solvent evaporation per unit time and unit area, by g. m -2 . The s -1 is composed of dimensions.
前述乾燥速度有較佳範圍,較佳為0.1g. m-2.s-1以上10g.m-2.s-1以下,更佳為0.1g.m-2.s-1以上5g.m-2.s-1以下。藉由使恒率乾燥區間中的乾燥速度成為此範圍,可防止因乾燥速度的不均勻所造成的不均。只要得到0.1g.m-2.s-1以上10g.m-2.s-1以下之範圍的乾燥速度,則不受特定的風速、溫度所特別限定。 The aforementioned drying speed has a preferred range, preferably 0.1 g. m -2 . s -1 or more 10g. m -2 . s -1 or less, more preferably 0.1g. m -2 . s -1 or more 5g. m -2 . s -1 or less. By making the drying speed in the constant-rate drying section into this range, it is possible to prevent unevenness due to unevenness in drying speed. Just get 0.1g. m -2 . s -1 or more 10g. m -2 . The drying speed in the range of s -1 or less is not particularly limited by the specific wind speed and temperature.
於本發明的積層薄膜之製造方法中,在減 率乾燥期間進行殘存溶劑的蒸發,同時進行聚矽氧烷鏈段及/或聚二甲基矽氧烷鏈段及氟化合物鏈段之配向。於此過程中,由於需要配向的時間,而在減率乾燥期間的膜面溫度上升速度有較佳的範圍存在,較佳為5℃/秒以下,更佳為1℃/秒以下。 In the method for producing a laminated film of the present invention, The evaporation of the residual solvent is carried out during the drying, and the alignment of the polyoxyalkylene segment and/or the polydimethyloxyalkylene segment and the fluorine compound segment is carried out simultaneously. In this process, since the time required for the alignment is required, the film surface temperature rising rate during the decrement drying period is preferably in the range of preferably 5 ° C / sec or less, more preferably 1 ° C / sec or less.
再者,亦可進行藉由照射熱或能量線而進 一步的硬化操作(硬化步驟)。 Furthermore, it can also be carried out by illuminating heat or energy rays. One-step hardening operation (hardening step).
又,藉由活性能量線進行硬化時,從泛用性之點來看,較佳為EB線及/或UV線。另外,藉由紫外線進行硬化時,從可防止氧阻礙來看,較佳為氧濃度儘可能地低,更佳為在氮氣環境下(氮沖洗)進行硬化。氧濃度高時,阻礙最表面之硬化,表面的硬化變不充分,自我修復性及密接耐久性有不充分之情況。又,作為照射紫外線時所用之紫外線燈的種類,例如可舉出放電燈方式、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其進行紫外線硬化時,係在紫外線之照度為100~3,000mW/cm2,較佳為200~2,000mW/cm2,更佳為300~1,500mW/cm2之條件下進行紫外線照射,而在紫外線之累積光量為100~3,000mJ/cm2,較佳為200~2,000mJ/cm2,更佳為300~1,500mJ/cm2之條件下進行紫外線照射。此處,所謂的紫外線之照度,係每單位面積受到的照射強度,係隨著燈輸出、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,照度係不隨著運送速率而變化。又,所謂的紫外線累積光量,係每單位面積受到的照射能量,而為到達其表面的光子之總量。累積光量係與通過光源下的照射速度呈反比例,與照射次數和燈數呈比例。 Further, when hardened by the active energy ray, it is preferably an EB line and/or an UV line from the viewpoint of versatility. Further, when curing by ultraviolet rays, it is preferable that the oxygen concentration is as low as possible from the viewpoint of preventing oxygen barrier, and it is more preferable to perform hardening in a nitrogen atmosphere (nitrogen flushing). When the oxygen concentration is high, the hardening of the outermost surface is inhibited, the hardening of the surface is insufficient, and the self-healing property and the adhesion durability are insufficient. Moreover, examples of the type of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash mode, a laser method, and an electrodeless lamp method. When ultraviolet ray hardening is performed by a high-pressure mercury lamp of a discharge lamp type, the illuminance of ultraviolet rays is 100 to 3,000 mW/cm 2 , preferably 200 to 2,000 mW/cm 2 , more preferably 300 to 1,500 mW/cm 2 . under ultraviolet irradiation conditions, the cumulative light quantity of ultraviolet light is 100 ~ 3,000mJ / cm 2, preferably 200 ~ 2,000mJ / cm 2, more preferably ultraviolet irradiation at 300 ~ 1,500mJ / cm 2 of conditions. Here, the illuminance of the ultraviolet ray is the intensity of the illumination per unit area, which varies depending on the lamp output, the luminescence spectral efficiency, the diameter of the illuminating bulb, the design of the mirror, and the distance from the light source of the object to be irradiated. However, the illuminance does not vary with the transport rate. Further, the amount of ultraviolet light accumulated is the amount of photons received per unit area, and is the total amount of photons reaching the surface. The cumulative amount of light is inversely proportional to the illumination rate through the light source, and is proportional to the number of illuminations and the number of lamps.
[用途例] [Example of use]
本發明之積層薄膜係活用成型性、自我修復性、密接耐久性及防污性等優點,在藉由成型而成型為各式各 樣的成型體之用途中,尤其可適用於要求高的耐擦傷性,希望傷痕不易顯眼的用途。 The laminated film of the present invention has the advantages of moldability, self-healing property, adhesion durability, and antifouling property, and is molded into various types by molding. Among the uses of the molded article, it is particularly applicable to applications requiring high scratch resistance and desirability of scarring.
若舉一例,可適用於眼鏡.太陽鏡、化妝 箱、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 glasses. Sunglasses, makeup Plastic molded products such as boxes and food containers, smart phone cases, touch panels, keyboards, and televisions. Home appliances, buildings, dashboards, and navigation navigators for remote controls such as air conditioners. Vehicle interiors such as touch panels and interior mirrors, and the respective surfaces of various printed materials.
其次,基於實施例來說明本發明,惟本發明不必受此等所限定。 Next, the present invention will be described based on the examples, but the present invention is not necessarily limited by the above.
[胺基甲酸酯(甲基)丙烯酸酯A] [urethane (meth) acrylate A]
[胺基甲酸酯(甲基)丙烯酸酯A1之合成] [Synthesis of urethane (meth) acrylate A1]
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乙酯(DAICEL化學工業股份有限公司製「Placcel」(註冊商標)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%之胺基甲酸酯(甲基)丙烯酸酯A1的甲苯溶液。 50 parts by mass of toluene, 50 parts by mass of hexamethylene diisocyanate modified type of isocyanurate ("Takenate" (registered trademark) D-170N, manufactured by Mitsui Chemicals, Inc.), 76 parts by mass Polycaprolactone-modified hydroxyethyl acrylate ("Placcel" (registered trademark) 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. Hold at 70 ° C for 5 hours. Then, 79 parts by mass of toluene was added to obtain a toluene solution of urethane (meth)acrylate A1 having a solid concentration of 50% by mass.
[胺基甲酸酯(甲基)丙烯酸酯A2之合成] [Synthesis of urethane (meth) acrylate A2]
混合50質量份的甲苯、67質量份的H6XDI Nurate(三井化學股份有限公司製D-127N,NCO含量13.5質量%)、76質量份的聚己內酯改性丙烯酸羥乙酯(DAICEL化學工業股份有限公司製「Placcel」(註冊商 標)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%之胺基甲酸酯(甲基)丙烯酸酯A2的甲苯溶液。 50 parts by mass of toluene, 67 parts by mass of H6XDI Nurate (D-127N manufactured by Mitsui Chemicals, Inc., NCO content 13.5 mass%), and 76 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (DAICEL Chemical Industry Co., Ltd.) Limited "Placcel" (Registrar) Standard) FA5), 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 urethane (meth) acrylate A 2 having a solid concentration of 50% by mass.
[胺基甲酸酯(甲基)丙烯酸酯A3之合成] [Synthesis of urethane (meth) acrylate A3]
混合50質量份的甲苯、50質量份的六亞甲基二異氰酸酯之縮二脲改性類型(旭化成化學股份有限公司製「Duranate」(註冊商標)24A-90CX,不揮發分:90質量%,異氰酸酯含量:21.2質量%)、92質量份的聚己內酯改性丙烯酸羥乙酯(DAICEL化學工業股份有限公司製「Placcel」(註冊商標)FA2D)、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82質量份的甲苯,得到固體成分濃度50質量%之胺基甲酸酯(甲基)丙烯酸酯A3的甲苯溶液。 a biuret modified type of 50 parts by mass of toluene and 50 parts by mass of hexamethylene diisocyanate (Duranate (registered trademark) 24A-90CX manufactured by Asahi Kasei Chemicals Co., Ltd., nonvolatile matter: 90% by mass, Isocyanate content: 21.2% by mass), 92 parts by mass of polycaprolactone-modified hydroxyethyl acrylate ("Placcel" (registered trademark) FA2D 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 was kept at 70 ° C for 5 hours. Then, 82 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate A3 having a solid concentration of 50% by mass.
[胺基甲酸酯(甲基)丙烯酸酯B] [urethane (meth) acrylate B]
[胺基甲酸酯(甲基)丙烯酸酯B1之合成] [Synthesis of urethane (meth) acrylate B1]
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(協和發酵麒麟股份有限公司製LDI)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」(註冊商標)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(共榮社化學股份有限公司製Light Ester HOA)、5質量份的二季戊四醇六丙烯酸酯(東亞合成股份有限公司製M-400)、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%之胺基甲酸酯(甲基)丙烯酸酯B1的甲苯溶液。 100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate (LDI manufactured by Kyowa Fermentation Kylin Co., Ltd.), and 119 parts by mass of polycarbonate diol (DAICEL Chemical Industry Co., Ltd.) "Placcel" (registered trademark) CD-210HL, which was heated to 40 ° C for 8 hours, and then added 28 parts by mass of 2-hydroxyethyl acrylate (Light Ester HOA, manufactured by Kyoeisha Chemical Co., Ltd.), 5 Parts by mass of dipentaerythritol hexaacrylate (M-400 manufactured by Toagosei Co., Ltd.) and 0.02 parts by mass of hydroquinone monomethyl ether were added at 0.02 ° C for 30 minutes, and then 0.02 parts by mass of dibutyltin laurate was added. Keep at 80 ° C 6 hours. Further, 97 parts by mass of toluene was finally added to obtain a toluene solution of urethane (meth)acrylate B1 having a solid concentration of 50% by mass.
[胺基甲酸酯(甲基)丙烯酸酯B2之合成] [Synthesis of urethane (meth) acrylate B2]
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(協和發酵麒麟股份有限公司製LDI)及150質量份的聚碳酸酯二醇(DAICEL化學工業股份有限公司製「Placcel」(註冊商標)CD-220),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(共榮社化學股份有限公司製Light Ester HOA)、5質量份的二季戊四醇六丙烯酸酯(東亞合成股份有限公司製M-400)、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%之胺基甲酸酯(甲基)丙烯酸酯B2的甲苯溶液。 100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate (LDI manufactured by Kyowa Ukrainian Kirin Co., Ltd.), and 150 parts by mass of polycarbonate diol (DAICEL Chemical Industry Co., Ltd.) "Placcel" (registered trademark) CD-220) was heated to 40 ° C for 8 hours. Then, 28 parts by mass of 2-hydroxyethyl acrylate (Light Ester HOA manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of dipentaerythritol hexaacrylate (M-400 manufactured by Toagosei Co., Ltd.), and 0.02 mass were added. The hydroquinone monomethyl ether was kept at 70 ° C for 30 minutes, and then 0.02 parts by mass of dibutyltin laurate was added and kept at 80 ° C for 6 hours. Further, 97 parts by mass of toluene was finally added to obtain a toluene solution of urethane (meth)acrylate B2 having a solid concentration of 50% by mass.
[胺基甲酸酯(甲基)丙烯酸酯C] [urethane (meth) acrylate C]
[胺基甲酸酯(甲基)丙烯酸酯C1之合成] [Synthesis of urethane (meth) acrylate C1]
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%之胺基甲酸酯(甲基)丙烯酸酯C1。 50 parts by mass of a modified isocyanurate modified from hexamethylene diisocyanate (Takenate (registered trademark) D-170N, manufactured by Mitsui Chemicals, Inc., isocyanate group content: 20.09% by mass), 53 mass Polyethylene glycol monoacrylate ("Blemmer" (registered trademark) AE-150, Nippon Oil Co., Ltd., hydroxyl value: 264 (mgKOH/g)), 0.02 parts by mass of dibutyltin laurate and 0.02 mass A portion of hydroquinone monomethyl ether. Then, the reaction was carried out by maintaining 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 liquid to obtain a urethane (meth) acrylate C1 having a solid concentration of 50% by mass.
[矽氧烷化合物] [矽 oxane compound]
[矽氧烷化合物1] [矽 oxane compound 1]
作為矽氧烷化合物1,使用矽二丙烯酸酯化合物(EBECRYL350 DAICEL.CYTEC股份有限公司製 固體成分濃度100質量%)。 As the decane compound 1, a decane diacrylate compound (solid content concentration: 100% by mass manufactured by EBECRYL350 DAICEL. CYTEC Co., Ltd.) was used.
[矽氧烷化合物2] [矽 oxane compound 2]
作為矽氧烷化合物2,使用矽六丙烯酸酯化合物(EBECRYL1360 DAICEL.CYTEC股份有限公司製 固體成分濃度100質量%)。 As the decane compound 2, a hexa hexaacrylate compound (solid content concentration: 100% by mass manufactured by EBECRYL 1360 DAICEL. CYTEC Co., Ltd.) was used.
[聚矽氧烷(a)之合成] [Synthesis of polyoxyalkylene (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,冷卻而得到黏稠的聚矽氧烷(a)。 In a 500 ml-capacity flask equipped with a stirrer, a thermometer, a condenser, and a 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 mass were charged. After maintaining hydrochloric acid at 85 ° C for 2 hours, ethanol was recovered and the temperature was maintained at 180 ° C for 3 hours. Then, it was cooled to obtain a viscous polyoxyalkylene (a).
[聚二甲基矽氧烷系嵌段共聚物(a)] [Polydimethyl siloxane series block copolymer (a)]
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、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)、30質量份的甲基丙烯酸甲酯、26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質量份的甲基丙烯酸及0.5質量份的1-硫甘油,在80℃使其反應8小時而得到聚二甲基矽氧烷系嵌段共聚物(a)。所得之溶液中的嵌段共聚物(a)之比例,係100質量%的溶液中50質量%。 Using the same apparatus as the synthesis of polyoxyalkylene (a), 50 parts by mass of toluene, 50 parts by mass of methyl isobutyl ketone, and 20 parts by mass of polydimethyl siloxane-based polymer polymerization start were added. Agent (VPS-0501, manufactured by Wako Pure Chemical Co., Ltd.), 30 parts by mass of methyl methacrylate, 26 parts by mass of butyl methacrylate, and 23 parts by mass of methacrylic acid 2- Hydroxyethyl ester, 1 part by mass of methacrylic acid, and 0.5 part by mass of 1-thioglycerol were reacted at 80 ° C for 8 hours to obtain a polydimethylsiloxane-based block copolymer (a). The ratio of the block copolymer (a) in the obtained solution was 50% by mass in a 100% by mass solution.
[聚二甲基矽氧烷系接枝共聚物(b)] [Polydimethylsiloxane-based graft copolymer (b)]
使用聚矽氧烷(a)之合成所用的裝置,加入50質量份的甲苯、50質量份的乙酸異丁酯,升溫至110℃為止。 另外,混合20質量份的甲基丙烯酸甲酯、20質量份的甲基丙烯酸丁酯、32質量份的己內酯甲基丙烯酸酯(DAICEL化學工業(股)製「Placcel」(註冊商標)FM-5)、23質量份的甲基丙烯酸2-羥基乙酯、10質量份的聚矽氧烷(a)、20質量份的一末端甲基丙烯酸改性聚二甲基矽氧烷(東亞合成化學工業(股)製,X-22-174DX)及1質量份的甲基丙烯酸、2質量份的1,1-偶氮雙環己烷-1-甲腈。 費2小時將此混合單體滴下至上述的甲苯、乙酸丁酯之混合液中。然後,在110℃使其反應8小時,得到固體成分濃度50質量%之具有羥基的聚二甲基矽氧烷系接枝共聚物(b)。所得之溶液中的接枝共聚物(b)之比例,係100質量%的溶液中50質量%。 Using a device used for the synthesis of polyoxyalkylene (a), 50 parts by mass of toluene and 50 parts by mass of isobutyl acetate were added, and the temperature was raised to 110 °C. Further, 20 parts by mass of methyl methacrylate, 20 parts by mass of butyl methacrylate, and 32 parts by mass of caprolactone methacrylate ("Placcel" (registered trademark) FM manufactured by DAICEL Chemical Industry Co., Ltd. were mixed. -5), 23 parts by mass of 2-hydroxyethyl methacrylate, 10 parts by mass of polyoxyalkylene (a), 20 parts by mass of a terminal methacrylic acid modified polydimethyl siloxane (East Asia Synthesis) Chemical Industry Co., Ltd., X-22-174DX) and 1 part by mass of methacrylic acid and 2 parts by mass of 1,1-azobiscyclohexane-1-carbonitrile. This mixed monomer was dropped to the above-mentioned mixed solution of toluene and butyl acetate for 2 hours. Then, the mixture was reacted at 110 ° C for 8 hours to obtain a polydimethylsiloxane-based graft copolymer (b) having a hydroxyl group concentration of 50% by mass. The ratio of the graft copolymer (b) in the obtained solution was 50% by mass in a 100% by mass solution.
[三環癸基化合物] [tricyclic fluorenyl compound]
[三環癸基化合物1] [tricyclic fluorenyl compound 1]
作為三環癸基化合物1,使用含有三環癸基鏈段的丙烯酸酯化合物(IRR214-K Daicel-Allnex股份有限公司製 固體成分濃度100質量%)。 As the tricyclic mercapto compound 1, an acrylate compound containing a tricyclodecyl group (solid content concentration: 100% by mass manufactured by IRR214-K Daicel-Allnex Co., Ltd.) was used.
[三環癸基化合物2] [tricyclic fluorenyl compound 2]
作為三環癸基化合物2,使用含有三環癸基鏈段的丙烯酸酯化合物(FA-513AS日立化成股份有限公司製 固體成分濃度100質量%)。 As the tricyclic mercapto compound 2, an acrylate compound (a solid content concentration of 100% by mass of FA-513AS Hitachi Chemical Co., Ltd.) containing a tricyclodecyl group was used.
[三環癸基化合物3] [tricyclic fluorenyl compound 3]
作為三環癸基化合物3,使用含有三環癸基鏈段的丙烯酸酯化合物(SR833S Sartomer股份有限公司製 固體成分濃度100質量%)。 As the tricyclic mercapto compound 3, an acrylate compound containing a tricyclodecyl group (solid content: 100 mass% manufactured by SR833S Sartomer Co., Ltd.) was used.
[氟化合物] [fluorine compound]
[氟化合物1] [Fluorochemical 1]
作為氟化合物1,使用含有氟聚醚鏈段的丙烯酸酯化合物(「Megafac」(註冊商標)RS-75 DIC股份有限公司製 固體成分濃度40質量%溶劑(甲苯及甲基乙基酮)60質量%)。 As the fluorine compound 1, an acrylate compound containing a fluoropolyether segment ("Megafac" (registered trademark) RS-75 DIC Co., Ltd. solid content concentration 40% by mass solvent (toluene and methyl ethyl ketone) 60 mass was used. %).
[氟化合物2] [fluorine compound 2]
作為氟化合物2,使用含有氟聚醚鏈段的矽氧烷化合物(KY-108信越化學工業股份有限公司製 固體成分濃度20質量%溶劑(甲醇及異丙醇)80質量%)。 As the fluorine compound 2, a fluoropolyether compound containing a fluoropolyether segment (KY-108 Shin-Etsu Chemical Co., Ltd. solid content concentration: 20% by mass solvent (methanol and isopropyl alcohol) 80% by mass) was used.
[光自由基聚合起始劑] [Photoradical polymerization initiator]
[光自由基聚合起始劑1] [Photoradical polymerization initiator 1]
作為光自由基聚合起始劑1,使用「Irgacure」(註冊商標)184(BASF日本股份有限公司製 固體成分濃度100質量%)。 As the photoradical polymerization initiator 1, "Irgacure" (registered trademark) 184 (solid content concentration: 100% by mass by BASF Japan Co., Ltd.) was used.
[塗料組成物A之調配] [Material Composition A Preparation]
[塗料組成物A1] [Coating composition A1]
混合以下之材料,使用甲基乙基酮來稀釋,得到固 體成分濃度30質量%之塗料組成物A1。 Mix the following materials and dilute with methyl ethyl ketone to obtain a solid A coating composition A1 having a body component concentration of 30% by mass.
[塗料組成物A2] [Coating composition A2]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A2。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A2 having a solid concentration of 30% by mass.
[塗料組成物A3] [Coating composition A3]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A3。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A3 having a solid concentration of 30% by mass.
[塗料組成物A4] [Coating composition A4]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A4。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 having a solid concentration of 30% by mass.
[塗料組成物A5] [Coating composition A5]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A5。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A5 having a solid concentration of 30% by mass.
[塗料組成物A6] [Coating composition A6]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A6。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A6 having a solid concentration of 30% by mass.
[塗料組成物A7] [Coating composition A7]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A7。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A7 having a solid concentration of 30% by mass.
[塗料組成物A8] [Coating composition A8]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A8。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A8 having a solid concentration of 30% by mass.
[塗料組成物A9] [Coating composition A9]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A9。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A9 having a solid concentration of 30% by mass.
[塗料組成物A10] [Coating composition A10]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A10。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A10 having a solid concentration of 30% by mass.
[塗料組成物A11] [Coating composition A11]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A11。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A11 having a solid concentration of 30% by mass.
[塗料組成物A12] [Coating composition A12]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A12。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A12 having a solid concentration of 30% by mass.
[塗料組成物A13] [Coating composition A13]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A13。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A13 having a solid concentration of 30% by mass.
[塗料組成物A14] [Coating composition A14]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物A14。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A14 having a solid concentration of 30% by mass.
[塗料組成物B之調配] [Material Composition B Preparation]
[塗料組成物B1]混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度40質量%之塗料組成物B1。 [Coating Composition B1] The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B1 having a solid concentration of 40% by mass.
.聚己內酯三醇 15質量份 . Polycaprolactone triol 15 parts by mass
(「Placcel」(註冊商標)308 DAICEL化學工業股份有限公司) ("Placcel" (registered trademark) 308 DAICEL Chemical Industry Co., Ltd.)
.六亞甲基二異氰酸酯 15質量份 . Hexamethylene diisocyanate 15 parts by mass
(「Takenate」(註冊商標)D-170三井化學股份有限公司製) ("Takenate" (registered trademark) D-170 Mitsui Chemicals Co., Ltd.)
.聚二甲基矽氧烷系嵌段共聚物(a)溶液 75質量 . Polydimethyloxane block copolymer (a) solution 75 mass
份 Share
(固體成分濃度50質量%) (solid content concentration: 50% by mass)
.聚矽氧烷(a) 10質量份。 . Polyoxyalkylene (a) 10 parts by mass.
[塗料組成物B2] [Coating composition B2]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度40質量%之塗料組成物B2。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B2 having a solid concentration of 40% by mass.
.聚二甲基矽氧烷系接枝共聚物(b)溶液 100質量份 . Polydimethylsiloxane coupled graft copolymer (b) solution 100 parts by mass
(固體成分濃度50質量%) (solid content concentration: 50% by mass)
.六亞甲基二異氰酸酯 12質量份 . Hexamethylene diisocyanate 12 parts by mass
(「Burnock」(註冊商標)DN-950,DIC股份有限公司製)。 ("Burnock" (registered trademark) DN-950, manufactured by DIC Corporation).
[塗料組成物C之調配] [Preparation of Coating Composition C]
[塗料組成物C1] [Coating composition C1]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物C1。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C1 having a solid concentration of 30% by mass.
[塗料組成物C2] [Coating composition C2]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物C2。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C2 having a solid concentration of 30% by mass.
[塗料組成物C3] [Coating composition C3]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物C3。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C3 having a solid concentration of 30% by mass.
[塗料組成物C4] [Coating composition C4]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物C4。
[塗料組成物C5] [Coating composition C5]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物C5。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C5 having a solid concentration of 30% by mass.
[塗料組成物D之調配] [Material Composition D Preparation]
[塗料組成物D1] [Coating composition D1]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度40質量%之塗料組成物D1。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition D1 having a solid concentration of 40% by mass.
[塗料組成物D2] [Coating composition D2]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度40質量%之塗料組成物D2。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition D2 having a solid concentration of 40% by mass.
.胺基甲酸酯(甲基)丙烯酸酯B2溶液(固體成分濃
[塗料組成物D3] [Coating composition D3]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物D3。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition D3 having a solid concentration of 30% by mass.
[塗料組成物D4] [Coating composition D4]
混合以下之材料,使用甲基乙基酮來稀釋,得到固體成分濃度30質量%之塗料組成物D4。 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition D4 having a solid concentration of 30% by mass.
[支撐基材] [support substrate]
[支撐基材A1] [Support substrate A1]
作為支撐基材A1,使用「Cosmoshine」(註冊商標)A4300(厚度125μm,東洋紡股份有限公司製)。 "Cosmoshine" (registered trademark) A4300 (thickness: 125 μm, manufactured by Toyobo Co., Ltd.) was used as the support substrate A1.
[支撐基材A2] [Support substrate A2]
作為支撐基材A2,使用「Panlite」(註冊商 標)PC-2151(厚度125μm,帝人化成股份有限公司製)。 As the support substrate A2, use "Panlite" (Registrar) Standard) PC-2151 (thickness 125 μm, manufactured by Teijin Chemicals Co., Ltd.).
[支撐基材B1] [Support substrate B1]
作為支撐基材1,使用「Lumirror」(註冊商標)U48(厚度125μm,東麗股份有限公司製)。 As the support substrate 1, "Lumirror" (registered trademark) U48 (thickness: 125 μm, manufactured by Toray Industries, Inc.) was used.
[支撐基材之評價] [Evaluation of support substrate]
對於支撐基材,實施以下所示的性能評價,表1中顯示所得之結果。除了特別事先指明之情況,測定係對於各樣品改變位置,進行3次測定,使用其平均值。 For the support substrate, the performance evaluation shown below was carried out, and the results obtained are shown in Table 1. The measurement was performed three times for each sample except for the case where it was specified in advance, and the average value was used.
[支撐基材的膨潤度指數] [Swelling index of support substrate]
支撐基材的膨潤度指數係由以下之方法算出。首先,測定支撐基材之霧值h1。其次,於支撐基材上,使用棒塗機(# 10)塗布甲基乙基酮,在溫度40℃放置1分鐘,使甲基乙基酮乾燥。然後,測定乾燥後的支撐基材之霧值h2(%)。使用此2個值,由以下之式算出膨潤度指數。 The swelling index of the support substrate was calculated by the following method. First, the haze value h 1 of the support substrate was measured. Next, on the support substrate, methyl ethyl ketone was applied using a bar coater (#10), and allowed to stand at a temperature of 40 ° C for 1 minute to dry the methyl ethyl ketone. Then, the haze value h 2 (%) of the support substrate after drying was measured. Using these two values, the swelling index was calculated from the following formula.
膨潤度指數:h=| h2-h1 | Swelling index: h=| h 2 -h 1 |
再者,霧度測定係根據JIS K 7136(2000),使用日本電色工業股份有限公司製霧度計,以自支撐基材之塗布有甲基乙基酮之側穿透光之方式,置於裝置上而測定。 In addition, the haze measurement was carried out by using a haze meter manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K 7136 (2000), and transmitting light from the side of the self-supporting substrate coated with methyl ethyl ketone. Determined on the device.
表1中彙總所得之支撐基材的評價結果。 The evaluation results of the support substrate obtained in Table 1 are summarized.
[積層薄膜之製造方法] [Manufacturing method of laminated film]
[積層薄膜之製作1] [Production of laminated film 1]
於支撐基材上,使用狹縫式模頭塗布器的連續塗布裝置,以乾燥後的表面層之厚度成為指定的膜厚之方式,調整來自狹縫的吐出流量,塗布前述塗料組成物A(A1~A14)、塗料組成物C(C1~C5)、塗料組成物D(D1~D4)。自塗布起至乾燥、硬化為止之間,吹向液膜的乾燥風之條件係如以下。 On the support substrate, a continuous coating apparatus 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 the coating composition A is applied ( A1~A14), coating composition C (C1~C5), and coating composition D (D1~D4). The conditions of the dry air blown to the liquid film from the time of coating to drying and hardening are as follows.
[乾燥步驟] [Drying step]
送風溫濕度:溫度:80℃,相對濕度:1%以下 Supply air temperature and humidity: temperature: 80 ° C, relative humidity: 1% or less
風速:塗布面側:5m/秒,反塗布面側:5m/秒 Wind speed: coated side: 5 m / sec, reverse coated side: 5 m / sec
風向:塗布面側:對於基材之面呈平行,反塗布面側:對於基材之面呈垂直 Wind direction: coated side: parallel to the surface of the substrate, side of the reverse coated side: vertical to the side of the substrate
滯留時間:2分鐘 Residence time: 2 minutes
[硬化步驟] [hardening step]
照射出力:400W/cm2 Irradiation output: 400W/cm2
累積光量:120mJ/cm2 Cumulative amount of light: 120mJ/cm2
氧濃度:0.1體積%。 Oxygen concentration: 0.1% by volume.
[積層薄膜之製作2] [Production of laminated film 2]
於支撐基材上,使用狹縫式模頭塗布器的連續塗布 裝置,以乾燥後的表面層之厚度成為指定的膜厚之方式,調整來自狹縫的吐出流量,塗布前述塗料組成物B(B1~B2)。自塗布起至乾燥、硬化為止之間,吹向液膜的乾燥風之條件係如以下。 Continuous coating using a slot die coater on a support substrate In the apparatus, the discharge flow rate from the slit is adjusted so that the thickness of the dried surface layer becomes a predetermined film thickness, and the coating composition B (B1 to B2) is applied. The conditions of the dry air blown to the liquid film from the time of coating to drying and hardening are as follows.
[乾燥步驟] [Drying step]
送風溫濕度:溫度:80℃,相對濕度:1%以下 Supply air temperature and humidity: temperature: 80 ° C, relative humidity: 1% or less
風速:塗布面側:5m/秒,反塗布面側:5m/秒 Wind speed: coated side: 5 m / sec, reverse coated side: 5 m / sec
風向:塗布面側:對於基材之面呈平行,反塗布面側:對於基材之面呈垂直 Wind direction: coated side: parallel to the surface of the substrate, side of the reverse coated side: vertical to the side of the substrate
滯留時間:1分鐘 Residence time: 1 minute
[硬化步驟] [hardening step]
送風溫濕度:溫度:160℃、相對濕度:1%以下 Supply air temperature and humidity: temperature: 160 ° C, relative humidity: 1% or less
風速:塗布面側:10m/秒、反塗布面側:10m/秒 Wind speed: coated side: 10 m / sec, reverse coated side: 10 m / sec
風向:塗布面側:對於基材之面呈垂直,塗布面側:對於基材之面呈垂直 Wind direction: coated side: vertical to the surface of the substrate, coated side: vertical to the side of the substrate
滯留時間:2分鐘 Residence time: 2 minutes
再者,前述風速、溫濕度係使用熱線式風速計(日本KANOMAX股份有限公司製Anemomaster風速.風量計MODEL6034)的測定值。 In addition, the wind speed, the temperature and humidity are measured values of a hot wire type anemometer (Anemomaster wind speed air flow meter MODEL6034 manufactured by KANOMAX Co., Ltd., Japan).
藉由以上之方法,作成實施例1~16、比較例1~11之積層薄膜。對應於各實施例、比較例的上述積層薄膜之作成方法及各自之各層的膜厚,係記載於後述之表2、3中。 The laminate films of Examples 1 to 16 and Comparative Examples 1 to 11 were produced by the above methods. The method for producing the laminated film corresponding to each of the examples and the comparative examples and the film thickness of each layer are described in Tables 2 and 3 to be described later.
[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,表2、3中顯示所得之結果。除了特別事先指明之情況,測定係在各實施例.比較例中,對於1個樣品,改變位置進行3次測定,使用其平均值。 For the laminated film produced, perform the performance evaluation shown below The price, the results obtained in Tables 2 and 3. Unless otherwise specified in advance, the assay is in each embodiment. In the comparative example, for one sample, the position was changed three times, and the average value was used.
[表面層的對數衰減率、相對儲存彈性模數(剛體擺錘試驗法)] [Logarithmic decay rate of surface layer, relative storage elastic modulus (rigid body pendulum test method)]
以剛體擺錘的自由衰減振動法為基礎(將此當作剛體擺錘試驗法),使用股份有限公司A&D公司製剛體擺錘型物性試驗機RPT-3000,測定表面層的對數衰減率與相對儲存彈性模數。試驗機係預先調溫至15℃,安裝樣品及擺錘後,以10℃/分鐘之速度升溫至150℃為止,邊升溫邊進行測定。測定係進行各5次,以其平均值來評價。再者,擺錘係使用以下者。 Based on the free-attenuation vibration method of the rigid body pendulum (this is taken as the rigid body pendulum test method), the logarithmic decay rate and relative of the surface layer are measured using the rigid body pendulum type physical property testing machine RPT-3000 manufactured by A&D Co., Ltd. Store the elastic modulus. The test machine was previously tempered to 15 ° C, and after the sample and the pendulum were attached, the temperature was raised to 150 ° C at a rate of 10 ° C / min, and the measurement was performed while raising the temperature. The measurement system was carried out 5 times each and evaluated by the average value thereof. Furthermore, the pendulum system uses the following.
使用邊緣:圓棒型柱狀邊緣(股份有限公司A&D公司製RBP-040)刀形狀邊緣(股份有限公司A&D公司製RBE-160) Edge: Round bar type edge (RBP-040, manufactured by A&D Co., Ltd.) Knife shape edge (RBE-160, A&D Co., Ltd.)
擺錘質量/慣性矩:15g/640g.cm(股份有限公司A&D公司製FRB-100) Pendulum mass / moment of inertia: 15g / 640g. Cm (FRB-100, A&D company)
再者,將在測定溫度25℃的相對儲存彈性模數當作Gr’25,將在測定溫度100℃的相對儲存彈性模數當作Gr’100。比較各值之大小,將Gr’25<Gr’100成立時當作Y,將不成立時當作N。 Further, the relative storage elastic modulus at a measurement temperature of 25 ° C was taken as Gr' 25, and the relative storage elastic modulus at a measurement temperature of 100 ° C was taken as Gr'100. The magnitude of each value is compared, and when Gr'25<Gr'100 is established, it is regarded as Y, and when it is not established, it is regarded as N.
[表面層的密接指數(延伸-煮沸密接試驗法)] [Adhesion index of surface layer (extension-boil tight test method)]
關於表面層的密接指數之評價,係如下述所示,藉由延伸處理、煮沸處理、密接試驗之3階段進行。再者, 將此一連串的流程當作延伸-煮沸密接試驗法。 The evaluation of the adhesion index of the surface layer was carried out in three stages of elongation treatment, boiling treatment, and adhesion test as described below. Furthermore, This series of processes was used as an extension-boil tight test.
[延伸處理] [Extension processing]
由積層薄膜切出20mm寬×200mm長,以朝向長邊方向延伸之方式,用夾頭抓住,藉由Instron型拉伸試驗機(INSTRON公司製超精密材料試驗機MODEL5848)以100mm/分鐘的拉伸速度來伸展。此時的測定環境為23℃。進行延伸處理直到應變量成為20%為止,採集試驗片。 The laminate film was cut to a length of 20 mm × 200 mm, and was grasped by a chuck so as to extend in the longitudinal direction, and was passed through an Instron type tensile tester (Instron type ultra-precision material testing machine MODEL 5848) at 100 mm/min. Stretching speed to stretch. The measurement environment at this time was 23 °C. The extension treatment was performed until the strain amount became 20%, and the test piece was collected.
再者,初期拉伸夾頭間距離為50mm,拉 伸夾頭間距離為a(mm),應變量x(%)係藉由以下之式算出。 Furthermore, the distance between the initial stretching chucks is 50mm, pulling The distance between the stretching chucks is a (mm), and the strain x (%) is calculated by the following formula.
應變量:x=((a-50)/50)×100。 The dependent variable: x = ((a-50) / 50) × 100.
[煮沸處理] [Boiled treatment]
其次,對於已進行延伸處理的試驗片,在由純水所構成的沸騰之熱水(100℃)中,浸漬試驗片6小時。然後,取出試驗片,使其乾燥。 Next, the test piece which had been subjected to the elongation treatment was immersed in the boiling hot water (100 ° C) composed of pure water for 6 hours. Then, the test piece was taken out and dried.
[密接試驗] [Close test]
再者,於煮沸處理後之試驗片的表面層,導入100個1mm2之交叉切割。作業係除了下述的一部分以外,依照JIS K5600-5-6(1999)的7項步驟進行。 Further, 100 pieces of 1 mm2 cross-cut were introduced into the surface layer of the test piece after the boiling treatment. The operation is carried out in accordance with seven steps of JIS K5600-5-6 (1999) except for the following.
試驗條件及試驗數:試驗條件為23℃、相對濕度65%。又,試驗數為1。 Test conditions and number of tests: The test conditions were 23 ° C and a relative humidity of 65%. Also, the number of tests is one.
試驗板之熟成:熟成條件為溫度23℃、相對濕度65%,熟成時間為1小時。 The aging of the test plate: the ripening conditions were a temperature of 23 ° C, a relative humidity of 65%, and a ripening time of 1 hour.
切割數:切割數為11。 Number of cuts: The number of cuts is 11.
切割之間隔:切割之間隔為1mm。 Interval of cutting: The interval between cuts is 1 mm.
藉由手動步驟的積層膜之切入及去除:未進行使用刷子的刷洗(brushing)。又,JIS K5600-5-6(1999)之7.2.6項係僅援用第2段落之規定(「將膠帶的中心,如第3圖所示地,在平行於方形切割的一組之方向,置於方格之上,以與施加於方格之部分的地方最低超過20mm之長度,用手指使膠帶成為平坦」,其它的規定係不援用。 再者,膠帶係使用透明膠帶(NICHIBAN(股)製「Cellotape」(註冊商標)CT405AP)。 Cutting and removal of the laminated film by a manual step: brushing using a brush was not performed. In addition, JIS K5600-5-6 (1999) 7.2.6 only refers to the provisions of paragraph 2 ("the center of the tape, as shown in Figure 3, in a direction parallel to the square cut group, Place it on the square and use the finger to make the tape flat with a length of more than 20mm from the part applied to the square. Other rules are not used. In addition, a scotch tape (Cellotape (registered trademark) CT405AP by NICHIBAN Co., Ltd.) was used for the tape.
又,膠帶的貼附係使用手壓輥 ((股)Audio-technica製HP515),以19.6N/m的荷重且5cm/秒的輥移動速度,往返推壓3次而進行。其次,在相對於表面層表面方向而言90度方向中,以秒速10cm/秒之速度撕下膠帶,根據在表面層所設置的方格之殘存個數,進行5等級評價。 Also, the tape is attached using a hand roller ((HP) 515 manufactured by Audio-technica) was carried out by pushing back and forth three times with a load of 19.6 N/m and a roll moving speed of 5 cm/sec. Next, the tape was peeled off at a speed of 10 cm/sec. at a speed of 10 cm/sec with respect to the surface direction of the surface layer, and the rating was evaluated based on the number of remaining squares provided on the surface layer.
密接指數5:表面層的殘存個數為100。 Bonding index 5: The number of remaining layers of the surface layer is 100.
密接指數4:表面層的殘存個數為90以上且少於100。 Bonding index 4: The number of remaining layers of the surface layer is 90 or more and less than 100.
密接指數3:表面層的殘存個數為80以上且少於90。 Bonding index 3: The number of remaining layers of the surface layer is 80 or more and less than 90.
密接指數2:表面層的殘存個數為50以上且少於80。 Bonding index 2: The number of remaining layers of the surface layer is 50 or more and less than 80.
密接指數1:表面層的殘存個數少於50。 Bonding index 1: The number of remaining layers of the surface layer is less than 50.
[抗染料轉移性] [Anti-dye transferability]
於經切成9cm×6cm的大小之積層薄膜的表面層上,使6cm×6cm的經水所潤濕的牛仔褲(含有染料)密接,以 6cm×6cm的玻璃板夾入。以水分不蒸發之方式,用聚乙烯薄膜包入,在玻璃板之上載置3kg的秤錘,置入70℃的烘箱中放置。24小時後取出,將積層薄膜放置在與後述之污染用灰階的白色部同等之白紙上,用污染用灰階(JIS L0805(2005)),以1~5級之等級(1級髒污係污染用灰階1號或超越其程度者(髒污深沉殘留),2級係髒污為污染用灰階2號程度者(髒污殘留相當大的量)、3級係髒污為污染用灰階3號程度者(髒污稍微殘留)、4級係髒污為污染用灰階4號程度者(髒污幾乎未殘留)、5級係髒污為污染用灰階5號程度者(髒污未殘留)),判斷表面層的表面之污染程度。再者,依照JIS L0805(2005)之記載,當為各級之間,例如1級與2級之間時,記載為「1-2」。 6 cm × 6 cm of water-wet jeans (containing dye) were adhered to the surface layer of the laminated film of a size of 9 cm × 6 cm. A 6 cm x 6 cm glass plate was sandwiched. In a manner that moisture does not evaporate, it is wrapped in a polyethylene film, and a 3 kg weight is placed on the glass plate, and placed in an oven at 70 ° C. After 24 hours, the laminated film was placed on a white paper equivalent to the white portion of the gray scale for pollution described later, and the gray scale for pollution (JIS L0805 (2005)) was used to rank 1 to 5 (Grade 1). For the pollution, the gray scale No. 1 or the extent of exceeding it (dirty and deep residue), the second-grade system is the pollution level with the gray scale No. 2 (the amount of dirty residue is quite large), and the third-grade system is dirty. In the case of the gray level No. 3 (slightly left), the fourth grade is the pollution, the gray level is 4 (the dirt is almost not left), and the 5th is the pollution. (dirty is not left)), and the degree of contamination of the surface of the surface layer is judged. Further, according to JIS L0805 (2005), when it is between the levels, for example, between the first level and the second level, it is described as "1-2".
[表面層之裂紋延伸度] [Crack extension of surface layer]
由積層薄膜切出10mm寬×200mm長,在長度方向中以夾頭抓住,藉由Instron型拉伸試驗機(Instron公司製超精密材料試驗機MODEL5848)以100mm/分鐘的拉伸速度來延伸。以測定溫度23℃進行。延伸時,觀察延伸中的樣品,一旦目視發生裂紋(龜裂)則停止(以停止時的應變量成為5之整數的方式調整)。之後所測定的樣品,係依照停止時的應變量,依序採集以5%單位降低應變量的樣品,進行直到最終目視沒有導入裂紋之應變量為止。 The laminate film was cut to a length of 10 mm wide by 200 mm, and was grasped by a chuck in the longitudinal direction, and was stretched at a stretching speed of 100 mm/min by an Instron type tensile tester (Instron-made ultra-precision material testing machine MODEL 5848). . The measurement was carried out at a measurement temperature of 23 °C. When extending, the sample in the extension is observed, and when cracks (cracks) are visually observed, the sample is stopped (the amount of the strain at the time of the stop is adjusted to be an integer of 5). Thereafter, the sample to be measured is subjected to a sample in which the amount of strain is reduced by 5% in accordance with the strain at the time of stopping, and the sample is subjected to the strain until the final visual observation is not introduced.
再者,初期拉伸夾頭間距離為50mm,拉伸夾頭間距離為a(mm),應變量x(%)係藉由以下之式算出。 Further, the distance between the initial stretching chucks was 50 mm, the distance between the stretching chucks was a (mm), and the strain x (%) was calculated by the following formula.
應變量:x=((a-50)/50)×100。 The dependent variable: x = ((a-50) / 50) × 100.
切出所採集的樣品之裂紋部分的薄膜截 面,以所觀察的表面層之厚度在透射型電子顯微鏡的觀察畫面上成為30mm以上之倍率,觀察表面層,將發生表面層的平均厚度之50%以上的裂紋之情況當作有裂紋(表面層有破壞),於被視為有裂紋的樣品之中,將具有最低應變量的樣品之應變量值當作裂紋延伸度。而且,合計進行3次的相同測定,將彼等之裂紋延伸度的平均值當作表面層的裂紋延伸度。 Cut out the film section of the cracked part of the collected sample The surface was observed to have a magnification of 30 mm or more on the observation screen of the transmission electron microscope, and the surface layer was observed, and cracks of 50% or more of the average thickness of the surface layer were regarded as cracks (surface). The layer is damaged. Among the samples considered to be cracked, the strain value of the sample with the lowest strain is taken as the crack elongation. Further, the same measurement was performed three times in total, and the average value of the crack elongations was taken as the crack elongation of the surface layer.
[表面層之剝離] [Separation of surface layer]
作為動態黏彈性法之前處理,藉由以下之方法,自積層薄膜僅剝離表面層,當作試驗樣品。 As a pre-treatment by the dynamic viscoelastic method, the self-laminated film was only peeled off from the surface layer by the following method, and it was used as a test sample.
首先,將積層薄膜浸於乙醇中,在25℃之 條件下放置10分鐘。然後,自支撐基材剝離積層薄膜之表面,採集樣品。 First, the laminated film is immersed in ethanol at 25 ° C. Leave under conditions for 10 minutes. Then, the surface of the laminated film was peeled off from the support substrate, and a sample was taken.
[表面層之儲存彈性模數、損失正切(動態 黏彈性法)] [Storage modulus of the surface layer, loss tangent (dynamic Viscoelastic method)]
以JIS K7244(1998)的拉伸振動-非共振法為基礎(將此當作動態黏彈性法),使用SEIKO儀器股份有限公司製之動態黏彈性測定裝置「DMS6100」,求得表面層之儲存彈性模數與損失彈性模數。 Based on the tensile vibration-non-resonance method of JIS K7244 (1998) (this is regarded as the dynamic viscoelastic method), the surface layer storage was obtained using the dynamic viscoelasticity measuring device "DMS6100" manufactured by SEIKO Instruments Co., Ltd. Elastic modulus and loss elastic modulus.
測定模式:拉伸 Measurement mode: stretching
夾頭間距離:20mm Distance between chucks: 20mm
試驗片之寬度:10mm Test piece width: 10mm
頻率:1Hz Frequency: 1Hz
應變振幅:10μm Strain amplitude: 10μm
力振幅初期值:400mN Initial amplitude of force amplitude: 400mN
測定溫度:自-150℃起至250℃為止 Measuring temperature: from -150 ° C to 250 ° C
升溫速度:5℃/分鐘 Heating rate: 5 ° C / min
再者,將在測定溫度25℃的儲存彈性模數當作G’25,將在測定溫度100℃的儲存彈性模數當作G’100。比較各值之大小,將G’25<G’100成立時當作Y,將不成立時當作N。 Further, the storage elastic modulus at a measurement temperature of 25 ° C was taken as G' 25 , and the storage elastic modulus at a measurement temperature of 100 ° C was taken as G' 100 . Compare the magnitude of each value, treat G' 25 <G' 100 as Y when it is established, and treat it as N when it is not established.
又,將在測定溫度25℃的損失彈性模數當作G”25,藉由以下之式,求得表示在測定溫度25℃的損失正切之tanδ25。 Further, the loss elastic modulus at a measurement temperature of 25 ° C was taken as G" 25 , and tan δ 25 indicating the loss tangent at a measurement temperature of 25 ° C was obtained by the following formula.
tanδ25=G”25/G’25。 Tanδ 25 =G" 25 /G' 25 .
[表面層之自我修復性] [self-healing of surface layer]
於溫度20℃放置12小時後,在相同環境下於表面層表面,對黃銅刷(TRUSCO製)施加下述之荷重,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,將4分以上當作合格。 After standing at a temperature of 20 ° C for 12 hours, the following load was applied to a brass brush (manufactured by TRUSCO) on the surface of the surface layer in the same environment, and scratched five times horizontally, and visually judged for 5 minutes in accordance with the following criteria. The recovery state of the scar after placement is considered to be 4 or more points.
10分:荷重9.8N(1kg重)時傷痕不殘留 10 points: no damage remains when the load is 9.8N (1kg weight)
7分:荷重9.8N(1kg重)時傷痕殘留,但6.9N(700g重)時傷痕不殘留 7 points: the residue remains when the load is 9.8N (1kg weight), but the scar does not remain when it is 6.9N (700g weight)
4分:荷重6.9N(700g重)時傷痕殘留,但4.9N(500g重)時傷痕不殘留 4 points: the residue remains when the load is 6.9N (700g weight), but the scar does not remain when it is 4.9N (500g weight)
1分:荷重4.9N(500g重)時傷痕殘留。 1 point: The residue remains when the load is 4.9N (500g weight).
[表面層之成型性] [Formability of surface layer]
表面層之成型性係對於前述表面層的裂紋延伸度,依照以下之基準進行判斷。 The moldability of the surface layer is determined based on the following criteria regarding the crack elongation of the surface layer.
10分:表面層之裂紋延伸度為40%以上。 10 points: The crack extension of the surface layer is 40% or more.
7分:表面層之裂紋延伸度為30%以上且小於40%。 7 points: The crack elongation of the surface layer is 30% or more and less than 40%.
4分:表面層之裂紋延伸度為20%以上且小於30%。 4 points: The crack elongation of the surface layer is 20% or more and less than 30%.
1分:表面層之裂紋延伸度小於20%。 1 point: The crack elongation of the surface layer is less than 20%.
[表面層之密接耐久性] [Sealing durability of surface layer]
表面層之密接耐久性係對於前述表面層之密接指數,依照以下之基準進行判斷。 The adhesion durability of the surface layer is judged by the following criteria based on the adhesion index of the surface layer.
10分:表面層的密接指數為5。 10 points: The adhesion index of the surface layer is 5.
9分:表面層的密接指數為4。 9 points: The adhesion index of the surface layer is 4.
7分:表面層的密接指數為3。 7 points: The adhesion index of the surface layer is 3.
4分:表面層的密接指數為2。 4 points: The adhesion index of the surface layer is 2.
1分:表面層的密接指數為1。 1 point: The adhesion index of the surface layer is 1.
[表面層之防污性] [Antifouling properties of surface layer]
表面層之防污性係對於前述表面層之抗染料轉移性,依照以下之基準進行判斷。 The antifouling property of the surface layer was judged based on the following criteria against the dye transfer resistance of the surface layer.
10分:表面層之抗染料轉移性為5級。 10 points: The surface layer has an anti-dye transferability of 5 grades.
7分:表面層之抗染料轉移性為4級以上且低於5級。 7 points: The anti-dye transfer property of the surface layer is 4 or more and less than 5.
4分:表面層之抗染料轉移性為3級以上且低於4級。 4 points: The anti-dye transfer property of the surface layer is 3 or more and less than 4.
1分:表面層之抗染料轉移性低於3級。 1 point: The surface layer has an anti-dye transferability lower than Grade 3.
表3中彙總最終所得的積層薄膜之評價結果。 The evaluation results of the finally obtained laminated film are summarized in Table 3.
本發明之積層薄膜係活用成型性、自我修復性、防污性及密接耐久性等優點,可適用於眼鏡.太陽鏡、化妝箱、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。 The laminated film of the invention has the advantages of moldability, self-healing property, antifouling property and adhesion durability, and can be applied to glasses. Plastic molded products such as sunglasses, cosmetic cases, food containers, smart phone cases, touch panels, keyboards, and televisions. Home appliances, buildings, dashboards, and navigation navigators for remote controls such as air conditioners. Vehicle interiors such as touch panels and interior mirrors, and the respective surfaces of various printed materials.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011136042A1 (en) * | 2010-04-27 | 2011-11-03 | 東レ株式会社 | Multilayer film and molded body |
JP2012139951A (en) * | 2011-01-05 | 2012-07-26 | Toray Ind Inc | Laminated film, and formed body |
TW201300237A (en) * | 2011-05-16 | 2013-01-01 | Toray Industries | Laminated film and molded body |
TW201331035A (en) * | 2011-12-21 | 2013-08-01 | Toray Industries | Laminated film |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US4843136A (en) * | 1986-09-26 | 1989-06-27 | Bayer Aktiengesellschaft | (Meth)-acrylates of siloxanes containing tricyclodecane groups |
JP3926461B2 (en) | 1998-02-13 | 2007-06-06 | ナトコ株式会社 | Paint composition |
JP2008062408A (en) | 2006-09-05 | 2008-03-21 | Nankai Tekunaato:Kk | Dye transfer preventing sheet |
JP5894741B2 (en) * | 2011-03-22 | 2016-03-30 | リケンテクノス株式会社 | Scratch prevention film |
JP5747640B2 (en) | 2011-04-28 | 2015-07-15 | 大日本印刷株式会社 | Encapsulant composition for solar cell module and encapsulant using the same |
JP2013119553A (en) * | 2011-12-06 | 2013-06-17 | Mitsubishi Chemicals Corp | Coating for lower layer formation used as groundwork of hard coat layer, and laminate formed by applying the coating for lower layer formation |
JP6127363B2 (en) | 2012-02-16 | 2017-05-17 | 三菱化学株式会社 | Active energy ray-curable resin composition and laminate using the same |
WO2015041175A1 (en) * | 2013-09-20 | 2015-03-26 | 東レ株式会社 | Layered film |
-
2015
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011136042A1 (en) * | 2010-04-27 | 2011-11-03 | 東レ株式会社 | Multilayer film and molded body |
JP2012139951A (en) * | 2011-01-05 | 2012-07-26 | Toray Ind Inc | Laminated film, and formed body |
TW201300237A (en) * | 2011-05-16 | 2013-01-01 | Toray Industries | Laminated film and molded body |
TW201331035A (en) * | 2011-12-21 | 2013-08-01 | Toray Industries | Laminated film |
Also Published As
Publication number | Publication date |
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CN105934339A (en) | 2016-09-07 |
JP6481607B2 (en) | 2019-03-13 |
JPWO2015115227A1 (en) | 2017-03-23 |
KR102314335B1 (en) | 2021-10-19 |
KR20160118211A (en) | 2016-10-11 |
CN105934339B (en) | 2018-01-23 |
WO2015115227A1 (en) | 2015-08-06 |
TW201545869A (en) | 2015-12-16 |
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