WO2014109177A1 - 積層フィルム - Google Patents
積層フィルム Download PDFInfo
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- WO2014109177A1 WO2014109177A1 PCT/JP2013/083550 JP2013083550W WO2014109177A1 WO 2014109177 A1 WO2014109177 A1 WO 2014109177A1 JP 2013083550 W JP2013083550 W JP 2013083550W WO 2014109177 A1 WO2014109177 A1 WO 2014109177A1
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- surface layer
- acrylate
- fingerprint
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/75—Printability
Definitions
- the present invention relates to a laminated film excellent in design and fingerprint resistance, in addition to the compatibility between molding followability and scratch resistance required for molding materials.
- a surface hardened layer is provided to prevent scratches during molding and to prevent scratches in the process of using the article after molding.
- the surface hardened layer lacks the elongation to follow the molding, so cracks occur at the time of molding, and in extreme cases, the film breaks or the surface hardened layer peels off.
- a surface hardened layer is formed after molding, or after being molded in a semi-cured state, such means as complete curing by heating or irradiation with active rays is applied.
- the molded article is processed three-dimensionally, it is very difficult to provide a surface hardened layer by post-processing, and when molding in a semi-cured state, depending on the molding conditions, May induce dirt.
- scratch-resistant materials that follow molding are desired, and attention is paid to “self-healing materials” or “self-healing materials” that can self-repair mild scratches within their elastic recovery range.
- the material that can visually recognize the wound repair process can directly recognize its function. Therefore, when used for an exterior member, the “designability” of the molding material can be improved. It is also attracting attention from a point.
- the materials of Patent Documents 1 and 2 have been proposed.
- molding materials particularly in applications that require a high glossiness, higher reflectance, and transparency.
- Patent Document 1 and Patent Document 2 proposed as the above-mentioned self-healing materials
- the present inventors have confirmed that although the moldability and the self-healing property are excellent, the fingerprint resistance is insufficient. there were.
- Patent Document 3 and Patent Document 4 described above the present inventors have confirmed the fingerprint resistance under various conditions. As long as these characteristics are satisfied, the fingerprint becomes inconspicuous, or the fingerprint is wiped off. The easy effect was insufficient. Further, these materials do not exhibit moldability or self-repairability, and are techniques that cannot be combined with the techniques of Patent Documents 1 and 2 described above.
- the problem to be solved by the present invention is to provide a laminated film satisfying moldability, self-repairability, designability, glossiness, and fingerprint resistance.
- the present inventors have intensively studied and as a result, completed the following invention. That is, the present invention is as follows. ⁇ 1> A laminated film having a surface layer on at least one surface of a supporting substrate, wherein the surface layer satisfies the following 1 to 3. 1. 1. 60 ° specular gloss specified by JIS Z8741 (1997) is 60% or more. Receding contact angle theta r oleic acid 50 ° or 3.
- the maximum displacement in the thickness direction of the surface layer when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement is 1.0 ⁇ m or more and 3.0 ⁇ m or less
- the creep displacement amount in the thickness direction of the surface layer is 0.05 ⁇ m or more and 0.5 ⁇ m or less
- the amount of permanent displacement in the thickness direction of the surface layer is 0.2 ⁇ m or more and 0.7 ⁇ m or less.
- a b (V 1 ⁇ V 2 ) / (S 1 ⁇ T) Formula (2) ⁇ 4>
- Simulated fingerprint adhesion conditions A dispersion composed of 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 ⁇ m is defined by JIS K0603 (1997) with Ra defined by JIS B0601 (2001) of 3 ⁇ m. 1.0 g / m 2 attached to a silicone rubber having a rubber hardness of 50 and attached to the target surface at 30 kPa. ⁇ 7> The laminated film according to any one of ⁇ 1> to ⁇ 6>, wherein the surface layer satisfies the following formulas (3) and (4).
- Simulated fingerprint adhesion conditions A dispersion composed of 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 ⁇ m is defined by JIS K0603 (1997) with Ra defined by JIS B0601 (2001) of 3 ⁇ m. 1.0 g / m 2 attached to a silicone rubber having a rubber hardness of 50 and attached to the target surface at 30 kPa.
- the median diameter (D P ) calculated from the area reference frequency distribution of oil droplets formed when a simulated fingerprint is attached to the surface layer by the following method is expressed by the following equations (7) and (8): ) The laminated film according to any one of ⁇ 1> to ⁇ 7>, wherein D P0.5 ⁇ 80 ⁇ m Formula (7) (D P0.5 -D P10 ) / D P0.5 ⁇ 0.5 Formula (8) D P0.5 : median diameter calculated from the area reference frequency distribution of oil droplets constituting the simulated fingerprint measured 30 minutes after the attachment of the simulated fingerprint D P10 : simulation measured 10 hours after the attachment of the simulated fingerprint Median size simulated fingerprint adhesion condition calculated from area-based frequency distribution of oil droplets constituting fingerprints: A dispersion composed of 70% by mass of oleic acid and 30% by mass of silica having a number average particle size of 2 ⁇ m was measured according to JIS B0601 (2001).
- Simulated fingerprint adhesion and simulated fingerprint wiping tests were performed on the surface layer under the following conditions, and simulation was performed based on the state before the simulated fingerprint adhesion obtained according to JIS Z8730 (2009) and JIS Z8722 (2009).
- Color difference ⁇ E * ab (di: 8 °) Sb10W10 (hereinafter referred to as ⁇ E SCI-2 ) including the specular reflection light after the fingerprint wiping test and the specular reflection light after the simulated fingerprint wiping test based on the state before adhering the simulated fingerprint
- ⁇ E SCI-2 Color difference ⁇ E * ab (di: 8 °) Sb10W10 (hereinafter referred to as ⁇ E SCI-2 ) including the specular reflection light after the fingerprint wiping test and the specular reflection light after the simulated fingerprint wiping test based on the state before adhering the simulated fingerprint
- ⁇ E SCE-2 the color difference ⁇ E * ab (de: 8 °) Sb10W10 satisfies the following formula (9): the film.
- the resins contained in the surface layer are the following (1) to (3) The laminated film according to any one of ⁇ 1> to ⁇ 9>, wherein (1) (poly) caprolactone segment, (2) Urethane bond, (3) A segment containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group and a fluorooxyalkanediyl group (hereinafter referred to as a fluorine compound segment) ⁇ 11> The laminated film according to ⁇ 10>, wherein the fluorine compound segment is a fluoropolyether segment. ⁇ 12> The laminated film according to ⁇ 10> or ⁇ 11
- a laminated film satisfying moldability, self-repairability, designability, glossiness, and fingerprint resistance can be obtained.
- FIG. 3 is a weight-indentation depth diagram when an indentation load / unloading test is performed on the laminated film of the present invention using a regular triangular pyramid.
- the laminated film of the present invention is a laminated film having a surface layer on at least one surface of a supporting substrate.
- the maximum displacement amount in the thickness direction of the surface layer, the creep displacement amount, and the permanent displacement amount when the load is released satisfy the following specific ranges.
- the laminated film of the present invention has a maximum displacement of 1.0 ⁇ m or more in the thickness direction of the surface layer when a 0.5 mN load is applied for 10 seconds in a microhardness meter measurement. 3.0 ⁇ m or less, more preferably 1.0 ⁇ m or more and 1.7 ⁇ m or less, and the creep displacement in the thickness direction of the surface layer is 0.05 ⁇ m or more and 0.5 ⁇ m or less, more preferably 0.2 ⁇ m or more and 0.5 ⁇ m or less.
- the amount of permanent displacement in the thickness direction of the surface layer is 0.2 ⁇ m or more and 0.7 ⁇ m or less, more preferably 0.4 ⁇ m or more and 0.65 ⁇ m or less.
- the maximum displacement in the thickness direction of the surface layer is larger than 3.0 ⁇ m, the self-repairing property of the surface layer may be incomplete. If the maximum displacement in the thickness direction of the surface layer is smaller than 1.0 ⁇ m, the surface layer Designability, that is, visibility in the recovery process may be deteriorated.
- the self-repairing property or the design property may be incomplete.
- the amount of permanent displacement in the thickness direction of the surface layer is greater than 0.7 ⁇ m, visible scratches may remain after the surface layer is self-repaired, and the appearance may deteriorate. From the viewpoint of the self-healing property of the surface layer, the smaller the amount of permanent displacement, the better. However, since the self-healing material generally undergoes plastic deformation, the lower limit of the amount of permanent displacement is 0.2 ⁇ m in this measurement method. Conceivable. A method for measuring the maximum displacement amount, creep displacement amount, and permanent displacement amount in the thickness direction of these micro hardness testers will be described later.
- the laminated film of the present invention preferably has a specular glossiness within a specific range, and is 60% or more as measured by the 60 ° specular glossiness specified in JIS Z8741 (1997). Is preferable, 70% or more is more preferable, and 80% or more is particularly preferable. If the specular gloss is less than 60%, the glossiness may be felt to be insufficient.
- the upper limit of the specular glossiness depends on the refractive index of the material, but is about 180% when a general material is used.
- the laminated film of the present invention in terms of fingerprint resistance is preferably receding contact angle theta r oleic acid to the surface layer is 50 ° or more, more preferably at least 55 °, particularly preferably 60 ° or more.
- the receding contact angle is lower than 50 °, the fingerprint component tends to adhere gradually and the fingerprint resistance is reduced. There is.
- fingerprint resistance particularly for fingerprint wiping-off property
- the relationship of the advancing contact angle theta a and receding contact angle theta r fingerprint component of the surface layer it is preferred to satisfy the equation (1) above.
- ( ⁇ a ⁇ r ) ⁇ 15 ° Formula (1) This is based on the fact that the fingerprint wiping property is governed by two factors: “easy transfer of the fingerprint component to the wiping material” and “easy mobility of the fingerprint component on the surface layer”.
- the receding contact angle the latter can be expressed by the advancing contact angle, and if the formula (1) integrating them is satisfied, it means that the attached fingerprint can be easily wiped off.
- the advancing contact angle ⁇ a and receding contact angle ⁇ r of the oleic acid in the surface layer satisfy the formula (1), that is, preferably 15 ° or less, more preferably 12 ° or less, and particularly preferably 10 ° or less. preferable. If the value of the formula (1) is 0 or a positive value, it is preferable for a small amount. On the other hand, if this value is larger than 15 °, the fingerprint wiping property is insufficient and the fingerprint resistance is lowered. There is.
- the contact angle of the liquid on the solid surface is essentially a thermodynamic quantity and should take a single value once the system is determined.
- the contact angle on the opposite side (retreat side) to the contact angle in the traveling direction often does not take the same value.
- the contact angle of the traveling method at this time is called a forward contact angle, and the contact angle on the opposite side is called a receding contact angle.
- the values of the advancing contact angle and the receding contact angle include values based on several measuring methods, but values based on the expansion / contraction method are preferable.
- the value of the advancing contact angle by the expansion-contraction method is that when a liquid (oleic acid) is applied on the surface layer to expand the droplet, the contact angle of the droplet is measured continuously several times, and the contact angle is constant. It is represented by the average value of where it became.
- the receding contact angle value is determined by applying liquid (oleic acid) on the surface layer and gradually discharging the liquid to expand the droplet, and then drawing the droplet and contracting the droplet. The contact angle of the droplet is continuously measured a plurality of times, and is expressed as an average value when the contact angle becomes constant.
- the advancing contact angle is 1 ⁇ L to 50 ⁇ L at the time of droplet ejection, and the receding contact angle is droplet suction. It can be determined by measuring at an interval of 1 ⁇ L between 50 ⁇ L and 1 ⁇ L of the hour and obtaining a value at which the contact angle of the droplet becomes substantially constant during the expansion or contraction of the liquid.
- the contact angle in the expansion contraction method can be measured using, for example, Drop Master (manufactured by Kyowa Interface Science Co., Ltd.).
- the laminated film of the present invention is preferably oleate absorption coefficient A b of the surface layer is 30 or more.
- index representing the is oleic acid absorption coefficient a b is oleic acid absorption coefficient a b.
- oleic acid absorption coefficient a b per unit volume is 30 or more, more preferably 40 or more.
- it oleate absorption coefficient A b of the surface layer is preferably higher in view of the absorption of the fingerprint component reduces the adhesion amount is 200 or less from the viewpoint of improving the fingerprint as a whole Is preferred.
- the volume specific measuring method of oleic acid absorption coefficient A b is wherein oleic acid for about 2 ⁇ l dropped on the surface layer of a thickness of T, was determined from the droplet shape upon ejection from the syringe (V 1), the dripping It refers to the dimensionless amount obtained by the following formula (2) from the area (S 1 ) at the time of dropping, the volume (V 2 ) after 10 hours of holding at 25 ° C. and no wind.
- a b (V 1 ⁇ V 2 ) / (S 1 ⁇ T) Formula (2)
- the measurement can be performed by Kyowa Interface Chemical Co., Ltd. contact angle measurement device DM500 and the company's analysis software DropMaster. Detailed procedures of the measurement will be described later.
- a method for measuring the thickness T of the surface layer will also be described later.
- the outermost surface layer of the surface layer In order for the surface layer of the present invention to exhibit the characteristic that the amount of fingerprint component adhering is as small as possible and disappears from the surface by absorbing the adhering fingerprint component into the coating film, the outermost surface layer of the surface layer must be The surface of the surface is uniformly coated with a compound containing fluorine to show high oil repellency, thereby reducing the adhesion amount of fingerprint components, and at the same time, the compound containing lipophilic dimethylsiloxane is a fine island or network. As a result, the fingerprint component slightly adhered to the surface diffuses into the outermost surface and the surface layer through the island-like or network-like lipophilic portion existing on the surface, and as a result, the fingerprint I think the dirt will disappear.
- a method for measuring the outermost surface of the surface layer using a time-of-flight secondary ion mass spectrometer (TOF-SIMS) will be described in the section of the examples.
- uniformly present means a coefficient of variation of secondary ion intensity at all measurement points measured in a 100 ⁇ m ⁇ 100 ⁇ m range of 128 vertical points ⁇ 128 horizontal points with a time-of-flight secondary ion mass spectrometer. Is within 0.4.
- “Existing in an island shape” means that, as shown in FIG. 2, when the secondary ion intensity of Si (CH 3 ) + at the measurement point where the measurement was performed is illustrated, the boundary value corresponds to 20% of the maximum intensity. It means that it is surrounded by an unfilled part (except for the one on the outer periphery of the figure). Details of the boundary value will be described later.
- the upper limit of the size of the island is practically required to be within the measurement range of the time-of-flight secondary ion mass spectrometer. Under the above measurement conditions, the diameter of the circumscribed circle is 50 ⁇ m or less. Is an island.
- the lower limit of the size is not particularly limited as long as it can be classified according to the above conditions, but in practice, it depends on the spatial resolution of the measuring instrument and is suggested to be about 0.8 ⁇ m in the above measurement conditions.
- “Existing in a network” means that when the secondary ion intensity of Si (CH 3 ) + fragment is illustrated as shown in FIG. 3, a region less than the boundary value exists in an island shape. Point to.
- “Existing in the form of islands and meshes” means that when the secondary ion intensity of Si (CH 3 ) + fragment is illustrated as shown in FIG. This refers to the coexistence of existing areas.
- the presence form of Si (CH 3 ) + fragment ions is more preferably “existing in the form of islands and meshes”, but this is the outermost surface layer of the fingerprint stain as compared with the case of “existing in the form of islands”. This is considered to be because of excellent diffusibility in the surface direction and excellent ability to reduce the amount of adhesion of fingerprint stains as compared with the case of “existing in a mesh”.
- the occupation ratio of the region where Si (CH 3 ) + fragment ions derived from dimethylsiloxane are present is preferably 30% or more and 70% or less, more preferably 30% or more and 50% or less, and 30% Above, 40% or less is particularly preferable.
- the occupation ratio refers to a ratio of points where Si (CH 3 ) + fragment ions are present at a boundary value or more among all measurement points.
- Si (CH 3) derived from dimethylsiloxane + the present area in other words the fragment ions, Si (CH 3 derived from dimethylsiloxane) + fragment ions If the ratio of the portion occupied by) is less than 30%, the ability to absorb the attached fingerprint component in the coating film is insufficient, and the disappearance of fingerprint stains may be reduced. The ability to reduce the amount of dirt attached may be reduced.
- Si is distributed on an arbitrary straight line that is perpendicular or parallel to the side direction of the “mapping diagram” (the diagram showing the secondary ion intensity of Si (CH 3) + fragment (for example, FIG. 2 and FIG. 3)).
- the length of each line segment in which Si (CH 3 ) + fragment ions are less than the boundary value on the same straight line is preferably divided into 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
- the lower limit of the length is not particularly limited as long as it can be classified according to the above conditions, but actually depends on the spatial resolution of the measuring instrument and is suggested to be about 0.8 ⁇ m in the above measurement conditions.
- the surface layer has a simulated fingerprint close to the actual fingerprint composition under the specific conditions shown below. It is preferable that the color difference between the specular reflection light before and after the attachment of the simulated fingerprint and the color difference of the specular reflection light removal are within a specific range as optical characteristics when the is attached under a certain condition.
- color difference including specular reflection light refers to a color difference measured under “conditions including a component that becomes specular reflection from a sample under geometric condition c” described in JIS Z8722 (2009).
- the “color difference for removal of specular reflection light” refers to the color difference measured under the condition “excluding the component that becomes specular reflection from the sample under the geometric condition c”.
- the color difference before and after the imitation fingerprint attachment and the color difference ( ⁇ E * ab (di: 8 °) Sb10W10) including the specular reflection light specified in JIS Z8730 (2009) and JIS Z8722 (2009) is 0.4 or less is preferable, 0.2 or less is more preferable, and 0.1 or less is particularly preferable. Since it is the color difference before and after attachment of the simulated fingerprint, it is preferable that the color difference is small. In addition, the color difference before and after attachment of the simulated fingerprint, and the color difference ( ⁇ E * ab (de: 8 °) Sb10W10) for specular reflection removal defined in JIS Z8730 (2009) and JIS Z8722 (2009) is 4 or less.
- the color difference before and after attachment of the simulated fingerprint it is preferable that the color difference is small.
- the color difference including the specular reflection light before and after the attachment of the simulated fingerprint and the color difference of the removal of the specular reflection light before and after the simulation fingerprint attachment exceed 0.4 and 4, respectively, the fingerprint attachment trace may be clearly recognized.
- the specific simulated fingerprint transfer procedure is as follows.
- Simulated fingerprint adhesion conditions A dispersion composed of 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 ⁇ m is defined by JIS K0603 (1997) with Ra defined by JIS B0601 (2001) of 3 ⁇ m.
- 1.0 g / m 2 is attached to a silicone rubber having a rubber hardness of 50 and attached to the target surface at 30 kPa.
- the molding material of the present invention has a color difference including specular reflection light before and after adhering a simulated fingerprint, and a color difference of specular reflection light removal not more than a specific value, and the temporal decrease in color difference is not less than a specific value. It is preferable to do. This corresponds to the effect of disappearance due to absorption of the fingerprint component by the surface layer. Specifically, it is as follows.
- the parameter K 0,5 represented by the following formula (5) is preferably 3 or less, more preferably 2 or less. preferable. If it exceeds 3, fingerprint adhesion traces are easily visible, and it may be difficult to obtain a sufficient penetration effect of the attached fingerprint.
- K 0.5 [( ⁇ E SCI ⁇ 0.5 ) 2 + ( ⁇ E SCE ⁇ 0.5 ) 2 ] 1/2 equation (5).
- the ⁇ ESCI -0.5 is a color difference before and after attaching the simulated fingerprint, and the color difference including the regular reflection light ( ⁇ E * ab (di :) defined by JIS Z8730 (2009) and JIS Z8722 (2009)). 8 °) Sb10W10), and ⁇ E SCE-0.5 is the color difference before and after attachment of the simulated fingerprint, and indicates the color difference ( ⁇ E * ab (de: 8 °) Sb10W10) for removing the regular reflection light.
- ⁇ E * ab (di: 8 °) Sb10W10 and ⁇ E * ab (de: 8 °) Sb10W10 are physical quantities having equivalent dimensions, and correspond to the distance from the origin in a two-dimensional coordinate system with each value as an axis. Decreasing the parameter K 0.5 corresponds to lowering the visibility of the fingerprint before and after attaching the simulated fingerprint. It can be said that the smaller the parameter K 0.5 is, the better the anti-fingerprint property is. However, in order to recognize the effect of fingerprint change with time, which will be described later, in the material having high gloss and transparency, which is the subject of the present invention. It is realistic to exceed 1 for.
- the term “immediately after attaching the simulated fingerprint” means 30 minutes after the simulated fingerprint is attached to the surface of the molding material by the method of attaching the simulated fingerprint described later.
- the amount of color difference with time before and after the attachment of the simulated fingerprint is preferably 1 or more, and more preferably 1.2 or more, in the following equation (4). If the value of the left side of the following formula (4) is less than 1, it may be difficult to obtain a feeling of disappearance of fingerprint smudges.
- K 0.5 -K 10 ⁇ 1 Formula (4) K 0.5 in the formula (4) is as described above, and K 10 is represented by the following formula (6).
- K 10 [( ⁇ E SCI-10 ) 2 + ( ⁇ E SCE-10 ) 2 ] 1/2 formula (6)
- ⁇ E SCI-10 in the formula (6) is a color difference between the JIS Z8730 (2009) and the JISZ8722 before and after imitation fingerprint attachment and after standing for 10 hours in a windless state at 25 ° C. (2009) refers to a color difference ( ⁇ E * ab (di: 8 °) Sb10W10) including specular reflection light
- ⁇ E SCE-2 is a color difference ( ⁇ E * ab (de: 8 °) refers to Sb10W10).
- a surface layer exhibiting these characteristics exhibits a characteristic shape of oil droplets formed when a fingerprint component is adhered, and behavior over time.
- the size of the oil droplets constituting the simulated fingerprint on the molding material of the present invention is preferably small. This is because the visibility of the fingerprint increases as the area occupied by the oil droplet adhering portion on the surface increases in the molding material.
- the median diameter DP0.5 calculated from the area reference frequency distribution of the oil droplets immediately after adhering the simulated fingerprint is preferably 80 ⁇ m or less, more preferably 70 ⁇ m or less, and 50 ⁇ m or less. It is particularly preferred. If this value is deviated, the fingerprint may be easily recognized due to light scattering by the oil droplets. The smaller the value of DP0.5, the harder it is to see the fingerprint. Therefore, there is no lower limit in terms of making the fingerprint difficult to see. On the other hand, when it becomes several hundred nm or less, oil droplets aggregate due to surface free energy. Or, since it volatilizes, there is actually no droplet of 100 nm or less.
- the time variation of the median diameter There is a preferable value in (D P0.5 -D P10 ) / D P0.5 , a value normalized by the median diameter D P0.5 immediately after adhering the simulated fingerprint. Specifically, this value is preferably 0.5 or more, particularly preferably 0.6 or more. If this value is less than 0.5, the fingerprint may remain visible even after a lapse of time.
- a simulated fingerprint is attached under certain conditions, then wiped off, and the reflection color after attachment and after wiping is measured by two methods including regular reflection light removal and regular reflection light removal, and the state before adhesion
- the color difference after wiping with reference to satisfy the above-mentioned formula (9). This is based on the fact that the human eye recognizes fingerprints or smudges caused by fingerprints based on changes in glossiness and changes in color tone. This is because the change in taste is evaluated by the color difference for removing the regular reflection light, and it has been found that it is difficult to visually recognize the fingerprint in a range satisfying Expression (9) in which these values are integrated.
- the surface layer was subjected to a simulated fingerprint adhesion and simulated fingerprint wiping test under the following conditions, and based on the state before the simulated fingerprint adhesion obtained according to JIS Z8730 (2009) and JIS Z8722 (2009).
- Simulated fingerprint wiping conditions Simulated fingerprints adhered under the above conditions are rubbed with a nonwoven fabric three times at a pressure of 30 kPa and a speed of 5 cm / sec.
- the resin contained in the surface layer of the laminated film preferably has the following (1) to (3).
- (poly) caprolactone segment (2) Urethane bond, (3) A segment containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group and a fluorooxyalkanediyl group (hereinafter referred to as a fluorine compound segment).
- the resin refers to a substance composed of a polymer compound, and the range includes a range from a polymer to an oligomer.
- the (1) (poly) caprolactone segment refers to a segment represented by Chemical Formula 1
- the (2) urethane bond refers to a bond represented by Chemical Formula 2.
- n is an integer from 1 to 35.
- (1) has a function of enhancing self-repairability
- (2) is a surface layer.
- (3) reduces the surface energy, thereby increasing the contact angle of the liquid constituting the fingerprint and reducing the amount of adhesion.
- the fluorine compound segment is a fluoropolyether segment.
- the fluoropolyether segment is a segment composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, etc., and has a structure represented by chemical formulas (3) and (4).
- n1 is an integer of 1 to 3
- n2 to n5 are integers of 1 or 2
- k, m, p, and s are integers of 0 or more
- p + s is 1 or more.
- n1 is 2 or more and n2 to n5 are integers of 1 or 2, more preferably n1 is 3, n2 and n4 are 2, and n3 and n5 are integers of 1 or 2.
- the surface layer can contain the molecule
- the carbon number 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.
- the number of carbon atoms is 3 or less, the surface energy is not sufficiently reduced, and thus the oil repellency may be lowered.
- the number is 13 or more, the solubility in a solvent is lowered, and the quality of the surface layer may be lowered.
- the resin contained in the surface layer of the laminated film of the present invention preferably has (4) (poly) siloxane segment and / or polydimethylsiloxane segment.
- the (poly) siloxane segment refers to a segment represented by Chemical Formula 5.
- the (poly) dimethylsiloxane segment refers to a segment represented by Chemical Formula 6.
- R 1 is either OH or an alkyl group having 1 to 8 carbon atoms.
- R 2 is either OH or an alkyl group having 1 to 8 carbon atoms.
- n is an integer of 100 to 300.
- M is an integer from 10 to 300.
- the laminated film of the present invention may be any one of a flat shape (film, sheet, plate) and a three-dimensional shape (molded product).
- the surface layer in the present invention is directed from the surface of the laminated film in the thickness direction (in the case of a planar shape) or in the internal direction (in the case of a three-dimensional shape), and the portion and element composition adjacent to the thickness direction or the internal direction.
- the shape and physical properties of inclusions (particles, etc.) can be distinguished by having a discontinuous boundary surface, and indicate a portion having a finite thickness.
- composition / element analyzers IR, XPS, XRF, EDAX, SIMS, etc.
- electron microscope transmission type, scanning type
- optical microscope optical microscope
- the surface layer is an object of the present invention, antireflection, antistatic, antifouling properties, conductivity, heat ray reflection, near infrared absorption, You may have other functions, such as electromagnetic shielding and easy adhesion.
- the thickness of the surface layer is not particularly limited, but is preferably 5 ⁇ m or more and 200 ⁇ m or less, more preferably 10 ⁇ m or more and 100 ⁇ m or less, and the thickness can be selected according to the other functions described above.
- the laminated film of the present invention can be obtained by providing the above-mentioned surface layer through a general coating process including coating, drying, and curing a coating composition on a supporting substrate described later.
- This coating composition contains at least the above-described (poly) caprolactone segment, a resin containing a urethane bond, a fluorine compound segment, or a material capable of forming them in the coating process (hereinafter referred to as a precursor).
- the resin contained in the surface layer can have these segments by using the coating composition in the production method described later.
- the first type is a coating composition that preferably includes at least the following materials (hereinafter referred to as coating composition A), and is cured by heat in the curing step of the coating process, or by curing with heat and active energy rays.
- coating composition A a coating composition that is preferably used in combination.
- the compound to be used is a fluorine compound segment and contains a fluorine compound D. Details of these materials will be described later.
- the coating composition A preferably contains 11% by mass or more and 22% by mass or less of the compound containing the isocyanate group in a total solid content concentration of 100% by mass.
- other crosslinking agents such as melamine crosslinking agents such as alkoxymethylol melamine, acid anhydride crosslinking agents such as 3-methyl-hexahydrophthalic anhydride, and amine crosslinking agents such as diethylaminopropylamine. It is also possible to include an agent.
- a crosslinking catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be used to accelerate the urethane bond formation reaction.
- polysiloxane and polydimethylsiloxane which will be described later, and may further contain various additives such as a solvent, a photopolymerization initiator, and a leveling agent.
- the second type is a coating composition that preferably includes at least the following materials (hereinafter referred to as coating composition B), and it is preferable to use curing with active energy rays in the curing step of the coating process.
- a coating composition which solves the above-mentioned problems of the present invention, and further has resistance to contamination by cosmetics containing oil and fat components such as hand cream compared to the coating composition A (hereinafter referred to as cosmetic resistance) It has excellent characteristics.
- the urethane (meth) acrylate B is excellent in self-repairing property
- the urethane (meth) acrylate C is a material excellent in cosmetic resistance.
- layers formed by curing each of them alone (X layer, Y layer)
- Each layer) is a material exhibiting specific characteristics, and by having these characteristics, both self-repairing properties and cosmetic resistance properties are achieved.
- the constituent materials of the coating composition will be described later.
- Content ratio of urethane (meth) acrylate B and urethane (meth) acrylate C in coating composition B (mass of urethane (meth) acrylate B / mass of urethane (meth) acrylate C) is 70/30 to 30 A range of / 70 is preferred.
- content ratio of urethane (meth) acrylate B and urethane (meth) acrylate C (mass of urethane (meth) acrylate B / mass of urethane (meth) acrylate C) is out of the range of 70/30 to 30/70. In some cases, it may be difficult to achieve both self-healing properties and cosmetic properties.
- the coating composition B preferably contains polysiloxane, polydimethylsiloxane, polyalkylene glycol, and may further contain various additives such as a solvent, a photopolymerization initiator, a curing agent, and a catalyst.
- the resin constituting the supporting substrate used in the laminated film of the present invention may be either a thermoplastic resin or a thermosetting resin, may be a homo resin, may be a copolymer or a blend of two or more types. Good. More preferably, the resin constituting the support substrate is preferably a thermoplastic resin because of good moldability.
- thermoplastic resins examples include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyester resins, polycarbonate resins, and polyarylate resins.
- Fluorine resins such as polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluoroethylene chloride resin, tetrafluoroethylene-6 fluoropropylene copolymer, vinylidene fluoride resin, acrylic Resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like can be used.
- the thermoplastic resin is preferably a resin having sufficient stretchability and followability.
- the thermoplastic resin is more preferably a polyester resin from the viewpoint of strength, heat resistance, and transparency.
- the polyester resin in the present invention is a general term for polymers having an ester bond as a main bond chain, and is obtained by polycondensation of an acid component and its ester with a diol component.
- Specific examples include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and the like. These may be copolymerized with other dicarboxylic acids and their esters or diol components as acid components or diol components.
- polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferable in terms of transparency, dimensional stability, heat resistance and the like.
- the support substrate may be either a single layer configuration or a laminated configuration.
- the surface of the support substrate can be subjected to various surface treatments before forming the surface layer.
- the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment.
- glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.
- the resin contained in the surface layer preferably has a fluorine compound segment.
- This fluorine compound segment refers to a segment containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group.
- a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group are alkyl groups, oxyalkyl groups, alkenyl groups, alkanediyl groups, and oxyalkanediyl groups.
- a part or all of the substituents are replaced by fluorine, each of which is mainly composed of fluorine atoms and carbon atoms, and there may be branching in the structure. Dimers, trimers, oligomers, and polymer structures may be formed.
- the fluorine compound segment is preferably a fluoropolyether segment, which is a substituent composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, etc., more preferably chemical formulas (3), (4) As described above, it is a fluoropolyether segment represented by
- the coating composition A or the coating composition B described above preferably contains the fluorine compound D.
- This fluorine compound D is a compound represented by Chemical Formula 7.
- R f1 represents a fluorine compound segment
- R 2 represents an alkanediyl group, alkanetriyl group, and an ester structure, urethane structure, ether structure, and triazine structure derived therefrom
- D 1 represents a reactive site.
- This reactive site refers to a site that reacts with other components by external energy such as heat or light.
- reactive sites include alkoxysilyl groups and silanol groups in which alkoxysilyl groups are hydrolyzed from the viewpoint of reactivity, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and the like. Can be mentioned. Of these, vinyl groups, allyl groups, alkoxysilyl groups, silyl ether groups, silanol groups, epoxy groups, and acryloyl (methacryloyl) groups are preferred from the viewpoints of reactivity and handling properties.
- fluorine compound D is a compound represented by the following chemical formula. 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltriisopropoxysilane, 3,3,3-trifluoropropyltrichlorosilane, 3,3,3-trifluoropropyltriisocyanate silane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluorooctylethyltriisopropoxysilane, 2-perfluorooctylethyltri Chlorosilane, 2-perfluorooctyl isocyanate silane, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobuty
- the fluorine compound D may have a plurality of fluoropolyether segments per molecule.
- the resin contained in the surface layer preferably has a (poly) caprolactone segment.
- the (poly) caprolactone segment refers to the segment represented by the above-described chemical formula 1.
- the surface layer can have a (poly) caprolactone segment by forming the surface layer using the coating composition A or the coating composition B containing a resin containing a (poly) caprolactone segment.
- the resin containing the (poly) caprolactone segment preferably has at least one hydroxyl group (hydroxyl group).
- the hydroxyl group is preferably at the end of the resin containing the (poly) caprolactone segment.
- (poly) caprolactone having a bi- to trifunctional hydroxyl group is particularly preferable.
- n is an integer from 1 to 25 and R is H or CH 3
- An active energy ray-polymerizable caprolactone such as can be used.
- active energy ray polymerizability is a property that crosslinking proceeds by active energy rays such as UV and EB, and corresponds to a compound having a functional group such as a (meth) acrylate group.
- active energy ray polymerizable caprolactones include (poly) caprolactone-modified hydroxypropyl (meth) acrylate, (poly) caprolactone-modified hydroxybutyl (meth) acrylate, and the like.
- the resin containing the (poly) caprolactone segment may contain (or copolymerize) other segments and monomers in addition to the (poly) caprolactone segment.
- a polydimethylsiloxane segment, a (poly) siloxane segment, and a compound containing an isocyanate compound described later may be contained (or copolymerized).
- the weight average molecular weight of the (poly) caprolactone segment in the resin containing the (poly) caprolactone segment is preferably 500 to 2,500, more preferably 1,000 to 1. , 500.
- the weight average molecular weight of the (poly) caprolactone segment is 500 to 2,500, the self-repairing effect is more exhibited and the scratch resistance is further improved.
- the total solid content concentration of the coating composition used to form the surface layer is 100% by mass.
- a caprolactone segment content of 5 to 50% by mass is preferred in terms of self-repairing and contamination resistance.
- the urethane bond refers to the bond represented by Formula 2 above.
- the coating composition used for forming the surface layer contains a commercially available urethane-modified resin
- the resin contained in the surface layer can have a urethane bond.
- a urethane composition is formed in the coating process by applying a coating composition containing a compound containing an isocyanate group and a compound containing a hydroxyl group as a precursor. Bonds can also be included.
- the resin contained in the surface layer preferably 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 and the self-repairing property can be improved.
- the resin containing the (poly) caprolactone segment described above, the resin containing the polysiloxane segment described later, or the resin containing the polydimethylsiloxane segment has a hydroxyl group
- these resins and precursors are heated by heat or the like. It is also possible to generate a urethane bond with a compound containing an isocyanate group.
- the compound containing an isocyanate group means a resin containing an isocyanate group, or a monomer or oligomer containing an isocyanate group.
- the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, and tolylene diisocyanate.
- Polyisocyanates such as isocyanurate bodies, isocyanurate bodies of hexamethylene diisocyanate, burette bodies of hexamethylene isocyanate, and block bodies of the above isocyanates can be mentioned.
- aliphatic isocyanates are preferred because of their high self-healing properties compared to alicyclic and aromatic isocyanates.
- the compound containing an isocyanate group is more preferably hexamethylene diisocyanate.
- the isocyanate group-containing compound is particularly preferably an isocyanate having an isocyanurate ring from the viewpoint of heat resistance, and most preferably an isocyanurate of hexamethylene diisocyanate. Isocyanates having an isocyanurate ring form a surface layer having both self-healing properties and heat resistance.
- urethane (meth) acrylate B which has excellent self-healing properties
- urethane (meth) acrylate C which has excellent cosmetic properties
- urethane (meth) acrylate B which has excellent self-healing properties
- urethane (meth) which has excellent cosmetic properties
- Urethane (meth) acrylate B is a compound having a urethane bond in the molecule, and a mixture of urethane (meth) acrylate B and a photoinitiator is cured to a thickness of 30 ⁇ m with ultraviolet light from a high-pressure mercury lamp with an illuminance of 400 mW / cm 2.
- the physical properties of the layer mean urethane (meth) acrylate in the following range. 1. 1.
- the mass increase rate of the X layer when oleic acid is applied to the surface of the X layer and kept at 60 ° C. for 1 hour is 45% by mass or less. 2.
- the maximum displacement in the thickness direction of the X layer when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement is 1.0 ⁇ m or more and 3.0 ⁇ m or less.
- the creep displacement amount in the thickness direction of the X layer is 0.4 ⁇ m or more and 0.7 ⁇ m or less.
- Urethane (meth) acrylate C is a compound having a urethane bond in the molecule, and a mixture of urethane (meth) acrylate C and a photoinitiator is irradiated with ultraviolet light from a high-pressure mercury lamp having an illuminance of 400 mW / cm 2 and a thickness of 30 ⁇ m.
- the urethane (meth) acrylate in which the physical properties of the layer (hereinafter referred to as Y layer) cured in the following range are included. 1. 1.
- the mass increase rate of the Y layer when oleic acid is applied to the surface of the Y layer and kept at 60 ° C. for 1 hour is 5.0% by mass or less. 2.
- the maximum displacement in the thickness direction of the Y layer when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement is 0.2 ⁇ m or more and 3.0 ⁇ m or less.
- the creep displacement amount in the thickness direction of the Y layer is 0.02 ⁇ m or more and 0.35 ⁇ m or less.
- the coating composition used for forming the surface layer contains urethane (meth) acrylate B and urethane (meth) acrylate C, the urethane (meth) acrylate B has a (poly) caprolactone segment, and the urethane (
- the (meth) acrylate C has a (poly) alkylene glycol (meth) segment, it is possible to obtain a surface layer that is more excellent in self-repairability and cosmetic resistance. This is because the (poly) alkylene glycol segment with excellent cosmetic resistance is unevenly distributed on the surface due to the difference between surface tension and intermolecular force, and the (poly) caprolactone segment with excellent self-healing properties is unevenly distributed in the inner layer. Is considered to be more prominent.
- the mass m of the (1) (poly) alkylene glycol segment in the resin contained in the surface layer and the mass n of the (3) (poly) caprolactone segment in the resin contained in the surface layer are 0.3 n ⁇ m ⁇ 10n is preferably satisfied, 0.3n ⁇ m ⁇ 5n is more preferable, and 0.65n ⁇ m ⁇ 1.20n is more preferable.
- the mass m of the (1) (poly) alkylene glycol segment in the resin contained in the surface layer and the mass n of the (3) (poly) caprolactone segment in the resin contained in the surface layer satisfy 0.3n ⁇ m ⁇ 10n.
- the mass m of the (1) (poly) alkylene glycol segment in the resin contained in the surface layer and the mass n of the (3) (poly) caprolactone segment in the resin contained in the A layer satisfy 0.3n ⁇ m ⁇ 10n.
- filling the dispersibility of each segment at the time of the above-mentioned hardening rises, and uneven distribution may become weak.
- the surface layer preferably has (4) (poly) siloxane segments and / or polydimethylsiloxane segments.
- the (poly) siloxane segment refers to a segment represented by the above chemical formula 5.
- the above-described coating composition used for forming the surface layer can include a resin containing the (poly) siloxane segment.
- Resins containing (poly) siloxane segments are tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, ⁇ -glycidoxypropyltrialkoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, ⁇ -methacryloxy Hydrolyzable on the surface of organosilica sol, organosilica sol dispersed in complete or partial hydrolysates of silane compounds with hydrolyzable silyl groups such as propyltrialkoxysilane and ⁇ -methacryloxypropylalkyldialkoxysilane, organic solvents The thing etc. which added the hydrolysis silane compound of the silyl group can be illustrated.
- the resin containing the (poly) siloxane segment may contain (copolymerize) other segments in addition to the (poly) siloxane segment.
- a monomer component having a (poly) caprolactone segment and a polydimethylsiloxane segment may be contained (copolymerized).
- a monomer having a hydroxyl group that reacts with an isocyanate group is copolymerized as a resin containing a (poly) siloxane segment.
- a resin having a hydroxyl group that reacts with an isocyanate group is copolymerized with a resin containing a (poly) siloxane segment, the toughness of the surface layer is improved.
- a coating composition comprising a resin (copolymer) containing a (poly) siloxane segment having a hydroxyl group and a compound containing an isocyanate group
- a surface layer is formed using, a surface layer having (poly) siloxane segments and urethane bonds can be efficiently formed.
- the (poly) siloxane segment is used in 100% by mass of all components of the coating composition used to form the surface layer. Is preferably from 1 to 20% by mass in terms of self-healing properties, stain resistance, weather resistance, and heat resistance.
- the solvent which does not participate in the reaction is not included in 100% by mass of all components of the coating composition.
- the monomer component involved in the reaction is included.
- polydimethylsiloxane segment refers to a segment represented by the above chemical formula 6.
- the polydimethylsiloxane segment is coordinated to the surface of the surface layer.
- the lubricity of the surface layer surface can be improved and the frictional resistance can be reduced. As a result, scratchability can be suppressed.
- the coating composition used for forming the surface layer can include a resin containing a polydimethylsiloxane segment.
- the resin containing a polydimethylsiloxane segment it is preferable to use a copolymer obtained by copolymerizing a vinyl monomer with a polydimethylsiloxane segment.
- the resin containing a polydimethylsiloxane segment is preferably copolymerized with a monomer having a hydroxyl group that reacts with an isocyanate group.
- a coating composition containing a resin (copolymer) containing a polydimethylsiloxane segment having a hydroxyl group and a compound containing an isocyanate group is used.
- any of a block copolymer, a graft copolymer, and a random copolymer may be used.
- the resin containing the polydimethylsiloxane segment is a copolymer with a vinyl monomer, this is referred to as a polydimethylsiloxane copolymer.
- Polydimethylsiloxane copolymer can be produced by living polymerization method, polymer initiator method, polymer chain transfer method, etc., but considering the productivity, polymer initiator method, polymer chain transfer method can be used. It is preferable to use it.
- n is an integer from 1 to 50
- M is an integer from 10 to 300
- n is an integer from 1 to 50
- a two-stage polymerization is carried out by synthesizing a prepolymer in which a peroxide group is introduced into the side chain by copolymerizing a peroxy monomer and polydimethylsiloxane having an unsaturated group at a low temperature, and then copolymerizing the prepolymer with a vinyl monomer. Can also be done.
- HS—CH 2 COOH, HS—CH 2 CH 2 COOH, etc. are added to form a compound having an SH group, and then the silicone compound and a vinyl monomer are copolymerized using chain transfer of the SH group.
- the block copolymer can be synthesized with
- a graft copolymer can be easily obtained by copolymerizing a methacrylic ester of polydimethylsiloxane and a vinyl monomer.
- vinyl monomers used in the copolymer with polydimethylsiloxane include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n -Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, ⁇ -methyl styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride , Vinyl fluoride, vinylidene fluoride, glycidyl accelerator
- Polydimethylsiloxane copolymers include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, ethanol, isopropyl alcohol, etc. It is preferable that the alcoholic solvent is produced by a solution polymerization method alone or in a mixed solvent.
- a polymerization initiator such as benzoyl peroxide or azobisisobutylnitrile is used in combination.
- the polymerization reaction is preferably carried out at 50 to 150 ° C. for 3 to 12 hours.
- the amount of the polydimethylsiloxane segment in the polydimethylsiloxane copolymer in the present invention is 1 to 30 in 100% by mass of all the components of the polydimethylsiloxane copolymer from the viewpoint of lubricity and stain resistance of the surface layer. It is preferable that it is mass%.
- the weight average molecular weight of the polydimethylsiloxane segment is preferably 1,000 to 30,000.
- the dimethylsiloxane segment is 1 to 4% in 100% by mass of the total components of the coating composition used to form the surface layer.
- the content is 20% by mass, it is preferable in terms of self-repairing property, contamination resistance, weather resistance, and heat resistance.
- the solvent which does not participate in the reaction is not included in 100% by mass of all components of the coating composition.
- the monomer component involved in the reaction is included.
- a resin containing a polydimethylsiloxane segment when used as the coating composition used for forming the surface layer, other segments are contained (copolymerized) in addition to the polydimethylsiloxane segment. May be.
- a (poly) caprolactone segment or a (poly) siloxane segment may be contained (copolymerized).
- the coating composition used to form the surface layer includes a copolymer of (poly) caprolactone segments and polydimethylsiloxane segments, a copolymer of (poly) caprolactone segments and (poly) siloxane segments, and (poly) caprolactone.
- a copolymer of a segment, a polydimethylsiloxane segment, and a (poly) siloxane segment can be used.
- the surface layer obtained using such a coating composition can have a (poly) caprolactone segment, a polydimethylsiloxane segment and / or a (poly) siloxane segment.
- This reaction can be copolymerized by appropriately adding a (poly) caprolactone segment and a polysiloxane segment during the synthesis of the polydimethylsiloxane copolymer.
- the surface layer preferably has a (poly) alkylene glycol segment.
- the (poly) alkylene glycol segment refers to a segment represented by Chemical Formula 14.
- n is an integer from 2 to 4
- m is an integer from 2 to 11.
- Alkylene glycol is a glycol having 2 to 4 carbon atoms. Furthermore, the number of repeating units m of the alkylene glycol is 2 to 11, preferably 3 to 6. When the carbon number n of the alkylene glycol exceeds 4, or when the number of repeating units m of the alkylene glycol exceeds 11, the molecular chain of the alkylene glycol becomes longer, the crosslink density of the cured product is lowered, and the hardness thereof is lowered. As a result, the coating strength, scratch resistance, etc. may decrease.
- the number of repeating units m of the alkylene glycol is less than 2, the molecular chain of the alkylene glycol is shortened, the crosslink density of the cured product is increased, and the cured product loses its flexibility. And workability may be reduced.
- the surface layer can have a (poly) alkylene glycol segment by forming the surface layer using a coating composition containing a resin containing a (poly) alkylene glycol segment.
- the resin containing a (poly) alkylene glycol segment preferably has at least one hydroxyl group (hydroxyl group).
- the hydroxyl group is preferably at the end of the resin containing the (poly) alkylene glycol segment.
- the resin containing a (poly) alkylene glycol segment is preferably a (poly) alkylene glycol (meth) acrylate having an acrylate group at the end in order to impart elasticity.
- the number of acrylate functional groups (or methacrylate functional groups) of the (poly) alkylene glycol (meth) acrylate is not limited, but is most preferably monofunctional from the viewpoint of self-healing properties of the cured product.
- Examples of the (poly) alkylene glycol (meth) acrylate contained in the coating composition used to form the surface layer include (poly) ethylene glycol (meth) acrylate, (poly) propylene glycol (meth) acrylate, (poly ) Butylene glycol (meth) acrylate.
- the structures are represented by the following chemical formula 15, chemical formula 16, and chemical formula 17, respectively.
- R is hydrogen (H) or a methyl group (—CH 3 ), and m is an integer from 2 to 11.
- polyethylene glycol (meth) acrylate which is ethylene glycol having 2 carbon atoms of alkylene glycol, is particularly preferable. Since (poly) ethylene glycol (meth) acrylate has the smallest carbon number n in Chemical Formula 14, it can contribute to both cosmetic resistance and scratch resistance of the resulting cured product.
- the surface layer is preferably (2) by reacting the above-mentioned compound containing an isocyanate group with a hydroxyl group of (poly) alkylene glycol (meth) acrylate and using it as a urethane (meth) acrylate in the surface layer. It can have a urethane bond and (3) a (poly) alkylene glycol segment, and as a result, the toughness of the surface layer can be improved and the self-repairing property can be improved.
- hydroxyalkyl (meth) acrylate, long-chain alcohol or the like can be blended.
- hydroxyalkyl (meth) acrylate the hardness of the surface layer that is a cured product can be increased.
- a long-chain alcohol the surface lubricity of the surface layer that is a cured product can be increased, and as a result, the scratch resistance can be improved.
- This long-chain alcohol is a compound included in the concept of the long-chain alkyl group-containing compound.
- hydroxyalkyl (meth) acrylate compounded at the same time during the urethanization reaction between the compound containing an isocyanate group and (poly) alkylene glycol (meth) acrylate examples thereof include hydroxybutyl (meth) acrylate.
- Long-chain alcohols to be blended at the same time during the urethanization reaction between the isocyanate group-containing compound and (poly) alkylene glycol (meth) acrylate include tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene mono Examples include stearate, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and glycerol monostearate.
- Particularly preferred long-chain alcohols include polyether-modified long-chain alcohols such as polyether-modified cetyl alcohol. This is because the use of a polyether-modified long-chain alcohol can impart an antistatic effect to the surface layer that is a cured product.
- the urethanation reaction between the isocyanate group-containing compound and (poly) alkylene glycol (meth) acrylate is carried out in an organic solvent in the presence of a catalyst, a polymerization inhibitor or the like.
- the reaction temperature in the urethanization reaction is preferably from room temperature to 100 ° C., and the reaction time is preferably from 1 to 10 hours.
- the reaction temperature is lower than room temperature or when the reaction time is shorter than 1 hour, the progress of the reaction is slow, and the yield of the target urethane (meth) acrylate may be reduced.
- the reaction temperature exceeds 100 ° C. or when the reaction time is longer than 10 hours, side reactions may easily occur.
- Examples of the organic solvent used in the urethanation reaction between the isocyanate group-containing compound and (poly) alkylene glycol (meth) acrylate are aromatic hydrocarbon solvents such as toluene and xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples include ketone solvents such as cyclohexanone; ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate.
- Examples of the catalyst include dibutyltin laurate, dibutyltin diethylhexoate, dibutyltin sulfite and the like.
- Examples of the polymerization inhibitor include hydroquinone monomethyl ether.
- the coating composition A and the coating composition B may contain a solvent.
- the number of solvent types is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and still more preferably 1 or more and 6 or less.
- solvent refers to a substance that is liquid at room temperature and normal pressure, which can evaporate almost the entire amount in the drying step after application.
- the type of solvent is determined by the molecular structure constituting the solvent. That is, the same elemental composition and the same type and number of functional groups have different bond relationships (structural isomers), which are not structural isomers, but what conformations are in three-dimensional space Those that do not overlap exactly even if they are removed (stereoisomers) are treated as different types of solvents. For example, 2-propanol and n-propanol are handled as different solvents.
- it when it contains a solvent, it is preferably a solvent that exhibits the following characteristics (condition 1).
- the relative evaporation rate of the solvent E is 0.3 or less.
- the relative evaporation rate based on n-butyl acetate is an 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 90% by mass of n-butyl acetate to evaporate under dry air.
- the relative evaporation rate of the solvent E When the relative evaporation rate of the solvent E is larger than 0.3, the time required for the orientation of the fluorine compound D on the surface is shortened, and the fingerprint resistance may be lowered.
- the lower limit of the relative evaporation rate of the solvent E is not a problem as long as it is a solvent that can be evaporated and removed from the coating film in the drying process, and may be 0.005 or more in a general coating process.
- isobutyl ketone (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 mono And ethyl ether (relative evaporation rate: 0.1).
- the coating compositions A and B preferably contain a polymerization initiator, a curing agent and a catalyst.
- a polymerization initiator and a catalyst are used to accelerate the curing of the surface layer.
- the polymerization initiator those capable of initiating or accelerating polymerization, condensation or crosslinking reaction by anion, cation, radical polymerization reaction or the like of components contained in the coating composition are preferable.
- polymerization initiators curing agents and catalysts
- the polymerization initiator, the curing agent, and the catalyst may be used alone, or a plurality of polymerization initiators, curing agents, and catalysts may be used simultaneously.
- acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like.
- thermal polymerization initiator include peroxides and azo compounds.
- the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, amine compounds, and the like.
- an alkylphenone compound is preferable from the viewpoint of curability.
- the alkylphenone type compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2.2-dimethoxy-1.2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl
- a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, etc. may be added to the coating compositions A and B used for forming the surface layer as long as the effects of the present invention are not impaired.
- the surface layer can contain a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, and the like.
- the leveling agent include an acrylic copolymer or a silicone-based or fluorine-based leveling agent.
- Specific examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, oxalic anilide-based, triazine-based and hindered amine-based ultraviolet absorbers.
- the antistatic agent include metal salts such as lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt and calcium salt.
- the surface layer formed on the surface of the laminated film of the present invention preferably uses a production method in which the above-mentioned coating composition is formed by applying-drying-curing on the above-mentioned supporting substrate.
- the production method of the laminated film by coating is not particularly limited, but the coating composition is supported by a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method or a die coating method (US Pat. No. 2,681,294). It is preferable to form a surface layer by applying to the surface. Further, among these coating methods, the gravure coating method or the die coating method is more preferable as the coating method.
- the liquid film applied on the support substrate or the like is dried.
- the drying step it is preferable to involve heating of the liquid film.
- drying methods include heat transfer drying (adherence to high-temperature objects), convection heat transfer (hot air), radiant heat transfer (infrared rays), and others (microwave, induction heating).
- heat transfer drying adherence to high-temperature objects
- convection heat transfer hot air
- radiant heat transfer infrared rays
- microwave, induction heating microwave, induction heating
- the drying process is generally divided into (A) a constant rate drying period and (B) a decreasing rate drying period. Since the former is the rate of drying, diffusion of solvent molecules into the atmosphere on the liquid film surface is The drying speed is constant in this section, the drying speed is governed by the partial pressure of the solvent to be evaporated in the atmosphere, the wind speed and the temperature, and the film surface temperature is constant at a value determined by the hot air temperature and the partial pressure of the solvent to be evaporated in the atmosphere. Become. In the latter, since the diffusion of the solvent in the liquid film is rate-limiting, the drying rate does not show a constant value in this section and continues to decrease, and is governed by the diffusion coefficient of the solvent in the liquid film, and the film surface temperature is To rise.
- the drying rate represents the amount of solvent evaporation per unit time and unit area, and has a dimension of g ⁇ m ⁇ 2 ⁇ s ⁇ 1 .
- the drying speed has a preferable range, and is preferably 10 g ⁇ m ⁇ 2 ⁇ s ⁇ 1 or less, more preferably 5 g ⁇ m ⁇ 2 ⁇ s ⁇ 1 or less.
- the lower limit is preferably 0.1 g ⁇ m ⁇ 2 ⁇ s ⁇ 1 or more.
- the wind speed and temperature are not particularly limited.
- the fluorine compound D is oriented along with the evaporation of the remaining solvent during the decreasing rate drying period.
- the film surface temperature increase rate during the decreasing drying period preferably 5 ° C./second or less, preferably 1 ° C./second or less. More preferably.
- a further curing operation by irradiating heat or energy rays may be performed.
- the coating composition A when used and is cured with heat, it is preferably from room temperature to 200 ° C., more preferably from 100 ° C. to 200 ° C. from the viewpoint of the activation energy of the curing reaction, More preferably, the temperature is 130 ° C. or higher and 200 ° C. or lower.
- the oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing in a nitrogen atmosphere (nitrogen purge) is more preferable.
- the oxygen concentration is high, the hardening of the outermost surface is hindered, the hardening of the surface becomes insufficient, and the fingerprint resistance may be insufficient.
- the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method.
- the illuminance of UV 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. It is preferable to perform ultraviolet irradiation under the following conditions: the condition that the cumulative amount of ultraviolet light is 100 to 3,000 mJ / cm 2 , preferably 200 to 2,000 mJ / cm 2 , more preferably 300 to 1,500 mJ / cm 2. More preferably, UV irradiation is performed.
- the illuminance of ultraviolet rays is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectrum efficiency, the diameter of the light emission bulb, the design of the reflector, and the light source distance to the irradiated object.
- the illuminance does not change depending on the conveyance speed.
- the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface.
- the integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.
- Fluorine compound D1 As the fluorine compound D1, an acrylate compound containing a fluoropolyether segment (“Megafac” manufactured by RS-75 DIC Corporation, solid content concentration: 40% by mass, solvent (toluene and methyl ethyl ketone) 60% by mass) was used.
- fluorine compound D2 As the fluorine compound D2, a siloxane 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.
- Fluorine compound D3 As the fluorine compound D3, a bifunctional acrylate compound containing a fluoropolyether segment (fluorotetraethylene glycol segment) (solid content concentration 100 mass% manufactured by FPTMG-A Oil & Fat Products Co., Ltd.) was used.
- a fluoropolyether segment fluorotetraethylene glycol segment
- Fluorine compound D4 As the fluorine compound D4, an acrylate compound containing a fluoroalkyl segment (triacryloyl-heptadecafluorononenyl-pentaerythritol, solid content concentration 100% by mass, manufactured by Kyoeisha Chemical Co., Ltd.) was used.
- Fluorine compound D5 An acrylate compound containing a fluoroalkyl segment (pentaacryloyl-heptadecafluorononenyl-dipentaerythritol, solid content concentration: 100% by mass, manufactured by Kyoeisha Chemical Co., Ltd.) was used as the fluorine compound D5.
- a polydimethylsiloxane block copolymer (a) was obtained.
- the obtained block copolymer had a solid content of 50% by mass (solvents (toluene and methyl isobutyl ketone) were 50% by mass).
- Polydimethylsiloxane graft copolymer (b) Using the apparatus used for the synthesis of polysiloxane (a), 50 parts by mass of toluene and 50 parts by mass of isobutyl acetate were charged, and the temperature was raised to 110 ° C.
- the obtained block copolymer (b) had a solid content concentration of 50% by mass (solvents (toluene and isobutyl acetate) were 50% by mass).
- Polydimethylsiloxane block copolymer (c) Using the same apparatus as the synthesis of polysiloxane (a), 50 parts by mass of toluene, 50 parts by mass of methyl isobutyl ketone, 20 parts by mass of polydimethylsiloxane polymer initiator (VPS-0501 manufactured by Wako Pure Chemical Industries, Ltd.) , 18 parts by weight of methyl methacrylate, 38 parts by weight of butyl methacrylate, 23 parts by weight of 2-hydroxyethyl methacrylate, 1 part by weight of methacrylic acid and 0.5 parts by weight of 1-thioglycerin were allowed to react at 180 ° C. for 8 hours.
- VPS-0501 manufactured by Wako Pure Chemical Industries, Ltd.
- a polydimethylsiloxane block copolymer (c) was obtained.
- the obtained block copolymer (c) had a solid content concentration of 50% by mass (solvents (toluene and methyl isobutyl ketone) were 50% by mass).
- the monomer composition is 20 parts by weight of methyl methacrylate, 26 parts by weight of butyl methacrylate, 23 parts by weight of 2-hydroxyethyl methacrylate, 10 parts by weight of polysiloxane (a), 1 part by weight of methacrylic acid, and methacrylic modified polydimethylsiloxane (Shin-Etsu).
- a polydimethylsiloxane graft copolymer (d) was synthesized in the same manner as the polydimethylsiloxane graft copolymer (b) except that 20 parts by mass of X-22-174DX) manufactured by Chemical Industry Co., Ltd. was used.
- the obtained graft copolymer (d) had a solid content concentration of 50% by mass (solvents (toluene and isobutyl acetate) were 50% by mass). there were.
- Polydimethylsiloxane compound (e) EBECRYL350 (bifunctional, silicone acrylate) manufactured by Daicel Cytec Co., Ltd. was used as the polydimethylsiloxane compound (e).
- Polydimethylsiloxane compound (f) EBECRYL 1360 (hexafunctional, silicone acrylate) manufactured by Daicel Cytec Co., Ltd. was used as the polydimethylsiloxane compound (f).
- ⁇ Synthesis of urethane (meth) acrylate B> [Urethane (meth) acrylate B1] 50 parts by mass of toluene, 50 parts by mass of isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Mitsui Chemicals, Inc.), 76 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate (Placcel FA5 manufactured by Daicel Chemical Industries, Ltd.) 0.02 part by mass of dibutyltin laurate and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate B1 having a solid content concentration of 50% by mass.
- urethane (meth) acrylate B2 having a solid concentration of 50% by mass.
- the repeating number of the caprolactone unit per acrylate monomer residue in this urethane (meth) acrylate is 10.
- urethane (meth) acrylate C1 having a solid content concentration of 50% by mass.
- the repeating number of the caprolactone unit per acrylate monomer residue in this urethane (meth) acrylate is 2.
- urethane (meth) acrylate C2 having a solid concentration of 50% by mass.
- the repeating number of the caprolactone unit per acrylate monomer residue in this urethane (meth) acrylate is 3.
- MEK methyl ethyl ketone
- Urethane (meth) acrylate C4 Urethane (meth) acrylate C3, except that polyethylene glycol monoacrylate was changed to 53 parts by weight of Bremer AE-150 (hydroxyl value: 264 (mgKOH / g)) and MEK of the reaction liquid was changed to 102 parts by weight.
- a toluene solution of urethane (meth) acrylate C4 was obtained in the same manner as C3.
- urethane (meth) acrylate C5 In urethane (meth) acrylate C3, except that polyethylene glycol monoacrylate was changed to 68 parts by mass of BLEMMER AE-200 (hydroxyl value: 205 (mgKOH / g)) and MEK of the reaction liquid was changed to 118 parts by mass, urethane (meth) acrylate A toluene solution of urethane (meth) acrylate C5 was obtained in the same manner as C3.
- Urethane methacrylate C3 is the same as urethane (meth) acrylate C3 except that polyethylene glycol monoacrylate is changed to 142 parts of Bremer AE-400 (hydroxyl value: 98 (mgKOH / g)) and MEK of the reaction liquid is changed to 192 parts by mass. Thus, a toluene solution of urethane (meth) acrylate C6 was obtained.
- Coating composition A1-1 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-1 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- a compound having an isocyanate group hexamethylene Isocyanurate of diisocyanate Takenate D-170N manufactured by Mitsui Chemicals Co., Ltd.
- Coating composition A1-2 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-2 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- 15 parts by mass Compound having an isocyanate group (hexamethylene Isocyanurate of diisocyanate Takenate D-170N manufactured by Mitsui Chemicals Co., Ltd.
- Coating composition A1-3 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-3 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- a compound having an isocyanate group hexamethylene Isocyanurate of diisocyanate Takenate D-170N manufactured by Mitsui Chemicals Co., Ltd.
- Coating composition A1-4 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-4 having a solid concentration of 40% by mass.
- Fluorine compound D2 solution solid content concentration 20% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- a compound having an isocyanate group hexamethylene Isocyanurate of diisocyanate Takenate D-170N manufactured by Mitsui Chemicals Co., Ltd.
- Coating composition A1-5 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-5 having a solid concentration of 40% by mass.
- Fluorine compound D3 2.4 parts by mass Polycaprolactone polyol (polycaprolactone triol, Daicel Chemical Industries, Ltd. Plaxel 308, weight average molecular weight 850) 15 parts by mass Compound having an isocyanate group (isocyanurate of hexamethylene diisocyanate Mitsui Chemicals) Takenate D-170N, Inc.
- polydimethylsiloxane block copolymer (a) solution (solid content 50% by mass) 75 parts by mass, polysiloxane (a) 10 parts by mass, ethylene glycol monobutyl ether 10 1 part by mass of an optical radical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.).
- an optical radical polymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition A1-6 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-6 having a solid concentration of 40% by mass.
- Fluorine compound D4 2.4 parts by mass Polycaprolactone polyol (polycaprolactone triol, Daicel Chemical Industries, Plaxel 308, weight average molecular weight 850) 15 parts by mass Compound having an isocyanate group (isocyanurate of hexamethylene diisocyanate Mitsui Chemicals) Takenate D-170N, Inc.
- polydimethylsiloxane block copolymer (a) solution (solid content 50% by mass) 75 parts by mass, polysiloxane (a) 10 parts by mass, ethylene glycol monobutyl ether 10 1 part by mass of an optical radical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.).
- an optical radical polymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition A1-7 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-7 having a solid concentration of 40% by mass.
- -Fluorine compound D5 2.4 parts by mass-Polycaprolactone polyol (polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850) 15 parts by mass-Compound having an isocyanate group (isocyanurate of hexamethylene diisocyanate Mitsui Chemicals, Inc.
- Coating composition A1-8 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-8 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- a compound having an isocyanate group hexamethylene Isocyanurate of diisocyanate Takenate D-170N manufactured by Mitsui Chemicals Co., Ltd.
- Coating composition A1-9 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-9 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- a compound having an isocyanate group hexamethylene Isocyanurate of diisocyanate Takenate D-170N manufactured by Mitsui Chemicals Co., Ltd.
- Coating composition A2 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A2 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- a compound having an isocyanate group hexamethylene Isocyanurate of diisocyanate Takenate D-170N manufactured by Mitsui Chemicals Co., Ltd.
- polydimethylsiloxane block copolymer (a) solution (solid content 50% by mass) 75 parts by mass, polysiloxane (a) 10 parts by mass Parts ⁇ ethylene glycol monobutyl ether 10 parts by mass ⁇ photoradical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1 part by mass.
- Coating composition A3 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A3 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- a compound having an isocyanate group hexamethylene Isocyanurate of diisocyanate Takenate D-170N manufactured by Mitsui Chemicals, Inc.
- polydimethylsiloxane block copolymer (a) solution (solid content 50% by mass) 75 parts by mass, polysiloxane (a) 10 parts by mass Parts ⁇ ethylene glycol monobutyl ether 10 parts by mass ⁇ photoradical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1 part by mass.
- Coating composition A4 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass 6 parts by mass
- Compound having an isocyanate group isocyanurate of hexanemethylene diisocyanate manufactured by Mitsui Chemicals, Inc.
- Coating composition A5 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A5 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Ltd.
- Plaxel 312 weight average molecular weight 1250 15 parts by mass
- Compound having an isocyanate group hexamethylene diisocyanate Isocyanurate body: Takenate D-170N, manufactured by Mitsui Chemicals, Inc.
- polydimethylsiloxane block copolymer (a) solution (solid content concentration 50% by mass) 75 parts by mass, polysiloxane (a) 10 parts by mass -10 parts by mass of ethylene glycol monobutyl ether-1 part by mass of photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.).
- photo radical polymerization initiator Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition A6 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A6 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- a compound having an isocyanate group hexamethylene Isocyanurate of diisocyanate Takenate D-170N manufactured by Mitsui Chemicals Co., Ltd.
- Coating composition A7 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A7 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- a compound having an isocyanate group hexamethylene Diisocyanate biuret manufactured by Bayer Co., Ltd.
- Desmodule N3200 15 parts by mass / polydimethylsiloxane block copolymer (a) solution (solid content 50% by mass) 75 parts by mass / polysiloxane (a) 10 parts by mass / ethylene 1 part by mass of glycol monobutyl ether 10 parts by mass, radical photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
- Coating composition A8 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A8 having a solid concentration of 40% by mass.
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Ltd. Placel 308, weight average molecular weight 850
- Compound having an isocyanate group isocyanurate of hexamethylene diisocyanate, Takenate D-170N, manufactured by Mitsui Chemicals
- Coating composition A9 ⁇ Formulation of raw material A8> The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A9 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- a compound having an isocyanate group hexamethylene Isocyanurate of diisocyanate Takenate D-170N, manufactured by Mitsui Chemicals, Inc.
- polydimethylsiloxane block copolymer (a) solution (solid content 50% by mass) 75 parts by mass, polysiloxane (a) 10 parts by mass 1 part by weight of a radical photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.).
- a radical photopolymerization initiator Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition A10 ⁇ Formulation of raw material A9> The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A10 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Polycaprolactone polyol polycaprolactone triol, manufactured by Daicel Chemical Industries, Placel 308, weight average molecular weight 850
- a compound having an isocyanate group hexamethylene Isocyanurate of diisocyanate Takenate D-170N manufactured by Mitsui Chemicals, Inc.
- polydimethylsiloxane block copolymer (a) solution (solid content 50% by mass) 75 parts by mass, polysiloxane (a) 10 parts by mass 1 part by weight of a radical photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.).
- a radical photopolymerization initiator Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition A11 ⁇ Formulation of raw material B1> The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A11 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Compound having an isocyanate group hexamethylene diisocyanate trimethylolpropane adduct DIC Corporation Barnock DN-950, solid content concentration: 75% by mass
- 12 1 part by mass of a polydimethylsiloxane graft copolymer (d) solution (solid content: 50% by mass) 100 parts by mass.
- Photoradical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.).
- Coating composition A12 ⁇ Formulation of raw material A11> The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A12 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration 40% by mass) 6 parts by mass ⁇ Polydimethylsiloxane graft copolymer (b) 100 parts by mass ⁇ Compound having an isocyanate group (isocyanurate of hexanemethylene diisocyanate manufactured by Mitsui Chemicals, Inc. Takenate D-170N) 25 parts by mass. Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1 part by mass.
- 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.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Urethane (meth) acrylate B1 solution solid content concentration 50% by mass
- Urethane (meth) acrylate C1 solution solid content concentration 50 50% by mass
- Monohydroxyethyl acrylate phthalate manufactured by Toagosei Co., Ltd.
- Coating composition 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. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 3.8 mass parts ⁇ Urethane (meth) acrylate B2 solution (solid content concentration: 50 mass%) 50 mass parts ⁇ Urethane (meth) acrylate C2 solution (solid content concentration: 50) 50% by mass) 10 parts by mass of ethylene glycol monobutyl ether. Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Photoradical polymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition B3 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B3 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Urethane (meth) acrylate B2 solution solid content concentration 50% by mass
- Urethane (meth) acrylate C2 solution solid content concentration 50 30% by mass
- Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B4 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B4 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Urethane (meth) acrylate B3 solution solid content concentration 50% by mass
- Urethane (meth) acrylate C2 solution solid content concentration 50 70% by mass
- 10 parts by mass of ethylene glycol monobutyl ether / radical polymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition B5 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B5 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Urethane (meth) acrylate B3 solution solid content concentration 50% by mass
- Urethane (meth) acrylate C1 solution solid content concentration 50 50% by mass
- Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B6 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B6 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Urethane (meth) acrylate B1 solution solid content concentration 50% by mass
- Urethane (meth) acrylate C3 solution solid content concentration 50 50% by mass
- Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B7-1 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-1 having a solid concentration of 40% by mass.
- ⁇ Fluorine compound D1 solution solid content concentration: 40 mass%) 3.6 mass parts
- mass parts ⁇ Urethane (meth) acrylate C4 solution (solid content concentration: 50) 50% by mass) 10 parts by mass of ethylene glycol monobutyl ether.
- Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B7-2 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-2 having a solid concentration of 40% by mass.
- ⁇ Fluorine compound D1 solution solid content concentration: 40 mass%) 1.3 mass parts ⁇ Urethane (meth) acrylate B1 solution (solid content concentration: 50 mass%) 50 mass parts ⁇ Urethane (meth) acrylate C4 solution (solid content concentration: 50) 50% by mass) 10 parts by mass of ethylene glycol monobutyl ether.
- Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B7-3 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-3 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration 40% by mass
- Urethane (meth) acrylate B1 solution solid content concentration 50% by mass
- Urethane (meth) acrylate C4 solution solid content concentration 50 50% by mass
- 10 parts by mass of ethylene glycol monobutyl ether ethylene glycol monobutyl ether.
- Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B7-4 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-4 having a solid concentration of 40% by mass.
- ⁇ Fluorine compound D2 solution solid content concentration 20 mass%) 7.5 mass parts
- ⁇ Urethane (meth) acrylate B1 solution solid content concentration 50 mass%)
- mass parts ⁇ Urethane (meth) acrylate C4 solution (solid content concentration 50 50% by mass) 10 parts by mass of ethylene glycol monobutyl ether.
- Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B7-5 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-5 having a solid concentration of 40% by mass.
- Fluorine compound D3 1.5 mass parts ⁇ Urethane (meth) acrylate B1 solution (solid content concentration 50 mass%) 50 mass parts ⁇ Urethane (meth) acrylate C4 solution (solid content concentration 50 mass%) 50 mass parts ⁇ Ethylene glycol 10 parts by mass of monobutyl ether / photo radical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- monobutyl ether / photo radical polymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition B7-6 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-6 having a solid concentration of 40% by mass.
- Fluorine compound D4 1.5 mass parts ⁇ Urethane (meth) acrylate B1 solution (solid content concentration 50 mass%) 50 mass parts ⁇ Urethane (meth) acrylate C4 solution (solid content concentration 50 mass%) 50 mass parts ⁇ Ethylene glycol 10 parts by mass of monobutyl ether / photo radical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- monobutyl ether / photo radical polymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition B7-7 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-7 having a solid concentration of 40% by mass.
- Fluorine compound D5 1.5 mass parts ⁇ Urethane (meth) acrylate B1 solution (solid content concentration 50 mass%) 50 mass parts ⁇ Urethane (meth) acrylate C4 solution (solid content concentration 50 mass%) 50 mass parts ⁇ Ethylene glycol 10 parts by mass of monobutyl ether / photo radical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- monobutyl ether / photo radical polymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition B7-8 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-8 having a solid concentration of 40% by mass.
- ⁇ Fluorine compound D1 solution solid content concentration: 40 mass%) 3.6 mass parts
- ⁇ Urethane (meth) acrylate C4 solution solid content concentration: 50) 50% by mass) 10 parts by mass of propylene glycol monoethyl ether.
- Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B7-9 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-9 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 50 mass parts ⁇ Urethane (meth) acrylate C4 solution (solid content concentration: 50 mass%) 50 mass parts ⁇ Radical radical polymerization initiator (Ciba Specialty Chemicals Co., Ltd.) Irgacure 184) 1.5 parts by weight.
- Coating composition B7-10 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-10 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 50 mass parts ⁇ Urethane (meth) acrylate C4 solution (solid content concentration: 50 mass%) 50 mass parts ⁇ Polydimethylsiloxane compound (e) 3 mass parts ⁇ Radical radical polymerization Initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B7-11 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-11 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 50 mass parts ⁇ Urethane (meth) acrylate C4 solution (solid content concentration: 50 mass%) 50 mass parts ⁇ Polydimethylsiloxane compound (f) 3 mass parts ⁇ Radical radical polymerization Initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B7-12 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-12 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 50 mass parts ⁇ Urethane (meth) acrylate C4 solution (solid content concentration: 50 mass%) 50 mass parts ⁇ Polydimethylsiloxane compound (e): 10 mass parts ⁇ Radical radical polymerization Initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B7-13 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-13 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 50 mass parts ⁇ Urethane (meth) acrylate C4 solution (solid content concentration: 50 mass%) 50 mass parts ⁇ Polydimethylsiloxane compound (e): 25 mass parts ⁇ Radical radical polymerization Initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B8 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B8 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 3.6 mass parts ⁇ Urethane (meth) acrylate B1 solution (solid content concentration: 50 mass%) 50 mass parts ⁇ Urethane (meth) acrylate C5 solution (solid content concentration: 50) 50% by mass) 10 parts by mass of ethylene glycol monobutyl ether. Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B9 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B9 having a solid concentration of 40% by mass.
- Fluorine compound D1 solution solid content concentration: 40 mass%) 3.6 mass parts
- Urethane (meth) acrylate B1 solution solid content concentration: 50 mass%) 50 mass parts
- Urethane (meth) acrylate C6 solution solid content concentration: 50 50% by mass) 10 parts by mass of ethylene glycol monobutyl ether.
- Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B10 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B10 having a solid concentration of 40% by mass.
- ⁇ Fluorine compound D1 solution solid content concentration: 40 mass%) 3.6 mass parts
- ⁇ Urethane (meth) acrylate C4 solution solid content concentration: 50 50% by mass) 10 parts by mass of ethylene glycol monobutyl ether.
- Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Coating composition B11 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B11 having a solid concentration of 40% by mass. -50 parts by mass of urethane (meth) acrylate B1 solution (solid content concentration 50% by mass)-50 parts by mass of urethane (meth) acrylate C4 solution (solid content concentration 50% by mass)-Photoradical polymerization initiator (Ciba Specialty Chemicals) Irgacure 184 manufactured by Co., Ltd.) 1.5 parts by mass.
- Coating composition B12 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B11 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 3.6 mass parts ⁇ Urethane (meth) acrylate B1 solution (solid content concentration: 50 mass%) 100 mass parts ⁇ Radical radical polymerization initiator (Ciba Specialty Chemicals Co., Ltd.) Company Irgacure 184) 1.5 parts by weight.
- Coating composition B13 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B13 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 3.6 mass parts ⁇ Urethane (meth) acrylate B2 solution (solid content concentration: 50 mass%) 100 mass parts ⁇ Radical radical polymerization initiator (Ciba Specialty Chemicals Co., Ltd.) Company Irgacure 184) 1.5 parts by weight.
- Coating composition B14 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B14 having a solid content concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 3.6 mass parts ⁇ Urethane (meth) acrylate B2 solution (solid content concentration: 50 mass%) 50 mass parts ⁇ Urethane (meth) acrylate B1 solution (solid content concentration: 50) 50% by mass) Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Photoradical polymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition B15 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B15 having a solid content of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 3.6 mass parts ⁇ Urethane (meth) acrylate B3 solution (solid content concentration: 50 mass%) 80 mass parts ⁇ Urethane (meth) acrylate C2 solution (solid content concentration: 50) 20% by mass) Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Photoradical polymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition B16 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B16 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 3.6 mass parts ⁇ Urethane (meth) acrylate B3 solution (solid content concentration: 50 mass%) 80 mass parts ⁇ Urethane (meth) acrylate B2 solution (solid content concentration: 50) 20% by mass) Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Photoradical polymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition B17 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B17 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 3.6 mass parts ⁇ Urethane (meth) acrylate B3 solution (solid content concentration: 50 mass%) 50 mass parts ⁇ Urethane (meth) acrylate B2 solution (solid content concentration: 50) 50% by mass) Photoradical polymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.5 parts by mass.
- Photoradical polymerization initiator Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.
- Coating composition B18 The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B18 having a solid concentration of 40% by mass. ⁇ Fluorine compound D1 solution (solid content concentration: 40 mass%) 3.6 mass parts ⁇ Urethane (meth) acrylate C7 solution (solid content concentration: 50 mass%) 100 mass parts ⁇ Radical radical polymerization initiator (Ciba Specialty Chemicals Co., Ltd.) Company Irgacure 184) 1.5 parts by weight.
- 1st drying process ventilation temperature and humidity Temperature: 80 ° C Wind speed: coating surface side: 5 m / sec, anti-coating surface side: 5 m / sec Wind direction: coating surface side: parallel to substrate surface, anti-coating surface side: vertical residence time to substrate surface: 1 Minutes 2nd drying process Air temperature and humidity: Temperature: 160 ° C Wind speed: coating surface side: 10 m / sec, anti-coating surface side: 10 m / sec Wind direction: coating surface side: perpendicular to substrate surface, anti-coating surface side: dwell time perpendicular to substrate surface: 2 Minute curing process Irradiation output: 400 W / cm 2 , Integrated light quantity: 120 mJ / cm 2 Oxygen concentration: 0.1% by volume.
- Blowing air temperature and humidity in the drying process Temperature: 80 ° C., Relative humidity: 1% or less
- Laminated films Y (Y1 to Y7) for evaluating the properties of (C1 to C17) were prepared.
- an enclosure was made of plastic to prevent oleic acid from flowing out (that is, an amount of oleic acid applied more than the amount absorbed by the laminated film).
- This was stored in an oven heated to 60 ° C. for 1 hour.
- the laminate film was wiped off using a hyze gauze until it was transparent, and stored for 24 hours in an atmosphere at 23 ° C. (that is, the coating composition that was not absorbed by the laminate film was wiped off).
- the mass of the film measured after this was set to B.
- the specific gravity of the X layer and the Y layer is measured in accordance with a density gradient tube method (JIS K7112 (1999)) using a sodium bromide aqueous solution as a section of a slice of the X layer and the Y layer from the laminated film. did. At this time, the measurement was performed on five samples, and the average value was adopted. The obtained results are shown in Tables 1 and 2.
- the advancing contact angle and receding contact angle of surface layer were measured by the expansion-contraction method, and using the contact angle meter Drop Master DM-501 manufactured by Kyowa Interface Science, the expansion-contraction method measurement manual of the same apparatus was used. Specifically, the advancing contact angle is obtained by continuously discharging oleic acid (Nacalai Standard Grade 1, manufactured by Nacalai Tesque Co., Ltd.) from the syringe to a final liquid volume of 50 ⁇ L at a liquid discharge speed of 8.5 ⁇ L / sec. Images were taken 30 times every 0.5 seconds from the start to the end of discharge, and the contact angles were determined from the images using the integrated analysis software “FAMAS” attached to the apparatus.
- oleic acid Nacalai Standard Grade 1, manufactured by Nacalai Tesque Co., Ltd.
- the contact angle during the expansion process of the droplet first changes with expansion and then shows a behavior that becomes almost constant. Therefore, when the contact angle data is arranged in the order of measurement and five consecutive points are selected in that order, five consecutive points are selected.
- the average value when the standard deviation of the first became 1 ° or less was defined as the advancing contact angle of the measurement, this measurement was performed five times for one sample, and the average value was defined as the advancing contact angle of the sample. Note that although imaging is performed for a certain period of time before the start of ejection and after the end of ejection, the analysis software excludes the imaging data before and after the termination of ejection from the five-point data for calculating the contact angle. It has become.
- the receding contact angle is that the initial droplet volume is 50 ⁇ L and the liquid discharge speed is 8.5 ⁇ L / sec.
- the droplet is continuously sucked, and the shape of the shrinking process of the droplet is photographed from before the suction starts to after the suction ends.
- Each contact angle was calculated
- the analysis software excludes the imaging data before the start of suction and after the end of suction from the five-point data for calculating the contact angle. It has become. Since the contact angle of the droplet shrinkage process changes with shrinkage and then becomes almost constant, the contact angles are arranged in the direction of droplet shrinkage, and five consecutive points are selected in that order.
- the average value when the standard deviation of five consecutive points first becomes 1 ° or less is set as the receding contact angle of the measurement, this measurement is performed five times for one sample, and the average value is set as the receding contact angle of the sample. did. Note that, depending on the sample, the contact angle during the contraction process of the droplets is not constant and continues to decrease, but for this, the receding contact angle was set to 0 °.
- the volume was calculated by approximating the shape of the attached oil droplet as a cut sphere, and the contact area was calculated as the area of the same circle assuming that the length of the contact line was the diameter of the circle. Further, the adhered oil droplets were allowed to stand for 10 hours at 25 ° C. in a windless state, and then the volume was measured by the same measurement.
- the thickness T of the surface layer was calculated based on the coating thickness at the time of forming the molding material.
- the coating thickness is unknown, as described above, when the cross section is observed with an electron microscope (transmission type, scanning type) or an optical microscope, the thickness is determined based on the presence of the discontinuous boundary surface. Can be estimated.
- Measurement conditions Primary ion species: Bi + Primary ion current: 1.000 pA Acceleration voltage: 25 kV Detection ion polarity: negative (F ⁇ ), positive (Si (CH 3 ) + ) Measurement range: 100 ⁇ m ⁇ 100 ⁇ m Resolution: 128 x 128 Number of scans: 36 times.
- the variation coefficient of the secondary ion intensity can be calculated based on the extracted secondary ion intensity value. That is, using all the extracted secondary ion intensity values, the standard deviation and average value of the secondary ion intensity are calculated, and the value of (standard deviation) / (average value) is used as the coefficient of variation.
- FIGS. Converted into a planar distribution image (mapping image) as shown in FIG.
- the secondary ion intensity scale is automatically set by the software from the maximum value and the minimum value in the measurement region.
- the oil repellency and lipophilic effects expected for the chemical species from which the fragment ions are derived cannot be sufficiently obtained.
- a boundary value a region that is less than this value is regarded as a region that is not substantially affected by the chemical species of interest, and is defined as a region that is less than the boundary value.
- the cross section of the crack portion of the collected sample is cut out, and the surface layer is observed at a magnification such that the thickness of the surface layer to be observed is 30 mm or more on the observation screen of the transmission electron microscope, and the average thickness of the surface layer is 50.
- % Of cracks were considered to be cracked (surface layer was broken), and the elongation value of the sample having the lowest elongation among the cracked samples was taken as the breaking elongation. And the same measurement was performed a total of 3 times, the average value of those breaking elongation was made into the breaking elongation of a surface layer, and 30% or more was set as the pass.
- the amount of displacement in the thickness direction (maximum displacement amount) from when the load is applied to when the load is unloaded, and the amount of displacement in the thickness direction when the load is held for 10 seconds after reaching the load of 0.5 mN ( Creep displacement amount) and the displacement amount (permanent displacement amount) in the thickness direction when the load was released to 0 mN after being held for 10 seconds.
- Apparatus Dynamic ultra micro hardness tester “DUH-201” (manufactured by Shimadzu Corporation)
- Working indenter Diamond regular triangular pyramid indenter (edge angle 115 °)
- Measurement mode 2
- Maximum load 0.5mN Holding time when 0.5 mN load is reached: 10 seconds
- Loading speed, unloading speed 0.1,422 mN / second.
- the number average particle diameter is observed at a magnification such that the number of aggregates of primary particles per field of view is 10 or more and 50 or less, and the diameter of the circumscribed circle of the primary particles is obtained from the obtained image.
- the number average particle size was determined from the value measured for 100 primary particles by increasing the number of observations as the particle size.
- This “simulated fingerprint sheet preparation paint” is applied to a wire bar (# 7) on “Lumirror” (registered trademark) U46 (manufactured by Toray Industries, Inc.) in which an easily adhesive paint is applied on a PET resin film as a supporting substrate. ) And dried at 50 ° C. for 2 minutes to remove isopropyl alcohol, and a simulated fingerprint liquid (a dispersion composed of 70% by mass of oleic acid and 30% by mass of silica) was uniformly developed on the film. A simulated fingerprint sheet was obtained.
- ( ⁇ E * ab (di: 8 °) Sb10W10) and ( ⁇ E * ab (di: 8 °) Sb10W10) are calculated from the reflection color before the attachment of the simulated fingerprint and the reflection color immediately after the attachment of the simulation fingerprint by the calculation method described in JIS Z8730 (2009). ⁇ E * ab (de: 8 °) Sb10W10) was determined.
- the color difference ( ⁇ E * ab (di: 8 °) Sb10W10) including the specular reflection light before and after the attachment of the simulated fingerprint is 0.4 or less, and the color difference ( ⁇ E * ab (de: 8 °) of the specular reflection removal before and after the attachment of the simulation fingerprint. ) Sb10W10) passed 4 or less.
- ( ⁇ E * ab (di: 8 °) Sb10W10, ⁇ E SCI-10 ) and ( ⁇ E * ab (de :) are calculated from the reflected color before adhesion and after 10 hours by the calculation method described in JIS Z8730 (2009). 8 °) Sb10W10, ⁇ E SCE-10 ). Then based on the measured values, it calculates the parameters K 10 defined by Equation (6) described above, as shown in Equation (4) described above, the difference between the parameter K 0.5 was regarded as passed 1 below .
- the image is converted to grayscale with the image processing software EasyAccess Ver 6.7.1.23, and the white balance is adjusted so that the brightest and darkest parts are within the 8-bit tone curve, and the boundary between the oil droplets is clear. The contrast was adjusted so that it could be distinguished.
- the image analysis software ImageJ 1.45s the pixels are binarized with the above-mentioned boundary as a boundary, the area formed by each oil drop is calculated, and the diameter when the area of the corresponding area is approximated by a circle is calculated as the area. The oil droplet diameter was determined.
- Fingerprint resistance (fingerprint adhesion) is placed on black paper with the evaluation surface of the laminated film facing up, and the finger (index finger) pressing the fingerprint and the thumb are rubbed three times, and then the finger ( The index finger) was slowly pressed, and the visibility of the attached fingerprint was evaluated according to the following evaluation criteria. 10 points: The fingerprint is not visually recognized or the difference from the non-attached part is not recognized. 7 points: The fingerprint is hardly visible or not recognized as the fingerprint. 5 points: The fingerprint is slightly visible, but hardly noticed. Points: Fingerprints are visually recognized. 1 point: The above evaluations were performed on 10 subjects who were clearly aware of fingerprints and were very worrisome, and the average value was obtained. The numbers after the decimal point were rounded off.
- Fingerprints are slightly visible, but are hardly worrisome 3 points: Fingerprints are visually recognized 1 point: Fingerprints are clearly visible and very anxious.
- the said evaluation was performed about ten subjects and the average value was calculated
- Fingerprint resistance (fingerprint wiping)
- Fingerprint wiping property evaluated the visibility after wiping with this wiping method on the following evaluation criteria, and made 5 points or more acceptable.
- Tables 1 and 2 show the physical properties of the laminated films X and Y having X and Y layers formed for evaluating the physical properties of urethane acrylates B and C.
- Tables 3-1, 3-2, 4-1, 4-2 The evaluation results and the like of the finally obtained laminated film are summarized in 5-1, 5-2. Evaluation items (60 ° specular gloss, breaking elongation, self-repairability, design, cosmetic resistance, color difference before and after simulated fingerprint attachment, K 0.5 , K 0.5 -K 10 , fingerprint resistance (fingerprint adhesion ), Fingerprint resistance (fingerprint disappearance), and fingerprint resistance (fingerprint wiping)).
- the laminated film according to the present invention can also be used for imparting similar functions to the surfaces of plastic molded products, home appliances, buildings, vehicle interior products, and various printed materials.
Landscapes
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
一方、成型材料の中でも、特に強い光沢感、さらに高い反射率、透明性が求められる用途においては、日常生活で表面に人の指が触れることによって指紋(ここで指紋とは、指先の皮膚にある汗腺の開口部が隆起した線(隆線)によりできる紋様、及び前記紋様が物体の表面に付着した跡をいう)が視認されやすく、さらにそれを容易に拭き取ることができないと、見た目が汚れたような不快な印象を与えるという問題がある。特に最近ではスマートフォン・タッチパネル、キーボード、テレビ・エアコンのリモコン等の様に、指で操作する電子機器が増加しており、例えばこれらの機器の筐体を掴むことで指紋が付着し、指紋が目立って清潔感が損なわれるというような問題がある。
<1>支持基材の少なくとも一方の面に表面層を有する積層フィルムであって、表面層が以下の1から3を満たすことを特徴とする積層フィルム。
1.JIS Z8741(1997年)で規定する60°鏡面光沢度が60%以上
2.オレイン酸の後退接触角θrが50°以上
3.微小硬度計測定において0.5mN荷重を10秒間加えたときの、前記表面層の厚み方向の最大変位量が1.0μm以上3.0μm以下であり、
前記表面層の厚み方向のクリープ変位量が0.05μm以上0.5μm以下であり、
荷重を0mNまで解放したときの、前記表面層の厚み方向の永久変位量が0.2μm以上0.7μm以下
<2>前記表面層のオレイン酸の前進接触角θa、後退接触角θrが下記式(1)を満たす<1>に記載の積層フィルム。
(θa-θr)≦ 15° ・・・ 式(1)
<3>前記表面層のオレイン酸吸収係数Abが30以上であることを特徴とする<1>または<2>に記載の積層フィルム。
ここで、オレイン酸吸収係数Abとは前記表面層にオレイン酸を2μl滴下し、シリンジからの吐出時に液滴形状から求めた体積(V1)、着滴時の着滴部の面積(S1)、25℃、無風状態にて10時間保持後の体積(V2)および前記表面層の厚み(T)から、以下の式(2)により求められる値を指す。
Ab=(V1-V2)/(S1×T) 式(2)
<4>前記表面層において、飛行時間型2次イオン質量分析計(TOF-SIMS)により測定される、フッ素に由来するF-フラグメントイオン(M/Z=19)が面内で均一に存在し、ジメチルシロキサンに由来するSi(CH3)+フラグメントイオン(M/Z=43)が以下のいずれかで存在することを特徴とする<1>から<3>のいずれかに記載の積層フィルム。
・島状に存在
・網目状に存在
・島状および網目状に存在
<5>前記表面層において、前記ジメチルシロキサンに由来するSi(CH3)+フラグメントイオンが存在する領域の占有率が30%以上、70%以下であることを特徴とする、<1>から<4>のいずれかに記載の積層フィルム。
<6>前記表面層に、下記の条件下で模擬指紋を付着した前後のJIS Z8730(2009年)およびJIS Z8722(2009年)で規定する正反射光込みの色差ΔE* ab(di:8°)Sb10W10が0.4以下、かつ、正反射光除去の色差ΔE* ab(de:8°)Sb10W10が4以下である<1>から<5>のいずれかに記載の積層フィルム。
模擬指紋付着条件:オレイン酸70質量%と数平均粒子径2μmのシリカ30質量%からなる分散物を、JIS B0601(2001年)で規定するRaが3μmで、JIS K6253(1997年)で規定するゴム硬度50のシリコーンゴムに1.0g/m2付着させ、これを対象とする面に30kPaで付着させたもの。
<7>前記表面層が、以下の式(3)および式(4)を満たすことを特徴とする<1>から<6>のいずれかに記載の積層フィルム。
K0.5≦3 式(3)
K0.5-K10≧1 式(4)
ここで、
K0.5=[(ΔESCI-0.5)2+(ΔESCE-0.5)2]1/2 式(5)
K10=[(ΔESCI-10)2+(ΔESCE-10)2]1/2 式(6)
ΔESCI-0.5、ΔESCE-0.5:
前記表面層に下記の方法で模擬指紋を付着する前の状態を基準とし、模擬指紋付着から30分後に測定したJIS Z8730(2009)およびJIS Z8722(2009)で規定するΔE* ab(di:8°)Sb10W10と、ΔE* ab(de:8°)Sb10W10をそれぞれ指す。
ΔESCI-10、ΔESCE-10:
前記表面層に前記方法で模擬指紋を付着する前の状態を基準とし、模擬指紋付着から10時間後に測定したJIS Z8730(2009)およびJIS Z8722(2009)で規定するΔE* ab(di:8°)Sb10W10と、ΔE* ab(de:8°)Sb10W10をそれぞれ指す。
模擬指紋付着条件:オレイン酸70質量%と数平均粒子径2μmのシリカ30質量%からなる分散物を、JIS B0601(2001年)で規定するRaが3μmで、JIS K6253(1997年)で規定するゴム硬度50のシリコーンゴムに1.0g/m2付着させ、これを対象とする面に30kPaで付着させたもの。
<8>前記表面層に、下記の方法で模擬指紋を付着させた時に形成される油滴の、面積基準頻度分布から算出したメジアン径(DP)が以下の式(7)および式(8)を満たすことを特徴とする<1>から<7>のいずれかに記載の積層フィルム。
DP0.5≦80μm 式(7)
(DP0.5-DP10)/DP0.5≧0.5 式(8)
DP0.5:前記模擬指紋の付着から30分後に測定した、模擬指紋を構成する油滴の面積基準頻度分布から算出したメジアン径
DP10:前記模擬指紋の付着から10時間後に測定した、模擬指紋を構成する油滴の面積基準頻度分布から算出したメジアン径
模擬指紋付着条件:オレイン酸70質量%と数平均粒子径2μmのシリカ30質量%からなる分散物を、JIS B0601(2001年)で規定するRaが3μmで、JIS K6253(1997年)で規定するゴム硬度50のシリコーンゴムに1.0g/m2付着させ、これを対象とする面に30kPaで付着させたもの。
<9>前記表面層に下記の条件下で模擬指紋付着および模擬指紋拭き取り試験を行い、JIS Z8730(2009年)およびJIS Z8722(2009年)に従って求めた模擬指紋付着前の状態を基準とした模擬指紋拭き取り試験後の正反射光込みの色差ΔE* ab(di:8°)Sb10W10(以降ΔESCI-2とする)および模擬指紋付着前の状態を基準とした模擬指紋拭き取り試験後の正反射光除去の色差ΔE* ab(de:8°)Sb10W10(以降ΔESCE-2とする)が、下記式(9)を満たすことを特徴とする<1>から<8>のいずれかに記載の積層フィルム。
((ΔESCI-2)2+(ΔESCE-2)2)1/2 ≦2.0・・・ 式(9)
模擬指紋付着および模擬指紋拭き取り試験の条件
・模擬指紋付着条件:オレイン酸70質量%と数平均粒子径2μmのシリカ30質量%からなる分散物を、JIS B0601(2001年)で規定するRaが3μmで、JIS K6253(1997年)で規定するゴム硬度50のシリコーンゴムに1.0g/m2付着させ、これを対象とする面に30kPaの圧力で付着させたもの。
・模擬指紋拭き取り条件:前記条件で付着した模擬指紋を不織布にて30kPaの圧力、5cm/秒の速度で3回擦る
<10>前記表面層に含まれる樹脂が以下の(1)から(3)を有していることを特徴とする<1>から<9>のいずれかに記載の積層フィルム。
(1)(ポリ)カプロラクトンセグメント、
(2)ウレタン結合、
(3)フルオロアルキル基、フルオロオキシアルキル基、フルオロアルケニル基、フルオロアルカンジイル基およびフルオロオキシアルカンジイル基からなる群より選ばれる少なくとも一つを含むセグメント(以降フッ素化合物セグメントとする)
<11>前記フッ素化合物セグメントが、フルオロポリエーテルセグメントであることを特徴とする<10>に記載の積層フィルム。
<12>前記表面層に含まれる樹脂が(4)(ポリ)シロキサンセグメント及び/またはポリジメチルシロキサンセグメントを有していることを特徴とする<10>または<11>に記載の積層フィルム。
(θa-θr)≦ 15° ・・・ 式(1)
これは、指紋拭き取り性が「指紋成分の拭き取る材料への転移しやすさ」と「表面層上での指紋成分の移動しやすさ」の2つの因子によって支配されることに着目し、前者が後退接触角、後者が前進接触角で表すことができ、これらを統合した式(1)を満たせば、付着した指紋を容易に拭き取ることができることを意味している。
Ab=(V1-V2)/(S1×T) 式(2)
ここで、V1、V2、S1にはいくつかの測定方法があるが、例えば協和界面化学株式会社接触角測定装置DM500、および同社解析ソフトDropMasterにより測定することができる。測定の詳しい手順については後述する。また前記表面層の厚みTの測定方法についても後述する。
K0.5=[(ΔESCI-0.5)2+(ΔESCE-0.5)2]1/2 式(5)。
なお、前記模擬指紋付着直後とは後述する模擬指紋の付着方法により成型材料表面に模擬指紋を付着してから30分後のことを指す。
K0.5-K10≧1 式(4)
ここで、式(4)中のK0.5は前述の通りであり、K10は以下の式(6)で表される。
ここで式(6)中のΔESCI-10は、模擬指紋付着前と、模擬指紋付着後に25℃、無風状態下で10時間静置した後の色差であって、JIS Z8730(2009)およびJISZ8722(2009)で規定される正反射光込みの色差(ΔE* ab(di:8°)Sb10W10)を指し、ΔESCE-2は、同じサンプルの正反射光除去の色差(ΔE* ab(de:8°)Sb10W10)を指す。
((ΔESCI-2)2+(ΔESCE-2)2)1/2 ≦2.0・・・ 式(9)
ここで、模擬指紋付着条件は前述の通りで、模擬指紋拭き取り試験の条件は以下のとおりである。
・模擬指紋拭き取り条件:前記条件で付着した模擬指紋を不織布にて30kPaの圧力、5cm/秒の速度で3回擦る
また、前記力学的、表面科学的、光学的な特性に加えて、本発明の積層フィルムの表面層に含まれる樹脂が以下の(1)から(3)を有していることが好ましい。
(1)(ポリ)カプロラクトンセグメント、
(2)ウレタン結合、
(3)フルオロアルキル基、フルオロオキシアルキル基、フルオロアルケニル基、フルオロアルカンジイル基およびフルオロオキシアルカンジイル基からなる群より選ばれる少なくとも一つを含むセグメント(以降フッ素化合物セグメントとする)。ここで樹脂とは高分子化合物からなる物質を指し、その範囲はポリマーからオリゴマーまでの範囲を含む。
前記フルオロポリエーテルセグメントの詳細については後述するが、表面層がこれを含むことにより最表面に低表面エネルギーを示す分子を高密度に存在させることができる。
本発明の積層フィルムは本発明の特性を示す表面層を有していれば平面状(フィルム、シート、プレート)、3次元形状(成型体)のいずれであってもよい。ここで、本発明における表面層とは、前記積層フィルムの表面から厚み方向(平面状の場合)または内部方向(3次元形状の場合)に向かい、厚み方向または内部方向に隣接する部位と元素組成、含有物(粒子等)の形状、物理特性が不連続な境界面を有することにより区別でき、有限の厚さを有する部位を指す。より具体的には、前記積層フィルムを表面から厚み方向に各種組成/元素分析装置(IR、XPS、XRF、EDAX、SIMS等)、電子顕微鏡(透過型、走査型)または光学顕微鏡にて断面観察した際、前記不連続な境界面により区別される。
本発明の積層フィルムは、後述する支持基材上に塗料組成物を塗布、乾燥、および硬化からなる一般的な塗布プロセスを経て、前述の表面層を設けることにより得ることができる。
・フッ素化合物D
・ポリカプロラクトンポリオールA、またはポリカプロラクトンポリオール共重合体A
・イソシアネート基を含有する化合物
すなわち塗料組成物Aは、(ポリ)カプロラクトンセグメントとして、ポリカプロラクトンポリオールAまたはポリカプロラクトンポリオール共重合体Aを、ウレタン結合を形成する前駆体として前記ポリオールとイソシアネート基を含有する化合物を、フッ素化合物セグメントとして、フッ素化合物Dを含むものである。これら各材料の詳細については後述する。
・フッ素化合物D
・ウレタン(メタ)アクリレートB
・ウレタン(メタ)アクリレートC
すなわち塗料組成物Bは、ウレタン(メタ)アクリレートB、ウレタン(メタ)アクリレートCの少なくとも一方に、後述するポリカプロラクトンセグメントを、両方がウレタン結合を含み、フッ素化合物Dがフッ素化合物セグメントを含むものである。
本発明の積層フィルムに用いられる支持基材を構成する樹脂は、熱可塑性樹脂、熱硬化性樹脂のいずれでもよく、ホモ樹脂であってもよく、共重合または2種類以上のブレンドであってもよい。より好ましくは、支持基材を構成する樹脂は、成型性が良好であるため、熱可塑性樹脂が好ましい。
本発明では、表面層に含まれる樹脂がフッ素化合物セグメントを有することが好ましい。このフッ素化合物セグメントは、フルオロアルキル基、フルオロオキシアルキル基、フルオロアルケニル基、フルオロアルカンジイル基およびフルオロオキシアルカンジイル基からなる群より選ばれる少なくとも1つを含むセグメントを指す。
[(ポリ)カプロラクトンセグメント]
本発明の積層フィルムにおいて、表面層に含まれる樹脂が(ポリ)カプロラクトンセグメントを有することが好ましい、ここで(ポリ)カプロラクトンセグメントとは前述の化学式1で示されるセグメントを指す。さらに(ポリ)カプロラクトンセグメントを含有する樹脂を含む塗料組成物Aもしくは塗料組成物Bを用いて表面層を形成することにより、表面層は(ポリ)カプロラクトンセグメントを有することができる。
または化学式9で示される(ポリ)カプロラクトントリオール、
などのポリカプロラクトンポリオールや化学式10で示される(ポリ)カプロラクトン変性ヒドロキシエチル(メタ)アクリレート
などの活性エネルギー線重合性カプロラクトンを用いることができる。
本発明において、ウレタン結合とは前述の化学式2で示される結合を指す。表面層を形成するために用いる塗料組成物が、市販のウレタン変性樹脂を含むことにより、表面層に含まれる樹脂はウレタン結合を有することが可能となる。また、表面層を形成する際に前駆体としてイソシアネート基を含有する化合物と水酸基を含有する化合物を含む塗料組成物を塗布することにより、塗布工程にてウレタン結合を生成させて、表面層にウレタン結合を含有させることもできる。
前述のように自己修復性に加えて耐化粧品性という特性を付与するには、表面層の形成に、自己修復性の優れたウレタン(メタ)アクリレートBと耐化粧品性の優れたウレタン(メタ)アクリレートCとを含む塗料組成物Bを用いることが好ましい。
1.X層表面にオレイン酸を塗布して60℃で1時間保持したときのX層の質量増加率が45質量%以下
2.微小硬度計測定において0.5mN荷重を10秒間加えたときのX層の厚み方向の最大変位量が1.0μm以上3.0μm以下
3.上記2の微小硬度計測定において、X層の厚み方向のクリープ変位量が0.4μm以上0.7μm以下。
1.Y層表面にオレイン酸を塗布して60℃で1時間保持したときのY層の質量増加率が5.0質量%以下
2.微小硬度計測定において0.5mN荷重を10秒間加えたときの、Y層の厚み方向の最大変位量が0.2μm以上3.0μm以下
3.上記2の微小硬度計測定において、Y層の厚み方向のクリープ変位量が0.02μm以上0.35μm以下。
本発明では、表面層が(4)(ポリ)シロキサンセグメント及び/又はポリジメチルシロキサンセグメントを有することが好ましい。本発明において、(ポリ)シロキサンセグメントとは、前述の化学式5で示されるセグメントを指す。
本発明において、ポリジメチルシロキサンセグメントとは、前述の化学式6で示されるセグメントを指す。
を用いて他のビニルモノマーと共重合させることができる。またペルオキシモノマーと不飽和基を有するポリジメチルシロキサンとを低温で共重合させて過酸化物基を側鎖に導入したプレポリマーを合成し、該プレポリマーをビニルモノマーと共重合させる二段階の重合を行うこともできる。
に、HS-CH2COOHやHS-CH2CH2COOH等を付加してSH基を有する化合物とした後、SH基の連鎖移動を利用して該シリコーン化合物とビニルモノマーとを共重合させることでブロック共重合体を合成することができる。
すなわちポリジメチルシロキサンのメタクリルエステルなどとビニルモノマーを共重合させることにより容易にグラフト共重合体を得ることができる。
本発明では、表面層が、(ポリ)アルキレングリコールセグメントを有することが好ましい。本発明において、(ポリ)アルキレングリコールセグメントとは、化学式14で示されるセグメントを指す。
前記塗料組成物A、塗料組成物Bは溶媒を含んでもよい。溶媒の種類数としては1種類以上20種類以下が好ましく、より好ましくは1種類以上10種類以下、さらに好ましくは1種類以上6種類以下である。
ここで、溶媒の酢酸n-ブチルを基準とした相対蒸発速度とは、ASTMD3539-87(2004年)に準拠して測定される蒸発速度である。具体的には、乾燥空気下で酢酸n-ブチルが90質量%蒸発するのに要する時間を基準とする蒸発速度の相対値として定義される値である。
前記塗料組成物A、Bには、重合開始剤や硬化剤や触媒を含むことが好ましい。重合開始剤および触媒は、表面層の硬化を促進するために用いられる。重合開始剤としては、塗料組成物に含まれる成分をアニオン、カチオン、ラジカル重合反応等による重合、縮合または架橋反応を開始あるいは促進できるものが好ましい。
本発明の積層フィルムの表面に形成される表面層は、前述の塗料組成物を前述の支持基材上に塗布-乾燥-硬化することにより形成する製造方法を用いることが好ましい。
[フッ素化合物D1]
フッ素化合物D1としてフルオロポリエーテルセグメントを含むアクリレート化合物(“メガファック” RS-75 DIC株式会社製 固形分濃度40質量% 溶媒(トルエンおよびメチルエチルケトン)60質量%)を使用した。
フッ素化合物D2としてフルオロポリエーテルセグメントを含むシロキサン化合物(KY-108 信越化学工業株式会社製 固形分濃度20質量% 溶媒(メタノールおよびイソプロピルアルコール)80質量%)を使用した。
フッ素化合物D3としてフルオロポリエーテルセグメント(フルオロテトラエチレングリコールセグメント)を含む2官能アクリレート化合物(FPTMG-A 油脂製品株式会社製 固形分濃度100質量%)を使用した。
フッ素化合物D4としてフルオロアルキルセグメントを含むアクリレート化合物(トリアクリロイル-ヘプタデカフルオロノネニル-ペンタエリスリトール 共栄社化学株式会社製 固形分濃度100質量%)を使用した。
フッ素化合物D5としてフルオロアルキルセグメントを含むアクリレート化合物(ペンタアクリロイル-ヘプタデカフルオロノネニル-ジペンタエリスリトール 共栄社化学株式会社製 固形分濃度100質量%)を使用した。
[ポリシロキサン(a)]
攪拌機、温度計、コンデンサおよび窒素ガス導入管を備えた500ml容量のフラスコにエタノール106質量部、テトラエトキシシラン320質量部、脱イオン水21質量部、および1質量%塩酸1質量部を仕込み、85℃で2時間保持した後、昇温しながらエタノールを回収し、180℃で3時間保持した。その後、冷却し、粘調なポリシロキサン(a)を得た。
攪拌機、温度計、コンデンサおよび窒素ガス導入管を備えた500ml容量フラスコにエタノール106質量部、メチルトリメトキシシラン270質量部、γ-メタクリロキシプロピルメチルジメトキシシラン23質量部、脱イオン水100質量部、1質量%塩酸1質量部及びハイドロキノンモノメチルエーテル0.1質量部を仕込み、80℃で3時間反応させ、ポリシロキサン(b)を合成した。これをメチルイソブチルケトンで50質量%に調整した。
[ポリジメチルシロキサン系ブロック共重合体(a)]
ポリシロキサン(a)の合成と同様の装置を用い、トルエン50質量部、およびメチルイソブチルケトン50質量部、ポリジメチルシロキサン系高分子重合開始剤(和光純薬株式会社製 VPS-0501)20質量部、メタクリル酸メチル18質量部、メタクリル酸ブチル38質量部、2-ヒドロキシエチルメタクリレート23質量部、メタクリル酸1重量部および1-チオグリセリン0.5質量部を仕込み、180℃で8時間反応させてポリジメチルシロキサン系ブロック共重合体(a)を得た。得られたブロック共重合体は、固形分濃度50質量%であった(溶媒(トルエンおよびメチルイソブチルケトン)が50質量%であった)。
ポリシロキサン(a)の合成に用いた装置を用い、トルエン50質量部、酢酸イソブチル50質量部を仕込み、110℃まで昇温した。別にメタクリル酸メチル20質量部、カプロラクトンメタクリルエステル(ダイセル化学工業株式会社製 プラクセルFM-5)32質量部、2-ヒドロキシエチルメタクリレート17質量部、ポリシロキサン(b)10質量部、片末端メタクリル基ポリジメチルシロキサン(東亞合成株式会社製 AK-32)20質量部、およびメタクリル酸1質量部、1,1-アゾビスシクロヘキサン-1-カルボニトリル2質量部を混合した。この混合モノマーを上記のトルエン、酢酸ブチルの混合液に2時間かけて滴下した。その後、110℃で8時間反応させ、固形分濃度50質量%の水酸基を有するポリジメチルシロキサン系グラフト共重合体(b)を得た。得られたブロック共重合体(b)は、固形分濃度50質量%であった(溶媒(トルエンおよび酢酸イソブチル)が50質量%であった)。
ポリシロキサン(a)の合成と同様の装置を用い、トルエン50質量部、およびメチルイソブチルケトン50質量部、ポリジメチルシロキサン系高分子重合開始剤(和光純薬株式会社製 VPS-0501)20質量部、メタクリル酸メチル18質量部、メタクリル酸ブチル38質量部、2-ヒドロキシエチルメタクリレート23質量部、メタクリル酸1重量部および1-チオグリセリン0.5質量部を仕込み、180℃で8時間反応させてポリジメチルシロキサン系ブロック共重合体(c)を得た。得られたブロック共重合体(c)は、固形分濃度50質量%であった(溶媒(トルエンおよびメチルイソブチルケトン)が50質量%であった)。
モノマー組成をメタクリル酸メチル20質量部、メタクリル酸ブチル26質量部、2-ヒドロキシエチルメタクリレート23質量部、ポリシロキサン(a)10質量部、メタクリル酸1質量部および片末端メタクリル変性ポリジメチルシロキサン(信越化学工業株式会社製 X-22-174DX)20質量部とした以外、ポリジメチルシロキサン系グラフト共重合体(b)と同様の方法でポリジメチルシロキサン系グラフト共重合体(d)を合成した。得られたグラフト共重合体(d)は、固形分濃度50質量%でであった(溶媒(トルエンおよび酢酸イソブチル)が50質量%であった)。
あった。
ポリジメチルシロキサン化合物(e)として、ダイセルサイテック株式会社製、EBECRYL350(2官能、シリコーンアクリレート)を用いた。
ポリジメチルシロキサン化合物(f)として、ダイセルサイテック株式会社製、EBECRYL1360(6官能、シリコーンアクリレート)を用いた。
[ウレタン(メタ)アクリレートB1]
トルエン50質量部、ヘキサメチレンジイソシアネートのイソシアヌレート変性タイプ(三井化学株式会社製タケネートD-170N)50質量部、(ポリ)カプロラクトン変性ヒドロキシエチルアクリレート(ダイセル化学工業株式会社製 プラクセルFA5)76質量部、ジブチル錫ラウレート0.02質量部、及びハイドロキノンモノメチルエーテル0.02質量部を混合し、70℃で5時間保持した。その後、トルエン79質量部を加えて固形分濃度50質量%のウレタン(メタ)アクリレートB1のトルエン溶液を得た。
トルエン50質量部、ヘキサメチレンジイソシアネートのイソシアヌレート変性タイプ(三井化学株式会社製 タケネートD-170N)25質量部、(ポリ)カプロラクトン変性ヒドロキシエチルアクリレート(ダイセル化学工業株式会社製 プラクセルFA10)162.8質量部、ジブチル錫ラウレート0.02質量部、及びハイドロキノンモノメチルエーテル0.02質量部を混合し、70℃で5時間保持した。その後、トルエン137.8部を加えて固形分濃度50質量%のウレタン(メタ)アクリレートB2のトルエン溶液を得た。なお、このウレタン(メタ)アクリレートにおけるアクリレートモノマー残基当たりのカプロラクトン単位の繰り返し数は10である。
トルエン100質量部、メチル-2,6-ジイソシアネートヘキサノエート(協和発酵キリン株式会社製 LDI)50質量部及びポリカーボネートジオール(ダイセル化学工業株式会社製 プラクセルCD-210HL)119質量部を混合し、40℃にまで昇温して8時間保持した。それから、2-ヒドロキシエチルアクリレート(共栄社化学株式会社製 ライトエステルHOA)28質量部、ジペンタエリストールヘキサアクリレート(東亞合成株式会社製 M-400)5部、ハイドロキノンモノメチルエーテル0.02質量部を加えて70℃で30分間保持した後、ジブチル錫ラウレート0.02質量部を加えて80℃で6時間保持した。そして、最後にトルエン97質量部を加えて固形分濃度50質量%のウレタン(メタ)アクリレートB3のトルエン溶液を得た。
トルエン50質量部、ヘキサメチレンジイソシアネートのイソシアヌレート変性タイプ(三井化学株式会社製 タケネートD-170N)50質量部、(ポリ)カプロラクトン変性ヒドロキシエチルアクリレート(ダイセル化学工業株式会社製 プラクセルFA5)70質量部、ポリジメチルシロキサン(信越化学工業株式会社製 X-22-160AS)8部ジブチル錫ラウレート0.02質量部、及びハイドロキノンモノメチルエーテル0.02質量部を混合し、70℃で5時間保持した。その後、トルエン79質量部を加えて固形分濃度50質量%のウレタン(メタ)アクリレートB4のトルエン溶液を得た。
トルエン50質量部、ヘキサメチレンジイソシアネートのイソシアヌレート変性タイプ(三井化学株式会社製 タケネートD-170N)34質量部、(ポリ)カプロラクトン変性ヒドロキシエチルアクリレート(ダイセル化学工業株式会社製 プラクセルFA10)57質量部、ポリカプロラクトン変性ヒドロキシエチルアクリレート(ダイセル化学工業株式会社製 プラクセルFA3)57質量部、ジブチル錫ラウレート0.02質量部、及びハイドロキノンモノメチルエーテル0.02質量部を混合し、70℃で5時間保持した。その後、トルエン137.8質量部を加えて固形分濃度50質量%のウレタン(メタ)アクリレートB5のトルエン溶液を得た。
[ウレタン(メタ)アクリレートC1]
トルエン50質量部、ヘキサメチレンジイソシアネートのビウレット変性タイプ(旭化成ケミカルズ株式会社製 デュラネート24A-90CX、不揮発分:90質量%、イソシアネート含有量:21.2質量%)50質量部、(ポリ)カプロラクトン変性ヒドロキシエチルアクリレート(ダイセル化学工業株式会社製 プラクセルFA2D)92質量部、ジブチル錫ラウレート0.02質量部、及びハイドロキノンモノメチルエーテル0.02質量部を混合し、70℃で5時間保持した。その後、トルエン82質量部を加えて固形分濃度50質量%のウレタン(メタ)アクリレートC1のトルエン溶液を得た。なお、このウレタン(メタ)アクリレートにおけるアクリレートモノマー残基当たりのカプロラクトン単位の繰り返し数は2である。
トルエン50質量部、ヘキサメチレンジイソシアネートのイソシアヌレート変性タイプ(三井化学株式会社製 タケネートD-170N)50質量部、(ポリ)カプロラクトン変性ヒドロキシエチルアクリレート(ダイセル化学工業株式会社製 プラクセルFA3)114質量部、ジブチル錫ラウレート0.02質量部、及びハイドロキノンモノメチルエーテル0.02質量部を加え、70℃で3時間保持した。その後、トルエン118.2質量部を加えて固形分濃度50質量%のウレタン(メタ)アクリレートC2のトルエン溶液を得た。なお、このウレタン(メタ)アクリレートにおけるアクリレートモノマー残基当たりのカプロラクトン単位の繰り返し数は3である。
ヘキサメチレンジイソシアネートのイソシアヌレート変性体(三井化学株式会社製 タケネートD-170N、イソシアネート基含有量:20.9質量%)50質量部、ポリエチレングリコールモノアクリレート(日油株式会社製 ブレンマーAE-90、水酸基価:332(mgKOH/g))42質量部、ジブチルスズラウレート0.02質量部及びハイドロキノンモノメチルエーテル0.02質量部を仕込んだ。そして、70℃で5時間保持して反応を行った。反応終了後、反応液にメチルエチルケトン(以下MEKという)92質量部を加え、固形分濃度50質量%のウレタン(メタ)アクリレートC3のトルエン溶液を得た。
ウレタン(メタ)アクリレートC3において、ポリエチレングリコールモノアクリレートをブレンマーAE-150(水酸基価:264(mgKOH/g))53質量部、反応液のMEKを102質量部に変更した以外はウレタン(メタ)アクリレートC3と同様にしてウレタン(メタ)アクリレートC4のトルエン溶液を得た。
ウレタン(メタ)アクリレートC3において、ポリエチレングリコールモノアクリレートをブレンマーAE-200(水酸基価:205(mgKOH/g))68質量部、反応液のMEKを118質量部に変更した以外はウレタン(メタ)アクリレートC3と同様にしてウレタン(メタ)アクリレートC5のトルエン溶液を得た。
ウレタンメタアクリレートC3において、ポリエチレングリコールモノアクリレートをブレンマーAE-400(水酸基価:98(mgKOH/g))142部、反応液のMEKを192質量部に変更した以外はウレタン(メタ)アクリレートC3と同様にしてウレタン(メタ)アクリレートC6のトルエン溶液を得た。
1,3-ビスイソシアネートメチルシクロヘキサンを50質量部、ヒドロキシアルキルアクリレートを100質量部、ジブチル錫ラウレート0.05質量部、ハイドロキノン2質量部を添加し、70℃で3時間保持した。その後85℃で2時間の熟成を行い、ウレタン(メタ)アクリレートC7のトルエン溶液を得た。
[塗料組成物A1-1]
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A1-1を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A1-2を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 2質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A1-3を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 10質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A1-4を得た。
・フッ素化合物D2溶液(固形分濃度20質量%) 12質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A1-5を得た。
・フッ素化合物D3 2.4質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A1-6を得た。
・フッ素化合物D4 2.4質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A1-7を得た。
・フッ素化合物D5 2.4質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308 重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A1-8を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・プロピレングリコールモノエチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A1-9を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A2を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 17質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A3を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 8質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A4を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリジメチルシロキサン系グラフト共重合体(b) 100質量部
・イソシアネート基を有する化合物(ヘキサンメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 12質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A5を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル312重量平均分子量1250) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A6を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(c)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A7を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのビウレット体 バイエル株式会社製 デスモジュールN3200) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A8を得た。
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 15質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部。
<原料A8の調合>
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A9を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 36質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
<原料A9の調合>
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A10を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリカプロラクトンポリオール(ポリカプロラクトントリオール ダイセル化学工業株式会社製 プラクセル308、重量平均分子量850) 15質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 25質量部
・ポリジメチルシロキサン系ブロック共重合体(a)溶液(固形分濃度50質量%) 75質量部
・ポリシロキサン(a) 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
<原料B1の調合>
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A11を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・イソシアネート基を有する化合物(ヘキサメチレンジイソシアネートのトリメチロールプロパンアダクト体 DIC株式会社製 バーノックDN-950、固形分濃度:75質量%) 12質量部
・ポリジメチルシロキサン系グラフト共重合体(d)溶液(固形分濃度50質量%) 100質量部
・光ラジカル重合開始剤 (チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
<原料A11の調合>
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物A12を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6質量部
・ポリジメチルシロキサン系グラフト共重合体(b) 100質量部
・イソシアネート基を有する化合物(ヘキサンメチレンジイソシアネートのイソシアヌレート体 三井化学株式会社製 タケネートD-170N) 25質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1質量部。
[塗料組成物B1]
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B1を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.8質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC1溶液(固形分濃度50質量%) 50質量部
・フタル酸モノヒドロキシエチルアクリレート(東亞合成株式会社製 M-5400 固形分濃度100質量%) 10質量部
・トルエン 10質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 3質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B2を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.8質量部
・ウレタン(メタ)アクリレートB2溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC2溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B3を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.8質量部
・ウレタン(メタ)アクリレートB2溶液(固形分濃度50質量%) 70質量部
・ウレタン(メタ)アクリレートC2溶液(固形分濃度50質量%) 30質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B4を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.8質量部
・ウレタン(メタ)アクリレートB3溶液(固形分濃度50質量%) 30質量部
・ウレタン(メタ)アクリレートC2溶液(固形分濃度50質量%) 70質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B5を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.8質量部
・ウレタン(メタ)アクリレートB3溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC1溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B6を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.8質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC3溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-1を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-2を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 1.3質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-3を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 6.3質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-4を得た。
・フッ素化合物D2溶液(固形分濃度20質量%) 7.5質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-5を得た。
・フッ素化合物D3 1.5質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-6を得た。
・フッ素化合物D4 1.5質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-7を得た。
・フッ素化合物D5 1.5質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-8を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・プロピレングリコールモノエチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-9を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-10を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・ポリジメチルシロキサン化合物(e) 3 質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-11を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・ポリジメチルシロキサン化合物(f) 3 質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-12を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・ポリジメチルシロキサン化合物(e) 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B7-13を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・ポリジメチルシロキサン化合物(e) 25質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B8を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC5溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B9を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC6溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B10を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートB4溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・エチレングリコールモノブチルエーテル 10質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B11を得た。
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートC4溶液(固形分濃度50質量%) 50質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B11を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 100質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B13を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートB2溶液(固形分濃度50質量%) 100質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B14を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートB2溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートB1溶液(固形分濃度50質量%) 50質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B15を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートB3溶液(固形分濃度50質量%) 80質量部
・ウレタン(メタ)アクリレートC2溶液(固形分濃度50質量%) 20質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B16を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートB3溶液(固形分濃度50質量%) 80質量部
・ウレタン(メタ)アクリレートB2溶液(固形分濃度50質量%) 20質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B17を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートB3溶液(固形分濃度50質量%) 50質量部
・ウレタン(メタ)アクリレートB2溶液(固形分濃度50質量%) 50質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
下記材料を混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物B18を得た。
・フッ素化合物D1溶液(固形分濃度40質量%) 3.6質量部
・ウレタン(メタ)アクリレートC7溶液(固形分濃度50質量%) 100質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
ウレタン(メタ)アクリレートB(B1~B5)、ウレタン(メタ)アクリレートC(C1~C7)の各組成について、下記比率で混合し、メチルエチルケトンを用いて希釈し固形分濃度40質量%の塗料組成物X(X1~X5)、Y(Y1~Y7)を得た。
・ウレタン(メタ)アクリレートB、またはC溶液(固形分濃度50質量%) 100質量部
・光ラジカル重合開始剤(チバ・スペシャルティ・ケミカルズ株式会社製 イルガキュア184) 1.5質量部。
[積層フィルムの作製A]
支持基材としてポリエチレンテレフタレート(以下、「PET」と称することがある)樹脂フィルム上に易接着性塗料が塗布されている厚み100μmの“ルミラー”(登録商標)U46(東レ株式会社製)を用いた。前記塗料組成物A(A1-1~A12)を、スロットダイコーターを有する連続塗布装置を用い、乾燥後の厚みが30μmになるようにダイスロットからの吐出流量を調整して塗布した。塗布から乾燥、硬化までの間に液膜にあたる乾燥工程、硬化工程の条件は下記の通りである。
送風温湿度 : 温度:80℃
風速 : 塗布面側:5m/秒、反塗布面側:5m/秒
風向 : 塗布面側:基材の面に対して平行、反塗布面側:基材の面に対して垂直
滞留時間 : 1分間
第2乾燥工程
送風温湿度 : 温度:160℃
風速 : 塗布面側:10m/秒、反塗布面側:10m/秒
風向 : 塗布面側:基材の面に対して垂直、反塗布面側:基材の面に対して垂直
滞留時間 : 2分間
硬化工程
照射出力:400W/cm2 、積算光量:120mJ/cm2
酸素濃度:0.1体積%。
支持基材としてPET樹脂フィルム上に易接着性塗料が塗布されている厚み100μmの“ルミラー”(登録商標)U46(東レ株式会社製)を用いた。前記塗料組成物B(B1~B18)、塗料組成物X(X1~X5)、塗料組成物Y(Y1~Y7)を、スロットダイコーターを有する連続塗布装置を用い、乾燥後の厚みが30μmになるようにダイスロットからの吐出流量を調整して塗布した。塗布から乾燥、硬化までの間に液膜にあたる乾燥風の条件は下記の通りである。
送風温湿度 : 温度:80℃、 相対湿度:1%以下
風速 : 塗布面側:5m/秒、反塗布面側:5m/秒
風向 : 塗布面側:基材の面に対して平行、反塗布面側:基材の面に対して垂直
滞留時間 : 2分間
硬化工程
照射出力:400W/cm2 、積算光量:120mJ/cm2
酸素濃度:0.1体積%。
[オレイン酸塗布時の質量増加率]
前述の方法で得られた支持基材上にウレタン(メタ)アクリレートB,ウレタン(メタ)アクリレートCを含む塗料組成物を塗布した積層フィルムX、およびYを200mm×200mm長に切り出し、この積層フィルムの質量をAとした。ベークライト板に固定し、X層、またはY層側の100mm幅×100mm長にオレイン酸を塗布した。塗布する際はプラスチックで囲いを作り、オレイン酸が流れ出ないようにした(すなわち、積層フィルムに吸収される量よりも多い量のオレイン酸を塗布した)。これを60℃に加熱したオーブンに1時間保存した。保存後、ハイゼガーゼを用いて積層フィルムが透明になるまで拭き取りを行い、23℃の雰囲気下で24時間保存した(すなわち、積層フィルムに吸収されなかった塗料組成物を拭き取った)。この後測定したフィルムの質量をBとした。このときのオレイン酸による質量増加率は以下の計算式より求めた。測定はそれぞれ3回行い、その平均値を採用した。
(B-A)/(100×t×d)×100
t:オレイン酸塗布前の、X層またはY層厚み(cm)
d:オレイン酸塗布前の、X層またはY層の比重(g/cm2)。
得られた結果を表1、表2に示す。
作製した積層フィルムについて、次に示す性能評価を実施し、得られた結果を表3-1、3-2、4-1、4-2、5-1、5-2に示す。特に断らない場合を除き、測定は各実施例・比較例において1つのサンプルについて場所を変えて3回測定を行い、その平均値を用いた。
積層フィルムの表面層の光沢度は、日本電色工業株式会社製 VG7000を用いて、積層フィルム表面の光沢度をJIS Z8741(1997年)に従い60°鏡面光沢度を測定し、60%以上を合格とした。
前進接触角、後退接触角の測定は拡張-収縮法により測定を行い、協和界面科学製接触角計Drop Master DM-501を用いて、同装置の拡張-収縮法測定マニュアルに従った。前進接触角は、具体的にはシリンジからオレイン酸(ナカライ規格一級 ナカライテスク株式会社製)を液吐出速度8.5μL/秒で最終液量50μLまで連続的に吐出し、液滴の形状を吐出開始前から吐出終了後まで0.5秒毎に30回撮影し、同画像から、同装置付属の統合解析ソフト“FAMAS”を用いてそれぞれの接触角を求めた。液滴の拡張過程での接触角は最初、拡張につれて変化し、次いでほぼ一定になる挙動を示すため、測定順に接触角データを並べ、その順に連続した5点を選択したとき、連続した5点の標準偏差が最初に1°以下になった時の平均値をその測定の前進接触角とし、この測定を1サンプルについて5回行い、その平均値を試料の前進接触角とした。なお、吐出開始前および吐出終了後も一定時間撮影はされるが、解析ソフトでは吐出開始前および吐出終了後の撮影データは接触角を算出するための5点のデータからは除外されるようになっている。
オレイン酸吸収係数の算出に必要な値のうち、表面層に着滴したオレイン酸の体積、および付着領域の面積の測定には協和界面科学株式会社 接触角計Drop Master DM-501を用いて、同装置の静的接触角測定マニュアルに従った。具体的にはシリンジ先端にオレイン酸(ナカライ規格一級 ナカライテスク)2μLの液滴を作成し、成型材料表面に着滴させた後、その付着状態の画像を撮影、同装置付属の統合解析ソフト“FAMAS”を用いて体積および接触面積を算出した。なお体積については付着油滴の形状を切断球形として近似し算出し、接触面積については接触線の長さを真円の直径と仮定した際の同真円の面積として算出した。更にこの付着油滴を25℃、無風状態下で10時間静置した後に同様の測定により体積を計測した。
ION TOF社製、飛行時間型2次イオン質量分析計TOF-SIMSVおよび同社測定ソフトSURFACE LAB 6を用い、積層フィルムの最表面について、2次イオン質量分析法によってF-フラグメントイオン(M/Z=19)とジメチルシロキサンに由来するSi(CH3)+フラグメントイオンを測定し、面内での各フラグメントイオンの分布を求めた。測定条件は以下の通りである。
一次イオン種 :Bi+
一次イオン電流:1.000pA
加速電圧 :25kV
検出イオン極性:negative(F-)、positive(Si(CH3)+)
測定範囲 :100μm×100μm
分解能 :128×128
スキャン回数 :36回。
積層フィルムを10mm幅×200mm長に切り出し、長辺方向へ延伸されるようにチャックで把持し、インストロン型引っ張り試験機(インストロン社製超精密材料試験機MODEL5848)にて引っ張り速度100mm/分で伸張した。この時の測定雰囲気は23℃・65RH%である。伸張する際に、伸張中のサンプルを観察しておき、目視でクラック(亀裂)が生じたら停止する(停止するときの伸度は5(%)の整数倍となるように調整する)。次から測定するサンプルは、停止時の伸度より、5%単位で伸張伸度を低くしていったサンプルを順次採取し、最終的に目視にてクラックが入らなくなる伸度まで行った。
平滑な金属板(ダイス鋼:SKD-11)に、東レ・ダウコーニング株式会社製「ハイバキュームグリース」を1g塗布し、それに積層フィルムの支持基材側をハイバキュームグリース塗布部分に貼り付け、積層フィルムの表面層側に濾紙を設置し、ハンドプレス機で空気が噛まないようにプレスした。このような方法で得られた静置された試料に対し、正三角錐を用いて押し込み負荷/除荷試験を行い、加重-押し込み深さ線図(図1参照)を取得した。
使用圧子:ダイヤモンド製正三角錐圧子(稜間角115°)
測定モード:2
最大荷重:0.5mN
0.5mN荷重に達したときの保持時間:10秒
荷重速度、除荷速度:0.1,422mN/秒。
温度20℃で12時間放置した後、同環境にて表面層表面を、真鍮ブラシ(TRUSCO製)に下記の荷重をかけて、水平に5回引っ掻いたのち、5分間放置後の傷の回復状態を、下記の基準に則り目視で判定を行い、4点以上を合格とした。
10点:荷重9.8N(1kg重)で傷が残らない
7点: 荷重9.8N(1kg重)では傷が残るが、6.9N(700g重)では傷が残らない
4点: 荷重6.9N(700g重)では傷が残るが、4.9N(500g重)では傷が残らない
1点: 荷重4.9N(500g重)で傷が残る。
温度20℃で12時間放置した後、同環境にて表面層表面を、真鍮ブラシ(TRUSCO製)に、500gの荷重をかけ、水平に5回引っ掻いたときの傷の回復状態を、下記の基準に則り目視で判定を行い、4点以上を合格とした。
10点:全ての傷が3秒未満に回復する。
7点: 全ての傷が3秒以上10秒未満に回復する。
4点: 全ての傷が10秒以上30秒未満に回復する。
1点: その他(全ての傷の回復が30秒以上かかるか、回復しない傷が存在するか、または、傷が入らないなど。)。
本発明の積層フィルムの対象とする面への模擬指紋の付着は、1.模擬指紋シートの作製、2.模擬指紋のシリコーンゴムへの転写、3.模擬指紋の積層フィルム表面への付着の3ステップで行った。
下記材料を下記比率で秤量後、30分間マグネチックスターラーにて攪拌して、模擬指紋シート作成用塗料を得た。
オレイン酸 14質量部
シリカ粒子(数平均粒子径 2μm) 6質量部
イソプロピルアルコール 80質量部
なお、前記シリカ粒子の数平均粒子径は走査型電子顕微鏡(SEM)にて観察、測定した。観察試料は前記シリカ粒子を分散媒(イソプロピルアルコール)に固形分濃度5質量%にて混合、超音波にて分散後、導電テープ上に滴下、乾燥して調整した。数平均粒子径は、1視野あたり一次粒子の集合体としての個数が10個以上50個以下になる倍率にて観察を行い、得られた画像から一次粒子の外接円の直径を求めてこれを粒子径とし、観察数を増やし一次粒子100個について測定した値から数平均粒子径を求めた。
JIS K6253(1997年)で規定するゴム硬度50のシリコーンゴムを#250の耐水ペーパーで表面を研磨し、JIS B0601(2001年)で規定するRaを3μmとした。次いで、前記耐水ペーパーで研磨したシリコーンゴムを模擬指紋シートに30kPaで押し付けた。シリコーンゴムへの模擬指紋液の付着量(g/m2)は、シリコーンゴムの面積と付着前後の質量差から求めた値を指し、上記手法で行った結果、いずれも1.0g/m2であった。
2.にて模擬指紋液が転写されたシリコーンゴムを、積層フィルム表面に30kPaで押し付けて積層フィルム表面に形成された痕跡を模擬指紋とした。
前記方法で対象とする面に模擬指紋を付着させた積層フィルムを平板上に固定し、積層フィルム上で間隔が10cmとなるようにA点とB点を決定した。そして積層フィルム上に折り上げ寸法が12.5×12.5cmのセルロース長繊維不織布ガーゼ(“ハイゼ”ガーゼ NT-4 川本産業株式会社製)を置き、その上に錘を載せることで30kPaの圧力をかけ、この錘を載せたセルロース長繊維不織布ガーゼを、5cm/秒の速度でA点とB点の間を3往復させることにより拭き取りをおこなった。
成型材料の対象とする面の反対面に黒ビニールテープを貼り付け、前述の模擬指紋の付着前と付着後の反射色をコニカミノルタ株式会社製分光測色計CM-3600Aを使用して、JIS Z8722(2009年)に基づき、正反射光除去の反射色を鏡面反射光トラップを用いた(de:8°)Sb10W10条件で、正反射光込みの反射色を鏡面反射光トラップを用いない(di:8°)Sb10W10条件で、JIS Z8730(2009年)に記載のCIE1976(L*a*b*)にて測定した。模擬指紋の付着後の測定は直後、付着から30分後、10時間後の3通りについて行った。
積層フィルムの対象とする面の反対面に黒ビニールテープを貼り付け、前述の模擬指紋の付着前と拭き取り後の反射色をコニカミノルタ株式会社製分光測色計CM-3600Aを使用して、JIS Z 8722(2009年)に基づき、正反射光除去の反射色を鏡面反射光トラップを用いた(de:8°)Sb10W10条件で、正反射光込みの反射色を鏡面反射光トラップを用いない(di:8°)Sb10W10条件で、JIS Z8730(2009年)に記載のCIE1976(L*a*b*)にて測定した。
前述の模擬指紋付着と同様の方法で成型材料表面に付着させた模擬指紋を対象に、この成型材料を25℃で24時間保管した後に、その油滴の表面投影像を、微分干渉顕微鏡を用いて撮影し、得られた画像に対して画像処理ソフトを用いて油滴径dpを求め、この結果を基に面積基準頻度分布、およびその累積頻度の推移を求めた。
油滴径dpの具体的な測定手順を以下に記す。
まず模擬指紋を付着させた防指紋成型材料の表面を微分干渉顕微鏡により100倍の倍率で画像を撮影した。続いて画像処理ソフトEasyAccess Ver6.7.1.23 にて画像をグレースケールに変換し、ホワイトバランスを最明部と最暗部が8bitのトーンカーブに収まるように調整、さらに油滴の境界が明確に見分けられるようにコントラストを調節した。次いで画像解析ソフトImageJ 1.45sを用いて前述の境界を境に画素の2値化を行い、個々の油滴のなす面積を算出し、そこから該当領域の面積を円形近似したときの直径として油滴径を求めた。
油滴の面積基準頻度分布の算出では、まず前述の処理により得られた油滴径dpをもとにそのヒストグラムを作成した。この時油滴径は5μm毎に区分し、これに基づいてMicrosoft Excel 2003のヒストグラム機能を用いて層別をおこなった。次いで得られたヒストグラムに対し表面投影像の面積による重み付けをするため、ヒストグラムの各層別の代表面積を各基数の中心値を代表径とした円と仮定して求め、これに各層別の頻度を乗じ、再度総面積で割ることにより、面積基準頻度分布を求めた。さらに前記の面積基準頻度分布について、縦軸を頻度、横軸を油滴径としてその累積頻度をグラフ化し、累積頻度50%における油滴径の値からメジアン径DPを求めた。具体的には、累積頻度50%となる点を挟む2つの層をヒストグラムから特定し、該当層の油滴径の中心値と累積頻度とで特定される2座標間を直線で結び、この直線上で累積頻度50%となる点の油滴径としてメジアン径DPを算出した。
前述の模擬指紋付着と同様の方法で模擬指紋を成型材料表面に付着させた後、この成型材料を25℃、無風条件下でそれぞれ30分、10時間静置した。次いで前述の油滴径の測定により30分後の油滴径と10時間後の油滴径を測定した。さらにそこから前記面積基準頻度分布に記載の解析により30分後のメジアン径DP0.5および10時間後のメジアン径DP10を算出した。
耐指紋性(指紋付着性)は、積層フィルムの評価する面を上にして黒画用紙上に置き、指紋を押し付ける指(人差し指)と親指を3回こすってから、前記表面層の表面に指(人差し指)をゆっくりと押し付け、付着した指紋の視認性を下記の評価基準で評価し、5点以上を合格とした。
10点: 指紋が視認されない、もしくは未付着部との差がわからない
7点: 指紋がほとんど視認できない、もしくは指紋だとは認識されない
5点: 指紋が僅かに視認されるが、ほとんど気にならない
3点: 指紋が視認される
1点: 指紋が明確に視認され、非常に気になる
上記評価を10人の対象者について行い、その平均値を求めた。小数点以下については四捨五入して取り扱った。
前記耐指紋性の評価と同様に指紋を転写した後に25℃、無風状態下で10時間静置した指紋の視認性を、前記評価「耐指紋性(指紋付着性)」に対して観察角を0°近傍(サンプルを横から眺める)から90°(真上から眺める)の範囲に広げて観察を行い、10点満点で評価した。放置後の指紋の視認性を下記の評価基準で評価し、7点以上を合格とした。
10点: 指紋が視認されない、もしくは未付着部との差がわからない。
7点 : 指紋がほとんど視認できない、もしくは指紋だとは認識されない。
5点 : 指紋が僅かに視認されるが、ほとんど気にならない
3点 : 指紋が視認される
1点 : 指紋が明確に視認され、非常に気になる。
上記評価を10人の対象者について行い、その平均値を求めた。小数点以下については四捨五入して取り扱った。
前述の方法で、指紋を付着させた後、次いで、折り上げ寸法が12.5×12.5cmのセルロース長繊維不織布ガーゼ(“ハイゼ”ガーゼ NT-4 川本産業株式会社製)を用いて拭き取りを行った。指紋拭き取り性は、この拭き取り方法で拭いた後の視認性を下記の評価基準で評価し、5点以上を合格とした。
10点: 1回拭くと、ほぼ視認されなくなる
7点: 1回拭くと、ほぼ気にならない程度になる
5点: 1回または2回拭いただけでは汚れが残るが、3回拭くと、ほぼ視認されなくなる
3点: 5回拭けば、ほぼ気にならない程度になる
1点: 5回以上拭いても、汚れが残る
上記評価を10人の対象者について行い、その平均値を求めた。小数点以下については四捨五入して取り扱った。
5cm角に切り出した試料に花王株式会社製 アトリックス「ハンドクリームA」(NO413)を0.5g塗布し、温度60℃、相対湿度95%の雰囲気下で6時間放置後、25℃相対湿度65%の雰囲気下で30分間放置し、表面をガーゼできれいに拭き取る。温度25℃、相対湿度65%の雰囲気下で24時間放置後、表面の状態を観察し、下記の基準に則り判定を行い、4点以上を合格とした。
10点:白斑の発生なし。
7点:白斑の発生がほとんどなし。
4点:白斑が発生するが、拭き取ればきれいになる。
1点:白斑が発生する。拭き取っても温度25℃、相対湿度65%の雰囲気下で24時間放置後に再度発生する。
2 クリープ変位量
3 永久変位量
4 厚み方向の変位量 h(μm)
5 荷重 P(mN)
6 加重工程
7 保持工程
8 除荷工程
9、11、13 ジメチルシロキサンに由来するSi(CH3)+フラグメントイオン(M/Z=43)が存在する領域
10、12、14 ジメチルシロキサンに由来するSi(CH3)+フラグメントイオン(M/Z=43)が境界値未満の領域
Claims (12)
- 支持基材の少なくとも一方の面に表面層を有する積層フィルムであって、表面層が以下の1から3を満たすことを特徴とする積層フィルム。
1.JIS Z8741(1997年)で規定する60°鏡面光沢度が60%以上
2.オレイン酸の後退接触角θrが50°以上
3.微小硬度計測定において0.5mN荷重を10秒間加えたときの、前記表面層の厚み方向の最大変位量が1.0μm以上3.0μm以下であり、
前記表面層の厚み方向のクリープ変位量が0.05μm以上0.5μm以下であり、
荷重を0mNまで解放したときの、前記表面層の厚み方向の永久変位量が0.2μm以上0.7μm以下 - 前記表面層のオレイン酸の前進接触角θa、後退接触角θrが下記式(1)を満たす請求項1に記載の積層フィルム。
(θa-θr)≦ 15° ・・・式(1) - 前記表面層のオレイン酸吸収係数Abが30以上であることを特徴とする請求項1または2に記載の積層フィルム。
ここで、オレイン酸吸収係数Abとは前記表面層にオレイン酸を2μl滴下し、シリンジからの吐出時に液滴形状から求めた体積(V1)、着滴時の着滴部の面積(S1)、25℃、無風状態にて10時間保持後の体積(V2)および前記表面層の厚み(T)から、以下の式(2)により求められる値を指す。
Ab=(V1-V2)/(S1×T) 式(2) - 前記表面層において飛行時間型2次イオン質量分析計(TOF-SIMS)により測定される、フッ素に由来するF-フラグメントイオン(M/Z=19)が面内で均一に存在し、ジメチルシロキサンに由来するSi(CH3)+フラグメントイオン(M/Z=43)が以下のいずれかで存在することを特徴とする請求項1から3のいずれかに記載の積層フィルム。
・島状に存在
・網目状に存在
・島状および網目状に存在 - 前記表面層において、前記ジメチルシロキサンに由来するSi(CH3)+フラグメントイオンが存在する領域の占有率が30%以上、70%以下であることを特徴とする、請求項1から4のいずれかに記載の積層フィルム。
- 前記表面層に、下記の条件下で模擬指紋を付着した前後のJIS Z8730(2009年)およびJIS Z8722(2009年)で規定する正反射光込みの色差ΔE* ab(di:8°)Sb10W10が0.4以下、かつ、正反射光除去の色差ΔE* ab(de:8°)Sb10W10が4以下である請求項1から5のいずれかに記載の積層フィルム。
模擬指紋付着条件:オレイン酸70質量%と数平均粒子径2μmのシリカ30質量%からなる分散物を、JIS B0601(2001年)で規定するRaが3μmで、JIS K6253(1997年)で規定するゴム硬度50のシリコーンゴムに1.0g/m2付着させ、これを対象とする面に30kPaで付着させたもの。 - 前記表面層が、以下の式(3)および式(4)を満たすことを特徴とする請求項1から6のいずれかに記載の積層フィルム。
K0.5≦3 式(3)
K0.5-K10≧1 式(4)
ここで、
K0.5=[(ΔESCI-0.5)2+(ΔESCE-0.5)2]1/2 式(5)
K10=[(ΔESCI-10)2+(ΔESCE-10)2]1/2 式(6)
ΔESCI-0.5、ΔESCE-0.5:
前記表面層に下記の方法で模擬指紋を付着する前の状態を基準とし、模擬指紋付着から30分後に測定したJIS Z8730(2009)およびJIS Z8722(2009)で規定するΔE* ab(di:8°)Sb10W10と、ΔE* ab(de:8°)Sb10W10をそれぞれ指す。
ΔESCI-10、ΔESCE-10:
前記表面層に下記の方法で模擬指紋を付着する前の状態を基準とし、模擬指紋付着から10時間後に測定したJIS Z8730(2009)およびJIS Z8722(2009)で規定するΔE* ab(di:8°)Sb10W10と、ΔE* ab(de:8°)Sb10W10をそれぞれ指す。
模擬指紋付着条件:オレイン酸70質量%と数平均粒子径2μmのシリカ30質量%からなる分散物を、JIS B0601(2001年)で規定するRaが3μmで、JIS K6253(1997年)で規定するゴム硬度50のシリコーンゴムに1.0g/m2付着させ、これを対象とする面に30kPaで付着させたもの。 - 前記表面層に、下記の方法で模擬指紋を付着させた時に形成される油滴の、面積基準頻度分布から算出したメジアン径(DP)が以下の式(7)および式(8)を満たすことを特徴とする請求項1から7のいずれかに記載の積層フィルム。
DP0.5≦80μm 式(7)
(DP0.5-DP10)/DP0.5≧0.5 式(8)
DP0.5:前記模擬指紋の付着から30分後に測定した、模擬指紋を構成する油滴の面積基準頻度分布から算出したメジアン径
DP10:前記模擬指紋の付着から10時間後に測定した、模擬指紋を構成する油滴の面積基準頻度分布から算出したメジアン径
模擬指紋付着条件:オレイン酸70質量%と数平均粒子径2μmのシリカ30質量%からなる分散物を、JIS B0601(2001年)で規定するRaが3μmで、JIS K6253(1997年)で規定するゴム硬度50のシリコーンゴムに1.0g/m2付着させ、これを対象とする面に30kPaで付着させたもの。 - 前記表面層に下記の条件下で模擬指紋付着および模擬指紋拭き取り試験を行い、JIS Z8730(2009年)およびJIS Z8722(2009年)に従って求めた模擬指紋付着前の状態を基準とした模擬指紋拭き取り試験後の正反射光込みの色差ΔE* ab(di:8°)Sb10W10(以降ΔESCI-2とする)および模擬指紋付着前の状態を基準とした模擬指紋拭き取り試験後の正反射光除去の色差ΔE* ab(de:8°)Sb10W10(以降ΔESCE-2とする)が、下記式(9)を満たすことを特徴とする請求項1から8のいずれかに記載の積層フィルム。
((ΔESCI-2)2+(ΔESCE-2)2)1/2 ≦2.0・・・ 式(9)
模擬指紋付着および模擬指紋拭き取り試験の条件
・模擬指紋付着条件:オレイン酸70質量%と数平均粒子径2μmのシリカ30質量%からなる分散物を、JIS B0601(2001年)で規定するRaが3μmで、JIS K6253(1997年)で規定するゴム硬度50のシリコーンゴムに1.0g/m2付着させ、これを対象とする面に30kPaの圧力で付着させたもの。
・模擬指紋拭き取り条件:前記条件で付着した模擬指紋を不織布にて30kPaの圧力、5cm/秒の速度で3回擦る - 前記表面層に含まれる樹脂が以下の(1)から(3)を有していることを特徴とする請求項1から9のいずれかに記載の積層フィルム。
(1)(ポリ)カプロラクトンセグメント、
(2)ウレタン結合、
(3)フルオロアルキル基、フルオロオキシアルキル基、フルオロアルケニル基、フルオロアルカンジイル基およびフルオロオキシアルカンジイル基からなる群より選ばれる少なくとも一つを含むセグメント(以降フッ素化合物セグメントとする) - 前記フッ素化合物セグメントが、フルオロポリエーテルセグメントであることを特徴とする請求項10に記載の積層フィルム。
- 前記表面層に含まれる樹脂が(4)(ポリ)シロキサンセグメント及び/またはポリジメチルシロキサンセグメントを有していることを特徴とする請求項10または11に記載の積層フィルム。
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TW201429721A (zh) | 2014-08-01 |
CN104903102B (zh) | 2017-12-19 |
JPWO2014109177A1 (ja) | 2017-01-19 |
TWI609784B (zh) | 2018-01-01 |
KR102281542B1 (ko) | 2021-07-26 |
CN104903102A (zh) | 2015-09-09 |
JP6375946B2 (ja) | 2018-08-22 |
KR20150113950A (ko) | 2015-10-08 |
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