JP2014149512A - Molding material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material capable of maintaining glossiness or transparency and preventing a fingerprint from being visually recognized.SOLUTION: The molding material having a front layer on at least one surface has following characteristics of 1 to 3: 1. a 60-degree specular glossiness defined by JIS Z8741 (1997) on the front layer is 60% or more; 2. a receding contact angle θof oleic acid on the front layer is 50° or more; 3. an oleic acid absorption coefficient Aon the front layer is 30 or more. The oleic acid absorption coefficient Aindicates a value calculated by a following formula (1) from a volume (V) calculated from the shape of a droplet ejected from a syringe when oleic acid of 2 μl is dropped on the front layer, an area (S) of a droplet landing portion when the droplet is landed, a volume (V) after the droplet is held at the same temperature for 10 hours in a windless state, and a thickness (T) of the front layer. The formula (1): A=(V-V)/(S×T).

Description

  The present invention relates to a molding material having excellent fingerprint resistance.

  Fingerprints by touching the surface of an object with a human finger (a fingerprint is a pattern formed by a line (ridgeline) in which the opening of a sweat gland on the skin of the fingertip is raised, and a mark on the surface of the object. Is attached, there is a problem that an unpleasant impression that the fingerprint is recognized and the appearance is dirty is given. For example, a fingerprint is attached by gripping the casing of a mobile phone, and the fingerprint is conspicuous and the sense of cleanliness is impaired. In recent years, electronic devices operated with fingers have been increasing recently, such as smartphones / touch panels, keyboards, TV / air conditioner remote controls, and the like.

  Furthermore, when fingerprints are attached to the image display unit of an image display device, a signal display unit such as a warning light, or the surface of a lens / mirror, the display image, display signal, reflection image is blurred, or the part where the fingerprint is attached There is a problem that visibility is deteriorated due to a difference in reflectance of a portion not attached. For example, LCD screens of smartphones, TVs, car navigation systems, personal computers, signal indicators for guidance, warning, and evacuation guidance, glasses, sunglasses, telescopes, camera lenses, transparent clock face covers, car rearview mirrors, Room mirror. Once a fingerprint is attached to these devices, the visibility of the object is reduced by the fingerprint.

  In recent years, glossy anti-reflective members (anti-reflection films) have been used on the surface of various displays such as smartphones, televisions, and personal computer monitors in order to make the contrast of images high. At the same time, fingerprints are easily visible, which is a problem.

With respect to such a problem, Patent Document 1 discloses a member that makes it difficult for a fingerprint to be visually recognized (hereinafter referred to as fingerprint resistance). On one surface, a low refractive index layer having a refractive index of less than 1.75 at a light wavelength of 550 nm, or a high refractive index layer having a refractive index of 1.75 or more at a light wavelength of 550 nm, or An optical thin film formed by forming a thin film layer containing at least both of them, and when the oleic acid having a dry film thickness of 20 μm is applied on the surface of the thin film layer, the oleic acid is applied. an optical thin film, D65 light source and the optical thin film which is not coated with the oleic acid, 5 ° incidence, 2 ° visual field, color difference Delta] E ^* _a of the CIELAB in the positive reflected light (according to JIS Z8729) ^{(= {(ΔL *) 2} + (Δa *) 2 + (Δb *) 2} 1/2) has been proposed an optical thin film ", characterized in that it is 5 or less.

  Further, as a technique that focuses on the shape of the surface in order to make it difficult to visually recognize a fingerprint, Patent Document 2 states that “the center line average roughness (Ra) of the surface shape of the roughened layer is 100 to 300 nm and the average of the unevenness. A “touch panel substrate” having a spacing (Sm) of 50 μm or more has been proposed.

Furthermore, as a physical property of a member having fingerprint resistance, in Patent Document 3, “a base material, an optical functional layer formed on the base material, a surface element ratio formed on the optical functional layer, and a silicon element ( Si) to carbon element (C) ratio Si / C is 0.25 to 1.0, and F / C, which is the ratio of fluorine element (F) to carbon element (C), is 0.10 to 1. An optical functional film having an antifouling layer having the following characteristics: a. A liquid paraffin contact angle of 65 ° or more and a liquid paraffin falling angle of 15 ° or less b. The contact angle is 35 ° or more and the black magic sliding angle is 15 ° or less c. The dynamic friction coefficient is less than 0.15 ”.

  Further, as an elemental structure of a member having fingerprint resistance, Patent Document 4 states that “a hard coat film having a hard coat layer on at least one surface on a transparent substrate and having a hard coat layer positioned on the outermost surface”. The hard coat layer contains a fluorine compound and / or a silicon-based compound, and the fluorine atom: oxygen atom: carbon atom abundance 20 atomic on the surface of the hard coat layer is measured with an X-ray photoelectron spectrometer. % Or more and less than 50 atomic%: 20 atomic% or more and less than 30 atomic%: 30 atomic% or more and less than 60 atomic%, and the silicon abundance is in the range of 0 atomic% or more and less than 10 atomic%, and surface contact. The surface free energy calculated from the corner is 15 mN / m or more and 20 mN Hard coat film "is proposed, wherein m is within the range.

  On the other hand, in Patent Document 5, “a fingerprint-disappearing material having a property of erasing attached fingerprint dirt with time, and comprising a polyfunctional monomer, an oil-absorbing particle, a polymerization initiator, and an oil component. “Disappearable materials” have been proposed.

JP 2009-122416 A Japanese Patent Laid-Open No. 2004-5005 International Publication No. 2008/038714 Pamphlet JP 2011-043606 A JP 2012-219116 A

  The problem to be solved by the present invention is to provide a molding material having fingerprint resistance while maintaining glossiness or transparency and scratch resistance necessary for practical use. The above-mentioned known technique is in the following situation for the above-mentioned problem.

  First, regarding fingerprint visibility, Patent Document 1 proposes an optical thin film in which the color difference before and after oleic acid application is a certain value or less, but the present inventors have confirmed the fingerprint visibility under various conditions. However, the effect of making the fingerprint inconspicuous is insufficient only with the characteristics of Patent Document 1.

  In addition, the technique of Patent Document 2 can surely reduce the visibility of fingerprints, but the required glossiness is not obtained, and the surface shape is rough, leading to the idea of the method of the present invention. Not in.

  Furthermore, although the technique of patent document 3 pays attention to the liquid paraffin contact angle and the falling angle, when the present inventors confirmed about various surface layers, the contact angle, the falling angle and fingerprint visibility, and the wiping property. Are not necessarily consistent, and it has been found that sufficient fingerprint resistance cannot be obtained even if the range of Patent Document 3 is satisfied. In addition, the technique of Patent Document 4 is a technique that pays attention to “increasing the abundance ratio of fluorine on the surface and reducing the abundance ratio of silicon as much as possible”. In some cases, fingerprints are easily noticeable, and the method of the present invention is not conceived. Furthermore, the technology of Patent Document 5 has been confirmed by the present inventors that the physical properties as a film, the visibility of the fingerprint, and its change with time are insufficient for glossiness and transparency. It was found that the disappearance effect was insufficient with fingerprints rich in sebum.

In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, completed the following invention. That is, the present invention is as follows.
1) A molding material having a surface layer on at least one surface and having the following characteristics 1 to 3.
1. 1. 60-degree specular gloss of the surface layer specified by JIS Z8741 (1997) is 60% or more. 2. The receding contact angle θ _r of oleic acid of the surface layer is 50 ° or more; Here oleate absorption coefficient A _b of the surface layer is 30 or more, and oleic acid absorption coefficient A _b oleic acid 2μl dropwise to the surface layer, the volume calculated from the droplet shape upon ejection from the syringe (V ₁ ), The area (S ₁ ) of the droplet deposition part at the time of droplet deposition, the volume (V ₂ ) after holding for 10 hours at 25 ° C. and no wind, and the thickness (T) of the surface layer, the following formula (1) Refers to the value obtained by.

_{A b = (V 1 -V 2} ) / (S 1 × T) Equation (1)
2) A molding material having a surface layer on at least one surface, the surface layer has a 60-degree specular gloss specified by JIS Z8741 (1997) of 60% or more, and a time-of-flight secondary ion mass spectrometer Measured by (TOF-SIMS), F ⁻ fragment ions (M / Z = 19) derived from fluorine exist uniformly in the plane, and Si (CH ₃ ) ⁺ fragment ions (M / Z derived from dimethylsiloxane). Z = 43) is present in any of the following:
・ Existing in islands ・ Existing in meshes ・ Existing in islands and meshes.
3) The molding material according to 2), wherein in the surface layer, the proportion of the portion where Si (CH ₃ ) ⁺ fragment ions derived from the dimethylsiloxane are present is 30% or more and 70% or less. .
4) A molding material having a surface layer on at least one surface, wherein the surface layer has a 60-degree specular gloss specified by JIS Z8741 (1997) of 60% or more,
A molding material having a surface layer having surface characteristics satisfying the following formulas (2) and (3):
K ₁ ≦ 3 Formula (2)
K ₁ −K ₂ ≧ 1 Formula (3)
here,
K ₁ = [(ΔESCI _-1 ) ² + (ΔESCE _-1 ) ² ] ^1/2 formula (4)
K ₂ = [(ΔE _SCI-2 ) ² + (ΔE _SCE-2 ) ² ] ^1/2 formula (5)
ΔE _SCI-1 , ΔE _SCE-1 :
ΔE ^* _ab (di: 8 °) Sb10W10 defined by JIS Z8730 (2009) and JIS Z8722 (2009) measured 30 minutes after the attachment of the simulated fingerprint on the surface layer as a reference, and ΔE ^* _Ab (de: 8 °) Sb10W10 respectively.
ΔE _SCI-2 , ΔE _SCE-2 :
ΔE * _ab (di: 8 °) Sb10W10 defined by JIS Z8730 (2009) and JIS Z8722 (2009) measured after 10 hours from the attachment of the simulated fingerprint on the surface layer as a reference, and ΔE * _Ab (de: 8 °) Sb10W10 respectively.
Simulated fingerprint attachment 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 μm is converted into a silicone rubber having a Ra specified by JIS B0601 (2001) of 3 μm and a rubber hardness of 50 specified by JIS K6253 (1997). 0.05 g / m ^{2 is} adhered, and is adhered to the target surface at 30 KPa.
5) The molding material according to any one of 2) to 4), wherein the surface layer has an oleic acid absorption coefficient _Ab of 30 or more.
Molding material according to any of 6) receding contact angle theta _r oleic acid of said surface layer is from 50 ° to 2) 5).
7) The number of peaks exceeding the root mean square roughness (RMS) observed by an atomic force microscope (AFM) at least in the surface layer is 500 or more and 1,500 or less per 25 μm ^2. The molding material according to any one of 1) to 6).
8) The median diameter (D _P ) calculated from the area reference frequency distribution of the oil droplet formed when the simulated fingerprint is attached to the surface layer satisfies the following formulas (6) and (7): The molding material according to any one of 1) to 7).

D _P1 ≦ 80 μm (6)
(D _P1 −D _P2 ) / D _P1 ≧ 0.5 Formula (7)
D _P1 : 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 _P2 : the simulated fingerprint measured 10 hours after the attachment of the simulated fingerprint Median diameter calculated from the area-based frequency distribution of the constituent oil droplets

  According to the present invention, it is possible to provide a molding material in which fingerprints are hardly visible while maintaining glossiness or transparency and scratch resistance necessary for practical use.

In the laminated film of the present invention, Si (CH ₃ ) ⁺ fragment ions (M / Z = 43) derived from dimethylsiloxane are examples in the form of islands. In the laminated film of the present invention, Si (CH ₃ ) ⁺ fragment ions (M / Z = 43) derived from dimethylsiloxane are examples in the form of a network. In the laminated film of the present invention, Si (CH ₃ ) ⁺ fragment ions (M / Z = 43) derived from dimethylsiloxane are examples in the form of islands and networks.

  Before describing the embodiment for carrying out the present invention, problems of the prior art will be considered from the viewpoint of the present inventor.

  First, regarding the fingerprint visual recognition mechanism, Patent Document 1 applies oleic acid and evaluates the color difference based on only regular reflection of the single incident light before and after the application, so that the state actually seen by humans cannot be reproduced. There is a problem with the point. In addition, oleic acid is used as a simulated fingerprint liquid for visibility evaluation, but the actual fingerprint is composed of water, organic salts (such as urate), sebum contained in the sweat supplied from the finger skin. In addition to (oleic acid, etc.), it is a so-called dispersion containing dust (sand dust, titanium oxide, zinc oxide, silica, etc.) contained in dust and cosmetics present in the living environment. It is considered that the influence of light scattering due to existence could not be evaluated.

  On the other hand, the method of Patent Document 2 is a technique for reducing the reflection of external light by providing a concavo-convex structure on the surface and making the fingerprint relatively inconspicuous. However, the amount of attached fingerprint itself cannot be reduced. Moreover, it is also difficult to obtain glossiness and transparency, which are the problems of the present invention.

  Next, regarding the fingerprint attachment mechanism, the technique of Patent Document 3 uses the liquid paraffin contact angle and the falling angle as the fingerprint adhesion parameters as described above, but the former is a liquid component such as fingerprint attachment and wiping. The latter is a parameter that indicates the dynamic behavior of the droplet and is greatly affected by the mass of the droplet from the principle of the measurement method. It is thought that the dynamic behavior of a very small amount of components could not be expressed.

  The technique of Patent Document 4 reduces the surface free energy and increases the amount of adhesion of fingerprint stains by increasing the fluorine content, but the remaining components create large oil droplets on the surface. It is considered that it is easily noticeable at a specific viewing angle.

  Furthermore, although the technique of Patent Document 5 is considered to generate capillary force by absorbing porous particles in the surface layer and absorb sebum components, since the porous particles are used, the glossiness and transparency are greatly reduced. In addition, since the amount of sebum dirt adhered increases, it is considered that the effect is hardly obtained with fingerprints rich in sebum.

Therefore, the present inventors have devised the following method as a method for solving the above problems.
First, the inventors pay attention to the behavior of the liquid when the liquid component of the fingerprint adheres to the surface of the molding material, and the receding contact angle formed on the molding material by the liquid component that constitutes the fingerprint stain exceeds a specific value. In addition, it has been found that it is effective to increase the amount of fatty acid absorbed per unit volume on the surface of the molding material to a specific value or more.

  As a result of focusing on whether the fingerprint component tends to stick between the finger and the molding material surface, the receding contact angle between the fingerprint component and the finger or the molding material surface dominates, and the surface layer of the molding material recedes. It is based on that it discovered that it became difficult to adhere when a contact angle exceeded a specific range, and this reduced the visibility of the fingerprint adhering to the said molding material surface.

  In addition, even a small amount of fingerprint components adhering to the surface layer can penetrate and diffuse inside the surface layer to further reduce the visibility of fingerprint smudges and frequently perform operations such as wiping with a cloth. It is found that fingerprint stains can be eliminated even without it, and it is preferable that the surface layer exhibiting such properties has both the oil repellent material and the lipophilic material in a specific form on the outermost surface. I also found out. The reason for this is that the surface layer of the present invention has the least amount of fingerprint component adhering to the surface layer and develops the characteristic of disappearing from the surface by absorbing the adhering fingerprint component into the coating film. The surface is uniformly coated with a compound containing fluorine to show high oil repellency, thereby reducing the amount of fingerprint components attached and at the same time, the compound containing lipophilic dimethylsiloxane is in the form of fine islands. Alternatively, by being present in a network shape, the fingerprint component slightly adhered to the surface diffuses into the outermost surface of the surface layer and the surface layer through the island-like or network-like lipophilic portion existing on the surface, As a result, it is believed that the fingerprint stain disappears.

  In addition to setting the receding contact angle and the fatty acid absorption amount to a specific value or more, the inventors of the present invention are effective to provide a very small uneven structure having a specific shape per unit area. I found out. The reason for this is that by introducing a very fine concavo-convex structure, the oil droplets made by the minutely attached fingerprint component are made finer, thereby increasing the contact area of the oil droplet per unit volume with the molding material, and the fingerprint component This is to promote the penetration of the. Here, the oil droplet refers to a microscopic aggregate of liquid and solid constituting a fingerprint and a simulated fingerprint attached to the surface of the molding material.

  Furthermore, the present inventors have found that the deterioration of quality derived from the above-described solubility can be reduced by introducing the above-described uneven structure. Although the reason is not clear, it is presumed that the particle components constituting the concavo-convex structure assist the formation of a homogeneous layer.

  In addition, the present inventors attach a simulated fingerprint close to the above-mentioned actual fingerprint composition to a glossy molding material, and measure the reflection color before and after adhesion by two methods including specular reflection light removal and regular reflection light removal. The obtained color difference value was set to a specific value or less, and the amount of decrease over time was set to a specific value or more, thereby achieving both glossiness and fingerprint visibility reduction effect. This is based on the fact that the human eye recognizes fingerprints based on changes in glossiness and changes in color, and changes in glossiness are detected by specular reflection light. Since the change in color is detected by diffuse reflected light, it is difficult to visually recognize a fingerprint if both of the color differences are below a certain value by evaluating the color difference by removing the regular reflected light. This is because it has been found that the fingerprint is lost due to the decrease.

Hereinafter, embodiments of the present invention will be specifically described.
First, the molding material of the present invention has a surface layer on at least one surface, the surface layer is a particular specular gloss, the receding contact angle theta _r oleic _acid, and have oleic acid absorption coefficient A _b preferable.

  The specular gloss shown here is a value measured according to JIS Z8741 (1997), preferably 60% or more, more preferably 70% or more, and particularly preferably 75% or more. If the specular gloss is less than 60%, the glossiness may be felt to be insufficient.

Further, the receding contact angle θ _r of oleic acid in the surface layer is preferably 50 ° or more, more preferably 60 ° or more, and particularly preferably 70 ° or more. Although the measurement method and meaning of the receding contact angle will be described later, there is no problem when the receding contact angle is high. On the other hand, when the receding contact angle is lower than 50 °, the fingerprint component tends to adhere.

  Here, there are several measurement methods for the receding contact angle value, but a method that is influenced by the droplet mass in principle, such as the falling angle method, should be avoided. Here, measurement by the expansion-contraction method will be described. The receding contact angle value by the expansion-contraction method is that the liquid (oleic acid) is applied on the surface layer and the liquid is gradually ejected to expand the liquid droplet, and then the liquid droplet is sucked to contract the liquid droplet. In the process, 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. Specifically, for example, in the case where liquid is discharged and aspirated between 1 to 50 μL (droplet expansion and contraction), the liquid is expanded by measuring at an interval of 1 μL from 50 μL to 1 μL at the time of droplet suction. Alternatively, it can be determined by obtaining a value at which the contact angle of the droplet becomes substantially constant during the contraction process. The contact angle in the expansion contraction method can be measured using, for example, Drop Master (Kyowa Interface Science Co., Ltd.).

In addition, when the oleic acid absorption coefficient A _b , that is, when oleic acid is adhered, the volume and area of the oleic acid adhering material immediately after adhering, the volume of the oleic acid adhering material after a certain time, and the molding material is calculated from the thickness of the surface layer is preferably oleate absorption coefficient a _b per unit volume is 30 or more, more preferably 40 or more.

The oleic acid absorption coefficient _Ab is specifically determined by dropping about 2 μl of oleic acid onto the surface layer having a thickness T, and determining the volume (V ₁ ) determined from the shape of the droplet when discharged from the syringe. It refers to the dimensionless amount determined by the following formula (1) from the area (S ₁ ) of the droplet landing part, the volume (V ₂ ) after 10 hours holding at 25 ° C. and no wind.
A _b = (V ₁ −V ₂ ) / (S ₁ × T)
Here, there are several measurement methods for V ₁ , V ₂ , and S ₁ , and for example, 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.

Further, the molding material of the present invention has a surface layer on at least one surface, the surface layer has a specific specular gloss, and both the oil repellent material and the lipophilic material have a specific form on the outermost surface. Is preferably present. More specifically, F ^- fragment ions derived from fluorine (M / Z = 19) measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS) of the surface layer are “uniformly” in the plane. Si (CH ₃ ) ⁺ fragment ion (M / Z = 43) derived from dimethylsiloxane is “island-like”, “existed in a network” or “island-like and network-like” More preferably, the F ⁻ fragment ions are “uniformly present” in the plane, and the Si (CH ₃ ) ⁺ fragment ions are “present in islands and networks”.

  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 in the surface layer through the island-like or network-like lipophilic portion existing on the surface, and as a result, the fingerprint stain disappears. thinking. In addition, the measuring method of the outermost surface of the surface layer by a time-of-flight secondary ion mass spectrometer (TOF-SIMS) will be described in the section of the examples.

  The term “uniformly present” means a coefficient of variation of secondary ion intensity at all measurement points measured in a 100 μm × 100 μm range of 128 vertical points × 128 horizontal points with a time-of-flight secondary ion mass spectrometer. Is within 0.3.

As shown in FIG. 1, “existing in the form of islands” is a boundary value corresponding to 20% of the maximum intensity when the secondary ion intensity of Si (CH ₃ ) ^{+ at} the measurement point where the measurement was performed is illustrated. 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. In addition, 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 μm or less. Is an island. On the other hand, the lower limit of the size is not particularly limited as long as it can be classified according to the above conditions.

“Existing in a network” means that when the secondary ion intensity of Si (CH ₃ ) ⁺ fragment is illustrated as shown in FIG. 2, a portion less than the aforementioned boundary value exists in an island shape. Point to.

“Existing in the form of islands and meshes” means that when the secondary ionic strength 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”.

Furthermore, the occupancy of the portion where Si (CH ₃ ) ⁺ fragment ions derived from dimethylsiloxane are 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. Here, 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. The calculation method of the occupation ratio will be described in the example section. When the proportion of the portion where Si (CH ₃ ) ⁺ fragment ions derived from dimethylsiloxane occupy is less than 30%, the adhered fingerprint component is applied to the coating film. In some cases, the ability to absorb the inside of the fingerprint is insufficient, and the disappearance of the fingerprint stain may be reduced. If it exceeds 70%, the ability to reduce the amount of fingerprint stain attached may be lowered.

  Furthermore, the molding material of the present invention makes the color difference including the specular reflection light and the color difference of removing the specular reflection light immediately before and after the attachment of the simulated fingerprint equal to or less than a specific value, and the temporal decrease amount of the color difference is equal to or more than a specific value. It is preferable. Specifically, it is as follows.

First, the color difference of the color difference inclusive specular reflection light immediately after deposition and before the simulated fingerprint and specular reflection light is removed, preferably 3 or less parameters K ₁ represented by the following formula (4) with 2 or less being more preferred. 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 ₁ = [(ΔESCI _-1 ) ² + (ΔESCE _-1 ) ² ] ^1/2 formula (4)
Here, the ΔESCI _-1 refers to the color difference (ΔE ^* _ab (di: 8 °) Sb10W10) before and after the adhesion of the simulated fingerprint including specular reflection light defined in JIS Z8730 (2009) and JIS Z8722 (2009), ESCE _-1 refers to the color difference (ΔE ^* _ab (de: 8 °) Sb10W10) before and after the attachment of the simulated fingerprint for removing the regular reflection light.

ΔE ^* _ab (de: 8 °) Sb10W10 and ΔE ^* _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. reducing the parameter K ₁ is equivalent to the reduction of the visibility of fingerprints before and after simulated fingerprint. Note parameter K ₁ is said to be good as the fingerprint antiadhesive small, the material having a high gloss and clarity of the present invention is an issue, in order to recognize the effects of aging of the later-described fingerprint It is realistic to exceed 1.
The term “immediately after attaching the simulated fingerprint” refers to about 30 minutes after the simulated fingerprint is attached to the surface of the molding material by a simulated fingerprint attaching method described later.

In addition, the amount of color difference that decreases with time is preferably 1 or more, and more preferably 1.2 or more, as expressed by the above-described formula (3). When the value represented by the above-mentioned formula (3) is less than 1, it may be difficult to obtain a feeling of disappearance of fingerprint smear.
K ₁ −K ₂ ≧ 1 Formula (3)
Here, K ₁ in the formula (3) is as described above, and K ₂ is represented by the following formula (5). K ₂ = [(ΔE _SCI-2 ) ² + (ΔE _SCE-2 ) ² ] ^1/2 formula (5)
Here, ΔE _SCI-2 in the formula (5) is the value before attaching the simulated fingerprint including the specular reflection light defined by JIS Z8730 (2009) and JISZ8722 (2009), and at 25 ° C. under no wind condition after attaching the simulated fingerprint. Refers to the color difference (ΔE ^* _ab (di: 8 °) Sb10W10) after standing, and ΔE _SCE-2 represents the color difference (ΔE ^* _ab (de: 8 °) Sb10W10) in removing the regular reflection light of the same sample. Point to.

Here, the simulated fingerprint is a transfer material prepared by roughening the surface of a silicone rubber having a rubber hardness of 50 defined by JIS K6253 (1997) to Ra of 3 μm defined by JIS B0601 (2001). Is used to attach a dispersion of 0.05 g / m ² composed of 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 μm to a target surface at 30 KPa. The variation of Ra is allowed to be ± 1 μm, and the amount of adhesion of the dispersion composed of 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 μm to the surface of the silicone rubber is ± 0.02 g / m ² . Variation is acceptable. A specific simulated fingerprint attachment procedure will be described later.

Next, the molding material of the present invention preferably has a layer having fine irregularities on the surface, and there is a preferred range in the number of irregularities in a specific range per unit area. Specifically, the number of peaks exceeding the root mean square roughness (RMS) observed by an atomic force microscope (AFM) is preferably 500 or more and 1,500 or less per 25 μm ² , and 800 or more 1 , More preferably 200 or less. If it is out of this range, the effect of reducing the size of the oil droplets constituting the aforementioned fingerprint may be insufficient.

  Here, the root mean square roughness (RMS) is a square root of a value obtained by averaging the squares of deviations from the mean line to the measurement curve, and refers to what is obtained from the roughness curve, and the peak is based on the mean line. And the distance to the measurement curve is greater than the mean square roughness. In general, arithmetic average roughness (Ra) based on JIS R 1683 is used as an index of the surface shape, but Ra is a numerical value representing average depth information over the entire surface, and the molding material of the present invention It is unsuitable as an index for evaluating the shape and number of local uneven structures such as these.

Next, it is preferable that the diameter of the oil droplets constituting the simulated fingerprint on the molding material of the present invention is small. Since the visibility of the fingerprint increases as the area occupied by the oil droplet adhesion portion on the surface of the molding material increases, the frequency distribution of the oil droplet diameter is calculated using the projected image of the oil droplet toward the surface of the molding material. The shape of the oil droplet can be evaluated by an area reference frequency distribution weighted according to the area. In the area-based frequency distribution is denoted diameters its cumulative frequency becomes N% of the total and D _N. Of these, the diameter of N ₌ 50 is particularly referred to as the median diameter (hereinafter D _P ). In the present invention, preferably the median diameter D _P1 which is calculated from the area reference frequency distribution immediately after the simulated fingerprint is 80μm or less, more preferably 70μm or less, particularly preferably 50μm or less. If this value is deviated, the fingerprint may be easily recognized due to light scattering by the oil droplets.

Further, after the simulated fingerprint, when 25 ° C., a median diameter calculated from the area-based frequency distribution of the 10 hour standing was the material surface under a windless state and D _P2, simulated fingerprint time change of median diameter There is a preferred value for the value normalized by the median diameter D _P1 immediately after adhesion, (D _P1 −D _P2 ) / D _P1 . Specifically, 0.5 or more is preferable, and 0.6 or more is particularly preferable. If this value is less than 0.5, the fingerprint may remain visible even after a lapse of time.

The constituent material of the molding material of the present invention having the above characteristics is not particularly limited, but one preferred form thereof is a layer mainly composed of the following constituent materials.
・ Fluorine compound A
・ Compound B
・ Binder component and particle component.

  Here, the main component means a component occupying 50% by mass or more of all components unless otherwise specified. In this case, the total of the fluorine compound A, the binder component, and the particles is 50% by mass or more. The details of the fluorine compound A, compound B, binder component and particles will be described later. The fluorine compound A reduces the surface energy, thereby increasing the contact angle of the liquid constituting the fingerprint and reducing the adhesion amount. Compound B is preferably an oligomer or polymer having a lipophilic moiety, particularly organic particles comprising a dimethylsiloxane copolymer, and the binder component serves to bind the particles and impart practically necessary scratch resistance. Have. The particles contribute to the formation of the fine concavo-convex structure described above, and the number average particle diameter of the primary particles is preferably 5 nm or more and 20 nm or less. If the number average particle diameter of the primary particles exceeds 20 nm, the required glossiness may not be obtained. On the other hand, if the number average particle diameter is less than 5 nm, the effect of refining the oil droplets constituting the aforementioned fingerprint deposit is obtained. It may not be possible. Details of the method for measuring the number average particle diameter will be described later, and preferred ratios of the fluorine compound A, the compound B, the binder component, and the particle component will also be described later.

  The fluorine compound A includes at least two selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group and a fluorooxyalkanediyl group, and two or more in one molecule. A compound having the following reactive site is preferable, and a material having a fluoropolyether site is more preferable. By using these materials, molecules showing low surface energy can be present at a high density on the outermost surface. The fluoropolyether part will be described later.

  The binder component is made of a raw material having 10 or more reactive sites in the molecule and a number average molecular weight of 1,500 to 3,000 from the viewpoint of film hardness, dispersibility of the fluorine compound A and the particle component. Is preferred. This binder component will be described later.

Furthermore, in the molding material of the present invention, the above-mentioned particle component has a preferable form, and specifically, it is preferably present in a bead-like and / or branched form. The details of these particles will be described later. By using silica as the particles, the so-called self-organization due to the interparticle interaction caused by the surface state of the particles and the lateral capillary force existing between the particles during the coating-drying process. It is easy to form and to form the preferable uneven structure.
Hereinafter, embodiments of the present invention will be described in detail.

[Molding materials and layers]
The molding material of the present invention may be any of a flat shape (film, sheet, plate) and three-dimensional shape (molded body) as long as it has the characteristics of the present invention and / or a layer containing the material on its surface. . Here, the “layer” in the present invention is directed from the surface of the molding material in the thickness direction, and the adjacent portion has a boundary surface where the elemental composition, the shape of the inclusion (particles, etc.), and the physical properties are discontinuous. Can be distinguished from each other, and refers to a part having a finite thickness. More specifically, cross-sectional observation of the molding material in the thickness direction from the surface with various composition / element analyzers (IR, XPS, XRF, EDAX, SIMS, etc.), electron microscope (transmission type, scanning type) or optical microscope In this case, the region is distinguished by the discontinuous boundary surface and indicates a portion having a finite thickness.
The layer preferably contains the following components in order to exhibit the aforementioned characteristics.
・ Fluorine compound A
・ Compound B
-Binder component-Particle component Details of these components will be described later.

  In addition to fingerprint resistance, the layer may have other functions such as antireflection, hard coating, antistatic, antifouling, conductivity, heat ray reflection, near infrared absorption, and easy adhesion.

  The thickness of the layer is not particularly limited, but is preferably 1 nm or more and 100 μm or less, and more preferably 5 nm or more and 50 μm or less.

[Coating composition]
The molding material of the present invention preferably forms the “surface layer” by a general coating process in which a coating composition described later is coated, dried, and cured on a supporting substrate. This coating composition refers to a composition that is liquid at room temperature, and preferably contains the following components in order to impart the aforementioned properties.
1) Fluorine compound A
2) Compound B
3) Binder raw material 4) Particle component Details of these components will be described later. Furthermore, the coating composition may further contain various additives such as a solvent, a photopolymerization initiator, a curing agent, and a catalyst. Moreover, there exists a preferable condition between the solubility of the fluorine compound A contained in the coating composition and the binder raw material.

Specifically, the conditions can be expressed by using Hansen's solubility parameter, in which the Hildebrand solubility parameter is divided into three components: a dispersion term σ _d , a polar term σ _p , and a hydrogen bond term σ _h . The dispersion term σ _d indicates the effect due to the nonpolar interaction, the polar term σ _p indicates the effect due to the force between the dipoles, and the hydrogen bond term σ _h indicates the effect due to the hydrogen bond force.

The dispersion term of the Hansen solubility parameter of the fluorine compound A is σ _d , the polar term is σ _p , the hydrogen bond term is σ _h , the dispersion parameter of the Hansen solubility parameter of the binder component is σ _Bd , the polar term is σ _Bp , hydrogen When the bond term is σ _Bh , the following conditions are preferably satisfied.
Condition 1 R = [(σ _d −σ _Bd ) ² + (σ _p −σ _Bp ) ² + (σ _h −σ _Bh ) ² ] ^{1/2 The} parameter R defined by ^1/2 is 3 (MPa) ^1/2 As described above, it has a value of 12 (MPa) ^1/2 or less.

Further, in condition 1, it is more preferable that the parameter R has a value of 3 (MPa) ^1/2 or more and 8 (MPa) ^1/2 or less, and 4 (MPa) ^1/2 or more and 6 (MPa) ^1/2 or less. It is particularly preferred to have a value of This parameter R is the coordinate point of the fluorine compound A (σ _d , σ _p , σ _h ) and the coordinates of the binder component in the three-dimensional coordinate axis with the Hansen solubility parameter dispersion term, polarity term, and hydrogen bond term as axes. This corresponds to the distance of the points (σ _Bd , σ _Bp , σ _Bh ). And the longer this distance is, the more difficult it is to mix them, and the closer they are, the easier they are to mix. Therefore, when the parameter R exceeds 12 (MPa) ^1/2 , the fluorine compound A and the binder component may not be sufficiently mixed, and the transparency and gloss may be deteriorated, while the parameter R is 3 (MPa). If it is less than ^½ , the fluorine compound A and the binder component are completely mixed together, making it difficult to form a layer and increasing the amount of fingerprint adhesion.

Further, it is desirable that the dispersion term σ _d of the Hansen solubility parameter of the fluorine compound A and the dispersion term σ _Bd of the Hansen solubility parameter of the binder component satisfy the following condition 2. Condition 2 σ _d <σ _Bd
The above-described separation of the surface layer of the fluorine compound A into the outermost surface and layer formation are the effects of van der Waals interaction, that is, it is considered to be derived from the dispersion term. Therefore, when the above conditions are not satisfied, it is difficult to form a layer on the outermost surface that makes the amount of attachment of the simulated fingerprint less than a certain value, and the amount of attachment of the fingerprint may increase.

  It should be noted that Hansen solubility parameter values have been investigated for many solvents and some resins. For example, “Polymer Handbook (Fourth Edition)”, J. Mol. The value is described in the BRANDRUP et al. Edition (John Wiley & Sons). On the other hand, with respect to the aforementioned fluorine compound A and binder component whose solubility parameter values are not described in the database as described above, the methods shown in the examples under the property that those having similar solubility parameter values are easy to dissolve. By defining the solubility in a solvent whose parameter value is known, Hansen Solubility Parameter in Practice (HSPIP) ver. Each parameter can be calculated using 3.1.03 (http://www.hansen-solubility.com/index.php).

[Fluorine compound A]
The fluorine compound A refers to a compound having a reactive site and a site 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. .

  Here, 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, all of which are mainly composed of fluorine atoms and carbon atoms, and there may be branches in the structure. A dimer, trimer, oligomer, or polymer structure may be formed.

  Further, the reactive site refers to a site that reacts with other components by external energy such as heat or light. Examples of such 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. From the viewpoint of reactivity and handling properties, alkoxysilyl group, silyl ether group or silanol group, epoxy group, acryloyl (methacryloyl) group are preferable, vinyl group, allyl group, acryloyl group, methacryloyl group are more preferable, An acryloyl group and a methacryloyl group are particularly preferable. In order to achieve both the effect of reducing the surface energy and the wear durability of the surface of the molding material, it is particularly preferable to have 2 to 5 reactive sites in the previous period. From the viewpoint of durability of the surface layer at the time of fingerprint wiping, it is desirable that the fluorine compound A has many reactive sites. On the other hand, if the reactive site is 6 or more in the molecule, the effect of reducing the surface energy is sufficient. May not be obtained.

An example of the fluorine compound A is a compound represented by the following general formula.
R ^f1 -R ² -D ¹ ... General formula (1)
(R ^f1 is a fluoroalkyl group, fluorooxyalkyl group, fluoroalkenyl group, fluoro alkanediyl group, the site containing the fluoroxy alkanediyl group, R ² is derived alkanediyl group, alkanetriyl groups, and from them An ester structure, a urethane structure, an ether structure, and a triazine structure, and D ¹ represents a reactive site).

  Examples of general formula (1) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluorobutyl- 2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluoro Decylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3 Perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorononyl acrylate , Hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl Methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodec Ethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methyl Hexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-7-methyloctylethyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl Methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobut Examples include til methacrylate and triacryloyl-heptadecafluorononenyl-pentaerythritol.

A preferable material as the fluorine compound A is a material having a fluoropolyether moiety. The fluoropolyether moiety is a moiety composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkyldiyl group, etc., and has a structure represented by general formulas (2) and (3).
_{CF n1 H (3-n1)} - (CF n2 H (2-n2)) k O-
_{- (CF n3 H (2-} n3)) m O-
... General formula (2)
_{- (CF n4 H (2-} n4)) p O- (CF n5 H (2-n5)) s O-
... General formula (3)
Here, n1 is an integer of 1 to 3, n2 to n5 are integers of 1 or 2, and k, m, p, and s are integers of 0 or more. Preferably, n1 is 2 or more, n2 to n5 are integers of 1 or 2, more preferably n1 is 3, n2 and n4 are 2, and n3 and n5 are integers of 1 or 2.

  There is a preferred range for the chain length of this fluoropolyether moiety, the carbon number is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and more preferably 6 or more and 8 or less. When the number of carbon atoms is less than 4, the surface energy does not decrease, and when it exceeds 12, the solubility in a solvent decreases.

  The fluorine compound A may have a plurality of fluoropolyether moieties per molecule.

  As a commercially available example of the fluorine compound A, as a material having a fluoropolyether part having 4 to 12 carbon atoms, RS-75 (DIC Corporation), Optool DSX, Optool DAC (Daikin Industries, Ltd.), C10GACRY C8HGOL (Oil Products Co., Ltd.) and the like, and these products can be used.

[Compound B]
The molding material of the present invention preferably has a compound B having a lipophilic property that imparts fingerprint permeability. From the viewpoints of dissolution, dispersion, and retention in the molding material, it is preferable to actually have an oligomer or polymer form. Moreover, it is preferable to have a reactive site in a part of the structure.

  Specifically, for example, a material having an organosiloxane skeleton, a long-chain alkyl group, an alkylene glycol group, a phosphate ester group or the like in a part of the structure, or a particulate material such as an organosiloxane copolymer can be given. In order to obtain particularly preferable surface characteristics of the present invention, organic particles made of a dimethylsiloxane polymer are preferable, and commercially available products satisfying this include silicone cross-linked product KSG series of Shin-Etsu Silicone Co., Ltd.

[Binder component, Binder raw material]
The molding material of the present invention preferably has a layer containing a “binder component”, and the coating composition suitable for forming the molding material of the present invention preferably contains a “binder raw material”.

  Here, the “binder raw material” is a compound contained in the coating composition, and is a raw material of the “binder component” present in the layer formed by applying, drying and curing the coating composition. That is, the binder material that is contained in the molding material and / or layer after the binder raw material contained in the coating composition is cured by heat or ionizing radiation is referred to as a binder component. In addition, some binder materials may exist in the same state as in the coating composition even in the molding material (there may exist unreacted). That's it.

  Although the binder raw material in the said coating composition is not specifically limited, From a viewpoint of manufacturability, it is preferable that it is a binder raw material which can be hardened | cured with a heat | fever and / or active energy ray. One kind of binder raw material in the coating composition may be used, or two or more kinds may be mixed and used.

  In the present invention, from the viewpoint of keeping the particles in the layer, monomers and oligomers having alkoxy groups, silanol groups, reactive double bonds, and functional groups capable of ring-opening reaction in the molecule are binder raw materials. Preferably there is. Further, in the case of curing with UV rays, oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing in an anaerobic atmosphere is more preferable. By reducing the oxygen concentration, the cured state of the outermost surface is improved and chemical resistance may be improved.

  Specifically, the binder raw material in such a coating composition is preferably a polyfunctional acrylate monomer, oligomer, alkoxysilane, alkoxysilane hydrolyzate, alkoxysilane oligomer or the like, and more preferably a polyfunctional acrylate monomer or oligomer.

  Examples of polyfunctional acrylate monomers include polyfunctional acrylates having 3 (more preferably 4 or 5) or more (meth) acryloyloxy groups in one molecule and modified polymers thereof, and specific examples include pentaerythritol. Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate hexanemethylene diisocyanate urethane polymer, or the like can be used. These monomers can be used alone or in combination of two or more. “(Meth) acrylate” represents acrylate and methacrylate, and “(meth) acryloyloxy group” is a generic term for acryloyloxy group and methacryloyloxy group. The same applies to the case where “).

  On the other hand, examples of the polyfunctional acrylate oligomer include epoxy acrylate, urethane acrylate, and polyester acrylate. Urethane acrylate is preferable for obtaining the surface shape of the molding material of the present invention. Furthermore, from the viewpoint of particle dispersion, the urethane acrylate has an alicyclic hydrocarbon (cyclohexyl, tricyclodecanyl, isobornyl skeleton) in the polyol skeleton, and 9 (more preferably 12) or more in one molecule. What consists of a unit structure which has a (meth) acryloyloxy group is especially preferable.

  In addition, commercially available polyfunctional acrylic compositions include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam” (registered trademark) series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol” (registered trademark) series, etc.) Shinnakamura Chemical Co., Ltd .; (trade name “NK Ester” series, etc.), DIC Corporation; (trade name “Unidic” (registered trademark), etc.), Toagosei Co., Ltd. (“Aronix” (registered trademark)) Series, etc.), Nippon Oil & Fats Co., Ltd. (“Blemmer” (registered trademark) series, etc.), Nippon Kayaku Co., Ltd. (trade name “KAYARAD” (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd .; (product name “ Light ester "series and the like), and these products can be used.

[particle]
It is preferable that the layer which the molding material of this invention has, and the coating composition suitable for forming the molding material of this invention contain particle | grains separately from the component which belongs to the said compound B. Here, the particles may be either inorganic particles or organic particles, but inorganic particles are preferred from the viewpoint of durability.

  The number of types of inorganic particles is preferably 1 or more and 20 or less. The number of types of inorganic particles is more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 3 or less. Here, “inorganic particles” include those subjected to surface treatment. This surface treatment is introduced by chemical bonding (including covalent bonding, hydrogen bonding, ionic bonding, van der Waals bonding, hydrophobic bonding, etc.) and adsorption (including physical adsorption and chemical adsorption) on the particle surface. Refers to that.

Here, the kind of inorganic particles is determined by the kind of elements constituting the inorganic particles, and when some surface treatment is performed, the kind is determined by the kind of elements constituting the particles before the surface treatment. For example, since titanium oxide (TiO ₂ ) and nitrogen-doped titanium oxide (TiO _2−x N _x ) in which part of oxygen in titanium oxide is replaced with nitrogen as an anion, the elements constituting the inorganic particles are different, Different types of inorganic particles. Further, if particles (ZnO) consisting only of the same element, for example, Zn, O, even if there are a plurality of particles having different number average particle diameters, and the composition ratio of Zn and O is different, These are the same type of particles. Even if there are a plurality of Zn particles having different oxidation numbers, as long as the elements constituting the particles are the same (in this example, all elements other than Zn are the same), these are the same kind of particles. .

  The inorganic particles are not particularly limited, but are preferably metal or metalloid oxides, nitrides, borides, chlorides, carbonates, sulfates, composite oxides containing two metals, metalloids, Different elements may be introduced between the lattices, lattice points may be replaced with different elements, or lattice defects may be introduced.

  The inorganic particles are oxide particles in which at least one metal or metalloid selected from the group consisting of Si, Al, Ca, Zn, Ga, Mg, Zr, Ti, In, Sb, Sn, Ba, and Ce is oxidized. More preferably.

Specifically, silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), tin oxide It is at least one metal oxide or semimetal oxide selected from the group consisting of (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ), and indium tin oxide (In ₂ O ₃ ). Particularly preferred is silica (SiO ₂ ).

  The number average particle diameter of the inorganic particles is preferably 5 nm or more and 20 nm or less. When the number average particle diameter of the inorganic particles is smaller than 5 nm, the ability to form irregularities may be insufficient, and when the number average particle diameter is larger than 20 nm, the gloss may be deteriorated.

  Furthermore, the form of the inorganic particles is not particularly limited, but the silica has a long chain structure in which the silica is connected in a bead shape (a shape in which a plurality of silicas are connected in a chain), or the connected silica is branched. The thing and the bent thing are preferable. These are hereinafter referred to as beaded and / or branched silica.

  The bead-like and / or branched silica is composed of primary particles of silica bonded with particles between particles through interposition of metal ions having a valence of 2 or more, preferably 5 or more, More preferably, 7 or more connected. The connection, branching, and bending states of the silica connected in the bead shape and / or branched can be confirmed using a scanning electron microscope (SEM). Commercially available products of this silica connected and / or branched in the form of beads are PS-S, PS-M (water dispersion), IPA-ST (IPA dispersion), MEK-ST (manufactured by Nissan Chemical Industries, Ltd.). MEK dispersion), PL-1-IPA (IPA dispersion), PL-1-MEK (MEK dispersion) manufactured by Fuso Chemical Industry Co., Ltd., and the like, and these products can be used.

  In order to obtain a particularly preferable surface shape of the present invention, it is particularly preferable that the surface modification necessary for stably dispersing the above-mentioned chain silica in a good solvent of the binder raw material is made. For example, when an acrylic monomer or oligomer is used as a binder raw material, the surface modification requires an alkyl group, an alkenyl group, a vinyl group, a (meth) acryl group or the like having 1 to 5 carbon atoms on the surface. It is preferably introduced.

  As described later, the number average particle diameter of the inorganic particles is determined by observing the primary particles using a scanning electron microscope (SEM), a transmission electron microscope or the like in any of the molding material and the coating composition, and circumscribing each primary particle. The diameter obtained from the number average value of the diameter of the circle is the equivalent particle diameter.

  In the case of a molding material, the number average particle diameter can be determined by observing the surface or cross section. In the case of a coating composition, the coating composition diluted with a solvent is dropped and dried. Thus, it is possible to prepare and observe a sample.

[solvent]
A coating composition suitable for forming the molding material of the present invention may comprise 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. Here, the “solvent” refers to a substance that is liquid at normal temperature and normal pressure, which can evaporate almost the entire amount in the drying step after application.

  Here, the kind 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.

[Other additives]
The coating composition suitable for forming the molding material of the present invention preferably further contains a photopolymerization initiator, a curing agent and a catalyst.
A photoinitiator and a catalyst are used in order to promote reaction between inorganic particles, between binder raw materials, and between inorganic particles and binder raw materials. As the initiator, those capable of initiating or accelerating polymerization and / or silanol condensation and / or crosslinking reaction of the coating composition by radical reaction or the like are preferable.

  Various initiators, curing agents, and catalysts can be used. A plurality of initiators may be used at the same time or may be used alone. Furthermore, you may use together an acidic catalyst, a thermal-polymerization initiator, and a photoinitiator. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, and amine compounds, but are not limited thereto, but from the viewpoint of curability. Alkylphenone compounds are preferred, and specific examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-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) Nyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenylketone, 2-methyl-1-phenylpropan-1-one, 1- [4- (2- Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, and the like.

The content ratio of the initiator and the curing agent is preferably 0.001 to 30 parts by mass, more preferably 0.05 parts by mass with respect to 100 parts by mass in total of the binder raw materials in the coating composition. 20 parts by mass, more preferably 0.1 to 10 parts by mass.
The coating composition suitable for forming the molding material of the present invention may further contain additives such as surfactants, thickeners and leveling agents as necessary.

[Content of each component]
The coating composition suitable for forming the molding material of the present invention includes the fluorine compound A, the compound B, the binder raw material, and the particles. The respective mass relationships in the coating composition will be described.

  In 100% by mass of the coating composition, the fluorine compound A is 0.025% by mass to 7% by mass, the compound B is 0.02% by mass to less than 30% by mass, the particles are 0.2% by mass to 55% by mass, The binder raw material is preferably 0.8% by mass or more and 66% by mass or less, the solvent is 30% by mass or more and 95% by mass or less, and the initiator, curing agent, and other components of the catalyst are preferably 0.025% by mass or more and 7% by mass or less. Is done. More preferably, the fluorine compound A is 0.05% by mass to 6% by mass, the particles are 0.4% by mass to 36% by mass, the binder raw material is 3.2% by mass to 56% by mass, and the solvent is 40% by mass. % To 90% by mass, and other components of the initiator, the curing agent, and the catalyst are 0.05% by mass to 6% by mass.

[Supporting substrate]
When the molding material of the present invention is planar, a support base material is required to provide the “surface layer”. There is no limitation in particular in a support base material, Any of a glass plate, a plastic film, a plastic sheet, a plastic lens, and a metal plate may be sufficient.

  Examples of using a plastic film or plastic sheet as a supporting substrate include cellulose esters (eg, triacetylcellulose, diacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamide, polycarbonate, polyester (Eg, polyethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate ), Polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene, polyethylene, polymethylpentene), polysulfone, poly Terusuruhon, polyarylate, polyetherimide, including but such as polymethyl methacrylate and polyether ketone, triacetyl cellulose obtained Among these, polycarbonates, polyethylene terephthalate and polyethylene naphthalate are preferred.

  Various surface treatments can be applied to the surface of the support substrate before forming the layer. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.

[Method of manufacturing molding material]
The “surface layer” formed on the surface of the molding material of the present invention is a solid phase such as vapor phase treatment such as vapor deposition, sputtering, CVD, liquid phase treatment such as coating, impregnation, plating, saponification, transfer, and bonding. Although it may be formed on the surface of the molding material by a treatment and a combination of these treatments, a gas phase treatment by vapor deposition or a liquid phase treatment by coating is preferred, and a liquid formed by applying a coating composition to a support substrate or the like Phase treatment is more preferred.

  The method for producing the molding material 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, a die coating method (US Pat. No. 2,681,294), or the like. It is preferable to form a layer by applying to the above. Further, among these coating methods, the gravure coating method or the die coating method is more preferable as the coating method. The method for producing the coating composition will be described later.

  Next, the liquid film applied on the support substrate or the like is dried. In addition to completely removing the solvent from the obtained molding material, it is preferable that the liquid film is heated in the drying step from the viewpoint of promoting the formation of the surface structure by the particles in the liquid film.

  Examples of the drying method include heat transfer drying (adherence to a high-temperature object), convection heat transfer (hot air), radiant heat transfer (infrared ray), and others (microwave, induction heating). Among these, in the manufacturing method of the present invention, a method using convective heat transfer or radiant heat transfer is preferable because it is necessary to make the drying speed uniform even in the width direction. Furthermore, from the viewpoint of controlling the movement and orientation of the fluorine compound A to the surface and the progress of self-organization of the particles, a drying method using both radiant heat transfer and convective heat transfer is particularly preferable.

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. Here, 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 preferred range, preferably 10 g · m ⁻² · s ⁻¹ or less, and more preferably 5 g · m ⁻² · s ⁻¹ or less. By setting the drying speed in the constant rate drying section within this range, unevenness due to nonuniform drying speed can be prevented.

As long as a drying speed in the range of 0.1 g · m ⁻² · s ⁻¹ or more and 10 g · m ⁻² · s ⁻¹ or less can be obtained, the wind speed and temperature are not particularly limited.

  In the production method of the present invention, the densification by the arrangement of the particles is performed along with the evaporation of the residual solvent during the decreasing rate drying period. Since this process requires time for the arrangement of particles, there is a preferred range for the film surface temperature rise rate during the rate of drying, and it is preferably 5 ° C./second or less, preferably 1 ° C./second. The following is more preferable.

  Furthermore, you may perform the further hardening operation (hardening process) by irradiating a heat | fever or an energy ray. When curing with heat in the curing step, the temperature is preferably from room temperature to 200 ° C, more preferably from 100 ° C to 200 ° C, and even more preferably from 130 ° C to 200 ° C, from the viewpoint of the activation energy of the curing reaction. It is as follows.

Moreover, when hardening with an energy ray, it is preferable that it is an electron beam (EB ray) and / or an ultraviolet-ray (UV ray) from a versatility point. In the case of curing with ultraviolet rays, 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. When the oxygen concentration is high, the curing of the outermost surface is inhibited, the curing becomes insufficient, and the scratch resistance and alkali resistance may be insufficient. Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. Case of UV cured using a high pressure mercury lamp is a discharge lamp type, illuminance of ultraviolet rays 100~3,000mW / cm ^2, preferably 200~2,000mW / cm ^2, more preferably 300~1,500mW / cm ² performing the ultraviolet irradiation is preferred, the accumulated light quantity of ultraviolet 100~3,000mJ / cm ^2, preferably 200~2,000mJ / cm ^2, more preferably a 300~1,500mJ / cm ² under the condition that the It is more preferable to perform ultraviolet irradiation under conditions. Here, the ultraviolet illuminance is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectral efficiency, the diameter of the light emitting bulb, the design of the reflector, and the light source distance to the irradiated object. However, the illuminance does not change depending on the conveyance speed. Further, 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.

[Method for producing coating composition]
A coating composition suitable for forming the molding material of the present invention is obtained by mixing a solvent and other additives (initiator, curing agent, catalyst, etc.) in addition to the fluorine compound A, particles and binder raw material. The production method is obtained by measuring the prescribed amounts of the above components by mass or volume, and mixing them by stirring. At this time, in addition, a solvent removal treatment using a reduced pressure or reverse osmosis membrane, a dehydration treatment using a molecular sieve, an ion exchange treatment using an ion exchange resin, or the like may be performed.

The stirring conditions and the stirring device at the time of preparing the coating composition are not particularly limited, but may be any device and rotational speed necessary for sufficient mixing of the entire liquid, and the local shear rate in the liquid is 1.0. A range smaller than × 10 ⁴ s ⁻¹ and a Reynolds number of 1,000 or more is preferable in order to prevent aggregation due to shear fracture of the particle dispersion, aggregation due to local residence, and poor mixing.

  The particles may be added in the form of a particle dispersion or powder, but handling in the form of a particle dispersion is preferable in terms of preventing aggregation and generation of foreign matter. When the powder is handled as a raw material, it is preferable that the powder is dispersed in a solvent (dispersion medium) by various dispersing machines such as a media type dispersing machine. As the formulation amount when added as a particle dispersion, the mass of the particles obtained from the product of the solid content concentration of the particle dispersion and the mass of the particle dispersion can be used.

The solid content concentration was measured by weighing about 2 g of the particle dispersion in an aluminum dish (this mass is W ₁ ) (this mass is W ₂ ), and then drying in a hot air oven at 120 ° C. for 1 hour. after cooling to room temperature in a desiccator, weighed (this weight and W _3), it is possible to determine the solid concentration according to the following equation.
Solid content concentration = (W ₃ −W ₁ ) / (W ₂ −W ₁ ) × 100
The obtained coating composition may be subjected to an appropriate filtration treatment before being applied. This appropriate filtration process is a choice of solvent, filter material that matches the polar state of the particle surface, and filter openings, shear rate that does not destroy the dispersion state of the particle dispersion, and pressure conditions that match the filter structure. More preferably, it is filtered.

  Next, although this invention is demonstrated based on an Example, this invention is not necessarily limited to these.

[Fluorine compound A]
[Fluorine compound A1]
Fluoropolyether-modified trimethoxysilane ("DOW CORNING" 2634 COATING Toray Dow Corning Co., Ltd.) was used as the fluorine compound A1.

[Fluorine compound A2]
A compound containing a fluoroalkyl moiety (triacryloyl-heptadecafluorononenyl-pentaerythritol Kyoeisha Chemical Co., Ltd.) was used as the fluorine compound A2.

[Fluorine compound A3]
A compound containing a fluoropolyether moiety (MA-78 Miwon Specialty Chemical Co., Ltd) was used as the fluorine compound A3.

[Compound B]
[Compound B1]
As compound B1, methacryl-modified silicone oil (X-22-164E Shin-Etsu Chemical Co., Ltd.) was used.

[Compound B2]
As the compound B2, a block copolymer (Modiper FS720 NOF Corporation) containing a silicon segment was used.

[Compound B3]
Dimethicone silicone cross-linked product (KGS-042Z Shin-Etsu Chemical Co., Ltd.) was used as Compound B3.

[Compound B4]
A polydimethylsiloxane compound (EBECRYL350 Daicel Ornex Co., Ltd.) was used as the compound B4.

[Binder raw material]
[Binder raw material 1]
As the binder raw material 1, dipentaerythritol hexaacrylate (“KAYARAD” DPHA Nippon Kayaku Co., Ltd.) was used.

[Binder raw material 2]
As binder raw material 2, urethane acrylate oligomer (“KRM” 8452 Daicel Cytec Co., Ltd.) was used.

[Binder raw material 3]
As binder raw material 3, urethane acrylate oligomer (“Art Resin” UN-904 Negami Kogyo Co., Ltd.) was used.

[Particle component]
[Particle 1]
As particles 1, organosilica sol (MEK-ST-UP Nissan Chemical Industries, Ltd.) was used.

[Particle 2]
As the particles 2, organosilica sol (OSCAL JGC Catalysts & Chemicals Co., Ltd., solid content concentration 5 mass%) was used.

[Particle 3]
As particles 3, organosilica sol (MIBK-SD Nissan Chemical Industries, Ltd.) was used.

[Preparation of paint composition]
[Coating composition 1]
The following materials were mixed to obtain a coating composition 1.
Fluorine compound A: Fluorine compound A1 0.2 parts by mass Compound B: Compound B1 1.5 parts by mass Particles: Particles 1 30 parts by mass Binder: Binder raw material 1 22.3 parts by mass Solvent: MEK 45.3 parts by mass Photopolymerization start Agent: 1-hydroxy-cyclohexyl-phenyl-ketone
(Irgacure 184 BASF) 0.7 parts by mass.

[Coating composition 2]
As shown in Table 1, a coating composition 2 was obtained in the same manner as in the coating composition 1, except that the fluorine compound A1 was replaced with the fluorine compound A2.

[Coating composition 3]
The following materials were mixed to obtain a coating composition 3.
Fluorine compound A: Fluorine compound A2 0.1 parts by mass Compound B: Compound B1 1.0 part by mass Particles: Particle 2 80 parts by mass Binder: Binder raw material 1 14.9 parts by mass Solvent: MEK 3.5 parts by mass Photopolymerization start Agent: 1-hydroxy-cyclohexyl-phenyl-ketone
(Irgacure 184 BASF) 0.5 parts by mass.

[Coating compositions 4, 5]
As shown in Table 1, coating compositions 4 and 5 were obtained in the same manner as in the coating composition 3 except that the fluorine compound A2 was replaced with the fluorine compound A3 and the compound B1 was replaced with 2.

[Coating composition 6]
The following materials were mixed and the coating composition 6 was obtained.
Fluorine compound A: Fluorine compound A3 0.2 parts by mass Compound B: Compound B1 1.5 parts by mass Particles: Particles 3 20 parts by mass Binder: Binder raw material 1 22.3 parts by mass Solvent: MEK 55.3 parts by mass Photopolymerization start Agent: 1-hydroxy-cyclohexyl-phenyl-ketone
(Irgacure 184 BASF) 0.7 parts by mass.

[Coating composition 7]
The following materials were mixed to obtain a coating composition 7.
Fluorine compound A: Fluorine compound A3 0.2 parts by mass Compound B: Compound B2 1.5 parts by mass Binder: binder raw material 1 28.3 parts by mass Solvent: MEK 69.1 parts by mass Photopolymerization initiator: 1-hydroxy-cyclohexyl -Phenyl-ketone
(Irgacure 184 BASF) 0.9 parts by mass.

[Coating composition 8]
The following materials were mixed to obtain a coating composition 8.
Fluorine compound A: Fluorine compound A3 0.2 parts by mass Compound B: Compound B1 0.3 parts by mass Particles: Particles 1 30 parts by mass Binder: Binder raw material 1 23.5 parts by mass Solvent: MEK 45.3 parts by mass Photopolymerization start Agent: 1-hydroxy-cyclohexyl-phenyl-ketone
(Irgacure 184 BASF) 0.7 parts by mass.

[Coating composition 9]
The following materials were mixed to obtain a coating composition 9.
Fluorine compound A: Fluorine compound A1 0.2 parts by mass Compound B: Compound B3 0.6 parts by mass Particles: Particles 1 30 parts by mass Binder: Binder raw material 1 23.2 parts by mass Solvent: MEK 45.3 parts by mass Photopolymerization start Agent: 1-hydroxy-cyclohexyl-phenyl-ketone
(Irgacure 184 BASF) 0.7 parts by mass.

[Coating compositions 10, 11]
As shown in Table 1, coating compositions 10 and 11 were obtained in the same manner with respect to the coating composition 9 except that the binder raw material 1 was replaced with the binder raw materials 2 and 3.

[Coating composition 12]
The following materials were mixed to obtain a coating composition 12.
Fluorine compound A: Fluorine compound A1 0.2 parts by mass Compound B: Compound B1 4.0 parts by mass Particles: Particles 1 30 parts by mass Binder: Binder raw material 1 19.8 parts by mass Solvent: MEK 45.3 parts by mass Photopolymerization start Agent: 1-hydroxy-cyclohexyl-phenyl-ketone
(Irgacure 184 BASF) 0.7 parts by mass.

[Coating composition 13]
The following materials were mixed to obtain a coating composition 13.
Fluorine compound A: Fluorine compound A1 0.2 parts by mass Compound B: Compound B4 1.5 parts by mass Particles: Particles 1 30 parts by mass Binder: Binder raw material 1 22.3 parts by mass Solvent: MEK 45.3 parts by mass Photopolymerization start Agent: 1-hydroxy-cyclohexyl-phenyl-ketone
(Irgacure 184 BASF) 0.7 parts by mass.

[Coating composition 14]
The following materials were mixed to obtain a coating composition 14.
Fluorine compound A: Fluorine compound A1 0.1 parts by mass Particles: Particles 2 80 parts by mass Binder: Binder raw material 1 15.9 parts by mass Solvent: MEK 3.5 parts by mass Photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl- Ketone
(Irgacure 184 BASF) 0.5 parts by mass.

[Coating composition 15]
The following materials were mixed to obtain a coating composition 15.
Compound B: Compound B1 1.5 parts by mass Particles: Particles 1 30 parts by mass Binder: Binder raw material 1 22.5 parts by mass Solvent: MEK 45.3 parts by mass Photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl-ketone
(Irgacure 184 BASF) 0.7 parts by mass.

[Coating composition 16]
The following materials were mixed to obtain a coating composition 16.
Particles: Particles 1 30 parts by mass Binder: Binder raw material 1 24 parts by mass Solvent: MEK 45.3 parts by mass Photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl-ketone
(Irgacure 184 BASF) 0.7 parts by mass.

[Production of molding material]
“Lumirror” (registered trademark), type U46 (Toray Industries, Inc.) in which an easy-adhesive paint is applied on a PET resin film was used as a supporting substrate. A gravure wire is used so that the coating thickness of the coating composition 1 to 14 is 4 μm using a continuous coating apparatus having a small-diameter gravure coater and an infrared panel heater in the first half of the drying chamber at a conveyance speed of 10 m / min. The number and the gravure roll speed ratio were adjusted and applied. The conditions of the wind that hits the liquid film from application to drying and curing are as follows.

First drying air temperature and humidity: Temperature: 45 ° C, relative humidity: 10%
Wind speed: Application surface side: 5 m / sec, Anti-application surface side: 5 m / sec Air direction: Application surface side: Parallel to the substrate, Anti-application surface side: Vertical residence time to the substrate: 1 minute panel heater setting Temperature: 80 ° C
Second drying blast temperature and humidity: Temperature: 100 ° C., relative humidity: 1%
Wind speed: coating surface side: 5 m / sec, anti-coating surface side: 5 m / sec Wind direction: coating surface side: perpendicular to the substrate, anti-coating surface side: vertical residence time to the substrate: 1 minute Curing process Irradiation Output 600 W / cm ² Integrated light quantity 120 mJ / cm ²
Oxygen concentration 0.1% by volume
In addition, the measured value by a hot-wire anemometer (Nippon Kanomax Co., Ltd. Anemomaster anemometer / air flow meter MODEL6034) was used for the wind speed and temperature and humidity. By the above method, about Examples 1-11 and Comparative Examples 1-3, the molding material was created without using an infrared panel heater.

[Evaluation of coating composition]
[Number average particle diameter (primary particles)]
Observation and measurement were performed with a scanning electron microscope (SEM). The observation sample was prepared by diluting the coating composition in a dispersion medium (isopropyl alcohol) to a solid content concentration of 0.5% by mass, dispersing with ultrasonic waves, and dropping and drying on a conductive tape. 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 with the number of observations increased with the equivalent particle size.

[Measurement of Hansen Solubility Parameters]
In the fluorine compound A and the binder component, 15 solvents having different solubility, water, acetone, 2-butanone, cyclopentanone, isopropyl alcohol, ethanol, 1-octanol, toluene, hexane, acetic acid, butyl acetate, aniline, methanamide, 2-Aminoethanol and 2-butoxyethanol were added in small portions each until they were completely dissolved. Based on the saturated solution concentration at this time, there are 6 levels of solubility in each solvent (6: insoluble, 5: mass percent concentration less than 5%, 4: mass percent concentration between 5% and less than 10%, 3: mass percent concentration of 10%. Or more, less than 30%, 2: mass percent concentration of 30% or more and less than 50%, 1: mass percent concentration of 50% or more. Based on the solubility information in each solvent thus obtained, Hansen Solubility Parameter in Practice (HSPIP) ver. The solubility parameter of Hansen was calculated by 3.1.17 (http://www.hansen-solubility.com/index.php).

[Parameter R]
The dispersion term of the Hansen solubility parameter of the fluorine compound A is σ _d , the polar term is σ _p , the hydrogen bond term is σ _h , the dispersion parameter of the Hansen solubility parameter of the binder component is σ _Bd , the polar term is σ _Bp , hydrogen When the bond term is σ _Bh , R = [(σ _d −σ _Bd ) ² + (σ _p −σ _Bp ) ² + (σ _h −σ _Bh ) ² ] ^1/2
Was defined as parameter R. It calculated using the solubility parameter of Hansen of the fluorine compound A and the binder component calculated by the above-mentioned method.

[Evaluation of molding materials]
The produced molding material was subjected to the following performance evaluation, and the results obtained are shown in Tables 2 and 3. Unless otherwise specified, the measurement was performed three times by changing the location of one sample in each example and comparative example, and the average value was used.

[60 degree specular gloss]
The 60 degree specular gloss of the target surface of the molding material is measured by a method based on JIS Z8741 (1997) using Nippon Denshoku Industries VG7000. did.

[Oleic acid receding contact angle]
The receding contact angle was measured by the expansion-contraction method, and the Kyowa Interface Science Co., Ltd. contact angle meter Drop Master DM-501 was used according to the expansion-contraction method measurement manual of the same apparatus. Specifically, oleic acid (Nacalai standard grade Nacalai Tesque) is continuously drawn from a syringe at an initial droplet volume of 50 μL and a liquid discharge speed of 8.5 μL / sec. 30 images were taken every 5 seconds, and contact angles were obtained from the images using the integrated analysis software “FAMAS” attached to the apparatus. 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 °.

[Oleic acid absorption coefficient]
Of the values required for calculating the oleic acid absorption coefficient, the volume of oleic acid on the surface layer and the area of the adhesion region were measured using Kyowa Interface Science Co., Ltd. Contact Angle Meter Drop Master DM-501. The static contact angle measurement manual was followed. Specifically, a 2 μL droplet of oleic acid (Nacalai standard grade Nacalai Tesque) is created at the tip of the syringe, and after landing on the surface of the molding material, an image of the attached state is taken, and integrated analysis software “ Volume and contact area were calculated using FAMAS ". 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 true circle when the length of the contact line was assumed to be the diameter of the true 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.

  Further, the thickness T of the surface layer was calculated based on the coating thickness at the time of forming the molding material. On the other hand, when 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.

[Time-of-flight secondary ion mass spectrometry: Measurement of in-plane distribution of F ^- fragment ions (M / Z = 19) and dimethylsiloxane-derived Si (CH ₃ ) ⁺ fragment ions by TOF-SIMS]
Using the time-of-flight secondary ion mass spectrometer TOF-SIMSV manufactured by ION TOF and the measurement software SURFACE LAB 6, the F ^- fragment ion (M / Z = 19) and Si (CH ₃ ) ⁺ fragment ions derived from dimethylsiloxane were measured to determine the distribution of each fragment ion in the plane. The measurement conditions are as follows.
Measurement conditions: Primary ion species: Bi ⁺
Primary ion current: 1.000 pA
Acceleration voltage: 25 kV
Detected ion polarity: negative (F ⁻ ), positive (Si (CH ₃ ) ⁺ )
Measurement range: 100 μm × 100 μm
Resolution: 128 x 128
Number of scans: 36 times.

  For analysis of measurement data, first, using software built in the secondary ion mass spectrometer, two-dimensional positional information on the outermost surface of the laminated film and secondary ions of each fragment ion at the corresponding position. Intensity information was extracted. The standard deviation of the secondary ion intensity can be calculated based on the extracted secondary ion intensity value.

  Next, using the software built in the secondary ion mass spectrometer, for each fragment ion, three-dimensional information obtained by adding the secondary ion intensity to the above-described two-dimensional position information is shown in FIG. 1 or FIG. Converted into a planar distribution image (mapping image) as shown in FIG. At this time, the secondary ion intensity scale is automatically set by the software from the maximum value and the minimum value in the measurement region. On the other hand, for the portion with low detection intensity, the oil repellency and lipophilic effects expected for the chemical species from which the fragment ions are derived cannot be sufficiently obtained. As 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.

A plane distribution image and a scale bar of F ^- fragment ions (M / Z = 19), Si (CH ₃ ) ⁺ fragment ions derived from dimethylsiloxane, and scale bars obtained from this result were obtained by using image processing software EasyAccess Ver6.7. Convert the image to gray scale in 1.23 and adjust the white balance so that the lightest and darkest parts fit within an 8-bit tone curve, and the above-mentioned boundary values in the secondary ion distribution can be clearly distinguished. The contrast was adjusted with reference to the scale bar. Next, using the image analysis software ImageJ 1.45s, the pixels were binarized with the above-mentioned boundary as a boundary, and only the planar distribution image was cut out, and then the area formed by the distribution region of each fragment ion was calculated. Furthermore, by dividing the area of the corresponding region by the area of the entire measurement range, the ratio and the occupation ratio of the portion where the fragment ions exist were obtained. In addition, from the above image, the distribution state is observed, and it is determined whether “uniformly present”, “island-like”, “net-like”, “island-like and mesh-like” are present. went.

[Abrasion resistance]
Against steel wool to be 500 g / cm ² load to antireflection member (# 0000) vertically, the length of 1cm describes the approximate number of scratches are visible upon 20 reciprocally performs classification below 3 The score was passed.
5 points: 0 4 points: 1 or more Less than 5 3 points: 5 or more Less than 10 2 points: 10 or more Less than 20 1 point: 20 or more.

[Simulated fingerprint attachment]
The adhesion of the simulated fingerprint to the molding material of the present invention is as follows. 1. Preparation of simulated fingerprint liquid 2. Create a simulated fingerprint sheet 3. Transfer of simulated fingerprint liquid from the simulated fingerprint sheet to silicone rubber. It consists of adhesion of the simulated fingerprint from the silicone rubber to the surface of the molding material.
1. The simulated fingerprint solution was prepared by weighing the following materials at the following ratio and stirring with a magnetic stirrer for 30 minutes.
Oleic acid 14 parts by mass Silica (number average particle size 2 μm) 6 parts by mass Isopropyl alcohol 80 parts by mass The number average particle size of the silica is obtained by using the silica particles in a dispersion medium (isopropyl alcohol) at a solid content concentration of 3% by mass. It was obtained in the same manner as in the above method except that the observation sample was prepared by mixing and dispersing with ultrasonic waves and then dropping on a conductive tape.
2. The simulated fingerprint sheet of “Lumirror” (registered trademark), in which an easy-adhesive paint is applied on a PET resin film with the fingerprint coating solution as a supporting substrate, type: U46 (Toray Industries, Inc.), a wire bar ( It was applied using # 3) and dried at 50 ° C. for 2 minutes.
3. The transfer of the simulated fingerprint to the silicone rubber was performed by polishing a silicone rubber having a rubber hardness of 50 defined in JIS K6253 (1997) with water resistant paper of # 250. At this time, the surface roughness specified in JIS B0601 (2001) on the surface of the silicone rubber was Ra = 2 μm or more and 4 μm or less. Next, the silicone rubber polished with the water-resistant paper was immersed in oleic acid overnight to swell. Subsequently, the silicone rubber that has been subjected to the polishing and oleophilic treatment is subjected to 2. And pressed against the simulated fingerprint sheet created in The adhesion amount (g / m ² ) of the simulated fingerprint liquid to the silicone rubber indicates a value obtained from the area of the silicone rubber and the mass difference before and after the adhesion, and as a result of performing the above method, both are 0.03 g / m ^2. It was 0.07 g / m ² or less.
4). 2. Adhering the simulated fingerprint to the surface of the molding material The silicone rubber to which the simulated fingerprint liquid was transferred was pressed against the surface of the molding material at 30 KPa, and the trace formed on the molding material surface was used as the simulated fingerprint.

  Note that “immediately after imitation fingerprint attachment” means approximately 30 minutes from the attachment, and when aging is observed, after the above attachment operation, the material left at 25 ° C. in a windless state for 10 hours is targeted. . In the examples and comparative examples, the above conditions are shown unless otherwise specified.

[Color difference between regular reflection light before and after fingerprint attachment and removal of regular reflection light]
A black vinyl tape is pasted on the opposite side of the target surface of the molding material, and the reflection color before and immediately after the attachment of the above-mentioned simulated fingerprint is determined using JIS Z8722 using a spectrophotometric colorimeter CM-3600A. Based on (2009), the reflection color for specular reflection removal is the Sb10W10 condition using a specular reflection light trap (de: 8 °), and the reflection color including the specular reflection light is not used (di: 8). °) Under Sb10W10 conditions, measurement was performed with CIE1976 (L ^* a ^* b ^* ) described in JIS Z8730 (2009).

Further, from the reflection color before and immediately after the adhesion, according to the calculation method described in JIS Z8730 (2009), (ΔE ^* _ab (di: 8 °) Sb10W10, ΔE _SCI-1 ) ΔE ^* _ab (de: 8 °) Sb10W10, ΔE _SCE-1 ) was determined. Next, a parameter K ₁ defined by the following formula was calculated based on the measured value, and a parameter K ₁ of 3 or less was regarded as acceptable.
Parameter K ₁ = [(ΔESCI _-1 ) ² + (ΔESCE _-1 ) ² ] ^1/2 .

[Change in time of color difference between regular reflection light before and after fingerprint attachment and removal of regular reflection light]
The black vinyl tape was affixed in the same manner as the color difference between the regular reflection light before and after the fingerprint attachment and the removal of the regular reflection light, and the molding material to which the simulated fingerprint was adhered was allowed to stand at 25 ° C. for 10 hours in a windless state. Next, the reflected color after 10 hours was measured in the same manner as the color difference of including the regular reflection light before and after the fingerprint attachment and removing the regular reflection light.

Furthermore, from the reflection color before and after 10 hours, according to the calculation method described in JIS Z8730 (2009), (ΔE ^* _ab (di: 8 °) Sb10W10, ΔE _SCI-2 ) ΔE ^* _ab (de: 8 °) Sb10W10, ΔE _SCE-2 ) was determined. Then calculates the parameters K ₂ defined by the following equation measurements based on the difference between the parameter K ₁ is evaluated as acceptable 1 below.
Parameter K ₂ = [(ΔESCI _-2 ) ² + (ΔESCE _-2 ) ² ] ^1/2 .

[Amount of simulated fingerprint attached]
The amount of simulated fingerprint adhering to the molding material surface is measured using a wavelength dispersive X-ray fluorescence device (Rigaku Denki Scanning X-ray fluorescence analyzer ZSX-Primus II) to measure the Kα-ray intensity of silicon contained in the simulated fingerprint solution. Was measured. Specifically, a calibration curve of simulated fingerprint adhesion amount-silicon Kα ray intensity is prepared by first measuring the Kα ray intensity of silicon with the above apparatus on a sample obtained by applying a certain amount of simulated fingerprint liquid on a PET film. did. Next, the Kα ray intensity of the silicon of the simulated fingerprint adhered by the above method was measured, and the adhesion amount was calculated from the calibration curve. The adhesion amount of the fingerprint obtained from this result was determined to be 0.05 g / m ² or less.

[Measurement of the number of peaks]
After cutting out the molding material at an arbitrary place, using an atomic force microscope (SII Corporation SPI3800), observation mode = DFM mode, scanner = FS-20A, cantilever = DF-3, observation field = 5 × 5 μm ² , Surface morphology was observed at a resolution of 1,024 × 512 pixels to obtain an observed image. Next, in order to set 100% of the mean square roughness to the peak threshold value, analysis was performed with “Peak Thrsh (% rms)” set to 100%, and the number of peaks was obtained.

[Fingerprint resistance (fingerprint adhesion)]
Fingerprint resistance (fingerprint adherence) is placed on black drawing paper with the evaluation surface of the molding material facing upward, rubs the finger (index finger) and thumb for pressing the fingerprint three times, and then slowly presses against the surface of the layer The visibility of the attached fingerprint was evaluated on a 10-point scale. The evaluation criteria are as follows.
10 points: The fingerprint is not visually recognized or the difference from the unattached part is not known.
7 points: The fingerprint is hardly visible or not recognized as a fingerprint.
5 points: 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 | required. The numbers after the decimal point were rounded off.

[Change in fingerprint resistance over time]
Similar to the evaluation of fingerprint resistance, the visibility of a fingerprint that was allowed to stand for 10 hours in a windless state at 25 ° C. after the fingerprint was transferred was evaluated on a 10-point scale. The evaluation criteria are as follows.
10 points: The fingerprint is not visually recognized or the difference from the unattached part is not known.
7 points: The fingerprint is hardly visible or not recognized as a fingerprint.
5 points: 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 | required. The numbers after the decimal point were rounded off.

[Measurement of oil droplet diameter]
After storing the molding material for a predetermined time at a temperature condition for the simulated fingerprint attached to the molding material surface in the same manner as the above-mentioned simulated fingerprint attachment, the surface projection image of the oil droplet is subjected to differential interference. were taken using a microscope, determine the oil droplet size d _p using image processing software on the obtained image, the result based on an area-based frequency distribution in a, and was determined the change of the cumulative frequency.

A specific procedure for measuring the oil droplet diameter d _p is described below.
First, an image of the surface of the anti-fingerprint molding material to which the simulated fingerprint was attached was taken at a magnification of 100 times with a differential interference microscope. Subsequently, 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. Next, using 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.

[Area-based frequency distribution]
In calculating the area-based frequency distribution, a histogram was first created based on the oil droplet diameter d _p obtained by the above-described processing. At this time, the oil droplet diameter was divided every 5 μm, and based on this, stratification was performed using the histogram function of Microsoft Excel 2003. Next, in order to weight the obtained histogram according to the area of the surface projection image, the representative area for each layer of the histogram is calculated assuming a circle with the central value of each radix as the representative diameter, and the frequency for each layer is calculated. The area-based frequency distribution was determined by multiplying and dividing by the total area again. Furthermore the area-based frequency distribution of the frequency on the vertical axis, graph the cumulative frequency on the horizontal axis as the oil droplet size was determined median diameter D _P from the value of the oil droplet diameter in the cumulative frequency of 50%. Specifically, two layers sandwiching a point with a cumulative frequency of 50% are specified from the histogram, and two coordinates specified by the center value of the oil droplet diameter of the corresponding layer and the cumulative frequency are connected by a straight line. It was calculated median diameter D _P as the oil droplet diameter of the point of 50% cumulative frequency above.

[Aging of area-based frequency distribution over time]
After the simulated fingerprint was adhered to the surface of the molding material by the same method as the above-mentioned simulated fingerprint adhesion, the molding material was allowed to stand at 25 ° C. under no wind for 30 minutes and 10 hours. Subsequently, the oil droplet diameter after 30 minutes and the oil droplet diameter after 10 hours were measured by the above-described measurement of the oil droplet diameter. Further, the median diameter D _P1 after 30 minutes and the median diameter D _P2 after 10 hours were calculated from the analysis described in the area reference frequency distribution.

  Table 1 summarizes the composition of the coating composition, and Tables 2 and 3 summarize the evaluation results of the molding materials obtained. Regarding evaluation items that did not pass even one item, it was judged that the problem was not achieved.

  As shown in Table 3, the examples of the present invention passed both glossiness and fingerprint resistance, and achieved the problems to be solved by the present invention.

1,3,5 Si (CH ₃ ) ⁺ fragment ion derived from dimethylsiloxane
Part 2, 4, 6 in which (M / Z = 43) exists Si (CH ₃ ) ⁺ fragment ion derived from dimethylsiloxane
Portion where (M / Z = 43) is less than the boundary value

  The molding material according to the present invention can be suitably used for imparting fingerprint resistance, as well as various plastic molded products, lenses on the outermost surface portion of cameras, lenses for spectacles, window glass for buildings and vehicles, and the like. It can also be used to give similar functions to the surfaces of various printed materials.

Claims (8)

A molding material having a surface layer on at least one surface and having the following characteristics 1 to 3.
1. 1. 60-degree specular gloss of the surface layer specified by JIS Z8741 (1997) is 60% or more. 2. The receding contact angle θ _r of oleic acid of the surface layer is 50 ° or more; Here oleate absorption coefficient A _b of the surface layer is 30 or more, and oleic acid absorption coefficient A _b oleic acid 2μl dropwise to the surface layer, the volume calculated from the droplet shape upon ejection from the syringe (V ₁ ), The area (S ₁ ) of the droplet deposition part at the time of droplet deposition, the volume (V ₂ ) after holding for 10 hours at 25 ° C. and no wind, and the thickness (T) of the surface layer, the following formula (1) Refers to the value obtained by.
_{A b = (V 1 -V 2} ) / (S 1 × T) Equation (1) A molding material having a surface layer on at least one surface, the surface layer has a 60-degree specular gloss specified by JIS Z8741 (1997) of 60% or more, and a time-of-flight secondary ion mass spectrometer (TOF) -SIMS) is measured by, derived from the fluorine F ^- fragment ion (M / Z = 19) are uniformly present in a plane, Si _(CH 3 derived from ^{dimethylsiloxane) +} fragment ions (M / Z = 43) is present in any of the following:
・ Existing in islands ・ Existing in meshes ・ Existing in islands and meshes _3. The molding material according to claim 2, wherein in the surface layer, a proportion of a portion where Si (CH ₃ ) ⁺ fragment ions derived from the dimethylsiloxane are present is 30% or more and 70% or less. A molding material having a surface layer on at least one surface, the 60-degree specular gloss specified by JIS Z8741 (1997) of the surface layer is 60% or more,
A molding material having a surface layer having surface characteristics satisfying the following formulas (2) and (3):
K ₁ ≦ 3 Formula (2)
K ₁ −K ₂ ≧ 1 Formula (3)
here,
K ₁ = [(ΔESCI _-1 ) ² + (ΔESCE _-1 ) ² ] ^1/2 formula (4)
K ₂ = [(ΔE _SCI-2 ) ² + (ΔE _SCE-2 ) ² ] ^1/2 formula (5)
ΔE _SCI-1 , ΔE _SCE-1 :
ΔE ^* _ab (di: 8 °) Sb10W10 defined by JIS Z8730 (2009) and JIS Z8722 (2009) measured 30 minutes after the attachment of the simulated fingerprint on the surface layer as a reference, and ΔE ^* _Ab (de: 8 °) Sb10W10 respectively.
ΔE _SCI-2 , ΔE _SCE-2 :
ΔE * _ab (di: 8 °) Sb10W10 defined by JIS Z8730 (2009) and JIS Z8722 (2009) measured after 10 hours from the attachment of the simulated fingerprint on the surface layer as a reference, and ΔE * _Ab (de: 8 °) Sb10W10 respectively.
Simulated fingerprint attachment 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 μm is converted into a silicone rubber having a Ra specified by JIS B0601 (2001) of 3 μm and a rubber hardness of 50 specified by JIS K6253 (1997). 0.05 g / m ^{2 is} adhered, and is adhered to the target surface at 30 KPa. The molding material according to claim 2, wherein the surface layer has an oleic acid absorption coefficient _Ab of 30 or more. The molding material according to claim 2, wherein the receding contact angle θ _r of oleic acid in the surface layer is 50 ° or more. The number of peaks exceeding the root mean square roughness (RMS) observed by at least the surface layer by an atomic force microscope (AFM) is 500 or more and 1,500 or less per 25 μm ^2. The molding material according to any one of 1 to 6. The median diameter (D _P ) calculated from the area reference frequency distribution of the oil droplet formed when the simulated fingerprint is attached to the surface layer satisfies the following expressions (6) and (7): The molding material according to any one of claims 1 to 7.
D _P1 ≦ 80 μm (6)
(D _P1 −D _P2 ) / D _P1 ≧ 0.5 Formula (7)
D _P1 : 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 _P2 : the simulated fingerprint measured 10 hours after the attachment of the simulated fingerprint Median diameter calculated from the area-based frequency distribution of the constituent oil droplets

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