WO2013105429A1

WO2013105429A1 - Molding material, coating composition, and method for manufacturing molding material

Info

Publication number: WO2013105429A1
Application number: PCT/JP2012/083460
Authority: WO
Inventors: 石田康之; 岩谷忠彦; 高田育
Original assignee: 東レ株式会社
Priority date: 2012-01-13
Filing date: 2012-12-25
Publication date: 2013-07-18
Also published as: CN104023969A; JP6102735B2; TWI565767B; KR20140113661A; CN104023969B; TW201335296A; JPWO2013105429A1; KR102061920B1

Abstract

The present invention attempts to solve the problem of providing the following: a molding material on which fingerprints are difficult to discern, despite said molding material exhibiting glossiness or transparency; a coating composition that can form a surface layer that exhibits the aforementioned effect; and a method for manufacturing the aforementioned molding material. This molding material has a surface layer on at least one surface, the 60° specular glossiness of said surface layer as defined by JIS Z8741:1997 is at least 60%, and the receding contact angle (θr) of oleic acid thereon is at least 60°.

Description

MOLDING MATERIAL, COATING COMPOSITION, AND METHOD FOR PRODUCING MOLDING MATERIAL

The present invention relates to a molding material having a surface layer excellent in fingerprint resistance, a coating composition capable of forming a surface layer excellent in fingerprint resistance, and a method for producing the molding material.

Fingers touching the surface of an object (a fingerprint is a pattern formed by a line (ridge) where the opening of a sweat gland on the skin of the fingertip is raised, and a pattern in which the pattern is attached to the surface of an object. If it cannot be easily wiped off, there is a problem of giving an unpleasant impression that the appearance is dirty. In particular, recently, electronic devices operated with fingers, such as smartphones / touch panels, keyboards, TV / air conditioner remote controls, etc., are increasing. For example, there is a problem that a fingerprint is attached by grasping a casing of a mobile phone, and the fingerprint is conspicuous and the clean feeling is impaired.

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 the visibility is lowered due to a difference in reflectance at a portion where it is not attached. For example, smartphones, TVs, car navigation systems, personal computer LCD screens, signal indicators for guidance / warning / evacuation guidance, glasses / sunglasses / telescopes / camera lenses, transparent clock face covers, car rearview mirrors, Such as a 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 problems, the characteristic that the fingerprint on the surface of the article is not conspicuous, difficult to see, or difficult to see, or can easily wipe off the attached fingerprint (the physical property is hereinafter referred to as fingerprint resistance). As a characteristic of the member having, it is disclosed in Patent Document 1 that “a low refractive index layer having a light refractive index of less than 1.75 on one surface of a substrate, or a light refractive index at a wavelength of 550 nm”. Is an optical thin film formed by forming a thin film layer including at least a high refractive index layer having a refractive index of 1.75 or more, or both, and an olein having a dry film thickness of 20 μm on the surface of the thin film layer When an acid is applied, the optical thin film coated with the oleic acid and the optical thin film not coated with the oleic acid in a D65 light source, 5 ° incidence, 2 ° field of view, and regular reflection light Color difference Delta] E ^* _ab of CIELAB (conforming to JIS Z 8729) (= {( ΔL *) 2 + (Δa *) 2 + (Δb *) 2} 1/2) optical thin film characterized in that it is 5 or less "Film" has been proposed.

In addition, as a characteristic indicating the ease of wiping off fingerprints, Patent Document 2 discloses that “a glossiness meter is used to measure a 75 to 20 degree specular gloss of a film formed on an object to be an initial gloss. Initial gloss measurement step, attaching anti-fingerprint evaluation liquid on the coating, anti-fingerprint evaluation liquid attaching step, measuring the specular gloss of the part to which the anti-fingerprint evaluation liquid is attached, pre-wiping gloss measurement step, Wipe off the attached anti-fingerprint evaluation solution, wipe off the anti-fingerprint evaluation solution, measure the specular gloss after wiping off the anti-fingerprint evaluation solution, process the measured glossiness after wiping, and the measured value obtained by the following formula Calculating the adhesion evaluation rate and the evaluation rate after wiping,
Adhesion evaluation rate (%) = (Glossiness before wiping) / (Initial glossiness) × 100
Evaluation rate after wiping (%) = (Glossiness after wiping) / (Initial glossiness) × 100
A method for evaluating the anti-fingerprint property of a film, including

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 comprising an antifouling layer having 0 and the following characteristics:

a. Liquid paraffin contact angle is 65 ° or more, and liquid paraffin falling angle is 15 ° or less b. Black magic contact angle is 35 ° or more and black magic sliding angle is 15 ° or less c. "The coefficient of dynamic friction is less than 0.15" has been proposed.

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 m / Have been proposed hard coat film ", characterized in that m is within the range.

Furthermore, as a material structure for imparting fingerprint resistance, Patent Document 5 describes that “at least one vinyl monomer selected from a vinyl monomer having an alkyl group having 6 to 22 carbon atoms (a1) and an aromatic vinyl monomer (a2)”. Polymerization containing (A) and vinyl monomer (B) having 5 to 13 fluorine atoms in the molecule in a weight ratio of (A) :( B) = 90 to 99.9: 0.1 to 10 "An anti-fingerprinting agent characterized by comprising a copolymer (I) obtained by polymerizing components" has been proposed.

JP 2009-122416 A JP 2011-99744 A International Publication No. 2008/038714 Pamphlet JP 2011-043606 A JP 2010-24283 A

Regarding the technologies of Patent Document 1 and Patent Document 2, the present inventors have confirmed the visibility of fingerprints under various conditions. As a result, only by satisfying these characteristics, the fingerprints are inconspicuous or the fingerprints can be easily wiped off. It was insufficient.

The technique of Patent Document 3 focuses on the liquid paraffin contact angle and the falling angle, but when the present inventors have confirmed various surface layers, the contact angle, the falling angle and the fingerprint visibility, and the wiping property are not necessarily obtained. It was found that even when the range of Patent Document 3 was satisfied, sufficient fingerprint resistance could not be obtained.

The techniques of Patent Documents 4 and 5 were confirmed by the present inventors, and the effect was limited. In particular, the technique was insufficient when a fingerprint having a lot of sebum was attached.

The problems to be solved by the present invention include a molding material excellent in fingerprint resistance, in particular, fingerprint wiping property while maintaining glossiness or transparency and scratch resistance necessary for practical use, a paint composition that can be formed, and It is providing the manufacturing method of a molding material.

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,
A molding material in which the surface layer has a 60 ° specular gloss specified by JIS Z8741: 1997 of 60% or more and a receding contact angle θ _{r of} oleic acid of 60 ° or more.

[2] A molding material having a surface layer on at least one surface,
The 60 ° specular gloss specified by JIS Z8741: 1997 of the surface layer is 60% or more,
When the surface layer is subjected to simulated fingerprint adhesion and simulated fingerprint wiping under the following conditions, the specular reflection light after wiping the simulated fingerprint based on the state before the simulated fingerprint adhesion obtained according to JIS Z8730: 2009 and JIS Z8722: 2009 Color difference ΔE ^* _ab (di: 8 °) Sb10W10 (hereinafter referred to as ΔE _SCI-2 ) and the color difference ΔE ^* _ab (de: 8 °) A molding material in which Sb10W10 (hereinafter referred to as ΔE _SCE-2 ) satisfies the range of the following formula (1).

((ΔE _SCI-2 ) ² + (ΔE _SCE-2 ) ² ) ^1/2 ≦ 2.0
... Formula (1)
・ Simulated fingerprint adhesion conditions: A dispersion composed of 70% by mass of oleic acid and 30% by mass of silica particles having a number average particle diameter of 2 μm has a Ra defined by JIS B0601: 2001 of 3 μm and a rubber defined by JIS K6253: 1997. 1.0 g / m ^{2 is} adhered to a silicone rubber having a hardness of 50, and this is adhered to the target surface at a pressure of 30 KPa.
Simulated fingerprint wiping conditions: The simulated fingerprint attached by the above method is rubbed three times with a nonwoven fabric at a pressure of 30 KPa and a speed of 5 cm / sec.

[3] The molding material according to [2], wherein the surface layer has a receding contact angle θ _r of oleic acid of 50 ° or more.

[4] The molding material according to any one of [1] to [3], wherein the advancing contact angle θ _a and receding contact angle θ _r of the oleic acid of the surface layer satisfy the following formula (2).

(Θ _a −θ _r ) ≦ 15 ° Formula (2).

[5] In the elemental composition obtained by analyzing the surface layer by X-ray photoelectron spectroscopy (XPS) at a photoelectron escape angle of 15 °, the proportion of fluorine is 50% or more in terms of the atomic ratio [1] To [4].

[6] In the form of the surface of the surface layer observed with an atomic force microscope, the ten-point average roughness Rz and the centerline average roughness Ra specified by JIS B0601: 2001 are the following formulas (3) and (4 ) The molding material according to any one of [1] to [5]. *

4 nm <Rz ≦ 25 nm (3)
Ra <= 4nm ... Formula (4).

[7] The molding material according to any one of [1] to [5], wherein the surface layer contains the following 1) to 3).

1) Fluorine compound A 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
2) Compound B having a site containing an alkyl group having 8 or more carbon atoms and / or an alkanediyl group and a reactive site
3) Binder component [8] The molding material according to any one of [1] to [6], wherein the surface layer contains the following 1) to 3).

1) Fluorine compound A 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
2) Binder component 3) Particle component comprising particle d (I) having a number average particle diameter of 5 nm to 20 nm and particle d (II) having a number average particle diameter of 50 nm to 300 nm [9] The surface layer is from 1) below The molding material according to [8] above, which contains 3).

1) 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, and a reactive site of 2 to 5 in one molecule Fluorine compound A (II) having
2) The binder raw material C (I), which is a compound having 10 or more reactive sites in the molecule and a number average molecular weight of 1500 to 3000, and a reactive site of 3 to 6 in the molecule, and having a number average molecular weight of 500 Binder component formed from binder raw material C (II) which is a compound of 1500 or less and 3 or less 3) Particle d (I) having a number average particle size of 5 nm or more and 20 nm or less and Particle d (II) having a number average particle size of 50 nm or more and 300 nm or less [10] A coating composition containing the following 1) to 3).

1) Fluorine compound A 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
2) Compound B having a site containing an alkyl group having 8 or more carbon atoms and / or an alkanediyl group and a reactive site
3) Binder raw material [11] A coating composition containing the following 1) to 3).

1) Fluorine compound A 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
2) Binder raw material 3) Particle component consisting of particles D (I) having a number average particle diameter of 5 nm or more and 20 nm or less and particles D (II) having a number average particle diameter of 50 nm or more and 300 nm or less [12] containing the following 1) to 3) The coating composition according to [11] above.

1) 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, and a reactive site of 2 to 5 in one molecule Fluorine compound A (II) having
2) The binder raw material C (I), which is a compound having 10 or more reactive sites in the molecule and a number average molecular weight of 1500 to 3000, and a reactive site of 3 to 6 in the molecule, and having a number average molecular weight of 500 Binder raw material consisting of binder raw material C (II) which is a compound of 1500 or less 3) It consists of particles D (I) having a number average particle diameter of 5 nm to 20 nm and particles D (II) having a number average particle diameter of 50 nm to 300 nm. Particle component [13] A method for producing a molding material, wherein the coating composition according to any one of [10] to [12] is applied to a surface.

According to the present invention, while maintaining glossiness and transparency and scratch resistance necessary for practical use, fingerprints are hardly visible and easy to wipe, a coating composition capable of forming a surface layer that exhibits the above effects, And the manufacturing method of the said surface layer can be obtained.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Before describing a mode 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. In addition, the technique of Patent Document 2 evaluates adhesion and wiping by changing the glossiness, but since the evaluation by glossiness only looks at the influence of light scattering due to adhesion, It is considered that the change in color due to adhesion could not be evaluated, and the correspondence with visibility was insufficient.

Next, oleic acid is used as a simulated fingerprint liquid for evaluating visibility, and oleic acid is used in Patent Document 1 and higher fatty acids and terpenes are used in Patent Document 2, but the liquid constituting the actual fingerprint is supplied from the finger skin. In addition to water and organic salts (such as uric acid salts) and sebum (such as oleic acid) contained in perspiration, particles in dust and cosmetics in the living environment (sand dust, titanium oxide, zinc oxide, silica, etc.) It is considered that the effects of light scattering due to the presence of particles could not be evaluated by the methods of Patent Documents 1 and 2.

Next, regarding the fingerprint attachment mechanism, the technique of Patent Document 3 uses the contact angle and the falling angle of the fingerprint-adhesive liquid paraffin as described above, and the former is a dynamic of liquid components such as fingerprint attachment and wiping. The latter is a parameter indicating the dynamic behavior of the droplet, and the latter is greatly affected by the mass of the droplet from the principle of the measurement method. It is thought that the dynamic behavior of was not able to be expressed.

Next, regarding the constituent elements of the surface layer, the technique of Patent Document 4 regulates the abundance ratio of fluorine atom: oxygen atom: carbon atom on the surface of the hard coat layer, but prevents adhesion of sebum components and further adheres. In order to easily separate the components, it is considered important that the oil repellent component, that is, the fluorine component, is selectively present on the surface layer. Therefore, it is considered that the range specified in Patent Document 4 is insufficient.

Moreover, regarding the material constituting the surface layer, the technique of Patent Document 5 uses a copolymer of a long-chain alkyl group and a fluorine compound, thereby preventing the uniform presence of the fluorine compound on the surface, resulting in an effect. Is considered to have been insufficient.

The present inventors attach a simulated fingerprint close to the actual fingerprint composition to a molding material having a glossy or transparent feeling under a certain condition, and then wipe it off. The color difference after wiping with reference to the pre-adhesion as a reference satisfies the specific relationship (formula (1) described later), and glossiness and fingerprint resistance, It was found that the fingerprint wiping property is excellent. This is due to the fact that the human eye recognizes fingerprints or smudges caused by fingerprints based on changes in glossiness and changes in color tone. This is because the change in taste is evaluated by the color difference of regular reflection removal, and it has been found that it is difficult to visually recognize the fingerprint in a range satisfying a specific relationship (formula (1) described later) obtained by integrating these values.

Further, the present inventors have focused on the behavior of the liquid when the liquid component of the fingerprint adheres to the surface of the molding material, and also found that the receding contact angle formed on the molding material by the liquid component has the above-mentioned preferable range. . Whether the fingerprint component is likely to stick between the finger or the molding material surface is governed by the receding contact angle between the fingerprint component and the finger or the molding material surface, and the receding contact angle of the surface layer of the molding material is This is because it has been found that the fingerprint component hardly adheres when exceeding a specific range.

In addition, it has been found that there is a preferable range for the relationship between the advancing contact angle and the receding contact angle of the fingerprint component of the surface layer of the molding material in order to achieve both glossiness and fingerprint resistance, in particular fingerprint wiping property. This is based on the fact that the fingerprint wiping property is governed by two factors: “easy transfer of the fingerprint component to the wiping material” and “easy mobility of the fingerprint component on the surface layer”. This is because the receding contact angle and the latter can be expressed by the advancing contact angle, and it has been found that if the specific relationship (formula (2) described later) is integrated, the attached fingerprint can be easily wiped off.

Furthermore, it has been found that the above physical properties can be obtained by setting the proportion of fluorine on the outermost surface of the surface layer of the molding material to the above-mentioned specific range. As a method for achieving this configuration, a specific fluorine compound (fluorine compound) It has also been found that it is effective to coat A) and a specific compound (compound B) in a mixed state without copolymerization.

In addition, the present inventors have found that the fingerprint resistance, in particular, the fingerprint wiping property can be further improved by making the surface satisfy a specific form (formula (3) and formula (4) described later). . This is because the fact that sebum adhering to the cloth when the fingerprint is wiped can be smoothly moved on the surface affects the wipeability of the fingerprint, and it has been found that this can be realized by reducing the contact area.

In addition, since the surface of the molding material is changed by rubbing with the cloth when wiping the fingerprint, the wiping property of the fingerprint deteriorates. Therefore, it is important to have durability against this change, that is, wiping durability. It has been found that the use of a fluorine compound A (II) having a specific number of reactive sites therein is effective in improving the wiping durability.

The molding material of the present invention has a surface layer on at least one surface, and the surface layer has a specific specular gloss and adheres a simulated fingerprint, then wipes off under certain conditions, and reflects the color before the simulated fingerprint is attached. The reflection color obtained after wiping off the simulated fingerprint was measured by the same method using two methods of specular reflection light inclusion and specular reflection light removal, and was obtained from the color difference obtained from the measurement. It is preferable to set the calculated value to a specific value or less.

The specular gloss shown here is a value obtained by measuring the 60 ° specular gloss specified in JIS Z8741: 1997, preferably 60% or more, more preferably 70% or more, and particularly preferably 80% 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 60 ° or more, more preferably 65 ° or more, and particularly preferably 70 ° or more. The measuring method and meaning of the receding contact angle will be described later. The receding contact angle has no problem when it is high. On the other hand, when the receding contact angle is lower than 60 °, the fingerprint component tends to adhere gradually and the fingerprint resistance may be lowered.

The surface layer was subjected to simulated fingerprint attachment and simulated fingerprint wiping under the following conditions, and the reflection of the specular reflection light after wiping the simulated fingerprint based on the state before the simulated fingerprint adhesion determined according to JIS Z8730: 2009 and JIS Z8722: 2009 Color difference ΔE ^* _ab (di: 8 °) Sb10W10 (hereinafter referred to as ΔE _SCI-2 ) and the color difference ΔE ^* _ab (de: 8 °) after removing the regular reflection light after wiping the simulated fingerprint based on the state before the dummy fingerprint is attached ) Sb10W10 (referred to as ΔE _SCE-2 ) preferably satisfies the following expression (1), that is, the value on the left side of expression (1) is 2.0 or less. If the value on the left side of Equation (1) is 0 or a positive value, there will be no problem if it is small. On the other hand, if this value is greater than 2.0, the fingerprint wiping property is insufficient, resulting in anti-fingerprint resistance. May decrease. From this viewpoint, the value on the left side of the formula (1) is more preferably 1.7 or less, and particularly preferably 1.5 or less.

((ΔE _SCI-2 ) ² + (ΔE _SCE-2 ) ² ) ^1/2 ≦ 2.0
... Formula (1)
Here, the conditions for simulated fingerprint attachment and simulated fingerprint wiping are as follows.
・ Simulated fingerprint adhesion conditions: A dispersion composed of 70% by mass of oleic acid and 30% by mass of silica particles having a number average particle diameter of 2 μm has a Ra defined by JIS B0601: 2001 of 3 μm and a rubber defined by JIS K6253: 1997. 1.0 g / m ^{2 is} adhered to a silicone rubber having a hardness of 50, and this is adhered to the target surface at a pressure of 30 KPa. The variation of Ra is allowed to be ± 1 μm, and the amount of the dispersion consisting 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 ± 0.1 g / m ² . Variation is acceptable. A specific simulated fingerprint attachment procedure will be described later.
Simulated fingerprint wiping conditions: The simulated fingerprint attached by the above method is rubbed three times with a nonwoven fabric at a pressure of 30 KPa and a speed of 5 cm / sec.

At this time, 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. The measuring method and meaning of the receding contact angle will be described later. On the other hand, there is no problem with a high receding contact angle. On the other hand, when the receding contact angle is lower than 50 °, the fingerprint component tends to adhere, and it may be difficult to satisfy the formula (1), and the fingerprint resistance may be lowered.

Furthermore, the advancing contact angle θ _a and receding contact angle θ _r of the oleic acid of the surface layer satisfy the following formula (2), that is, 15 ° or less, preferably 12 ° or less, more preferably 10 °. The following are particularly preferred: If the value of the formula (2) is 0 or a positive value, it is preferable for a small amount. On the other hand, if this value is larger than 15 °, the fingerprint wiping property is insufficient and the fingerprint resistance is lowered. There is.

(Θ _a −θ _r ) ≦ 15 ° Formula (2).

Here, the above-described backward contact angle and forward contact angle will be described. The contact angle of the liquid on the solid surface is essentially a thermodynamic quantity and should take a single value once the system is determined. However, when the liquid actually moves on the surface of the solid, the contact angle on the opposite side (retreat side) to the contact angle in the traveling direction often does not take the same value. The contact angle of the traveling method at this time is called a forward contact angle, and the contact angle on the opposite side is called a receding contact angle.

There are several methods for measuring the advancing contact angle and receding contact angle, but methods that are influenced by the drop mass in principle, such as the falling angle method, should be avoided. Here, the measurement by the expansion-contraction method will be described. The value of the advancing contact angle by the expansion-contraction method is that when a liquid (oleic acid) is applied on the surface layer to expand the droplet, the contact angle of the droplet is measured continuously several times, and the contact angle is constant. It is represented by the average value of where it became. Similarly, the receding contact angle value is determined by applying liquid (oleic acid) on the surface layer and gradually discharging the liquid to expand the droplet, and then drawing the droplet and contracting the droplet. The contact angle of the droplet is continuously measured a plurality of times, and is expressed as an average value when the contact angle becomes constant. Specifically, for example, when liquid is discharged and sucked between 1 and 50 μL (droplet expansion and contraction), the advancing contact angle is 1 μL to 50 μL at the time of liquid-liquid discharging, and the receding contact angle is 50 μL at the time of droplet suction. 1 to 1 μL, and can be determined by obtaining a value at which the contact angle of the droplet becomes substantially constant during the expansion or contraction process of the liquid. The contact angle in the expansion contraction method can be measured using, for example, Drop Master (manufactured by Kyowa Interface Science Co., Ltd.).

Further, as the elemental composition of the surface layer, the elemental composition at a photoelectron escape angle of 15 ° by X-ray photoelectron spectroscopy (XPS) of the surface layer preferably contains 50% or more of fluorine by atomic ratio, 55% The above is more preferable, and 60% or more is particularly preferable.

As the elemental composition of the surface layer, there is no problem with a large amount of fluorine from the viewpoint of durability, but since a skeleton for forming the layer is required, the upper limit is practically about 80%, Above that, reactive sites in the surface layer are likely to be damaged, and it may be difficult to obtain sufficient hardness.

Here, X-ray photoelectron spectroscopy refers to a method for analyzing the constituent elements of a sample and their electronic states by irradiating the sample surface with X-rays and measuring the energy of the resulting photoelectrons. By controlling, it is possible to know the elemental composition of the portion (˜10 nm or less) very close to the surface. In the present invention, in the elemental composition obtained by analysis at a photoelectron escape angle of 15 °, when the amount of fluorine is less than 50%, fingerprint adhesion and fingerprint wiping may be deteriorated. Elements other than fluorine are not particularly limited, but carbon, oxygen, silicon, and the like are preferably included from the relationship of constituting the compound.

Furthermore, as the surface form of the surface layer, the surface form observed by an atomic force microscope of the surface layer is a large concavo-convex structure that reduces the contact area of the surface and a fine structure that reduces the visibility of the attached fingerprint. It is preferable that an uneven structure coexists. Here, the coexistence of a large concavo-convex structure and a fine concavo-convex structure means a state in which a region having a large concavo-convex structure and a region having a fine concavo-convex structure are mixed. In addition, each region does not need to form a separate region, and may be in a state in which a fine concavo-convex structure is further present on a part or the entire surface of a large concavo-convex structure. Specifically, it is preferable that the ten-point average roughness Rz and the centerline average roughness Ra specified by JIS B0601: 2001 satisfy the following formulas (3) and (4).

4 nm <Rz ≦ 25 nm (3)
Ra ≦ 4 nm Formula (4)
That is, Rz is preferably more than 4 nm and 25 nm or less, more preferably 5 nm or more and 20 nm or less, and Ra is preferably 4 nm or less, more preferably 2 nm or less. Moreover, about Ra, 0.30 nm or more is more preferable, and 0.35 nm or more is further more preferable.

Here, the ten-point average roughness Rz is a value obtained by calculating the average of the top five values for the height of the convex portion and the depth of the concave portion of the concavo-convex structure on the surface, and taking the sum. This is a value that characterizes a large uneven structure existing at a low frequency. On the other hand, the center line average roughness Ra is a value that captures all of the in-plane uneven structures on the average. Therefore, Ra does not exceed Rz. Further, when Ra is larger than 4 nm, sufficient transparency of the molding material may not be obtained, and when Ra is smaller than 0.30 nm, the effect of introducing a fine uneven structure may not be obtained. . On the other hand, when Rz is smaller than 4 nm, the effect of reducing the contact area due to the surface form may not be obtained, and when Rz is larger than 25 nm, the value of the receding contact angle is small and sufficient. Fingerprint resistance may not be obtained.

Further, the surface layer is a fluorine compound A 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. And a compound B having a site containing an alkyl group having 8 or more carbon atoms and / or an alkanediyl group and a reactive site, and a binder component. Here, the fluorine compound A, the compound B, and the binder component are included not only when they are mixed in an unreacted state, but also, for example, the reactive site of the fluorine compound A, the compound B, and / or the binder. The case where a chemical bond is formed at a site where a part or all of the reactive sites among the components can react (hereinafter, the same applies to the molding material and the coating composition of the present invention). More preferably, the fluorine compound A, the compound B and the binder component are the main components of the surface layer. In the present specification, 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 compound B, and the binder component indicates 50% by mass or more. The details and preferable content ratios of the fluorine compound A, the compound B, and the binder component will be described later. The fluorine compound A is attached by increasing the contact angle of the liquid constituting the fingerprint by reducing the surface energy. The compound B acts as an auxiliary agent for allowing the fluorine compound A to be present at a high density on the surface, and the binder component immobilizes these components in the surface layer and binds to the base material. And has a role of imparting practically necessary scratch resistance.

The surface layer is a fluorine compound A 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. And a binder component, and a particle d (I) having a number average particle size of 5 nm to 20 nm and a particle d (II) having a number average particle size of 50 nm to 300 nm are preferable. Fluorine having 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, and 2 to 5 reactive sites in one molecule Compound A (II) and The binder component C (I), which is a compound having 10 or more reactive sites in the molecule and having a number average molecular weight of 1500 or more and 3000 or less, and having 3 or more and 6 or less reactive sites in the molecule as the binder component, the number average A binder component formed from a binder raw material C (II) which is a compound having a molecular weight of 500 or more and 1500 or less, and as a particle, a particle d (I) having a number average particle size of 5 nm to 20 nm and a number average particle size of 50 nm to 300 nm It is more preferable that the surface layer contains the particles d (II).

The details and preferred content ratios of the fluorine compound A and the fluorine compound A (II), the binder raw material C (I) and the binder raw material C (II), the particles d (I) and the particles d (II) will be described later. Each function is as follows. Fluorine compound A (II) is a compound in which the reactive sites are specified as 2 or more and 5 or less in fluorine compound A, and by selecting and using such a specific compound among fluorine compounds A, the cloth width is particularly determined during wiping. Thus, it is possible to further improve the wiping durability, which is the durability to the change in the surface of the molding material due to rubbing. In addition, the binder component formed from the binder raw material C (I) contributes particularly to the improvement of hardness, and the binder component formed from the binder raw material C (II) is particularly useful for fixing the fluorine compound A. Contribute. And by containing particle | grains d (I) and particle | grains d (II), the form of the specific surface represented by above-mentioned Formula (3) and Formula (4) is formed on the surface.

The coating composition of the present invention is a fluorine 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. It is preferable to contain the compound A, the compound B having a reactive site and a site containing an alkyl group having 8 or more carbon atoms and / or an alkanediyl group, and a binder raw material. Moreover, it is preferable that the fluorine compound A and the compound B are not couple | bonded in the form of a copolymer etc. in the state of a coating composition.

The coating composition of the present invention is a fluorine 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. It is preferable to contain the compound A, a binder raw material, a particle D (I) having a number average particle size of 5 nm to 20 nm, and a particle D (II) having a number average particle size of 50 nm to 300 nm. , 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, and a reactive site of 2 to 5 in one molecule With fluorine compound A (II) The binder raw material has 10 or more reactive sites in the molecule, the binder raw material C (I), which is a compound having a number average molecular weight of 1500 to 3000, and 3 to 6 reactive sites in the molecule. Binder raw material C (II) which is a compound having a molecular weight of 500 to 1500, particles D (I) having a number average particle size of 5 nm to 20 nm and particles D (II) having a number average particle size of 50 nm to 300 nm as particles It is more preferable to contain. The function of each component is as described for the molding material (in this case, d (I) is read as D (I) and d (II) is read as D (II)).

Details of the fluorine compound A and the fluorine compound A (II), the binder raw material C (I) and the binder raw material C (II), the particles D (I) and the particles D (II), and preferred ratios thereof will be described later.

[Molding material and surface layer]
The molding material of the present invention may be any of a flat shape (film, sheet, plate) and three-dimensional shape (molded product) as long as it has the characteristics of the present invention and / or a surface layer containing the material. Here, the surface layer in the present invention refers to a portion and an elemental composition that are directed from the surface of the molding material in the thickness direction (in the case of a planar shape) or in the internal direction (in the case of a three-dimensional shape) and adjacent in the thickness direction or the internal direction. The shape and physical properties of inclusions (particles, etc.) can be distinguished by having a discontinuous boundary surface, and indicate a portion having a finite thickness. More specifically, cross-sectional observation of the molding material in the thickness direction from the surface using various composition / element analyzers (IR, XPS, XRF, EDAX, SIMS, etc.), electron microscope (transmission type, scanning type) or optical microscope Are distinguished by the discontinuous boundary surface.

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

The thickness of the surface layer is not particularly limited, but is preferably 1 nm or more and 100 μm or less, more preferably 5 nm or more and 50 μm or less, and the thickness can be selected according to the other functions described above.

[Coating composition]
The coating composition of the present invention is a liquid composition at room temperature that can form the “surface layer” on the surface of the molding material by a general coating process including coating, drying, and curing, and a process such as vapor deposition. It preferably contains fluorine compound A, compound B, binder raw material C, and particles D, and may further contain various additives such as a solvent, a photopolymerization initiator, a curing agent, and a catalyst. Details of the fluorine compound A, the compound B, the binder raw material C, and the particles D will be described later.

[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, both of which are mainly composed of fluorine atoms and carbon atoms, and there may be branching in the structure. A plurality of linked dimers, trimers, oligomers, and polymer structures may be formed.

Also, 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. Can be mentioned. Of these, vinyl, allyl, alkoxysilyl, silyl ether or silanol, epoxy, and acryloyl (methacryloyl) groups are preferred from the viewpoints of reactivity and handling, and vinyl, allyl, and acryloyl (methacryloyl) are preferred. ) Group is more preferable, and acryloyl (methacryloyl) group is particularly preferable. Further, in order to achieve both the effect of reducing the surface energy and the wiping durability, which is the durability against changes in the surface of the molding material due to being rubbed by the cloth during wiping, in particular, fluorine having 2 to 5 of the reactive sites described above. Particular preference is given to applying compound A (II). 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 chemical formula (1).

R ^f1 -R ² -D ¹ ... Chemical 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 D ¹ represents a reactive site in the ester structure, urethane structure, ether structure, and triazine structure).

Examples of the compound of the chemical 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-per Fluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethylacrylate 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-perf Orodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5 -Methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoro Heptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluo And robutyl methacrylate, triacryloyl-heptadecafluorononenyl-pentaerythritol, and the like.

In addition, there is a preferable material for the fluorine compound A, one of which has a plurality of fluoroalkyl groups as the R ^f1 part and a plurality of acryloyl (methacryloyl) groups at the D ¹ part in the chemical formula (1), R ² is a so-called fluorine-containing dendrimer having a multi-branched structure, and the other is a fluoro group consisting of a fluorooxyalkyl group and a fluorooxyalkanediyl group as R ^f1 moiety in the chemical formula (1). It is a material having a so-called fluoropolyether moiety having a polyether moiety, an alkanediyl group at the R ² moiety, and an acryloyl (methacryloyl) group at the D ¹ moiety.

Here, the fluorine-containing dendrimer refers to a dendrimer containing a group such as a fluoroalkyl group or fluorooxyalkyl, a fluoroalkenyl group, a fluoroalkanediyl group, or a fluorooxyalkanediyl group. Dendrimers include, for example, Hawker, et. al. J. et al. Chem. Soc. , Chem. Commun. 1990, (15), 1010-1013. , D. A. Tomalia, et. al. Angew. Chem. Int. Ed. Engl. 29, 138-175 (1990). J. et al. M.M. J. et al. Frechet, Science, 263, 1710. (1994), Masaaki Enomoto; Kagaku, Vol. 50, p. 608 (1995), etc., is a general term for branched polymers having regular dendritic branches, and such molecules are ordered from the center of the molecule. For example, D.M. A. Tomalia, et. al. Angew. Chem. Int. Ed. Engl. 29, 138-175 (1990). As described in (1), due to the extreme steric crowding of the branched ends that occurs as the molecular weight increases, a spherical molecular form comes to be taken.

The weight average molecular weight (hereinafter abbreviated as Mw) of the fluorine-containing dendrimer is preferably 1000-200000, more preferably 2000-100000, and most preferably 5000-60000 in terms of polystyrene by gel permeation chromatography (GPC).

The fluoropolyether moiety is a moiety comprising a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, etc., and has a structure represented by chemical formulas (2) and (3).
_{_{CF n1 H (3-n1)}} - (CF n2 H (2-n2)) k O- (CF n3 H (2-n3)) m O-
... Chemical formula (2)
_{_{- (CF n4 H (2-}} n4)) p O- (CF n5 H (2-n5)) s O- ··· formula (3)
Here, n1 is an integer of 1 to 3, n2 to n5 are integers of 1 or 2, k, m, p, and s are integers of 0 or more, and p + s is 1 or more. Preferably, n1 is 2 or more, n2 to n5 are integers of 1 or 2, more preferably n1 is 3, n2 and n4 are 2, and n3 and n5 are integers of 1 or 2.

There is a preferred range for the chain length of this fluoropolyether moiety, preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and particularly preferably 6 or more and 8 or less. When the number of carbon atoms is 3 or less, the surface energy is not sufficiently reduced, so that the oil repellency may be lowered. When the carbon number is 13 or more, the solubility in a solvent is lowered, so that the quality of the coating film may be lowered.

The fluorine compound A may have a plurality of fluoropolyether moieties per molecule.
Examples of commercially available fluorine compound A include RS-75 (DIC Corporation), OPTOOL DSX, OPTOOL DAC (Daikin Industries, Ltd.), C10GACRY, C8HGOL (Oil Products), and the like. These products can be used.

[Compound B]
Compound B refers to a compound having a reactive site and a site containing an alkyl group having 8 or more carbon atoms and / or an alkanediyl group. The reactive site is as described in the section of the fluorine compound A.

An example of compound B is a compound represented by the following chemical formula (4).
R ¹⁰ -R ¹¹ -D ¹² ... Chemical formula (4)
(R ¹⁰ is a site containing an alkyl group having 8 or more carbon atoms and / or an alkanediyl group, R ¹¹ is an alkanediyl group, an alkanetriyl group, and an ester structure, urethane structure, ether structure, triazine derived therefrom) In the structure, D ¹² represents a reactive site).

Specifically, the compound B represented by the chemical formula (4) is preferably a (meth) acrylate monomer, oligomer, alkoxysilane, alkoxysilane hydrolyzate, alkoxysilane oligomer, or the like, and more preferably an acrylate monomer.

Examples of acrylate monomers include acrylates having one or more (meth) acryloyloxy groups in one molecule, and specific examples include isobornyl (meth) acrylate, (iso) stearyl (meth) acrylate, and lauryl. (Meth) acrylate, (iso) decyl (meth) acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate, 2-methyl-1,8 octanediol di (meth) acrylate, tetradecyl (meth) acrylate, cetyl (meth) ) Acrylate, 1,10 decanediol di (meth) acrylate, 1,9 nonanediol di (meth) acrylate, dimethylolcyclodecane di (meth) acrylate, and the like. These monomers can be used alone or in combination of two or more.

In addition, “(meth) acrylate” represents acrylate and methacrylate, and “(meth) acryloyloxy group” represents acryloyloxy group and methacryloyloxy group generically. (The same applies to the case where “(meth) acryl ...” is contained in the compound in addition to the above).

In addition, commercially available (meth) acrylate monomers include Shin-Nakamura Chemical Co., Ltd. (trade name “NK Ester” series, etc.), Toagosei Co., Ltd. (“Aronix” (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd. (Product name: “light acrylate”, “light ester” series, etc. can be mentioned, and these products can be used.

[Binder component, Binder raw material]
The binder raw material is a compound contained in the coating composition, and is a raw material for the binder component present in the surface layer formed by applying, drying, and curing the coating composition. That is, the binder raw material contained in the surface layer after the binder raw material contained in the coating composition of the present invention is cured by heat or ionizing radiation is referred to as a binder component. Some binder materials may exist in the surface layer in the same state as in the coating composition (may be left unreacted), and even in that case, the material in the surface layer is the binder component. That's it.

The binder raw material in the coating composition is not particularly limited, but is preferably a binder raw material that can be cured by heat and / or active energy rays from the viewpoint of manufacturability. One type of binder raw material in the coating composition may be used, or two or more types may be mixed and used.

In the present invention, from the viewpoint of retaining the fluorine compound A and the compound B in the surface layer, the monomer having an alkoxy group, silanol group, reactive double bond, and functional group capable of ring-opening reaction in the molecule. The oligomer is preferably a binder raw material. 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.

Further, as a more preferable binder raw material, a binder raw material C (I) which is a compound having 10 or more reactive sites in the molecule and having a number average molecular weight of 1500 to 3000 and 3 to 6 reactive sites in the molecule. And binder raw material C (II) which is a compound having a number average molecular weight of 500 or more and 1500 or less, and it is preferable to form a binder component using either or both of these as raw materials.

When the binder raw material C (I) is added to form the binder component, there is an effect of improving the hardness of the surface layer of the molding material obtained thereby. The molecular weight and reactive site of the binder raw material C (I) are preferably sufficiently large. On the other hand, when the molecular weight is too large, the solubility is lowered and the constituent components such as the fluorine compound A and the particles D are dispersed. In some cases, the transparency and smoothness of the surface of the molding material may be impaired. Therefore, the binder raw material C (I) is preferably a compound having 10 or more reactive sites in the molecule and a molecular weight of 1500 or more and 3000 or less.

When the binder raw material C (II) is added to form a binder component, the surface layer of the molding material obtained thereby is preferable because the dispersion of the fluorine compound A is preferable. It is particularly preferable that it is formed from a mixed system containing the binder raw material C (II) in addition to the raw material C (I). The binder raw material C (II) is preferable because it has an effect of improving the dispersion of the fluorine compound A in the surface layer as described above. The binder raw material C (II) has a reactive site number close to that of the fluorine material and preferably has a smaller molecular weight. However, the binder raw material C (II) has a molecular weight that can maintain the hardness of the molding material and the number of crosslinks. A compound having a reactive site and a molecular weight of 500 or more is preferable. On the other hand, when the molecular weight is greater than 1500 or the number of reaction sites is more than 7, the fluidity is impaired, the fluorine compound A cannot be dispersed in the surface layer, and the effect of reducing the surface energy is sufficiently obtained. It may not be possible.

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 three or more (meth) acryloyloxy groups in one molecule and modified polymers thereof. Specific examples include pentaerythritol tri (meth) acrylate and 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 and the like can be used. These monomers can be used alone or in combination of two or more.

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.), NOF Corporation; (“Blemmer” (registered trademark) series, etc.), Nippon Kayaku Co., Ltd .; (trade name “KAYARAD” (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd .; Light ester "series and the like), and these products can be used.

[Particle component, particle D, particle d]
It is preferable that the layer which the molding material of this invention has, and a coating composition contain a particle component. Here, the particles may be either inorganic particles or organic particles, but inorganic particles are preferred from the viewpoint of durability.

Here, “inorganic particles” include those subjected to surface treatment. This surface treatment means introducing a compound onto the particle surface by chemical bonds (including covalent bonds, hydrogen bonds, ionic bonds, van der Waals bonds, hydrophobic bonds, etc.) and adsorption (including physical adsorption and chemical adsorption). Even if the compound introduced by the surface treatment is an organic compound, it is an inorganic particle if the underlying particle is an inorganic particle.

The type of inorganic particles contained is preferably 1 or more and 20 or less. As for the kind of inorganic particle, 1 type or more and 10 types or less are further more preferable, and 2 or more types and 4 types or less are especially preferable. Here, the kind of inorganic particles is determined by the kind of elements constituting the inorganic particles, and when any surface treatment is performed, it is decided 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 of titanium oxide is substituted with nitrogen as an anion, the elements constituting the inorganic particles are different, Suppose that they are 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. And

Further, the particles contained in the coating composition of the present invention are contained in the surface layer in a form in which the surface state is changed by heat, ionizing radiation or the like in the treatment such as coating, drying, curing treatment or vapor deposition. In some cases. Therefore, the particle component present in the coating composition of the present invention is the particles D (I) or D (II), and the coating layer is applied to the surface layer formed by a treatment such as coating, drying, curing or vapor deposition. The existing particle component is referred to as particle d (I) or d (II). Note that some of the particles d (I) or d (II) present in the surface layer may exist in the same state as in the coating composition even in the surface layer (when they remain unreacted). In this case, the particles in the surface layer are expressed as particles d.

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 semimetal 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 preferably 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 .SnO ₂ ). Particularly preferred is silica (SiO ₂ ).

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 obtained by bonding particles between particles by interposing metal ions having a valence of 2 or more, preferably 3 or more, more preferably 5 or 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 linked and / or branched silica 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 form of the present invention, it is particularly preferable that the above-described chain silica is subjected to a surface treatment necessary for stable dispersion in a good solvent as a binder raw material. For example, when an acrylic monomer or oligomer is used as the binder raw material, the surface treatment requires an alkyl group, alkenyl group, vinyl group, (meth) acryl group or the like having a carbon number of 1 to 5 or less on the surface. It is preferably introduced.

Further, the molding material of the present invention preferably contains two types of particles d (I) and particles d (II). Similarly, the coating composition contains two types of particles D (I) and particles D (II). Is preferred. For particle d (I) or particle D (I) and particle d (II) or particle D (II), there is a particularly preferred number average particle size, respectively. The particles d (I) or the particles D (I) are components that contribute to the fingerprint resistance. The fine particles are dispersed on the surface to provide an effect of making the fingerprints less noticeable. The number average particle diameter of the particles d (I) or the particles D (I) is preferably 5 nm or more and 20 nm or less. If the number average particle diameter is smaller than 5 nm, the above-described effect of making the fingerprint inconspicuous may not be sufficiently obtained. If it is larger than 20 nm, the transparency of the molding material may be impaired.

On the other hand, the particle d (II) or the particle D (II) is a component that contributes to the fingerprint wiping property. By reducing the surface frictional resistance during wiping, the surface layer is prevented from being deteriorated and the wiping property is improved. effective. The number average particle diameter of the particles d (II) or the particles D (II) is preferably 50 nm or more and 300 nm or less. When the number average particle diameter is smaller than 50 nm, the above-described friction reducing effect may not be sufficiently obtained. If it is large, the concavo-convex structure formed thereby may trigger the value of the aforementioned receding contact angle.

Here, the number average particle diameter of the inorganic particles means the number-based arithmetic average length diameter described in JIS Z8819-2: 2001, and both the particles d in the molding material and the particles D in the coating composition are scanning electrons. A primary particle is observed using a microscope (SEM), a transmission electron microscope, etc., and the diameter of the circumscribed circle of each primary particle is defined as an equivalent particle diameter, and is a value obtained from the number-based average value. 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]
The coating composition of the present invention may contain a solvent. As a kind of solvent, 1 type or more and 20 types or less are preferable, More preferably, they are 1 type or more and 10 types or less, More preferably, they are 1 type or more and 6 types or less. Here, the “solvent” refers to a substance that is liquid at room temperature and normal pressure, which can evaporate almost the entire amount in the drying step after coating.

Here, the type of solvent is determined by the molecular structure constituting the solvent. That is, the same elemental composition and the same type and number of functional groups have different bond relationships (structural isomers), which are not structural isomers, but what conformations are in three-dimensional space Those that do not overlap exactly even if they are removed (stereoisomers) are treated as different types of solvents. For example, 2-propanol and n-propanol are handled as different solvents.

[Other additives]
The coating composition of the present invention preferably further contains a photopolymerization initiator, a thermal polymerization initiator, a curing agent, and a catalyst.

A photopolymerization initiator, a thermal polymerization initiator, a curing agent, and a catalyst are used for promoting the reaction between the binder raw materials, and further between the binder raw material, the fluorine compound A, and the compound B. As the photopolymerization initiator, thermal polymerization initiator, curing agent and catalyst, 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 photopolymerization initiators, thermal polymerization 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 thermal polymerization initiators include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, and amine compounds. From the viewpoint of curability, alkylphenone compounds are preferable. Examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- (4-phenyl) -1-butane, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4 Morpholinyl) phenyl] -1-butane, 1-cyclohexyl-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 photopolymerization initiator, the thermal polymerization initiator, the curing agent, and the catalyst is preferably 0.001 to 30 parts by mass, more preferably 100 parts by mass with respect to a total of 100 parts by mass of the binder raw material in the coating composition. Is 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.

The coating composition of the present invention may further contain additives such as surfactants, thickeners and leveling agents as necessary.

[Content of each component in the coating composition]
Although the coating composition of this invention contains the fluorine compound A, the compound B, the binder raw material C, and the particle | grains D, each mass relationship in a coating composition is demonstrated. Here, the binder raw material C indicates the total of the binder raw material C (I) and the binder raw material C (II), and the particle D indicates the total of the particle D (I) and the particle D (II).

In 100% by mass of the coating composition of the present invention, the fluorine compound A is 0.025% by mass to 7% by mass, and when the compound B is contained, 0.2% by mass to 55% by mass and the binder raw material C is 0%. 8% by mass or more and 66% by mass or less, and when particles D are contained, 0.1% to 35% by mass, the solvent is 30% by mass to 95% by mass, the initiator, the curing agent, and other components of the catalyst. 0.025 mass% or more and 7 mass% or less are illustrated preferably. More preferably, the fluorine compound A is 0.05 mass% to 6 mass%, the compound B is 0.4 mass% to 36 mass%, the binder raw material C is 3.2 mass% to 56 mass%, and the solvent is 40 mass% or more and 90 mass% or less, and other components of a photoinitiator, a thermal polymerization initiator, a hardening | curing agent, and a catalyst are 0.05 mass% or more and 6 mass% or less.

[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, Although a glass plate, a plastic film, a plastic sheet, a plastic lens, a metal plate etc. are mentioned, it is not limited to these.

Examples of using plastic films and plastic sheets as supporting substrates include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (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 Polyether sulfone, polyarylate, polyetherimide, but such as polymethyl methacrylate and polyether ketones, in particular triacetyl cellulose Among these, polycarbonates, polyethylene terephthalate and polyethylene naphthalate are preferred.

The surface of the support substrate can be subjected to various surface treatments before forming the surface layer. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, 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 vapor phase treatment such as vapor deposition, sputtering, CVD, liquid phase treatment such as coating, impregnation, plating, saponification, solid phase treatment such as transfer, bonding, It may be formed on the surface of the molding material by a combination of these treatments, but a vapor phase treatment by vapor deposition and a liquid phase treatment by coating are preferred, and a liquid formed by coating a coating composition on a supporting 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 the surface layer by coating on a material or the like. Further, among these coating methods, the gravure coating method or the die coating method is more preferable as the coating method. The manufacturing method of the coating composition applied to these coating methods will be described later.

Next, the liquid film coated on the support substrate is dried. In addition to completely removing the solvent from the molding material to be obtained, it is preferable to involve heating of the liquid film in the drying step from the viewpoint of promoting movement of the fluorine compound A in the liquid film to the surface.

Examples of drying methods include heat transfer drying (adherence to high-temperature objects), convection heat transfer (hot air), radiant heat transfer (infrared rays), and others (microwave, induction heating). 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.

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 preferable range, and is preferably 10 g · m ⁻² · s ⁻¹ or less, 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 fluorine compound A is oriented along with the evaporation of the remaining solvent during the rate of drying. Since this process requires time for orientation, there is a preferred range for the film surface temperature increase rate during the decreasing drying period, preferably 5 ° C./second or less, preferably 1 ° C./second or less. More preferably.

Furthermore, a further curing operation (curing process) may be performed by irradiating heat or energy rays. In the curing step, when cured with heat, the temperature is preferably from room temperature to 200 ° C, more preferably from 100 ° C to 200 ° C from the viewpoint of the activation energy of the curing reaction, and from 130 ° C to 200 ° C. More preferably.

In addition, when curing with energy rays, electron beams (EB rays) and / or ultraviolet rays (UV rays) are preferable from the viewpoint of versatility. 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, durability, and alkali resistance (saponification 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. When UV curing is performed using a high-pressure mercury lamp which is a discharge lamp method, UV irradiation is performed under the condition that the illuminance of UV is 100 to 3000 mW / cm ² , preferably 200 to 2000 mW / cm ² , more preferably 300 to 1500 mW / cm ^2. preferably performing, integrated light quantity of 100 ~ 3000mJ / cm ² of ultraviolet rays, preferably 200 ~ 2000mJ / cm ^2, more preferably it is more preferable to carry out ultraviolet irradiation under the condition that the 300 ~ 1500mJ / cm ^2. 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]
The coating composition of the present invention is obtained by mixing a solvent and other additives (particle dispersion such as an initiator, a curing agent, a catalyst, etc.) in addition to the fluorine compound A, the compound B and the 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 rotation speed necessary for sufficient mixing of the entire liquid, and the local shear rate in the liquid is 10 ⁴ S. It is preferably in a range smaller than ⁻¹ and having a Reynolds number of 1000 or more.

The obtained coating composition may be subjected to an appropriate filtration treatment before coating. The appropriate filtration treatment is more preferably performed by selecting a solvent, a binder raw material, a filter material matched to the polarity of the additive, and a filter opening and filtering.

Next, the present invention will be described based on examples, but the present invention is not necessarily limited thereto.

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

[Fluorine compound A2]
As the fluorine compound A2, a compound containing a fluoropolyether moiety (“Megafac” manufactured by RS-75 DIC Corporation) was used.

[Fluorine compound A3]
As the fluorine compound A3, a compound containing a fluoropolyether moiety (“OPTOOL” DAC manufactured by Daikin Industries, Ltd.) was used.

[Fluorine compound A4]
A fluorine-containing dendrimer was used as the fluorine compound A4. The synthesis method is as follows.
A 200 mL reaction flask was charged with 32 g of toluene, and nitrogen was introduced for 5 minutes while stirring, and the mixture was heated until the internal temperature was refluxed (temperature 110 ° C. or higher). In another 100 mL reaction flask, 4.0 g (20 mmol) of ethylene glycol dimethacrylate (EGDMA), 8.6 g (20 mmol) of 2- (perfluorohexyl) ethyl methacrylate C, dimethyl 2,2-azobisisobutyrate (MAIB) 2. 3 g (10 mmol) and 32 g of toluene were charged, and nitrogen was introduced for 5 minutes while stirring, followed by nitrogen substitution, and cooling to 0 ° C. in an ice bath.

The contents were added dropwise from the 100 mL reaction flask charged with EGDMA, C6FM and MAIB into the refluxed toluene in the 200 mL reaction flask using a dropping pump over 30 minutes. After completion of dropping, the mixture was aged for 1 hour.

Next, this reaction solution was added to 277 g of hexane / toluene (mass ratio 4: 1) to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure, redissolved using 36 g of THF, and a THF solution of this polymer was added to 277 g of hexane to reprecipitate the polymer in a slurry state. The slurry was filtered under reduced pressure and dried under reduced pressure to obtain a white powder of fluorine compound A4. The weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained fluorine compound A4 was 16000, and the dispersity Mw / Mn was 1.8.

[Fluorine compound A5]
As the fluorine compound A5, a bifunctional acrylate compound containing a fluorotetraethylene glycol moiety (FPTMG-A manufactured by Yushi Co., Ltd.) was used. This fluorine compound A5 corresponds to fluorine compound A (II).

[Fluorine compound A6]
A compound containing a fluoroalkyl moiety (triacryloyl-heptadecafluorononenyl-pentaerythritol manufactured by Kyoeisha Chemical Co., Ltd.) was used as the fluorine compound A6. This fluorine compound A6 corresponds to fluorine compound A (II).

[Fluorine compound A7]
A compound containing a fluoroalkyl moiety (pentaacryloyl-heptadecafluorononenyl-dipentaerythritol manufactured by Kyoeisha Chemical Co., Ltd.) was used as the fluorine compound A7. This fluorine compound A7 corresponds to fluorine compound A (II).

[Fluorine compound A8]
As the fluorine compound A8, a compound containing a fluoropolyether moiety (MA-78 Miwon Specialty Chemical Co., Ltd.) was used. This fluorine compound A8 corresponds to fluorine compound A (II).

[Fluorine compound A9]
A compound containing a fluoropolyether moiety (X-7366, manufactured by Nikka Chemical Co., Ltd.) was used as the fluorine compound A9.

[Fluorine compound A10]
As the fluorine compound A10, a compound containing a fluoropolyether part (MF-12 Miwon Specialty Chemical Co., Ltd.) was used. This fluorine compound A10 corresponds to fluorine compound A (II).

[Compound B]
[Compound B1]
Isodecyl acrylate (SR395 Sartomer Japan, Inc.) was used as compound B1.

[Compound B2]
As compound B2, stearyl acrylate (SR257 Sartomer Japan, Inc.) was used.

[Compound B3]
As compound B3, 1,9 nonanediol diacrylate (A-NOD-N manufactured by Shin-Nakamura Chemical Co., Ltd.) was used.

[Compound B4]
As compound B4, isoamyl acrylate ("light acrylate" IAA manufactured by Kyoeisha Chemical Co., Ltd.) was used.

[Compound B5]
As compound B5, isooctyl acrylate ("Miramer" M1084 by Miwon Specialty Chemical Co. Ltd) was used.

[Binder raw material C]
[Binder raw material C1]
Dipentaerythritol hexaacrylate (“KAYARAD” DPHA manufactured by Nippon Kayaku Co., Ltd.) was used as the binder material C1. This binder raw material C1 corresponds to binder raw material C (II).

[Binder raw material C2]
Pentaerythritol triacrylate (“KAYARAD” PET30 manufactured by Nippon Kayaku Co., Ltd.) was used as the binder material C2.

[Binder raw material C3]
As the binder raw material C3, urethane acrylate oligomer (“UNIDIC” 17-806 manufactured by DIC Corporation) was used.

[Binder raw material C4]
Urethane acrylate oligomer ("KRM" 8655 manufactured by Daicel-Cytec Co., Ltd.) was used as the binder material C4. This binder raw material C4 corresponds to the binder raw material C (I).

[Binder raw material C5]
A urethane acrylate oligomer (“KRM” 8200 manufactured by Daicel-Cytec Co., Ltd.) was used as the binder material C5. This binder raw material C5 corresponds to the binder raw material C (II).

[Binder raw material C6]
As the binder material C6, a polyester acrylate oligomer (“EBECRYL” 1830 manufactured by Daicel-Cytec Co., Ltd.) was used. This binder raw material C6 corresponds to binder raw material C (II).

[Binder raw material C7]
As the binder material C7, urethane acrylate oligomer (“KRM” 8452 manufactured by Daicel Cytec Co., Ltd.) was used.

[Binder raw material C8]
Urethane acrylate oligomer (“Art Resin” UN-904, manufactured by Negami Kogyo Co., Ltd.) was used as the binder material C8.

[Binder raw material C9]
As the binder material C9, urethane acrylate oligomer (“KRM” 8804 manufactured by Daicel Cytec Co., Ltd.) was used.

[Binder raw material C10]
As the binder raw material C10, pentaerythritol tetraacrylate (“EBECRYL” 180 manufactured by Daicel Cytec Co., Ltd.) was used.

[Binder raw material C11]
As the binder material C11, a polyester acrylate oligomer (“EBECRYL” 884 manufactured by Daicel Cytec Co., Ltd.) was used.

[Particle component]
[Particle D1]
As particles D1, organosilica sol (MEK-ST-UP manufactured by Nissan Chemical Industries, Ltd.) was used. The present particle D1 corresponds to the particle D (I).

[Particle D2]
As particles D2, organosilica sol (MEK-ST-2040, manufactured by Nissan Chemical Industries, Ltd.) was used. The present particle D2 corresponds to the particle D (II).

[Particle D3]
Organosilica sol (OSCAL JGC Catalysts & Chemicals Co., Ltd. solid content concentration 5%) was used as the particles D3. The present particle D3 corresponds to the particle D (I).

[Particle D4]
As particles D4, organosilica sol (MIBK-SD manufactured by Nissan Chemical Industries, Ltd.) was used. The present particle D4 corresponds to the particle D (I).

[Particle D5]
Silica particles (High Presica SP 300 nm, manufactured by Ube Nitto Kasei Co., Ltd.) were used as the particles D5. The present particle D5 corresponds to the particle D (II).

[Particle D6]
As particles D6, organosilica sol (MIBK-SD-L manufactured by Nissan Chemical Industries, Ltd.) was used. The present particle D6 corresponds to the particle D (II).

[Particle D7]
Silica particles (High Presica SP 600 nm, manufactured by Ube Nitto Kasei Co., Ltd.) were used as the particles D7.

[Preparation of paint composition]
[Coating composition 1] The following materials were mixed to obtain a coating composition 1.
Fluorine compound A: Fluorine compound A1 0.64 parts by mass Compound B: Compound B1 5.8 parts by mass Binder raw material: Binder raw material C1 13.5 parts by mass Solvent: MIBK 79.6 parts by mass Other additives (photopolymerization initiator) :
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by BASF)
0.5 parts by weight.

[Coating compositions 2 to 12, 30 and 31] As shown in Table 1, with respect to the coating composition 1, the fluorine compound A1 is the fluorine compounds A2 to A6, the compound B1 is the compounds B2 to B5, and the binder raw material C1 is Coating compositions 2 to 12 and coating compositions 30 and 31 were obtained in the same manner except that the binder raw materials C2 and 3 were replaced.

[Coating composition 13] A coating composition 13 was obtained by mixing the following materials.
Fluorine compound A: Fluorine compound A2 0.64 parts by mass Binder raw material C: binder raw material C1 19.3 parts by mass Particle D (I): Particle D1 49.8 parts by mass Particle D (II): Particle D2 0.5 parts by mass Solvent: MEK 29.3 parts by mass Other additives (photopolymerization initiator):
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by BASF)
0.5 parts by weight.

[Coating composition 14] A coating composition 14 was obtained by mixing the following materials.
Fluorine compound A: Fluorine compound A2 0.03 parts by mass Binder raw material C: Binder raw material C1 8.77 parts by mass Particle D (I): Particle D3 70.5 parts by mass Particle D (II): Particle D2 0.2 parts by mass Solvent: MEK 20.0 parts by mass Other additives (photopolymerization initiator):
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by BASF)
0.5 parts by weight.

[Coating composition 15] A coating composition 15 was obtained by mixing the following materials.
Fluorine compound A: Fluorine compound A2 0.64 parts by mass Binder raw material C: Binder raw material C1 19.3 parts by mass Particle D (I): Particle D4 33.2 parts by mass Particle D (II): Particle D2 0.5 parts by mass Solvent: MIBK 45.9 parts by mass Other additives (photopolymerization initiator):
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by BASF)
0.5 parts by weight.

[Coating composition 16] A coating composition 16 was obtained by mixing the following materials.
Fluorine compound A: Fluorine compound A2 0.64 parts by mass Binder raw material C: binder raw material C1 19.3 parts by mass Particle D (I): Particle D1 49.8 parts by mass Solvent: MEK 29.8 parts by mass Other additives (light Polymerization initiator):
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by BASF)
0.5 parts by weight.

[Coating composition 17] A coating composition 17 was obtained by mixing the following materials.
Fluorine compound A: Fluorine compound A2 0.64 parts by mass Binder raw material C: binder raw material C1 19.3 parts by mass Particle D (I): Particle D1 49.8 parts by mass Particle D (II): Particle D5 0.2 parts by mass Solvent: MEK 29.6 parts by mass Other additives (photopolymerization initiator):
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by BASF)
0.5 parts by weight.

[Coating composition 18] A coating composition 17 was obtained by mixing the following materials.
Fluorine compound A: Fluorine compound A2 0.64 parts by mass Binder raw material C: Binder raw material C1 19.3 parts by mass Particle D (I): Particle D1 49.8 parts by mass Particle D (II): Particle D6 0.6 part by mass Solvent: MEK 29.2 parts by mass Other additives (photopolymerization initiator):
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by BASF)
0.5 parts by weight.

[Coating composition 19] A coating composition 19 was obtained by mixing the following materials.
Fluorine compound A: Fluorine compound A7 0.64 parts by mass Binder raw material C (I):
Binder raw material C4 14.5 parts by mass Binder raw material C (II):
Binder raw material C5 4.8 parts by mass Particle D (I): Particle D1 49.8 parts by mass Particle D (II): Particle D5 0.2 parts by mass Solvent: MEK 29.6 parts by mass Other additives (photopolymerization initiator) ):
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by BASF)
0.5 parts by weight.

[Coating compositions 20 to 29] As shown in Table 1, with respect to the coating composition 13, except that fluorine compound A7 was replaced with fluorine compounds A8 to A10, and binder raw materials C4 and C5 were replaced with binder raw materials C6 to C11. Similarly, coating compositions 20 to 28 were obtained.

[Coating composition 32] The following materials were mixed to obtain a coating composition 13.
Fluorine compound A: Fluorine compound A2 0.64 parts by mass Binder raw material C: binder raw material C1 19.3 parts by mass Particle D (I): Particle D1 49.8 parts by mass Particle D (II): Particle D2 0.5 parts by mass Solvent: MEK 29.3 parts by mass Other additives (photopolymerization initiator):
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 manufactured by BASF)
0.5 parts by weight.

[Production of molding material]
“Lumirror” (registered trademark) U46 (manufactured by Toray Industries, Inc.) in which an easy-adhesive paint was applied on a PET resin film was used as a supporting substrate. Using the continuous coating apparatus having a small-diameter gravure coater under the condition of a conveyance speed of 10 m / min, the coating compositions 1 to 14 were subjected to the number of gravure lines and the gravure roll speed ratio so that the solid coating thickness was 2 μm. The coating was adjusted. The conditions of the wind hitting the liquid film from coating to drying and curing are as follows.

1st drying process ventilation temperature and humidity: Temperature: 45 degreeC,
Relative humidity: 10%
Wind speed: coating side: 5m / sec,
Anti-coating surface side: 5 m / sec Wind direction: Coating surface side: Parallel to the surface of the substrate,
Anti-coating surface side: Vertical residence time with respect to the surface of the substrate: 1 minute.

2nd drying process ventilation temperature and humidity: Temperature: 100 degreeC,
Relative humidity: 1%
Wind speed: coating side: 5m / sec,
Anti-coating surface side: 5 m / sec. Wind direction: Coating surface side: perpendicular to the surface of the substrate,
Anti-coating surface side: Vertical residence time with respect to the surface of the substrate: 1 minute Photocuring 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 / humidity.
The molding materials of Examples 1 to 29 and Comparative Examples 1 to 3 were prepared by the above method.

[Evaluation of molding materials]
About the produced molding material, the following performance evaluation was implemented and the obtained result is shown in Table 2. 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 ° specular gloss]
The glossiness of the target surface of the molding material is determined by measuring the 60 ° specular glossiness according to JIS Z 8741: 1997 using a VG7000 manufactured by Nippon Denshoku Industries Co., Ltd. did.

[Oleic acid advancing contact angle, receding contact angle]
The advancing contact angle and receding contact angle were measured by the expansion-contraction method, and using the contact angle meter Drop Master DM-501 manufactured by Kyowa Interface Science, the expansion-contraction method measurement manual of the same apparatus was used. Specifically, the advancing contact angle is obtained by continuously discharging oleic acid (manufactured by Nacalai Standard No. 1 Nacalai Tesque) from a syringe to a final liquid volume of 50 μL at a liquid discharge speed of 8.5 μL / sec. Images were taken 30 times per second, and the respective contact angles were determined from the images using the integrated analysis software “FAMAS” attached to the apparatus. The contact angle during the expansion process of the droplet first changes with expansion and then shows a behavior that becomes almost constant. Therefore, when the contact angle data is arranged in the order of measurement and five consecutive points are selected in that order, five consecutive points are selected. The average value when the standard deviation of the first became 1 ° or less was defined as the advancing contact angle of the measurement, this measurement was performed five times for one sample, and the average value was defined as the advancing contact angle of the sample.

With respect to the receding contact angle, droplets are continuously sucked at an initial droplet amount of 50 μL and a liquid discharge speed of 8.5 μL / second, the shape of the shrinking process of the droplet is photographed, and each contact angle is set in the same manner. Asked. 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 °.

[Measurement of surface elemental composition by X-ray photoelectron spectroscopy]
The elemental composition of the surface was measured with the following equipment and conditions, and the ratio of the number of fluorine atoms among the detected elements was determined.
Equipment: Quantera SXM (PHI)
Excitation X-ray: monochromic Al Kα1,2 ray (1486.6 eV)
X-ray diameter: 200 μm
Photoelectron escape angle: 15 °.

[10-point average roughness Rz, centerline average roughness Ra by atomic force microscope]
The surface structure was measured under the following apparatus and conditions, and the 10-point average roughness Rz and the centerline average roughness Ra defined by JIS B0601: 2001 were determined.
Apparatus: Nanoscope IIIa (manufactured by Digital Instruments)
Measurement mode: Tapping mode Scanning range: 5 μm × 5 μm
Resolution: 512 × 512 pixels.

[Simulated fingerprint attachment method]
The adhesion of the simulated fingerprint to the target surface of the molding material of the present invention is as follows. 1. Preparation of simulated fingerprint liquid 2. Production of simulated fingerprint sheet 3. Transfer of simulated fingerprint liquid to silicone rubber. The simulation fingerprinting was performed in four steps: attachment to the surface of the molding material.
1. Preparation of simulated fingerprint liquid The following materials were weighed at the following ratios, and then stirred for 30 minutes with a magnetic stirrer.
Oleic acid 14 parts by mass Silica particles (number average particle diameter 2 μm) 6 parts by mass Isopropyl alcohol 80 parts by mass The number average particle diameter of the silica particles is 5% by mass in solid content in the dispersion medium (isopropyl alcohol). It is a value obtained in the same manner as in the above method except that the observation sample was prepared by mixing the mixture at, and dispersing with ultrasonic waves, and dropping it onto the conductive tape.
2. Preparation of Simulated Fingerprint Sheet A wire bar (#) on “Lumirror” (registered trademark) U46 (manufactured by Toray Industries, Inc.), in which an easy-adhesive paint is coated on a PET resin film using the fingerprint coating solution as a supporting substrate. 7) and dried at 50 ° C. for 2 minutes.
3. Transfer of Simulated Fingerprint to Silicone Rubber A silicone rubber having a rubber hardness of 50 of JIS K6253: 1997 was polished with # 250 water-resistant paper to a surface roughness of JIS B0601: 2001 to Ra = 3 μm. Next, the silicone rubber polished with the water-resistant paper was pressed against the simulated fingerprint sheet prepared in item 2 at 30 KPa. The adhesion amount (g / m ² ) of the simulated fingerprint liquid to the silicone rubber refers to 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 0.9 g / m ^2. It was 1.1 g / m ² or more.
4). 2. Adhesion of simulated fingerprint on the surface of molding material The silicone rubber onto 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.

[Simulated wipe method for simulated fingerprints]
A molding material in which a simulated fingerprint is adhered to the target surface by the above method is fixed on a flat plate, and a cellulose long fiber nonwoven fabric gauze (“Hize” gauze NT-) having a folded size of 12.5 × 12.5 cm is fixed thereon. (4 manufactured by Kawamoto Sangyo Co., Ltd.) was placed, a weight was placed thereon, a pressure of 30 KPa was applied, and it was wiped by reciprocating 10 cm three times at a speed of 5 cm / sec.

[Color difference between specular reflection light removal and specular reflection light removal before and after simulated fingerprint wiping]
A black vinyl tape is pasted on the opposite side of the target surface of the molding material, and the reflection color before and after wiping off the above-mentioned simulated fingerprint is measured using a spectral colorimeter CM-3600A manufactured by Konica Minolta Co., Ltd. Based on Z8722: 2009, the reflection color for specular reflection removal is a 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 CIE 1976 (L ^* a ^* b ^* ) described in JIS Z8730: 2009.
Further, from the reflection color after the dummy fingerprint is wiped off by the calculation method described in JIS Z8730: 2009 from the reflection color after the dummy fingerprint is wiped off (ΔE ^* _ab (di: 8 °)) Sb10W10) and (ΔE ^* _ab (de: 8 °) Sb10W10) were determined, and the former was designated as ΔE _SCI-2 and the latter as ΔE _SCE-2 .

[Fingerprint resistance (fingerprint adhesion)]
The anti-fingerprint property was placed on a black drawing paper with the evaluation surface of the molding material facing up, rubbed the finger (index finger) and thumb for pressing the fingerprint three times, and then slowly pressed and adhered to the surface of the surface layer. The visibility of the fingerprint was evaluated according to the following evaluation criteria, and 5 points or more were regarded as acceptable.
10 points: The fingerprint is not visually recognized or the difference from the non-attached part is not recognized. 7 points: The fingerprint is hardly visible or not recognized as the fingerprint. 5 points: The fingerprint is slightly visible, but hardly noticed. Points: Fingerprints are visually recognized. 1 point: The above evaluations were performed on 10 subjects who were clearly aware of fingerprints and were very worrisome, and the average value was obtained. The numbers after the decimal point were rounded off.

[Fingerprint resistance (fingerprint wiping)]
After attaching the fingerprint by the above-mentioned method, then, using a cellulose long-fiber nonwoven fabric gauze (“Hize” gauze NT-4 manufactured by Kawamoto Sangyo Co., Ltd.) with a folded size of 12.5 × 12.5 cm, it is wiped off. went. Fingerprint wiping property evaluated the visibility after wiping with this wiping method on the following evaluation criteria, and made 5 points or more acceptable.
10 points: When wiped once, it becomes almost unrecognizable. 7 points: When wiped once, it becomes almost unnoticeable. 5 points: When wiped three times, it becomes almost unrecognizable. 1 point: The above evaluation was performed on 10 subjects who remained dirty even after wiping 5 times or more, and the average value was obtained. The numbers after the decimal point were rounded off.

[Wipe durability]
The above-mentioned method after rubbing the surface of the molding material 100 times continuously using a cellulose long fiber nonwoven fabric gauze (“Hize” gauze NT-4 manufactured by Kawamoto Sangyo Co., Ltd.) having a folded dimension of 12.5 × 12.5 cm A fingerprint was attached. The visibility of the attached fingerprint was evaluated according to the following evaluation criteria, and 5 points or more were regarded as acceptable.
10 points: The fingerprint is not visually recognized or the difference from the non-attached part is not recognized. 7 points: The fingerprint is hardly visible or not recognized as the fingerprint. 5 points: The fingerprint is slightly visible, but hardly noticed. Points: Fingerprints are visually recognized. 1 point: The above evaluations were performed on 10 subjects who were clearly aware of fingerprints and were very worrisome, and the average value was obtained. The numbers after the decimal point were rounded off.

Table 1 summarizes the composition of the coating composition, and Table 2 summarizes 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 2, the examples of the present invention pass both glossiness and fingerprint resistance, and achieve the problems to be solved by the present invention.

Examples 8 and 10 in which the value of θa-θr in formula (2) deviates from the preferred range of the present invention, the value of θa-θr in formula (2), and the structure of compound B are within the preferred range of the present invention. Example 11 which deviates from the above was slightly inferior in fingerprint resistance, but was in an acceptable range.

The molding material, the coating composition, and the method for producing the molding material according to the present invention can be suitably used for imparting fingerprint resistance, as well as various plastic molded articles, lenses on the outermost surface portion of the camera, and glasses. It can also be used to impart similar functions to the surfaces of lenses, window glass of buildings and vehicles, and various printed materials.

Claims

A molding material having a surface layer on at least one surface,
A molding material in which the surface layer has a 60 ° specular gloss specified by JIS Z8741: 1997 of 60% or more and a receding contact angle θ r of oleic acid of 60 ° or more.
A molding material having a surface layer on at least one surface,
The 60 ° specular gloss specified by JIS Z8741: 1997 of the surface layer is 60% or more,
When the surface fingerprint is subjected to simulated fingerprint attachment and simulated fingerprint wiping under the following conditions, the specular reflection light after wiping the simulated fingerprint based on the state before the simulated fingerprint adhesion obtained in accordance with JIS Z8730: 2009 and JIS Z8722: 2009 Color difference ΔE * ab (di: 8 °) Sb10W10 (hereinafter referred to as ΔE SCI-2 ) and the color difference ΔE * ab (de: 8 °) A molding material in which Sb10W10 (hereinafter referred to as ΔE SCE-2 ) satisfies the range of the following formula (1).
((ΔE SCI-2 ) 2 + (ΔE SCE-2 ) 2 ) 1/2 ≦ 2.0
... Formula (1)
・ Simulated fingerprint adhesion conditions: A dispersion composed of 70% by mass of oleic acid and 30% by mass of silica particles having a number average particle diameter of 2 μm has a Ra defined by JIS B0601: 2001 of 3 μm and a rubber defined by JIS K6253: 1997. 1.0 g / m 2 is adhered to a silicone rubber having a hardness of 50, and this is adhered to the target surface at a pressure of 30 KPa.
Simulated fingerprint wiping conditions: The simulated fingerprint attached by the above method is rubbed three times with a nonwoven fabric at a pressure of 30 KPa and a speed of 5 cm / sec.
The molding material of Claim 2 whose receding contact angle (theta) r of the oleic acid of the said surface layer is 50 degrees or more.
The molding material in any one of Claim 1 to 3 with which the advancing contact angle (theta) a and receding contact angle (theta) r of the oleic acid of the said surface layer satisfy | fills following formula (2).
(Θ a −θ r ) ≦ 15 ° Formula (2)
5. The element composition obtained by analyzing the surface layer by X-ray photoelectron spectroscopy (XPS) at a photoelectron escape angle of 15 °, wherein the proportion of fluorine is 50% or more by atomic ratio. Molding material according to crab.
In the form of the surface of the surface layer observed with an atomic force microscope, the ten-point average roughness Rz and the centerline average roughness Ra specified by JIS B0601: 2001 satisfy the following formulas (3) and (4). The molding material according to any one of claims 1 to 5.
4 nm <Rz ≦ 25 nm (3)
Ra ≦ 4 nm Formula (4)
The molding material according to any one of claims 1 to 5, wherein the surface layer contains the following 1) to 3).
1) Fluorine compound A 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
2) Compound B having a site containing an alkyl group having 8 or more carbon atoms and / or an alkanediyl group and a reactive site
3) Binder component
The molding material in any one of Claim 1 to 6 in which the said surface layer contains the following 1) to 3).
1) Fluorine compound A 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
2) Binder component 3) Particle component comprising particle d (I) having a number average particle diameter of 5 nm to 20 nm and particle d (II) having a number average particle diameter of 50 nm to 300 nm
The molding material according to claim 8, wherein the surface layer contains the following 1) to 3).
1) 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, and a reactive site of 2 to 5 in one molecule Fluorine compound A (II) having
2) The binder raw material C (I), which is a compound having 10 or more reactive sites in the molecule and a number average molecular weight of 1500 to 3000, and a reactive site of 3 to 6 in the molecule, and having a number average molecular weight of 500 Binder component formed from binder raw material C (II) which is a compound of 1500 or less and 3 or less 3) Particle d (I) having a number average particle size of 5 nm or more and 20 nm or less and Particle d (II) having a number average particle size of 50 nm or more and 300 nm or less Particle component consisting of
The coating composition containing the following 1) to 3).
1) Fluorine compound A 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
2) Compound B having a site containing an alkyl group having 8 or more carbon atoms and / or an alkanediyl group and a reactive site
3) Binder raw material
The coating composition containing the following 1) to 3).
1) Fluorine compound A 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
2) Binder raw material 3) Particle component consisting of particles D (I) having a number average particle diameter of 5 nm to 20 nm and particles D (II) having a number average particle diameter of 50 nm to 300 nm
The coating composition according to claim 11, comprising the following 1) to 3).
1) 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, and a reactive site of 2 to 5 in one molecule Fluorine compound A (II) having
2) The binder raw material C (I), which is a compound having 10 or more reactive sites in the molecule and a number average molecular weight of 1500 to 3000, and a reactive site of 3 to 6 in the molecule, and having a number average molecular weight of 500 Binder raw material consisting of binder raw material C (II) which is a compound of 1500 or less 3) It consists of particles D (I) having a number average particle diameter of 5 nm to 20 nm and particles D (II) having a number average particle diameter of 50 nm to 300 nm. Particle component
The manufacturing method of the molding material which coats the coating composition in any one of Claim 10 to 12 on the surface.