KR102061920B1 - Molding material, coating composition, and method for manufacturing molding material - Google Patents

Abstract

The problem to be solved by the present invention is to provide a molding material in which fingerprints are hardly visible while maintaining glossiness or transparency, a coating composition capable of forming a surface layer expressing the above effects, and a method of producing the molding material. The molding material of the present invention is a molding material having a surface layer on at least one side thereof, the 60 ° mirror glossiness defined in JIS Z8741: 1997 of the surface layer is 60% or more, and the receding contact angle (θ _r ) of oleic acid is 60 ° or more. to be.

Description

Molding material, coating composition and manufacturing method of molding material {MOLDING MATERIAL, COATING COMPOSITION, AND METHOD FOR MANUFACTURING MOLDING MATERIAL}

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

Fingerprints (fingerprints refer to patterns formed by raised lines (ridges) of the openings of the sweat glands in the skin of the fingertips, and marks on the surface of the object) due to human fingers touching the surface of the object. If it is attached and cannot be wiped off easily, there is a problem that it gives an unpleasant impression that the appearance is dirty. In recent years, electronic devices operated by a finger, such as a smart phone touch panel, a keyboard, a remote control of a television air conditioner, etc., are increasing. For example, there is a problem that fingerprints are attached by the housing of the cellular phone, and the fingerprints stand out and the cleanliness is impaired.

In addition, when fingerprints are attached to image display units, signal display units such as warning lamps, surfaces of lenses and mirrors, and the like, unclearness in the display image, display signals, reflections, or parts to which fingerprints are attached. There exists a problem that visibility is reduced by the difference in reflectance of a site | part. For example, smartphone, television, car navigation system, LCD screen of personal computer, signal indicator for guidance, warning, evacuation guidance, lens of glasses, sunglasses telescope, camera, transparent cover of clockface, rearview mirror of car Room mirrors; Once the fingerprint is attached to the device, the visibility of the object is reduced by the fingerprint.

In recent years, in various displays such as smartphones, televisions, and personal computer monitors, glossy anti-reflective members (anti reflection films) are used on the surface to show high contrast of images. Fingerprint becomes easy to be visualized, and has become a subject.

For such a problem, the fingerprint on the surface of the article has a characteristic that is hard to stand out, a property that is hard to be seen, or a property that is difficult to see, or that can easily wipe off the attached fingerprint (the above-mentioned physical property is referred to as fingerprinting). As a characteristic of the member, Patent Literature 1 discloses, on one surface of a substrate, a low refractive index layer having a refractive index of less than 1.75 at a wavelength of 550 nm of light, a high refractive index layer having a refractive index of at least 1.75 of a wavelength of 550 nm of light, or both. Forming an oleic acid having a dry film thickness of 20 μm on the surface of the thin film layer, the optical thin film coated with the oleic acid and the optical thin film not coated with the oleic acid. Color difference (ΔE ^* _ab ) (= {(ΔL ^* ) ² + (Δa ^* ) of CIELAB (according to JIS Z 8729) in D65 light source, 5 ° incidence, 2 ° field of view, specular reflection ² + (Δb ^* ) ² } ^1/2 ) is 5 or less.

Moreover, as a characteristic which shows the ease of wiping of a fingerprint, patent document 2 says "the initial glossiness measurement process which measures the glossiness of 75 degree-20 degree to the film formed on the to-be-coated object using a glossmeter, and makes it initial glossiness, said A process of attaching a fingerprint evaluation solution to attach the fingerprint evaluation solution to the film, a gloss measurement process before wiping to measure the mirror glossiness of the portion to which the fingerprint evaluation solution is attached, and a fingerprint evaluation solution to wipe off the attached fingerprint evaluation solution A wiping step, a wiping glossiness measurement step for measuring the mirror glossiness after wiping the anti-fingerprint liquid, and a calculated step of treating the obtained evaluation value by the following equation to obtain an adhesion evaluation rate and an evaluation rate after wiping off

Adhesion evaluation rate (%) = (glossiness before wiping) / (initial glossiness) x 100

Evaluation rate after wiping (%) = (gloss after wiping) / (initial gloss) x 100

Containing an anti-fingerprint evaluation method ”.

Moreover, as physical properties of a member having anti-fingerprint, Patent Document 3 discloses that "the base, the optical functional layer formed on the base material, and the optical functional layer are formed on the surface, and the element ratio of the surface is silicon element (Si) and carbon element (C). ) Has a ratio (Si / C) of 0.25 to 1.0, F / C, which is a ratio of fluorine element (F) and carbon element (C), is 0.10 to 1.0, and has an antifouling layer having the following characteristics. Optical function film:

a. The floating paraffin contact angle is above 65 ° and the floating paraffin drop angle is below 15 °

b. Black Magic contact angle is over 35 °, Black Magic Tumble angle is under 15 °

c. Dynamic friction coefficient of less than 0.15 ".

In addition, as an element structure of a member having anti-fingerprint, Patent Document 4 discloses that "a hard coating layer is provided on at least one surface on a transparent base material, and the hard coating layer is located at the outermost surface, and the hard coating layer is fluorine. The presence rate of the fluorine atom: oxygen atom: carbon atom on the surface of the hard coat layer including the compound and / or the silicon-based compound and measured by an X-ray photoelectron spectroscopy device is 20 atomic% or more and less than 50 atomic%: 20 Atomic% or more and less than 30 atomic%: The range of 30 atomic% or more and less than 60 atomic%, the abundance of silicon is in the range of 0 atomic% or more and less than 10 atomic%, and the surface free energy calculated from the surface contact angle is Hard coating film which exists in the range of 15 mN / m or more and 20 mN / m or less "is proposed.

Moreover, as a material structure which provides anti-fingerprint, Patent Document 5 describes, "At least one vinyl monomer (A) selected from a vinyl monomer (a1) having an alkyl group having 6 to 22 carbon atoms and an aromatic vinyl monomer (a2) and A copolymer (I) obtained by polymerizing a polymerization component containing a vinyl monomer (B) having 5 to 13 fluorine atoms in a molecule in a weight ratio of (A) :( B) = 90 to 99.9: 0.1 to 10. Anti-fingerprint enhancer characterized by including the above.

Japanese Patent Publication No. 2009-122416 Japanese Patent Laid-Open No. 2011-99744 International Publication No. 2008/038714 Japanese Patent Laid-Open No. 2011-043606 Japanese Patent Laid-Open No. 2010-24283

As a result of the present inventors confirming the visibility of a fingerprint on the technique of patent document 1 and the patent document 2 in various conditions, it was not enough to make a fingerprint stand out or to wipe a fingerprint only by satisfying such a characteristic.

The technique of Patent Document 3 focuses on the floating paraffin contact angle and tumble angle. As a result of the present inventors confirming with respect to various surface layers, the contact angle, tumble angle and visibility of fingerprints and wiping are not necessarily identical, and the scope of Patent Document 3 It could be seen that even if it satisfies, sufficient fingerprints cannot be obtained.

As a result of the present inventors confirming the technique of patent documents 4 and 5, the effect is limited and it is inadequate especially when a fingerprint with many sebums is attached.

The problem to be solved by the present invention is to provide a molding material, a moldable coating composition, and a method for producing the molding material that are excellent in anti-fingerprint, in particular fingerprint wiping, while maintaining glossiness or transparency and scratch resistance practically necessary.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors earnestly researched and completed the following invention. That is, this invention is as follows.

[1] a molding material having a surface layer on at least one side thereof,

A molding material having a 60 ° mirror glossiness defined in JIS Z8741: 1997 of the surface layer 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 side thereof,

60 degree mirror glossiness prescribed | regulated to JIS Z8741: 1997 of the said surface layer is 60% or more,

Color difference with specular reflection after the simulated fingerprint wiping based on the state before the simulated fingerprint adhesion obtained in accordance with JIS Z8730: 2009 and JIS Z8722: 2009 when the surface layer is subjected to the simulation fingerprint wiping and the simulation fingerprint wiping under the following conditions. (ΔE ^* _ab ) (di: 8 °) Sb10W10 (hereinafter referred to as ΔE _{SCI- 2} ), and color difference (ΔE ^* _ab ) of specular light removal after simulated fingerprint wiping based on the state prior to mock fingerprint attachment (de: 8 °) A molding material in which Sb10W10 (hereinafter referred to as ΔE _{SCE -2} ) satisfies the range of the following equation (1).

<Equation (1)>

((ΔE _{SCI -2} ) ² + (ΔE _{SCE -2} ) ² ) ^1/2 ≤2.0

Conditions for Simulated Fingerprinting: A dispersion containing 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 of 3 μm defined in JIS B0601: 2001, and is specified in JIS K6253: 1997. 1.0 g / m <^{2> is made to} adhere to the silicone rubber of rubber hardness 50 to make it, and this is made to adhere to the surface made into the target at the pressure of 30 KPa.

Conditions for Wiping a Fingerprint: The simulated fingerprint attached by the above method is rubbed with a nonwoven fabric three times at a pressure of 30 KPa and a speed of 5 cm / sec.

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

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

<Equation (2)>

(θ _a -θ _r ) ≤15 °

[5] The above-mentioned [1] to [4], wherein the proportion of fluorine is 50% or more by the atomic ratio in the elemental composition obtained by analysis at the photoelectron escape angle of 15 ° by X-ray photoelectron spectroscopy (XPS) of the surface layer. The molding material according to any one of claims.

[6] In the form of the surface observed with an atomic force microscope of the surface layer, the ten-point average roughness Rz and the centerline average roughness Ra prescribed by JIS B0601: 2001 are represented by the following formulas (3) and ( The molding material as described in any one of said [1]-[5] which satisfy | fills 4).

<Equation (3)>

4nm <Rz≤25nm

<Equation (4)>

Ra≤4nm

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

1) A fluorine compound A having a site and a reactive site including 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 and a reactive site containing an alkyl group and / or alkanediyl group having 8 or more carbon atoms

3) binder components

[8] The molding material according to any one of [1] to [6], in which the surface layer contains the following 1) to 3).

1) A fluorine compound A having a site and a reactive site including 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 components

3) Particle component comprising particle d (I) having a number average particle diameter of 5 nm or more and 20 nm or less and particle d (II) having a number average particle diameter of 50 nm or more and 300 nm or less

[9] The molding material according to the above [8], wherein the surface layer contains the following 1) to 3).

1) at least 2 and at most 5 reactive in a moiety and at least one moiety comprising 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 Fluorine compound A (II) having a site

2) Binder raw material C (I) which is a compound which has 10 or more reactive site | part in a molecule | numerator, and is a compound of number average molecular weights 1500 or more and 3000 or less, and a compound which has 3 or more and 6 or less reactive site | parts in a molecule, and has a number average molecular weight 500 or more and 1500 or less Binder component formed from phosphorus binder raw material C (II)

3) Particle component comprising particle d (I) having a number average particle diameter of 5 nm or more and 20 nm or less and particle d (II) having a number average particle diameter of 50 nm or more and 300 nm or less

[10] A coating composition containing the following 1) to 3).

1) A fluorine compound A having a site and a reactive site including 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 and a reactive site containing an alkyl group and / or alkanediyl group having 8 or more carbon atoms

3) binder raw material

[11] A coating composition containing the following 1) to 3).

1) A fluorine compound A having a site and a reactive site including 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 comprising particle D (I) having a number average particle diameter of 5 nm or more and 20 nm or less and particle D (II) having a number average particle diameter of 50 nm or more and 300 nm or less

[12] The coating composition according to the above [11], which contains the following 1) to 3).

1) at least 2 and at most 5 reactive in a moiety and at least one moiety comprising 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 Fluorine compound A (II) having a site

2) Binder raw material C (I) which is a compound which has 10 or more reactive site | part in a molecule | numerator, and is a compound of number average molecular weights 1500 or more and 3000 or less, and a compound which has 3 or more and 6 or less reactive site | parts in a molecule, and has a number average molecular weight 500 or more and 1500 or less Binder raw material containing phosphorus binder raw material C (II)

3) Particle component comprising particle D (I) having a number average particle diameter of 5 nm or more and 20 nm or less and particle D (II) having a number average particle diameter of 50 nm or more and 300 nm or less

[13] A method for producing a molding material, wherein the coating composition according to any one of [10] to [12] is coated on a surface.

According to the present invention, it is possible to obtain a molding material which is hard to be recognized by fingerprints while maintaining glossiness, transparency and scratch resistance practically necessary, a molding material which is easy to wipe off, a coating composition capable of forming a surface layer expressing the effect, and a method of producing the surface layer. have.

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

First, regarding the mechanism of visual recognition of a fingerprint, in the patent document 1, since oleic acid is apply | coated and color difference is evaluated only by specular reflection of the single incident light before and behind application | coating, there exists a problem in the point which cannot actually reproduce the state which human visually recognizes, In addition, although the technique of patent document 2 evaluates adhesiveness and wiping property by the change of glossiness, since the evaluation by glossiness only sees the influence of the light scattering by adhesion, the change of the color feeling by adhesion can be evaluated. There seems to be insufficient correspondence with visibility.

Subsequently, as the simulated fingerprint liquid used for evaluation of visibility, 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 applied to the sweat supplied from the skin of the finger. In addition to water, organic salts (such as urate), and sebum (oleic acid, etc.) included, so-called dust, particles, etc. contained in cosmetics (photo, titanium oxide, zinc oxide, silica, etc.) present in the living environment As a dispersion, it is thought that the influence of the light scattering by the presence of particle was not able to be evaluated by the method of patent documents 1, 2.

Next, regarding the fingerprint attachment mechanism, the technique of Patent Literature 3 uses the contact angle and tumble angle of the fingerprint-adhesive liquid paraffin as described above, and the former sees the dynamic behavior of liquid components such as fingerprint adhesion and wiping. There is a problem in that it is impossible, and the latter is a parameter indicating the dynamic behavior of the droplets, and it is thought that the dynamic behavior of very small components such as fingerprints could not be represented because it is greatly influenced by the mass of the droplets from the principle of the measurement method. .

Next, regarding the constituent elements of the surface layer, the technique of Patent Literature 4 defines the abundance of fluorine atoms: oxygen atoms: carbon atoms on the surface of the hard coating layer. In order to make it easy to fall off, since it is thought that it is important that a oil repellent component, ie, a fluorine component selectively exists in a surface layer, it is thought that it was insufficient in the range prescribed | regulated by this patent document 4.

In addition, regarding the material which comprises a surface layer, since the technique of patent document 5 uses the copolymer of a long-chain alkyl group and a fluorine compound, it interrupted uniform presence of the fluorine compound on the surface, and as a result, the effect was inadequate. I think.

MEANS TO SOLVE THE PROBLEM The present inventors apply the simulated fingerprint close | similar to actual fingerprint composition to a molding material which has glossiness or transparency under constant conditions, and continues wiping, and reflects the reflection color after wiping before and after attachment of a specular reflection light and a specular reflection light removal. Measured by two methods, it was found that the color difference after wiping on the basis of the attachment before satisfying a specific relationship (Equation (1) to be described later) was excellent in glossiness and fingerprinting, in particular, fingerprint wiping. This is based on the fact that the human eye perceives fingerprints or contamination caused by fingerprints according to the change in the glossiness and the change in the color, so that the change in the glossiness is the color difference including the specular reflection and the color difference is the color difference in the specular removal. This is because it has been found that it is difficult to visually recognize the fingerprint in a range that satisfies a specific relationship (Equation (1) described later) in which these values are integrated.

In addition, the inventors have focused on the liquid behavior when the liquid component of the fingerprint adheres to the molding material surface, and have also found that the above-mentioned preferred range of the receding contact angle that the liquid component makes on the molding material. This is governed by the receding contact angle between the fingerprint component and the finger or the molding material surface, which fingerprint component is likely to stick to between the finger and the molding material surface, so that the fingerprint when the receding contact angle of the surface layer of the molding material exceeds a certain range. It is because it discovered that a component was difficult to adhere.

In addition, in order to achieve both glossiness and anti-fingerprint, in particular fingerprint wiping, it was found that there is a preferable range in the relationship between the forward contact angle and the receding contact angle of the fingerprint component of the surface layer of the molding material. This is based on the fact that fingerprint wiping is governed by two factors: "ease of transfer of fingerprint components to the wiping material of fingerprint components" and "ease of movement of fingerprint components on the surface layer", and the former is used as the retracting contact angle and the latter as the forward contact angle. This is because it has been found that the attached fingerprints can be easily wiped off if the specific relationship (the equation (2) described later) that incorporates them is satisfied.

In addition, it is found that the above-described physical properties are obtained by setting the fluorine ratio of the outermost surface of the surface layer of the molding material to the specific range described above, and as a method of achieving this configuration, a specific fluorine compound (fluorine compound A) and a specific compound (compound B) It was also found that coating without mixing the copolymer) was effective.

In addition, the inventors have found that by satisfying the specific shape (Equations (3) and (4) described later), the fingerprinting property, in particular, the fingerprint wiping property can be made better. This is because it has been found that the smoothness of the surface between the gun gun and the attached sebum when wiping the fingerprint affects the wiping property of the fingerprint, and this can be achieved by reducing the contact area.

In addition, it is important to have durability against this change, i.e., wipe durability, because the wiping property of the fingerprint is deteriorated by rubbing by the gun gun when wiping the fingerprint, thereby changing the surface of the molding material. It has been found that using fluorine compound A (II) having a reactive site is effective for improving wiping durability.

The molding material of the present invention has a surface layer on at least one surface, the surface layer has a specific gloss glossiness, and a mock fingerprint is attached, followed by wiping under constant conditions, so that the reflected color before the mock fingerprint is included with specular reflection light. It is preferable to measure by the same method the reflection color obtained after wiping a mock fingerprint based on this by measuring with two methods of a specular reflection removal, and to make the calculated value obtained from the color difference calculated | required from it below below a specific value.

As for the mirror glossiness shown here, as a value by the measurement of the 60 degree mirror glossiness prescribed | regulated to JISZ8741: 1997, 60% or more is preferable, 70% or more is more preferable, 80% or more is especially preferable. If the mirror glossiness is less than 60%, the glossiness may be felt to be insufficient.

Moreover, it is preferable that the receding contact angle (theta) _r of oleic acid of the said surface layer is 60 degrees or more, 65 degrees or more are more preferable, 70 degrees or more are especially preferable. The measuring method and meaning of the receding contact angle will be described later. The receding contact angle does not have a problem of being high, while if it is lower than 60 °, the fingerprint component tends to be gradually attached, and the fingerprinting property may be lowered.

Color difference including ΔE after the simulated fingerprint wiping on the surface layer based on the condition before the simulated fingerprint adhesion obtained by applying the simulated fingerprint and the simulated fingerprint wiping under the conditions described below to JIS Z8730: 2009 and JIS Z8722: 2009. _{^{* ab) (di: 8 °}} ) Sb10W10 ( ΔE after _{SCI -2} &quot;) color difference (ΔE ^* _ab between the simulated fingerprint attached regularly reflected light removal after wiping off the fingerprint by simulating a state before) (de: 8 °) Sb10W10 (called ΔE _{SCE -2} ) satisfies the following Equation (1), that is, the value on the left side of Equation (1) is preferably 2.0 or less. If the value on the left side of Equation (1) is 0 or a positive value, there is no problem in that the value is smaller. On the other hand, when this value is larger than 2.0, the wiping property of the fingerprint may be insufficient, resulting in deterioration of fingerprinting. From this viewpoint, it is more preferable that the value of the left side of Formula (1) is 1.7 or less, and 1.5 or less are especially preferable.

<Equation (1)>

((ΔE _{SCI -2} ) ² + (ΔE _{SCE -2} ) ² ) ^1/2 ≤2.0

Here, the conditions for applying a simulated fingerprint and wiping a simulated fingerprint are as follows.

Conditions for Simulated Fingerprinting: A dispersion containing 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 of 3 μm defined in JIS B0601: 2001, and is specified in JIS K6253: 1997. 1.0 g / m <^{2> is made to} adhere to the silicone rubber of rubber hardness 50 to make it, and this is made to adhere to the surface made into the target at the pressure of 30 KPa. In addition, Ra can tolerate fluctuation of ± 1 μm, and the adhesion amount on the surface of the silicone rubber of the dispersion containing 70 mass% of oleic acid and 30 mass% of silica having a number average particle diameter of 2 μm is ± 0.1 g / m ^2. Variation of can be tolerated. The procedure of a specific simulation fingerprint application is mentioned later.

Conditions for Wiping a Fingerprint: The simulated fingerprint attached by the above method is rubbed with a nonwoven fabric three times at a pressure of 30 KPa and a speed of 5 cm / sec.

At this time, it is preferable that the receding contact angle (theta) _r of oleic acid of the said surface layer is 50 degrees or more, 60 degrees or more are more preferable, 70 degrees or more are especially preferable. The measuring method and meaning of the receding contact angle will be described later. The receding contact angle does not have a problem of being high, while if it is lower than 50 °, the fingerprint component easily adheres, and it is difficult to satisfy the above formula (1), and the fingerprinting property may be lowered.

Further, it is preferable that the forward contact angle θ _a and the receding contact angle θ _r of the oleic acid of the surface layer satisfy the following Equation (2), that is, 15 ° or less, more preferably 12 ° or less, 10 ° or less is particularly preferred. If the value of the formula (2) is 0 or a positive value, it is preferable to be small. On the other hand, if the value is larger than 15 °, the wiping property of the fingerprint is insufficient, and thus the fingerprinting property may be lowered.

<Equation (2)>

(θ _a -θ _r ) ≤15 °

Here, the above-mentioned receding contact angle and forward contact angle will be described. The liquid contact angle of the solid surface is originally a thermodynamic amount and will take one value once the system is established. In reality, however, when the liquid moves on the solid surface, the contact angles on the opposite side (retreat side) and the contact angles in the advancing direction often do not take the same value. The contact angle of the advancing 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 measurement methods for the values of forward and receding contact angles, but methods that are affected by droplet mass in principle, such as the drop angle method, should be avoided. Here, the measurement by the expansion-contraction method will be described. The value of the forward contact angle by the expansion-contraction method is expressed as an average value where the contact angle is constant by measuring the contact angle of the droplet continuously several times when applying liquid (oleic acid) on the surface layer to expand the droplet. Similarly, the value of the receding contact angle is given to the liquid layer (oleic acid) on the surface layer, and the liquid is gradually discharged to expand the droplet, and then the contact angle of the droplet is continuously measured a plurality of times in the process of sucking the droplet and shrinking the droplet. It is expressed as the average value where the contact angle becomes constant. Specifically, for example, in the case of discharging-aspirating (expanding and contracting liquid droplets) between 1 and 50 µL, the forward contact angle is from 1 µL to 50 µL at the time of liquid ejection, and the receding contact angle is from 50 µL to 1 µL at the time of droplet aspiration. This can be determined by measuring at intervals of 1 μL and determining where the contact angle of the droplets has become substantially constant during the expansion or contraction of the liquid. The measurement of the contact angle in the expansion and contraction method can be measured using, for example, Drop Master (manufactured by Kyowa Kaimen Kagaku Co., Ltd.).

Further, as the elemental composition of the surface layer, it is preferable that the elemental composition of the photoelectron escape angle 15 ° by X-ray photoelectron spectroscopy (XPS) of the surface layer contains 50% or more of fluorine in atomic ratio, more preferably 55% or more. More preferably 60% or more.

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 it requires a skeleton for forming a layer, the upper limit is practically about 80%, and the reactivity in the surface layer is higher than that. It is easy to damage a site | part, and sufficient hardness may be difficult to obtain.

Here, X-ray photoelectron spectroscopy refers to a method of analyzing the constituent elements of the sample and its electronic state by measuring the energy of photoelectrons generated by irradiating X-rays on the surface of the sample, and by controlling the photoelectron escape angle, The elemental composition of the nearest part (~ 10 nm or less) is known. In the present invention, in the element composition obtained by analysis at the photoelectron escape angle of 15 °, when the fluorine content is less than 50%, fingerprint adhesion and fingerprint wiping property may be deteriorated. Although elements other than fluorine are not specifically limited, It is preferable that carbon, oxygen, a silicon, etc. are contained from the relationship which comprises a compound.

Moreover, as a form of the surface of the said surface layer, with respect to the form of the surface observed with the atomic force microscope of the said surface layer, the big uneven structure which reduces the contact area of a surface, and the fine uneven structure which reduces the visibility of an attached fingerprint coexist. It is desirable to. Here, the coexistence of a large uneven structure and a fine uneven structure means a state in which a region having a large uneven structure and a region having a fine uneven structure are mixed. In addition, each area | region does not need to form a separate area | region, and the state in which the fine uneven | corrugated structure further exists in the part or whole surface on the surface of a large uneven | corrugated structure may be sufficient. Specifically, it is preferable that the 10-point average roughness Rz and the center line average roughness Ra prescribed by JIS B0601: 2001 satisfy the following formulas (3) and (4).

<Equation (3)>

4nm <Rz≤25nm

<Equation (4)>

Ra≤4nm

That is, more than 4 nm and 25 nm or less are preferable about Rz, 5 nm or more and 20 nm or less are more preferable, It is preferable that it is 4 nm or less, and 2 nm or less is more preferable about Ra. Moreover, about Ra, 0.30 nm or more is more preferable and 0.35 nm or more is more preferable.

Here, 10-point average roughness Rz is the value which calculated and summed the average of the top 5 values, respectively about the height of the convex part of the uneven structure on the surface, and the depth of the concave part, and has a low frequency within the measurement range. This characterizes the large uneven structure present. On the other hand, center line average roughness Ra is a value which catches all the uneven structure in surface inside on average. Therefore, Ra does not exceed Rz. Moreover, when Ra is larger than 4 nm, sufficient transparency of a 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 acquired. On the other hand, when Rz is smaller than 4 nm, the effect of surface area reduction by the shape of the surface may not be obtained. When Rz is larger than 25 nm, the value of the receding contact angle described above becomes small, and sufficient anti-fingerprint is not obtained. There is a case.

In addition, the surface layer is a fluorine compound having a site and a reactive 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 A, the compound B which has a site | part containing a C8 or more alkyl group and / or alkanediyl group, and a reactive site, and a binder component. Here, containing fluorine compound A, compound B, and a binder component is not only the case where each is mixed in an unreacted state, but, for example, the reactive site of fluorine compound A and the said reactive site in compound B and / or binder component. It should also include the case where some or all of the forms a chemical bond at a site capable of reacting (hereinafter, the same applies to the molding material and the coating composition of the present invention). Moreover, it is more preferable that the said fluorine compound A, the said compound B, and the said binder component are main components of the said surface layer. In this specification, unless otherwise indicated, a main component refers to the component which occupies 50 mass% or more of all components. In this case, the sum total of a fluorine compound A, a compound B, and a binder component is 50 mass% or more. Details and preferable content ratios of the fluorine compound A, the compound B, and the binder component, respectively, will be described later. The fluorine compound A reduces the amount of adhesion by increasing the contact angle of the liquid constituting the fingerprint by lowering the surface energy. Acts as an adjuvant for the high density of the fluorine compound A on the surface, and the binder component has a role of immobilizing these components in the surface layer and further binding with the substrate to impart scratch resistance practically necessary.

In addition, the surface layer is a fluorine compound having a site and a reactive 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 A, the binder component, and particle | grains d (I) of 5 nm-20 nm of number average particle diameters, and particle | grains d (II) of 50 nm-300 nm of number average particle diameters, Among these, especially as fluorine compound A , At least one moiety selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group and a fluorooxyalkanediyl group, and at least one reactive site 2 to 5 or less A fluorine compound A (II) having and a binder component, which have 10 or more reactive sites in the molecule, and are a compound having a number average molecular weight of 1500 or more and 3000 or less A binder component formed of binder raw material C (I) and a binder raw material C (II) which has a reactive site of 3 or more and 6 or less in the molecule and is a compound having a number average molecular weight of 500 or more and 1500 or less, and the number average particles as particles. It is more preferable that it is a surface layer containing particle | grains d (I) of 5 nm-20 nm in diameter, and particle | grains d (II) of 50 nm-300 nm of number average particle diameters.

Details and preferable 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. The function is as follows. Fluorine Compound A (II) is a compound having a reactive site of 2 or more and 5 or less in the fluorine compound A, and by selecting and using such a specific compound among the fluorine compound A, the molding due to rubbing with the gun gun during wiping, in particular, It is possible to further improve the wiping durability, which is resistant to changes in the material surface. Moreover, the binder component formed from binder raw material C (I) contributes especially to the improvement of hardness, and the binder component formed from binder raw material C (II) contributes especially to immobilization of the said fluorine compound A. And by containing particle | grain d (I) and particle | grain d (II), the shape of the specific surface represented by Formula (3) and Formula (4) mentioned above is formed in a surface.

In addition, the coating composition of the present invention has a site and a reactive site comprising 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 fluorine compound A, the compound B which has a site | part containing a C8 or more alkyl group and / or alkanediyl group, and a reactive site, and a binder raw material. Moreover, it is preferable that fluorine compound A and the compound B do not couple | bond the fluorine compound A and the compound B in the form of a copolymer etc. in the state of a coating composition.

In addition, the coating composition of the present invention has a site and a reactive site comprising 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 fluorine compound A, the binder raw material, particle | grains D (I) of 5 nm-20 nm of number average particle diameters, and particle | grains D (II) of 50 nm-300 nm of number average particle diameters, Among these, especially fluorine compound A As a moiety comprising 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 at least two reactive sites in one molecule A fluorine compound A (II) having a compound and a binder raw material having 10 or more reactive sites in the molecule and having a number average molecular weight of 1500 or more and 3000 or less Binder raw material C (I) which is water, and binder raw material C (II) which is a compound with number average molecular weights 500-6500 with a reactive site of 3 or more and 6 or less in a molecule | numerator, and a number average particle diameter of 5 nm or more and 20 nm or less as particle | grains It is more preferable that particle | grains D (I) and particle | grains D (II) of 50 nm or more and 300 nm or less of number average particle diameters are contained. The function of each component is as described for the molding material (in this case, d (I) is replaced by D (I) and d (II) is replaced by 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 their respective preferred ratios will be described later.

[Molding material and surface layer]

As long as it has the surface layer containing the characteristic and / or material of this invention, the molding material of this invention may be any of planar shape (film, sheet, plate), and three-dimensional shape (molded object). Here, the surface layer in this invention means the site | part adjacent to a thickness direction or an inner direction, an elemental composition, and a content from the surface of the said molding material toward thickness direction (in case of planar shape) or internal direction (in case of three-dimensional shape). By having a boundary surface where the shape and physical properties of the particles (such as particles) are discontinuous, it is possible to distinguish a portion having a finite thickness. More specifically, the cross-sectional observation of the molding material in the thickness direction from the surface with various composition / element analyzers (IR, XPS, XRF, EDAX, SIMS, etc.), electron microscope (transmission type, scanning type) or optical microscope, It is distinguished by the discontinuous interface.

In addition to anti-fingerprint, the surface layer may have other functions such as antireflection, hard coating, antistatic, antifouling, conductive, heat ray reflection, near infrared absorption, electromagnetic shielding, and easy adhesion.

Although the thickness of the said surface layer does not have limitation in particular, 1 nm or more and 100 micrometers or less are preferable, 5 nm or more and 50 micrometers or less are more preferable, The thickness can be selected according to the other function mentioned above.

Coating Composition

The coating composition of the present invention refers to a liquid composition at room temperature that is capable of forming the "surface layer" on the surface of a molding material by a general coating process including coating, drying and curing, or by a process such as vapor deposition. It is preferable that B, the binder raw material C, and the particle | grains D are included, and also various additives, such as a solvent and a photoinitiator, a hardening | curing agent, a catalyst, can also be included. The details of the fluorine compound A, the compound B, the binder raw material C, and the particle D will be described later.

[Fluorine Compound A]

Fluorine compound A refers to a compound having a site and a reactive site including 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 part of hydrogen which a fluoroalkyl group, a fluorooxyalkyl group, a fluoro alkenyl group, a fluoro alkanediyl group, and a fluorooxy alkanediyl group has an alkyl group, an oxyalkyl group, an alkenyl group, an alkanediyl group, and an oxyalkanediyl group Or all of which are substituents substituted with fluorine, all of which are substituents mainly composed of fluorine atoms and carbon atoms, and may have branches in the structure, to form dimers, trimers, oligomers, and polymer structures in which a plurality of structures having these moieties are connected. You may be.

In addition, a reactive site refers to the site | part which reacts with another component by external energy, such as heat or light. Examples of such reactive sites include silanol groups hydrolyzed by alkoxysilyl groups and alkoxysilyl groups, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, methacryloyl groups and the like. Especially, a vinyl group, an allyl group, an alkoxy silyl group, a silyl ether group, or a silanol group, an epoxy group, and an acryloyl (methacryloyl) group are preferable from a viewpoint of reactivity and handleability, and a vinyl group, an allyl group, and an acryl Loyl (methacryloyl) group is more preferable, and acryloyl (methacryloyl) group is especially preferable. In addition, in order to achieve the effect of reducing the surface energy and the wiping durability which is durable against the change of the surface of the molding material due to rubbing by the gun when wiping, in particular, the fluorine compound A having 2 or more and 5 or less of the above reactive sites ( Particular preference is given to applying II). From the viewpoint of durability of the surface layer when wiping a fingerprint, it is preferable that the fluorine compound A has a large number of reactive sites. On the other hand, when the reactive sites become 6 or more in the molecule, the effect of lowering the surface energy may not be sufficiently obtained. .

An example of fluorine compound A is a compound represented by following General formula (1).

<Formula (1)>

R ^f1 -R ² -D ¹

(R ^f1 represents a moiety containing a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, a fluorooxyalkanediyl group, and R ² represents an alkanediyl group, an alkanetriyl group, and Derived ester structure, urethane structure, ether structure, triazine structure, D ¹ represents a reactive site)

Examples of the compound of formula (1) include 2,2,2-trifluoroethylacrylate, 2,2,3,3,3-pentafluoropropylacrylate, 2-perfluorobutylethylacrylate, 3- Perfluorobutyl-2-hydroxypropylacrylate, 2-perfluorohexylethylacrylate, 3-perfluorohexyl-2-hydroxypropylacrylate, 2-perfluorooctylethylacrylate, 3- Perfluorooctyl-2-hydroxypropylacrylate, 2-perfluorodecylethylacrylate, 2-perfluoro-3-methylbutylethylacrylate, 3-perfluoro-3-methoxybutyl-2 -Hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl 2-hydroxypropyl acrylate, tetrafluoro propyl acrylate, octafluoro pentyl acrylate, dodecouple Fluoroheptyl acrylate, hexadecafluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropylmetha Acrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2- Hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropylmetha Acrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate Acrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octaflu Lopentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl Methacrylate, triacryloyl-heptadecafluorononenyl-pentaerythritol, etc. are mentioned.

In addition, the fluorine compound A has a preferable material, one has a plurality of fluoroalkyl groups as R ^f1 part in the formula (1), and has a plurality of acryloyl (methacryloyl) groups in the portion of D ¹ , A part of R ² is a so-called fluorine-containing dendrimer having a multi-branched structure, and another has a fluoropolyether moiety containing a fluorooxyalkyl group and a fluorooxyalkanediyl group as the R ^f1 moiety in the formula (1). And a so-called fluoropolyether moiety having an alkanediyl group at a portion of R ^{2 and} an acryloyl (methacryloyl) group at a portion of D ¹ .

Here, a fluorine-containing dendrimer refers to a dendrimer containing groups, such as a fluoroalkyl group and a fluorooxyalkyl, a fluoro alkenyl group, a fluoro alkanediyl group, and a fluorooxy alkanediyl group. Dendrimers are described, for example, in Hawker et al., J. Chem. Soc., Chem. Commun. 1990, (15), 1010-1013, d. a. D. A. Tomalia et al. Angew. Chem. Int. Ed. Engl., 29, 138-175 (1990)]. M. second. Branches with regular resin-like branches described in JMJ Frechet et al. (Science, 263, 1710. (1994)) and Kakimoto Masaaki (Chemistry, Vol. 50, p. 608 (1995)). General term for polymers, since these molecules have a polymer structure with a regular branching from the center of the molecule, for example D. a. D. A. Tomalia et al. Angew. Chem. Int. Ed. Engl., 29, 138-175 (1990)], takes the spherical molecular form by the extreme three-dimensional crowding of the branch ends that occur as a result of high molecular weight.

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

The fluoropolyether moiety is a moiety containing a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group and the like, and is a structure represented by the formulas (2) and (3).

<Formula (2)>

CF _n1 H _{(3- n1 )} -(CF _n2 H _{(2- n2 )} ) _k O- (CF _n3 H _{(2- n3 )} ) _m O-

<Formula 3>

-(CF _n4 H _{(2- n4 )} ) _p O- (CF _n5 H _{(2- n5 )} ) _s O-

N1 is an integer of 1 to 3, n2 to n5 are an integer 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-n5 is an integer of 1 or 2, More preferably, n1 is 3, n2 and n4 are 2, n3 and n5 are an integer of 1 or 2.

The chain length of this fluoropolyether site | part has a preferable range, C4 or more and 12 or less are preferable, 4 or more and 10 or less are more preferable, 6 or more and 8 or less are especially preferable. When the carbon number is 3 or less, since the surface energy does not sufficiently decrease, oil repellency may be lowered, and when it is 13 or more, the solubility in a solvent is lowered, so the quality of the coating film may be lowered.

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

Commercially available examples of the fluorine compound A include RS-75 (DIC Corporation), Optool DSX, Optool DAC (Daikin Kogyo Corporation), C10GACRY, C8HGOL (Yushisei Corporation). These products can be used.

[Compound B]

Compound B refers to a compound having a moiety and a reactive moiety including an alkyl group having 8 or more carbon atoms and / or an alkanediyl group. In addition, a reactive site is as having described in the term of fluorine compound A.

An example of compound B is a compound represented by following General formula (4).

<Formula 4>

R ¹⁰ -R ¹¹ -D ¹²

(R ¹⁰ represents a moiety containing an alkyl group and / or alkanediyl group having 8 or more carbon atoms, and R ¹¹ represents an alkanediyl group, an alkantriyl group, and an ester structure, urethane structure, ether structure, triazine structure derived therefrom. And D ¹² represents a reactive site)

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

As an example of an acrylate monomer, the acrylate which has one or more (meth) acryloyloxy group in 1 molecule is shown, As a specific example, isobonyl (meth) acrylate, (iso) stearyl (meth) acrylate, 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 decane diol di (meth) acrylate, 1, 9 nonane diol di (meth) acrylate, dimethylol cyclodecane di (meth) acrylate, etc. are mentioned. Can be. This monomer can be used 1 type or in mixture of 2 or more types.

In addition, "(meth) acrylate" shall represent an acrylate and a methacrylate, and "(meth) acryloyloxy group" shall collectively represent an acryloyloxy group and a methacryloyloxy group (In addition to the above, in a compound The same applies to the case in which (meth) acryl… ”is included).

Moreover, as a commercially available (meth) acrylate monomer, Shin-Nakamura Chemical Co., Ltd .; (Brand name "NK ester" series, etc.), Toagosei Kabushiki Kaisha; ("Aronix" (registered trademark) series, etc.), Kyoesha Kagaku Kabushiki Kaisha; (The brand name "light acrylate", the "light ester" series, etc. are mentioned, Such a product can be used.

[Binder component, binder raw material]

A binder raw material is a compound contained in the said coating composition, and is a raw material of the binder component which exists in the said surface layer formed by coating, drying, and hardening the said coating composition. That is, what the binder raw material contained in the coating composition of this invention hardens | cures by heat, ionizing radiation, etc., and is contained in a surface layer is called binder component. In addition, about some binder raw materials, even in a surface layer, it may exist in the same state as in a coating composition (it may exist in an unreacted state), and even in that case, what is in a surface layer is a binder component.

Although the binder raw material in the said coating composition is not specifically limited, It is preferable that it is a binder raw material which can be hardened by heat and / or an active energy ray etc. from a viewpoint of manufacturability. The binder raw material in a coating composition may be one type, and may mix and use two or more types.

In the present invention, from the viewpoint of maintaining the fluorine compound A and the compound B in the surface layer, it is preferable that the monomer and oligomer having an alkoxy group, silanol group, reactive double bond, and ring-opening reaction functional group in the molecule are binder raw materials. Moreover, when hardening with UV rays, since oxygen inhibition can be prevented, it is preferable that oxygen concentration is as low as possible, and it is more preferable to harden under anaerobic atmosphere. By lowering the oxygen concentration, the hardened state of the outermost surface may be improved, and the chemical resistance may be improved.

Moreover, as a more preferable binder raw material, it has binder active material C (I) which is 10 or more reactive site | part in a molecule | numerator, and is a compound of number average molecular weight 1500 or more and 3000 or less, and has a reactive site | part of 3-6 or more in a molecule | numerator, and a number average molecular weight Binder raw material C (II) which is a compound of 500 or more and 1500 or less is mentioned, It is preferable to form a binder component using either or both of these as raw materials.

When binder raw material C (I) is added and a binder component is formed, there exists an effect of improving the hardness of the surface layer of the molding material obtained by this. It is preferable that the molecular weight and the reactive site of the binder raw material C (I) are sufficiently large. On the other hand, when the molecular weight is too large, the solubility decreases and components such as fluorine compound A, particle D, and the like cannot be dispersed. Transparency and smoothness may be impaired. Therefore, it is preferable that binder raw material C (I) has a reactive site | part of 10 or more in a molecule | numerator, and is a compound of molecular weight 1500-3000.

When binder raw material C (II) is added and a binder component is formed, since the dispersion | distribution of the said fluorine compound A is favorable in the surface layer of the molding material obtained by this, it is preferable.

Moreover, it is especially preferable that a binder component is formed by the mixed system containing binder raw material C (II) in addition to said binder raw material C (I). Since the binder raw material C (II) has the effect of making the dispersion of the fluorine compound A favorable in a surface layer as mentioned above, it is preferable. The binder raw material C (II) has a reactive site number close to that of the fluorine material, and the molecular weight is preferably smaller, but has three or more reactive sites in one molecule from the molecular weight and the crosslinked water capable of maintaining the hardness of the molding material, Moreover, the compound whose molecular weight is 500 or more is preferable. On the other hand, when the molecular weight is larger than 1500 or the number of reaction sites is greater than 7, the fluidity is impaired and the fluorine compound A cannot be dispersed in the surface layer, and the effect of lowering the surface energy may not be sufficiently obtained.

As a binder raw material in such a coating composition, a polyfunctional acrylate monomer, an oligomer, an alkoxysilane, an alkoxysilane hydrolyzate, an alkoxysilane oligomer, etc. are specifically, preferable, A polyfunctional acrylate monomer and an oligomer are more preferable.

As an example of a polyfunctional acrylate monomer, the polyfunctional acrylate which has three or more (meth) acryloyloxy groups in 1 molecule, and its modified polymer, a specific example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethyl All propane tri (meth) acrylate, pentaerythritol triacrylate hexane methylene diisocyanate urethane polymer, etc. can be used. This monomer can be used 1 type or in mixture of 2 or more types.

Moreover, as a commercially available polyfunctional acryl-type composition, Mitsubishi Rayon Co., Ltd .; (Trade name "Dia Beam" (registered trademark) series, etc.), Nagase Sangyo Co., Ltd .; (Trade name "Denacol" (registered trademark) series, etc.), Shin-Nakamura Kagaku Kabushiki Kaisha; (Trade name "NK ester" series, etc.), DIC Corporation; (Trade name "UNIDIC" (registered trademark) and the like), Toagosei Kabuki Kaisha; ("Aronix" (registered trademark) series, etc.), Nichiyu Kabushiki Kaisha; ("Brenma" (registered trademark) series, etc.), Nippon Kayaku Co., Ltd .; (Trade name "KAYARAD" (registered trademark) series, etc.), Kyoesha Chemical Co., Ltd .; (Brand name "light ester" series etc.) etc. are mentioned, Such a product 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. Although particle | grains may be either an inorganic particle or organic particle | grains here, an inorganic particle is preferable from a viewpoint of durability.

"Inorganic particle" includes the thing which surface-treated here. This surface treatment means that a compound is introduced to a particle surface by chemical bonds (including covalent bonds, hydrogen bonds, ionic bonds, van der Waals bonds, hydrophobic bonds, etc.) or by adsorption (including physical adsorption and chemical adsorption). In addition, even if the compound introduce | transduced by surface treatment is an organic compound, if an underlying particle is an inorganic particle, it shall be an inorganic particle.

As a kind of inorganic particle contained, one type or more and 20 types or less are preferable. As for the kind of inorganic particle, 1 type or more and 10 types or less are more preferable, and 2 or more types and 4 types or less are especially preferable. Here, the kind of inorganic particle is determined according to the kind of the element which comprises an inorganic particle, and when a certain surface treatment is performed, it is determined by the kind of element which comprises the particle | grains before surface treatment. For example, nitrogen-doped titanium oxide (TiO _{2 -x} N _x ) in which a part of oxygen of titanium oxide (TiO ₂ ) and titanium oxide is replaced with an anion nitrogen is different because the elements constituting the inorganic particles are different. It is assumed that it is an inorganic particle of. Moreover, if it is the particle | grains (ZnO) containing only the same element, for example, Zn and O, even if there exist several particle | grains from which the number average particle diameter differs, and even if the composition ratio of Zn and O differs, they are the same kind of particle | grains. Moreover, even if there exist two or more Zn particle | grains which differ in oxidation number, as long as the element which comprises particle | grains is the same (as long as all elements other than Zn are the same in this example), these shall be the same kind of particle | grains.

Moreover, the particle | grains contained in the coating composition of this invention may be contained in the said surface layer in the form which changed the surface state by heat, ionizing radiation, etc. in processes, such as coating, drying, hardening treatment, or vapor deposition. Therefore, the particle component present in the coating composition of the present invention is a particle D (I) or D (II), the particle composition present in the surface layer formed by the coating composition, such as coating, drying, curing treatment or vapor deposition It is described as d (I) or d (II). In addition, about some particle | grains of particle | grain d (I) or d (II) which exist in a surface layer, it may exist in the same state as in coating composition even in a surface layer (it may exist in an unreacted state), Also in that case, what is in a surface layer is described with particle | grain d.

The inorganic particles are not particularly limited, but are preferably oxides of metals or semimetals, nitrides, borides, chlorides, carbonates, sulfates, and complex oxides containing two kinds of metals and semimetals, and are heterogeneous between lattice. An element may be introduced, the lattice point may be substituted with a heterogeneous element, or a lattice defect may be introduced.

The inorganic particles are more preferably 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. Do.

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 ( SnO ₂ ), antimony oxide (Sb ₂ O ₃ ) and indium tin oxide (In ₂ O ₃ · SnO ₂ ) are preferably at least one metal oxide or semimetal oxide selected from the group consisting of. Especially preferred is silica (SiO ₂ ).

In addition, although the form of an inorganic particle is not specifically limited, It is preferable that silica has a long chain structure connected in the columnar shape (shape connected with several silica in chain shape), or that the connected silica was branched or curved. These are hereinafter referred to as silicas that are linked and / or branched in the form of beads.

The silica connected and / or branched in the form of the beads is a combination of particle-particles between primary particles of silica via divalent or higher metal ions, and three or more, preferably five or more, more preferably 7 or more connected. The connection, branching, and bending state of the silica connected and / or branched in the beads shape can be confirmed using a scanning electron microscope (SEM). Commercially available products of silica connected and / or branched in the form of this beads include PS-S, PS-M (water dispersion), IPA-ST (IPA dispersion), and MEK-ST (MEK dispersion) manufactured by Nissan Chemical Industries, Ltd. Sieve), PL-1-IPA (IPA dispersion) manufactured by Fuso Kagaku Kogyo Co., Ltd., PL-1-MEK (MEK dispersion), etc. can be mentioned, Such a product can be used.

In order to obtain the form of the particularly preferable surface of the present invention, it is particularly preferable that the surface treatment necessary for stably dispersing the above-described chain-shaped silica is dispersed in the good solvent of the binder raw material. For example, when using an acryl-type monomer and an oligomer as a binder raw material, as surface treatment, the C1-C5 alkyl group, alkenyl group, vinyl group, (meth) acryl group, etc. are introduce | transduced into the surface as minimum as needed. desirable.

Moreover, it is preferable that the molding material of this invention contains two types of particle | grains d (I) and particle | grains d (II), and it is likewise that a coating composition contains two types of particle | grains D (I) and particle | grains D (II). desirable. Particularly preferred number average particle diameters exist for particle d (I) or particle D (I) and particle d (II) or particle D (II), respectively. Particle d (I) or particle D (I) is a component contributing to the above fingerprinting property, and gives the effect of making the fingerprint hard to stand out by finely dispersing the deposit of the fingerprint on the surface. It is preferable that the number average particle diameter of particle | grains d (I) or particle | grains D (I) is 5 nm or more and 20 nm or less, and when smaller than 5 nm, the effect which makes it difficult to stand out the above-mentioned fingerprint may not be fully acquired, and it is more than 20 nm. When large, the transparency of a molding material may be impaired.

On the other hand, Particle d (II) or Particle D (II) is a component contributing to the fingerprint wiping property, and has an effect of preventing deterioration of the surface layer and improving wiping by reducing the surface frictional resistance during wiping. . It is preferable that the number average particle diameter of particle | grains d (II) or particle | grains D (II) is 50 nm or more and 300 nm or less, and when smaller than 50 nm, the above-mentioned friction reduction effect may not be fully acquired, and when larger than 300 nm, The concave-convex structure formed by this is an occasion, and the value of the above-mentioned receding contact angle may become small.

Herein, the number average particle diameter of the inorganic particles means the number-based arithmetic mean length diameter described in JIS Z8819-2: 2001, and the scanning electron microscope (SEM) in any case of the particle d in the molding material and the particle D in the coating composition is used. Primary particles are observed using a transmission electron microscope or the like, and the circumscribed circle diameter of each primary particle is made the equivalent particle diameter, and the value obtained from the number-based average value is indicated. In the case of a molding material, a number average particle diameter can be calculated | required by observing a surface or a cross section, and in the case of a coating composition, a sample can be manufactured and observed by dripping and drying the coating composition diluted with the solvent.

[menstruum]

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. "Solvent" refers to the substance which is liquid at normal temperature and normal pressure which can evaporate almost whole quantity in the drying process after coating here.

The kind of solvent is determined by the molecular structure which comprises a solvent here. That is, they have the same elemental composition and have different bonding relationships even if they have the same kind and number of functional groups (structural isomers), but they are not structural isomers, but do not overlap completely in any three-dimensional space (stereoisomers). Silver is treated as a solvent different in kind. For example, 2-propanol and n-propanol are treated as different solvents.

[Other additives]

As a coating composition of this invention, what further contains a photoinitiator, a thermal polymerization initiator, a hardening | curing agent, and a catalyst is preferable.

A photoinitiator, a thermal polymerization initiator, a hardening | curing agent, and a catalyst are used in order to accelerate | stimulate the reaction between binder raw materials, and a binder raw material, a fluorine compound A, and a compound B. As a photoinitiator, a thermal polymerization initiator, a hardening | curing agent, and a catalyst, it is preferable that a coating composition can start or accelerate superposition | polymerization and / or silanol condensation and / or crosslinking reaction by a radical reaction etc.

Various types of photoinitiators, thermal polymerization initiators, curing agents and catalysts can be used. In addition, several initiators may be used simultaneously and may be used independently. Moreover, an acidic catalyst, a thermal polymerization initiator, and a photoinitiator can also be used together. As an example of an acidic catalyst, hydrochloric acid aqueous solution, formic acid, acetic acid, etc. are mentioned.

As an example of a thermal polymerization initiator, a peroxide and an azo compound are mentioned. Moreover, as an example of a photoinitiator, an alkyl phenone type compound, a sulfur containing type compound, an acyl phosphine oxide type compound, an amine type compound, etc. are mentioned, An alkyl phenone type compound is preferable from a curable viewpoint, As a specific example, 2,2 is mentioned. -Dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino- 1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) 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 etc. are mentioned.

Moreover, as for the content rate of a photoinitiator, a thermal polymerization initiator, a hardening | curing agent, and a catalyst, 0.001 mass part-30 mass parts are preferable with respect to a total of 100 mass parts of the binder raw material in a coating composition, More preferably, 0.05 mass part-20 mass parts More preferably, they are 0.1 mass part-10 mass parts.

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

[Content of Each Component in Coating Composition]

The coating composition of the present invention contains a fluorine compound A, a compound B, a binder raw material C, and particles D, but the respective mass relationships in the coating composition will be described. Here, the binder raw material C denotes the total of the binder raw material C (I) and the binder raw material C (II), and the particle D denotes the total of the particle D (I) and the particle D (II).

100 mass% of coating compositions of this invention WHEREIN: When fluorine compound A contains 0.025 mass% or more and 7 mass% or less, and compound B, 0.2 mass% or more and 55 mass% or less, and the binder raw material C is 0.8 mass% or more and 66 mass% When it contains% or less and particle | grains D, 0.1% or more and 35% or less, 30 mass% or more and 95 mass% or less of solvent, 0.025 mass% or more and 7 mass% or less of the other components of an initiator, a hardening | curing agent, and a catalyst are preferably illustrated. do. More preferably, fluorine compound A is 0.05 mass% or more and 6 mass% or less, compound B is 0.4 mass% or more and 36 mass% or less, the binder raw material C is 3.2 mass% or more and 56 mass% or less, and the solvent is 40 mass% or more 90 It is 0.05 mass% or more and 6 mass% or less of mass% or less, a photoinitiator, a thermal polymerization initiator, a hardening | curing agent, and other components of a catalyst.

[Support material]

When the molding material of this invention is planar shape, a support base material is needed in order to provide said "surface layer". There is no restriction | limiting 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.

As an example in the case of using a plastic film and a plastic sheet for a support base material, a cellulose ester (for example, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamide, polycar Carbonates, polyesters (e.g. polyethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4, 4'-dicarboxylate, polybutylene terephthalate), polystyrene (e.g. syndiotactic polystyrene), polyolefins (e.g. polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, Polyetherimide, polymethylmethacrylate, polyetherketone, and the like, among which triacetyl is particularly preferred. The rules agarose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred.

It is also possible to give various surface treatments to the surface of a support base material before forming the said 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 preferable, and glow discharge treatment and ultraviolet treatment are more preferable.

[Method of Manufacturing Molding Material]

The surface layer formed on the surface of the molding material of the present invention is formed by vapor phase treatment such as vapor deposition, sputtering, CVD, liquid phase treatment such as coating, impregnation, plating, saponification, solid state treatment such as transfer and bonding, and a combination of these treatments. Although it may form on the surface of a material, the gas phase process by vapor deposition and the liquid phase process by coating are preferable, and the liquid phase process formed by coating a coating composition with a support base material etc. is more preferable.

Although the manufacturing method of the molding material by coating is not specifically limited, A coating composition is used for a support base material etc. by the dip coating method, the roller coating method, the wire bar coating method, the gravure coating method, the die coating method (US Pat. No. 2,268,942 specification), etc. It is preferable to form a surface layer by coating. In this coating method, 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 this coating method is mentioned later.

Subsequently, the liquid film coated on the supporting substrate or the like is dried. In addition to removing the solvent completely from the resulting molding material, from the viewpoint of promoting the movement of the fluorine compound A in the liquid film to the surface, it is preferable to include heating of the liquid film in the drying step.

Examples of the drying method include electrothermal drying (adhesion to a high temperature object), convective heat transfer (hot air), radiant heat transfer (infrared), and others (microwave, induction heating). Among these, in the manufacturing method of this invention, since it is necessary to make a uniform drying rate even in the width direction precisely, the method using convective heat transfer or radiant heat transfer is preferable.

The drying process is generally divided into (A) constant drying period and (B) reduction drying period, and the former is constant in this section because the diffusion of solvent molecules from the liquid film surface into the atmosphere is at the rate of drying. The drying rate is governed by the partial pressure of evaporated solvent in the air, the wind speed and the temperature, and the membrane surface temperature is constant at a value determined by the hot air temperature and the partial pressure of evaporated solvent in the air. Since the latter is the diffusion rate of the solvent in the liquid film, the drying rate is continuously reduced without showing a constant value in this section, and the temperature is increased when the film is dominated by the diffusion coefficient of the solvent in the liquid film. Here, a drying rate shows the amount of solvent evaporation per unit time and unit area, and consists of a dimension of g * m <^-2> s <^-1> .

The drying rate has a preferred range, preferably 10 g · m ⁻² · s ⁻¹ or less, and more preferably 5 g · m ⁻² · s ⁻¹ or less. By setting the drying rate in the constant drying section to this range, it is possible to prevent stains caused by nonuniformity of the drying rate.

If the drying rate of the range of 0.1 g * m <^-2> s <^-1> or more and 10g * m <^-2> s- ¹ or less is obtained, it will not be specifically limited to a specific wind speed and temperature.

In the manufacturing method of this invention, in the rate reduction drying period, orientation of the fluorine compound A is performed with evaporation of a residual solvent. In this process, since a time for orientation is required, a preferable range exists in the film surface temperature rise rate in the reduction rate drying period, preferably 5 ° C / sec or less, and more preferably 1 ° C / sec or less.

Moreover, you may perform another hardening operation (hardening process) by irradiating heat or an energy ray. When hardening by heat at a hardening process, it is preferable that they are room temperature-200 degreeC, From a viewpoint of the activation energy of a hardening reaction, 100 degreeC or more and 200 degrees C or less are more preferable, It is more preferable that they are 130 degreeC or more and 200 degrees C or less.

Moreover, when hardening with an energy ray, it is preferable that it is an electron beam (EB ray) and / or an ultraviolet ray (UV ray) from the point of versatility. Moreover, when hardening by ultraviolet-ray, since oxygen inhibition can be prevented, it is preferable that oxygen concentration is as low as possible, and it is more preferable to harden in nitrogen atmosphere (nitrogen purging). When the oxygen concentration is high, hardening of the outermost surface is inhibited and curing is insufficient, and scratch resistance, durability, and alkali resistance (saponification resistance) may be insufficient.

Moreover, as a kind of ultraviolet lamp used when irradiating an ultraviolet-ray, a discharge lamp system, a flash system, a laser system, an electrodeless lamp system etc. are mentioned, for example. In the case of ultraviolet curing using a high-pressure mercury lamp, which is a discharge lamp system, the ultraviolet light is 100 to 3000 mW / cm ² , preferably 200 to 2000 mW / cm ² , more preferably 300 to 1500 mW / cm ² It is preferable to irradiate, and it is more preferable to irradiate an ultraviolet-ray on the conditions which will be accumulated light quantity of an ultraviolet-ray 100-3000mJ / cm <^2> , Preferably 200-2000mJ / cm <^2> , More preferably, 300-1500mJ / cm <^2> . . Ultraviolet illuminance is the intensity of irradiation received per unit area and varies depending on the lamp output, the emission spectrum efficiency, the diameter of the light emission valve, the design of the reflector, and the light source distance from the irradiated object. However, roughness does not change with the conveyance speed. The amount of ultraviolet light accumulated is the irradiation energy received per unit area, and the total amount of photons reaching the surface. The accumulated light amount is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiation times and the number of lamps.

[Method for Producing Coating Composition]

The coating composition of this invention is obtained by mixing a solvent and other additives (particle dispersions, such as an initiator, a hardening | curing agent, a catalyst, etc.) in addition to the fluorine compound A, the compound B, and a binder raw material. Its manufacturing method is obtained by measuring the prescribed amount of the above components by mass or volume and mixing them by stirring. At this time, the solvent may be further subjected to desolvation treatment with reduced pressure or reverse osmosis membrane, dehydration treatment with molecular sieve, ion exchange treatment with ion exchange resin, or the like.

Although the stirring conditions and stirring apparatus at the time of paint composition combination are not specifically limited, What is necessary is just the apparatus and rotation speed required for the whole liquid to fully mix, and the local shear rate in a liquid is less than 10 <^4> S- ¹ , and Reynolds number It is preferable that it is the range of 1000 or more.

The obtained coating composition can also perform a suitable filtration process before coating. As for this appropriate filtration process, it is more preferable to select and filter the filter material and filter mesh which matched the polarity of a solvent, a binder raw material, and an additive.

<Example>

Next, although an Example demonstrates this invention, this invention is not necessarily limited to these.

[Fluorine Compound A]

[Fluorine Compound A1]

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

[Fluorine Compound A2]

As the fluorine compound A2, a compound containing a fluoropolyether moiety (manufactured by "Megaface" RS-75 DIC Corporation) was used.

[Fluorine Compound A3]

As the fluorine compound A3, a compound containing a fluoropolyether moiety (manufactured by "Optool" DAC Daikin Kogyo Co., Ltd.) was used.

[Fluorine Compound A4]

As the fluorine compound A4, a fluorine-containing dendrimer was used. The synthesis method is as follows.

32 g of toluene was added to a 200 mL reaction flask, nitrogen was introduced for 5 minutes while stirring, and the mixture was heated until reflux (temperature 110 ° C. or higher). Ethylene glycol dimethacrylate (EGDMA) 4.0 g (20 mmol), 2- (perfluorohexyl) ethyl methacrylate C6FM 8.6 g (20 mmol), 2,2- azobisisobutyric acid in a separate 100 mL reaction flask 2.3 g (10 mmol) of dimethyl (MAIB) and 32 g of toluene were added, nitrogen was introduced for 5 minutes while stirring, and nitrogen substitution was performed, followed by cooling to an ice bath at 0 ° C.

To the refluxed toluene in the above-mentioned 200 mL reaction flask, the contents were dripped over 30 minutes from the said 100 mL reaction flask which EGDMA, C6FM, and MAIB were thrown in using the dropping pump. Aged 1 hour after the end of dropping.

Subsequently, this reaction solution was added to 277 g of hexane / toluene (mass ratio 4: 1) to precipitate a polymer in a slurry state. The slurry was filtered under reduced pressure, redissolved using 36 g of THF, and the THF solution of this polymer was added to 277 g of hexane to reprecipitate the polymer in the 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 obtained fluorine compound A4 was 16000, and dispersion degree (Mw / Mn) was 1.8.

[Fluorine Compound A5]

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

[Fluorine Compound A6]

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

[Fluorine Compound A7]

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

[Fluorine Compound A8]

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

[Fluorine Compound A9]

As the fluorine compound A9, a compound containing a fluoropolyether moiety (manufactured by X-7366 Nikka Chemical Co., Ltd.) was used.

[Fluorine Compound A10]

As the fluorine compound A10, a compound containing a fluoropolyether moiety (manufactured by MF-12 Miwon Specialty Chemical Co., Ltd) was used. This fluorine compound A10 corresponds to fluorine compound A (II).

[Compound B]

[Compound B1]

As compound B1, isodecyl acrylate (made by SR395 Satoma Japan Co., Ltd.) was used.

[Compound B2]

As the compound B2, stearyl acrylate (SR257 SATOMA Japan Co., Ltd. product) was used.

[Compound B3]

As compound B3, 1, 9 nonane diol diacrylate (A-NOD-N Shin-Nakamura Chemical Co., Ltd. make) was used.

[Compound B4]

As compound B4, isoamyl acrylate ("light acrylate" IAA Kyoeisha Chemical Co., Ltd. product) was used.

[Compound B5]

As compound B5, isooctylacrylate ("Miramer" M1084 manufactured by Miwon Specialty Chemical Co. Ltd) was used.

[Binder raw material C]

[Binder raw material C1]

As binder raw material C1, dipentaerythritol hexaacrylate ("KAYARAD" DPHA Nippon Kayaku Co., Ltd. product) was used. This binder raw material C1 corresponds to binder raw material C (II).

[Binder raw material C2]

As binder raw material C2, pentaerythritol triacrylate ("KAYARAD" PET30 Nippon Kayaku Co., Ltd. product) was used.

[Binder raw material C3]

As the binder raw material C3, a urethane acrylate oligomer (manufactured by "UNIDIC" 17-806 DIC Corporation) was used.

[Binder raw material C4]

Urethane acrylate oligomer ("KRM" 8655 Daicel Cytec Co., Ltd. product) was used as binder raw material C4. This binder raw material C4 corresponds to binder raw material C (I).

[Binder raw material C5]

Urethane acrylate oligomer ("KRM" 8200 Daicel Cytec Co., Ltd. product) was used as binder raw material C5. This binder raw material C5 corresponds to binder raw material C (II).

[Binder Raw Material C6]

As the binder raw material C6, a polyester acrylate oligomer ("EBECRYL" 1830 Daicel Cytec Co., Ltd. product) was used. This binder raw material C6 corresponds to binder raw material C (II).

[Binder Raw Material C7]

Urethane acrylate oligomer ("KRM" 8452 Daicel Cytec Co., Ltd. product) was used as binder raw material C7.

[Binder raw material C8]

As binder raw material C8, urethane acrylate oligomer ("Aresin" UN-904 Negami Kogyo Co., Ltd. product) was used.

[Binder raw material C9]

Urethane acrylate oligomer ("KRM" 8804 Daicel Cytec Co., Ltd. product) was used as binder raw material C9.

[Binder Raw Material C10]

As binder raw material C10, pentaerythritol tetraacrylate ("EBECRYL" 180 Daicel Cytec Co., Ltd. product) was used.

[Binder raw material C11]

As the binder raw material C11, a polyester acrylate oligomer ("EBECRYL" 884 Daicel Cytec Co., Ltd. product) was used.

[Particle component]

[Particle D1]

As the particle D1, organo silica sol (made by MEK-ST-UP Nissan Chemical Industries, Ltd.) was used. This particle | grain D1 corresponds to particle | grain D (I).

[Particle D2]

As particle | grain D2, organo silica sol (made by MEK-ST-2040 Nissan Chemical Industries, Ltd.) was used. This particle | grain D2 corresponds to particle | grain D (II).

[Particle D3]

As the particle D3, an organo silica sol (solid content concentration 5% by OSCAL Nikki Shokubai Kasei Co., Ltd.) was used. This particle | grain D3 corresponds to particle | grain D (I).

[Particle D4]

As the particle D4, organo silica sol (manufactured by MIBK-SD Nissan Chemical Industries, Ltd.) was used. This particle | grain D4 corresponds to particle | grain D (I).

[Particle D5]

As the particle D5, silica particles (manufactured by Hifreshica SP 300nm Ubenitto Kasei Co., Ltd.) were used. This particle | grain D5 corresponds to particle | grain D (II).

[Particle D6]

As particle | grain D6, organo silica sol (made by MIBK-SD-L Nissan Chemical Industries, Ltd.) was used. This particle | grain D6 corresponds to particle | grain D (II).

[Particle D7]

As the particle D7, silica particles (manufactured by Hifreshica SP 600nm Ubenitto Kasei Co., Ltd.) were used.

[Production of Coating Composition]

COATING COMPOSITION 1 The following material was mixed and the coating composition 1 was obtained.

Fluorine Compound A: 0.64 parts by mass of fluorine compound A1

Compound B: 5.8 parts by mass of compound B1

Binder raw material: Binder raw material C1 13.5 parts by mass

Solvent: 79.6 parts by mass of MIBK

Other additives (photoinitiator):

1-hydroxy-cyclohexyl-phenyl-ketone

0.5 parts by mass (manufactured by Irgacure 184 BASF)

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

COATING COMPOSITION 13 The following material was mixed and the coating composition 13 was obtained.

Fluorine Compound A: 0.64 parts by mass of fluorine compound A2

Binder raw material C: Binder raw material C1 19.3 parts by mass

Particle D (I): 49.8 parts by mass of particle D1

Particle D (II): 0.5 part by mass of particle D2

Solvent: MEK 29.3 parts by mass

Other additives (photoinitiator):

1-hydroxy-cyclohexyl-phenyl-ketone

0.5 parts by mass (manufactured by Irgacure 184 BASF)

COATING COMPOSITION 14 The following material was mixed and the coating composition 14 was obtained.

Fluorine Compound A: 0.03 parts by mass of fluorine compound A2

Binder raw material C: Binder raw material C1 8.77 parts by mass

Particle D (I): 70.5 parts by mass of particles D3

Particle D (II): 0.2 part by mass of particle D2

Solvent: MEK 20.0 parts by mass

Other additives (photoinitiator):

1-hydroxy-cyclohexyl-phenyl-ketone

0.5 parts by mass (manufactured by Irgacure 184 BASF)

COATING COMPOSITION 15 The following material was mixed and the coating composition 15 was obtained.

Fluorine Compound A: 0.64 parts by mass of fluorine compound A2

Binder raw material C: Binder raw material C1 19.3 parts by mass

Particle D (I): 33.2 parts by mass of particle D4

Particle D (II): 0.5 part by mass of particle D2

Solvent: 45.9 parts by mass of MIBK

Other additives (photoinitiator):

1-hydroxy-cyclohexyl-phenyl-ketone

0.5 parts by mass (manufactured by Irgacure 184 BASF)

COATING COMPOSITION 16 The following material was mixed and the coating composition 16 was obtained.

Fluorine Compound A: 0.64 parts by mass of fluorine compound A2

Binder raw material C: Binder raw material C1 19.3 parts by mass

Particle D (I): 49.8 parts by mass of particle D1

Solvent: MEK 29.8 parts by mass

Other additives (photoinitiator):

1-hydroxy-cyclohexyl-phenyl-ketone

0.5 parts by mass (manufactured by Irgacure 184 BASF)

COATING COMPOSITION 17 The following material was mixed and the coating composition 17 was obtained.

Fluorine Compound A: 0.64 parts by mass of fluorine compound A2

Binder raw material C: Binder raw material C1 19.3 parts by mass

Particle D (I): 49.8 parts by mass of particle D1

Particle D (II): 0.2 part by mass of particle D5

Solvent: MEK 29.6 parts by mass

Other additives (photoinitiator):

1-hydroxy-cyclohexyl-phenyl-ketone

0.5 parts by mass (manufactured by Irgacure 184 BASF)

COATING COMPOSITION 18 The following material was mixed and the coating composition 17 was obtained.

Fluorine Compound A: 0.64 parts by mass of fluorine compound A2

Binder raw material C: Binder raw material C1 19.3 parts by mass

Particle D (I): 49.8 parts by mass of particle D1

Particle D (II): 0.6 parts by mass of particles D6

Solvent: MEK 29.2 parts by mass

Other additives (photoinitiator):

1-hydroxy-cyclohexyl-phenyl-ketone

0.5 parts by mass (manufactured by Irgacure 184 BASF)

COATING COMPOSITION 19 The following material was mixed and the coating composition 19 was obtained.

Fluorine Compound A: 0.64 parts by mass of fluorine compound A7

Binder raw material C (I): 14.5 parts by mass of binder raw material C4

Binder raw material C (II): Binder raw material C5 4.8 parts by mass

Particle D (I): 49.8 parts by mass of particle D1

Particle D (II): 0.2 part by mass of particle D5

Solvent: MEK 29.6 parts by mass

Other additives (photoinitiator):

1-hydroxy-cyclohexyl-phenyl-ketone

0.5 parts by mass (manufactured by Irgacure 184 BASF)

COATING COMPOSITION 20-29 As shown in Table 1, about the said coating composition 13, except having replaced the said fluorine compound A7 with said fluorine compound A8-A10, binder raw materials C4, and C5 with binder raw materials C6-C11, Coating compositions 20 to 28 were obtained.

COATING COMPOSITION 32 The following material was mixed and the coating composition 13 was obtained.

Fluorine Compound A: 0.64 parts by mass of fluorine compound A2

Binder raw material C: Binder raw material C1 19.3 parts by mass

Particle D (I): 49.8 parts by mass of particle D1

Particle D (II): 0.5 part by mass of particle D2

Solvent: MEK 29.3 parts by mass

Other additives (photoinitiator):

1-hydroxy-cyclohexyl-phenyl-ketone

0.5 parts by mass (manufactured by Irgacure 184 BASF)

[Production of Molding Materials]

As a support base material, "Lumirror" (registered trademark) U46 (manufactured by Toray Co., Ltd.) on which an easy-to-adhesive coating was coated on a PET resin film was used. The coating compositions 1 to 14 were subjected to a gravure roll and a gravure roll speed ratio so as to have a solid coating film thickness of 2 µm using a continuous coating apparatus having a small diameter gravure coater at a conveyance speed of 10 m / min. It was. The conditions of the wind which touches a liquid film from coating to drying and hardening are as follows.

First drying process

Blowing temperature and humidity: temperature: 45 ℃,

Relative Humidity: 10%

Wind speed: Coating side: 5 m / sec,

Surface side: 5 m / s

Wind direction: Coating surface side: parallel to the surface of the substrate,

Semiconducting surface side: perpendicular to the surface of the substrate

Retention time: 1 minute

2nd drying process

Blowing temperature and humidity: temperature: 100 ℃,

Relative Humidity: 1%

Wind speed: Coating side: 5 m / sec,

Surface side: 5 m / s

Wind direction: Coating surface side: perpendicular to the surface of the substrate,

Semiconducting surface side: perpendicular to the surface of the substrate

Retention time: 1 minute

Photocuring process

Probe output: 600W / cm ²

Accumulated light quantity: 120mJ / cm ²

Oxygen Concentration: 0.1% by volume

In addition, the wind speed and temperature-humidity used the measured value by the heat-type anemometer (Nihon Kanomax, Inc. anemone master wind speed and air volume meter MODEL6034). By the above method, the molding materials of Examples 1-29 and Comparative Examples 1-3 were produced.

[Evaluation of Molding Material]

About the produced molding material, the performance evaluation shown below was performed and the result obtained is shown in Table 2. Except the case where there is no notice in particular, the measurement performed the measurement three times by changing a place with respect to one sample in each Example and the comparative example, and used the average value.

[60 ° mirror gloss]

As for the glossiness of the surface targeted for molding material, 60 ° mirror surface glossiness was measured according to JIS Z 8741: 1997, and the glossiness of the surface of the molding material was measured using Nippon Denshoku Kogyo VG7000. .

[Oleic acid advancing contact angle, receding contact angle]

The advancing contact angle and the receding contact angle were measured by the expansion-contraction method, and using the Kyowa Kaimen Kagaku Co., Ltd. Drop Master DM-501, according to the expansion-contraction method manual of the device. The advancing contact angle specifically discharges oleic acid (made by Nakarai's first-class Nakarai Tesque) from the syringe continuously at a liquid discharge rate of 8.5 μL / sec to a final liquid volume of 50 μL, photographing the shape of the droplet 30 times every 0.5 seconds, Each contact angle was obtained using the integrated analysis software "FAMAS" attached to the device. Since the contact angle in the droplet expansion process changes first with the expansion and continues to be substantially constant, the contact angle data is arranged in the order of measurement, and when five consecutive points are selected in that order, The average value when the five standard deviations became 1 degree or less for the first time was made into the forward contact angle of the measurement, and this measurement was performed 5 times with respect to 1 sample, and the average value was made into the forward contact angle of the sample.

The receding contact angle was continuously sucked into the droplets at an initial droplet amount of 50 µL and a liquid discharge rate of 8.5 µL / sec, photographing the shape of the reduction process of the droplets, and obtaining the respective contact angles in the same manner. Since the contact angle of the droplet contraction process first changes with shrinkage and shows a substantially constant behavior, when the contact angles are arranged in the direction in which the droplet contracts, and five consecutive points are selected in that order The average value when the continuous five standard deviations became 1 degrees or less for the first time was made into the retreat contact angle of the measurement, and this measurement was performed 5 times with respect to one sample, and the average value was made into the retreat contact angle of the sample. Moreover, depending on the sample, although the contact angle of the shrinkage | contraction process of a droplet does not become constant, it may continue to fall continuously, About this, the receding contact angle was 0 degrees.

[Measurement of Elemental Compositions on Surfaces by X-ray Photoelectron Spectroscopy]

The element composition of the surface was measured by the following apparatus and conditions, and the ratio of the number of fluorine atoms among the detected elements was calculated | required.

Device: Quantera SXM (manufactured by PHI)

X-ray excitation: monochromatic Al Kα1, 2-ray (1486.6 eV)

X-ray diameter: 200㎛

Photoelectric escape angle: 15 °

[10-point average roughness (Rz) and centerline average roughness (Ra) by atomic force microscope]

The surface structure was measured on the following apparatuses and conditions, and 10-point average roughness Rz and centerline average roughness Ra prescribed | regulated to JISB0601: 2001 were calculated | required.

Device: Nanoscope IIIa (manufactured by Digital Instruments)

Measurement mode: tapping mode

Scanning Range: 5㎛ × 5㎛

Resolution: 512 × 512pixel

[Mock fingerprint application method]

The adhesion of the simulated fingerprint to the surface targeted for the molding material of the present invention includes: 1. Preparation of the simulated fingerprint solution, 2. Preparation of the simulated fingerprint sheet, 3. Transfer of the simulated fingerprint solution to the silicone rubber, 4. Simulation simulation fingerprint Was carried out in four steps of adhesion to the molding material surface.

1. Preparation of simulated fingerprint solution

After weighing-in the following material at the following ratio, it stirred for 30 minutes with the magnetic stir bar and obtained.

14 parts by mass of oleic acid

6 parts by mass of silica particles (number average particle diameter 2 μm)

Isopropyl Alcohol 80 parts by mass

In addition, the number average particle diameter of the said silica particle mixes the said silica particle with 5 mass% of solid content concentration in a dispersion medium (isopropyl alcohol), disperse | distributes by ultrasonic wave, and it is dripped on a electrically conductive tape, except having manufactured the observation sample except the said It is the value obtained by carrying out similarly to the method.

2. Fabrication of simulated fingerprint sheet

The fingerprint coating liquid was coated on the PET resin film as a supporting substrate using a wire bar (# 7) on "Lumir" (registered trademark) U46 (manufactured by Toray Co., Ltd.), which was coated with an easy-to-adhesive paint at 50 ° C. It dried for 2 minutes.

3. Transfer for Silicone Rubber of Simulated Fingerprint

Silicone rubber of rubber hardness 50 of JIS K6253: 1997 was polished to # 250 m of surface roughness Ra of JIS B0601: 2001 with a water resistant paper of # 250. Subsequently, the silicone rubber polished with the water-resistant paper was pressed to the simulated fingerprint sheet produced in Clause 2 at 30 KPa. The adhesion amount (g / m ² ) of the simulated fingerprint solution to the silicone rubber refers to a value obtained from the area of the silicone rubber and the mass difference before and after the attachment, and as a result of the above method, all were 0.9 g / m ² or more and 1.1 g / m ^2. Or less.

4. Attachment of the simulated fingerprint to the molding material surface

The silicone rubber to which the simulated fingerprint solution was transferred in step 3 was pressed to the surface of the molding material at 30 KPa, and the trace formed on the surface of the molding material was used as the simulation fingerprint.

[How to Wipe Simulated Fingerprints]

Cellulose long-fiber nonwoven gauze ("Haize" gauze NT-4 Kawamoto Sangyo Kabushi) having a dimension of 12.5 x 12.5 cm fixed on the flat plate by fixing a molding material having a simulated fingerprint attached to the target surface in the above method. (Manufactured by Shiki Kaisha Co., Ltd.), a pressure of 30 KPa was applied by placing a weight on it, and then wiped off by carrying out three round trips of 10 cm at a speed of 5 cm / sec.

[Color Difference of Specular Reflective Light Removal with Specular Reflective Light after Simulated Fingerprint Wipe before Simulated Fingerprint]

A black vinyl tape was attached to the opposite surface of the molding material, and the reflected color before and after wiping off the above-described simulated fingerprint was obtained using Konica Minolta Co., Ltd. spectrophotometer CM-3600A using JIS Z8722: Based on 2009, the reflection color of specular reflection removal is Sb10W10 using specular reflection light trap (de: 8 °), and the reflection color of specular reflection is applied to Sb10W10 condition using no specular reflection light trap (di: 8 °). And CIE1976 (L ^* a ^* b ^* ) described in JIS Z8730: 2009.

In addition, from the reflection color after the simulation fingerprint wiping before the simulation fingerprint adhesion, from the reflection color after the simulation fingerprint wiping before the simulation fingerprint attachment (ΔE ^* _ab (di: 8 °) by the calculation method described in JIS Z8730: 2009. Sb10W10) and (ΔE ^* _ab (de: 8 °) Sb10W10) were obtained, the former was ΔE _{SCI -2} and the latter was ΔE _{SCE -2} .

[Fingerprint resistance]

Anti-fingerprint adhesion is placed on the black drawing paper with the evaluation surface of the molding material facing up, and rubs the finger (forefinger) and thumb that presses the fingerprint three times, and then slowly presses on the surface of the surface layer, thereby preventing the visibility of the attached fingerprint. Was evaluated by the following evaluation criteria and 5 or more points were made into the pass.

10 points | pieces: A fingerprint is not recognized or the difference with an unattached part is unknown.

7 points | pieces: A fingerprint can hardly be recognized or it is not recognized.

5 points | pieces: A fingerprint is visually recognized but it does not mind very much.

3 points | pieces: A fingerprint is recognized.

One point: Fingerprint is clearly recognized and is very worried.

The said evaluation was performed about ten subjects and the average value was calculated | required. About the decimal point, it rounded and handled.

[Fingerprint resistance]

After the fingerprint was affixed by the method described above, wiping was performed using a cellulose long-fiber nonwoven gauze ("Haize" gauze NT-4 Kawamoto Sangyo Co., Ltd.) having a fold up dimension of 12.5 x 12.5 cm. . Fingerprint wiping property evaluated the visibility after wiping by this wiping method by the following evaluation criteria, and set five or more points as the pass.

10 points: When wiped once, it is hardly recognized.

7 points | pieces: When it is wiped once, it is hardly worried.

5 points | pieces: When it washes three times, it becomes hardly recognized.

3 points | pieces: When it is wiped five times, it becomes hardly worried.

1 point | piece: Contamination remains even if it wipes five times or more.

The said evaluation was performed about ten subjects and the average value was calculated | required. About the decimal point, it rounded and handled.

[Wiping durability]

The method described above after rubbing the surface of the molding material 100 times continuously using a cellulose long fiber nonwoven gauze having a fold up dimension of 12.5 × 12.5 cm (manufactured by "HIZE" gauze NT-4 Kawamoto Sangyo Co., Ltd.). Fingerprints were attached. The visibility of the attached fingerprint was evaluated by the following evaluation criteria, and 5 or more points were made into the pass.

10 points | pieces: A fingerprint is not recognized or the difference with an unattached part is unknown.

7 points | pieces: A fingerprint can hardly be recognized or it is not recognized.

5 points | pieces: A fingerprint is visually recognized but it does not mind very much.

3 points | pieces: A fingerprint is recognized.

One point: Fingerprint is clearly recognized and is very worried.

The said evaluation was performed about ten subjects and the average value was calculated | required. About the decimal point, it rounded and handled.

In Table 1, the composition of the coating composition was integrated with the evaluation results of the molding materials obtained in Table 2. It was judged that the subject was unsuccessful about what did not pass even one item in an evaluation item.

As shown in Table 2, the Example of this invention passed all the cases of glossiness and fingerprinting, and achieved the subject which this invention is trying to solve.

Examples 8 and 10, wherein the value of (θa-θr) in Equation (2) deviates from the preferred range of the present invention, the value of (θa-θr) in Equation (2), and the structure of Compound B Example 11, which deviates from the preferred range of the present invention, was slightly tolerated, but was an acceptable range.

Table 1-1

TABLE 1-2

Table 1-3

Table 1-4

TABLE 2-1

Table 2-2

TABLE 2-3

Table 2-4

The molding material, the coating composition and the manufacturing method of the molding material according to the present invention can be suitably used for imparting anti-fingerprint, as well as various plastic molded articles, lenses of the outermost surface of a camera, lenses of glasses, buildings and vehicles, etc. It can also be used to impart the same function to each surface of the window glass and various printed matter.

Claims (13)

It is a molding material which has a surface layer on at least one side,
The surface layer contains the following 1) to 3),
60 degree mirror glossiness prescribed | regulated to JIS Z8741: 1997 of the said surface layer is 60% or more,
In the form of the surface observed with the atomic force microscope of the said surface layer, 10-point average roughness (Rz) and centerline average roughness (Ra) prescribed | regulated to JISB0601: 2001 are represented by following formula (3) and (4) Satisfied,
Molding materials with a receding contact angle (θ _r ) of oleic acid greater than 60 °:
1) A fluorine compound A having a site and a reactive site including 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 components
3) Particle d (II) comprising particles d (I) which are silica particles having a number average particle diameter of 5 nm or more and 20 nm or less and particles d (II) which are silica particles having a number average particle diameter of 200 nm or more and 300 nm or less. Particle component to contain in the range of 0.2 mass% or more and 0.5 mass% or less
<Equation (3)>
4nm <Rz≤25nm
<Equation (4)>
Ra≤4nm The method of claim 1,
Color difference with specular reflection after the simulated fingerprint wiping based on the state before the simulated fingerprint adhesion obtained in accordance with JIS Z8730: 2009 and JIS Z8722: 2009 when the surface layer is subjected to the simulation fingerprint wiping and the simulation fingerprint wiping under the following conditions. (ΔE ^* _ab ) (di: 8 °) Sb10W10 (hereafter 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):
<Equation (1)>
((ΔE _SCI-2 ) ² + (ΔE _SCE-2 ) ² ) ^1/2 ≤2.0
Conditions for Simulated Fingerprinting: A dispersion containing 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 of 3 μm defined in JIS B0601: 2001, and is specified in JIS K6253: 1997. 1.0 g / m <^{2> is made to} adhere to the silicone rubber of rubber hardness 50 to make it, and this is made to adhere to the surface made into the target at the pressure of 30 KPa.
Conditions for Wiping a Fingerprint: The simulated fingerprint attached by the above method is rubbed with a nonwoven fabric three times at a pressure of 30 KPa and a speed of 5 cm / sec. The molding material according to claim 2, wherein the receding contact angle θ _r of oleic acid of the surface layer is 50 ° or more. The molding material according to any one of claims 1 to 3, wherein the forward contact angle (θ _a ) and the receding contact angle (θ _r ) of the oleic acid of the surface layer satisfy the following equation (2).
<Equation (2)>
(θ _a -θ _r ) ≤15 ° The elemental composition according to any one of claims 1 to 3, wherein in the elemental composition obtained by analysis at the photoelectron escape angle of 15 ° by X-ray photoelectron spectroscopy (XPS), the ratio of fluorine is 50 in atomic ratio. Molding material that is at least%. delete The molding material according to any one of claims 1 to 3, wherein the surface layer contains the following 1) to 3):
1) Fluorine compound A having a site and a reactive site including 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 and a reactive site containing an alkyl group and / or alkanediyl group having 8 or more carbon atoms
3) binder components. The molding material according to claim 1, wherein the surface layer contains the following 1) to 3):
1) at least 2 and at most 5 reactive in a moiety and at least one moiety comprising 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 Fluorine compound A (II) having a site
2) Binder raw material C (I) which is a compound which has 10 or more reactive site | part in a molecule | numerator, and is a compound of number average molecular weights 1500 or more and 3000 or less, and a compound which has 3 or more and 6 or less reactive site | parts in a molecule, and has a number average molecular weight 500 or more and 1500 or less Binder component formed from phosphorus binder raw material C (II)
3) Particle d (II) comprising particles d (I) which are silica particles having a number average particle diameter of 5 nm or more and 20 nm or less and particles d (II) which are silica particles having a number average particle diameter of 200 nm or more and 300 nm or less. Particle component contained in the range of 0.2 mass% or more and 0.5 mass% or less. Coating composition containing the following 1) to 4):
1) A fluorine compound A having a site and a reactive site including 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 and a reactive site containing an alkyl group and / or alkanediyl group having 8 or more carbon atoms
3) binder raw material
4) Particle D (II) comprising particle D (I) which is silica particles having a number average particle diameter of 5 nm or more and 20 nm or less and particle D (II) which is silica particles having a number average particle diameter of 200 nm or more and 300 nm or less. Particle component contained in the range of 0.2 mass% or more and 0.5 mass% or less. Coating composition containing the following 1) to 3):
1) A fluorine compound A having a site and a reactive site including 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 D (II) comprising particles D (I) which are silica particles having a number average particle diameter of 5 nm or more and 20 nm or less and particles D (II) which are silica particles having a number average particle diameter of 200 nm or more and 300 nm or less. Particle component contained in the range of 0.2 mass% or more and 0.5 mass% or less. The coating composition according to claim 10, which contains the following 1) to 3).
1) at least 2 and at most 5 reactive in a moiety and at least one moiety comprising 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 Fluorine compound A (II) having a site
2) Binder raw material C (I) which is a compound which has 10 or more reactive site | part in a molecule | numerator, and is a compound of number average molecular weights 1500 or more and 3000 or less, and a compound which has 3 or more and 6 or less reactive site | parts in a molecule, and has a number average molecular weight 500 or more and 1500 or less Binder raw material containing phosphorus binder raw material C (II)
3) Particle D (II) comprising particles D (I) which are silica particles having a number average particle diameter of 5 nm or more and 20 nm or less and particles D (II) which are silica particles having a number average particle diameter of 200 nm or more and 300 nm or less. Particle component contained in the range of 0.2 mass% or more and 0.5 mass% or less. The manufacturing method of the molding material which coats the coating composition of any one of Claims 9-11 on the surface. delete