JP2014092770A - Molding material and method for manufacturing molding material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material capable of maintaining glossiness or transparency and practically required scratch resistance and obtaining both fingerprint resistance and antireflection, and a method for manufacturing the molding material.SOLUTION: The molding material has surface layers consisting of a second layer and a first layer having different refractive indexes in this order on at least one surface of a support base material and satisfies following conditions 1 to 4. A condition 1: the first layer surface has 40% or more of a 60-degree specular gloss defined by JIS Z8741 (1997). A condition 2: the first layer surface has 60° or more of a receding contact angle θof oleic acid. A condition 3: the first layer surface has an advancing contact angle θand the receding contact angle θof the oleic acid which satisfy a formula (1), (θ-θ)≤15° (1). A condition 4: The minimum reflectance of incident light in a wavelength of 380-780 nm is 2% or less.

Description

  The present invention relates to a molding material having a surface layer excellent in fingerprint resistance and antireflection properties, and a method for producing the molding material.

  Fingers touching the surface of an object (a fingerprint is a pattern formed by a line (ridge) where the opening of a sweat gland in the skin of the fingertip is raised, and the pattern attached to the surface of the object. Is attached, there is a problem that an unpleasant impression that the fingerprint is recognized and the appearance is dirty is given. For example, a fingerprint is attached by gripping the casing of a mobile phone, and the fingerprint is conspicuous and the sense of cleanliness is impaired. In particular, electronic devices operated with fingers are increasing recently, such as smartphones / tablets PCs, keyboards, televisions, air conditioner remote controls, and the like.

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

  In addition, in various displays such as smartphones, televisions, and personal computer monitors, an anti-reflective member (anti-reflection) having a glossy surface is used to make the contrast of the image high. Such an anti-reflective member is touched with a finger. There is a problem that fingerprints are easily visible, and fingerprints are difficult to be visually recognized or easily wiped off. (Hereafter, the characteristic that the fingerprint on the surface of the article is difficult to be visually recognized or easily wiped off is referred to as “fingerprint resistance”).

In order to solve such a problem, as a reflection preventing member in which fingerprints are hard to be visually recognized, Japanese Patent Application Laid-Open No. H10-228707 discloses “a low refractive index layer having a refractive index of less than 1.75 on one surface of a substrate at a light wavelength of 550 nm. Or an optical thin film formed by forming a thin film layer containing at least a high refractive index layer having a refractive index of 1.75 or more at a wavelength of light of 550 nm, or both, and the surface of the thin film layer When the oleic acid having a dry film thickness of 20 μm is applied thereon, the optical thin film coated with the oleic acid and the optical thin film not coated with the oleic acid have a D65 light source of 5 ° The color difference ΔE ^* _ab (= {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2 ) of CIELAB (according to JIS Z 8729) in incident, 2 ° field of view and specularly reflected light is 5 Must be Optical thin film is characterized. "Has been proposed.

  Further, as an antireflection film member for a touch panel in which an antifouling layer and an antireflection layer are laminated, Patent Document 2 discloses that “a light transmissive substrate and the substrate are arranged so as to face each other with a predetermined interval therebetween”. A light-transmissive conductive layer is formed on the substrate and on the surface of the film substrate facing the substrate, and the film substrate Further, at least a hard coat layer, an adhesion layer, an antireflection layer, and an antifouling layer are laminated in this order, and the antireflection layer is formed by laminating at least two refractive index layers having a predetermined refractive index. In addition, in Patent Document 3, “a first transparent substrate having a transparent conductive film on at least one surface and a second transparent substrate are opposed to each other. Arranged so that A panel comprising: (a) a hard coat layer comprising a cured product of a curable resin that is cured by irradiation with active energy rays, and an antireflection hard coat comprising two or more layers having different refractive indexes as the outermost layer of the touch panel (B) each layer having a different refractive index of the antireflection hard coat layer is a layer mainly composed of a cured product of a curable resin that is cured by irradiation with active energy rays, or the cured product and a metal oxide. A touch panel characterized by being a layer mainly composed of particles has been proposed.

  Furthermore, as a technology that focuses on the shape of the surface in order to make the fingerprints less visible, Patent Document 4 states that “a substrate, a silicon compound and hydrophilic metal oxide fine particles having an average particle diameter of 1 to 100 nm are included on the surface of the substrate. A composite material having a fingerprint-resistant coating film formed thereon, wherein the coating film has a glossiness of 8 or less and a color difference of less than 4.6. "Material" has been proposed.

JP 2009-122416 A JP 2004-21550 A JP 2004-46728 A JP 2010-259971 A

  The problem to be solved by the present invention is to provide a molding material having a surface layer capable of achieving both fingerprint resistance and antireflection properties while maintaining glossiness or transparency and scratch resistance necessary for practical use, and a molding material It is to provide a manufacturing method. The above-mentioned known technique is in the following situation for the above-mentioned problem.

  First, in Patent Documents 1 to 3, the antireflection property is excellent, but when the present inventors have confirmed the visibility of fingerprints under various conditions, the structures and characteristics of Patent Documents 1 to 3 have poor fingerprint resistance. It was enough.

  In Patent Document 4, the fingerprint resistance is good, but the glossiness is greatly lowered and the antireflection function cannot be obtained. In addition, the surface shape has not been conceived with respect to the fine shape used in the present invention.

In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, completed the following invention. That is, the present invention is as follows.
1) A molding material having a surface layer composed of a second layer and a first layer having different refractive indexes in this order on at least one surface of a supporting substrate, and satisfying the following conditions 1 to 4.
Condition 1. The 60 ° specular glossiness specified by JIS Z8741 (1997) on the surface of the first layer is 40% or more.
Condition 2. Receding contact angle theta _r oleic acid in the first layer surface than 60 °.
Condition 3. Advancing contact angle theta _a and receding contact angle theta _r oleic acid in the first layer surface satisfy the formula (1).
(Θ _a −θ _r ) ≦ 15 ° Formula (1)
Condition 4. The minimum reflectance of incident light at a wavelength of 380 nm to 780 nm is 2% or less.
2) The molding material according to 1), wherein the first layer satisfies the following conditions 5 and 6, and the second layer satisfies the following condition 7.
Condition 5. The refractive index of incident light at a wavelength of 580 nm is 1.45 or more and 1.50 or less.
Condition 6. The layer thickness is 80 nm or more and 120 nm or less.
Condition 7. The refractive index of incident light at a wavelength of 580 nm is 1.60 or more and 1.75 or less.
3) The number of peaks having a height exceeding the root mean square roughness (RMS) observed by an atomic force microscope (AFM) on the surface of the first layer is 500 or more and 1500 or less per 25 μm ^2. The molding material according to either 1) or 2).
4) Fluorine in which the first layer has a reactive site and a site containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group and a fluorooxyalkanediyl group The molding material according to any one of 1) to 3), comprising Compound A, binder component A, and particles a having a number average particle diameter of 5 nm to 250 nm.
5) The molding material according to 4), wherein the particles a are silica linked in a bead shape and / or branched.
6) The molding material is
(1) Step (2) of forming a second layer on a supporting substrate On the second layer formed in (1), a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and Coating composition comprising fluorine compound A having at least one site selected from the group consisting of fluorooxyalkanediyl groups and a reactive site, binder raw material A, and particles a having a number average particle size of 5 nm to 250 nm The manufacturing method of the molding material in any one of 1) to 5) which consists of the process of forming said 1st layer by apply | coating, drying, and hardening A.
7) The method for producing a molding material according to 6), wherein the particles a are silica linked in a bead shape and / or branched.

  According to the present invention, it is possible to obtain a molding material that satisfies both fingerprint resistance and antireflection properties while maintaining glossiness or transparency and scratch resistance necessary for practical use, and a method for producing the molding material.

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

  First, the mechanism by which an observer recognizes a fingerprint is that a difference in gloss and color is detected between a portion to which a component constituting the fingerprint is attached and a non-attached portion. This difference in gloss is attributed to the difference in the light reflectance between the adhering part and the non-adhered part and the form of the adhering material, and the difference in the light reflectance is attributed to the difference in the refractive index of the adhering component and the refractive index of the surface layer. Conceivable.

  On the other hand, a general antireflection member expresses an antireflection function using the interference effect of light in the visible light region, and the refractive index of the layer most touched by the atmosphere, that is, the layer touched by human hands, is as much as possible. Since it is advantageous in optical design to approach the refractive index, this method is usually used.

  In addition, as described above, countermeasures against adhesion of fingerprints with conventional antireflection members use methods such as preventing or facilitating adhesion of fingerprints by adding an oil repellent material such as a fluorine-based material as described above. In this method, the difference in refractive index from the outermost surface is large, and deposits with a high contact angle tend to gather in one place, so that they become very conspicuous, and as a result, the effect is insufficient.

  From the above points, the reason why fingerprints are conspicuous in the conventional anti-reflective member is that the components having relatively high refractive index adhere to the low-refractive index layer on the surface of the anti-reflective member. It is thought that it is very conspicuous.

  Therefore, the present inventors have achieved both the fingerprint resistance and the antireflection property by the following three guidelines. That is, firstly, the amount of transfer from the finger to the surface is reduced, and the amount of adhesion is reduced by improving the wiping property of the deposit on the surface. Second, light scattering is reduced by controlling the form of the deposit, and thirdly Is a reduction in the difference in reflectance by bringing the refractive index of the deposit and the surface closer.

  As a form of the present invention based on the above guidelines, in order to solve the above problems, 60 ° specular glossiness defined by JIS Z8741 (1997) of the surface layer, the receding contact angle of oleic acid, olein It has been found that this can be achieved by defining the difference between the advancing contact angle θa and the receding contact angle θr of the acid and the reflectance.

  That is, the measured value of 60 ° specular glossiness defined in JIS Z8741 (1997) on the surface of the first layer is preferably 40% or more, more preferably 50% or more, particularly preferably 60% or more, and the larger the value. Although it is good in terms of glossiness, a realistic upper limit value that enables compatibility with antireflection properties seems to be about 100%. Further, when the specular gloss is less than 40%, glossiness may be felt to be insufficient.

Further, the receding contact angle θ _r of oleic acid on the surface of the first layer is preferably 60 ° or more, and more preferably 70 ° or more. The measuring method and meaning of the receding contact angle will be described later. On the other hand, there is no problem with the receding contact angle. On the other hand, when the receding contact angle is lower than 60 °, the fingerprint component tends to adhere and the fingerprint resistance may be lowered.

Furthermore, the advancing angle contact angle θ _a and the receding contact angle θ _r of oleic acid on the surface of the first layer satisfy the following formula (1), that is, 15 ° or less, more preferably 12 ° or less. Preferably, it is 10 ° or less. If the value of the formula (1) is 0 or a positive value, it is preferable for a small amount. On the other hand, if this value is larger than 15 °, the fingerprint wiping property is insufficient and the fingerprint resistance is lowered. There is.
(Θ _a −θ _r ) ≦ 15 ° Formula (1)
Here, the aforementioned backward contact angle and forward contact angle will be described. The contact angle of the liquid on the solid surface is essentially a thermodynamic quantity and should take a single value once the system is determined. However, in reality, when the liquid moves on the solid surface, the contact angle on the opposite side (retreat side) to the contact angle in the traveling direction often does not take the same value. The contact angle of the traveling method at this time is called a forward contact angle, and the contact angle on the opposite side is called a receding contact angle.

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

  Further, it is preferable that the minimum reflectance of incident light at a wavelength of 380 nm to 780 nm is 2% or less. More preferably, it is 1.5% or less, and the smaller the value, the better the antireflection and visibility, but it is difficult to make it 0%, and the practical lower limit is about 0.01%. Seem. In addition, when the reflectance is greater than 2%, the amount of light reflected on the film surface increases, so that external light may be reflected and visibility may be reduced. Details of the method of measuring the minimum reflectance will be described later.

  Next, in the molding material of the present invention, in order to achieve the above-described characteristics, it is preferable that the refractive index and thickness of the first layer and the refractive index of the second layer be in a specific range. That is, the refractive index of the incident light of the first layer of the present invention at a wavelength of 580 nm is preferably 1.45 or more and 1.50 or less, more preferably 1.46 or more and 1.48 or less. When the refractive index is less than 1.45 or greater than 1.50, fingerprint resistance may be lowered due to the fact that fingerprints are easily visible when attached to the surface.

  The layer thickness of the first layer is preferably 80 nm to 120 nm, more preferably 85 nm to 115 nm, and particularly preferably 90 nm to 110 nm.

  Further, the refractive index of the incident light of the second layer at a wavelength of 580 nm is preferably 1.60 or more and 1.75 or less, more preferably 1.60 or more and 1.72 or less, and particularly preferably 1.65 or more and 1.70 or less.

  When the layer thickness of the first layer is less than 80 nm or greater than 120 nm, and when the refractive index of the second layer is less than 1.60 or greater than 1.75, the light interference effect is in the visibility region. In some cases, the reflection preventing function is insufficient because the reflection of external light is strongly felt. A method for measuring the refractive index and layer thickness of each layer will be described later.

  Next, in the molding material of the present invention, in order to obtain the above characteristics, it is preferable that there is a layer having fine unevenness on the surface of the first layer, and particularly preferable for the number of unevenness in a specific range per unit area. There is a range. The reason for this is not clear, but by introducing a specific fine concavo-convex structure, the oil droplets created by the attached fingerprint components are made finer, and the light scattering and absorption caused by the attached matter are reduced, making it less visible. For the reason. In addition, an oil drop means here the microscopic aggregate of the liquid and solid which comprise the fingerprint adhering to the 1st layer surface.

Specifically, the number of peaks having a height exceeding the root mean square roughness (RMS) observed by the atomic force microscope (AFM) on the first layer surface is 500 or more and 1500 or less per 25 μm ^2. Is preferable, and more preferably 800 or more and 1200 or less. If it is out of this range, the effect of reducing the size of the oil droplets constituting the aforementioned fingerprint may be insufficient.

  Here, the root mean square roughness (RMS) is a square root of a value obtained by averaging the squares of deviations from the mean line to the measurement curve, and refers to what is obtained from the roughness curve, and the peak is based on the mean line. And the distance to the measurement curve is greater than the mean square roughness.

  In general, arithmetic average roughness (Ra) based on JIS R1683 (2007) is used as an index of the surface shape. Ra is a numerical value representing average depth information over the entire surface, and the molding of the present invention. It is not suitable as an index for evaluating the shape and number of local uneven structures such as the material has.

  Next, the first layer of the molding material of the present invention preferably contains a fluorine compound A, a binder component A, and particles a having a number average particle size of 5 nm to 250 nm. Although details of the fluorine compound A, the binder component A, and the particles a will be described later, the fluorine compound A reduces the surface energy, thereby increasing the contact angle of the liquid constituting the fingerprint and reducing the adhesion amount. It has a function of adjusting the refractive index, and the binder component A has a role of binding the particles a and imparting scratch resistance necessary for practical use. The particles a are used to form the fine uneven structure described above. In addition, the preferable ratio of each of the fluorine compound A, the binder component A, and the particles a will be described later. Here, the number average particle diameter of the particles a means the number-based arithmetic average length diameter described in JIS Z8819-2 (2001), and is a value obtained by observing a cross section of the molding material with a transmission electron microscope (TEM). The specific measurement method will be described later.

  Next, in the molding material of the present invention, the aggregate of the particles a has a preferable form, and specifically, it is preferably present in a bead-like and / or branched form. Although details of the particles a will be described later, by using silica as the particles, so-called self-organization due to the interparticle interaction caused by the surface state of the particles a and the transverse capillary force existing between the particles in the coating-drying process. It is easy to form the preferable uneven structure.

  Next, in the molding material of the present invention, the fluorine compound A reacts with a site containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group and a fluorooxyalkanediyl. A compound having a functional moiety is preferred, more preferably one is a fluorine-containing dendrimer and the other is a material having a fluoropolyether moiety. By using these materials, molecules showing low surface energy can be present at a high density on the outermost surface. The fluorine-containing dendrimer and fluoropolyether moiety will be described later. Hereinafter, the present invention will be described element by element.

[Molding material and surface layer]
The molding material of the present invention may be any of a flat shape (film, sheet, plate) and three-dimensional shape (molded product) as long as it has a surface layer containing the characteristics of the present invention and / or the material. Good. Here, the “surface layer” in the present invention is composed of a second layer and a first layer having different refractive indexes, and the second layer and the first layer are arranged in this order on at least one surface of the support base material. The surface layer can be distinguished from the surface of the molding material in the thickness direction by having a boundary surface that is discontinuous in the adjacent part and element composition, the shape of inclusions (particles, etc.) and physical properties. Refers to a site having More specifically, cross-sectional observation of the molding material in the thickness direction from the surface with various composition / element analyzers (IR, XPS, XRF, EDAX, SIMS, etc.), electron microscope (transmission type, scanning type) or optical microscope In this case, the region is distinguished by the discontinuous boundary surface and indicates a portion having a finite thickness.

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

[Coating composition A]
The coating composition A is a liquid composition at room temperature that can form the first layer on the second layer by a general coating process including coating, drying, and curing in the manufacturing method of the present invention. In particular, it preferably contains a fluorine compound A, a binder raw material A, and particles a having a number average particle size of 5 nm to 250 nm, and the coating composition A includes a solvent and a photopolymerization initiator in addition to the above. Various additives such as a curing agent and a catalyst may be included. Details of the constituent materials will be described later.

[Fluorine compound A]
The fluorine compound A is a fluorine compound having at least one part selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group and a fluorooxyalkanediyl group and a reactive part Point to.

  Here, a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group are alkyl groups, oxyalkyl groups, alkenyl groups, alkanediyl groups, and oxyalkanediyl groups. A part or all of the substituents are replaced by fluorine, all of which are mainly composed of fluorine atoms and carbon atoms, and there may be branches in the structure. A dimer, trimer, oligomer, or polymer structure may be formed.

  Further, the reactive site refers to a site that reacts with other components by external energy such as heat or light. Examples of such reactive sites include alkoxysilyl groups and silanol groups in which alkoxysilyl groups are hydrolyzed from the viewpoint of reactivity, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and the like. From the viewpoint of reactivity and handling properties, alkoxysilyl group, silyl ether group or silanol group, epoxy group, acryloyl (methacryloyl) group are preferable, vinyl group, allyl group, acryloyl group, methacryloyl group are more preferable, An acryloyl group and a methacryloyl group are particularly preferable.

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

  Examples of general formula (1) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluorobutyl- 2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluoro Decylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3 Perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorononyl acrylate , Hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl Methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodec Ethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methyl Hexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-7-methyloctylethyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl Methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobut Examples include til methacrylate and triacryloyl-heptadecafluorononenyl-pentaerythritol. The Hansen solubility parameters of these fluorine compounds A are characterized according to the properties of the reactive sites described above.

  Further, one of the preferred materials for the fluorine compound A is a material having a fluoropolyether moiety, and the fluoropolyether moiety is a moiety comprising a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkyldiyl group, etc. This is a structure represented by formulas (2) and (3).

_{CF n1 H (3-n1)} - (CF n2 H (2-n2)) k O-
_{- (CF n3 H (2-} n3)) m O-
... General formula (2)
_{- (CF n4 H (2-} n4)) p O- (CF n5 H (2-n5)) s O-
... General formula (3)
Here, n1 is an integer of 1 to 3, n2 to n5 are integers of 1 or 2, and k, m, p, and s are integers of 0 or more. Preferably, n1 is 2 or more, n2 to n5 are integers of 1 or 2, more preferably n1 is 3, n2 and n4 are 2, and n3 and n5 are integers of 1 or 2.

  There is a preferred range for the chain length of this fluoropolyether moiety, the carbon number is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and further preferably 6 or more and 8 or less. If the number of carbon atoms is less than 4, the surface energy may decrease, and if it exceeds 12, the solubility in a solvent may decrease.

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

  Examples of commercially available fluorine compounds A include FA-200 (Nissan Chemical Co., Ltd.) as a fluorine-containing dendrimer, and RS-75 (DIC) as a material having a fluoropolyether moiety having 4 to 12 carbon atoms. Co., Ltd.), OPTOOL DSX, OPTOOL DAC (Daikin Industries Co., Ltd.), C10GACRY, C8HGOL (Oil Products Co., Ltd.), etc., and these products can be used.

[particle]
The surface layer of the molding material of the present invention and the coating composition used in the method for producing the molding material preferably include particles, and one of the first layer and the second layer constituting the surface layer may include, Both may include. The particles may be either inorganic particles or organic particles, but inorganic particles are preferable from the viewpoint of durability. The number of types of inorganic particles is preferably 1 or more and 20 or less. The number of types of inorganic particles is more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 3 or less.

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

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

[Particle a]
The particles a may be either inorganic particles or organic particles, but are preferably inorganic particles from the viewpoint of durability, and may be metal or metalloid oxides, nitrides, borides, chlorides, carbonates, sulfates. It is preferable that a complex oxide containing two kinds of metals and metalloids, a different element is introduced between the lattices, a lattice point is replaced with a different element, or a lattice defect is introduced.

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

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

  Furthermore, the number average particle diameter of the particles a is preferably 5 nm or more and 250 nm or less. When the number average particle diameter of the inorganic particles is smaller than 5 nm, the ability to form irregularities may not be sufficient, and when the number average particle diameter is larger than 250 nm, the gloss may be lowered.

  Further, the form of the particles a is not particularly limited, but the particles a have a long chain structure in which silica is connected in a bead shape (a shape in which a plurality of silicas are connected in a chain), or the connected silica is branched. Those are preferred. These are hereinafter referred to as beaded and / or branched silica.

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

In order to obtain a particularly preferable surface shape of the present invention, the above-mentioned bead-like and / or branched silica is stably dispersed in a good solvent of the binder raw material A contained in the coating composition A. It is particularly preferred that the necessary surface modification is made. For example, when an acrylic monomer or oligomer is used as a binder raw material, the surface modification requires an alkyl group, an alkenyl group, a vinyl group, a (meth) acryl group or the like having 1 to 5 carbon atoms on the surface. It is preferably introduced. As a commercial product satisfying this, there is MEK-ST-UP (MEK dispersion).
The particles a contained in the coating composition A of the present invention are contained in the first layer in a state in which the surface state is changed by heat, ionizing radiation, or the like in a process such as coating, drying, curing or vapor deposition. May be included. That is, the coating composition A is subjected to a treatment such as coating, drying, curing treatment or vapor deposition, and the particles a in the coating composition A react with each other, so that the particles a contained in the surface layer are particles. For some particles a contained in the surface layer even when the functional groups on the surface are different from those after coating, drying, curing treatment or vapor deposition in the coating composition A, the coating composition A In some cases, the particles a exist in the same state as the particles a contained therein (that is, the particles a remain unreacted).

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

  The number average particle size of the particles a can be determined by observing the surface or the cross section, and the number average particle size of the particles a can be determined from the coating composition A diluted with a solvent. It is possible to prepare and observe a sample by dropping and drying.

[Second layer constituent material]
As described above, the refractive index of the second layer of the molding material has a preferable range. Furthermore, the layer thickness of the second layer is preferably 80 nm or more, and more preferably 100 nm or more. If the thickness of the second layer is less than 80 nm, the antireflection function may be insufficient. There is no particular problem if the thickness of the second layer is 80 nm or more. However, the upper limit of the thickness of the second layer is about 4000 nm. If it is thicker than that, antireflection performance and transparency may be insufficient.

  The second layer of the molding material preferably contains particles b and a binder component B as main components. In this specification, the main component means a component occupying 50% by mass or more of all components unless otherwise specified. In this case, the sum of the particles b and the binder component B is 50% by mass or more. The method for producing the second layer of the molding material is not particularly limited, but a method of applying, drying, and curing a coating composition (hereinafter referred to as coating composition B) on a supporting substrate. Is preferably used. The coating composition B preferably contains the particles b and the binder raw material B as main components. The binder component B and the binder raw material B will be described later.

  The particles b contained in the coating composition B of the present invention are applied to the second layer in a state in which the surface state is changed by heat, ionizing radiation or the like in a process such as coating, drying, curing or vapor deposition. May be included.

  That is, the coating composition B is subjected to a treatment such as coating, drying, curing treatment or vapor deposition, and the particles b in the coating composition B react to form particles b in the surface layer. Even if the surface functional groups are different from those in the coating composition B after coating, drying, curing treatment or vapor deposition, some of the particles b contained in the surface layer are coated with the coating composition B. In some cases, the particles b exist in the same state as the particles b contained therein (that is, the particles b remain unreacted).

  The particle b may be either an inorganic particle or an organic particle, but is preferably an inorganic particle from the viewpoint of durability, and may be a metal or metalloid oxide, nitride, boride, chloride, carbonate or sulfate. It is preferable that a complex oxide containing two kinds of metals and metalloids, a different element is introduced between the lattices, a lattice point is replaced with a different element, or a lattice defect is introduced.

  The particles b are preferably inorganic particles of a different type from the particles a. The particles b are not particularly limited, but are preferably metal elements, metalloid oxides, nitrides, borides, carbonates, sulfates, Ga, Zr, Ti, Al, In, Zn, Sb, Sn. And oxide particles of at least one element selected from the group consisting of Ce and Ce.

Specifically, the particles b are composed of zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO). ₂ ), at least one selected from the group consisting of antimony oxide (Sb ₂ O ₃ ), and indium tin oxide, or a solid solution therebetween, and some elements are substituted, or some elements enter between the lattices Or a solid solution in which some elements are deficient, or inorganic particles in which different types of inorganic particles are joined. The particles b are particularly preferably phosphorus-containing tin oxide (PTO), antimony-containing tin oxide (ATO), gallium-containing zinc oxide (GZO), titanium oxide (TiO ₂ ), or zirconium oxide (ZrO ₂ ).

  The particles b are preferably inorganic particles having a higher refractive index than the particles a. The refractive index of the particle b is preferably 1.60 to 2.80, more preferably 1.65 to 2.50. When the refractive index of the inorganic particle portion of the particle b is smaller than 1.60, the refractive index of the second layer containing the particles b of the molding material to be obtained is lowered, and the refractive index difference from the first layer containing the particles a is small. Therefore, the reflection preventing function may be insufficient. When the refractive index of the particles b is greater than 2.80, the reflected color may be strong.

Furthermore, in the molding material obtained by the production method of the present invention, when the particles a are silica particles, it is particularly preferable that the particles b are inorganic particles having a higher refractive index than the silica particles. As the high inorganic particles, inorganic compounds having a refractive index of 1.60 to 2.80 are preferably used. Specific examples of such inorganic compounds include antimony oxide, antimony-containing zinc oxide, antimony-containing tin oxide (ATO), phosphorus-containing tin oxide (PTO), gallium-containing zinc oxide (GZO), and zirconium oxide (ZrO ₂ ). , And / or titanium oxide (TiO ₂ ), with titanium oxide and zirconium oxide having a particularly high refractive index being more preferred.

[Binder Component A, Binder Component B, Binder Raw Material A, Binder Raw Material B]
The first layer of the molding material preferably includes the binder component A, the second layer of the molding material preferably includes the binder component B, the coating composition A preferably includes the binder raw material A, The coating composition B preferably contains a binder raw material B.

  Here, the binder raw material A and the binder raw material B are compounds contained in the coating composition A and the coating composition B. By applying, drying, and curing the coating composition A and the coating composition B, It is a raw material of the binder component A and the binder component B present in the formed layer. That is, the binder raw material A and the binder raw material B contained in the coating composition A and the coating composition B are cured by heat, ionizing radiation or the like, and are contained in the first layer and the second layer. A and the binder component B are called. In addition, some binder materials may exist in the same state as in the coating composition even in the molding material (there may exist unreacted), but even in that case, the one in the molding material is the binder component That's it.

  The binder raw material A and the binder raw material B in the coating composition are not particularly limited, and may be the same or different. Moreover, it is preferable that it can harden | cure with a heat | fever and / or active energy ray etc. from a viewpoint of manufacturability. The binder raw material A and the binder raw material B in the coating composition A and the coating composition B may be one kind or a mixture of two or more kinds.

  Further, from the viewpoint of holding the particles a and particles b in the surface layer, monomers and oligomers having alkoxy groups, silanol groups, reactive double bonds, and functional groups capable of ring-opening reaction in the molecule are binders. It is preferable that it is the raw material A and the binder raw material B. Further, in the case of curing with UV rays, oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing in an anaerobic atmosphere is more preferable. By reducing the oxygen concentration, the cured state of the outermost surface is improved and chemical resistance may be improved.

  Specifically, the binder raw material A and the binder raw material B in such a coating composition are preferably polyfunctional acrylate monomers, oligomers, alkoxysilanes, alkoxysilane hydrolysates, alkoxysilane oligomers, and the like. Is more preferable.

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

  Commercially available polyfunctional acrylic compositions include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam” (registered trademark) series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol” (registered trademark) series, etc.) Shinnakamura Chemical Co., Ltd. (trade name “NK Ester” series, etc.), DIC Corporation; (trade name “UNIDIC” (registered trademark), etc.), Toagosei Co., Ltd. (“Aronix” (registered trademark) series, etc. ), NOF Corporation; (“Blemmer” (registered trademark) series, etc.), Nippon Kayaku Co., Ltd .; (trade name “KAYARAD” (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd .; "Series" etc.), and these products can be used.

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

The Hansen solubility parameter of the binder raw material A is characterized according to its functional group. There are favorable conditions for the solubility parameter of Hansen, the binder raw material. Specifically, the dispersion term of Hansen solubility parameter of fluorine compound A is σ _d , the polar term is σ _p , the hydrogen bond term is σ _h , the dispersion term of Hansen solubility parameter of binder component is σ _Bd , and the polar term is When σ _Bp and the hydrogen bond term are σ _Bh ,
R = [(σ _d −σ _Bd ) ² + (σ _p −σ _Bp ) ² + (σ _h −σ _Bh ) ² ] ^1/2
The parameter R defined by is preferably 3 (MPa) ^1/2 or more and 12 (MPa) ^1/2 or less, preferably 3 (MPa) ^1/2 or more and 8 (MPa) ^1/2 or less. More preferably, it has a value of 4 (MPa) ^1/2 or more and 6 (MPa) ^1/2 or less. When the parameter R exceeds 12 (MPa) ^1/2 , the transparency and glossiness decrease. On the other hand, when the parameter R is less than 3 (MPa) ^1/2 or when σ _d <σ _Bd is not satisfied, the fingerprint adhesion amount increases.

[solvent]
The coating composition A and the coating composition B may contain a solvent. The number of solvent types is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and still more preferably 1 or more and 6 or less. Here, the “solvent” can dissolve or disperse the particles a, particles b, fluorine compound A, binder raw material A, and binder raw material B described above, and is almost processed through coating, drying, and curing steps. It refers to a substance that is liquid at room temperature and pressure that can be evaporated in its entirety.

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

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

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

  The content ratio of the initiator and the curing agent is preferably 0.001 to 30 parts by mass, more preferably 0.05 parts by mass with respect to 100 parts by mass in total of the binder raw materials in the coating composition. 20 parts by mass, more preferably 0.1 to 10 parts by mass.

  The coating composition A and the coating composition B may further contain additives such as a surfactant, a thickener, and a leveling agent as necessary.

[Content of each component in coating composition A]
The coating composition A includes the fluorine compound A, the binder raw material A, and the particles a. The mass relationship in the coating composition A will be described.

  In 100% by mass of the coating composition A, the fluorine compound A is 0.025% by mass to 40% by mass, the particle a is 0.2% by mass to 55% by mass, and the binder raw material A is 0.8% by mass to 66% by mass. Hereinafter, the solvent is preferably 10% by mass to 95% by mass, and the initiator, the curing agent, and the other components of the catalyst are preferably 0.025% by mass to 7% by mass.

  More preferably, the fluorine compound A is 0.05% by mass to 30% by mass, the particles a are 0.4% by mass to 50% by mass, the binder raw material A is 3.2% by mass to 56% by mass, and the solvent is 40 mass% or more and 90 mass% or less, and other components of an initiator, a hardening | curing agent, and a catalyst are 0.05 mass% or more and 6 mass% or less.

[Content of each component in coating composition B]
Although the said coating composition B contains the binder raw material B and the particle | grains b, each mass relationship in the coating composition B is demonstrated.

In 100% by mass of the coating composition B, the particle b is 0.2% by mass to 95% by mass, the binder raw material B is 0.8% by mass to 60% by mass, the solvent is 30% by mass to 95% by mass, and the initiator. The other components of the curing agent and the catalyst are preferably exemplified by 0.025% by mass or more and 7% by mass or less.
More preferably, the particle b is 0.4% by mass to 90% by mass, the binder raw material B is 3.2% by mass to 50% by mass, the solvent is 40% by mass to 90% by mass, an initiator, a curing agent, The other components of the catalyst are 0.05% by mass or more and 6% by mass or less.

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

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

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

[Method of manufacturing molding material]
The surface layer formed on the surface of the molding material of the present invention, that is, the second layer and the first layer are vapor phase treatment such as vapor deposition, sputtering, and CVD, liquid phase treatment such as coating, impregnation, plating, saponification, and transfer. It may be formed on the surface of the molding material by solid phase treatment such as pasting and a combination of these treatments, but vapor phase treatment by vapor deposition and liquid phase treatment by coating are preferred, and the coating composition is applied to a supporting substrate or the like. A liquid phase treatment formed by coating is more preferable. The two layers may be formed by different methods or by the same method.

  The method for producing the molding material by coating is not particularly limited, but the coating composition is supported by a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method or a die coating method (US Pat. No. 2,681,294). It is preferable to form a layer by applying to the above. Further, among these coating methods, the gravure coating method or the die coating method is more preferable as the coating method. The method for producing the coating composition will be described later.

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

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

The drying process is generally divided into (A) a constant rate drying period and (B) a decreasing rate drying period. Since the former is the rate of drying, diffusion of solvent molecules into the atmosphere on the liquid film surface is The drying speed is constant in this section, the drying speed is governed by the partial pressure of the solvent to be evaporated in the atmosphere, the wind speed and the temperature, and the film surface temperature is constant at a value determined by the hot air temperature and the partial pressure of the solvent to be evaporated in the atmosphere. Become. In the latter, since the diffusion of the solvent in the liquid film is rate-limiting, the drying rate does not show a constant value in this section and continues to decrease, and is governed by the diffusion coefficient of the solvent in the liquid film, and the film surface temperature is To rise. Here, the drying rate represents the amount of solvent evaporation per unit time and unit area, and has a dimension of g · m ⁻² · s ⁻¹ .

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

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

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

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

Moreover, when hardening with an energy ray, it is preferable that it is an electron beam (EB ray) and / or an ultraviolet-ray (UV ray) from a versatility point. In the case of curing with ultraviolet rays, the oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing in a nitrogen atmosphere (nitrogen purge) is more preferable. When the oxygen concentration is high, the curing of the outermost surface is inhibited, the curing becomes insufficient, and the scratch resistance and alkali resistance may be insufficient. Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. When the discharge lamp type to ultraviolet cured using a high pressure mercury lamp is, illuminance 100~3000mW / cm ² of ultraviolet, ultraviolet irradiation under the conditions preferably 200~2000mW / cm ^2, further preferably a 300~1500mW / cm ² preferably performing, integrated light quantity of ultraviolet 100~3000mJ / cm ^2, preferably 200~2000mJ / cm ^2, more preferably it is more preferable to carry out ultraviolet irradiation under the condition that the 300~1500mJ / cm ^2. Here, the ultraviolet illuminance is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectral efficiency, the diameter of the light emitting bulb, the design of the reflector, and the light source distance to the irradiated object. However, the illuminance does not change depending on the conveyance speed. Further, the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

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

[Fluorine Compound A]
[Fluorine compound A1]
A compound containing a fluoropolyether moiety (RS-75 manufactured by DIC Corporation) was used as the fluorine compound A1.

[Fluorine compound A2]
A fluorine-containing dendrimer (FA-200 manufactured by Nissan Chemical Industries, Ltd.) was used as the fluorine compound A2.

[Preparation of coating composition A]
[Coating composition A1] The following materials were mixed to obtain a coating composition A1.
Fluorine compound A: Fluorine compound A1 18.7 mass%
Particle a: Chained organosilica sol MEK-ST-UP
(Nissan Chemical Industries, Ltd. solid content concentration 20%) 45% by mass
Binder raw material A: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 13.5% by mass
Solvent: MEK 21.8% by mass
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass
[Coating composition A2] The following materials were mixed to obtain a coating composition A2.
Fluorine compound A: Fluorine compound A1 11.2% by mass
Particle a: Chained organosilica sol MEK-ST-UP
(Nissan Chemical Industries, Ltd. solid content concentration 20%) 45% by mass
Binder raw material A: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 16.5% by mass
Solvent: 26.3% by mass of MEK
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass
[Coating composition A3] The following materials were mixed to obtain a coating composition A3.
Fluorine compound A: Fluorine compound A1 2.2 mass%
Particle a: Chained organosilica sol MEK-ST-UP
(Nissan Chemical Industries, Ltd. solid content concentration 20%) 15% by mass
Binder raw material A: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 26.1% by mass
Solvent: 55.7% by mass of MEK
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass
[Coating composition A4] The following materials were mixed to obtain a coating composition A4.
Fluorine compound A: Fluorine compound A2 7.5% by mass
Particle a: Chained organosilica sol MEK-ST-UP
(Nissan Chemical Industries, Ltd. solid content concentration 20%) 45% by mass
Binder raw material A: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 13.5% by mass
Solvent: MEK 33 mass%
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass
[Coating composition A5] The following materials were mixed to obtain a coating composition A5.
Fluorine compound A: Fluorine compound A1 37.5% by mass
Particle a: Chained organosilica sol MEK-ST-UP
(Nissan Chemical Industries, Ltd. solid content concentration 20%) 45% by mass
Binder raw material A: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 6% by mass
Solvent: MEK 10.5 mass%
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass
[Coating composition A6] The following materials were mixed to obtain a coating composition A6.
Fluorine compound A: Fluorine compound A1 3.7% by mass
Particle a: Oxidized zirconium oxide particle F75
(CIK Nanotech Co., Ltd. solid content concentration 30%) 25% by mass
Binder raw material A: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 21% by mass
Solvent: MEK 49.3 mass%
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass
[Coating composition A7] The following materials were mixed to obtain a coating composition A7.
Fluorine compound A: Fluorine compound A1 37.5% by mass
Particle a: Organosilica sol IPA-ST-L
(Nissan Chemical Industries, Ltd. solid content concentration 30%) 30% by mass
Binder raw material A: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 6% by mass
Solvent: MEK 25.5% by mass
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass
[Coating composition A8] The following materials were mixed to obtain a coating composition A8.
Fluorine compound A: Fluorine compound A2 37.5% by mass
Particle a: Silica particle Hypsika SP 600 nm
(Ube Nitto Kasei Corporation powder) 30% by mass
Binder raw material A: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 6% by mass
Solvent: MEK 25.5% by mass
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass
[Coating composition A9] The following materials were mixed to obtain a coating composition A9.
Fluorine compound A: None
Particle a: None Binder raw material A: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 30% by mass
Solvent: MEK 69 mass%
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass.

[Preparation of coating composition B]
[Coating composition B1] The following materials were mixed to obtain a coating composition B1.
Particle b: Titanium oxide-containing particle TO-1027TIV
(Solid content concentration 30% by JGC Catalysts & Chemicals Co., Ltd.) 80% by mass
Binder raw material B: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 6% by mass
Solvent: MEK 13% by mass
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass
[Coating composition B2] The following materials were mixed to obtain a coating composition B2.
Particle b: Titanium oxide-containing particle TO-1027TIV
(JGC Catalysts Chemical Co., Ltd. solid content concentration 30%) 90% by mass
Binder raw material B: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 3% by mass
Solvent: MEK 6 mass%
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass
[Coating composition B3] The following materials were mixed to obtain a coating composition B1.
Particle b: Titanium oxide-containing particle TO-1027TIV
(Solid content concentration 30% by JGC Catalysts & Chemicals Co., Ltd.) 10% by mass
Binder raw material B: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 27 mass%
Solvent: MEK 62 mass%
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass
[Coating composition B4] The following materials were mixed to obtain a coating composition B1.
Particle b: Titanium oxide-containing particle TO-1027TIV
(Solid content concentration 30%, manufactured by JGC Catalysts & Chemicals, Inc.) 95% by mass
Binder raw material B: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 1.5 mass%
Solvent: MEK 2.5% by mass
Photopolymerization initiator: 1-hydroxycyclohexyl phenyl ketone
(Irgacure 184 manufactured by BASF) 1% by mass.

[Production of molding material]
“Lumirror” U46 (manufactured by Toray Industries, Inc.) in which an easy-adhesive paint was applied on a PET resin film was used as a supporting substrate. First, as the formation of the second layer, the coating composition B is coated with a solid content using a continuous coating apparatus having a small-diameter gravure coater and an infrared panel heater in the first half of the drying chamber under the condition of a conveyance speed of 10 m / min. The second layer was formed by adjusting the number of gravure lines and the gravure roll speed ratio so that the desired film thickness was obtained. The conditions of the wind from coating to drying, curing, and liquid film are as follows.

First drying blast temperature and humidity: Temperature: 45 ° C, Relative humidity: 10%
Wind speed: Coated surface side: 5 m / second, Anti-coated surface side: 5 m / second Wind direction: Coated surface side: parallel to the substrate, anti-coated surface side: Vertical residence time with respect to the substrate: 1 minute panel heater setting Temperature: 80 ° C
Second drying blast temperature and humidity: Temperature: 100 ° C, Relative humidity: 1%
Wind speed: coating surface side: 5 m / sec, anti-coating surface side: 5 m / sec Wind direction: coating surface side: parallel to the substrate, anti-coating surface side: vertical residence time with respect to the substrate: 1 minute Curing process irradiation Output: 600W / cm ²
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 0.1% by volume
In addition, the measured value by a hot-wire anemometer (Nippon Kanomax Co., Ltd. Anemomaster anemometer / air flow meter MODEL6034) was used for the wind speed and temperature and humidity.

  Subsequently, on the surface formed with the second layer, as a first layer, an infrared panel heater is applied to the small-diameter gravure coater and the first half of the drying chamber on the condition that the coating composition A is transported at a speed of 10 m / min. Using the continuous coating apparatus, the first layer was formed by adjusting the number of gravure lines and the gravure roll speed ratio so that the solid coating thickness would be the desired thickness. The conditions of wind from coating to drying, curing, and liquid film are the same as those for forming the second layer.

  By the above method, the molding material was created about Examples 1-13 and Comparative Examples 1-2.

[Evaluation of molding materials]
About the produced molding material, the following performance evaluation was implemented and the obtained result is shown to a table | surface. Unless otherwise specified, the measurement was performed three times by changing the location of one sample in each example and comparative example, and the average value was used.

[60 ° specular gloss]
The glossiness of the surface of the molding material is measured by using a VG7000 made by Nippon Denshoku Industries Co., Ltd. with the back surface of the measurement surface roughened with sandpaper and painted with black paint. According to JIS Z 8741 (1997), the 60 ° specular gloss was measured, and 100% or more was regarded as acceptable.

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

  With respect to the receding contact angle, droplets are continuously sucked at an initial droplet amount of 50 μL and a liquid discharge speed of 8.5 μL / second, and the shape of the contraction process of the droplets is photographed. Asked. Since the contact angle of the droplet shrinkage process changes with shrinkage and then becomes almost constant, the contact angles are arranged in the direction of droplet shrinkage, and five consecutive points are selected in that order. The average value when the standard deviation of five consecutive points first becomes 1 ° or less is set as the receding contact angle of the measurement, this measurement is performed five times for one sample, and the average value is set as the receding contact angle of the sample. did. Note that, depending on the sample, the contact angle during the contraction process of the droplets is not constant and continues to decrease, but for this, the receding contact angle was set to 0 °.

[Minimum reflectance]
In order to remove the reflection of the back surface of the measurement surface, the antireflection function is measured by using a spectrophotometer UV-3100 manufactured by Shimadzu Corporation with the back surface roughened with sandpaper and filled with black paint. A 5 ° and −5 ° specular reflection spectrum at 780 nm was measured. The lowest value was calculated | required from the spectral reflectance of the range of 380 to 780 nm obtained, this was made into the minimum reflectance, and 2% or less was set as the pass.

[Average film thickness of first layer and second layer]
By observing a cross section using a transmission electron microscope (TEM), the thickness of the 1st layer and the 2nd layer on a support base material was measured. The thickness of each layer was measured according to the following method. The thickness of each layer was read by software (image processing software ImageJ) from an image obtained by photographing an ultrathin section of the cross section of the laminated film at a magnification of 200,000 times with a TEM. The average value obtained by measuring the layer thickness of 30 points in total was defined as the average film thickness.

[Refractive indices of first layer and second layer]
The individual refractive indexes of the first layer and the second layer are in the range of 300 to 800 nm with respect to the laminated film of the molding material by a reflection spectral film thickness meter (manufactured by Otsuka Electronics Co., Ltd., trade name [FE-3000]). The refractive index at 550 nm was measured according to the method described in [Film thickness measuring device general catalog P6 (nonlinear least squares method)] manufactured by Otsuka Electronics Co., Ltd. using the software [FE-Analysis] attached to the device. Asked.
The optical constants (C1, C2, C3) were calculated by the least square method (curve fitting method) using Cauchy's dispersion formula (Formula 1) as an approximate expression of the wavelength dispersion of the refractive index, and the refractive index at 580 nm was measured.

[Measurement of the number of peaks]
After cutting the molding material at an arbitrary location, using an atomic force microscope (SII, SPI3800), observation mode = DFM mode, scanner = FS-20A, cantilever = DF-3, observation field = 5 × 5 μm ^2. Surface morphology was observed with a resolution of 1024 × 512 pixels to obtain an observed image. Next, in order to set 100% of the mean square roughness as a peak threshold, analysis was performed by setting “Peak Thrsh (% rms)” to 100%, and the number of peaks was obtained.

[Number average particle diameter of particles a]
Observation and measurement were performed with a scanning electron microscope (SEM). The observation sample was prepared by diluting the coating composition A in a dispersion medium (isopropyl alcohol) to a solid content concentration of 0.5% by mass, dispersing it with ultrasonic waves, dropping it on a conductive tape and drying it. The number average particle diameter is observed at a magnification such that the number of aggregates of primary particles per field of view is 10 or more and 50 or less, and the diameter of the circumscribed circle of the primary particles is obtained from the obtained image. The number average particle size was determined from the value measured for 100 primary particles with the number of observations increased with the equivalent particle size.

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

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

[Abrasion resistance]
Addressed the steel wool to be 500 g / cm ² load to a surface of interest of the molding material (# 0000) vertically, and wherein the number of scratches is visually length of 1cm upon 20 reciprocally, classification below And scored 3 or more points.
5 points: 0 4 points: 1 or more Less than 5 3 points: 5 or more Less than 10 2 points: 10 or more Less than 20 1 point: 20 or more.

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 fingerprint resistance and antireflection properties, as well as various plastic molded products, the lens on the outermost surface portion of the camera. It can also be used to impart the same function to the surfaces of glasses lenses, glass windows for smartphones, televisions, car navigation systems, personal computers, window glass and various printed materials.

Claims (7)

A molding material comprising a surface layer composed of a second layer and a first layer having different refractive indexes in this order on at least one surface of a supporting substrate, and satisfying the following conditions 1 to 4.
Condition 1. The 60 ° specular glossiness specified by JIS Z8741 (1997) on the surface of the first layer is 40% or more.
Condition 2. Receding contact angle theta _r oleic acid in the first layer surface than 60 °.
Condition 3. Advancing contact angle theta _a and receding contact angle theta _r oleic acid in the first layer surface satisfy the formula (1).
(Θ _a −θ _r ) ≦ 15 ° Formula (1)
Condition 4. The minimum reflectance of incident light at a wavelength of 380 nm to 780 nm is 2% or less. The molding material according to claim 1, wherein the first layer satisfies the following conditions 5 and 6, and the second layer satisfies the following condition 7.
Condition 5. The refractive index of incident light at a wavelength of 580 nm is 1.45 or more and 1.50 or less.
Condition 6. The layer thickness is 80 nm or more and 120 nm or less.
Condition 7. The refractive index of incident light at a wavelength of 580 nm is 1.60 or more and 1.75 or less. The number of peaks having a height exceeding the root mean square roughness (RMS) observed by an atomic force microscope (AFM) on the surface of the first layer is 500 or more and 1500 or less per 25 μm ^2. The molding material in any one of Claim 1 or Claim 2.   Fluorine compound A in which the first layer has a reactive site and a site containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group and a fluorooxyalkanediyl group 4. The molding material according to claim 1, comprising: a binder component A; and a particle a having a number average particle diameter of 5 nm or more and 250 nm or less.   The molding material according to claim 4, wherein the particles a are silica linked in a bead shape and / or branched. The molding material is
(1) Step (2) of forming a second layer on a supporting substrate On the second layer formed in (1), a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and Fluorine compound A that is a compound having at least one site selected from the group consisting of fluorooxyalkanediyl groups and a reactive site, binder raw material A, and particles a having a number average particle size of 5 nm to 250 nm are included. The method for producing a molding material according to any one of claims 1 to 5, comprising a step of forming the first layer by applying, drying and curing the coating composition A.   The method for producing a molding material according to claim 6, wherein the particles a are silica connected in a bead shape and / or branched.