JP2018024244A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate capable of obtaining an excellent flaw inhibitory effect under a practical condition without depending on a specific evaluation condition.SOLUTION: There is provided a laminate having a surface layer at least on one side of a support substrate. The laminate satisfied following (A) and (B), when measuring the surface layer from the outermost surface side: (A) LN<10, (B) |Lsk|<1.0, LN: the number of boundaries formed by regions having horizontal force of 50% or more in a horizontal force distribution on a straight line of 5 μm, |Lsk|: an absolute value of skewness in the horizontal force distribution of 10 μm square.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a laminate having both high surface hardness, particularly scratch resistance and pencil hardness.

  Conventionally, a plastic film provided with a surface layer made of a synthetic resin or the like has been used for the purpose of protecting the surface of optical materials such as color filters and flat panel displays (for preventing scratches and imparting antifouling properties). These surface layers are required to have scratch resistance as an important characteristic from the viewpoint of surface protection. Therefore, in general, “high cross-linking by coating-drying-heating or UV curing a coating composition containing various prepolymers such as organosilanes and polyfunctional acrylics described in Non-Patent Document 1, oligomers, etc. "Density material" is used to provide scratch resistance. Further, scratch resistance is imparted by using a so-called “hard coat material” in which the surface hardness of the surface layer is increased using an “organic-inorganic hybrid material” combined with various surface-modified fillers.

  On the other hand, “pencil hardness” is one of the indices that are actively used as an index of the scratch resistance of the surface layer. As represented by the scratch hardness (pencil method) described in JIS K 5600-5-4 (1999), this is a technique for comparing and classifying the hardness of the surface of the material with the hardness of the pencil. It is actively used as an indicator of hardness. As a technique paying attention to pencil hardness, for example, in Patent Document 1, “a colloidal silica dispersed in an organic solvent is reacted with an isocyanate compound having an isocyanate group and a polymerizable unsaturated group, and the hydroxyl group of the colloidal silica and the isocyanate are reacted. A hard coat agent mainly comprising a colloidal silica-containing monomer in which a group is bonded via a urethane bond is disclosed. Specifically, "reacting colloidal silica dispersed in an organic solvent with an isocyanate compound having an isocyanate group and a polymerizable unsaturated group, and bonding the hydroxyl group of the colloidal silica and the isocyanate group via a urethane bond. A hard coat agent comprising a colloidal silica-containing monomer as a main component, wherein the content of silica in the colloidal silica-containing monomer is 40% by weight or more in solid content ratio. Proposed.

In other hard coat materials, there are methods called “steel wool resistance” and “steel wool test” as an index of scratch resistance. This method is a method for evaluating the presence or absence of scratches on a material by repeatedly abrading steel wool and the material that define the contact area and load. As a laminate focusing on such a technique, for example, in Patent Document 2, “a hard coat layer is formed with a cured product of a radical polymerizable composition containing a specific fluorine-containing urethane (meth) acrylate and a fluorine-free vinyl compound”. “A hard coat film having excellent scratch resistance” is disclosed. Specifically, “a hard coat film including a hard coat layer formed of a cured product of a radical polymerizable composition containing a fluorine-containing urethane (meth) acrylate and a fluorine-free vinyl compound, wherein the fluorine-containing urethane The pencil hardness (500 g load) of the cured product of (meth) acrylate is 3B or more, the water contact angle of the hard coat layer is 100 ° or more, and a steel wool # 0000 is applied with a load of 5 kg / cm ^2. "A hard coat film that is not damaged even if the surface of the hard coat layer is slid back and forth 10 times" has been proposed.

  Further, Patent Document 3 discloses “a laminated film having high scratch resistance effective against high hardness materials, rubbing under high load conditions, and repeated rubbing with low hardness materials”. Specifically, “in a laminated film in which a surface layer composed of at least one layer is formed on a supporting substrate, 5% of the surface layer thickness from the surface layer (hereinafter referred to as position A), 35 % (Hereinafter referred to as position B), 65% (hereinafter referred to as position C), and 95% (hereinafter referred to as position D) at the cross sections of the elastic modulus EA, EB, EC by the atomic force microscope The laminated film is characterized in that ED satisfies all of the following conditions 1, 2 and 3. Condition 1: EA ≦ EB ≦ EC <ED, Condition 2: EA is 100 MPa or less, Condition 3: ED Is 1 GPa or more. "

JP 2005-163035 A JP 2015-138150 A Japanese Patent Laid-Open No. 2006-028888

Plastic Hard Coat Applied Technology CM Publishing Co., Ltd. 2004

  However, the index for evaluating the scratch resistance of the surface layer often has no correlation with the occurrence of practical scratches. For example, with regard to the above-mentioned “pencil hardness” and “steel wool resistance”, even in a configuration with extremely high pencil hardness as represented by Patent Document 1, scratches may easily occur in the steel wool test. . This is because “pencil hardness” evaluates the resistance against single wear by a pencil, whereas in steel wool resistance, the surface is gradually fatigued and destroyed by multiple wear on the surface. Due to

  On the other hand, the configuration described in Patent Document 2, that is, “excellent scratch resistance obtained by forming a hard coat layer with a cured product of a radically polymerizable composition containing a specific fluorine-containing urethane (meth) acrylate and a fluorine-free vinyl-based compound. When the present inventors investigated "hard coat film", it confirmed that pencil hardness was as low as about 2H. In addition, the idea of uniformity of horizontal force of the surface layer of the present invention has not yet been reached, and “a hard coat film is attached to a black acrylic plate with an optical adhesive and is equipped with a three-wavelength fluorescent tube as described in the literature. The method of “observing the state of the surface under a fluorescent lamp” certainly does not make the scratches conspicuous, but the observation with transmitted light confirmed the generation of fine scratches.

Furthermore, the structure proposed in Patent Document 3 is “a film using a so-called“ self-healing material ”that achieves scratch resistance by repairing scratches on the surface by deformation of the elastic recovery range of the material of the surface layer. It is. However, the present inventors have confirmed these structures. When a hard material such as steel wool is applied and a high load of 1.0 kg / cm ² or more is applied, the surface is broken due to repeated wear. Confirmed that it will be.

  Then, the objective of this invention is providing the laminated body which can acquire the inhibitory effect of the outstanding damage | wound on practical conditions irrespective of specific evaluation conditions.

In solving the above problems, the present inventors first tried to analyze the scratches formed on the surface of the material. When the shape of the wound visually recognized by the naked eye was analyzed by a measuring method such as an optical microscope or a probe microscope, it was found that the true shape of the wound was a slight dent formed on the surface of the substrate. As a result of intensive studies to solve the above problems, the present inventors have completed the following invention. That is, the present invention is as follows.
(1) A laminate having a surface layer on at least one surface of a support substrate, wherein the laminate satisfies the following (A) and (B) when measured from the outermost surface side of the surface layer.
(A) LN <10
(B) | Lsk | <1.0
LN: Number of boundaries formed by a region having a horizontal force of 50% or more in a horizontal force distribution on a straight line of 5 μm | Lsk |: Absolute value of skewness of horizontal force distribution of 10 μm square (2) From the outermost surface side of the surface layer The laminate according to (1), wherein the measured critical load for fracture in the micro scratch test is 60 mN or more and 200 mN or less.
(3) The laminate according to claim 2, wherein (C) and (D) are satisfied when measured from the outermost surface side of the surface layer.
(C) The outermost adhesive wear parameter ε _L represented by the following formula 1 is 6.5 or more and 10 or less.
(Equation _{1) ε L = E IT /} 1,000 × (πr 2 / F)
ε _L : Adhesive wear parameter, E _IT : Indentation elastic modulus, F: Critical load at break, r: Indenter curvature (D) Indentation elastic modulus E _IT is 4 GPa or more and 12 GPa or less.
(D) Indentation elastic modulus E _IT is 4 GPa or more and 12 GPa or less.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which has durability excellent in scratch resistance, especially repeated abrasion can be provided. The laminate of the present invention can particularly achieve both “pencil hardness” and “steel wool resistance”.

It is a schematic diagram of the horizontal force measurement by an atomic force microscope. It is a schematic diagram of the number (LN) of the boundary which the area | region of 50% or more of relative horizontal forces makes. It is an example (multilayer slide die coat) of the manufacturing method which forms a surface layer. It is an example (multilayer slot die coat) of the manufacturing method which forms a surface layer. It is an example (wet-on-wet coat) of the manufacturing method which forms a surface layer.

First, the characteristics of the flaws visually recognized with the naked eye among the flaws formed with the surface layer will be described. When the surface layer of various laminates made of various materials was worn 5,000 times with a load of 1.0 kg / cm ² using # 0000 steel wool, the surface shape obtained was observed below. It carried out on condition of this.
Measuring device: Burker Corporation Bruker AXS atomic force microscope (AFM)
Measurement mode: LFM
Cantilever: Burker Corporation Bruker AXS SCM-PIC (material: silicon Si, spring constant K: 0.2 (N / m), tip radius of curvature R: 20 (nm))
Measurement atmosphere: 23 ° C., measurement range in air: 30 (μm) square resolution: 512 × 512
Cantilever moving speed: 20 (μm / s)
As a result, it was confirmed that when the surface shape after abrasion satisfies the following conditions, it was recognized that the surface was scratched.
(Formula 1) Rmax> 50 nm, (Formula 2) | Rsk |> 0.7
Rmax: Maximum height difference in a 30 μm square range Rsk: Roughness skewness in a 30 μm square range.

  Here, Rmax means the depth of the groove on the surface cut by the steel wool, and it means that even a dent of only about 50 nm from the surface is visually recognized as a flaw. The value of Rsk is an index indicating the degree of sharpness of the surface shape, and the closer to 0, the closer to the normal distribution, which means that the surface has a gentle uneven shape.

  The reason why the dent formed on the surface is visually recognized as a flaw is largely due to the “angle deviation from the surface” rather than the “absolute value of the depth of the dent”. In other words, even if the depth is a very shallow dent of several tens of nanometers, when a steep valley is formed, the reflected light or transmitted light on the surface is observed discontinuously, resulting in scratches. It is recognized that In order to reduce the occurrence of such scratches on the surface layer and maintain the quality of the surface layer, "suppress surface layer damage as much as possible" or "form a surface on which the surface layer is evenly worn. "Is necessary.

  As a result of investigations by the present inventors based on the above design guidelines, the above-described method of “suppressing damage to the surface layer as much as possible” is close to the idea of the cited reference 1, that is, the initial surface hardness. Although it is high, it was weak against repeated wear, and once it was destroyed, it was confirmed that there was a weak point that the hard member that formed the surface layer worn the surface.

  On the other hand, it has been found that the above-mentioned “formation of a surface on which the surface layer is uniformly worn” is possible by providing a surface layer that satisfies the conditions described later. Hereinafter, preferred forms of the surface layer will be described.

[Horizontal force distribution on the surface layer]
First, an outline of horizontal force measurement of the surface layer will be described. It is effective to use an atomic force microscope for the analysis of the surface physical properties of the minute region of interest of the present invention. The atomic force microscope is a technique for obtaining information such as the shape and elastic modulus of a surface by tracing the surface using a probe having a minute tip diameter on the order of nm. Information on the minute displacement when the probe comes into contact with the surface is amplified and detected by the optical lever as the displacement of the laser beam reflected from the upper part of the probe. There is a technique called a horizontal force microscope (LFM) that applies such an atomic force microscope technique to measure the frictional force and shear force in the horizontal direction. Hereinafter, an outline of horizontal force measurement using an atomic force microscope will be described with reference to the drawings.

  As shown in FIG. 1, measurement is performed by tracing the outermost surface 2 of the surface layer in the laminate using a probe 1 that has been processed to reflect light on the back surface. At this time, an inclination 3 is generated in the probe according to the horizontal force generated in the probe. Since this inclination is increased or decreased according to the interaction between the probe and the surface, the horizontal force in a minute region can be visualized by grasping the magnitude of the inclination with the light reflection 4. In addition to the frictional force, components that contribute to the horizontal force include mechanical properties due to the surface shape, surface physical properties such as material adhesion and viscosity. Using such a technique, the horizontal force distribution on the surface of the laminate can be visualized.

[Number of boundaries (LN) created by areas with relative horizontal force of 50% or more]
In the laminate of the present invention, the number of boundaries (LN) formed by a region having a relative horizontal force of 50% or more in a horizontal force distribution on a straight line of 5 μm measured from the outermost surface of the surface layer is preferably 10 or less. Details of this parameter will be described with reference to FIG. The details of the method of measuring “the number of boundaries created by the region having a relative horizontal force of 50% or more” will be described later.

  FIG. 2 shows a schematic diagram of a horizontal force distribution in which the horizontal axis represents the horizontal distance and the vertical axis represents the relative horizontal force. The relative horizontal force on the vertical axis is a value normalized by a relative value with the maximum value of the horizontal force measured in the range of 10 μm × 10 μm square being 100% (5). The number of boundaries created by a region having a relative horizontal force of 50% or more means the number of intersections 7 with the horizontal force distribution when the horizontal force distribution is divided by a straight line 6 crossing the vertical axis 50% as shown in FIG. To do.

  The presence of a plurality of regions with a horizontal force of 50% or more per unit length means that there are many chances of forming scratches on the surface, so “the number of boundaries created by a region with a horizontal force of 50% or more” is Less is preferable. Specifically, when the “number of boundaries created by a region having a horizontal force of 50% or more” exceeds 10, the above-mentioned minute dent is likely to occur in the surface layer, and as a result, the surface is likely to be scratched. There is a case.

[Absolute Skewness of Horizontal Force Distribution (| Lsk |)]
In the laminate of the present invention, the absolute value (| Lsk |) of the skewness of the horizontal force distribution measured from the outermost surface of the surface layer is preferably smaller than 1.0. The absolute value of the skewness of the horizontal force distribution is an index indicating the number of sudden changes in the horizontal force, and the closer to 0, the less the change is abrupt. When the absolute value is 1.0 or more, there are many chances of forming scratches on the surface, and as a result, scratches are likely to occur on the surface.

  The change in the horizontal force is caused not only by the shape of the protrusion due to the addition of a particle component, but also by an abrupt change in the elastic modulus at the surface layer and adhesion by a viscous material. The details of the method for measuring “the absolute value of the skewness of the horizontal force distribution” will be described later.

[Critical load of fracture by micro scratch test]
The micro scratch test is a method of performing a scratch test while pressing the surface with a minute indenter, and can detect a signal corresponding to a fracture in addition to a frictional force. Depending on the shape of the tip of the indenter, it is possible to obtain stress from the indenter with a small tip diameter near the surface, and with an indenter with a large tip diameter from the surface layer to a deeper depth, and corresponding physical property values can be obtained. Even in the case of a material or laminate having a high crosslink density that is difficult to form, it is possible to detect a signal corresponding to the physical properties of the surface layer.

  The critical load for rupture refers to the load value when a signal corresponding to rupture of the coating film is detected when measurement is performed while gradually applying a load in the micro scratch test. This corresponds to a load in which the tensioned surface layer is irreversibly broken. In general, the measurement of the critical load for fracture by the micro scratch test is a parameter unique to the laminate reflecting not only the outermost surface of the surface layer but also the physical properties of the inner layer and the supporting substrate from the applied load.

  The laminated body of the present invention has a preferable numerical range for the critical load of fracture according to the micro scratch test measured from the outermost surface side of the surface layer. Specifically, it is preferably 60 mN or more and 200 mN or less, more preferably 70 mN or more and 160 mN or less, and particularly preferably 80 mN or more and 120 mN or less. When the critical load for fracture exceeds 200 mN, the surface becomes hard and may be easily damaged when repeatedly worn. On the other hand, when the critical load for fracture is less than 60 mN, the strength of the surface layer may not be sufficiently obtained, and scratches may be easily obtained with a slight load. Details of the measurement and analysis method will be described later. Hereinafter, embodiments of the present invention will be described in detail.

[Indentation modulus of surface layer]
In the laminate of the present invention, there is a preferred range for the indentation elastic modulus _EIT of the surface layer. Specifically, 4 GPa or more and 12 GPa or less are preferable. When the indentation elastic modulus is less than 4 GPa, the amount of strain increases in both indentation and wear, and the laminate surface may be easily damaged. On the other hand, when the indentation elastic modulus exceeds 12 GPa, the surface layer becomes brittle, and cracking may easily occur during impact.

[Adhesive wear parameters of laminates]
In the laminate of the present invention, the adhesion wear parameter ε _L shown in Formula 1 is preferably in a specific range. Here, each physical quantity constituting the adhesion wear parameter ε _L and its meaning will be described. E _IT corresponds to the above-described indentation elastic modulus, and F corresponds to the critical load for fracture in the above-described micro scratch test. r represents the radius of the stylus used to measure the critical load F. Detailed conditions of nanoindentation measurement and micro scratch tester measurement will be described later.

  Nanoindentation is a technique to push the surface vertically using a small indenter and measure its hardness. By adjusting the indentation depth, the elastic modulus information on the laminate surface is selectively extracted. Can do. On the other hand, the micro scratch tester is a measurement that wears the surface of the laminated body while applying a time-dependent vertical load to the indenter and extracts the displacement of the laminated body surface corresponding to the fracture. Since the indenter is constantly vibrated during wear, the behavior of the film breaking can be followed by the dynamic friction force that increases with time.

Here, the denominator of the adhesion wear parameter ε _L is a parameter representing the durability against wear, which is calculated from the normal force when the film is broken by wear and the contact area of the indenter at that time, and its dimension is It is [N / m ² ] similarly to the elastic modulus. That is, the adhesion wear parameter ε _L is an index indicating whether the hardness of the surface is strong against fracture in the vertical direction or in the in-plane direction. Means hard against horizontal wear. On the other hand, when the load is kept constant, the elastic modulus and the amount of strain are inversely proportional to each other. Therefore, when the adhesion wear parameter ε _L is large, the strain amount with respect to wear is relatively large, and when the load is small, the amount of strain is indented. This means that the amount of distortion with respect to is relatively large.

The adhesion wear parameter ε _L of the laminate of the present invention is particularly preferably 6.5 or more and 10 or less. If it exceeds 10, distortion tends to occur during wear, and as a result, the surface of the laminate may be easily damaged. On the other hand, if it is less than 6.5, the amount of strain in the indentation direction will increase, leading to the occurrence of breakage and cracking. Again, the laminate is likely to be scratched on the surface, making it difficult to achieve both pencil hardness and wear resistance. There is a case.

[Laminated body and surface layer]
The “surface layer” in the present invention refers to a layer formed on a support substrate, and a combination of all the series of layers including the surface layer and the support substrate is referred to as a “laminate”. That is, when only one layer is formed on the support base material, the one layer becomes a “surface layer”. For example, when two or more layers are formed on a supporting base material, all the two or more layers excluding the supporting base material are referred to as one “surface layer”.

  Here, the “layer” refers to a part having a finite thickness that can be distinguished by having a boundary surface and a part adjacent to the part in the thickness direction from the surface side of the laminate in the thickness direction. More specifically, when the cross section of the said laminated body is cross-sectional-observed with an electron microscope (a transmission type, a scanning type) or an optical microscope, it points out what is distinguished by the presence or absence of a discontinuous interface. The laminate of the present invention may be in a planar state or a three-dimensional shape after being molded as long as it has a surface layer exhibiting the above-mentioned physical properties. The thickness of the entire surface layer is not particularly limited, but is preferably 1 μm or more and 50 μm or less, and more preferably 3 μm or more and 30 μm or less.

  In addition to the scratch resistance, particularly the repeated scratch resistance, the laminate is a subject of the present invention, as well as moldability, antifouling properties, antireflection properties, antistatic properties, antifouling properties, electrical conductivity, heat ray reflectivity, and near infrared rays. It may have a layer having other functions such as absorption, electromagnetic wave shielding, and easy adhesion, and these functions may be imparted to the surface layer.

[Supporting substrate]
The material constituting the support substrate used in the laminate of the present invention may be either a thermoplastic resin or a thermosetting resin, may be a homo resin, may be a copolymer or a blend of two or more types. Good. More preferably, the resin constituting the support substrate is preferably a thermoplastic resin from the viewpoint of moldability.

  Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyester resins, polycarbonate resins and polyarylate resins. Fluorine resins such as polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluoroethylene resin, tetrafluoroethylene-6-fluoropropylene copolymer, vinylidene fluoride resin, acrylic Resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. The thermoplastic resin is more preferably a polyester resin or a polyamide, an aromatic polyamide, a polyimide, an aromatic polyimide, a polyamideimide, an aromatic polyamideimide, a polycarbonate resin, or a methacrylic resin from the viewpoint of strength, heat resistance, and transparency. A polyester resin is particularly preferable from the viewpoint of transparency and coloring. From the viewpoint of strength and heat resistance, a film that is at least one resin selected from the group consisting of polyamide, aromatic polyamide, polyimide, aromatic polyimide, polyamideimide, and aromatic polyamideimide is particularly preferable.

  The polyester resin in the present invention is a general term for polymers having an ester bond as a main bond chain, and is obtained by polycondensation of an acid component and its ester and a diol component. Specific examples include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and the like. These may be copolymerized with other dicarboxylic acids and their esters or diol components as acid components or diol components. Among these, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferable in terms of transparency, dimensional stability, heat resistance, and the like.

  Hereinafter, an example using a polyamide film as a film that is at least one resin selected from the group consisting of polyamide, aromatic polyamide, polyimide, aromatic polyimide, polyamideimide, and aromatic polyamideimide will be described. It is not limited to this.

  Various methods can be used as a method for obtaining a polyamide solution, that is, a film forming stock solution. For example, a low temperature solution polymerization method, an interfacial polymerization method, a melt polymerization method, a solid phase polymerization method, and the like can be used. When it is obtained from a low temperature solution polymerization method, that is, from carboxylic acid dichloride and diamine, it is synthesized in an aprotic organic polar solvent.

  Carboxylic acid dichlorides include terephthalic acid dichloride, 2 chloro-terephthalic acid dichloride, 2 fluoro-terephthalic acid dichloride, isophthalic acid dichloride, naphthalene dicarbonyl chloride, 4,4′-biphenyl dicarbonyl chloride, terphenyl dicarbonyl chloride, 1, Examples include 4-cyclohexanedicarboxylic acid chloride, 1,3-cyclohexanedicarboxylic acid chloride, and 2,6-decalin dicarboxylic acid chloride, and preferably 1,4-cyclohexanedicarboxylic acid chloride, terephthalic acid dichloride, 4,4′- Biphenyl dicarbonyl chloride and isophthalic acid dichloride are used.

  Examples of the diamine include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, and 2,2′-ditrifluoromethyl-4,4. '-Diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis (4-Aminophenyl) hexafluoropropane, o-tolidine, 2,2'-dimethyl-4,4'- Examples thereof include aminobiphenyl (m-tolidine), 1,1-bis (4-aminophenyl) cyclohexane, 3,3 ′, 5,5′-tetramethylbenzidine, and the like, preferably 2,2′-ditrifluoromethyl. -4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl sulfone. Polyamide solution uses acid dichloride and diamine as monomers to produce hydrogen chloride as a by-product. When neutralizing this, inorganic neutralizers such as calcium hydroxide, calcium carbonate, lithium carbonate, and ethylene Organic neutralizers such as oxide, propylene oxide, ammonia, triethylamine, triethanolamine, diethanolamine are used. The reaction between isocyanate and carboxylic acid is carried out in an aprotic organic polar solvent in the presence of a catalyst.

  When diamine and dicarboxylic acid dichloride are used as raw materials, they are amine terminals or carboxylic acid terminals depending on the composition ratio of the raw materials. Alternatively, the end capping may be performed with other amine, carboxylic acid chloride, or carboxylic acid anhydride.

  Compounds used for end-capping include benzoyl chloride, substituted benzoyl chloride, acetic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 4-ethynylaniline, 4-phenylethynylphthalic anhydride, maleic anhydride, etc. It can be illustrated.

  Examples of the aprotic polar solvent used in the production of polyamide include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and N, N. Acetamide solvents such as dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol , Phenolic solvents such as halogenated phenols and catechols, hexamethylphosphoramide, γ-butyrolactone, etc., and these are preferably used alone or as a mixture. Tribe The use of hydrogen is possible. Furthermore, for the purpose of accelerating the dissolution of the polymer, 50% by mass or less of an alkali metal or alkaline earth metal salt can be added to the solvent.

  The film-forming stock solution prepared as described above is formed into a film by a so-called solution casting method. The solution casting method includes a dry-wet method, a dry method, a wet method, etc., and any method may be used, but here, the dry-wet method will be described as an example.

  In the case of forming a film by a dry-wet method, the stock solution is extruded from a die onto a support such as a drum, an endless belt, or a support film to form a thin film, and then dried until the thin film layer has self-holding property. Drying conditions can be performed in the range of room temperature to 220 ° C. and within 60 minutes, for example. Further, the smoother the surface of the drum, endless belt, and support film used in this drying step, the smoother the surface. The film (sheet) that has been subjected to the dry process is peeled off from the support and introduced into the wet process, where desalting and solvent removal are performed, and further, stretching, drying, and heat treatment are performed to form a film. The heat treatment temperature is preferably 280 to 340 ° C, more preferably 300 to 320 ° C, from the viewpoint of strength and heat resistance described above. If it exceeds 340 ° C., yellowness (YI) may increase. The heat treatment time is preferably 30 seconds or longer, more preferably 1 minute or longer, still more preferably 3 minutes or longer, more preferably 5 minutes or longer. The heat treatment is preferably performed in an inert atmosphere such as nitrogen or argon.

  A base film made of any one of polyamide, aromatic polyamide, and polyimide containing fluorine in the polymer structure can also be used as a laminated film. As the production method, it is preferable to use a dry-wet process of a solution film-forming method in which an organic solvent solution of a resin is extruded from a die and cast on a support, and is dried, solvent-extracted and heat-set, and a laminated film is produced. In this case, at any stage of this process, the organic solvent solution of the resin composition comprising any one of polyamide, aromatic polyamide, and polyimide containing fluorine in the polymer structure is placed before or in the die. Lamination and casting to a support. Examples of a method of laminating in front of the die include a method of laminating using a laminating apparatus called a pinole, a composite tube, or a feed block. Moreover, as a method of laminating in the die, a method using a multilayer die or a multi-manifold die can be mentioned. An organic solvent solution of a resin and an organic solvent solution of a polymer (resin composition) such as an aromatic polyamide often have different solution viscosities. For this reason, it may be difficult to obtain a good laminated structure by a method of laminating before a die such as pinol. For this reason, it is preferable to laminate using a multi-manifold base.

  As the method for producing the film, from the viewpoint of the strength and heat resistance described above, the longitudinal direction of the film (the film-conveying direction; hereinafter referred to as MD) and the width direction (the direction perpendicular to the longitudinal direction in the film plane. (It may be called TD) It is preferable to extend | stretch by the draw ratio of 1.05 times or more and 10.0 times or less. The draw ratio in the MD direction is preferably 1.05 times to 5.0 times, more preferably 1.05 times to 3.0 times, still more preferably 1.05 times to 2.00 times, most preferably It is 1.05 times or more and 1.50 times or less. The draw ratio in the TD direction is preferably 1.05 times to 5.0 times, more preferably 1.05 times to 3.00 times, still more preferably 1.05 times to 2.00 times, most preferably It is 1.05 times or more and 1.50 times or less. Further, the draw ratio in the TD direction is preferably 1.0 times or more and 1.5 times or less with respect to the draw ratio in the MD direction. More preferably, it is 1.05 times or more and 1.20 times or less, and most preferably 1.1 times or more and 1.15 times or less.

  The structure of the film is determined by its raw materials. In the case of conducting a structural analysis of a film whose raw material is unknown, mass spectrometry, analysis by a nuclear magnetic resonance method, spectroscopic analysis, or the like can be used.

  In addition, for the support substrate, various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, thermal stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, A dopant for adjusting the refractive index may be added. The support substrate may be either a single layer configuration or a laminated configuration.

  Various surface treatments can be applied to the surface of the support substrate before the surface layer is formed. 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.

  In addition to the surface layer of the present invention, a functional layer such as an easy-adhesion layer, an antistatic layer, an undercoat layer, and an ultraviolet absorption layer can be provided in advance on the surface of the support substrate. In this case, it is preferable to provide an easy adhesion layer.

[Coating composition]
The laminate of the present invention forms a surface layer having a structure capable of achieving the above-mentioned physical properties by applying, drying and curing a coating composition on a supporting substrate using a laminate production method described later. can do. Here, the “coating composition” is a liquid composed of a solvent and a solute, and is a material that can be applied to the above-mentioned supporting substrate and volatilized, removed, and cured in a drying process to form a surface layer. Point to. Here, the “type” of the coating composition refers to liquids that are different in part even in the type of solute constituting the coating composition. This solute is, for example, a resin or a material capable of forming them in a coating process (hereinafter referred to as a precursor), a particulate material, a polymerization initiator, a curing agent, a catalyst, a leveling agent, an ultraviolet absorber, an antioxidant. And various other additives.

  The surface layer of the present invention is obtained by applying the coating composition A capable of forming the above-mentioned “horizontal force distribution of the surface layer” on a supporting substrate, or by sequentially or simultaneously applying the coating composition A on the upper layer of another coating layer. It is preferable to form.

[Coating composition A]
The above-mentioned “horizontal force distribution of the surface layer” and a preferable characteristic “critical load at break” of the laminate of the present invention are realized by, for example, a combination of a preferable coating composition A and a preferable coating process. Here, the preferable form of the coating composition A is demonstrated. As described above, when the surface layer is repeatedly worn, if the hardness is too high, the surface tends to be easily damaged, and the elastic modulus of the coating film single layer may be in the range of about 500 MPa to 5 GPa. preferable. As specific control factors, regarding the coating composition A, in addition to the number of reactive sites and the molecular weight between crosslinks of the binder material described later, a compound having surface orientation, such as a fluorine compound, is mixed as an additive. Can adjust the average molecular weight of the additive unevenly distributed on the outermost surface and the binder material by the mixing ratio. The degree of orientation of the surface orientation additive to the laminate surface layer depends on the dry curing process described later in addition to the mixing ratio. In general, the “horizontal force distribution of the surface layer” and the “critical load at break” can be confirmed each time.

  Examples of the preferred coating composition A capable of constituting the surface layer of the present invention include, for example, “Daicel Ornex Co., Ltd .; modified acrylates (EBECRYL series and KRM series)”, etc. Additives such as “agent (optool)” and particulate materials such as “Bic Chemie Japan Co., Ltd .; surface-treated alumina nanoparticles (NanoBYK series)” are added to adjust to a preferable “horizontal force distribution of the surface layer”. .

[Coating composition B]
In the case of imparting pencil hardness to the laminate of the present invention, it is preferable to have a high elastic modulus layer made of the coating composition B separately from the coating composition A suitable for forming the surface layer. As the coating composition B, a hard coat coating material for forming a coating layer having a high elastic modulus can be suitably used. The elastic modulus of the coating layer single layer film preferably has an elastic modulus of 6 GPa to 200 GPa. As specific components, it is preferable to have a highly crosslinkable binder material containing a large number of reactive sites and a particle material for imparting elastic modulus. As a coating material capable of forming a hard coat layer having a particularly high elastic modulus, it is preferable to use a composite coating material of an organic material and an inorganic material called an organic-inorganic hybrid coating material. Examples of organic-inorganic hybrid coating materials include “Taisei Fine Chemical Co., Ltd .; (organic-inorganic hybrid coating material“ STR-SiA ”)” and “Toagosei Co., Ltd. (trade name“ Photocuring SQ Series ”)” And “Toyo Ink Co., Ltd .; (trade name“ Rioduras ”(registered trademark))” and the like, and these materials can be preferably used. A typical form of the organic-inorganic hybrid coating material preferably includes a highly crosslinkable binder material composed of an inorganic particle material having a high elastic modulus and an organic compound. Preferred particle materials and binder materials will be described later.

[Particulate material, particle component]
The surface layer of the laminate of the present invention may contain a particle component. Here, the particles may be either inorganic particles or organic particles, but inorganic particles are preferred from the viewpoint of durability.

  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 4 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 and 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. .

  In addition, the particulate material contained in the coating composition suitable for forming the surface layer of the present invention changes its surface state due to heat, ionizing radiation, etc. in the treatment such as coating, drying, curing treatment or vapor deposition. It is preferable to be included in the surface layer in the form of being formed. Here, the particles present in the coating composition used in the present invention are “particulate material”, and the coating composition is present in the surface layer formed by a process such as coating, drying, curing or vapor deposition. The particles are called “particle components”.

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

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

Specifically, silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), tin oxide It is 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 preferably, the coating composition A is aluminum oxide (Al ₂ O ₃ ), and the coating composition B is silica (SiO ₂ ).

The reason why aluminum oxide (Al ₂ O ₃ ) is particularly preferable in the coating composition A is that when it is repeatedly worn because it contains boehmite (AlOOH) which is a hydrate in a part of the structure, the hardness decreases. This is presumably because destruction is easily suppressed. On the other hand, the particulate material suitably used for the coating composition B is not limited as described above, but silica (SiO ₂ ) is preferably used from the viewpoint of easy design of the surface treatment described later.

  As the particulate material of the coating composition A and the coating composition B forming the surface layer of the present invention, it is particularly preferable that the surface modification necessary for stably dispersing the particles in the good solvent of the binder material is made. preferable. For example, when an acrylic monomer or oligomer is used as the binder material, the surface modification requires an alkyl group having 1 to 5 carbon atoms, an alkenyl group, a vinyl group, a (meth) acryl group, etc. It is preferable to be introduced on the surface.

  Here, the number average particle diameter of the inorganic particles means the number-based arithmetic average length diameter described in JIS Z8819-2 (2001). In both the particle component and the particle material, the primary particles are observed using a scanning electron microscope (SEM), a transmission electron microscope, etc., and the diameter of the circumscribed circle of each primary particle is defined as the particle diameter. Refers to the calculated value. In the case of a laminate, the number average particle diameter can be determined by observing the surface or cross section. In the case of a coating composition, the coating composition diluted with a solvent is dropped and dried. Thus, it is possible to prepare and observe a sample.

[Binder material, binder component]
The coating composition suitable for forming the surface layer of the present invention preferably contains a binder material. Here, the binder refers to a compound having a reactive site or a higher order compound formed by the reaction. Here, the binder present in the coating composition used in the present invention is “binder material”, and the binder present in the surface layer formed by coating, drying, curing treatment, vapor deposition or the like of the coating composition. Is called “binder component”. The reactive site refers to a site that reacts with other components by external energy such as heat or light. Among such reactive sites, preferred are silanol groups in which alkoxysilyl groups and alkoxysilyl groups are hydrolyzed from the viewpoint of reactivity, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, And a methacryloyl group.

[solvent]
The coating composition A preferably contains a solvent. The number of solvent types is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and still more preferably 1 or more and 6 or less. Here, the “solvent” refers to a substance that is liquid at room temperature and normal pressure, and can be removed from the coating film by evaporating almost the whole amount in the drying step after coating.

  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.

  A preferred solvent is present in the coating composition A suitable for forming the surface layer of the laminate of the present invention. By adjusting the surface energy and drying speed of the solvent used, it becomes easy to obtain the horizontal force distribution required by the present invention. The preferable drying rate of the solvent contained in the coating composition A is preferably 1 or less when the butyl acetate is 100 in the relative evaporation rate based on butyl acetate (ASTM D3539-87 (2004)). It is especially preferable that it is 0.1 or less. Specifically, N-methyl-2-pyrrolidone and γ-butyrolactone are preferable, and γ-butyrolactone is particularly preferable. By including the above-mentioned solvent, it becomes easy to keep the shape of the surface layer smooth, and as a result, the occurrence of the above-mentioned dent in the surface layer can be suppressed.

[Other additives]
The coating composition A and the coating composition B preferably contain a polymerization initiator, a curing agent, and a catalyst. A polymerization initiator and a catalyst are used to accelerate the curing of the surface layer. As the polymerization initiator, those capable of initiating or accelerating polymerization, condensation or crosslinking reaction by anion, cation, radical polymerization reaction or the like of components contained in the coating composition are preferable.

  Various polymerization initiators, curing agents and catalysts can be used. In addition, the polymerization initiator, the curing agent, and the catalyst may be used alone, or a plurality of polymerization initiators, curing agents, and catalysts may be used simultaneously. 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, amine compounds, and the like.

  As the photopolymerization initiator, an alkylphenone compound is preferable from the viewpoint of curability. Specific examples of the alkylphenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropane-1-o , 1- [4- (2-Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, and materials thereof And the like having a high molecular weight.

  The progress of the polymerization reaction by the thermal polymerization initiator or photopolymerization initiator can be controlled by the amount of heat or the amount of light applied, and when the surface layer is formed by sequential coating, the progress of the polymerization is incomplete. By applying the next layer, a mixed layer having intermediate physical properties can be formed without forming a clear interface.

  In addition, a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, etc. may be added to the coating composition A and the coating composition B used for forming the surface layer as long as the effects of the present invention are not impaired. . Thereby, the surface layer can contain a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, and the like. Examples of the leveling agent include acrylic copolymers, silicone-based and fluorine-based leveling agents. Specific examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, oxalic acid anilide-based, triazine-based and hindered amine-based ultraviolet absorbers. Examples of the antistatic agent include metal salts such as lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt and calcium salt.

[Manufacturing method of laminate]
The production method of the laminate of the present invention uses a production method in which at least the above-mentioned coating composition A and coating composition B are formed by applying, drying and curing on the above-mentioned supporting substrate sequentially or simultaneously. More preferred.

  Here, “sequentially apply” or “sequentially apply” means that a surface layer is formed by applying-drying-curing one type of coating composition and then applying-drying-curing a different type of coating composition. Intended to form. The surface layer formed in “sequential application” can be selected by appropriately selecting the type and number of coating compositions to be used. You can control the size. The surface layer formed by “sequential application” usually has a “multilayer structure” having a plurality of interfaces, but by appropriately selecting the type, composition, drying conditions, and curing conditions of the coating composition, It is also possible to control the separation and diffusion of the material species to form a pseudo gradient structure. With the layer structure as described above, the elastic modulus distribution in the surface layer can be changed stepwise or continuously.

  Another production method is a method in which two or more kinds of coating compositions are formed by applying, drying and curing “simultaneously” on a supporting substrate. There are no particular restrictions as long as the number of types of coating compositions is two or more. Here, “simultaneous application” or “simultaneous application” is intended to dry and cure after applying two or more types of liquid films on a supporting substrate in the application step. The surface layer formed in “simultaneous application” forms an “inclined structure” having no clear interface.

In this production method, the coating method is 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) when the aforementioned coating composition is sequentially applied. It is preferable to form a surface layer by applying it to a supporting base material, etc. In addition, when simultaneously applying two or more kinds of coating compositions as described above, after laminating liquid films in order before application “Multi-layer slide die coat” to be applied (FIG. 3), “Multi-layer slot die coat” to be laminated simultaneously with application on the substrate (FIG. 4), and a single layer of liquid film formed on the support substrate, and then undried Any of “wet-on-wet coat” (FIG. 5) or the like in which another layer is laminated.

  Next, the liquid film applied on the support substrate or the like is dried. In addition to removing the solvent from the resulting laminate, the drying process preferably involves heating 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, you may perform the further hardening operation (hardening process) by irradiating a heat | fever or an energy ray. In the curing step, when the coating composition A and the coating composition B are used and cured by heat, the temperature is preferably from room temperature to 200 ° C., and from the viewpoint of the activation energy of the curing reaction, 80 ° C. or more and 200 ° C. The following is more preferable, and in order to form the above-described smooth surface layer, the temperature is particularly preferably 80 ° C. or higher and 100 ° C. or lower.

  Moreover, when hardening with an active 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 outermost surface can prevent oxygen inhibition, so that the oxygen concentration is preferably as low as possible, and it is more preferable to cure in a nitrogen atmosphere (nitrogen purge). When the oxygen concentration is high, the hardening of the outermost surface is inhibited, and the surface hardening may be insufficient. On the other hand, in the layer forming the inside of the surface layer, it is preferable because the next coating layer easily penetrates by promoting oxygen inhibition, and the mixed layer having the above-mentioned intermediate physical properties is easily formed. .

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, it is preferable that the illuminance of the ultraviolet rays is 100~3,000mW / cm ^2, more preferably 200~2,000mW / cm ^2, 300~ more preferably performed with ultraviolet radiation under conditions to be 1,500 mW / cm ^2, preferably integrated light quantity of ultraviolet light is 100~3,000mJ / cm ^2, to be 200~2,000mJ / cm ² More preferably, ultraviolet irradiation is more preferably performed under the condition of 300 to 1,500 mJ / cm ² . Here, the illuminance of ultraviolet rays 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.

[Application example]
Since the laminate of the present invention has excellent scratch resistance, it can be widely used for a member having a surface, for example, a display, an electric appliance, an automobile interior member, a building member, and the like.

  Examples include plastic products such as glasses / sunglasses, cosmetic boxes, food containers, smartphone housings, touch panels, keyboards, home appliances such as remote controls for TVs and air conditioners, buildings, dashboards, car navigation systems, touch panels, and rooms. It can be suitably used for vehicle interior parts such as mirrors, and the surfaces of various printed materials.

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

<Binder material>
The following materials were used as binder materials. The combinations of the binder material and other materials are shown in Table 1.
Binder material 1: Urethane acrylate ("New Frontier MF-101", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Binder material 2: Urethane acrylate ("EBECRYL 8254" manufactured by Daicel Ornex Co., Ltd.)
Binder Material 3: Polymer Type Acrylate (“Unidic V-6850” manufactured by DIC Corporation)
Binder material 4: Urethane acrylate ("purple light UV-1700B" manufactured by Nippon Synthetic Chemical Co., Ltd.).

<Fluorine additive>
The following materials were used as fluorine additives. Table 1 shows combinations of fluorine additives and other materials.
Fluorine additive 1: Antifouling hard coat ("X-12-2441F" manufactured by Shin-Etsu Chemical Co., Ltd.)
Fluorine additive 2: Antifouling additive (MEGAFACE “RS-75” DIC Corporation).

<Particle material>
The following materials were used as the particle materials. The combinations of the particulate material and other materials are described in Table 1.
Particle material 1: Alumina dispersion (“NANOBYK-3602” manufactured by Big Chemie Japan Co., Ltd.)
Particle material 2: Silica particle dispersion ("MEK-AC-2140Z" Nissan Chemical Industries, Ltd.).

<Preparation of coating compositions 1-11>
The above materials were mixed at the following ratios to obtain coating compositions 1 to 11.

[Coating composition 1]
-Binder material 1 26.0 parts by mass-Fluorine additive 1 2.0 parts by mass-Particle material 1 41.2 parts by mass-Photoradical polymerization initiator 1.2 parts by mass ("Irgacure" (registered trademark) 184 BASF Japan Corporation)
-29.6 mass parts of butyl acetate.

[Coating composition 2]
-Binder material 1 38.0 parts by mass-Fluorine additive 1 2.0 parts by mass-Photo radical polymerization initiator 1.2 parts by mass ("Irgacure" (registered trademark) 184 BASF Japan Ltd.)
-58.8 mass parts of butyl acetate.

[Coating composition 3]
-Binder material 1 38.0 parts by mass-Fluorine additive 1 2.0 parts by mass-Photo radical polymerization initiator 1.2 parts by mass ("Irgacure" (registered trademark) 184 BASF Japan Ltd.)
-Butyl acetate 48.8 mass parts-gamma-butyrolactone 10.0 mass parts.

[Coating composition 4]
Binder material 2 38.0 parts by mass Fluorine additive 1 2.0 parts by mass Photoradical polymerization initiator 1.2 parts by mass ("Irgacure" (registered trademark) 184 BASF Japan Ltd.)
-58.8 mass parts of butyl acetate.

[Coating composition 5]
-Binder material 1 26.0 parts by mass-Fluorine additive 1 2.0 parts by mass-Particle material 2 26.7 parts by mass-Photoradical polymerization initiator 1.2 parts by mass ("Irgacure" (registered trademark) 184 BASF Japan Corporation)
-44.1 mass parts of butyl acetate.

[Coating composition 6]
-Binder material 1 38.0 parts by mass-Fluorine additive 2 5.0 parts by mass-Photo radical polymerization initiator 1.2 parts by mass ("Irgacure" (registered trademark) 184 BASF Japan Ltd.)
-55.8 mass parts of butyl acetate.

[Coating composition 7]
-Binder material 1 40.0 parts by mass-Photoradical polymerization initiator 1.2 parts by mass ("Irgacure" (registered trademark) 184 BASF Japan Ltd.)
-58.8 mass parts of butyl acetate.

[Coating composition 10]
-Binder material 3 34.0 parts-Fluorine additive 1 2.0 parts-Particle material 2 8.9 parts-Photo radical polymerization initiator 1.2 parts ("Irgacure" (registered trademark) 184 BASF Japan Corporation)
-53.9 mass parts of butyl acetate.

[Coating composition 11]
-Binder material 4 38.0 parts by mass-Fluorine additive 1 2.0 parts by mass-Photoradical polymerization initiator 1.2 parts by mass ("Irgacure" (registered trademark) 184 BASF Japan Ltd.)
-58.8 mass parts of butyl acetate.

<Coating compositions 8 and 9>
The following coating materials were used as the coating compositions 8 and 9, respectively.
Coating composition 8: Organic / inorganic hybrid hard coat (compound “HUV U70DM04” manufactured by Atomics Co., Ltd.) (indicated as “hard coat coating material” in Table 1)
Coating composition 9: Self-healing coat (Forseed “No. 521C” manufactured by China Paint Co., Ltd.) (indicated as “self-healing coating material” in Table 1).

<Method for producing laminate>
"Lumirror" (registered trademark) U40 (manufactured by Toray Industries, Inc., hereinafter referred to as substrate film A) having a thickness of 23 μm and 50 μm, on which an easy-adhesive paint is applied as a supporting substrate on a PET resin film, and the following substrate film B Was used. Table 2 shows the method for producing the laminate, the coating composition to be used, and the film thickness of each layer corresponding to each example and comparative example.

(1) Base film B
Stirrer (the shape of the stirring blade is 1,000 L glass-lined reaction tank equipped with three retreating blades, 19.9 kg of diamine 1 and 3.85 kg of diamine 2 and anhydrous lithium bromide (Honjo Chemical Co., Ltd.) 7.0 kg and N-methyl-2-pyrrolidone (433 kg) were added, cooled to 0 ° C. in a nitrogen atmosphere, and acid dichloride 2 was added in 4.33 kg over 5 minutes with stirring over 90 minutes. After stirring for 1 minute, 12.46 kg of acid dichloride 1 was added in 10 portions, and after stirring for 1 hour, the hydrogen chloride generated in the reaction was neutralized with lithium carbonate to prepare a polymer solution having a polymer concentration of 7% by mass. Obtained.

The obtained polymer solution was cast on an endless belt having a mirror-like surface so that the final film thickness was 23 μm using a die having a lip gap of 0.7 mm. Next, the cast polymer solution was heated with hot air at 130 ° C. for 6 minutes to evaporate the solvent, and peeled off from the endless belt while stretching 1.11 times in the longitudinal direction. Subsequently, it introduce | transduced into the water tank which 40 degreeC pure water flows, and desalted and desolvated. Furthermore, the film that came out of the water tank was introduced into a tenter, stretched 1.29 times at 260 ° C., then relaxed 0.98 times at 340 ° C., and further heat treated at the same temperature to obtain a base film B It was.
"Sequential application"
The coating compositions A and B are applied onto the supporting base material using a wire bar, adjusting the count so that the thickness of the surface layer after drying becomes the specified film thickness, and then drying under the following conditions: A curing step was performed. A surface layer was formed on the support substrate by sequentially repeating these series of coating, drying, and curing.
"Simultaneous application"
Coating compositions A and B are applied onto a supporting substrate by using a “multilayer slot die coat” (FIG. 4) and adjusting the coating amount so that the thickness of the surface layer after drying becomes a specified film thickness. Then, a surface layer was formed on the support substrate by performing a drying step and a curing step under the following conditions.
"Drying process of UV curing 1"
Air temperature and humidity: Temperature: 100 ° C
Wind speed: coating surface side: 5 m / sec, anti-coating surface side: 5 m / sec Wind direction: coating surface side / anti-coating surface side: dwell time perpendicular to the substrate surface: 2 minutes “UV curing 1 curing process”
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: Atmospheric atmosphere.
"Drying process of UV curing 2"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coating surface side: 5 m / sec, anti-coating surface side: 5 m / sec Wind direction: coating surface side: parallel to substrate surface, anti-coating surface side: vertical residence time to substrate surface: 3 Minutes "UV curing 2 curing process"
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 200 ppm or less The laminates of Examples 1 to 13 and Comparative Examples 1 to 4 were prepared by the above method.

<Evaluation of laminate>
About the created laminated body, the following performance evaluation was implemented and the obtained result is shown in Table 3. Unless otherwise specified, the measurement was performed five times at different locations for each sample in each example and comparative example, and the average value was used.

[Measurement of horizontal force by atomic force microscope]
Measurement was performed from the outermost surface side of the surface layer in the prepared laminate using an AFM (NanoScopeV DimensionIcon manufactured by Burker Corporation Bruker AXS) in the LFM mode under the following conditions. The specific operation method is shown below.

  First, as a calibration of the cantilever to be used, according to the manual of PeakForceQNM mode, the cantilever warpage sensitivity and the spring constant in the thermal tune mode were calibrated with a sapphire glass standard calibration sample. Although the spring constant varies depending on individual cantilevers, a cantilever satisfying a spring constant of 0.15 N / m or more and 0.25 N / m or less was adopted and used for measurement as a range that does not affect the measurement.

Then, according to the LFM mode manual, measurement was performed under the following conditions, and the data of the obtained Friction channel Retrace was adopted as the horizontal force distribution measured from the surface layer side. The measurement conditions are shown below.
Measuring device: Burker Corporation Bruker AXS atomic force microscope (AFM)
Measurement mode: LFM
Cantilever: Burker Corporation Bruker AXS SCM-PIC (material: silicon Si, spring constant K: 0.2 (N / m), tip radius of curvature R: 20 (nm))
Measurement atmosphere: 23 ° C, measurement range in air: 10 (μm) square resolution: 512 × 512
Cantilever moving speed: 20 (μm / s)
Indentation load (Peak Force Setpoint): 5 (nN).

[Number of boundaries created by an area with a horizontal force of 50% or more]
Next, the data of the obtained Friction channel Retrace was analyzed by the following procedure using analysis software “NanoScope Analysis V1.40”. First, using PlaneFit, smoothing was performed by processing with Plane Fit Mode: XY and Plane Fit Order: 1st.
Next, using Bearing Analysis, a threshold was specified with a horizontal force of 50%, and the region with a horizontal force of 50% or more was filled.

  The image obtained by the above processing is binarized by using software (image processing software ImageJ / developer: National Institutes of Health (NIH)), and is divided into an area where the horizontal force is 50% or more and an area where it is less than 50%. Painted separately. Furthermore, one straight line having a Pixel number corresponding to a length of 5 μm was created in the obtained image so as to pass through the center of the image, and the number of intersections with the boundaries of each region was calculated. Next, by rotating the created straight line by 45 ° from the center of the image by 45 °, three straight lines are drawn in the same manner, and a total of four straight lines are measured. It was adopted as the number of boundaries created by more than% area.

[Absolute Skewness of Horizontal Force Distribution (| Lsk |)]
The data of the precision channel obtained in the same manner as the measurement of the horizontal force described above was analyzed using the analysis software “NanoScope Analysis V1.40” according to the following procedure.

  First, using PlaneFit, smoothing was performed by processing with Plane Fit Mode: XY and Plane Fit Order: 1st.

  Next, the entire image obtained was selected using Roughness and analyzed to calculate the value of the Skewness term, and the absolute value was extracted. Similar measurement and analysis were repeated 5 times, and the average value of the obtained absolute values was adopted as the absolute value | Lsk | of the skewness of the horizontal force distribution.

[Measurement of critical load of fracture by micro scratch test]
First, the measurement principle will be briefly explained. In the micro scratch test, an indenter having a certain radius of curvature is brought into contact with the sample. The indenter is scratched while being excited at a constant frequency perpendicular to the scratch direction and horizontally to the sample surface. At this time, if a load is gradually applied in a direction perpendicular to the sample surface, the excitation is delayed due to the frictional force generated between the indenter and the sample. Due to this delay, a change occurs in the positional relationship between the magnet interlocked with the indenter and the coil inside the apparatus, and an electric signal corresponding to a frictional force generated between the indenter and the sample can be detected as a sensor output. In actual measurement, the following three graphs are obtained with respect to the measurement distance on the horizontal axis.
G1: graph of applied load that increases linearly with respect to the measurement distance G2: graph of sensor output G3: Fourier transform of sensor output to reduce noise components, and after decomposition into frequency components, only even order components are accumulated , Graph output for measurement distance (Fourier transform analysis graph)
The specific operation method is shown below.

  First, the prepared laminate was allowed to stand under normal conditions (24 ° C., relative humidity 65%) for 12 hours, and then the micro scratch tester (Nano-Layer Scratch Tester CSR-2000, manufactured by RHESCA) was applied to the outermost surface of the surface layer. Was used to measure the critical load of fracture measured from the outermost surface side of the surface layer.

  Next, the two-dimensional measurement software ArtMeasure (art Ray Co., Ltd. ver1.3.8.2) was activated, and the calibration of the sample observation screen was performed using a calibration gauge. Next, the device standard measurement analysis software CSR-2000 Data Analyzing System (ver 3.6.0) was started, an indenter needle (stylus) was attached, and the sample was suction fixed at the center of the stage. A needle cleaning solution (High Clean 801 manufactured by Nagaoka Trading Co., Ltd.) was applied to the stylus and washed, and then measured under the following conditions. The applied load of G1 at the position of the peak top in G3 obtained by measurement was taken as the critical load for fracture.

Here, in ArtMeasure, the distance between the break start point and the end point, that is, the length of the break mark (L1) is measured, and the distance between the peak top position in G3 and the measurement end point (L2) And the validity of L1 was verified by the following formula 3.
| (L1-L2) /L1|≦0.05 (Formula 3)
When Expression 3 was satisfied, the applied load of G1 at the peak top position in G3 described above was set as the critical load for fracture. On the other hand, when Expression 3 is not satisfied, the measurement end application load is decreased by 100 mN, and the above-described operation is repeated until Expression 3 is satisfied. The load was the critical load for fracture. The above procedure was repeated 5 times, and the average value was adopted as the critical load for fracture.
Measuring apparatus: Nano-Layer Scratch Tester CSR-2000 manufactured by RHESCA
Stylus: Exchange needle manufactured by RHESCA Co., Ltd. (material: diamond, spring constant: 100 (g / mm), stylus diameter: 15 (μm))
Measurement atmosphere: 23 ° C./Scratch speed in air: 10 (μm / s)
Excitation level: 100 (μm)
Excitation frequency: 45 (Hz)
Measurement end time: 60 (sec)
Applied load at the end of measurement: 1,000 (mN).

[Measurement of indentation elastic modulus by nanoindenter]
For measurement, a nanoindenter “ENT-2100” manufactured by Elionix Co., Ltd. was used. One drop of “Aron Alpha” (registered trademark) professional impact resistance manufactured by Toagosei Co., Ltd. is applied on the opposite side of the measurement surface of the laminate, and the laminate is put on a dedicated sample fixing base via instant adhesive. The measurement was performed using the surface layer of the laminate as the measurement surface. For the measurement, a triangular pyramid diamond indenter (Berkovich indenter) having a ridge angle of 115 ° was used. The measurement data was processed by “ENT-2100” dedicated analysis software (version 6.18), and the indentation elastic modulus E _IT [GPa] measured from the outermost surface side of the laminate was calculated.

Measurement mode: Load-unloading test Maximum load: 0.5 mN
Holding time when the maximum load is reached: 1 second Loading speed, unloading speed: 10 mN / sec.

[Calculation of adhesion wear parameter ε _L ]
The indentation elastic modulus E _IT [GPa] measured from the outermost surface side of the laminate obtained from the above measurement is converted into [MPa = N / mm ² ], the critical load F [N] of fracture, and the curvature of the indenter Using r (stylus diameter) 5 [μm] = 0.005 [mm], an adhesion wear parameter ε _L was calculated according to the formula (Formula 2) ε _L = E _IT × (πr ² / F).

[Surface hardness measurement by pencil hardness test method of surface layer]
The prepared laminate was allowed to stand under normal conditions (24 ° C., relative humidity 65%) for 12 hours, and then in accordance with the scratch hardness (pencil method) described in JIS K 5600-5-4 (1999) in the same environment. The surface hardness of the layer was measured.

[Scratch resistance of surface layer]
Normal under (24 ° C., 65% relative humidity) the laminate created was allowed to stand 12 hours, the steel to a plane having a surface layer, a 1,000 g / cm ² load and 2,000 g / cm ² load Wool (# 0000) was placed vertically and the approximate number of scratches visually observed when the length of 5 cm was reciprocated 5,000 times was described, and the following classification was performed.
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.

[Curlability of laminate]
The prepared laminate was allowed to stand under normal conditions (24 ° C., relative humidity 65%) for 12 hours, then cut into a 10 cm square shape and left on a horizontal plane. Next, the distance between the four corner points of the laminate and the horizontal plane was measured, and classified into five levels based on the average of the numerical values.
5 points: less than 1 mm 4 points: 1 mm or more, less than 10 mm 3 points: 10 mm or more, less than 20 mm 2 points: 20 mm or more 1 point: cylindrical and cannot be measured.

[Adhesion of surface layer]
The prepared laminate was allowed to stand under normal conditions (24 ° C., relative humidity 65%) for 12 hours, and then 100 pieces of 1 mm ² crosscuts were placed on the surface having the surface layer, and “Cello tape” (registered) manufactured by Nichiban Co., Ltd. (Trademark) is affixed on it, reciprocated 3 times at a load of 19.6 N using a rubber roller, pressed, peeled in the direction of 90 degrees, and evaluated on a five-point scale based on the number of remaining surface layers (5:96) -100, 4: 81-95, 3: 71-80, 2: 61-70, 1: 0-60).

  The laminate according to the present invention can also be used for imparting similar functions to the surfaces of plastic molded products, home appliances, buildings, vehicle interiors, and various printed materials.

DESCRIPTION OF SYMBOLS 1 Probe of atomic force microscope 2 Outermost surface of surface layer 3 Inclination which arises in probe according to horizontal force 4 Reflection of light by inclined probe 5 Maximum value of horizontal force measured in range of 10 μm × 10 μm square And vertical axis value of relative horizontal force of 100% 6 straight line crossing at horizontal force of 50% 7 intersection of straight line crossing at horizontal force of 50% and horizontal force distribution 8 multilayer slide die 9 multilayer slot die 10 single layer slot Die

Claims (3)

A laminate having a surface layer on at least one surface of a support substrate, wherein the laminate satisfies the following (A) and (B) when measured from the outermost surface side of the surface layer.
(A) LN <10
(B) | Lsk | <1.0
LN: Number of boundaries created by a region with a horizontal force of 50% or more in a horizontal force distribution on a straight line of 5 μm | Lsk |: absolute value of skewness of a horizontal force distribution of 10 μm square 2. The laminate according to claim 1, wherein a critical load of fracture in a micro scratch test measured from the outermost surface side of the surface layer is 60 mN or more and 200 mN or less. The laminate according to claim 2, wherein (C) and (D) are satisfied when measured from the outermost surface side of the surface layer.
(C) The outermost adhesive wear parameter ε _L represented by the following formula 1 is 6.5 or more and 10 or less.
(Equation _{1) ε L = E IT /} 1,000 × (πr 2 / F)
ε _L : Adhesion wear parameter, E _IT : Indentation elastic modulus, F: Critical load at break, r: Indenter curvature (D) Indentation elastic modulus E _IT is 4 GPa or more and 12 GPa or less