JP2019127531A - Resin molded body and manufacturing method therefor, coating composition used for the method - Google Patents

Abstract

To provide a resin molded body and a laminate film having excellent heat conductivity especially in a thickness direction.SOLUTION: There is provided a resin molded body containing a resin component and at least one or more kind of inorganic filler component, and satisfying all Conditions 1 to 4. Condition 1: volume packing rate of the inorganic filler component in whole thickness direction of the resin molded body is 5% to 30%. Condition 2: Volume packing rate of the inorganic filler component in a zone of 5% to 15% of thickness from a surface in the thickness direction of the resin molded body Fand volume packing rate of the inorganic filler component in a zone of 85% to 95% of the thickness from the surface F, satisfy a specific relational expression. Condition 3: The resin component of the resin molded body contains a segment with a specific chemical formulation. Condition 4: Dielectric breakdown voltage of the resin molded body is 4 kV or more.SELECTED DRAWING: None

Description

  The present invention particularly relates to a resin molded product excellent in heat diffusion in the thickness direction, a method for producing the same, and a coating composition used for the method.

  With the high integration and high performance of electronic components in recent years, microcomputers are mounted on many devices such as home appliances, automobiles, and homes, and various functions and services are provided by their control, and the heat emitted from the elements Divergence is very important in terms of performance and life. In the image display devices such as personal computers, televisions, and liquid crystal displays, in particular, with the progress of downsizing and thinning, the formation of efficient heat dissipation paths is actively sought. On the other hand, in small information terminals such as mobile phones and smartphones, with the addition of functions that require airtightness such as waterproofing and dustproofing, there is an increasing demand for thermally conductive members for efficiently radiating heat.

  In response to such demands, materials such as metals and carbon nanotubes that are excellent in thermal conductivity may induce a short circuit of the circuit due to their electrical conductivity, so that usable portions may be limited. Therefore, attention has recently been particularly focused on the use of ceramic materials such as metal nitrides.

  In addition to the excellent thermal conductivity, the necessary characteristics of the thermal conductive member as described above include electrical insulation and adhesion that allows elements to contact each other without air. Generally, it is designed by the combination of a filler component responsible for conductivity and a resin material responsible for insulation and adhesion. However, it is difficult to obtain sufficient thermal conductivity simply by mixing both, and a technique for effectively diffusing and unevenly distributing the filler component is required. In particular, in the case of a sheet-like thermally conductive member, it is difficult to impart thermal conductivity in the thickness direction (that is, the direction in which the length of the sheet-like member is the shortest), and these problems are solved Technology is required.

  For example, Patent Document 1 discloses that a coating film is formed by applying a coating liquid containing dispersed fine particles having shape anisotropy to a substrate as “a cured film having anisotropy in physical properties against light, heat, electricity, etc.” Then, after orienting the long axis direction of the dispersed fine particles in the film thickness direction of the coating film using an electric field, the coated film is cured to produce a cured film in which the dispersed fine particles are oriented. Has been proposed.

  Further, in Patent Document 2, as “a sheet-like composite material in which a filler is oriented in a predetermined direction in an organic resin matrix by an electric field”, “fillers are aggregated in a dendritic shape and oriented in a thickness direction in the organic resin matrix. , "Sheet-like composite material" is disclosed in Patent Document 3 as "a heat conductive sheet having excellent heat dissipation characteristics in which a heat conductive filler is dispersed in a polymer matrix" and "aspherical heat conductive filler is dispersed in a polymer matrix" In the heat conductive sheet, at least a part of the heat conductive filler is oriented in the thickness direction of the sheet, and the degree of orientation of the heat conductive filler in the thickness direction of the sheet is When the largest portion is the orientation center, and the axis perpendicular to the sheet surface passing through the orientation center is the orientation central axis, the thermally conductive filler is directed toward one point on the orientation central axis. A thermally conductive sheet having a portion in which the degree of orientation of the thermally conductive filler in the thickness direction of the sheet is decreased from the orientation center toward the peripheral portion of the sheet It is done.

  Furthermore, as an example in which the thermal conductivity in the in-plane direction is improved, Patent Document 4 discloses “a reinforcing layer, a first layer formed on one surface of the reinforcing layer and containing a thermally conductive inorganic filler and a binder. An anisotropic heat conductive film having a heat conductive layer and a second heat conductive layer formed on the other surface of the reinforcing layer and containing a heat conductive inorganic filler and a crosslinked rubber has been proposed.

  On the other hand, as a manufacturing method, as a technique for orienting a conductive filler, Patent Document 5 discloses that a conductive filler coating layer is formed by applying a conductive filler dispersion liquid in which a conductive filler is dispersed in a conductive liquid, Patent Document 6 discloses a method of manufacturing a conductive filler oriented body in which the conductive filler is oriented in the horizontal direction with respect to the substrate surface by applying an electric field to the coated substrate until the conductive filler coated layer is dried. "A step of placing a film precursor containing nanotubes or nanoparticles on a comb electrode having a circular cross section through a support, and the film precursor on the comb electrode. In the surface direction of the film, characterized by comprising a voltage applying step of applying an alternating voltage to the comb electrode and a film forming step of forming the film precursor into a film. Method of producing a film containing oriented nanotubes or nanoparticles "have been proposed respectively I.

JP 2005-218889 A JP, 2007-332224, A JP 2013-087204 A JP 2013-103375 A Japanese Patent Laying-Open No. 2015-178067 International Publication No. 2012/033167

  However, in the method currently proposed conventionally, heat conductivity is not enough and it is the condition where the further functional improvement is calculated | required. For example, in the method using a DC electric field described in Patent Document 1, a sufficient effect cannot be obtained when the filler material is not a ferroelectric material, and there is also a problem in productivity that a necessary charge increases as the sheet thickness increases. There is.

  On the other hand, the present inventors have verified the thermal conductive sheets described in Patent Documents 2 and 3, and the method described in Patent Document 2 results in insufficient alignment in the vicinity of the interface of the sheet material, resulting in sufficient thermal conductivity. Was not obtained. It is presumed that the ionic curing accelerator contained in the resin composition cancels the electric field in addition to the idea of the shear viscosity and the electrode shape.

  Further, in the method described in Patent Document 3, the effect of giving interaction between particles and promoting the formation of a heat conduction path was not confirmed, and the heat conductivity was insufficient.

  Furthermore, when the present inventors verified a technique for selectively improving the thermal conductivity in a specific orientation like the thermal conductive film described in Patent Document 4, in a general method for forming a coating film, The alignment arrangement in the in-plane direction is easily promoted, and in particular, the thermal conductivity in the thickness direction becomes insufficient.

  On the other hand, the filler orientation techniques described in Patent Document 5 and Patent Document 6 are based on the premise of the orientation of the conductive filler, and cannot be directly used for the electrical insulating filler orientation.

  Therefore, an object of the present invention is to provide a resin molded body excellent in heat diffusibility, a method for producing the same, and a coating composition used for the method.

  In order to solve the above-described problems, the present inventors firstly conducted extensive research, and as a result, the present inventors completed the following invention. That is, the present invention is as follows.

(1) A resin molded body comprising a resin component and at least one or more inorganic filler components, wherein all of the following conditions 1 to 4 are satisfied.

  Condition 1: The volume filling ratio of the inorganic filler component in the entire thickness direction of the resin molded body is 5% or more and 30% or less.

Condition 2: in the thickness direction of the resin molded body, and the volume filling ratio F _A of the inorganic filler component in the 5% to 15% of the area of the thickness from the surface, from the surface of the inorganic filler component in the 85% to 95% of the area of the thickness volume filling ratio and F _B satisfies equations 1 and 2 below.

_{0.5 ≦ F A / F B ≦} 1.5 ··· ( Equation 1)

5% <F _A <20% (Equation 2)

  Condition 3: The resin component of the resin molded body contains the segment of Chemical Formula 1.

  Condition 4: The dielectric breakdown voltage of the resin molded body is 4 kV or more.

(2) A method for producing a resin molded body, characterized in that steps 1 to 4 are sequentially performed.

(Step 1) A step of forming a coated layer by applying a coating composition on at least one surface of a supporting substrate to form a laminated film

(Step 2) A pair of comb electrodes (hereinafter referred to as electrodes A and B) are formed on the upper and lower sides of the laminated film including the coating layer, and the plane of the laminated film and the surface formed by the electrodes are parallel to each other. A step of arranging an angle formed by the comb teeth of the electrode B with respect to the direction of the comb teeth to be not less than 10 degrees and not more than 170 degrees, and applying an alternating electric field between the electrode A and the electrode B

(Step 3) A step of irradiating the applied layer with active energy rays to obtain a resin molded body

(Process 4) The process of peeling the said resin molding from the said support base material.

(3) The method for producing a resin molded body according to (2), wherein a change rate of mass per unit area of the coating layer is 3% or less between the step 1 and the step 3. .

(4) A coating composition used for the production of a resin molded body, which includes an inorganic filler material, a dispersion medium, and a dispersant, the dispersion medium including a portion curable by active energy rays, and having a temperature of 25 ° C. and a viscosity _{V a} at a shear rate of 0.01s ^-1, coating composition viscosity _{V B} at a temperature 25 ° C. and a shear rate of 1,000 s ^-1 and satisfies the equations 3 and 4.

V _A > 1,000 mPa · s (Formula 3)

V _B <250 mPa · s (Formula 4)

(5) The coating composition according to (4), which contains 70% by mass or more of the dispersion medium as a total of the dispersion medium, which satisfies Formula 5.

D _P / D _M > 4 (Equation 5)
D _M : relative permittivity of dispersion medium, D _P : relative permittivity of inorganic filler

  According to the present invention, it is possible to provide a resin molded body having excellent thermal conductivity, particularly in the thickness direction. Further, in the resin molding of the present invention, in particular, "thermal conductivity", "electrical insulation" and "adhesion" can be compatible.

It is a cross-sectional schematic diagram of a resin molding and a support base material. It is a cross-sectional schematic diagram in the case of peeling a resin molding from a support base material. It is a cross-sectional schematic diagram of the resin molding which consists of two layers, and a support base material. It is a schematic diagram (a cross-sectional view (A) and a perspective view (B)) of a comb-tooth electrode. It is a schematic diagram (perspective view) of thickness direction arrangement | sequence by one pair of comb electrodes. It is a schematic diagram (plan view) of thickness direction arrangement | sequence by one pair of comb-tooth electrode.

  First, the problem of the thickness direction arrangement examined by the present inventors will be described. In order to promote heat conduction in the thickness direction, it is necessary to form an array of filler materials in the thickness direction in the resin molded body. In the conventional technology, when the thickness of the resin molding is thin, the arrangement state tends to be controlled. However, when the thickness is large, particularly when the thickness exceeds 200 μm, the sedimentation of the filler material is caused by gravity, so the arrangement is disturbed. We confirmed the tendency to be prone.

  This tendency does not depend on the diameter of the filler material. That is, the smaller the diameter of the filler material, the less susceptible to sedimentation due to gravity, but on the other hand, the force induced by the ground or electric field also becomes smaller, making effective arrangement difficult. On the other hand, when the diameter of the filler material is increased, the arrangement becomes easy, but conversely, the influence of gravity is also increased, and the structure tends to be greatly disturbed in a short time until the curing after the arrangement. The resin molded product of the present invention is characterized in that the above-mentioned disorder in arrangement is overcome.

  Specifically, the resin molded body of the present invention is characterized by containing an inorganic filler component and a resin component, and the following two conditions are satisfied. In addition, the preferable composition of an inorganic filler component and a resin component is mentioned later.

  Condition 1: The volume filling ratio of the inorganic filler component in the entire thickness direction of the resin molded body is 5% or more and 30% or less. If it is less than 5%, sufficient thermal conductivity may not be obtained, and if it exceeds 30%, sufficient flexibility may not be imparted to the resin molding.

Condition 2: in the thickness direction of the resin molded body, and the filling factor F _A of the inorganic filler component in the 5% to 15% of the area of the thickness from the surface, filled from the surface of the inorganic filler component in the 85% to 95% of the area of the thickness The rate F _B satisfies the following formulas 1 and 2.

_{0.5 ≦ F A / F B ≦} 1.5 ··· ( Equation 1)

5% <F _A <20% (Equation 2)

In the following, the filling rate F _A of the inorganic particles in the region of 5% to 15% of the thickness from the surface is simply “F _A ”, and the filling rate F _B of the inorganic particles in the region of 85% to 95% of the thickness from the surface is It may be simply described as "F _B ". Note will be described later specific measurement method F _A and F _B, but using the area occupancy in each of the region including the inorganic filler component in the cross-sectional observation images of the scanning electron microscope (SEM) as a fill factor.

When F _A / F _B is less than 0.5, it means that the inorganic filler settles and a sufficient alignment can not be formed in the thickness direction. In this case, since the inorganic filler component is partially unevenly distributed, not only the overall thermal conductivity is impaired, but sufficient flexibility may not be obtained. On the other hand, the resin molded body of the present invention is not limited to the production method thereof, and for example, a case where F _A / F _B exceeds 1 by a method such as inversion of the upper and lower sides is conceivable. In particular, when F _A / F _B exceeds 1.5, the thermal conductivity and the flexibility of the resin molding may be impaired as well.

On the other hand, the volume filling rate of the inorganic filler component in the vicinity of the surface strongly affects the adhesion and thermal conductivity of the member. Specifically, it is preferable that the condition of Formula 2 is satisfied. F _A is sometimes sufficient thermal conductivity in the case of less than 5% is not obtained, F _A is insufficient adhesion in the case of 20% or more, biting the air layer when used as an element It may be easier.

  Furthermore, the resin molded product of the present invention satisfies the following two conditions.

  Condition 3: The resin component of the resin molded body contains the segment of the chemical formula 1.

  Condition 4: The dielectric breakdown voltage of the resin molded body is 4 kV or more.

  If the condition 3 is not satisfied, it may be difficult to configure the space distribution of the inorganic filler as described above in a short time. Moreover, when not satisfy | filling the conditions 4, it may not be able to use as a heat conductive member especially for an electronic board | substrate.

Here, Chemical Formula 1 is a segment obtained by a polymerization reaction of a methacryloyl group or an acryloyl group, and in Chemical Formula 1, R ¹ represents hydrogen or a methyl group. R ² represents any one of the following (a) to (d). n represents an integer of 1 or more.

(A) a substituted or unsubstituted alkylene group (b) a substituted or unsubstituted arylene group (c) an alkylene group of the above (a) having an ether group, an ester group or an amide group therein (d The arylene group of (b), which has an ether group, an ester group or an amide group inside.

  Hereafter, the resin molded object, its manufacturing method, and the preferable form of the coating composition used for manufacture are demonstrated.

[Resin molded body, coated layer and laminated film]
The resin molded body, the coating layer and the laminated film in the present invention will be described with reference to FIGS. 1 to 3. “Resin molding” means a cured film formed in layers on the support substrate 2 or a layered resin cured independent of the support substrate 2 by peeling from the support substrate 2 after formation as shown in FIG. Refers to things. On the other hand, the “applied layer” refers to the same layer 1 as that of the resin molded body, but particularly means that it is a form before curing. The resin molded body or a combination 3 of all the series of layers including the coating layer and the supporting substrate is referred to as “laminated film”. That is, the "laminated film" may show either form before or after curing depending on the process of interest.

  As shown in FIG. 3, the “resin molded body” may be composed of a plurality of different layers. For example, a plurality of coating layers are formed on the support substrate by repeating a preferable manufacturing method described later. In this case, all layers except for the supporting substrate 2 are collectively referred to as "resin molding". Specific examples of the supporting substrate will be described later.

  Further, “layer”, “layer” or “sheet” can be distinguished by having a boundary surface and a boundary surface adjacent to each other in the thickness direction from the surface side of the resin molded body or laminated film to the thickness direction, and is finite. The site | part which has the thickness of. More specifically, when the cross section of the resin molded body or the laminated film is observed with an electron microscope (transmission type, scanning type) or an optical microscope, the resin molded body or the laminated film is distinguished by the presence or absence of a discontinuous boundary surface. The laminated film of the present invention may be either in a flat state or in a curved shape after being formed as long as it has a boundary surface exhibiting the above-mentioned physical properties.

  The thickness of the entire laminated film is not particularly limited, but is preferably 50 μm or more and 1,050 μm or less, and more preferably 200 μm or more and 500 μm or less. On the other hand, the thickness of the resin molded body is preferably 20 μm or more and 1,000 μm or less, and particularly preferably 200 μm or more and 500 μm or less. If the total thickness of the laminated film is less than 50 μm, the strength of the film is insufficient and processing suitability such as transportability may be insufficient. On the other hand, if the thickness of the resin molding is less than 20 μm, it may be easily broken. Moreover, in order to reduce the unevenness of the member and to conduct heat efficiently, a thick film of 200 μm or more is particularly preferable. On the other hand, if it exceeds 1,000 μm, the orientation of the above-mentioned filler may not be sufficiently promoted, and a sufficient thermal diffusivity may not be obtained.

  The laminated film may have a layer having other functions such as moldability, antistatic property, antifouling property, electromagnetic wave shielding property, and coloring in addition to the thermal conductivity which is the subject of the present invention. This function may be imparted to the resin molded body.

[Supporting substrate]
The material constituting the support substrate used in the laminated film 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 supporting 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, polyarylate resins , Polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluorochlorinated ethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer, fluorine resin such as 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 preferably a polyester resin, or a polyamide, an aromatic polyamide, a polyimide, an aromatic polyimide, a polyamideimide, an aromatic polyamideimide, a polycarbonate resin, a methacrylic resin from the viewpoint of strength, heat resistance and smoothness. A polyester resin is particularly preferable from the viewpoint of strength, smoothness and cost.

  The polyester resin in the present invention is a general term for a polymer having an ester bond as the main bond chain of the main chain, and is obtained by polycondensation of an acid component and its ester and diol component. Specific examples thereof include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, and polybutylene terephthalate. Moreover, what co-polymerized other dicarboxylic acid and its ester and diol component as an acid component and a diol component may be used for these. Among these, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferable in terms of transparency, dimensional stability, heat resistance and the like.

  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.

  It is also possible to apply various surface treatments to the surface of the supporting substrate before obtaining the resin molded body. 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.

  In addition, functional layers such as a mold release layer, an adhesive layer, an antistatic layer, an undercoat layer, and an ultraviolet absorbing layer can be provided in advance on the surface of the supporting substrate separately from the molded resin of the present invention. In particular, in the case of using as a sheet having adhesiveness, it is preferable to provide a releasing layer.

[Method for producing resin molded body and laminated film]
The method for producing a resin molded body and laminated film of the present invention is a production method in which a coating composition described later is applied on the above-mentioned support substrate, and the orientation of the inorganic filler material is accelerated by applying an electric field, followed by curing. More preferably, it is used.

  Specifically, it is preferable to be a method for producing a resin molded body, characterized in that the following steps 1 to 4 are sequentially performed.

(Step 1) A step of forming a coating layer by applying a coating composition to at least one surface of a supporting substrate

(Step 2) A pair of comb-shaped electrodes (electrode A and electrode B) are formed on the upper and lower sides of the laminated film including the coating layer, and the plane of the laminated film and the surface formed by the electrodes are parallel to each other. A step of applying an alternating electric field between the electrodes A and B by arranging so that the angle formed by the comb teeth of the electrode B is 10 degrees or more and 170 degrees or less based on the direction

(Step 3) A step of irradiating the coating layer with active energy rays to form a resin layer

(Step 4) Step of peeling off the resin layer from the supporting substrate to obtain a resin molded body First, with respect to Step 1, in this production method, the coating method is dip coating, roller coating, wire bar coating, gravure coating, It is preferable to form a coating layer as a base of the resin molded body by coating on a supporting base material by a die coating method (US Pat. No. 2,681,294).

  Next, for step 2, the electrode used for applying an electric field in the present production method is preferably a comb-like comb electrode. The configuration of the comb electrode is shown in FIG. Examples of the electrode include a method using an electrode wire having a circular cross section, but the material is not particularly limited. For example, copper, tungsten, or platinum can be used. Next, the structure of the electrode of the present invention will be described with reference to FIGS. In the manufacturing method of the present invention, as shown in FIGS. 5 and 6, a pair of comb-shaped electrodes (hereinafter referred to as electrodes A and B) is formed such that the plane of the laminated film and the surface formed by the electrodes are parallel to each other. When based on the direction of the teeth, the electrodes B are preferably arranged such that the direction of the comb teeth is 10 degrees or more and 170 degrees or less from parallel. When the angle formed by the comb teeth of the electrode A and the electrode B is less than 10 degrees or exceeds 170 degrees, there is a sufficient area where a strong electric field expressed by the intersection of the comb teeth in the plan view shown in FIG. It may not be formed and sufficient thermal conductivity may not be obtained.

  On the other hand, according to the manufacturing method of the present invention, an alternating voltage is applied between the pair of comb electrodes, and the alternating voltage is preferably 1 kV to 6 kV per 1 mm of the electrode line distance, particularly preferably It is 4 kV. The alternating voltage to be applied is preferably 10 Hz to 28 kHz, and particularly preferably 4 kHz. Below this applied voltage and frequency, the orientation of the resin molded product may be insufficient, and sufficient thermal conductivity may not be obtained. In addition, when the applied voltage and frequency are increased, the cost of the power supply may be required.

  On the other hand, in the case of the filler component oriented between the electrodes using a pair or plural pairs of parallel flat plate electrodes as in the prior art, a strong electric field is biased in the vicinity of the electrode surface. Differences are likely to occur in the structure, and in particular, surface adhesion and thermal diffusivity may be insufficient. On the other hand, in this invention, since it orientates by the electric field which arises between the upper and lower sides of the comb electrode which consists of an electrode wire of circular cross section, the resin molding which arranged the inorganic filler component effectively can be obtained.

  Furthermore, the arrangement of the inorganic filler material is averaged in the resin molded body by uniformly rocking at least one of the comb electrode and the laminated film in a direction parallel to the longitudinal direction of the support base. Can do.

  Next, for step 3, in the present production method, it is preferable to irradiate active energy rays to obtain a resin molded body. A further curing operation (curing step) may be performed by irradiating, for example, heat or energy rays as active energy rays. In the curing step, when the coating composition is cured with heat, it is preferably from room temperature to 100 ° C., more preferably from 60 ° C. to 100 ° C. from the viewpoint of the activation energy of the curing reaction. It is particularly preferable that the temperature is 60 ° C. or more and 80 ° C. or less in order to maintain the alignment state of

  Moreover, when it hardens | cures with an active energy ray, it is preferable from an versatility point that it is an electron beam (EB beam) and / or an ultraviolet-ray (UV ray). 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 resin molded body, by promoting oxygen inhibition on the other hand, the next coating layer is likely to penetrate and to easily form the mixed layer having the above-mentioned intermediate physical properties. preferable.

Moreover, as a kind of ultraviolet ray lamp used when irradiating an ultraviolet-ray, a discharge lamp system, a flash system, a laser system, an electrodeless lamp system etc. are mentioned, for example. When the discharge lamp type to ultraviolet cured using a high pressure mercury lamp is preferably illuminance of ultraviolet rays is 100~3,000mW / cm ^2, more preferably 200~2,000mW / cm ^2, more preferably 300~1,500mW / cm ² and comprising condition often irradiated with ultraviolet rays, the integrated light quantity of ultraviolet rays is preferably 100～3,000MJ / cm ^2, more preferably 200～2,000MJ / cm ^2, more preferably from 300 to 1, It is preferable to perform ultraviolet irradiation under the conditions of 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 transport 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.

  Further, by removing the resin molded body from the support base material in step 4, a resin molded body having high thermal conductivity independent of the thermal conductivity of the support base material can be extracted.

  Moreover, it is preferable that the change rate of the mass per unit area of a coating layer is 3% or less between the process 1 and the process 3 of a series of these manufacturing methods. For specific mass measurement timing, it means that the step 1 is finished, the state where the coating layer is formed and the step 3 is finished, the coating layer is cured and becomes a resin molded body, and in each state It is possible to calculate by subtracting the mass of the support substrate of the same size after collecting the support substrate together as a 5 cm × 5 cm slice and measuring the mass as including the support substrate.

  When the mass change rate exceeds 3%, the arrangement structure is formed by volatilization or sublimation of a resin component or an additive, and, if included, a solvent or the like in the arrangement of step 2 or curing of step 3. It may be disturbed and thermal conductivity may decrease.

[Coating composition]
The resin molded article and the coating layer of the present invention are formed in such a manner that the above-mentioned physical properties can be achieved by applying, drying and curing the coating composition on the above-mentioned supporting substrate using the above-mentioned production method. be able to. Here, the "coating composition" is a liquid containing a resin material described later, which is applied on the above-mentioned supporting substrate, and after promoting the orientation of the filler component by application of an electric field, a resin molded body by curing. Refers to materials that can be formed. 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 a resin or a material capable of forming them in the coating process (hereinafter referred to as a precursor), inorganic particles, and a polymerization initiator, curing agent, catalyst, dispersant, leveling agent, UV absorber, oxidation agent It consists of various additives such as inhibitors.

  The resin molded body and laminated film of the present invention are prepared by applying a coating composition capable of developing thermal conductivity on a supporting substrate and satisfying the volume filling rate and dielectric breakdown voltage of the inorganic filler component described above. It is particularly preferable to form by promoting the orientation of the filler component.

There is a preferred shear viscosity range for the coating composition of the present invention. Specifically 25 ° C. of the coating composition, and the viscosity _{V A} at a shear rate of 0.01s ^-1, 25 ° C., and a viscosity _{V B} at a shear rate of 1,000 s ^-1 is, Equation 3 and Equation 4 below It is preferable to satisfy.

V _A > 1,000 mPa · s (Formula 3)

V _B <250 mPa · s (Formula 4)

When the viscosity V _{A at a} shear rate of 0.01 s ⁻¹ is 1,000 mPa · s or less, the processing of the above-described step 2 may be terminated, and the arrangement state of the filler material may be disturbed in the process of moving to step 3. In some cases, sufficient thermal conductivity can not be obtained. On the other hand, if the viscosity _{V B} at a shear rate 1,000 s ^-1 of more than 250 mPa · s, the sequence in step 2 is inhibited, thermal conductivity, sufficient array structure can be obtained may be lowered.

[Inorganic filler component]
The resin molded product of the present invention is characterized by containing an inorganic filler component (hereinafter, "inorganic filler" may be expressed as "inorganic particles"). The number of types of inorganic particles is preferably 1 or more, more preferably 1 or more and 20 or less, still more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 4 or less. Here, "inorganic particles" also 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 type of inorganic filler is determined by the type of element constituting the inorganic filler, and when some surface treatment is performed, it is determined by the type of element 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 substituted with nitrogen as an anion, the elements constituting the inorganic filler are different, Different types of inorganic fillers. In addition, if the inorganic filler (ZnO) is composed only of the same element, for example, Zn and O, even if there are a plurality of inorganic fillers having different number average particle diameters, the composition ratio of Zn and O is different. Also, these are the same kind of inorganic fillers. Also, for example, even if a plurality of Zn having different oxidation numbers exist, as long as the elements constituting the inorganic filler are the same (in this example, as long as all elements other than Zn are the same), these are the same kind of inorganic It is a filler.

  Moreover, the number average particle diameter of an inorganic particle means the number-based arithmetic mean length diameter as described in JISZ8819-2 (2001) here. 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 laminated film, 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.

  On the other hand, the filler material contained in the coating composition suitable for obtaining the resin molded body 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 may be included in the resin molded body in the form of being made. Here, an inorganic filler present in the coating composition used in the present invention is an “inorganic filler material”, and the resin molding is formed by applying, drying, curing, or vapor-depositing the coating composition. Inorganic fillers present in are referred to as “inorganic filler 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, A different element may be introduced between the lattices, a lattice point may be replaced with a different element, or a lattice defect may be introduced.

  From the viewpoint of insulation, the inorganic particles are a group consisting of beryllia, aluminum nitride (hereinafter also referred to as AlN), boron nitride (hereinafter also referred to as BN), silicon carbide, alumina, magnesia, and titania. More preferably, at least one metal or metalloid selected from is an oxidized oxide particle or a nitrided nitride particle.

  As such an inorganic particle component, it is possible to use, for example, hexagonal boron nitride filler "SHOBN" (registered trademark) manufactured by Showa Denko KK or aluminum nitride fine powder "toyal nite" (registered trademark) manufactured by Toyo Aluminum Co., Ltd. .

  In the manufacturing method of the resin molding especially mentioned later, 1 micrometer-50 micrometers are preferable, and, as for the particle diameter of an inorganic filler, 5 micrometers-20 micrometers are especially preferable. When the particle diameter is less than 1 μm, sufficient force may not be obtained when the arrangement of the inorganic filler material is promoted by a force field such as an electric field, a local field, or a gravitational field. On the other hand, when the particle diameter exceeds 50 μm, sedimentation due to gravity may be dominant. It is also possible to mix a plurality of particles having different particle diameters, and in particular, by using two types of filler materials having different particle diameters together, a heat conduction path can be efficiently formed from the difference in mobility.

[Resin component, resin material or dispersion medium]
The coating composition suitable for obtaining the resin molded body of the present invention preferably contains a resin material. Here, the resin (or binder) refers to a compound having a reactive site or a higher order compound formed by the reaction. Here, the resin or binder present in the coating composition used in the present invention is a “resin (binder) material”, and the coating composition is coated, dried, cured, or vapor deposited. The resin or binder present in the molded body is referred to as "resin (binder) component". At this time, since the resin material present in the paint composition can be regarded as a medium for dispersing the inorganic filler material which is also a constituent material of the paint composition, the resin material may be described as a dispersion medium. .

  On the other hand, 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.

  Furthermore, as a binder material for imparting adhesion to the resin molded body of the present invention, acrylic adhesive, rubber adhesive, silicone adhesive, rosin adhesive, urethane adhesive, polyether adhesive, polyester A system adhesive can be used. On the other hand, from the viewpoint of rapid curing in step 3 of the production method described above, it is more preferable to include a portion that can be cured with active energy rays, and from the viewpoint that the obtained resin molded product has a segment of chemical formula 1, Acryloyl and / or methacryloyl groups are particularly preferred as the line-curable site.

  On the other hand, in the case of arranging the inorganic filler material by applying an alternating electric field, which is a preferable manufacturing method of the present invention, the conductivity of the resin material is preferably sufficiently low. Specifically, 10 μS or less is preferable, and 1 μS or less is particularly preferable. The conductivity can be measured by using a commercially available conductivity meter (for example, a conductivity meter ES-71 manufactured by Horiba, Ltd.).

Furthermore, it is preferable to include 70% by mass or more of the dispersion medium as the total dispersion medium, which satisfies the following formula 5. Here, D _M indicates the relative dielectric constant of the dispersion medium, and D _P indicates the relative dielectric constant of the inorganic filler.

D _P / D _M > 4 (Equation 5)

  Here, 70% by mass or more of the total dispersion medium means that 70% by mass or more is occupied when the total dispersion medium is 100% by mass.

In the preferred production method of the present invention, providing a difference between the dielectric constants of the inorganic filler and the dispersion medium leads to an improvement in the migration force generated in the particles. Therefore, in the case where D _P / D _M is 4 or less, the arrangement of the inorganic filler may be insufficient and sufficient thermal conductivity may not be obtained. An LCR meter (for example, LCR meter A4284A manufactured by Agilent Technologies) is used for the relative dielectric constant ε _L , and the equivalent parallel capacity C _p [F] average thickness d [m] of the liquid or powder sample and the electrode area A It can be calculated from [m ² ] and the dielectric constant ε _{0 of} vacuum, using Equation 6. When the obtained relative dielectric constant ε _L is a numerical value of the inorganic filler, it is treated as D _P , and when it is a numerical value of the dispersion medium, it is treated as D _M.

  Examples of the binder material satisfying the above conditions include “Nissets” (registered trademark) manufactured by Nippon Carbide Industries Co., Ltd., “Oribine” (registered trademark) manufactured by Toyochem Co., Ltd., “Arontack” (registered trademark) manufactured by Toagosei Co., Ltd. “Cybinol” (registered trademark), manufactured by Soken Chemical Co., Ltd. “SK Dyne” (registered trademark), “Acryset” (registered trademark) manufactured by Nippon Shokubai Co., Ltd., “Vinsol” manufactured by Lion Specialty Chemicals, Inc. Nagase Sangyo Co., Ltd. as an acrylic copolymer such as (registered trademark), Showa Denko “Vinirole” (registered trademark), or an acrylic composition for viscosity adjustment; (trade name “Denacol” (registered trademark) series Etc.), Shin-Nakamura Chemical Co., Ltd .; (brand name "NK Ester" series etc.), DIC Corporation; Trade names "UNIDIC" (registered trademark) etc., Toagosei Co., Ltd .; ("ALONIX" (registered trademark) series etc.), NOF Corporation ("Blenmar" (registered trademark) series etc.), Nippon Kayaku Co., Ltd. (Trade name “KAYARAD” (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd. (trade name “light ester” series, etc.), etc., and these products can be used.

[Dispersing agent]
The coating composition preferable for producing the resin molded body of the present invention preferably contains a dispersant that promotes the dispersion of the inorganic filler material. Since the dispersant can physically or chemically adsorb on the surface of the inorganic filler material to control the aggregation state of the filler material, the aforementioned shear viscosity can be adjusted. On the other hand, when the anionic or cationic dispersant is added in excess, the conductivity of the entire coating composition to be described later is increased, so that the potential may be canceled by the ionic component when the electric field is applied. Therefore, as the dispersant, an amphoteric or nonionic dispersant is more preferable.

  Examples of dispersants that do not have a site of crosslinking with the surface of the filler material include, but are not limited to, those manufactured by Big Chemie Japan Ltd .; (“BYK” (registered trademark) series, dispersant DisperBYK, etc.) and Matsumoto Fine Chemical Co., Ltd .; "(Registered trademark) series, titanium chelate and alkoxide). On the other hand, examples of reactive dispersants include silane coupling agents manufactured by Toray Dow Corning Co., Ltd. These products can be used.

[Other additives]
A preferable coating composition for preparing the resin molding of the present invention can contain a polymerization initiator, a curing agent, and a catalyst. The polymerization initiator and the catalyst are used to accelerate the curing of the resin molding. 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.

  In addition, when applying the above-mentioned preferable manufacturing method, it is preferable that the conductivity of the whole coating composition is sufficiently low like the resin component. Specifically, 10 μS or less is preferable, and 1 μS or less is particularly preferable. When it exceeds 10 μS, the ion component as a charge carrier may cancel the electrolysis by being coordinated near the electrode. Therefore, it is particularly preferable to use a nonionic additive.

  Various polymerization initiators, curing agents and catalysts can be used. Further, the polymerization initiator, the curing agent and the catalyst may be used alone, respectively, or a plurality of polymerization initiators, curing agents and catalysts may be used simultaneously. Furthermore, an acidic catalyst, a thermal polymerization initiator or a photopolymerization initiator may be used in combination. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of thermal polymerization initiators include peroxides and azo compounds. Moreover, as an example of a photoinitiator, an alkyl phenone type compound, a sulfur-containing type compound, an acyl phosphine oxide type compound, an amine type compound etc. are mentioned.

  From the viewpoint of curability, the photopolymerization initiator is preferably an alkylphenone compound. 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-cyclohyxyl-phenyl ketone, 2-methyl-1-phenylpropan-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 with the thermal polymerization initiator or the photopolymerization initiator can be controlled by the amount of heat or the amount of light applied. When obtaining a resin molding by sequential application, the progress of the polymerization is incomplete. By applying the next layer, it is possible to form a mixed layer having intermediate physical properties without forming a clear interface.

  Further, a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, and the like may be added to the coating composition used for obtaining the resin molding as long as the effects of the present invention are not impaired. Thereby, the resin molding 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.

  On the other hand, a solvent can also be included in the paint composition used to obtain the resin molded body as long as the effects of the present invention are not impaired. However, it is particularly preferable not to contain a solvent from the viewpoint of disorder of arrangement during drying. Here, the term "solvent" refers to a substance that is liquid at normal temperature and normal pressure and can be removed from the coating film by evaporating substantially the entire amount in the drying step after application. In addition, even if it is liquid at normal temperature and normal pressure, a substance having a reaction site is treated as a binder material.

  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.

[Application example]
Since the resin molded body of the present invention has excellent thermal conductivity, it can be used for heat dissipation of electronic devices, for example, many devices such as household appliances, automobiles, and houses, especially image display devices such as personal computers, televisions, and liquid crystal displays, and mobile phones. It can be widely used as a substrate of a small information terminal such as a telephone or a smartphone.

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

<Inorganic filler material A>
The following materials were used as the inorganic filler material A, respectively. The combinations of inorganic filler material A and other materials are described in Table 1.
Inorganic filler material A1: Aluminum nitride filler ("Toyaltec filler TFZ-A10P" manufactured by Toyo Aluminum Co., Ltd.)
Inorganic filler material A2: Aluminum nitride filler ("TOYAL TECH Filler TFZ-A02P" manufactured by Toyo Aluminum Co., Ltd.)
Inorganic filler material A3: Aluminum nitride filler (“Toyaltec filler TFZ-A15P” manufactured by Toyo Aluminum Co., Ltd.)

<Binder material B>
The following materials were used as the binder material B, respectively. The combinations of binder material B and other materials are described in Table 1. Of the binder materials contained in the coating composition, the material with the largest mass is referred to as the first binder material, and the material with the second largest mass is referred to as the second binder material.
Binder material B1: Urethane acrylate ("purple light UV3200B" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Binder material B2: Acrylate polyol ("ARUFON UH-2000" manufactured by Toho Gosei Co., Ltd.)
Binder material B3: Acrylate monomer ("Biscoat # 230" made by Osaka Organic Chemical Co., Ltd.)
Binder material B4: Acrylate monomer ("Biscoat # 150" made by Osaka Organic Chemical Co., Ltd.)
Binder material B5: Acrylate monomer ("Light Acrylate POB-A" manufactured by Kyoeisha Chemical Co., Ltd.)
Binder material B6: Polyisocyanate ("CORONATE HX" manufactured by Tosoh Corporation)

<Preparation of Coating Compositions 1 to 11>
The above materials were mixed in the following proportions to obtain coating compositions 1 to 11. First, in the case of adding the inorganic filler materials A1 to A3, the first binder, the dispersant and the organic solvent, the organic solvent was divided into screw tube bottles (No. 8 manufactured by As One Co., Ltd .; body diameter 40 40). Subsequently, 5.0 parts by mass of zirconia beads “Niimi NZ beads NZ30” manufactured by Niimi Sangyo Co., Ltd. are added to the screw tube bottle obtained by separating the above-mentioned materials, and mixed rotor VMRC-5 manufactured by As One Corporation is used. Mixing was carried out for 8 hours at a rotational speed of 40 rpm. Thereafter, the second binder was additionally added, and mixing was further carried out at a rotational speed of 60 rpm for 4 hours. After removing the zirconia beads from the obtained mixture using a 200 mesh stainless steel net, a photoinitiator was added to obtain a coating composition.

[Coating composition 1]
· Inorganic filler material A1 24.04 parts by mass · Binder material B3 64.90 parts by mass · Binder material B1 7.21 parts by mass · Dispersant 0.96 parts by mass (“DISPER BYK 2013” BIC-CHEMY JAPAN CORPORATION)
Photoradical polymerization initiator 2.88 parts by mass (“Irgacure” (registered trademark) 754 BASF Japan Ltd.)

[Coating composition 2]
Inorganic filler material A2 33.65 parts by mass Binder material B3 56.25 parts by mass Binder material B1 6.25 parts by mass Dispersant 1.35 parts by mass (“DISPER BYK 2013” by BIC-CHEMY JAPAN CORPORATION)
Photo radical polymerization initiator 2.50 parts by mass (“Irgacure” (registered trademark) 754 BASF Japan Ltd.)

[Coating composition 3]
Inorganic filler material A3 14.42 parts by mass Binder material B3 73.56 parts by mass Binder material B1 8.17 parts by mass Dispersant 0.58 parts by mass (“DISPER BYK 2013” by BIC-CHEMY JAPAN CORPORATION)
Photoradical polymerization initiator 3.27 parts by mass (“Irgacure” (registered trademark) 754 BASF Japan Ltd.)

[Coating composition 4]
-Inorganic filler A1 19.23 parts by mass-Binder material B3 51.92 parts by mass-Binder material B1 5.77 parts by mass-Dispersant 0.77 parts by mass ("DISPER BYK 2013" BYK-Chemie Japan Ltd.)
Photoradical polymerization initiator 2.31 parts by mass (“Irgacure” (registered trademark) 754 BASF Japan Ltd.)
· 20.00 parts by mass of cyclohexanone

[Coating composition 5]
· Inorganic filler A1 24.04 parts by mass · Binder material B4 64.90 parts by mass · Binder material B1 7.21 parts by mass · Dispersant 0.96 parts by mass (“DISPER BYK 2013” by Big Chemie Japan Ltd.)
Photoradical polymerization initiator 2.88 parts by mass (“Irgacure” (registered trademark) 754 BASF Japan Ltd.)

[Coating composition 6]
Inorganic filler material A1 24.04 parts by mass Binder material B3 72.12 parts by mass Dispersant 0.96 parts by mass (“DISPER BYK 2013” BYK Chemie Japan Co., Ltd.)
Photoradical polymerization initiator 2.88 parts by mass (“Irgacure” (registered trademark) 754 BASF Japan Ltd.)

[Coating composition 7]
· Inorganic filler material A1 24.04 parts by mass · Binder material B5 64.90 parts by mass · Binder material B1 7.21 parts by mass · Dispersant 0.96 parts by mass (“DISPER BYK 2013” BIC-CHEMY JAPAN CORPORATION)
Photoradical polymerization initiator 2.88 parts by mass (“Irgacure” (registered trademark) 754 BASF Japan Ltd.)

[Coating composition 8]
-Inorganic filler material A1 24.04 parts by mass-Binder material B5 50.48 parts by mass-Binder material B1 21.60 parts by mass-Dispersant 0.96 parts by mass ("DISPER BYK 2013" BIC-CHEMY JAPAN CORPORATION)
Photoradical polymerization initiator 2.88 parts by mass (“Irgacure” (registered trademark) 754 BASF Japan Ltd.)

[Coating composition 9]
· Inorganic filler material A1 40.08 parts by mass · Binder material B3 43.27 parts by mass · Binder material B1 4.81 parts by mass · Dispersant 1.92 parts by mass (“DISPER BYK 2013” by Big Chemie Japan Ltd.)
Photoradical polymerization initiator 1.92 parts by mass (“Irgacure” (registered trademark) 754 BASF Japan Ltd.)

[Coating composition 10]
-Inorganic filler material A1 4.81 parts by mass-Binder material B3 82.21 parts by mass-Binder material B1 9.13 parts by mass-Dispersant 0.19 parts by mass ("DISPER BYK 2013" BYK-Chemie Japan Ltd.)
・ Photo radical polymerization initiator 3.65 parts by mass (“Irgacure” (registered trademark) 754 BASF Japan Ltd.)

[Coating composition 11]
· Inorganic filler material A1 24.75 parts by mass · Binder material B2 51.98 parts by mass · Binder material B6 22.28 parts by mass · Dispersant 0.99 parts by mass (“DISPER BYK 2013” BIC-CHEMY JAPAN CORPORATION)

<Evaluation of coating composition>
[Measurement of relative permittivity]
Each coating composition obtained above was centrifuged at 8,000 rpm for 10 minutes in a general-purpose centrifuge 444315-200 manufactured by ASONE, and separated into an inorganic filler component and a dispersion medium component. Next, using an LCR meter A4284A manufactured by Agilent Technologies and a dedicated electrode, the equivalent capacity C of the inorganic filler component and the dispersion medium was measured under the conditions of 4 kHz and 20 V, respectively. Next, the relative dielectric constant ε _L was calculated using Equation 6. And D _P or D _M the relative dielectric constant epsilon _L of each component further obtained in accordance with the combination of the foregoing coating compositions was calculated values of D _{P /} D _M using Equation 5.

[Measurement of shear viscosity]
2 g of each coating composition obtained above was sampled and the shear viscosity was measured. A 40 mm cone plate was used for measurement using a Malvern Instruments rheometer Bohlin Gemini HR nano. The shear rate was set to 0.01 s ⁻¹ and 1,000 s ⁻¹ and the shear viscosity was measured. Triplicate measurements, the mean value of the results obtained was taken as V _A and V _B.

<Method for producing laminated film>
As a support substrate, “Therapy” (registered trademark) SY (manufactured by Toray Film Processing Co., Ltd.) having a thickness of 38 μm, in which a releasable paint is applied on a PET resin film, was used. In addition, the preparation methods of the said laminated | multilayer film corresponding to each Example and comparative example, the coating composition to be used, and the film thickness of each layer were described in Table 1.

"Application"
The coating composition is coated on a support substrate using a wire bar, and the coat is adjusted so that the thickness of the molded resin after drying becomes a specified thickness, and then applied under the following conditions: electric field application, curing The process was performed.

"Electric field application"
Grooves were provided at an interval of 1 cm on an acrylic plate (5 cm square), and electrode wires (tungsten, 0.06 mmφ) were arranged there as an electric field applying means, to produce a comb electrode. The electrode wire was connected to a power source, and the upper portion of the electrode wire was covered with parafilm (registered trademark, manufactured by Pesny Plastic Packaging). Subsequently, the support base material to which the coating composition was applied was disposed on the top of the electrode plate. Subsequently, a comb tooth or a copper plate similarly prepared above the coating film was placed at a position 1 mm above the lower electrode through a spacer having a thickness of 1 mm. Then, voltage application was performed between both electrodes. In Example 1, voltage application was performed for 10 minutes, and ultraviolet irradiation was performed for 10 minutes 5 minutes after the start of the voltage application. The power supply uses 20 / 20C (Trek) and a neon inverter transformer (Lecile), which is a primary voltage connected to a 50Hz autotransformer Slack (registered trademark), and the voltage is per cm of electrode wire distance. The frequency was 4 kV and 4 kV was applied. The electrode configuration and the voltage application conditions of the other examples are described in Table 2.

"Curing"
Integrated light quantity: 120mJ / cm ²
Oxygen concentration: Atmospheric atmosphere

“Curing Comparative Example 5”
Curing was carried out by blowing hot air with a drier for 10 minutes.
Oxygen concentration: Atmospheric atmosphere

  The laminated film of Examples 1-10 and Comparative Examples 1-5 was created by the above method.

  In addition, since the crosslinking site contained in the binder materials B1 and B3 to B5 causes a segment of the chemical formula 1 by reaction, the resin component of the resin molded product of Examples 1 to 10 and Comparative Examples 1 to 4 has the chemical formula 1 Includes segments.

<Evaluation of molded resin>
The following performance evaluations were performed on the produced resin molded articles, and the obtained results are 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. The resin molded body was measured as it was.

[Measurement of thermal diffusivity by flash analyzer]
First, the related physical quantities of the thermal conductivity of the resin molded body and the laminated film will be described. A physical quantity generally used as an index of thermal conductivity, that is, heat transferability, is thermal conductivity, and its unit is represented by W / (m · K). The measurement method is roughly classified into a stationary method and an unsteady method, and each is calculated by the following theoretical formula. (Λ: thermal conductivity, J: heat flux, T: temperature, α: thermal diffusivity, ρ: density, Cp: specific heat capacity)

(Formula 7) Thermal conductivity by the steady state method

(Equation 8) Thermal conductivity by unsteady method

In a material having a high thermal diffusivity, the temperature gradient grad T tends to be small, so that measurement by the steady method is difficult, and the characteristics are generally estimated by the unsteady method using (Equation 8). Non-stationary methods include laser flash method, calorimeter method, probe method, etc., but all calculate the thermal diffusivity α (m ² / s) from the time change of temperature against heating and distance information such as thickness It is a technique to do. The measurement method of each parameter by the flash method used as a general measurement method is described in detail in JIS R 1611 (2010).

  As a measurement method, first, the support substrate was removed from the produced laminated film by peeling or cutting to obtain a single film of a resin molded body. Next, the sample was cut out according to the size of the holder, and antireflection treatment was performed on both sides of the sample using a black guard spray manufactured by Fine Chemical Japan. Then, the sample and the sample holder were set in the apparatus, and the measurement was performed under the following conditions.

Measuring device: Xenon flash analyzer LFA 447 made by NETZSCH
Software: Nanoflash ver 1.28
Measurement atmosphere: 25 ° C, in the atmosphere Specific gravity: 1.0 kg / m ³
Specific heat capacity: 1.0 kg · K
Measurement mode: SingleLayer and In-Plain
Holder: 10.0sq (SingleLayer) and
In-Plane (In-Plane)
Analysis mode: Cowan + pulse correction (SingleLayer)
Adiabatic + pulse correction (In-Plane)

  The measurement was performed for two shots per sample, and the first shot was excluded because it became unstable, and the measured values for the second shot were respectively analyzed in the above analysis mode. The validity of the analysis was determined by the fitting rate, and when the displayed fitting rate was less than 95%, an error value was set, and only the result with a fitting rate of 95% or more was adopted. The same operation was repeated until five data were adopted, and the average value was defined as the thermal diffusivity. The value measured in the sample holder 10.0 sq and measurement mode SingleLayer is the thermal diffusivity in the thickness direction, and the value measured in the sample holder In-Plane and measurement mode In-Plane is the thermal diffusivity in the in-plane direction. did.

[Measurement of breakdown voltage]
The dielectric breakdown voltage was obtained by measuring the produced resin molded product with a pressure tester TOS 8700 manufactured by Kikusui Electronics. Specifically, first, a 3 cm × 3 cm section was cut out from the resin molded body. Next, φ25 plate electrodes were placed up and down as electrodes, and the slices prepared above were placed between the electrodes. After adjusting the shape so that air did not enter between the electrode and the sample, a voltage was applied to detect leakage current. The voltage setting value was set in 1 kV steps from 1 kV to 10 kV, CUTOFF CURRENT was set to 1 mA, and the voltage one stage before the determination was NG was adopted as the breakdown voltage.

[Calculation of volume filling rate by cross-sectional SEM]
The shape of the inorganic filler contained in the cross section of the resin molded body was measured by observing the cross section using a field emission scanning electron microscope (FE-SEM SU 8020) manufactured by Hitachi High-Technologies Corporation. The shape of the inorganic filler was measured according to the following method. First, a cross section of the resin molded body was photographed by SEM at a magnification of 30,000 times, and the magnification was adjusted so that the thickness of the resin molded body was displayed in 75 to 85% of the short side of the image. Next, the image processing software EasyAccess Ver 6.7.1.23 converts the photographed image into a gray scale, and adjusts the white balance so that the brightest part and the darkest part fall within an 8-bit tone curve. The contrast was adjusted so that the boundaries of the area occupied by can be clearly identified. Subsequently, the surface of the resin molded body (symbol 1 in FIGS. 1 to 3) was rotated so as to be horizontal, and trimming was performed so that only the cross section of the resin molded body was displayed. Next, using the software (image processing software ImageJ / Developer: National Institutes of Health (NIH)), the pixels are binarized on the boundary described above, and each inorganic particle is analyzed by the Analyze Particles (particle analysis) function. A region formed by the filler component A was extracted, and the total occupied area ratio of the corresponding region was calculated therefrom to obtain a volume filling rate.

  The “volume filling rate of the inorganic filler in the entire thickness direction of the resin molded body” under Condition 1 was calculated as the occupied area rate of the inorganic filler in the entire thickness direction of the resin molded body (region of 0% to 100% of thickness).

Next, from the image trimmed so that only the cross section of the resin molded body is displayed as described above, an area of 5% to 15% of the thickness from the surface and an area of 85% to 95% of the thickness from the surface are displayed. Each was extracted by trimming. Similarly Software: using (image processing software ImageJ / developers National Institute of Health (NIH)), it calculates the total occupied area of the inorganic filler, and the _{F A} and _{F B,} respectively.

[Evaluation of adhesion of resin molding]
Using a rubber roll, a PET resin film "Lumirror" (registered trademark) U40 (made by Toray Industries, Inc., 50 μm thick) coated with a 5 cm × 5 cm easy-adhesive paint on the surface on the resin molded body side of the produced laminated film. Crimped. Furthermore, after leaving still for 1 hour on 25 degreeC and the conditions of 40% of humidity, force was inserted from the edge part of a PET resin film, and the ease of peeling at the time of peeling was classified into the following five steps.

5: Difficult to peel off the resin molded body.
4: Requires a strong force for peeling.
3: Feel the adhesion when peeling.
2: Peel immediately when air is introduced from the end.
1: Peel immediately without the need for force.

[Measurement of breaking elongation]
The produced resin molded body was cut out to 3 cm × 1 cm, and while being pinched with a finger, it was slowly stretched in the long side direction. The length until breakage was classified into the following three stages.

It breaks after being stretched by about 10% over 3: 5%.
After 2 to 5% elongation, it breaks.
1: Split immediately without any deformation.

  Since the resin molded body according to the present invention has excellent thermal conductivity, it can be used for imparting similar functions to plastic molded products, home appliances, buildings, vehicle interior products, and the like.

DESCRIPTION OF SYMBOLS 1 Resin molding 2 Support base material 3 Laminated | multilayer film 4 Electrode wire 5 with a circular cross section The support body 6 which holds an electrode 6 Power supply device 7 The support body 8 which holds the electrode A arrange | positioned under the support base material 8 Support base Of the electrode A of the electrode A disposed below the support material 10 for holding the electrode B disposed above the support substrate electrode 10 of the electrode B disposed above the support substrate electrode of the electrode A Angle between the wire and the electrode wire of electrode B

Claims (5)

A resin molding comprising a resin component and at least one inorganic filler component, wherein all of the following conditions 1 to 4 are satisfied.
Condition 1: The volume filling rate of the inorganic filler component in the entire thickness direction of the resin molding is 5% or more and 30% or less.
Condition 2: in the thickness direction of the resin molded body, and the volume filling ratio F _A of the inorganic filler component in the 5% to 15% of the area of the thickness from the surface, from the surface of the inorganic filler component in the 85% to 95% of the area of the thickness volume filling ratio and F _B satisfies equations 1 and 2 below.
_{0.5 ≦ F A / F B ≦} 1.5 ··· ( Equation 1)
_{5% <F A <20%} ··· ( Equation 2)
Condition 3: The resin component of the resin molded body contains the segment of Chemical Formula 1.

Condition 4: The dielectric breakdown voltage of the resin molded body is 4 kV or more. A method for producing a resin molded body, comprising performing step 1 to step 4 in order.
(Step 1) Step of forming a coating layer by applying a coating composition on at least one surface of a supporting substrate to form a laminated film (Step 2) A pair of layers is formed above and below the laminated film including the coating layer. The planes of the laminated film and the plane formed by the electrodes are parallel, and the angle formed by the comb teeth of the electrode B with respect to the direction of the comb teeth of the electrode A is A step of arranging an electric field between 10 and 170 degrees and applying an alternating electric field between the electrode A and the electrode B (step 3) A step of irradiating the coating layer with an active energy ray to obtain a resin molding ( Process 4) The process of peeling the said resin molding from the said support base material   The method for producing a resin molded body according to claim 2, wherein a rate of change in mass per unit area of the coating layer is 3% or less between the step 1 and the step 3. A paint composition for use in the production of a resin molded article, comprising an inorganic filler material, a dispersion medium and a dispersant, wherein the dispersion medium contains a site curable by active energy rays, and has a temperature of 25 ° C. and shear. coating composition and the viscosity _{V a} at rate 0.01s ^-1, the viscosity _{V B} at a temperature 25 ° C. and a shear rate of 1,000 s ^-1 and satisfies the equations 3 and 4.
V _A > 1,000 mPa · s (Formula 3)
V _B <250 mPa · s (Formula 4) The coating composition according to claim 4, comprising a dispersion medium satisfying Formula 5 in an amount of 70% by mass or more of the total amount of the dispersion medium.
D _P / D _M > 4 (Equation 5)
D _M : relative permittivity of dispersion medium, D _P : relative permittivity of inorganic filler