JP2010275404A - Glass cloth-containing white film, metal laminate and substrate for led loading - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass cloth-containing white film which is excellent in dimensional stability, has high heat resistance and high reflectance in a visible light region, substantially avoids lowering of reflectance in a hot thermally loaded environment, can meet the demand for a larger area, and can be used for a printed wiring board for LED mounting, and to provide a metal laminate obtained using the white film and a substrate for LED loading. <P>SOLUTION: The glass cloth-containing white film comprises white films 100 of a resin composition containing a thermoplastic resin and an inorganic filler and glass cloth 400, and has predetermined reflection properties. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a glass cloth-containing white film having excellent heat resistance and dimensional stability and having high reflectance characteristics, a metal laminate using the white film, and an LED mounting substrate. The present invention relates to a glass cloth-containing white film that is capable of mounting a light emitting diode (Light Emitting Diode, LED) or the like, in which a decrease in reflectance is suppressed even under a thermal load environment.

  Since chip-type LEDs that are mounted directly on the printed circuit board pattern and are resin-sealed are advantageous for miniaturization and thinning, they can be used in electronic devices such as numeric keypad lighting for mobile phones and backlights for small liquid crystal displays. Widely used.

In recent years, the improvement in the technology for increasing the brightness of LEDs has been remarkably improved, and the LEDs have become more bright, but along with this, the amount of heat generated by the LED elements themselves has increased, and the thermal load on the periphery of the printed circuit board has increased, The LED element ambient temperature is sometimes over 100 ° C. Moreover, in the manufacturing process of the LED mounting substrate, the thermosetting treatment of the sealing resin and the use of lead (Pb) -free solder have progressed, and in the reflow process, a temperature of about 260 to 300 ° C. may be applied. Exposed to thermal environment. Under such heat load environment, the white printed wiring board made of the thermosetting resin composition that has been used in the past has a tendency to decrease in whiteness such as yellowing and inferior reflection efficiency. There was still room for improvement as a substrate for the generation high-intensity LED mounting. In addition, products equipped with conventional white printed wiring boards have a tendency to deteriorate in whiteness, such as yellowing under light irradiation, particularly under ultraviolet irradiation, and have a tendency to have poor reflectance, and there is still room for improvement. . On the other hand, ceramic substrates are superior in heat resistance, but they are hard and brittle, so there is a limit to reducing the area and thickness due to their hard and brittle nature, making it difficult to handle as a substrate for future general lighting and display applications. There has been a demand for the development of a white printed wiring board having heat resistance that does not change color, does not decrease reflectance, and can cope with a large area under high-temperature heat load and UV irradiation.
Moreover, white LEDs, which are currently mainstream, are composed of blue LEDs (wavelength 470 nm), yellow phosphors, and the like, and have a high reflectance in the visible light region (400 to 800 nm) and in the vicinity of the emission wavelength 470 nm of blue LEDs. It was sought after.

  In order to solve these problems, Patent Document 1 discloses that 100 parts by weight of a thermoplastic resin, 0.001 to 10 parts by weight of a specific silicon compound, and 0.05 to 1.0 μm in average particle diameter are used. A thermoplastic resin composition comprising 0.05 to 25 parts by weight of rutile titanium oxide whose surface is treated with at least one compound selected from acid hydrates is described, and the thermoplastic resin composition (Specifically, a 100 × 100 × 2 mm square plate obtained by injection-molding the thermoplastic resin composition) has a high reflectivity of about 90%, dispersibility, surface appearance, and mechanical properties. There is a description that it is excellent in strength and can be suitably used in a wide range of industrial fields.

  Patent Document 2 discloses a white material having an average particle diameter of 0.05 μm to 5 μm as a reflector used in lighting, a display device or the like that does not require a troublesome process and has a high reflectance. A reflector having a surface roughness of 0.5 to 50 μm comprising a pigment and a resin composition containing an inorganic filler having an average particle diameter of 0.5 μm to 10 mm is described, for example, polyaryl ketone, titanium oxide, In addition, a 3 cm square 1 mm square plate is disclosed in which a resin composition containing glass fiber is injection molded.

  Patent Document 3 discloses that 5 to 100 parts by mass of titanium oxide, 0.5 to 30 parts by mass of magnesium hydroxide, and fibrous fillers and needle-like fillers with respect to 100 parts by mass of a specific polyamide resin. The polyamide resin composition for molding an LED reflector containing 20 to 100 parts by mass of the reinforcing agent is described. Specifically, the polyamide resin composition is injection-molded with a thickness of 1 mm, a width of 40 mm, and a length of 100 mm. A plate is disclosed. The reflector made of the resin composition maintains high whiteness without decreasing the reflectance at a wavelength of 470 nm even under a heat load (2 hours at 170 ° C.).

  Patent Document 4 discloses a prepreg and a copper-clad laminate comprising a resin composition containing a cyanate ester compound, a novolac-type epoxy resin and titanium dioxide, and a base material.

  Patent Document 5 discloses an insulating base material in which a glass fiber woven fabric is embedded in a thermoplastic resin.

Japanese Patent No. 3470730 JP 2007-218980 A JP 2006-257314 A JP 2007-131842 A JP 2008-141008 A

  Although the above Patent Documents 1 to 3 disclose a molded article in which a titanium oxide or the like is added to a thermoplastic resin composition to increase the reflectance, all of the disclosed forms are injection molded. A white film that is only a molded product that has been processed into a film and has improved heat resistance or the like has not been studied. Moreover, although the copper clad laminated board of patent document 4 is suppressing the fall of the reflectance under a heat load (180 degreeC 1 hour) compared with the conventional board | substrate (it falls from 80% to 64%), In the future, the LED will be reduced in brightness, and considering the Pb-free solder reflow process, it cannot be said that the heat resistance in a higher temperature environment is sufficient. Further, Patent Document 5 discloses an insulating base material having improved heat resistance strength by using a glass fiber woven fabric using a high heat resistance thermoplastic resin composition, but it has heat discoloration and reflection characteristics. No white film is disclosed.

  The present inventors have previously found a white film having excellent heat resistance, reduced anisotropy, and high reflection characteristics (Japanese Patent Application No. 2007-309035). However, this white film still has room for improvement in heat resistance and dimensional stability in the Pb-free solder reflow process (260 ° C.).

  Therefore, the problems of the present invention are excellent in dimensional stability, high heat resistance, high reflectivity in the visible light region, and low decrease in reflectivity under a high temperature heat load environment, and can cope with a large area. It is providing the glass cloth containing white film which can be used for the printed wiring board for LED mounting, the metal laminated body which uses this white film, and the board | substrate for LED mounting.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are composed of a resin composition containing a thermoplastic resin and an inorganic filler and a glass cloth, and an average reflectance at a wavelength of 400 to 800 nm is 70%. It was found that the above problem can be solved by a glass cloth-containing white film having a reflectance reduction rate of 10% or less at a wavelength of 470 nm after heat treatment at 200 ° C. for 4 hours. The invention has been completed.

  That is, the first present invention comprises a resin composition containing a thermoplastic resin and an inorganic filler, and a glass cloth, and has an average reflectance of 70% or more at a wavelength of 400 to 800 nm, and at 200 ° C. A glass cloth-containing white film characterized in that the reflectance reduction rate at a wavelength of 470 nm after heat treatment for 4 hours is 10% or less.

  In the first aspect of the present invention, the thermoplastic resin includes a crystalline thermoplastic resin having a crystal melting peak temperature of 260 or higher, an amorphous thermoplastic resin having a glass transition temperature of 260 ° C. or higher, and a liquid crystal transition temperature of 260 ° C. or higher. Any one or more selected from the above liquid crystal polymers is preferable.

  In the first aspect of the present invention, the inorganic filler preferably contains at least titanium oxide.

  In the first invention, the thickness of the film is preferably 3 to 500 μm.

  Furthermore, in the first aspect of the present invention, it is preferable that the rate of decrease in reflectance at a wavelength of 470 nm after heat treatment at 260 ° C. for 5 minutes is 10% or less.

  2nd this invention is a metal laminated body formed by laminating | stacking a metal layer on the at least single side | surface of the glass cloth containing white film of 1st this invention.

  3rd this invention is a board | substrate for LED mounting formed using the metal laminated body of 2nd this invention.

  According to the present invention, a glass cloth-containing white film and a metal laminate having excellent dimensional stability, high reflectance in the visible light region, high heat resistance, and little reduction in reflectance under a high temperature heat load environment are provided. These can be suitably used for a printed wiring board for LED mounting because of their characteristics.

FIG. 1 is a view showing an embodiment of an LED mounting substrate and a manufacturing method thereof according to the present invention. FIG. 2 is a view showing an embodiment of an LED mounting substrate and a manufacturing method thereof according to the present invention. FIG. 3 is a view showing an embodiment of the LED mounting substrate and the manufacturing method thereof according to the present invention.

  Hereinafter, although embodiment of this invention is described, the scope of the present invention is not limited to this embodiment.

<White film containing glass cloth>
The glass cloth-containing white film according to the first aspect of the present invention comprises a resin composition containing a thermoplastic resin and an inorganic filler and a glass cloth, and has an average reflectance of 70% or more at a wavelength of 400 to 800 nm. In addition, the glass cloth-containing white film is excellent in dimensional stability and visible as long as the rate of decrease in reflectance at a wavelength of 470 nm after heat treatment at 200 ° C. for 4 hours is 10% or less. The excellent effect that the reflectance in the light region is high and the decrease in reflectance under a high temperature heat load environment is extremely small can be achieved.

  As described above, the glass cloth-containing white film of the first invention needs to have an average reflectance of 70% or more at a wavelength of 400 to 800 nm, which is higher as the reflectance in the visible light region is higher. This is because the brightness of the LED to be mounted tends to be high, and if it is in the above range, it can be suitably used as a substrate for mounting a white LED. Moreover, since there exists a tendency for a brightness | luminance to become high so that the reflectance of 470 nm vicinity corresponding to the average wavelength (470 nm) of blue LED is high, it is more preferable that the reflectance in 470 nm is 70% or more, and a reflectance is 75%. More preferably.

(Thermoplastic resin)
Examples of the thermoplastic resin include polyether ether ketone (PEEK), polyether ketone (PEK), polyphenylene sulfide (PPS), polyether sulfone (PES), polyphenylene ether (PPE), polyamideimide (PAI), Examples thereof include polyetherimide (PEI), polyphenylsulfone (PPSU), and liquid crystal polymer (LCP), and these may be used alone or in combination. Among these, for reasons of heat resistance, a crystalline thermoplastic resin having a crystal melting peak temperature of 260 ° C. or higher, an amorphous thermoplastic resin having a glass transition temperature of 260 ° C. or higher, and a liquid crystal having a liquid crystal transition temperature of 260 ° C. or higher. It is preferable to use at least one selected from polymers, a crystalline thermoplastic resin having a crystal melting peak temperature (Tm) of 260 ° C. or higher, and an amorphous heat having a glass transition temperature (Tg) of 260 ° C. or higher. It is more preferable to use at least one selected from plastic resins. By using a thermoplastic resin in the above range, it is possible to have heat resistance against Pb-free solder reflow. In addition, it is possible to prevent oxidative deterioration in a high heat environment and suppress a decrease in reflectance. Crystalline thermoplastic resins having a crystal melting peak temperature of 260 ° C. or higher include polyether ether ketone (PEEK: Tg = 145 ° C., Tm = 335 ° C.), polyether ketone (PEK: Tg = 165 ° C., Tm = 355 ° C.). Polyaryl ketones (PAr), polyphenylene sulfide (PPS: Tg = 100 ° C., Tm = 280 ° C.) and the like are preferably used. As the amorphous thermoplastic resin having a glass transition temperature of 260 ° C. or higher, polyamideimide (PAI: Tg = 280 ° C.), polyetherimide (PEI) having a high Tg of 260 ° C. or higher, and the like are preferably used.

  This polyaryl ketone resin is a thermoplastic resin having an aromatic nucleus bond, an ether bond and a ketone bond in its structural unit, and representative examples thereof include polyether ketone, polyether ether ketone, polyether ketone ketone and the like. Of these, polyetheretherketone is preferred. Polyether ether ketone is commercially available as “PEEK151G”, “PEEK381G”, “PEEK450G” (all are trade names of VICTREX), and the like.

  This crystalline thermoplastic resin may be used alone, or a mixed resin composition obtained by mixing a plurality of crystalline thermoplastic resins may be used. Moreover, you may use the mixed resin composition which mixed amorphous thermoplastic resins, such as polyetherimide (PEI), with this crystalline thermoplastic resin. Among them, a resin composition comprising a crystalline polyaryl ketone resin (A) having a crystal melting peak temperature of 260 ° C. or higher and 80 to 20% by weight and an amorphous polyetherimide resin (B) 20 to 80% by weight. More preferably, it is used. By using this resin composition, it becomes possible to ensure extremely good adhesion to a substrate (hereinafter also simply referred to as “substrate”) on which an LED, which will be described later, is mounted. Has heat resistance.

  As a mixing ratio of the polyaryl ketone resin and the amorphous polyetherimide resin, considering the adhesion to the metal layer, the polyaryl ketone resin is contained in an amount of 20% by mass or more and 80% by mass or less, and the balance is amorphous. It is preferable to use a mixed composition composed of a conductive polyetherimide resin and inevitable impurities. More preferably, they are 30 mass% or more and 75 mass% or less, More preferably, they are 40 mass% or more and 70 mass% or less. By setting the upper limit of the content of the polyaryl ketone resin within the above range, it is possible to suppress the increase in crystallinity of the thermoplastic resin constituting the glass cloth-containing white film, and to reduce the adhesion with the substrate. Can be prevented. Moreover, by setting the lower limit of the content of the polyaryl ketone resin within the above range, it is possible to prevent the crystallinity of the thermoplastic resin constituting the glass cloth-containing white film from being lowered, and to prevent a decrease in heat resistance. Furthermore, it becomes easy to contain resin in the glass cloth.

  The polyaryl ketone resin (A) is a thermoplastic resin having an aromatic nucleus bond, an ether bond and a ketone bond in its structural unit. Specific examples thereof include polyether ketone (glass transition temperature [hereinafter referred to as “Tg”]: 157 ° C., crystal melting peak temperature (hereinafter referred to as “Tm”]: 373 ° C.), polyether ether ketone (Tg: 143 C, Tm: 334 ° C.), polyether ether ketone ketone (Tg: 153 ° C., Tm: 370 ° C.), and the like. Among these, from the viewpoint of improving the heat resistance, it exhibits crystallinity and preferably has a Tm of 260 ° C. or higher, particularly 300 to 380 ° C. Moreover, as long as the effect of this invention is not inhibited, you may contain a biphenyl structure, a sulfonyl group, etc., or another repeating unit.

  Among the polyaryl ketone resins (A), a polyaryl ketone resin (A) mainly composed of a polyether ether ketone having a repeating unit represented by the following structural formula (1) is particularly preferably used. Here, the main component means that the content exceeds 50% by mass. Commercially available polyether ether ketones include trade names “PEEK151G” (Tg: 143 ° C., Tm: 334 ° C.), “PEEK381G” (Tg: 143 ° C., Tm: 334 ° C.), “PEEK450G” manufactured by VICTREX. (Tg: 143 ° C., Tm: 334 ° C.) and the like. In addition, polyaryl ketone-type resin (A) can be used individually or in combination of 2 or more types.

  Specific examples of the amorphous polyetherimide resin (B) include an amorphous polyetherimide resin having a repeating unit represented by the following structural formula (2) or (3).

  The amorphous polyetherimide resin having a repeating unit represented by the structural formula (2) or (3) is composed of 4,4 ′-[isopropylidenebis (p-phenyleneoxy)] diphthalic dianhydride and p- As a polycondensate with phenylenediamine or m-phenylenediamine, it can be produced by a known method. Commercially available products of these amorphous polyetherimide resins include “Ultem 1000” (Tg: 216 ° C.), “Ultem 1010” (Tg: 216 ° C.) or “Ultem CRS 5001” (Tg 226) manufactured by General Electric. Among them, an amorphous polyetherimide resin having a repeating unit represented by the structural formula (2) is particularly preferable. In addition, polyetherimide resin (B) can be used individually or in combination of 2 or more types.

(Inorganic filler)
Examples of the inorganic filler include talc, mica, mica, glass flake, boron nitride (BN), calcium carbonate, aluminum hydroxide, silica, titanate (potassium titanate, etc.), barium sulfate, alumina, kaolin, Examples include clay, titanium oxide, zinc oxide, zinc sulfide, lead titanate, zircon oxide, antimony oxide, and magnesium oxide. These may be added singly or in combination of two or more.

  Inorganic fillers are those whose surface is treated with silicone compounds, polyhydric alcohol compounds, amine compounds, fatty acids, fatty acid esters, etc. in order to improve dispersibility in thermoplastic resins. Can be used. Among them, those treated with a silicone compound (silane coupling agent) can be preferably used.

  In consideration of light reflectivity, it is preferable that the thermoplastic resin contains an inorganic filler having a large refractive index difference from the thermoplastic resin. Specifically, calcium carbonate, barium sulfate, zinc oxide, titanium oxide, titanate, or the like having a refractive index of 1.6 or more is preferably used, and titanium oxide is particularly preferably used.

  The titanium oxide has a significantly higher refractive index than other inorganic fillers, and can increase the difference in refractive index from the thermoplastic resin. Therefore, the titanium oxide is less blended than when other fillers are used. Excellent reflectivity can be obtained in an amount. Even if the film is thinned, a glass cloth-containing white film having high reflectivity can be obtained.

  The titanium oxide is preferably a crystalline titanium oxide such as anatase type or rutile type. Among them, a rutile type titanium oxide is preferable from the viewpoint of a large difference in refractive index from the base resin.

  Moreover, although the manufacturing method of a titanium oxide has a chlorine method and a sulfuric acid method, it is preferable to use the titanium oxide manufactured by the chlorine method from the point of whiteness.

  The titanium oxide is preferably one whose surface is coated with an inert inorganic oxide. By coating the surface of titanium oxide with an inert inorganic oxide, the photocatalytic activity of titanium oxide can be suppressed, and deterioration of the film can be prevented. As the inert inorganic oxide, it is preferable to use at least one selected from the group consisting of silica, alumina, and zirconia. When these inert inorganic oxides are used, a decrease in the molecular weight of the thermoplastic resin and yellowing can be suppressed during high temperature melting without impairing high reflectivity.

  In addition, in order to improve dispersibility in the resin composition, titanium oxide has at least one inorganic compound selected from the group consisting of siloxane compounds, silane coupling agents, etc., a polyol, polyethylene glycol, and the like. Those surfaced with at least one organic compound selected from the group are preferred. In particular, those treated with a silane coupling agent are preferable from the viewpoint of heat resistance.

  The particle size of titanium oxide is preferably 0.1 to 1.0 μm, more preferably 0.2 to 0.5 μm. When the particle size of titanium oxide is in the above range, the dispersibility in the resin composition is good, the interface with the resin composition is densely formed, and high reflectivity can be imparted.

  The content of titanium oxide is preferably 15 parts by mass or more, more preferably 25 parts by mass or more, and most preferably 35 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin. By setting it within the above range, good reflection characteristics can be obtained, and good reflection characteristics can be obtained even when the thickness of the film is reduced.

  In order to impart more dimensional stability, an inorganic filler having an average particle size of 15 μm or less and an average aspect ratio (average particle size / average thickness) of 30 or more may be used.

  Examples of the filler 1 having an average particle size of 15 μm or less and an average aspect ratio (average particle size / average thickness) of 30 or more are, for example, synthetic mica, natural mica (mascobite, phlogopite, sericite, szolite, etc.), fired. In addition, inorganic scale-like (plate-like) fillers such as natural or synthetic mica, boehmite, talc, illite, kaolinite, montmorillonite, vermiculite, smectite, and plate-like alumina, and scale-like titanates can be mentioned. According to these inorganic fillers, the ratio of the linear expansion coefficient between the plane direction and the thickness direction of the surface thermoplastic resin layer can be kept low. In consideration of light reflectivity, scaly titanate is more preferable because of its high refractive index. In addition, the said filler can be used individually or in combination of 2 or more types. By using a scaly filler with a high aspect ratio, moisture permeation (moisture absorption) to the film can be suppressed, oxidation deterioration of the thermoplastic resin in a high heat environment can be prevented, and reduction in reflectance can be suppressed. In addition, the rigidity of the film is improved and the film can be used for a thinner substrate.

  The content of the filler is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin composition. preferable. If it is the said range, it is possible to improve the dimensional stability of the obtained glass cloth containing white film.

(Glass cloth)
A well-known thing can be used as said glass cloth, For example, the glass fiber which does not absorb in visible region is used. Among them, it is preferable to use S glass, T glass, NE glass, and quartz glass that are easily available. Moreover, it is possible to improve adhesiveness with a thermoplastic resin by processing the surface of a glass cloth with a silane coupling agent or various surfactants. The thickness, woven density, and woven structure of the glass cloth are selected according to the target glass cloth-containing white film. Further, in order to improve the impregnation property of the thermoplastic resin, it is also possible to physically open the yarn bundle of the glass cloth.

(Reduction rate of reflectivity)
The white film of the present invention requires that the reflectance decrease rate at a wavelength of 470 nm after heat treatment at 200 ° C. for 4 hours is 10% or less, and among others, at a wavelength of 470 nm after heat treatment at 260 ° C. for 5 minutes. It is preferable that the reflectance decrease rate is 10% or less.

  The grounds for the above conditions are described below. When manufacturing an LED mounting substrate, a thermosetting process (100 to 200 ° C., several hours) of a sealing agent such as a conductive adhesive, epoxy, or silicone resin, a soldering process (Pb-free solder reflow, peak temperature 260 ° C., (Several minutes) and wire bonding process, and so on. Further, even in an actual use environment, development of high-brightness LEDs has progressed, the thermal load on the substrate tends to increase, and the LED element ambient temperature may exceed 100 ° C. in some cases. In the future, it will be important to maintain a high reflectance without discoloration even under such a high heat load environment. The wavelength 470 nm is the average wavelength of the blue LED.

  Therefore, if the rate of decrease in reflectance at a wavelength of 470 nm under the above conditions (200 ° C., 4 hours later, 260 ° C., 5 minutes later) is 10% or less, the decrease in reflectance in the manufacturing process is suppressed. In addition, since it is possible to suppress a decrease in reflectance during actual use, it can be suitably used as an LED mounting substrate. More preferably, it is 5% or less, More preferably, it is 3% or less, Especially preferably, it is 2% or less.

(Thickness of glass cloth-containing white film)
The glass cloth-containing white film of the first invention preferably has a thickness of 3 to 500 μm. More preferably, it is 10-300 micrometers, Furthermore, it is 20-100 micrometers. Within such a range, it can be suitably used as a chip LED used as a surface light source for a cellular phone backlight or a liquid crystal display backlight that is required to be thin.

(Additives, etc.)
The resin composition constituting the glass cloth-containing white film of the first invention has various additives other than other resins and inorganic fillers, such as a heat stabilizer and an ultraviolet absorber, to the extent that the properties are not impaired. , Light stabilizers, nucleating agents, colorants, lubricants, flame retardants, and the like may be appropriately blended. Moreover, it does not restrict | limit especially as a preparation method of the resin composition of this invention, A well-known method can be used. For example, (a) a master obtained by mixing various additives in a suitable base resin such as a polyaryl ketone resin and / or an amorphous polyetherimide resin at a high concentration (typically 10 to 60% by weight). A batch is prepared separately, the concentration is adjusted and mixed with the resin to be used, and mechanically blended with a kneader or an extruder. (B) Various additives are directly kneaded with the resin to be used. Or a mechanical blending method using an extruder or the like. Among the above mixing methods, the method of preparing and mixing the master batch (a) is preferable from the viewpoint of dispersibility and workability. Furthermore, the surface of the film may be appropriately subjected to embossing, corona treatment or the like for improving handling properties.

(Method for forming glass cloth-containing white film)
As a manufacturing method of the glass cloth containing white film of 1st this invention, if it is a well-known method, it will not specifically limit, For example, the thermoplastic resin film containing the inorganic filler is extract | collected, Then, A method of sandwiching the glass cloth on both sides with a film and incorporating the glass cloth into the film can be employed. As a method of containing the glass cloth, a vacuum press may be used, or the glass cloth may be contained by being sandwiched continuously using a heated and pressurized metal roll. In addition, as a method for forming a thermoplastic resin film, a known method, for example, an extrusion casting method using a T-die or a calendar method can be adopted, and the film forming property of the sheet is not particularly limited. From the standpoint of stability and productivity, an extrusion casting method using a T die is preferred. The molding temperature in the extrusion casting method using a T-die is appropriately adjusted depending on the flow characteristics and film forming properties of the composition, but is generally about the melting point or higher and 430 ° C. or lower. In addition, when a crystalline resin is used, a crystallization treatment method for imparting heat resistance is not particularly limited. For example, a method of crystallization at the time of extrusion casting (cast crystallization method) or film formation In-line crystallization methods using heat treatment rolls or hot-air ovens (in-line crystallization method) and out-of-film crystallization methods in hot-air ovens or hot presses (outline crystallization methods). it can.

<Metal laminate>
As a metal laminated body which is 2nd this invention, if a metal layer is laminated | stacked on the at least single side | surface of the said glass cloth containing white film, it will not restrict | limit in particular, As a metal layer, copper, gold | metal | money, silver, A metal foil having a thickness of about 5 to 70 μm, such as aluminum, nickel, or tin, can be used. Among these, as the metal foil, a copper foil is usually used, and a metal foil having a surface subjected to chemical conversion treatment such as black oxidation treatment is preferably used. In order to enhance the adhesive effect, it is preferable to use a conductor foil that has been chemically or mechanically roughened on the contact surface (surface to be overlapped) side in advance. Specific examples of the conductor foil that has been subjected to surface roughening treatment include a roughened copper foil that has been electrochemically treated when an electrolytic copper foil is produced.

  As for the method for laminating the metal foil, a known method can be adopted as a heat fusion method without interposing an adhesive layer as long as it is a method by heating and pressurization, and is not particularly limited. For example, a hot pressing method, a hot laminating roll method, or a combination of these methods can be suitably employed.

<LED mounting board>
The LED mounting substrate according to the third aspect of the present invention is not particularly limited as long as it uses the metal laminate, and examples thereof include a double-sided substrate and a composite substrate with an aluminum plate.
When the heat dissipation is required as the brightness of the LED increases, it is possible to improve the heat dissipation by compositing with an aluminum plate. As the structure of the composite substrate with the aluminum plate, the metal laminate made of the glass cloth-containing white film of the present invention is laminated on the entire surface of the aluminum plate, or the cavity (recess) is formed in the metal laminate made of the white film of the present invention. A case where the structural window frame is removed and laminated is mentioned. The aluminum used is preferably roughened in consideration of adhesion to the thermoplastic resin, but when considering the cavity structure, mirror aluminum is used to efficiently reflect the light from the LED. It is preferable to use it. In terms of improving heat dissipation, it is preferable that the thickness of the film is thin.

  The method for producing the LED mounting substrate of the present invention is not particularly limited, and in the case of a double-sided substrate, for example, it can be produced according to the method shown in FIG. As shown in FIG. 1, (a) First, two white films (100), a glass cloth (400) and two copper foils (10) to be a metal layer are prepared, and (b) a white film ( 100), copper foil (10) is laminated on both sides of glass cloth (400) by vacuum pressing to produce a metal laminate, and (c) copper foil (10) is etched or plated on copper to form a wiring pattern ( 20) to form an LED mounting substrate. (D) The LED (200) is mounted on this substrate, and is used by being connected to the wiring pattern (20) by the bonding wire (30) (LED mounting substrate).

  In the case of a double-sided substrate, for example, it can also be manufactured according to the method shown in FIG. As shown in FIG. 2, (a) First, two single-sided copper-clad films in which a copper foil (10) is laminated on a white film (100) on one side and a glass cloth (400) are prepared, and (b) glass A metal laminate is manufactured by laminating a single-sided copper-clad film on both sides of the cloth (400) by vacuum pressing, and (c) a copper foil (10) is etched or plated on copper to form a wiring pattern (20). LED mounting board. (D) The LED (200) is mounted on this substrate, and is used by being connected to the wiring pattern (20) by the bonding wire (30) (LED mounting substrate).

Moreover, in the case of a composite substrate with an aluminum plate (metal radiating part), it can be manufactured, for example, according to the method shown in FIG. As shown in FIG. 3, (a) etching a single-sided copper-clad film in which a copper foil (10) is laminated on a white film (100) on one side to form a wiring pattern (20), and (b) forming a wiring pattern Prepared a single-sided copper-clad film, a glass cloth (400), and a white film (100), and (c) laminated an aluminum plate (300) on the surface opposite to the surface on which the wiring pattern (20) was formed by vacuum pressing. LED mounting board. (D) The LED (200) is mounted on this substrate, and is used by being connected to the wiring pattern (20) by the bonding wire (30) (LED mounting substrate).
[Example]

  Hereinafter, although an Example and a comparative example demonstrate in more detail, this invention is not limited to these.

  In addition, the various measured values and evaluation about the film etc. which are shown in this specification were calculated | required as follows.

[Crystal melting peak temperature (Tm)]
Using a differential scanning calorimeter “DSC-7” (manufactured by Perkin Elmer), the temperature was determined from a thermograph when 10 mg of a sample was heated at a heating rate of 10 ° C./min according to JIS K7121.

[Average reflectance]
An integrating sphere is attached to a spectrophotometer ("U-4000", manufactured by Hitachi, Ltd.), and the reflectance when the reflectance of the alumina white plate is 100% is measured at intervals of 0.5 nm over a wavelength range of 400 nm to 800 nm. did. The average value of the measured values obtained was calculated, and this value was taken as the average reflectance.

[Reflectance after heat treatment]
The hot air circulation oven was heat-treated at 200 ° C. for 4 hours and 260 ° C. for 5 minutes. The reflectance after the heat treatment was measured in the same manner as described above, and the reflectance at 470 nm was read.

[Measurement of linear expansion coefficient]
Using a thermal stress strain measuring device TMA / SS6100 manufactured by Seiko Instruments Inc., a strip-shaped test piece (length: 10 mm) cut out from the film is fixed with a tensile load of 0.1 g, and from 30 ° C. to 5 ° C./min. The temperature dependence was raised to 300 ° C. at a rate of 30 ° C. to 140 ° C. when the thermal expansion amounts of MD (α1 (MD)) and TD (α1 (TD)) were lowered.

[Average particle size]
Using a powder specific surface measuring instrument (transmission method) of model “SS-100” manufactured by Shimadzu Corporation, a sample tube having a cross-sectional area of 2 cm ² and a height of 1 cm was filled with 3 g of sample, and 20 cc with a 500 mm water column. The air permeation time was measured, and the average particle size of titanium oxide was calculated from this.
[Storage modulus measurement]
The obtained sample was cut into a size of 4 mm x 60 mm, and using a viscoelastic spectrometer (made by IT Measurement Co., Ltd .: DVA-200), the vibration frequency was 1 Hz, the strain was 0.1%, the chuck was 2.5 cm, and the temperature was raised. TD was measured in the range from −50 ° C. to 400 ° C. at a rate of 3 ° C./min, and the storage elastic modulus at 260 ° C. was measured.

  Produced by the chlorine method with respect to 100 parts by mass of a resin mixture consisting of 40% by mass of polyetheretherketone resin (PEEK450G, Tm = 335 ° C.) and 60% by mass of amorphous polyetherimide resin (Ultem UF5011S). A resin composition obtained by mixing 67 parts by mass of titanium oxide (average particle size 0.23 μm, alumina treatment, silane coupling agent treatment) was melt-kneaded, and set temperature 380 using an extruder equipped with a T die. A white film having a thickness of 50 μm was prepared at a temperature of 0 ° C. Thereafter, the above film was laminated on both sides of a glass cloth (Asahi Kasei Electronics 3313AW 70 μm thick) with a vacuum press at 350 ° C., 5 MPa for 30 minutes to produce a 130 μm thick glass cloth-containing white film. The evaluation results are shown in Table 1.

  In Example 1, a white film having a thickness of 30 μm was prepared, a glass cloth (1027MS, thickness 19 μm manufactured by Asahi Kasei Electronics) was used, and a white film / glass cloth / white film / glass cloth / white film were sequentially used in a vacuum press. Lamination was performed under the same conditions to produce a glass cloth-containing white film having a thickness of 100 μm. The evaluation results are shown in Table 1.

The thermoplastic resin composition similar to Example 1 is melt-kneaded and extruded, and at the same time, a copper foil (12 μm) is laminated from one side to produce a single-sided copper foil film having a single-sided copper foil of 12 μm and a resin thickness of 50 μm, Then, using the glass cloth similar to Example 1, the single-sided copper foil film was laminated | stacked on the same conditions from the both sides with the vacuum press device, and the double-sided copper foil film was produced. The evaluation results are shown in Table 1. The measurement was performed in the same manner as in Example 1 after etching the entire surface of the double-sided copper foil. The reflectance was measured on the etched surface.
[Comparative Example 1]

In Example 1, a white film having a thickness of 100 μm was produced without containing glass cloth, and then heat treatment was performed in a vacuum press at 260 ° C. for 30 minutes, followed by measurement in the same manner as in Example 1.
[Comparative Example 2]

The copper foil on both sides of a double-sided copper-clad laminate (CCL-HL820WDB, resin thickness 100 μm) manufactured by Mitsubishi Gas Chemical Co., Ltd. was etched on the entire surface, and then measured in the same manner as in Example 1. The evaluation results are shown in Table 1.
[Comparative Example 3]

  The copper foil on both sides of a double-sided copper-clad laminate (CS-3965, resin thickness 100 μm) manufactured by Risho Kogyo Co., Ltd. was etched on the entire surface, and then measured in the same manner as in Example 1. The evaluation results are shown in Table 1.

From the results in Table 1, in Examples 1 to 3, the reflectance, the reflectance after heat treatment, and the dimensional stability are excellent, and the rigidity (storage elastic modulus) at 260 ° C. is high. It was also confirmed that the heat resistance to the mounting process (260 ° C.) was excellent.
On the other hand, in Comparative Example 1, although the reflectance after heat treatment is excellent, the dimensional stability and heat resistance to the mounting process are inferior. In Comparative Examples 2-3, although the initial reflectance is high, the heating is It was confirmed that the decrease in reflectance after the treatment was large.

10 Copper foil 20 Conductor pattern, wiring pattern 30 Bonding wire 100 White film 200 LED
300 Aluminum plate 400 Glass cloth

Claims (7)

  It consists of a resin composition containing a thermoplastic resin and an inorganic filler, and glass cloth. The average reflectance at a wavelength of 400 to 800 nm is 70% or more, and the heat treatment is performed at 200 ° C. for 4 hours at a wavelength of 470 nm. A glass cloth-containing white film having a reflectance reduction rate of 10% or less.   The thermoplastic resin is selected from a crystalline thermoplastic resin having a crystal melting peak temperature of 260 ° C. or higher, an amorphous thermoplastic resin having a glass transition temperature of 260 ° C. or higher, and a liquid crystal polymer having a liquid crystal transition temperature of 260 ° C. or higher. The glass cloth containing white film of Claim 1 which is any 1 type or more.   The glass cloth-containing white film according to claim 1 or 2, wherein the inorganic filler contains at least titanium oxide.   The glass cloth containing white film in any one of Claims 1-3 whose thickness of a film is 3-500 micrometers.   The glass cloth-containing white film according to any one of claims 1 to 4, wherein a reduction rate of reflectance at a wavelength of 470 nm after heat treatment at 260 ° C for 5 minutes is 10% or less.   The metal laminated body formed by laminating | stacking a metal layer on the at least single side | surface of the glass cloth containing white film in any one of Claims 1-5.   The board | substrate for LED mounting formed using the metal laminated body of Claim 6.

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