CN104025726A - Coverlay film, printed wiring board to be equipped with light-emitting element, and light source device - Google Patents
Coverlay film, printed wiring board to be equipped with light-emitting element, and light source device Download PDFInfo
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- CN104025726A CN104025726A CN201380004632.9A CN201380004632A CN104025726A CN 104025726 A CN104025726 A CN 104025726A CN 201380004632 A CN201380004632 A CN 201380004632A CN 104025726 A CN104025726 A CN 104025726A
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- resin bed
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- inorganic filler
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45144—Gold (Au) as principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/20—Details of printed circuits not provided for in H05K2201/01 - H05K2201/10
- H05K2201/2054—Light-reflecting surface, e.g. conductors, substrates, coatings, dielectrics
Abstract
Provided are: a coverlay film which is particularly applicable to a printed wiring board on which an LED is to be mounted; and so on. This coverlay film exhibits a high reflectivity in a visible light region, suffers from little lowering in reflectivity even under an environment with high-temperature heat load and under an environment for testing light resistance, and can accommodate large-area printed wiring boards. A coverlay film which is to be used for the protection of a conductor circuit of a printed wiring board and which is provided with a resin layer that contains both a polyorganosiloxane and an inorganic filler, wherein the average reflectivity of the coverlay film in a wavelength region of 400 to 800nm is 85% or higher and the lowering thereof in the reflectivity at a wavelength of 450nm is 5% or less as determined after the heat treatment at 260 DEG C for 10 minutes.
Description
Technical field
The present invention relates to printed wiring board, particularly in order to protection, be equipped with substrate for mounting light-emitting element and the light supply apparatus that for protection, surface protection film, this surface protection film of lamination form of the conductor circuits such as metal line of the substrate surface of the light-emitting components such as LED.More specifically; relate to and there is high reflectance; even if reduction that still can inhibitory reflex rate in high temperature heat load environment or after experience light fastness test environment, can keep high reflectance, the surface protection film that can also use as interception material (dam materials) etc. when filling is dispersed with the sealing resin of fluorophor.
Background technology
LED be directly installed on the pattern of printed circuit board and be conducive to miniaturization, slimming through the resin-sealed chip-type LED forming, being therefore widely used in the numerical key illumination of mobile phone, the electronic equipments such as backlight of small-scale liquid crystal display.
In recent years, the high brightness technology of LED significantly improves, and LED has realized further high brightness.Accompany therewith, the caloric value of LED element itself increases, and cause sometimes LED component periphery temperature to surpass 100 ℃ etc., and this heat load that can cause the component parts such as printed circuit board increases.In addition, with regard to the manufacturing process of LED mounted board, in the hot curing of sealing resin, process, utilize in reflow process after the joint that unleaded (Pb) scolder carries out etc., heating-up temperature can reach 260～300 ℃ of left and right etc., makes LED component periphery not only in it uses but also also will be exposed under high thermal environment in manufacturing process.
For the white light-cured resin substrate that used all the time, such as for the coated white printed circuit board that forms compositions of thermosetting resin that thermosetting solder resist forms etc., confirmed in the environment that is subject to heat load as above and had the tendency that the whiteness such as solder resist, printed wiring board generation xanthochromia decline, reflection efficiency declines.Therefore,, in the exploitation of high-brightness LED board for mounting electronic of new generation from now on, need to be improved the decline of such reflection efficiency.
In addition, for coated, form for the goods that are equipped with white printed wiring board that white solder mask forms, in the environment of irradiation ultraviolet radiation, also confirmed with above-mentioned heat load environment in the same tendency that the whiteness such as xanthochromia decline, reflectivity declines.
On the other hand, for the substrate of being made by pottery, although it is excellent aspect thermal endurance, owing to thering is hard and crisp character, therefore seeking there is restriction aspect large area and slimming.Therefore the substrate that, should be made by pottery may be difficult in conduct from now on for the substrate of general lighting purposes, display applications.Based on this, as can not there is variable color and reflectivity under high temperature heat load yet, do not decline, can tackle large area and there is stable on heating substrate, the printed circuit board that requires exploitation stack surface diaphragm to form.
In addition, LED chip is being installed in the operation of printed circuit board, is carrying out filling to its mounting portion the operation of the sealing resin (organic siliconresin, epoxy resin etc.) that is dispersed with fluorophor.Now, for sealing resin is not spilt to peripheral part, comprise the formation of the interception material of heat reactive resin (for example organic siliconresin, epoxy resin).
When forming such interception parts, conventionally utilize the formation interception materials such as distributor and make its hot curing.But, when making resin hot curing, may cause wiring portion polluted and wire-bonded is brought to impact, or it is hot deteriorated to cause that white solder mask, printed circuit board material occur, this has become the problem while forming interception material.Therefore in addition,, due to needs manufacturing cost, require exploitation send as an envoy to protective cover of conductor and the interception integrated surface protection film of material of metal line etc. and the printed wiring board that the such surface protection film of lamination forms.
For above-mentioned problem; even if proposed a kind of by the surface protection film also can inhibitory reflex rate in high temperature heat load environment or in light fastness test environment declining that uses that following resin combination for example obtains in prior art; in described resin combination; with respect to by crystal melting peak temperature being resin combination 100 mass parts that 260 ℃ of above poly aryl ketone resins and amorphism polyetherimide resin form; contain inorganic filler 5～100 mass parts (for example,, referring to patent documentation 1).
In this patent documentation 1, a kind of surface protection film is disclosed; it utilizes thermoplastic resin composition's crystallinity; when the low temperature being heated to below 260 ℃, demonstrate and be suitable for the characteristic of printed wiring board surface binded, can occur within a short period of time bondingly, and demonstrate 260 ℃ of heat resisting temperatures after hot melt is sticky.
Prior art document
Patent documentation
Patent documentation 1: No. 2009-302110, TOHKEMY
Summary of the invention
The problem that invention will solve
The initial stage reflectivity of the film of recording in above-mentioned patent documentation 1 and fast light discolouration are not enough.And, for its also can as interception material etc. such can extensive use technology both unexposed also without implying.
The substrate for mounting light-emitting element and the light supply apparatus that the object of the present invention is to provide this surface protection film of a kind of surface protection film and lamination to form; described surface protection film has high reflectance, high-fire resistance in visible region; the reduction of the reflectivity in high temperature heat load environment or in fast light environment is few; and can tackle large area, particularly can be used in LED installation printed circuit board.
The method of dealing with problems
In order further to improve the problem of above-mentioned reflectivity, the inventor etc. conduct in-depth research, found that, by using polysiloxane as thermosetting resin, and utilize gamma-rays isoradial that the resin combination that contains this resin and inorganic filler is solidified, can improve in visible region, be specially the average reflectance under wavelength 400～800nm, and can to improve in ultra-violet (UV) band be the reflectivity under wavelength 350～400nm, moreover, even reduction that also can inhibitory reflex rate in high temperature heat load environment or in fast light environment.Also find in addition, used the conductor circuit protection of the printed wiring board of this resin combination can solve above-mentioned problem with surface protection film, thereby completed the present invention.
; the 1st invention of the present invention relates to a kind of conductor circuit protection surface protection film of printed wiring board; it possesses resin bed; this resin bed contains polysiloxane and inorganic filler; wherein; the average reflectance of this surface protection film under wavelength 400～800nm is more than 85%, and, in 260 ℃ carry out heat treatment in 10 minutes after the rate of descent of reflectivity under wavelength 450nm be below 5%.
In addition, in the 1st invention, the rate of descent of preferred above-mentioned surface protection film reflectivity under wavelength 450nm after light fastness test as follows is below 5%.
(light fastness test): use xenon arc weatherometer at temperature 63 ℃ of (blackboard temperature), humidity 50%, irradiance (295～400nm) 60W/m
2lower irradiation 50 hours.
In addition, in the 1st invention, preferred above-mentioned resin bed is the layer forming through radiation curing.
In addition, in the 1st invention, preferably inorganic filler is titanium oxide.
In addition, in the 1st invention, the thickness of preferred surface diaphragm is 30～500 μ m.
In addition, in the 1st invention, the average reflectance of preferred above-mentioned surface protection film under wavelength 350～400nm is more than 40%.
In addition; in the 1st invention; preferred above-mentioned surface protection film possesses above-mentioned resin bed (A) and resin bed (B), and this resin bed (B) contains polysiloxane and the inorganic filler different from inorganic filler contained in resin bed (A).
Now, in preferred above-mentioned resin bed (B), contained inorganic filler is aluminium oxide.
The 2nd invention of the present invention relates to a kind of substrate for mounting light-emitting element; it possesses and has for carrying to form on the substrate of more than at least 1 light-emitting component the structure that the protective layer of resin bed (A) forms; described resin bed (A) contains polysiloxane and inorganic filler; the average reflectance of this protective layer under wavelength 400～800nm is more than 85%; and, in 260 ℃ carry out heat treatment in 10 minutes after the rate of descent of reflectivity under wavelength 450nm be below 5%.
In addition; the 3rd invention of the present invention relates to a kind of light supply apparatus; it possesses following structure: on substrate, form conductor circuit and at this conductor circuit superimposed layer protective layer; and; element mounted on aforesaid substrate and make above-mentioned conductor circuit and above-mentioned light-emitting component conducting; this light-emitting component is carried out resin-sealed, wherein
Above-mentioned protective layer is the layer that possesses resin bed (A); this resin bed (A) contains polysiloxane and inorganic filler; the average reflectance of this protective layer under wavelength 400～800nm is more than 85%; and, in 260 ℃ carry out heat treatment in 10 minutes after the rate of descent of reflectivity under wavelength 450nm be below 5%.
The effect of invention
Surface protection film of the present invention not only in visible region, in ultra-violet (UV) band, also there is high reflectance, high-fire resistance, and can obtain the few effect of reduction of the reflectivity in high temperature heat load environment, in light fastness test environment.Thus, surface protection film of the present invention is useful as the conductor circuit protection of printed circuit board with surface protection film.In addition, the surface protection film of the application of the invention, can manufacture the substrate for mounting light-emitting element and the light supply apparatus that are formed with conductor circuit protective layer.
Accompanying drawing explanation
[Fig. 1] is the figure that an example of substrate for mounting light-emitting element of the present invention execution mode is illustrated.
[Fig. 2] is the figure that an example of substrate for mounting light-emitting element of the present invention execution mode is illustrated.
Symbol description
10 Copper Foils
20 wiring patterns
30 resin beds that contain polysiloxane and inorganic filler
40 bonding wires
100 substrates of being made by thermoplastic resin or thermosetting resin
200 protective layers
300?LED
400 aluminium sheets
Embodiment
Below, for embodiments of the present invention, describe.But scope of the present invention is not limited to this execution mode.
This surface protection film of < >
The surface protection film of the 1st execution mode of the present invention (being called " this surface protection film ") possesses the resin bed (A) that contains polysiloxane and inorganic filler; and the average reflectance of this surface protection film under wavelength 400～800nm is more than 85%; and, in 260 ℃ carry out heat treatment in 10 minutes after the rate of descent of reflectivity under wavelength 450nm be below 5%.
(reflectivity)
As mentioned above, it is more than 85% being necessary to make the average reflectance of this surface protection film under wavelength 400～800nm.Its reason is, has the higher higher tendency of brightness that is equipped on the LED of substrate of reflectivity of visible region, in the time of in above-mentioned scope, can be suitable for the surface protection film as LED board for mounting electronic.Viewpoint based on such, this average reflectance is preferably more than 90%, is particularly preferably more than 95%.
In addition, owing to there being near the higher tendency of the higher brightness of reflectivity of the 450nm corresponding with the mean wavelength (450nm) of blue led, therefore more preferably the reflectivity under 450nm is more than 85%, wherein more preferably more than 90%, be particularly preferably more than 95%.
In addition, obtain in the situation of the white light that has used the blue led that is at present main flow, near reflectivity 450nm becomes important.Therefore,, in order to obtain the more white light of high-color rendering, developed ultraviolet (near ultraviolet) LED and type red, green, blue emitting phophor combination.In this case, corresponding with the emission wavelength of ultraviolet (near ultraviolet) LED, need to make surface protection film also reflect the light of 350～400nm wavelength and the light of visible region (400～800nm) wavelength the two.
Therefore, preferably this surface protection film at the average reflectance of 350～400nm, be more than 40%, wherein more preferably more than 60%, be particularly preferably more than 80%.
It should be noted that, as the reflectivity under the reflectivity under the average reflectance under wavelength 400～800nm, 450nm and ultraviolet (near ultraviolet) district (350～400nm) wavelength being increased to the method for given range, can enumerate and make to contain inorganic filler in polysiloxane and form resin bed (A), obtain thus extremely excellent reflection characteristic, the contamination of used inorganic filler is carried out to the method for suitably adjusting simultaneously.Wherein, when the average reflectance under wish raising wavelength 400～800nm, the reflectivity under 450nm, from the viewpoint of the refringence between increase and polysiloxane, consider, preferably selective oxidation titanium is as inorganic filler.On the other hand, when wish improves the reflectivity under ultraviolet (near ultraviolet) district (350～400nm) wavelength, preferably selective oxidation aluminium is as inorganic filler.
In addition, in order to improve the reflectivity of ultraviolet (near ultraviolet) district (350～400nm) and these two range of wavelength of visible region (400～800nm), also can in polysiloxane, coordinate respectively to give the preferable additives of the reflectivity under each wavelength, and make the laminated resin stratification that formed by each resin combination.
It should be noted that, be not limited to these methods.
(rate of descent of heat treatment back reflection rate)
Be necessary to make this surface protection film in 260 ℃ carry out heat treatment in 10 minutes after the rate of descent of reflectivity under wavelength 450nm be below 5% of reflectivity before this heat treatment.
Foundation for above-mentioned condition, is described below.
While manufacturing LED mounted board, the hot curing operation (100～200 ℃, a few hours), scolder welding sequence (lead-free solder Reflow Soldering, peak temperature 260 ℃, several minutes), wire-bonded operation etc. that need to experience the sealants such as electrically conducting adhesive or epoxy resin, organic siliconresin apply the operation of high heat load.And, the tendency that the heat load that also exists development because of exploitation high-brightness LED to cause putting on substrate in the environment for use of light-emitting device that is equipped with LED increases, LED component periphery temperature is sometimes over 100 ℃.Therefore, in such high heat load environment, also can keep high reflectance and variable color can not occur in future, can become more and more important.
In addition, the mean wavelength that wavelength 450nm is blue led.
Therefore, if in 260 ℃ carry out heat treatment in 10 minutes after the rate of descent of reflectivity under wavelength 450nm be below 5% of reflectivity before this heat treatment, can be suppressed at the reduction of reflectivity in manufacturing process, and the decline of reflectivity in the time of can suppressing actual use, therefore applicable to LED mounted board.
Viewpoint based on such, this rate of descent is preferably below 4% in above-mentioned scope, particularly, more preferably, below 3%, is wherein especially preferably below 2%.
(rate of descent of light fastness test back reflection rate)
In addition, preferably the rate of descent of the reflectivity of this surface protection film after light fastness test is subsequently below 5% of reflectivity before light fastness test.
(light fastness test); Use xenon arc weatherometer at temperature 63 ℃ of (blackboard temperature), humidity 50%, irradiance (295～400nm) 60W/m
2lower irradiation 50 hours.
Foundation for above-mentioned condition, is described below.
As mentioned above, the tendency that the heat load that also exists development because of exploitation high-brightness LED to cause putting on substrate in the environment for use of light-emitting device that is equipped with LED increases.Therefore, in such light resistance that also high reflectance can be kept in being subject to environment that high output illumination penetrates and variable color can not occur, in future, can become more and more important.
Therefore,, if the rate of descent of above-mentioned light fastness test back reflection rate is below 5% of reflectivity before light fastness test, the decline of reflectivity in the time of can being suppressed at actual use, therefore applicable to LED mounted board.
Viewpoint based on such, this rate of descent is preferably below 4% in above-mentioned scope, particularly, more preferably, below 3%, is wherein especially preferably below 2%.
It should be noted that; for this surface protection film; in order to make the rate of descent of reflectivity rate of descent after its heat treatment and light fastness test back reflection rate in desired scope, preferably when forming resin bed (A), utilize as described later radioactive ray, particularly gamma-rays that the resin combination that contains polysiloxane and inorganic filler is solidified.But not and be defined in the method.
[resin bed (A)]
This surface protection film possesses the resin bed (A) that contains polysiloxane and inorganic filler.
As the polysiloxane for this surface protection film, specifically refer to the material that for example there is the siloxane backbone shown in formula (1) and cross-linking reaction can not occur.As polysiloxane, there is no particular restriction, suitably select and determine known any polysiloxane in the past.
[Chemical formula 1]
(n is more than 2 integer)
Wherein, in formula (1), " R " represents the halogen substituted hydrocarbon radicals such as the alkyl such as alkyl, vinyl, phenyl such as methyl, ethyl or fluoro-alkyl etc.
Specifically can enumerate: " R " in formula (1) is all that the dimethyl silicone polymer of methyl is, the various polysiloxane that the part methyl of dimethyl silicone polymer is formed by one or more replacements in above-mentioned alkyl or above-mentioned halogen substituted hydrocarbon radical.
As the polysiloxane for this surface protection film, can be used alone or as a mixture two or more in above-mentioned dimethyl silicone polymer, various poly-alkylsiloxane.
While forming resin bed (A), make polysiloxane resin solidification.
As the curing of polysiloxane, can known any means, suitably select and determine in the past from add-on type, condensed type, peroxide curing type etc.
As condensed type, can enumerate dealcoholysis, desacetoxy, de-oxime, dehydrogenation type.Wherein, preferably use while solidifying and can not produce the polysiloxane of the add-on type of accessory substance.
As making the curing method of polysiloxane, can enumerate and add the method for curing catalysts, the method for carrying out high-temperature heating, the method for adding crosslinking agent and the cross-linking method based on radiation exposure etc.
As curing catalysts, for example can enumerate: the catalyst of amino silane class, nickel salt class, ammonium salt class.In addition, also can enumerate the metal soaps such as the caprylates such as Al, Fe, Co, Mn, Zn, naphthenate, platinum catalyst etc.
Carry out in the situation of high-temperature heating, as its condition, conventionally by the heating of carrying out about 30 minutes～2 hours at 150 ℃～250 ℃, be cured.It should be noted that, during heating, also can add above-mentioned catalyst.By adding this catalyst, can make heating-up temperature reduce.Particularly, can make heating-up temperature reach for example 100 ℃～180 ℃.In addition, also can make to shorten to heating time about for example 10 minutes～30 minutes, therefore preferably.
Wherein, for solidifying of the resin bed that comprises polysiloxane (A) for this surface protection film, can utilize radioactive ray to carry out.
Utilizing curing (being cross-linked of polysiloxane) that radioactive ray carry out is polysiloxane not to be applied to hot method, there is not residue by cross-linked material etc. and cause the impaired worry of heat-resisting, fast light reliability, can significantly obtain effect of the present invention, therefore preferably.
For this surface protection film, as the curing radioactive ray for polysiloxane, can enumerate such as electron beam, X ray, gamma-rays etc.These radioactive ray are widely used in industry, can easily be used, and are the good methods of energy efficiency.In these radioactive ray, preferably utilize and substantially do not have absorption loss, gamma-rays that permeability is high.
For this surface protection film, by the polysiloxane of non cross-linked state is irradiated to for example gamma-rays, cause cross-linking reaction, thereby polysiloxane is solidified.Owing to can cross-linking reaction being carried out by irradiating gamma-ray, even if therefore do not use crosslinking agent also can cause cross-linking reaction.
Thus, can avoid viewed by crosslinking agent variable color therefore when using crosslinking agent to be cross-linked, and can prevent the residual of the accessory substance that caused by the reaction of crosslinking agent, thereby can obtain the resin bed that thermal endurance, light resistance are more excellent (A).
As gamma-ray radiation dose, can be according to the amount of resin kind, crosslinking group and radiogenic kind and suitably select and determine, be generally 10～150kGy.Wherein be preferably 20～100kGy, be particularly preferably 30～60kGy.
In addition, this radiation dose preferably in the situation that except considering the crosslink density of polysiloxane, also consider thermoplastic resin, the radiation resistance of the plastic film that uses as operation film selects to determine.In this regard, normally excellent to the patience of radioactive ray, the basis material that is suitable for operation film of the present invention of crystallinity polyester resin.
[for the inorganic filler of resin bed (A)]
Inorganic filler as for above-mentioned resin bed (A), is not particularly limited, and can use known any inorganic filler in the past.For example, can enumerate: talcum, mica, mica, sheet glass, boron nitride (BN), aluminium nitride, calcium carbonate, aluminium hydroxide, silicon dioxide, titanate (potassium titanate etc.), barium sulfate, aluminium oxide, kaolin, clay, titanium oxide, zinc oxide, zinc sulphide, lead titanates, zirconia, antimony oxide, magnesium oxide etc.These inorganic fillers can add separately a kind, also can combine and add two or more.
In order further to improve the dispersiveness in comprising the resin bed of polysiloxane (A), for the inorganic filler of above-mentioned resin bed (A), can use and utilize organosilicon compound, multicomponent alcoholics compound, aminated compounds, aliphatic acid, fatty acid ester etc. to carry out surface-treated filler to the surface of inorganic filler.Wherein, preferably utilize organosilicon compound (siloxanes, silane coupler etc.) to carry out the inorganic filler of processing.
As the inorganic filler for above-mentioned resin bed (A), in the situation that consider the light reflective of this surface protection film, preferably use the material large with the specific refractivity of polysiloxane.Wherein, preferred index is more than 1.6 inorganic filler, specifically can enumerate such as the calcium carbonate in above-mentioned, barium sulfate, zinc oxide, titanium oxide, titanate etc., especially preferential oxidation titanium.
In addition, from improving the viewpoint of the reflectivity of low wavelength zone, consider preferential oxidation aluminium.
The refractive index of titanium oxide is apparently higher than other inorganic filler, can strengthen and as the refringence between the polysiloxane of base resin, therefore, compare with using the situation of other filler, can obtain with less use level excellent reflectivity, therefore preferably.
In above-mentioned resin bed (A), as the titanium oxide being matched with in polysiloxane, preferably such as the titanium oxide of the such crystal type of Detitanium-ore-type, rutile-type, wherein, from the viewpoint that the refringence with polysiloxane is large, consider, preferably the titanium oxide of rutile-type.
In addition; for be applicable to use using ultraviolet (near ultraviolet) LED with the element of the type of red, green, blue emitting phophor combination for the situation of the surface protection film of the substrate of semiconductor light-emitting elements; need to make surface protection film also reflect the light of the 350～400nm wavelength corresponding with the emission wavelength of ultraviolet (near ultraviolet) LED and the light of reflect visible light district (400～800nm) wavelength; the titanium oxide of the Detitanium-ore-type that therefore, preferably the light absorption in 400nm region is few.
The manufacture method of titanium oxide generally includes chlorine method and sulfuric acid process, and as the manufacture method for titanium oxide of the present invention, from the viewpoint of whiteness, preferably uses the titanium oxide that utilizes chlorine method to manufacture.
Titanium oxide is preferably the titanium oxide that coated processing has been carried out through nonactive inorganic oxide in surface.By titania surface being coated to processing with nonactive inorganic oxide, can suppressing the photocatalytic activity of titanium oxide, thereby can suppress the deteriorated of surface protection film of the present invention, therefore preferably.
As nonactive inorganic oxide, concrete preferably use is for example selected from least a kind in silicon dioxide, aluminium oxide and zirconia.By using these nonactive inorganic oxides, in the time of can suppressing high-temperature fusion in the situation that not destroying highly reflective, there is molecular resin amount and reduce and xanthochromia, therefore preferably.
In addition, for titanium oxide, in order to improve its dispersiveness in resin combination, preferably utilize at least a kind of organic compound that is selected from least a kind of inorganic compound in silicone compounds, silane coupler etc. or is selected from polyalcohol, polyethylene glycol etc. to carry out surface treatment to its surface.Particularly, from the viewpoint of thermal endurance, preferably utilize silane coupler to process, from the viewpoint of dispersed, preferably utilize silicone compounds to process.
Particle diameter for the inorganic filler of above-mentioned resin bed (A) can be arbitrary size, according to the purposes of surface protection film of the present invention, thickness, suitably selects to determine.Conventionally use the inorganic filler with the particle diameter below surface protection film thickness, particularly, for example, as average grain diameter, be preferably 0.05～50 μ m, wherein more preferably 0.1～30 μ m, be particularly preferably 0.15～15 μ m.
When the particle diameter of inorganic filler is 0.05 μ m～50 μ m, its favorable dispersibility in resin, and between resin, form fine and close interface, can give highly reflective, therefore preferably.
Wherein, use in the situation of titanium oxide as the inorganic filler for above-mentioned resin bed (A), its particle diameter is preferably 0.1 μ m～1.0 μ m, 0.2 μ m～0.5 μ m more preferably wherein.The particle diameter of titanium oxide is in above-mentioned scope time, its favorable dispersibility in resin, and between resin, form fine and close interface, can give highly reflective, therefore preferably.
For the content of the inorganic filler of above-mentioned resin bed (A) with respect to polysiloxane 100 mass parts be preferably 10～1000 mass parts, wherein more preferably 20～500 mass parts, more preferably 25～200 mass parts, be particularly preferably 30～100 mass parts.The content of inorganic filler by being used in resin bed (A), within the scope of this, can obtain good reflection characteristic, even and also can obtain good reflection characteristic when the thin thickness of film, therefore preferably.
[resin bed (B)]
Except above-mentioned resin bed (A), this surface protection film can also possess resin bed (B), and described resin bed (B) contains polysiloxane and the different inorganic filler of inorganic filler from contained in resin bed (A).
For example, can make resin bed (A) for (400～800nm) has the floor of high reflectance, makes resin bed (B) be to have in ultraviolet (near ultraviolet) district (350～400nm) floor etc. of high reflectance in visible region, and (B) combine thering is the not resin bed of same-action (A).
The polysiloxane of above-mentioned resin bed (B) and above-mentioned resin bed (A) are same, are not particularly limited, and suitably select and determine known any polysiloxane in the past.In addition, the curing of polysiloxane also can adopt the method same with above-mentioned resin bed (A).
[for the inorganic filler of resin bed (B)]
As the inorganic filler for above-mentioned resin bed (B), so long as the inorganic filler different from inorganic filler contained in above-mentioned resin bed (A) there is no particular restriction.Can enumerate such as talcum, mica, mica, sheet glass, boron nitride (BN), aluminium nitride, calcium carbonate, aluminium hydroxide, silicon dioxide, titanate (potassium titanate etc.), barium sulfate, aluminium oxide, kaolin, clay, titanium oxide, zinc oxide, zinc sulphide, lead titanates, zirconia, antimony oxide, magnesium oxide etc.These inorganic fillers can add separately a kind, also can combine and add two or more.
For example, in the situation that for the inorganic filler of resin bed (A) be titanium oxide, in particular for Titanium Dioxide Rutile Top grade, because it produces light absorption in ultraviolet (near ultraviolet) district (350～400nm), therefore, as the inorganic filler for resin bed (B), be preferably chosen in few anatase-type titanium oxide or the aluminium oxide of light absorption in 400nm region.
In addition; by above-mentioned resin bed (A) surface protection film (B) that comprises when " this substrate for mounting light-emitting element " described later; preferably with metal level lamination, and make to have used anatase-type titanium oxide that light absorption in 400nm region is few or aluminium oxide as the resin bed (B) of inorganic filler as use face (as exposed side).Thus, the light in ultraviolet (near ultraviolet) district (350～400nm) is reflected by resin bed (B), the light of visible region (400～800nm), by resin bed (B) and the two reflection of the resin bed (A) that comprises Titanium Dioxide Rutile Top grade, therefore can improve reflectivity in wide wave-length coverage.
Particle diameter for the inorganic filler of above-mentioned resin bed (B) can be arbitrary size, according to the purposes of surface protection film of the present invention, thickness, suitably selects to determine.Conventionally use the inorganic filler with the particle diameter below surface protection film thickness, for example, as average grain diameter, be preferably 0.05～50 μ m, wherein more preferably 0.1 μ m is above or 30 μ m are following, it is above or below 15 μ m to be wherein especially preferably 0.15 μ m.
When the particle diameter of inorganic filler is 0.05 μ m～50 μ m, its favorable dispersibility in resin, and between resin, form fine and close interface, can give highly reflective, therefore preferably.
For the content of the inorganic filler of resin bed (B) with respect to polysiloxane 100 mass parts be preferably 10～1000 mass parts, wherein more preferably 20 mass parts are above or 500 mass parts are following, wherein more preferably 30 mass parts are above or 300 mass parts are following, it is above or below 200 mass parts to be wherein particularly preferably 50 mass parts.The content of inorganic filler by being used in resin bed (B), within the scope of this, can obtain good reflection characteristic, even and also can obtain good reflection characteristic when the thin thickness of film, therefore preferably.
(additive etc.)
Above-mentioned resin bed (A) and resin bed (B) can contain other resin, inorganic filler various additives in addition in the scope of not destroying its character.For example, can suitably coordinate heat stabilizer, ultra-violet absorber, light stabilizer, nucleator, colouring agent, lubricant, fire retardant etc.
(thickness of surface protection film)
The thickness of this surface protection film is not particularly limited, and suitably selects to determine.Be generally 1 μ m～1000 μ m, with regard to this surface protection film, be preferably 10 μ m～1000 μ m.Wherein, more preferably 10 μ m～800 μ m, more preferably 20 μ m～500 μ m, be especially preferably 20 μ m～300 μ m, be particularly preferably 30 μ m～200 μ m.
In addition; want in the scope of high reflectance, to seek effect of the present invention, be that the rate of descent of reflectivity is less during such effect; the thickness that preferably makes this surface protection film be 50 μ m above, be particularly preferably 100 μ m, its upper limit is generally 1000 μ m, is wherein preferably 500 μ m.
Therefore in the time of in above-mentioned scope, owing to can guaranteeing reflectivity, can be suitable for use as the conductor circuit protection surface protection film that requires slim backlight mobile phone for, liquid crystal display with the chip LED mounted board of the area source use of backlight.In addition, when as interception materials'use, for sealing LED chip, metal wire, be also sufficient thickness.
(manufacture method of surface protection film)
As in order to forming the resin combination of above-mentioned resin bed (A) and resin bed (B), form the preparation method of the resin combination of the resin bed contain polysiloxane, be not particularly limited, can adopt known method.Can enumerate such as: (a) in advance various additives be take to high concentration (typical content be 10～90 % by weight) and are mixed in the suitable base resin such as polysiloxane and make in addition masterbatch, and this masterbatch is mixed in after concentration adjustment to used resin, utilize kneader, extruder etc. to carry out the method for mechanical blending.In addition, also can enumerate: (b) directly various additives are mixed in used resin, and utilize kneader, extruder etc. to carry out method of mechanical blending etc.
In these methods, from the viewpoint of dispersiveness and operability, the method for preferably mixing after the making masterbatch of (a).
Then, as by the method for above-mentioned resin combination masking, can enumerate known film-forming method, for example, can enumerate and use the resin combination that polysiloxane and inorganic filler are obtained by mixing, by using extruding casting method, rolling process or being coated on the method that method on matrix material film (PET film etc.) etc. is carried out film forming of T-shaped mould.
For the film of such formation, utilize hot curing, radiation curing etc. that the polysiloxane of non cross-linked state is solidified.
(purposes of surface protection film)
This surface protection film can be used as the conductor circuit protection of printed circuit board and uses with surface protection film.For example, can be to form conductor circuit and at above-mentioned this surface protection film of conductor circuit superimposed layer on substrate, on the other hand, element mounted on aforesaid substrate and the mode of above-mentioned conductor circuit and this light-emitting component conducting is used.Now; by this surface protection film of lamination, can prevent that conductor circuit from sustaining damage and causing broken string, and the short circuit that causes of the solder attachment can prevent by installing light emitting element time; in addition, can give play to and prevent the function that occurs to get an electric shock while touching power supply terminal portion etc. waiting with finger.
This substrate for mounting light-emitting element of < >
The substrate for mounting light-emitting element of the 2nd execution mode of the present invention (being called " this substrate for mounting light-emitting element ") is to possess protective layer for carrying on the substrate of more than at least 1 light-emitting component; this protective layer has the resin bed (A) that comprises polysiloxane and inorganic filler; the average reflectance of this protective layer under wavelength 400～800nm is more than 85%; and, in 260 ℃ carry out heat treatment in 10 minutes after the rate of descent of reflectivity under wavelength 450nm be below 5%.
With regard to this substrate for mounting light-emitting element, as long as meet above-mentioned condition, shape, the material for substrate etc. is not particularly limited, and can use known any substrate in the past.Particularly, for example, as " for the substrate of element mounted ", at at least one resin/metal laminate that lamination metal layer forms of the resin baseplate material of being made by thermosetting resin, thermoplastic resin, or at least one side having at above-mentioned resin baseplate material forms the structure that wiring pattern (conductor circuit) forms.
When such " for the substrate of element mounted " upper formation possesses protective layer above-mentioned specific physical property, that have the resin bed that comprises polysiloxane and inorganic filler; while being above-mentioned this surface protection film of lamination, can realize the protection to conductor circuit.And this protective layer, owing to having high reflectance, therefore can play following excellent effect: can give play to the function as reflecting plate, also contribute to the raising of this substrate reflectivity.
(metal level)
As the metal level can be used in the resin/metal laminate of this substrate for mounting light-emitting element, can enumerate such as the copper as metal species, gold, silver, aluminium, nickel, tin etc.In addition, the thickness of metal level can be any thickness, suitably selects to determine, is generally 1 μ m～100 μ m, is wherein preferably 5 μ m～70 μ m.
Wherein, as metal species, preferably copper, copper alloy, further preferred surface has been passed through the material that the chemical conversions such as black oxidation processing are processed.For the conductor foil as this metal level, preferably use and in order to improve adhesive effect, in advance the face contacting with surface protection film (superposed surfaces) side has been implemented the conductor foil of the roughening of chemical mode or mechanical system.As the concrete example that has passed through the conductor foil that surface roughening processes, specifically can enumerate such as the roughening Copper Foil etc. that has passed through the processing of electrochemical means when manufacturing electrolytic copper foil.
In addition, also can resin/metal laminate lamination of the substrate as for this substrate for mounting light-emitting element is a plurality of.This laminating method is so long as the method based on heating, pressurization without the hot-melt adhesive method across adhesive linkage, can adopt known method, the method of for example, can suitable employing pressure sintering, hot lamination roller method, utilizing casting roll to form at extruding layer platen press or these Combination of Methods of the resin superimposed layer of extruding.
In addition, as " for the substrate of element mounted ", in the situation that requiring higher exothermicity, also can be by replacing above-mentioned resin/metal laminate to improve exothermicity with the high composition of material of the conductive coefficients such as the potteries such as metal material, aluminium nitride such as copper coin, aluminium sheet or graphite cake.
For example, as the formation of the composite base plate being composited with aluminium sheet, can be set forth in the situation of whole superimposed layer metal laminate as above of aluminium sheet or to the die-cut cavity of this metal laminate (recess) structure with window frame and carry out the situation of lamination.For used aluminium, while considering the adaptation with resin, be preferably the aluminium through roughening, but in the situation that considering cavity structure, in order to make effectively to reflect from the light of LED, preferably use high reflective aluminum.
As high reflective aluminum, can enumerate the aluminium that surface has been passed through the aluminium that grinds, passed through the aluminium that pellumina processes and passed through the inorganic oxides such as evaporation titanium, silicon dioxide or the reflection enhancing coating of the metal such as silver is processed.And then, as the reflectivity of this aluminium, preferably the average reflectance under wavelength 400～800nm be more than 80%, wherein more preferably more than 90%, be particularly preferably more than 95%.
(manufacture method of substrate for mounting light-emitting element)
The manufacture method of this substrate for mounting light-emitting element can be any means, is not particularly limited.Here, first, as the concrete manufacture method of this substrate for mounting light-emitting element, the manufacture method of the two sides substrate two sides lamination metal layer at substrate being formed in conjunction with Fig. 1 describes.
As shown in Figure 1, (a): first prepare the substrate (100) made by thermoplastic resin or thermosetting resin and as 2 Copper Foils (10) of metal level, (b): by vacuum pressing-combining at the two sides of the substrate of being made by thermoplastic resin or thermosetting resin (100) lamination Copper Foil (10), thereby manufacture resin/metal laminate.
(c): then, Copper Foil (10) is carried out etching or on copper, after plating, forms wiring pattern (20), make by " for the substrate of element mounted ".(d): at this substrate superimposed layer protective layer (200), (it should be noted that; here lamination is this surface protection film) and make substrate for mounting light-emitting element, described protective layer (200) possesses implements the resin bed that contains inorganic filler in polysiloxane (30) of windowing and processing to position to be installed.
(e): then, carry out gold-plated processing, LED (300) is installed, utilize bonding wire (40) to be connected with wiring pattern (20), and utilize given resin to seal (not shown), thereby can obtain light supply apparatus.
It should be noted that, the method for the processing of windowing can be any means, there is no particular restriction.Specifically can adopt such as the method for using punch die, excavate the method for processing, carry out the method for laser processing etc.In addition, when the formation of protective layer, except above-mentioned, can also be coated with the resin bed (30) that contains polysiloxane and inorganic filler and form protective layer.
Below, in conjunction with Fig. 2, the manufacture method of this substrate for mounting light-emitting element as aluminium composite base plate is described.
For example, as shown in Figure 2, (a): at a lamination Copper Foil (10) of the substrate of being made by thermoplastic resin or thermosetting resin (100), thereby manufacture metal laminate.Then, (b): Copper Foil (10) is carried out etching and forms wiring pattern (20), implement gold-plated processing, then use punch die that substrate (100) is die-cut into cavity frame (50).
Then, (c): by vacuum pressing-combining be formed with through the protective layer (200) of the processing of the windowing face superimposed layer aluminium sheet (400) contrary with the face of wiring pattern (20), made substrate for mounting light-emitting element.On this substrate, (d): LED (300) is installed, utilizes bonding wire (40) to be connected with wiring pattern (20), and utilize given resin to seal (not shown), thereby can obtain light supply apparatus.
It should be noted that, as the method that is die-cut into cavity frame, be not limited to use the method for above-mentioned punch die, also can for example excavate processing or form with laser.In addition, in above-mentioned manufacture method, carried out once the lamination of one-side band copper foil membrane (in Fig. 2 (b)), protective layer and aluminium sheet, but also can by they successively lamination, then carry out molding and form conductive pattern.
This light supply apparatus of < >
Light supply apparatus (being called " this light supply apparatus ") as the 3rd execution mode of the present invention, so long as on above-mentioned substrate for mounting light-emitting element, form conductor circuit so that this substrate be equipped on the light-emitting component conducting of this substrate and this light-emitting component carried out to the resin-sealed light supply apparatus forming, be not particularly limited.Specifically can be listed below formation: on substrate, form conductor circuit, at this conductor circuit superimposed layer protective layer, element mounted and make above-mentioned conductor circuit and above-mentioned light-emitting component conducting on aforesaid substrate simultaneously, and carry out resin-sealed to this light-emitting component.
Protective layer in this light supply apparatus possesses the characteristic of above-mentioned resin bed (A), therefore possess the average reflectance under wavelength 400～800nm for example and be more than 85% and in 260 ℃ carry out heat treatment in 10 minutes after the rate of descent of reflectivity under wavelength 450nm be 5% with inferior characteristic.Thus; by forming in this wise protective layer; can effectively realize the protection to conductor circuit; even also can not cause the decline of reflectivity in high temperature heat load environment, in light fastness test environment; therefore, light supply apparatus of the present invention can be used in the various uses such as the backlight apparatus of illumination use, projector light source, liquid crystal indicator etc., vehicle-mounted purposes, handset use.
< term explanation >
Generally speaking, described " sheet " refer to, in JIS definition, thin and for length and width, its thickness is less smooth goods conventionally; Generally speaking, described " film " refers to, compares with length and width, and thickness is minimum, and the maximum ga(u)ge thin and flat goods that can limit arbitrarily, and it supplies with (the JIS K6900 of Japanese Industrial Standards) with the form of volume conventionally.For example, with regard to thickness, in a narrow sense, sometimes materials more than 100 μ m is called to sheet, the material lower than 100 μ m is called to film.But, between sheet and film, there is no obvious boundary, in the present invention, there is no need on word, both to be distinguished, therefore in the present invention, while being called " film ", also comprise " sheet ", while being called " sheet ", also comprise " film ".
While in this specification, being expressed as " X～Y " (X, Y are Any Digit), in the situation that being not particularly limited, represent the implication of " X is above and Y is following ", also comprise the implication of " being preferably greater than X " and " being preferably less than Y ".
In addition, be expressed as in the situation of " more than X " (X is Any Digit) or " Y is following " (Y is Any Digit), also comprise the implication of " being preferably greater than X " or " being preferably less than Y ".
Embodiment
Below, in conjunction with the embodiments and comparative example carry out more specific detail.But within not departing from the scope of technological thought of the present invention, the present invention is not limited to following embodiment.
Wherein, for the various measured values of the film shown in this specification etc. and evaluate and obtain as described below.
(average reflectance)
Integrating sphere is installed on to spectrophotometer (" U-4000 ", Hitachi Co., Ltd's system), within the scope of wavelength 400nm～800nm with the measuring space of 0.5nm the reflectivity when reflectivity of aluminium oxide blank is made as to 100%.Calculate the mean value of gained measured value, using this value as average reflectance.Then, for the average reflectance of wavelength 350～400nm, measure similarly.
(reflectivity after heat treated)
With stationary fixture, the white films obtaining is fixed, in heated air circulation type baking oven, carry out 10 minutes heat treated in 260 ℃, similarly measured the reflectivity after heat treated with said method, and read the reflectivity under 450nm.
(test that utilizes xenon arc weatherometer to carry out)
Use the xenon arc weatherometer that Suga Test Instruments company manufactures (model: SX-75) to the surface protection film obtaining at temperature 63 ℃ of (blackboard temperature), humidity 50%, irradiance (295～400nm) 60W/m
2lower irradiation 50 hours, has then similarly measured reflectivity with said method, and has read the reflectivity under 450nm.
< embodiment 1>
Utilize planetary-type mixer that polysiloxane (TSE2571-5U, Momentive company system) 100 mass parts and Titanium Dioxide Rutile Top grade (R105, DuPont company system, average grain diameter 0.31 μ m) 67 mass parts are obtained by mixing to resin combination, and utilize extruder by gained resin combination in 100 ℃ of design temperatures, on demoulding PET film, obtained the surface protection film precursor of thick 100 μ m.Then, utilize gamma-rays with the radiation dose of 50kGy, it to be solidified and obtain the surface protection film that comprises resin bed (A), and utilize said method to evaluate this surface protection film.Result is as shown in table 1.
< embodiment 2>
Utilize planetary-type mixer that polysiloxane (TSE2571-5U, Momentive company system) 100 mass parts, the vulcanizing agent as heat cross-linking material (TC-12, Momentive company system) that is 1.5 mass parts with respect to these polysiloxane 100 mass parts and the titanium oxide (R105, DuPont company system, average grain diameter 0.31 μ m) of 67 mass parts are obtained by mixing to resin combination, and utilize extruder by gained resin combination in 100 ℃ of design temperatures, on demoulding PET film, obtained the surface protection film precursor of thick 100 μ m.Then, by carrying out heat treatment in 15 minutes, within 4 hours, make it solidify in 200 ℃ of heat treatments again in 125 ℃, thereby obtain the surface protection film that comprises resin bed (A), this surface protection film is evaluated.Result is as shown in table 1.
< embodiment 3>
Except making thickness, be 300 μ m, utilize the method identical with embodiment 1 to make the surface protection film that comprises resin bed (A), and evaluate.Result is as shown in table 1.
< embodiment 4>
Except making titanium oxide, be 400 mass parts, utilize the method identical with embodiment 1 to make the surface protection film that comprises resin bed (A), and evaluate.Result is as shown in table 1.
< embodiment 5>
Except making titanium oxide, be 25 mass parts, utilize the method identical with embodiment 1 to make the surface protection film that comprises resin bed (A), and evaluate.Result is as shown in table 1.
< embodiment 6>
Except making thickness, be 50 μ m, utilize the method identical with embodiment 1 to make the surface protection film that comprises resin bed (A), and evaluate.Result is as shown in table 1.
< embodiment 7>
Except using anatase-type titanium oxide (SA-1, Sakai Chemical Industry Co., Ltd.'s system, average grain diameter 0.3 μ m) 25 mass parts as titanium oxide; utilize the method identical with embodiment 1 to make the surface protection film that comprises resin bed (A), and evaluate.Result is as shown in table 1.
< embodiment 8>
Except using polysiloxane (TSE2913-U, Momentive company system) as polysiloxane, utilize the method identical with embodiment 1 to make the surface protection film that comprises resin bed (A), and evaluate.Result is as shown in table 1.
< embodiment 9>
Except use aluminium oxide (AA04, Sumitomo Chemical Co's system, average grain diameter 0.4 μ m) 150 mass parts replace titanium oxide; utilize the method identical with embodiment 1 to make the surface protection film that comprises resin bed (A), and evaluate.Result is as shown in table 1.
< embodiment 10>
Except making thickness, be 150 μ m, utilize the method identical with embodiment 8 to make the surface protection film that comprises resin bed (A), and evaluate.Result is as shown in table 1.
< embodiment 11>
Except making thickness, be 150 μ m, utilize the method identical with embodiment 9 to make the surface protection film that comprises resin bed (A), and evaluate.Result is as shown in table 1.
< embodiment 12>
Utilize the method identical with embodiment 8 to obtain the surface protection film precursor that comprises resin bed (A) of thick 100 μ m; then utilize the method identical with embodiment 9 to make the surface protection film precursor that comprises resin bed (B) of thick 50 μ m; by the surface protection face laminating of two precursors; then utilize gamma-rays that it is solidified; made the surface protection film with laminated construction, and evaluated.Result is as shown in table 1.It should be noted that, in the mensuration of reflectivity, the face that comprises resin bed (B) is measured.
< embodiment 13>
Except making the thickness of resin bed (B), be 100 μ m, utilize the method identical with embodiment 12 to make the surface protection film with laminated construction, and evaluate.Result is as shown in table 1.It should be noted that, in the mensuration of reflectivity, the face that comprises resin bed (B) is measured.
< comparative example 1>
Resin combination 100 mass parts that will be formed by polyether-ether-ketone resin (PEEK450G, Tm=335 ℃) 40 quality % and amorphism polyetherimide resin (Ultem1000) 60 quality %; and the Titanium Dioxide Rutile Top grade that is 67 mass parts with respect to these resin combination 100 mass parts (R108, DuPont company system, average grain diameter 0.23 μ m) is obtained by mixing composition; said composition is carried out to melting mixing; and use the extruder possess T-shaped mould at 380 ℃ of design temperatures, to make the surface protection film of thick 100 μ m, carried out the evaluation identical with embodiment 1.Result is as shown in table 1.
[table 1]
Result is as shown in Table 1 known, and in embodiments of the invention 1～13, reflectivity Characteristics is good, even and if still can access the excellent surface protection film that reflectance varies is few after heat run or after light fastness test (xenon arc weatherometer test).For example, in embodiment 9,11, owing to having filled aluminium oxide in polysiloxane, therefore for comparative example, high at the reflectivity of visible region, at the reflectivity of ultraviolet region (350～400nm), also significantly improve.On the other hand, in comparative example 1, reflectivity, the reflectivity after light fastness test of visible region are bad.
In addition, for embodiment 1～8,10, owing to having filled titanium oxide in polysiloxane, therefore especially in visible region, (400～800nm) demonstrated extra high reflectivity.In addition, for embodiment 7, owing to having filled anatase-type titanium oxide, therefore compare with the embodiment 1～6,8,10 that has filled Titanium Dioxide Rutile Top grade, at ultraviolet region, demonstrate high reflectance.
In addition, in embodiment 12,13, by forming, in polysiloxane, be filled with Titanium Dioxide Rutile Top grade resin bed (A), with polysiloxane in be filled with the laminated construction of the resin bed (B) of aluminium oxide, therefore within the scope of two of ultraviolet region (350～400nm) and visible region (400～800nm), all demonstrate high reflectance.
Claims (10)
1. the conductor circuit protection surface protection film of a printed wiring board; it possesses resin bed (A); this resin bed (A) contains polysiloxane and inorganic filler; wherein; the average reflectance of this surface protection film under wavelength 400～800nm is more than 85%; and, in 260 ℃ carry out heat treatment in 10 minutes after the rate of descent of reflectivity under wavelength 450nm be below 5%.
2. surface protection film according to claim 1, the rate of descent of its reflectivity after light fastness test as follows is below 5%,
Light fastness test: use xenon arc weatherometer at temperature 63 ℃ of (blackboard temperature), humidity 50%, irradiance (295～400nm) 60W/m
2lower irradiation 50 hours.
3. surface protection film according to claim 1 and 2, wherein, described resin bed (A) is the layer forming through radiation curing.
4. according to the surface protection film described in any one in claim 1～3, wherein, in described resin bed (A), contained inorganic filler is titanium oxide.
5. according to the surface protection film described in any one in claim 1～4, its thickness is 30 μ m～500 μ m.
6. according to the surface protection film described in any one in claim 1～5, its average reflectance under wavelength 350～400nm is more than 40%.
7. according to the surface protection film described in any one in claim 1～6; it possesses described resin bed (A) and resin bed (B), and this resin bed (B) contains polysiloxane and the inorganic filler different from inorganic filler contained in resin bed (A).
8. surface protection film according to claim 7, wherein, in described resin bed (B), contained inorganic filler is aluminium oxide.
9. a substrate for mounting light-emitting element, it possesses and has for carrying to form on the substrate of more than at least 1 light-emitting component the structure that the protective layer of resin bed (A) forms, and described resin bed (A) contains polysiloxane and inorganic filler,
The average reflectance of this protective layer under wavelength 400～800nm is more than 85%, and, in 260 ℃ carry out heat treatment in 10 minutes after the rate of descent of reflectivity under wavelength 450nm be below 5%.
10. a light supply apparatus, it possesses following structure: on substrate, form conductor circuit and at this conductor circuit superimposed layer protective layer, and; element mounted on described substrate and make described conductor circuit and described light-emitting component conducting; this light-emitting component is carried out resin-sealed, wherein
Described protective layer is the layer that possesses resin bed (A); this resin bed (A) contains polysiloxane and inorganic filler; the average reflectance of this protective layer under wavelength 400～800nm is more than 85%; and, in 260 ℃ carry out heat treatment in 10 minutes after the rate of descent of reflectivity under wavelength 450nm be below 5%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-026792 | 2012-02-10 | ||
| JP2012026792 | 2012-02-10 | ||
| PCT/JP2013/052685 WO2013118752A1 (en) | 2012-02-10 | 2013-02-06 | Coverlay film, printed wiring board to be equipped with light-emitting element, and light source device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104025726A true CN104025726A (en) | 2014-09-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380004632.9A Pending CN104025726A (en) | 2012-02-10 | 2013-02-06 | Coverlay film, printed wiring board to be equipped with light-emitting element, and light source device |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5676785B2 (en) |
| KR (1) | KR20140130161A (en) |
| CN (1) | CN104025726A (en) |
| WO (1) | WO2013118752A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111919519A (en) * | 2018-04-12 | 2020-11-10 | 三菱电机株式会社 | Printed circuit board coated with protective film and method for manufacturing same |
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| JP6720470B2 (en) * | 2014-11-28 | 2020-07-08 | 三菱ケミカル株式会社 | Method for producing phosphor-containing silicone sheet |
| JP2018060989A (en) * | 2016-10-04 | 2018-04-12 | 日本特殊陶業株式会社 | Frame member, light-emitting device, and manufacturing method thereof |
| JP2018085368A (en) * | 2016-11-21 | 2018-05-31 | 日本特殊陶業株式会社 | Lid member, light emitting device using the same, and manufacturing method of the same |
| US11304291B2 (en) * | 2017-06-29 | 2022-04-12 | Kyocera Corporation | Circuit board and light emitting device including circuit board |
| EP3701549A1 (en) | 2017-10-26 | 2020-09-02 | Syed Taymur Ahmad | Composition comprising non-newtonian fluids for hydrophobic, oleophobic, and oleophilic coatings, and methods of using the same |
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- 2013-02-06 WO PCT/JP2013/052685 patent/WO2013118752A1/en active Application Filing
- 2013-02-06 CN CN201380004632.9A patent/CN104025726A/en active Pending
- 2013-02-06 JP JP2013557536A patent/JP5676785B2/en active Active
- 2013-02-06 KR KR1020147024910A patent/KR20140130161A/en not_active Application Discontinuation
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| JPH11327150A (en) * | 1998-03-17 | 1999-11-26 | Mitsubishi Chemical Corp | Positive photoresist composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111919519A (en) * | 2018-04-12 | 2020-11-10 | 三菱电机株式会社 | Printed circuit board coated with protective film and method for manufacturing same |
| CN111919519B (en) * | 2018-04-12 | 2024-01-12 | 三菱电机株式会社 | Printed circuit board covered with protective film and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5676785B2 (en) | 2015-02-25 |
| JPWO2013118752A1 (en) | 2015-05-11 |
| KR20140130161A (en) | 2014-11-07 |
| WO2013118752A1 (en) | 2013-08-15 |
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