CN1237134C - Coating decoration material with fine heat radiation property for electronic instrument part - Google Patents

Coating decoration material with fine heat radiation property for electronic instrument part Download PDF

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Publication number
CN1237134C
CN1237134C CNB021270201A CN02127020A CN1237134C CN 1237134 C CN1237134 C CN 1237134C CN B021270201 A CNB021270201 A CN B021270201A CN 02127020 A CN02127020 A CN 02127020A CN 1237134 C CN1237134 C CN 1237134C
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coating
decoration material
mentioned
record
coating decoration
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CN1465644A (en
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渡濑岳史
平野康雄
奥村和生
山本哲也
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Kobe Steel Ltd
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Kobe Steel Ltd
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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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Computer Hardware Design (AREA)
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Abstract

The objective of the present invention is to provide a novel coated body for an electronic instrument member, which achieves the reduction of the temperature of the electronic instrument member (thermal radiation properties) while satisfying characteristics (the assurance of airtightness with accompanied waterproof/dustproof properties, miniaturization, and weight reduction) inherently required by the electronic instrument member. The solution of the present invention is that a coated body for electronic instrument member is obtained by coating front and rear surfaces of a substrate with a heat radiation film having heat radiation properties, a heat radiation evaluation apparatus shown in figure 1 is used, and difference Delta T1 (=T1B-T1A) between the temperature T1A of the T1 position when the coated body is used as a material to be tested, and the temperature T1B at the T1 position when a substrate not coated with coating film is used as a material to be tested is 1.5 DEG C or more.

Description

The electronic instrument part coating decoration material of fine heat radiation property
Technical field
The present invention relates to can be used as electronic instrument part basket, that exothermicity the is good coating decoration material of electronics, electrical equipment, opticinstrument (following represent with electronic machine sometimes) etc.; Exothermicity reaches from the good electronic instrument part coating decoration material of the property cooled off; Further relate to the also good above-mentioned electronic instrument part coating decoration material of electroconductibility; The electronic instrument part that these characteristics are all good; Useful coating composition in forming exothermicity and high conductive coating decoration material; And the exothermicity evaluating apparatus that is used to estimate the measured body exothermicity.Coating decoration material of the present invention suitably contains black additives such as carbon black based on the relation with coating thickness, and therefore, exothermic character is very good, is suitable for information record fields such as CD, LD, DVD, CD-ROM, CD-RAM, PDP, LCD; The field that electrical equipment such as computer, カ-Na PVC, カ-AV, electronics, communication are correlated with etc.; The AV instrument that further can be used as projector, TV, video recorder, game machine etc.; Duplicating machine such as duplicating machine, printing press; Various electronic instrument part baskets such as the power supply box shell of air-conditioner outdoor unit etc., controlling box shell, vending machine, refrigerator.And, coating decoration material of the present invention can not contain the coating decoration material that does not contain chromium of deleterious 6 valency chromium as all yet, and have the erosion resistance that is equal to mutually with the chromate treating steel plate and the adaptation of filming, and can provide very useful aspect the coating decoration material that does not contain chromium that has good processibility concurrently.
Background technology
In recent years, be accompanied by high performance, the miniaturization of electronics, electrical equipment, opticinstrument etc., produce problems (the high thermalization of electronic machine inside) such as cabinet inside thermal value increase (high temperatureization), high thermalization such as electronic machine.Someone points out that the internal temperature of electronic machine is about 40～70 ℃ under common envrionment temperature, be up to the high temperature about 100 ℃, like this, the heat resisting temperature that has surpassed IC, CPU (semiconductor element), disk, electric motor etc., therefore, existing problems aspect stable operation.And if the temperature rising, also cause semiconductor element to damage, the problem that the lost of life of electronic instrument part is such such as break down.
Therefore, as the heat dissipation that is used for reducing (heat releaseization) electronic machine internal temperature, the someone proposes the method that the basket (display panels such as basket body, frame, screen shell, liquid crystal etc.) at electronic machine is upward installed thermal components such as scatterer or heat pipe.But, adopt this method, the thermodiffusion that has only obtained at most to emit from the thermal source (heating element) of electronic machine inside particularly under the little situation of basket volume, can't obtain required radiating effect to the intravital effect of whole basket.And, this thermal component is installed is taken a lot of work, must guarantee in addition the place is set, there is the high problem of cost etc., be not suitable for the purposes of the electronic machine that carries out miniaturization, cost degradation.
In addition, also the someone proposes to adopt metal sheet (coating decoration material) in the basket of electronic machine, on this metal sheet the hole is set, and fan is installed, the method for utilizing convection current to dispel the heat.But usually, electronic machine is not water-fast or dust, therefore, is difficult to use according to purposes, and is identical with the situation of above-mentioned scatterer etc. in addition, increases at the cost of product, installs and take a lot of work and guarantee aspect existing problems such as installing space.
Therefore, be desirable to provide the original characteristic that satisfies the electronic machine requirement (follow waterproof and dustproof etc. guarantee resistance to air loss, miniaturization, lightweight), and can reduce the novel electron instrument component basket of this electronic machine internal temperature (heat dissipation characteristics).
On the other hand, in the electronic machine basket, except above-mentioned heat dissipation characteristics, also requirement can suppress the rising of this basket self temperature.This is because in the running of electronic machine product, can prevent that the human consumer from contacting danger such as this basket generation scald, provides safe goods like this.For this " suppressing the characteristic that electronic machine basket self temperature rises " distinguished with above-mentioned " thermal diffusivity ", in the present invention, be referred to as " property cooled off certainly " especially.When the good basket of this two specific character of preparation, adopt above-mentioned heat radiation countermeasure (method of thermal components such as scatterer or heat pipe is installed, the hole perhaps is set, the method for fan etc. is installed) on metal sheet, still found same problem.Therefore, it would also be desirable to provide the basket that possesses this two specific character.
In addition, to the basket of electronic machine, except above-mentioned characteristic, also require electroconductibility also good.But the thickness of the black coating film of the present black coated steel plate that uses (steel plate of lining black coating film) etc. is blocked up, and resistance value increases, and has the problem that can not obtain required ground connection when being used for electronic machine.
In addition, be conceived to substrate-side, from viewpoints such as erosion resistance, the adaptations of filming, substrate carried out chromate treating in the past, but because the deleterious 6 valency chromium of a large amount of uses, thereby environmental pollution problems is serious.Therefore, require to replace deleterious chromate treating, seek the method for the non-chromate processing that does not contain chromium.But known when not carrying out chromate treating, the erosion resistance and the adaptation of filming, and processibility is also poor.Therefore, even urgently be desirable to provide a kind of chromate treating that do not carry out, the coating decoration material that does not contain chromium that erosion resistance, the adaptation of filming and processibility are also good, and a kind of above-mentioned thermal diffusivity and the property cooled off is also good certainly electronic instrument part basket are provided.
Summary of the invention
The present invention is conceived to above-mentioned situation, its purpose is to provide a kind of novel coating decoration material, it is the coating decoration material as the basket use of electronic machine, satisfy the desired original characteristic of electronic instrument part (be accompanied by waterproof and dustproof etc. guarantee resistance to air loss, miniaturization and lightweight), and can reduce this electronic machine temperature inside; Further provide and suppress the also good electronic instrument part coating decoration material of characteristic (property cooled off certainly) that this coating decoration material self temperature rises; In addition, also provide high conductive electronic instrument part coating decoration material; Also provide erosion resistance good, the electronic instrument part coating decoration material that does not contain chromium that processibility is good with the adaptation of filming; The electronic instrument part of the coating decoration material lining that is had these good characteristics simultaneously is provided; Effective coating composition in forming thermal diffusivity and high conductive coating decoration material; A kind of not containing chronium is applicable to the coating composition of the substrate that has carried out bottom layer treatment, i.e. the coating composition of thermal diffusivity, electroconductibility, erosion resistance, the adaptation of filming and excellent processability; And the thermal diffusivity evaluating apparatus that is used to estimate the measured body thermal diffusivity.
The main points that can solve the coating decoration material (below be sometimes referred to as first coating decoration material) of the fine heat radiation property of the present invention of above-mentioned problem are, cover cooling coating film in substrate table the inside with thermal diffusivity, index as expression " good thermal diffusivity " satisfies following (I) or characteristic (II).
(I) the thermal diffusivity evaluating apparatus that adopts subsequent figures 1 to represent
Temperature in the T1 position when using above-mentioned coating decoration material as test materials is T1 A, the temperature in the T1 position when using the substrate that not lining films as test materials is T1 B, poor Δ the T1 (=T1 of the two B-T1 A) be more than 2.6 ℃.
The integration emissivity of the infrared rays when (II) above-mentioned coating decoration material being heated to 100 ℃ (wavelength: 4.5～15.4 microns) satisfies following formula (1); And as the scheme of further recommendation, in a 〉=0.65 and/or b 〉=0.65, and/or the maximum value A of the beam split emissivity in 4.5～15.4 microns the wavelength region and poor (A-B) of minimum value B are below 0.35.
a×b≥0.42 ……(1)
A: the infrared rays integration emissivity of the coating decoration material of surface-coated cooling coating film
B: the infrared rays integration emissivity of the coating decoration material of the inside lining cooling coating film
In order to obtain the coating decoration material of this fine heat radiation property, the concrete main points that constitute are that being covered in the table the inside of substrate has the cooling coating film of thermal diffusivity, and at least one face in this cooling coating film contains the black additive, and, satisfy following formula (2).
(X-3)×(Y-0.5)≥15 ……(2)
In the formula, X represents the amount (quality %) of black additive contained in the cooling coating film, and Y represents coating thickness (micron).
Wherein, X (amount of contained black additive in the cooling coating film) satisfies 4≤X＜15[formula (3)]; Y (coating thickness) satisfies Y＞1 micron; And then the median size of black additive satisfies 5～100nm; The black additive is a carbon black, obtain aspect the better thermal diffusivity effective.
In addition, the main points that can solve " thermal diffusivity and the property cooled off is good certainly the coating decoration material (below be sometimes referred to as second coating decoration material) " of the present invention of above-mentioned problem are, table the inside lining at substrate is filmed, and lining has the cooling coating film of thermal diffusivity on the surface at least of substrate, as the index of expression " good cooling certainly ", satisfy following (III) or (IV); Index as " the good heat dissipation characteristics " of representing this second coating decoration material satisfies following (V).
(III) adopt above-mentioned thermal diffusivity evaluating apparatus shown in Figure 1, the coating decoration material temperature when measuring above-mentioned coating decoration material as test materials is T2 A, the substrate temperature when using the substrate that not lining films as test materials is T2 B, poor Δ the T2 (=T2 of the two B-T2 A) be more than 0.5 ℃.
The integration emissivity of the infrared rays when (IV) above-mentioned coating decoration material being heated to 100 ℃ (wavelength: 4.5～15.4 microns) satisfies following formula (4).
b≤0.9(a-0.05)…(4)
The integration emissivity of the infrared rays when (V) above-mentioned coating decoration material being heated to 100 ℃ (wavelength: 4.5～15.4 microns) satisfies following formula (5).
(a-0.05)×(b-0.05)≥0.08……(5)
A: the infrared rays integration emissivity of the coating decoration material of surface-coated cooling coating film
B: the infrared rays integration emissivity of the coating decoration material of the inside lining cooling coating film
This in order to obtain " thermal diffusivity and the property cooled off " certainly good coating decoration material, the concrete main points that constitute are, film in the table the inside lining of substrate, and lining has the cooling coating film of thermal diffusivity on the surface at least of substrate, this cooling coating film contains the black additive, and, satisfy following formula (6).
(X-3)×(Y-0.5)≥3……(6)
In the formula, X represents the amount (quality %) of black additive contained in the cooling coating film, and Y represents coating thickness (micron).
Wherein, X (amount of contained black additive in the cooling coating film) satisfies 4≤X＜15[formula (7)]; Y (coating thickness) satisfies Y＞1 micron; And then the median size of black additive satisfies 5～100nm; The black additive is a carbon black, obtain more aspect the excellent characteristic effective.
In addition, the main points that can solve " thermal diffusivity (further being from the property cooled off) and the high conductive coating decoration material (following the 3rd coating decoration material that is referred to as sometimes) " of the present invention of above-mentioned problem are, except above-mentioned characteristic, also satisfying resistance is below 100 Ω, specifically, in above-mentioned cooling coating film, contain electroconductive stuffing (preferred Ni).
In the coating decoration material (first～the 3rd coating decoration material) of the invention described above, as the resin that forms cooling coating film, if adopt non-hydrophilic resin (preferred polyester resinoid), then erosion resistance improves, and is preferred scheme therefore.
And in the present invention, the transparent coating that is covered on above-mentioned cooling coating film can improve anti-defect and anti-finger printing, and is therefore useful.
Coating decoration material of the present invention also can be applicable to the coating decoration material that does not contain chromium.That is to say that aforesaid substrate does not contain the bottom layer treatment of chromium, and cooling coating film also to contain rust-preventive agent be preferred mode.Specifically, the formation composition recommendation of above-mentioned cooling coating film contains epoxide modified polyester resin and/or introduced polyester resin and linking agent (the preferred isocyanate resinoid and/or the melamine resinoid of phenol derivatives in skeleton, more preferably merge and use the two), like this, can guarantee superior corrosion resistance (area occupation ratio of the outward appearance abnormal portion in the salt spray testing corrosion resistance test of stipulating among the JIS-Z-2371 (72 hours): below 10%), the adaptation of filming (with the situation of peeling off of filming behind the band winding bend), processibility (fracture number among the JIS K 5400 in the driving fit pliability test of regulation: below 5).And, go up the two coating film structures that covering is filmed if be formed in above-mentioned filming, then can prevent the stripping of rust-preventive agent, therefore can access further superior corrosion resistance (area occupation ratio of the outward appearance abnormal portion in the salt spray testing corrosion resistance test of stipulating among the JIS-Z-2371 (120 hours): below 10%), thus very useful.Wherein, if make filming of covering on above-mentioned filming become transparent coating, then anti-defect and anti-finger printing also further improve.
And, if in above-mentioned filming, add electroconductive stuffing (preferred Ni), also can guarantee good electroconductibility (resistance is that 100 Ω are following).In addition, if add electroconductive stuffing in filming, then erosion resistance reduces, but by will show that the inside covers film in surperficial at least film thickness monitoring more than 2 microns, can keep good anti-corrosion.
In addition, the electronic instrument part of the present invention that can solve above-mentioned problem is with the main points of coating composition, in whole film to be formed into be divided into 100 quality %, contain above black additive of 3 quality % and the electroconductive stuffing of 10～50 quality %, adopt this coating composition, can form thermal diffusivity and high conductive filming.Here, the median size of above-mentioned black additive is 5～100nm; Above-mentioned black additive is a carbon black; Above-mentioned electroconductive stuffing is Ni, is preferred scheme.
And, in the present invention, also comprise a kind of electronic instrument part coating composition, this electronic instrument part coating composition is to be applicable to have carried out the not coating composition of the substrate of containing chronium bottom layer treatment, contains the above epoxide modified polyester resin of 35 mass parts and/or introduced the electroconductive stuffing of linking agent, the black additive more than 3 mass parts and 10～50 mass parts of rust-preventive agent, 1～20 mass parts of polyester resin, 2～25 mass parts of phenol derivatives in skeleton.Wherein, above-mentioned linking agent is with respect to 100 mass parts isocyanic ester resinoids, and preferably the ratio with 5～80 mass parts contains the melamine resinoid.In addition, the median size of recommending above-mentioned black additive is 5～100nm, uses carbon black.In addition, above-mentioned electroconductive stuffing preferably uses Ni.If use the coating composition that satisfies this composition, the not containing chronium that then can form thermal diffusivity, electroconductibility, erosion resistance, the adaptation of filming and excellent processability is filmed.
And, in the present invention, electronic instrument part at the built-in heating element in space that seals, be whole or a part of electronic instrument parts that constitute with coating decoration material by the electronic instrument part of the invention described above (for example, information record goods such as CD, LD, DVD, CD-ROM, CD-RAM, PDP, LCD of its outer wall; The goods that electrical equipment such as computer, カ-Na PVC, カ-AV, electronics, communication are correlated with; AV instruments such as projector, TV, video recorder, game machine; Duplicating machine such as duplicating machine, printing press; The power supply box shell of air-conditioner outdoor unit etc., controlling box shell, vending machine, refrigerator etc.) be also included within the scope of the present invention.
In addition, also comprise the thermal diffusivity evaluating apparatus within the scope of the present invention, it is a thermal diffusivity evaluating apparatus of estimating the Board Under Test thermal diffusivity in the present invention, constitute by above-mentioned measured body the whole or a part of of top board face, on the bottom surface of the casing that side and bottom surface are made of thermal insulation material heating element is set, and substantial middle partly is provided with temperature measuring equipment in casing.Wherein, the thermal diffusivity evaluating apparatus of the protecting component of blocking-up ambient conditions is set above above-mentioned Board Under Test, can prevent to have dysgenic factor (come from the outside or the wind of air conditioning machinery etc. etc.) to thermal diffusivity, can stably estimate heat dissipation characteristics, therefore very effective.
Description of drawings
Fig. 1 is in coating decoration material of the present invention, estimates Δ T1 (thermal diffusivity) and the sketch of the device that adopts.
Fig. 2 is the heat dissipation characteristics (figure of scope of a * b) of expression the present invention first coating decoration material.
Fig. 3 is the figure of the good scope of the property cooled off certainly of expression the present invention second coating decoration material and heat dissipation characteristics.
Fig. 4 is the long-pending (figure of the relation of a * b) of the infrared emission rate of expression Δ T1 and surface, the inside.
Fig. 5 is the amassing of the infrared emission rate (figure of the relation of a * b) of expression P value [=(X-3) * (Y-0.5)] and surperficial, the inside.
Fig. 6 is among the expression embodiment 5, Δ T2 and the Q value (figure of=0.9a-b) relation.
Fig. 7 is among the expression embodiment 5, the figure of the relation of Δ T1 and R value [=(a-0.05) * (b-0.05)].
Fig. 8 is the sketch of the thermal diffusivity evaluating apparatus that partly covers with protecting component.
Fig. 9 is the sketch with the whole thermal diffusivity evaluating apparatus that cover of protecting component.
Figure 10 is the brief description figure of the optimum position of the expression temperature measuring equipment that apparatus of the present invention adopted.
Figure 11 is among the expression embodiment 1, the figure of the relation of content of carbon black (X) and coating thickness (Y).
Figure 12 is the figure of the relation of the expression No.1 middle infrared (Mid-IR) wavelength of embodiment 2 and emissivity.
Figure 13 is the figure of the relation of the expression No.2 middle infrared (Mid-IR) wavelength of embodiment 2 and emissivity.
Figure 14 is the figure of the relation of the expression No.3 middle infrared (Mid-IR) wavelength of embodiment 2 and emissivity.
Figure 15 is the figure of the relation of the expression No.4 middle infrared (Mid-IR) wavelength of embodiment 2 and emissivity.
Wherein, 1 test materials (measured body); 2 thermal insulation materials; 3 heating elements; 4 protecting components (cover); 5 temperature measuring equipments.
Embodiment
Electronic instrument part of the present invention comprises three kinds of modes of following (first)～(the third) with coating decoration material.
The electronic instrument part of (first) fine heat radiation property coating decoration material (first coating decoration material)
(second) thermal diffusivity and the electronic instrument part coating decoration material (second coating decoration material) that the property cooled off is good certainly
(the third) in the coating decoration material of above-mentioned (first) and (second), the coating decoration material that electroconductibility is also high (the 3rd coating decoration material)
At first, above-mentioned (first)～(third) common basic thought is described.
Present inventors satisfy the desired original characteristic of electronic machine (be accompanied by waterproof and dustproof etc. guarantee resistance to air loss, miniaturization, lightweight, low cost etc.) in order to provide, and can realize reducing the novel electron instrument component coating decoration material of this electronic machine internal temperature (heat dissipation characteristics), be the center particularly, carried out research with keen determination with the thermal diffusivity that improves this coating decoration material self.Given the filming of lining on the table the inside of substrate found that, if then can reach required purpose.
Its mechanism is, " with thermal source (heating element) liberated heat (radiant heat) of absorption (radiation) of filming of the inside from electronic machine inside; and with the cooling coating film radiation of this heat from the surface ", its maximum feature is that the consideration to so-called " hot pass-through mode " is used for electronic instrument part dexterously.The idea of this " hot pass-through mode " is used for electronic instrument part, will be from the electronic machine liberated heat from " the inside of substrate " → absorb on " surface of substrate " → coating decoration material of its radiation is not known at present, be novel.
Secondly, before each coating decoration material is described, the relation of first coating decoration material (coating decoration material of fine heat radiation property) and second coating decoration material (thermal diffusivity and the good coating decoration material of the property cooled off) is certainly described.
First coating decoration material and second coating decoration material are used for aspect the electronic instrument part raising thermal diffusivity in the idea with foregoing " heat by ", and basic thought is consistent.But, the two problem (main solution problem) of doing one's utmost to solve, be used to solve the technological thought of this solution problem and constitute all inequality.Promptly, first coating decoration material is to be that the solution problem of maximum discloses to improve thermal diffusivity (reducing the electronic machine internal temperature), based on " amassing of the infrared emission rate of preferred surface, the inside is high as much as possible " this thought, surface, the inside are determined the formation of this cooling coating film as the one that constitutes cooling coating film; Different therewith, second coating decoration material is to utilize above-mentioned " idea that heat is passed through " to keep heat dissipation characteristics to a certain degree, and with " temperature that suppresses coating decoration material self rises " serves as that the maximum problem that solves discloses, be conceived to respectively " the infrared emission rate by his-and-hers watches the insides is provided with difference energetically; make infrared emission rate specific surface low of the inside; make the infrared emission rate on surface high as much as possible; thereby emit the heat that coating decoration material absorbs " and this thought, respectively to the surface, the formation of filming of the inside is controlled, thus, the two different invention of purpose directivity of can being known as.
That is, it is very good that first coating decoration material is included in the thermal diffusivity aspect, but the scheme that is wanting in the property cooled off certainly.On the other hand, second coating decoration material also comprises from the property cooled off very good, but thermal diffusivity is than the lower scheme of first coating decoration material.In order to further specify the difference of the two, the zone of the first coating decoration material defined [satisfying the good scope of heat dissipation characteristics of following formula (1)] as shown in Figure 2, the zone of the second coating decoration material defined [satisfy the good scope of the heat dissipation characteristics of following formula (5) and satisfy the repeating part of the good scope of the property cooled off certainly of following formula (4)] as shown in Figure 3.These coating decoration materials also comprise overlapped part, and [show the long-pending height of the infrared emission rate of the inside, therefore, heat dissipation characteristics is good, and, compare the infrared emission rate height on surface with the inside, therefore, the property cooled off is also good certainly], this part is heat dissipation characteristics and all very good zone of the property cooled off certainly.
Below each coating decoration material of the present invention is described.
The electronic instrument part of (first) fine heat radiation property coating decoration material (first coating decoration material)
Following formula first coating decoration material serves as that the basis produces with the following formula basic thought, has the given cooling coating film of thermal diffusivity if find to be covered on the table the inside of substrate, then can reach required purpose, thereby finish.
Promptly, above-mentioned first coating decoration material is as the electronic instrument part coating decoration material, by using [in the present invention in the surface of substrate and the inside, from this coating decoration material, the extraneous air side is called " surface ", the inboard of this coating decoration material is called " the inside "] lining satisfies the coating decoration material of the cooling coating film of given range at any integration emissivity (following " infrared rays integration emissivity " or " the infrared emission rate " of being designated as simply sometimes) of infrared wavelength range (wavelength: 4.5～15.4 microns), guaranteeing the thought that possesses skills aspect the good thermal diffusivity.
Subsidiary mentioning, as existing coating decoration material, can enumerate the back coating material that cover with paint, lacquer, colour wash, etc. processing back such as press process for example, the precoated material of before processing, covering with paint, lacquer, colour wash, etc. in advance etc., but they not exclusively resemble " when using with basket as electronic instrument part, using the idea of hot pass-through mode to improve thermal diffusivity " of the present invention this thought, therefore, there is not lining to have the cooling coating film of given thermal diffusivity in the table the inside of substrate.In fact, these existing coating decoration materials, its appearance (surface) is considered to have carried out covering with paint, lacquer, colour wash, etc. to handle from aesthetic property or functional (erosion resistance) equal angles, but its heat dissipation characteristics is low.On the other hand, present situation is its inside (coating decoration material inside face) even do not cover with paint, lacquer, colour wash, etc. or cover with paint, lacquer, colour wash, etc., and has also only implemented to guarantee the covering with paint (therefore, can't obtain required heat dissipation characteristics) of MIN erosion resistance degree substantially.Therefore, adopt such single face coating decoration material, can't obtain required heat dissipation characteristics, this situation is confirmed by embodiment described later.
Below, above-mentioned coating decoration material is specifically described.
Above-mentioned first coating decoration material has the cooling coating film of thermal diffusivity in the table the inside lining of substrate, as the index of expression " good thermal diffusivity ", satisfy the Δ T1 (electronic machine internal temperature poor) of following (I) expression or " a * b " of following formula (II) expression (the infrared emission rate of the surface of coating decoration material and the inside long-pending).
" a * b " wherein is defined as the long-pending of the ultrared emissivity of emitting from coating decoration material, and be useful as the index of expression coating decoration material radiating effect.On the other hand, Δ T1 is defined as the radiating effect of the realistic scale of simulation electronic instrument component purposes, can estimate envrionment temperature (according to the kind of electronic machine etc. according to the supposition of this purposes, the envrionment temperature difference, be roughly 50～70 ℃, be up to about 100 ℃) under heat dissipation characteristics, thereby adopt in the present invention.
Said two devices all is effectively as the index of expression " thermal diffusivity ", and, have good correlationship.As a reference, the result's (table 1 and table 3) with aftermentioned embodiment maps as shown in Figure 4.Among the figure, ● the cooling coating film of expression table the inside is formed the result of different coating decoration materials, and the cooling coating film of zero expression table the inside is formed the result of the coating decoration material of identical (using carbon black as the black additive).
Above-mentioned first coating decoration material of this heat dissipation characteristics is satisfied in employing, be accompanied by high performance, the miniaturization of electronic machine, even the thermal value of cabinet inside increases (high temperatureization) high thermalization etc. take place, because heat dissipation characteristics is good, therefore, can reduce the electronic machine temperature inside.Therefore, can prolong electronic instrument part life-span, save electric power, reduce noise, the degree of freedom (high speed, multifunction and miniaturization etc.) of further expansion instrument design etc., very useful.
Below each characteristic is described.
Here, T1 AAftermentioned thermal diffusivity evaluating apparatus shown in Figure 1, the temperature of T1 position when using coating decoration material of the present invention as test materials are adopted in expression; T1 BSame above-mentioned thermal diffusivity evaluating apparatus shown in Figure 1, the temperature of T1 position when not being covered the substrate of filming of adopting of expression as the test materials employing.
Above-mentioned Δ T1 compares with the situation of using substrate (the not exposed raw sheet that is covered and films), under the situation of using coating decoration material of the present invention, be defined as to reduce the index of electronic machine internal temperature, in the present invention, device as measuring Δ T1 adopts the distinctive thermal diffusivity evaluating apparatus of the present invention shown in Figure 1.The device of Fig. 1 is as estimating envrionment temperature according to the purposes supposition of electronic machine etc. (according to the kind of electronic machine etc., the atmosphere temperature difference, be roughly 50～70 ℃, be up to about 100 ℃) the device of heat dissipation characteristics extremely useful, adopt it, can correctly estimate the radiating effect under the realistic scale of simulation electronic instrument purposes.At present, also do not have to estimate the efficient apparatus of thermal diffusivity, therefore, comprise that the thermal diffusivity evaluating apparatus of the device of Fig. 1 is also included within (aftermentioned) within the scope of the present invention.
Fig. 1 is that the internal space is the cubes device of 100mm (length) * 130mm (wide) * 100mm (height).Among Fig. 1, and 1 expression test materials (measured body, measuring area is 100 * 130mm), 2 expression thermal insulation materials, [floorage is 1300mm to 3 expression heating elements 2, the longest collinear length that can draw in this heating element area (being cornerwise length in Fig. 1) is 164mm], 5 expression temperature measuring equipments.
Wherein, heating element 3 uses and has adopted silicon rubber heater, thereon the structure that forms of driving fit aluminium sheet (the infrared emission rate is below 0.1).And [middle body of internal space (apart from heating element 3 50mm top)] is as temperature measuring equipment 5 stationary heat galvanic couples in the T1 position of Fig. 1.In addition, in order to eliminate thermal-radiating influence, lid is installed in the bottom of thermopair from heating element.In addition, thermal insulation material 2 is according to its kind or user mode etc., make envrionment temperature in the case change (also influential) to thermal diffusivity, therefore adopting the infrared emission rate is 0.03～0.06 metal sheet [for example electrogalvanizing steel plate (JIS SECC etc.)], according to method described later, adjust the tension force of thermal insulation material etc., make the envrionment temperature (absolute value temperature) of T1 position be about 73～74 ℃.In addition,, adjust equally, make the envrionment temperature (absolute value temperature) of T1 position be about 73～74 ℃ for the factor that thermal diffusivity is exerted an influence (for example fixation method of test materials etc.).
Describe at the method that adopts said apparatus to estimate heat dissipation characteristics below.
When measuring,, condition determination is controlled to be temperature in order to eliminate the data deviation that ambient conditions (wind etc.) causes: 23 ℃, relative humidity: 60%.
At first, place each test materials 1, opening power is heated to 140 ℃ with hot plate 3.The temperature-stable of hot plate is at 140 ℃, the temperature of determining the T1 position be more than 60 ℃ after, take out test materials immediately.When the temperature inside the box drops to 50 ℃, place test materials once more, after the placement, measure 90 minutes interior temperature of rear cabinet.Poor (the Δ T1) of temperature when then, calculate adopting above-mentioned test materials and the temperature when adopting the nothing of filming to cover with paint, lacquer, colour wash, etc. raw sheet.
In addition, each measures 5 times Δ T1 to each test materials, remove wherein maximum value and other 3 the data mean value of minimum value be decided to be Δ T1 of the present invention.
The Δ T1 that calculates like this is big more, means that heat dissipation characteristics is good more.Preferred order is more than 2.7 ℃, more than 3.0 ℃, more than 3.3 ℃, more than 3.5 ℃, more than 3.7 ℃, more than 4.0.
And the index of heat dissipation characteristics (target level) is because of the differences such as kind of electronic machine, still, according to the present invention, such as described later, by according to suitably controlling black additive contained in the cooling coating film, can adjust to the heat dissipation characteristics of defined at an easy rate with the relation of coating thickness.
(II) formula (1): a * b 〉=0.42
In the formula, when a and b represent respectively to be heated to 100 ℃ at the coating decoration material of the table of substrate the inside lining cooling coating film in the integration emissivity of infrared rays (wavelength: 4.5～15.4 microns), the infrared rays integration emissivity (a) on surface and the infrared rays integration emissivity (b) of the inside.Infrared rays integration emissivity can adopt method described later to measure, and can measure the infrared rays integration emissivity of surface or the inside respectively.
Above-mentioned " infrared rays integration emissivity " is meant the easy degree (the easy degree of absorption) that infrared rays (heat energy) sheds in other words.Therefore, above-mentioned infrared emission rate is high more, and the shed heat energy of (absorption) of expression is big more.For example, when giving heat energy 100% radiation of object (being coating decoration material in the present invention), this infrared rays integration emissivity is 1.
In the present invention, infrared rays integration emissivity when determining to be heated to 100 ℃, but, this considers that coating decoration material of the present invention is used for electrical equipment instrument purposes (because of differences such as parts, but common envrionment temperature is roughly 50～70 ℃, and is the highest about 100 ℃), for consistent, Heating temperature is decided to be 100 ℃ with the temperature of this realistic scale.But, even be heated to 200 ℃, infrared rays integration emissivity is also almost constant, infrared rays integration emissivity when being heated to 200 ℃ is compared with 100 ℃ infrared rays integration emissivity, general high by about 0.02, still, confirm that by test roughly unanimity is (in addition, in embodiment described later, the infrared emission rate when record is heated to 100 ℃ and 200 ℃ simultaneously).
The measuring method of the infrared rays integration emissivity among the present invention is as described below.
Device: NEC (strain) system " JIR-5500 type Fierie transform infrared spectrophotometer " and radiation detection Unit " IRR-200 "
Total range of wavelength: 4.5～15.4 microns
Measure temperature: the Heating temperature of sample is decided to be 100 ℃.
Integral number of times: 200 times
Resolution: 16cm -1
Adopt said apparatus, be determined at the spectroradio intensity (measured value) of the sample in the infrared wavelength range (4.5～15.4 microns).And, because the measured value yield of radiation as a setting of above-mentioned sample and device function addition/additional numerical value are measured, therefore, for it is proofreaied and correct, adopt emissivity to measure program [NEC (strain) system emissivity is measured program], calculate the integration emissivity.The details of method of calculation is as follows.
[several 1]
In the formula
ε (λ): the beam split emissivity (%) of af at wavelength lambda sample
E (T): temperature T (℃) time sample integration emissivity (%)
M (λ, T): wavelength X, temperature T (℃) the spectroradio intensity (measured value) of sample
A (λ): device function
K FB(λ): the spectroradio intensity of the fixed background of wavelength X (the not background that changes because of sample)
K TB(λ, T TB): wavelength X, temperature T TB(℃) the spectroradio intensity of baffle plate black matrix
K B(λ, T): wavelength X, temperature T (℃) the spectroradio intensity (value of calculating by the theoretical formula of barren) of black matrix
λ 1, λ 2: the wavelength region of integration.
Here, above-mentioned A (λ: install function) and above-mentioned K FB(λ: the spectroradio intensity of fixed background) be based on the spectroradio intensity (value of calculating by the theoretical formula of barren) of the black matrix of the measured value of spectroradio intensity of two blackbody furnaces (80 ℃, 160 ℃) and this temperature range, calculate by following formula.
[several 2]
In the formula,
M 160 ℃(λ, 160 ℃): the spectroradio intensity (measured value) of 160 ℃ of blackbody furnaces of af at wavelength lambda
M 80 ℃(λ, 80 ℃): the spectroradio intensity (measured value) of 80 ℃ of blackbody furnaces of af at wavelength lambda
K 160 ℃(λ, 160 ℃): the spectroradio intensity of 160 ℃ of blackbody furnaces of af at wavelength lambda (by the value of the theoretical formula calculating of barren)
K 80 ℃(λ, 80 ℃): the spectroradio intensity of 80 ℃ of blackbody furnaces of af at wavelength lambda (by the value of the theoretical formula calculating of barren)
In addition, when calculating integration emissivity E (T=100 ℃), consider K TB(λ, T TB) be because when measuring, around sample, the baffle plate black matrix of water-cooled has been installed.By above-mentioned baffle plate black matrix is set, can (mean the background radiation that changes per sample with changing background radiation.Reflected by sample surfaces from the radiation around the sample, therefore, the measured value of the spectroradio intensity of sample is with adding that the numerical value of this background radiation represents) the spectroradio intensity control in lower value.Above-mentioned baffle plate black matrix uses the false black matrix of emissivity 0.96, above-mentioned K TB[(λ, T TB): wavelength X, temperature T TB(℃) the spectroradio intensity of baffle plate black matrix] following calculating:
K TB(λ，T TB)＝0.96×K B(λ，T TB)
In the formula, K B(λ, T TB) expression wavelength X, temperature T TB(℃) the spectroradio intensity of black matrix.
The integration emissivity [above-mentioned E (T=100 ℃)] of the infrared rays (4.5～15.4 microns of wavelength) that first coating decoration material of the present invention is measured like this, promptly the surface is gone up infrared rays integration emissivity (b) long-pending of coating decoration material of the infrared rays integration emissivity (a) of coating decoration material of lining cooling coating film and the inside lining cooling coating film (a * b) is more than 0.42, satisfied [formula (1)].As mentioned above, the numerical value that calculates with " a * b " (the infrared rays integration emissivity that sheds from coating decoration material long-pending) is effective as the index of the radiating effect of expression coating decoration material self, the coating decoration material that satisfies following formula is in above-mentioned wavelength region, average the high radiation characteristic of performance, therefore, the target value with the heat dissipation characteristics of above-mentioned first coating decoration material is decided to be " a * b 〉=0.42 ".The value of " a * b " (being 1 to the maximum) big more (more near 1) is waved good heat dissipation characteristics all the more, is more than 0.49, more than 0.56, more than 0.61, more than 0.64, more than 0.72 according to preferred order.
And, in following formula first coating decoration material, as long as satisfy the target value of above-mentioned heat dissipation characteristics, be not particularly limited the relation of surface red outside line emissivity and the inside infrared emission rate, comprise the scheme that the surface and the infrared emission rate of the inside there are differences, and the two sides has the scheme of the emissivity of same degree.Relative therewith, second coating decoration material of the present invention is a main purpose to improve from the property cooled off except thermal diffusivity, aspect the high coating decoration material of the infrared emission rate that only limits to the surface ratio the inside, and the two difference (on the books in (second) described later).
Specifically, have only the heat dissipation characteristics that satisfies above-mentioned (1) " a * b 〉=0.42 ", could determine any infrared emission rate of surface/the inside.But, because the maximum value of infrared emission rate is 1, above-mentioned in order to satisfy (1), the infrared emission rate of single face must be more than 0.42 at least; In order to satisfy a * b 〉=0.56, the infrared emission rate of single face must be more than 0.56 at least; In order to satisfy a * b 〉=0.62, the infrared emission rate of single face must be more than 0.64 at least.
Here, the infrared emission rate of single face is the bigger the better, and satisfying the infrared emission rate of single face at least and being more than 0.65 is embodiment preferred.According to preferred order, be more than 0.7, more than 0.75, more than 0.8.The two sides be more than 0.65 coating decoration material more preferably.
In above-mentioned first coating decoration material, the maximum value A of the beam split emissivity in any wavelength region of above-mentioned infrared rays (4.5～15.4 microns of wavelength) and poor (A-B) of minimum value B are preferably below 0.35.This " A-B " is illustrated in the emissivity rangeability in the above-mentioned infrared wavelength range, and " A-B≤0.35 " is meant, even in any range of above-mentioned Infrared wavelength, stablizes the high radiation characteristic of performance.Therefore, satisfy above-mentioned main points, for example also applicable etc. in the purposes such as electronic machine of having carried the different goods of various Infrared wavelength of emitting, be expected to enlarge the purposes in electronic instrument part.Specifically, measure any emissivity of measuring as mentioned above, will calculate in the maximum value (A) of the beam split emissivity of this wavelength region and poor (A-B) conduct " rangeability of emissivity " of minimum value (B).The value of above-mentioned " A-B " is the smaller the better, can obtain stable heat dissipation characteristics, more preferably below 0.3, further preferably below 0.25.
Below the concrete formation that is used to obtain above-mentioned first coating decoration material is described.
Above-mentioned coating decoration material is the coating decoration material that lining has the cooling coating film of thermal diffusivity on substrate table the inside, still, and by based on suitably controlling amount X (the quality % of the black additive that the single face at least of cooling coating film contains with the relation of coating thickness Y (micron); Below unless otherwise specified, " % " is meant " quality % "), can obtain required heat dissipation characteristics.Specifically, above-mentioned X and Y satisfy following formula (2), and wherein X preferably satisfies following formula (3), and Y preferably satisfies Y＞1 micron.
1. formula (2): (X-3) * (Y-0.5) 〉=15
Below, the calculated value of [(X-3) * (Y-0.5)] on the left side is represented with the P value sometimes.
Above-mentioned (2) as the integrant that is used to obtain above-mentioned heat dissipation characteristics [Δ T1 or (index of expression of a * b)], determines in the cooling coating film amount X (%) of the black additive that single face at least is contained and the relation of coating thickness Y (micron).The implication of following formula is in order to ensure determine " heat dissipation characteristics " in first coating decoration material, must be based on suitably controlling black additives such as carbon black with the relation of coating thickness, discoverys of the present invention of what is called " when thickness approaches; must increase the content (promptly increasing the content of the black pigment of unit thickness) of black pigment; and thickness is when thick; can reduce the content (that is, the content of the black pigment of unit thickness reduces) of black pigment " is formulistic.
Here, P value [=(X-3) * (Y-0.5)] and heat dissipation characteristics roughly have good correlationship.Fig. 5 is based on result's (table 4 and table 5) of aftermentioned embodiment, present in diagrammatic form P value and heat dissipation characteristics (relation of a * b), shown in this figure, target value (a * b 〉=0.42 of the heat dissipation characteristics that discloses in order to ensure following formula first coating decoration material, Δ T1 〉=2.6 ℃), must make following formula P value is more than 15.Adopt the present invention to have following advantage,, just calculate the P value corresponding,, only, just can guarantee required heat dissipation characteristics at an easy rate by suitably adjusting the scope of X and Y respectively in order to obtain this P value with it in case determined the index of heat dissipation characteristics.
In order to obtain better heat dissipation characteristics, following formula P value is the bigger the better, and according to preferred sequence, is more than 7, more than 11, more than 15, more than 30.
But, even make the P value quite big, heat dissipation characteristics is saturated, the amount of the black additive that only increase to use etc., waste economically, in addition, if the basket of coating decoration material of the present invention as electronic machine used, consider also to require processibility and electroconductibility etc. that recommending the upper limit with the P value is 240,200,150,100 according to preferred sequential control.
2. formula (3): 4%≤X＜15%
In the present invention,, be recommended as more than 4% being prerequisite more than 3% with black content of additive X.Here, be prerequisite with " X＞3% ", be the coefficient on this formula left side (X-3) just is being necessary for (＞0) because in order to satisfy following formula (2).
And, when obtaining good heat dissipation characteristics,, determine the lower limit of above-mentioned X, thereby, can't obtain desired characteristic below 3% in order to ensure coating decoration material self characteristics (covering with paint property, outward appearance etc.).Preferred lower limit is 5%, 7%, 8% and 10% in proper order.On the other hand, the upper limit of X with the relation of heat dissipation characteristics in not special restriction, still, if more than 15%, covering with paint property variation then takes place to apply uneven, produces bad order.Therefore, the good upper limit of consider covering with paint, lacquer, colour wash, etc. property etc. is less than 15%, 13%, 11% in order.
3. Y＞1 micron
In the present invention, about the coating thickness Y of cooling coating film,, recommend more than 1 micron to be prerequisite more than 0.5 micron.Here, be that prerequisite is because in order to satisfy following formula (4), the coefficient on this formula left side (Y-0.5) just is being necessary for (＞0) with " Y＞0.5 micron ".
The lower limit of above-mentioned Y is definite in order to obtain good especially heat dissipation characteristics, and Y even increase the black additive, also can't obtain required radiating effect below 0.5 micron the time.Preferred lower limit is 3 microns, 5 microns, 7 microns, 10 microns in order.
The upper limit of following formula Y with the relation of heat dissipation characteristics in be not particularly limited, still, the purpose of coating decoration material of the present invention is to be used for electronic instrument part, is fastening with the pass of this purposes, also requires to improve processibility; If particularly consider to prevent the cracking and peel off etc. of filming when bending machining, recommendation is controlled at (is below 45 microns, below 40 microns, below 35 microns, below 30 microns according to preferred order) below 50 microns.
When possessing good processibility,, recommend following formula Y is controlled at (according to preferred order is below 11 microns, further preferred below 10 microns) below 12 microns in order to ensure good electroconductibility.
More than X in the following formula (2) (black content of additive) and Y (coating thickness) are illustrated.
As black additive used in the present invention, as long as can give black, have no particular limits, can enumerate carbon black typically, in addition, also can use the metal fine powder etc. of oxide compound, sulfide, carbide or the black of Fe, Co, Ni, Cu, Mn, Mo, Ag, Sn etc.Carbon black most preferably.
Here, film in the addition (X) of carbon black can measure by following method.
At first, in measured body (analytic sample), add solvent and heat, decompose the organism in the measured body.The kind of solvent for use is according to the kind of base resin and difference, according to each dissolving resin degree, can use appropriate solvent, for example, when adopting polyester based resin or polyurethane series resin as base resin, in the container that has added sodium hydroxide-methanol solution (eggplant type flask etc.), add measured body,, decompose the organism in the measured body the heating in water bath of this container with 70 ℃.
Then, filter this organism with glass filter (0.2 micron in aperture), the carbon in the residue that obtains with burning infrared ray absorption standard measure calculates the carbon black concentration in filming.
The median size of above-mentioned black additive preferably is controlled in 5～100nm.During the median size of following formula additive is not enough 5nm, can not get required heat dissipation characteristics, in addition, the bad stability of coating is covered with paint, lacquer, colour wash, etc. degraded appearance.On the other hand, if median size surpasses 100nm, not only heat dissipation characteristics reduces, and the outward appearance after covering with paint, lacquer, colour wash, etc. is also inhomogeneous.Be preferably below the above 90nm of 10nm; More preferably below the above 80nm of 15nm.Except heat dissipation characteristics, if take all factors into consideration be coated with membrane stability, the outward appearance homogeneity after covering with paint, lacquer, colour wash, etc. etc., it probably is 20～40nm that the best median size of black additive is recommended.
And, the kind of the resin that adds in filming (forming the base resin of cooling coating film) is from the viewpoint of heat dissipation characteristics, unqualified, can suitably use acrylic resin, urethane is resin, polyolefin-based resins, polyester based resin, fluorine resin, silicone-based resin and their mixing or modified resin etc.But, for coating decoration material of the present invention being used as the basket of electronic machine, except thermal diffusivity, if consider also to require to improve processibility, the preferred non-hydrophilic resin of above-mentioned base resin [specifically, be that satisfied contact angle with water is the material of (more preferably more than 50 °, further preferred more than 70 °) more than 30 °].The resin that satisfies this non-hydrophilic characteristics also can change according to mixedness or modification degree etc., for example preferably use polyester based resin, polyolefin-based resins, fluorine resin, silicone-based resin and their mixing or modified resin etc., wherein, recommend to use the polyester based resin (epoxide modified polyester based resin, Thermocurable polyester based resin such as polyester based resin or the unsaturated polyester of having introduced phenol derivatives in skeleton are resin) of polyester based resin or modification.
In above-mentioned filming, in the scope that does not influence effect of the present invention, except black additives such as carbon black, can also add pigment such as rust-stabilising pigment, silicon-dioxide.Perhaps, within the scope that does not influence effect of the present invention, can add the additive (TiO for example that except the black additive other have thermal diffusivity 2, pottery, ferric oxide, aluminum oxide, barium sulfate, silicon oxide etc. one or more kinds of at least a).
And, in above-mentioned filming, can add linking agent.As the linking agent that adopts among the present invention, can enumerate for example melamine based compound or isocyanic ester based compound etc., recommend they are a kind of or two or morely add in the scope of 0.5～10 quality %.
This coating decoration material of the present invention has been covered and has contained the cooling coating film of black pigments such as carbon black, but at present, and the coated steel plate that adds black pigment such as carbon black in resin coating film is open.
For example, in the Te Kaiping 3-120378 communique, the manufacture method of the employed far-infrared radiation plate of hot device component (forming the ceramic layer with far infrared rays characteristic on base material) is disclosed, put down in writing " in given black acrylic resin tunicle, can add black pigments such as carbon black, can bring into play the far infrared radiation characteristic thus; Its add-on, per 100 parts by weight resin are 0.1～10 weight part, resin coating is thick to be generally 0.1～5 micron ".
But the far-infrared radiation plate of putting down in writing in the above-mentioned communique has only only formed ceramic layer on the single face of base material, be not coated with plaque as the present invention, forms on the table the inside of substrate and films, thereby can not get required thermal diffusivity.
The two is owing to use object (purposes) difference, so also different as the consideration method on the basis that solves the problem means, integrant is also different.Promptly; the far-infrared radiation plate of above-mentioned communique can be used for requiring to have the field of the hot utensil (being heating stove etc. typically) of radiation characteristic under about 200～300 ℃ of very high like this temperature; and show no sign of as coating decoration material of the present invention; usually be about 40～70 ℃, the meaning in the highest about the 100 ℃ electronic instrument part under the envrionment temperature especially for internal temperature.Therefore, in above-mentioned communique, just to improve the idea of the emissivity (radiant ratio) of the far infrared rays that sheds from hot utensils such as heating stoves as much as possible, also only added carbon black for this reason, except being the object with hot utensil, produce as the present invention at all, " in order to reduce the internal temperature of electronic machine, heat absorption that will shed from electronic machine and radiation in the inside of substrate → surface through compiling " leeway of idea of this what is called " hot pass-through mode ".
In fact, because above-mentioned radial lamella is only covered with paint, lacquer, colour wash, etc. on single face, therefore, when under the condition of the present invention record, adjusting the rangeability of integration emissivity and emissivity, confirm to obtain good heat dissipation characteristics (No.19 of table 5 described later) resemble the present invention by test.
In above-mentioned communique, be that substrate carries out the black processing with plating Zn-Ni alloy steel plate, form black coating, and then layer is gone up lining black resin tunicle thereon, thus, can bring into play far infrared radiation characteristic, still at high temperature range, (compare as the electronic instrument part of object if this radial lamella is directly used in the present invention with far-infrared radiation plate, can in much lower temperature range, use), according to the difference of purposes, require characteristic also different, therefore, there is variety of issue.That is, 1. compare with hot utensil purposes, electronic instrument part requires harsh more bendability, therefore, the crack takes place in alloy-plated layer, is starting point with this crack, and black resin tunicle or galvanized impurity are peeled off, come off, and produces bad order; If 2. this peel off or obscission produces in the inside of alloy-plated layer, tunicle of peeling off or galvanized impurity adhere to, are deposited on the parts of electronic machine, cause problems such as electronic machine may break down.
Therefore think that the present invention and above-mentioned radial lamella are different inventions.
More than the cooling coating film that contains the black additive is illustrated.In above-mentioned first coating decoration material, at least the single face of the cooling coating film of lining mainly contains the black additive on the table the inside of substrate, but, another cooling coating film is not limited to this, in order to satisfy the required heat dissipation characteristics of the present invention's regulation, except the black additive, can also add the black additive additive with thermal diffusivity (being called " other thermal diffusivity additive " sometimes) in addition and form cooling coating film.Certainly, all to have the coating decoration material of the cooling coating film that contains the black additive that satisfies above-mentioned relation be particularly preferred scheme the table of substrate the inside.
Here, as above-mentioned " other thermal diffusivity additive ", can enumerate for example TiO 2, pottery, ferric oxide, aluminum oxide, barium sulfate, silicon oxide etc. one or more kinds of at least a.The thickness of cooling coating film that mainly contains these " other thermal diffusivity additives " is according to the kind of " other thermal diffusivity additive " that use or purposes etc., in order to obtain required heat dissipation characteristics, it is thick to set suitable membrane, but is recommended as 15～30 microns usually.
Specifically, contain TiO 2Film the time, if form about 25～30 microns in filming, contain the 40～60%TiO that has an appointment 2Tunicle, can obtain the infrared emission rate about 0.8 usually.In above-mentioned filming, if also add black additives such as carbon black etc., the infrared emission rate further increases.And when imposing metal and transfer filming of outward appearance, the A1 scale of adding about 5～30% etc. during filming makes coating thickness be about 5～30 microns, then can obtain about 0.6～0.7 infrared emission rate.
(second) thermal diffusivity and the electronic instrument part coating decoration material (second coating decoration material) that the property cooled off is good certainly
Above-mentioned second coating decoration material is to be covered to film on the table the inside of substrate, and, lining has the coating decoration material of the cooling coating film of thermal diffusivity on the surface at least of substrate, as the index of expression " good cooling certainly ", satisfy the Δ T2 (the inhibition degree that coating decoration material self temperature rises) of following (III) expression or the formula (4) [b≤0.9 (a-0.05)] of following formula (IV) expression; And, as the index of " good thermal diffusivity " in above-mentioned second coating decoration material of expression, satisfy the formula (5) [(a-0.05) * (b-0.05) 〉=0.08] of following (V) expression.
At first, the index of the property cooled off is certainly described.
Its Chinese style (4) is decided to be with the infrared emission rate of the inside to be compared, and expression improves the infrared emission rate on surface, the transfer of heat of coating decoration material absorption is arrived the index of the radiating effect in the outside; On the other hand, Δ T2 is decided to be the radiating effect of coating decoration material of the realistic scale of simulation electronic instrument component purposes.
These two index as expression " property cooled off certainly " all is effectively, has good correlationship.As a reference, the result of embodiment described later is made chart, as shown in Figure 6.The longitudinal axis of Fig. 6 is to change in the formula (0.9a-b 〉=0.05) of following formula (4) calculated value of the left side (0.9a-b) (the following Q value representation of using sometimes).
Satisfy this above-mentioned second coating decoration material if adopt from the property cooled off, the temperature that can suppress coating decoration material self rises, therefore, when this coating decoration material is used as the basket of electronic machine, in electronic machine when running, be not even heat etc. is felt in operator's contact yet, from operator's angle, can provide safe electronic machine.And above-mentioned coating decoration material also has good thermal diffusivity concurrently, and therefore, the electronic instrument part that has this two specific character concurrently is very effective aspect further expansion purposes.
Each characteristic to (III)～(V) describes below.
Figure C0212702000251
Here, T2 AAbove-mentioned thermal diffusivity evaluating apparatus shown in Figure 1 is adopted in expression, the coating decoration material temperature when measuring coating decoration material of the present invention as measured body; T2 BThe same thermal diffusivity evaluating apparatus that adopts above-mentioned Fig. 1 of expression, the substrate temperature when not being covered the substrate of filming as the measured body use.In addition, Δ T1 and preceding described identical mensuration.And, the temperature when calculate using measured material and adopting do not impose film do not cover with paint, lacquer, colour wash, etc. raw sheet the time poor (the Δ T2) of temperature.
In addition, Δ T2 measures 5 times each measured material, wherein, 3 data mean value removing upper and lower bound is decided to be Δ T2 among the present invention.
Compare with adopting substrate (not lining film exposed raw sheet) time, when adopting coating decoration material of the present invention, above-mentioned Δ T2 is decided to be the index (property cooled off certainly) that coating decoration material self temperature in the time of whether suppressing the electronic machine running rises, in the present invention, as the device of measuring Δ T2, adopt the thermal diffusivity evaluating apparatus of uniqueness of the present invention shown in Figure 1.
In order to obtain good cooling certainly, above-mentioned Δ T2 is the bigger the better.The preferred sequence of Δ T2 is more than 1.0 ℃, more than 1.5 ℃, more than 2.0 ℃, more than 2.5 ℃.
(IV) formula (4): b≤0.9 (a-0.05)
In the formula, the measuring method of the implication of a and b and infrared rays integration emissivity is identical with above-mentioned (II) record.
As mentioned above, above-mentioned (4) also are effective as the index of " property cooled off certainly " that suppress the rising of coating decoration material self temperature.Following formula is based on the thought of " comparing with the inside (electronic machine private side) of substrate; by imposing high the filming of infrared emission rate of substrate surface (outside); suppress the rising of coating decoration material self temperature ", can guarantee specific the forming of relational expression of infrared emission rate of surface, the inside of required cooling certainly (Δ T2 〉=0.5 ℃).
When coating decoration material was used for the basket of electronic machine, if improve the infrared emission rate of basket inside face (the inside), the infrared ray absorption amount of emitting from the electronic machine endogenous pyrogen increased, and the temperature of coating decoration material self rises.On the other hand, if improve the emissivity of basket outside (surface), increase to the infrared rays discharging amount that the outside emits from coating decoration material, the temperature of coating decoration material also reduces.The present invention is based on this discovery, repeat various tests, determined following formula, according to the present invention, by comparing, from the face side radiating heat increase of substrate with the heat that is absorbed (radiation) by the inside of substrate, therefore, the temperature that can more effectively suppress coating decoration material self rises.
With the inside different the filming of heat dissipation characteristics is set on the surface of substrate like this, keeps the level of heat dissipation characteristics to a certain extent, and the coating decoration material that has also suppressed the rising of coating decoration material temperature is ignorant at present, is novel.
Therefore, in above-mentioned second coating decoration material, the difference of the infrared emission rate of a and b is big more, can access good cooling certainly more.Specifically, above-mentioned Q value (=0.9a-b) being the bigger the better, preferred order is more than 0.13, more than 0.24, more than 0.35, more than 0.47.
(V) formula (5): (a-0.05) * (b-0.05) 〉=0.08
Following formula (5) is according to the index of the heat dissipation characteristics of long-pending specific second coating decoration material of the infrared rays integration emissivity of table the inside, and the calculated value of the left side [(a-0.05) * (b-0.05)] (following sometimes with the representative of R value) is big more, and expression heat dissipation characteristics (Δ T1) is good more.Preferred lower limit is 0.35 (about 2.6 ℃ of Δ T1), 0.52 (about 3.5 ℃ of Δ T1) in order.
Following formula (5) and above-mentioned Δ T1 (" the electronic machine internal temperature poor " that illustrate in first coating decoration material) have good correlationship.As a reference, the result of aftermentioned embodiment is made chart, as shown in Figure 7.
The level of the level of the heat dissipation characteristics of above-mentioned second coating decoration material (if be converted into Δ T1, Δ T1 〉=1.5 ℃) and first coating decoration material (Δ T1 〉=2.6 ℃) is compared, and tolerable limit is wide.This is based in second coating decoration material, and with improving from the property cooled off as mainly solving problem and being disclosed, as long as finish this problem, the level that comprises heat dissipation characteristics is compared the discovery of low slightly scheme and fixed with first coating decoration material.
Below the concrete formation that is used to obtain above-mentioned second coating decoration material is described.
Above-mentioned coating decoration material be covered on the table of substrate the inside and films, and is covered on the surface at least of substrate and has the cooling coating film of thermal diffusivity.In order to ensure required cooling certainly, compare with the inside, improve the infrared emission rate on surface, must satisfy following formula (4), and heat dissipation characteristics must satisfy following formula (5) at least.In the second such coating decoration material, for make the surface different with the level of the desired heat dissipation characteristics in the inside, below the branch situation describe.
At first, " cooling coating film on surface " of above-mentioned second coating decoration material comprises following (i) and scheme (ii).
(i) mainly add the black additive, be coated with based on relation control heat radiation with the thickness of filming (Y) The scheme of contained black additive (X) in the film
In the filming of surface, add the black additive with under the situation that improves heat dissipation characteristics,, can suitably control X and Y for addition (X) and the coating thickness (Y) that makes the black additive satisfies following formula (6).Particularly as shown in the formula 4.～6..
4. formula (6): (X-3) * (Y-0.5) 〉=3
Following formula (6) is the X that determines for the target value that realizes the thermal diffusivity in second coating decoration material (Δ T1 〉=1.5 ℃) and the relational expression of Y, the P value [=(X-3) * (Y-0.5)] big more, good heat dissipation characteristics can be obtained more.Preferred order is more than 7, more than 11, more than 15, more than 30, more than 50.
But, even further increase the P value, heat dissipation characteristics is saturated, the amount by the black additive that increase to use etc. only, except wasting economically, if the basket of coating decoration material of the present invention as electronic machine used, consider also to require processibility or electroconductibility etc., recommend the P value upper limit is controlled to be 240,200,150,100 according to preferred sequence.
In addition, the lower value of the formula (2) of defined is compared little in the lower limit of following formula (6) and first coating decoration material.This is to compare the low slightly scheme of heat dissipation characteristics level of second coating decoration material, so tolerable limit expansion because can comprise with first coating decoration material.
5. formula (7): 4%≤X＜15%
, be recommended as more than 4% being prerequisite more than 3% with black content of additive X.Here, be that prerequisite is that the coefficient on this formula left side (X-3) just is being necessary for (＞0) because in order to satisfy following formula (6) with " X＞3% ".
In addition, the lower limit of following formula X is to determine in order to guarantee coating decoration material self characteristics (covering with paint property, outward appearance etc.) when obtaining good heat dissipation characteristics, can not get required characteristic when following 3%.Preferred lower limit is 5%, 7%, 8% and 10% in order.On the other hand, the upper limit of X with the relation of heat dissipation characteristics in be not particularly limited, if but more than 15%, covering with paint property variation then produces and applies unevenly, and bad order takes place.Therefore, the preferred upper limit of consider covering with paint, lacquer, colour wash, etc. property etc. is less than 15%, 13% and 11% in order.
6. Y＞1 micron
The coating thickness Y of cooling coating film recommends more than 1 micron to be prerequisite more than 0.5 micron.Here, with " Y＞0.5 micron " be prerequisite because in order to satisfy following formula (6), the coefficient on this formula left side (Y-0.5) just is being necessary for (＞0).
The lower limit of following formula Y is definite in order to obtain good especially heat dissipation characteristics, and Y even increase the black additive, also can't obtain required radiating effect below 0.5 micron the time.Preferred lower limit is 3 microns, 5 microns, 7 microns, 10 microns in order.
In addition, the upper limit of following formula Y with the relation of heat dissipation characteristics in be not particularly limited, still, the purpose of coating decoration material of the present invention is to be used for electronic instrument part, based on the relation of this purposes, also require to improve processibility; If particularly consider when bending machining, to prevent the crack or peel off etc. of filming, recommend to be controlled at (is below 45 microns, below 40 microns, below 35 microns, below 30 microns according to preferred order) below 50 microns.
When possessing good processibility,, recommend above-mentioned Y is controlled at (according to preferred order is below 11 microns, further preferred below 10 microns) below 12 microns in order to ensure good electroconductibility.
(ii) mainly add the scheme of other additive outside the black additive
In order to improve the heat dissipation characteristics of surface coatings, when the additive that uses except that the black additive,, can enumerate for example TiO as these other additives 2, pottery, ferric oxide, aluminum oxide, barium sulfate, silicon oxide etc.These can use a kind of or two or more.Can also add black additives such as carbon black.In order to obtain required heat dissipation characteristics, the thickness of above-mentioned cooling coating film can be determined suitable thickness according to the kind of the additive that uses etc., is recommended as 15～30 microns usually.
Particularly, containing TiO 2Film the time, in filming, can add general 50～70% titanium oxide, recommend to make the thickness of filming be about 25～30 microns.And, when imposing metal and transfer filming of outward appearance, recommend to add about 5～30% Al scale etc., make coating thickness be about 5～30 microns.
Then, " the filming of the inside " to second coating decoration material of the present invention describes.Above-mentioned " surface film " must be cooling coating film in order to ensure good cooling certainly, and still, " filming of the inside " is just passable as long as can access the characteristic that second coating decoration material disclosed, and needn't be cooling coating film.Promptly, in above-mentioned second coating decoration material, the inside that is not included in substrate does not impose " single face coated steel plate " (the infrared emission rate of the raw sheet of not filming is roughly 0.04, can't obtain required cooling certainly) of filming, as long as but satisfy following formula (4), can adopt arbitrarily and film.
Particularly, separately or and with other additive outside above-mentioned black additive, the black additive, according to the emissivity of surface coatings, suitably adjust addition and the thickness of filming, filming inside can forming.And, when adopting the black additive to form filming of the inside, the relation of above-mentioned X and Y needn't necessarily satisfy above-mentioned (6) formula, even almost there is not film (above-mentioned P value is less than 0) of thermal diffusivity, as long as the infrared emission rate of surface coatings is suitably controlled, can guarantee required cooling certainly (referring to the No.1 and 11 of table 6 described later).
Perhaps, can also adopt and do not add the above-mentioned additive and film (referring to the No.3 and 7 of described later table 6) of film thickness monitoring that will film fully at given range (about more than 2.5 microns).This is because only by resin contained in filming, and just can obtain heat dissipation characteristics to a certain degree.
Particularly, for example when forming resin as filming and adopt non-hydrophilic polyester based resin, the thickness of filming can be adjusted to roughly more than 2.5 microns.
More than for the black additive of filming/other additive that forms surface, the inside in second coating decoration material of the present invention, its basic comprising has been described.In addition, in above-mentioned filming, the kind and the median size of the black additive of use; The kind of the additive outside the black additive; Film the resin of interpolation and the kind of additive etc. according to illustrated in above-mentioned first coating decoration material.
(the third) in the coating decoration material of above-mentioned (first) and (second), improved the electronic instrument of electroconductibility again Device parts coating decoration material (the 3rd coating decoration material)
The 3rd coating decoration material of the present invention also has better electroconductibility, as its index, sets below resistance 100 Ω.Be preferably below 10 Ω.
Here, the measuring method of resistance is as follows.
The electroconductibility determinator uses Mitsubishi Chemical's system " Roresta EP ", and detector uses Mitsubishi Chemical's system 2 probe detectors (MCP-TO01).During mensuration, in the middle of the probe and working sample of detector, with mutually non-touching mode place two thick 0.8mm, size is the square copperplate of 20mm, measures the impedance (Ω) of measured material.
When obtaining high conductive coating decoration material, in the filming of the surface and/or the back side, contain 10～50% electroconductive stuffing.And, coating decoration material of the present invention is covered on any one the table the inside of substrate of first coating decoration material, second coating decoration material and films, if all add electroconductive stuffing on surface and two sides, the inside, can obtain very good electroconductibility, but,, also can only on single face, add electroconductive stuffing according to purposes, even like this, also can guarantee the electroconductibility of defined.
Here, electroconductive stuffing used in the present invention can be enumerated metal monomers such as Ag, Zn, Fe, Ni, Cu; Metallic compounds such as FeP.Wherein preferred especially Ni.And its shape is not particularly limited, and still, in order to obtain better electroconductibility, recommends to use lepidiod material.
And, the content of above-mentioned electroconductive stuffing (is meant except that base resins such as vibrin for forming composition with respect to filming, also comprising as required the linking agent and black additive and the electroconductive stuffing that add, and the formation of the additive that adds the as required all the components of filming) 100% (being converted into solid substance) be 10～50%.Less than 10% o'clock, can not get required effect.Be preferably more than 15%, more preferably more than 20%, further preferably more than 35%.On the other hand, the content of electroconductive stuffing surpasses at 50% o'clock, and processibility reduces.Particularly, when covering with paint, lacquer, colour wash, etc. metal sheet and require the position of height bendability like that, be recommended in below 45% being used for.More preferably below 40%, further preferably 35%.
More than describe in detail for giving filming of coating decoration material feature of the present invention.As mentioned above, the most important main points of the present invention are to make to film to have specific formation, and the substrate outside filming is not particularly limited.Therefore, the present invention uses substrate to exemplify, 1. be metal sheet typically, steel plate class, known metal sheets etc. such as the steel plate of various metals such as cold-rolled steel sheet, hot-rolled steel sheet, electrogalvanizing steel plate (EG), hot-dip galvanized steel sheet (GI), alloy galvanized steel plate (GA), 5% plating Al-Zn steel plate, 55% plating Al-Zn steel plate, plating Al, stainless steel plate are suitable for all specifically, in addition, 2. the substrate outside the metal sheet is specially wire rod, bar, tubing, stupalith etc.Wherein, electrical good metallic substance such as metal sheet, the pottery of preferred thermal conductance.
In addition, to improve erosion resistance, to improve the adherence of filming etc. is purpose, above-mentioned metal sheet 1. also can carry out surface treatments such as chromate treating or phosphatizing, consider environmental pollution etc., also can use and implement the metal sheet that non-chromate is handled, any mode includes within the scope of the present invention.
Here, the structure that the coating decoration material of the present invention that metal sheet that non-chromate handles obtains has been implemented in use describes.
At first, aforesaid substrate has implemented not contain the bottom layer treatment of chromium, and cooling coating film (surface at least) is necessary further to contain rust-preventive agent.The known non-chromate that carries out is generally speaking handled then erosion resistance reduction, and in order to improve erosion resistance, the use of rust-preventive agent is indispensable.
Here, above-mentioned " bottom layer treatment that does not contain chromium " there is no particular limitation, can carry out normally used known bottom layer treatment usually.Particularly, recommend to adopt individually or simultaneously the bottom layer treatment of phosphoric acid salt, silica-based, titanium class, zirconium class etc.
In addition, as rust-preventive agent, for example silicon-dioxide compounds, phosphoric acid salt compound, phosphite compounds, polyphosphate compounds, sulphur class organic compound, benzotriazole, tannic acid, molybdate compounds, tungstates compound, vanadium compounds, silane coupling agent etc., these materials can use separately or use simultaneously.Especially preferably use silicon-dioxide compounds (for example calcium ion-exchanged silicon-dioxide etc.) and phosphoric acid salt compound, phosphite compounds, polyphosphate compounds (for example three Tripyrophosphoric acid aluminium etc.) simultaneously, recommend with the silicon-dioxide compounds: the mass ratio of (phosphoric acid salt compound, phosphite compounds or polyphosphate compounds) is 0.5～9.5: use simultaneously in the scope of 9.5～0.5 (more preferably 1: 9～9: 1).By being controlled in this scope, can guarantee required erosion resistance and processibility two aspects.
In addition, these rust-preventive agent also can be used for above-mentioned bottom layer treatment.
By using above-mentioned rust-preventive agent can guarantee erosion resistance, on the other hand, also known because interpolation rust-preventive agent causes processibility to reduce.Therefore in the present invention, formation composition as cooling coating film, particularly be careful the combination of resin and linking agent, recommendation be used in combination epoxide modified polyester resin and/or in skeleton, introduced amphyl polyester resin and linking agent (preferred isocyanate resinoid and/or trimeric cyanamide resinoid more preferably use both simultaneously).
Wherein, epoxide modified polyester resin and in skeleton, introduced amphyl polyester resin (for example in skeleton, having introduced the polyester resin of dihydroxyphenyl propane etc.) compare with polyester resin, the erosion resistance and the adherence of filming are good.
On the other hand, the isocyanates linking agent has the effect that improves processibility and (is meant the effect that improves the outward appearance after processing, in aftermentioned embodiment, estimate with the fracture number in the adherence pliability test), also can guarantee good processibility even therefore add rust-preventive agent.
In addition, the melamine class linking agent has superior corrosion resistance and is able to clearly by the inventor's discussion result.Therefore, in the present invention,, can access very good anti-corrosion by using above-mentioned rust-preventive agent simultaneously.
Among the present invention, also above-mentioned isocyanates linking agent and melamine class linking agent can be used separately,, processibility and erosion resistance can be further improved if use both simultaneously.Specifically, with respect to isocyanic ester 100 mass parts, recommend to contain the trimeric cyanamide resinoid with the ratio of 5～80 mass parts.When the trimeric cyanamide resinoid is lower than 5 mass parts, can not get required erosion resistance, on the other hand, when the trimeric cyanamide resinoid surpasses 80 mass parts, adding the effect of isocyanic ester resinoid generation can not bring into play well, can not get the effect of required raising processibility.Be more than 10 mass parts, below 40 mass parts more preferably, more than further preferred 15 mass parts, below 30 mass parts with respect to the isocyanic ester resinoid.
In addition, the ratio for the resin, rust-preventive agent, linking agent, black additive and the electroconductive stuffing that constitute the above-mentioned formation composition of filming describes in following " coating composition ".
Satisfy the coating decoration material erosion resistance of this formation, the adaptation of filming and excellent processability.Specifically, about erosion resistance, the area occupation ratio that satisfies the unusual position of outward appearance (paint blister, get rusty etc.) of the salt spray testing corrosion resistance test of stipulating among the JIS-Z-2371 (72 hours) is (more preferably below 5%) below 10%.The kind of the linking agent that uses by suitable control (for example add separately specified rate for improving the useful melamine class linking agent of erosion resistance), perhaps adopting with the stripping that suppresses rust-preventive agent is purpose implements to film on the filming structure of (preferably transparent is filmed) formation two coating films etc., further improve above-mentioned characteristic, the unusual area occupation ratio of outward appearance that the result satisfies more severe test (the salt spray testing corrosion resistance test of stipulating among the JIS-Z-2371 (120 hours)) is (more preferably below 5%) below 10%.
And film adherence and processibility of above-mentioned coating decoration material is also good.Here, " adherence of filming ", " processibility " all possess common character on " good appearance after the processing " this point, in the present invention, particularly for " processibility ", adopt " crack (be full of cracks) of the adherence pliability test of regulation is several among the JIS K 5400 " to estimate that (fracture number that coating decoration material of the present invention satisfies in the above-mentioned adherence pliability test is below 5, following below 2, further preferred 0), on the other hand, " adherence of filming " usefulness " adherence of filming of processing part " is estimated.
And, except above-mentioned characteristic (erosion resistance, the adherence of filming and processibility), also want to guarantee the occasion of electroconductibility, can in filming, add electroconductive stuffing, thereby can controlling resistance be below 100 Ω.The optimal way of the electroconductive stuffing that uses as mentioned above.In addition, if add electroconductive stuffing in filming, then erosion resistance reduces, but by the gauge control of will film more than 2 μ m, even do not contain the coating decoration material of chromium, also can guarantee erosion resistance and electroconductibility.More preferably more than the 3 μ m, further more than the preferred 5 μ m.On the other hand, its upper limit recommends to be controlled at 12 μ m following (more preferably 10 μ m are following) as mentioned above.
More than, the coating decoration material of the present invention that metal sheet that non-chromate handles obtains has been implemented in use be illustrated.
More than Shuo Ming coating decoration material of the present invention for the individual layer substrate being implemented film by membrane structure, but the present invention comprises that also multilayer that further covering films more than a kind or 2 kinds obtains is by the mode of membrane structure thereon.Particularly in the present invention,, particularly use the occasion of black coating film, recommend to be formed on the structure that imposes the two-layer tunicle of transparent coating on this black coating film in order to give anti-defect and anti-finger printing.Because black coating film is with the black covering with paint of dark color system, there is the shortcoming that stays fingerprint when taking easily with hand, visual appearance descends, and still, by forming transparent coating, has improved anti-finger printing.And, even on black coating film, produce flaw,, also exist and eliminate the such advantage of this flaw by imposing transparent coating.
Here, in order to keep required characteristic (heat dissipation characteristics/property cooled off) certainly, improve anti-defect and anti-finger printing simultaneously, the thickness of control transparent coating is important, when also making it to have good electroconductibility except thermal diffusivity, the preferable range of this transparent coating thickness changes.
That is to say, during filming, do not add the occasion of the coating decoration material of electroconductive stuffing,, improve anti-defect and anti-finger printing simultaneously, advise that film thickness monitoring with transparent coating is at 0.1～10 μ m in order to keep the property cooled off of good heat dissipation characteristics/certainly.During less than 0.1 μ m, the effect that can't obtain to improve anti-defect and anti-finger printing.More preferably more than 0.2 μ m, further preferably more than 0.3 μ m.But even thickness surpasses 10 μ m, the effect that improves anti-defect etc. reaches capacity, and only increases the tunicle cost, and is uneconomical, therefore preferably is limited to 10 μ m on it.More preferably below the 8 μ m, further preferably below 7 μ m.
On the other hand, in filming, add the occasion of the coating decoration material of electroconductive stuffing, be necessary to keep heat dissipation characteristics/certainly property cooled off and good electrical conductivity, improve anti-defect and anti-finger printing simultaneously, for this reason, suggestion with the film thickness monitoring of transparent coating at 0.1～3.0 μ m.During less than 0.1 micron, the effect that can't obtain to improve anti-defect and anti-finger printing.More preferably more than 0.2 μ m, further preferably more than 0.3 μ m.But, if thickness is blocked up, electroconductibility there is detrimentally affect, therefore, preferably make and be limited to 3.0 μ m on it.More preferably below the 2.0 μ m, further preferably below 1.5 μ m.
As mentioned above, form two coating film structures by on filming, covering transparent coating, compare, can improve anti-defect significantly with the individual layer coating structure that constitutes separately of filming, aspect the irrealizable raising anti-finger printing of this individual layer coating structure, the formation of transparent coating is very effective simultaneously.
Here, the resin as constituting above-mentioned transparent coating is not particularly limited, and the resin that can form transparent coating is all included.Particularly, can enumerate acrylic resin, urethane is resins such as resin, polyolefin-based resins, vibrin, fluorine resin, silicone resin, and the mixing of these resins or modified resin etc.In transparent coating, in the scope of not damaging effect of the present invention, can further add additives such as linking agent, wax, matting agent.Thus, can adjust the oilness of filming and intensity etc. at an easy rate, the result can further improve anti-defect.As the additive that uses among the present invention, so long as normally used and material that can effectively bring into play above-mentioned effect gets final product in filming, be not particularly limited, can enumerate for example is that trimeric cyanamide is that linking agent, blocked isocyanate are linking agents such as linking agent.
In addition, as mentioned above, also comprise to coating decoration material of the present invention implement to film but not multilayer that transparent coating obtains by the material of membrane structure, at this moment, can in resin that constitutes above-mentioned transparent coating and additive, further add pigment such as tinting pigment etc.
And in the present invention, the coating composition that contains black additive 3 mass parts and electroconductive stuffing 10～50 mass parts with respect to the formation composition of filming is also included within the scope of the present invention.Wherein, the important document (preferred Ni) of important document of above-mentioned black additive (preferred carbon black is controlled at 5～100nm with median size, and the relation of content and coating thickness recommends to satisfy the relation of above-mentioned formula) and electroconductive stuffing be described in detail above identical.If use coating composition of the present invention, can form thermal diffusivity and high conductive filming, therefore be particularly suitable for acting on the coating of electron gain instrument component with coating decoration material.
In addition, coating composition as the substrate that is applicable to the bottom layer treatment of having implemented not contain chromium, contain epoxide modified polyester resin and/or in skeleton, introduced amphyl more than polyester resin 35 mass parts (more than preferred 40 mass parts, more preferably more than 45 mass parts), rust-preventive agent 2～25 mass parts are above (more than preferred 3 mass parts, below 20 mass parts, more preferably more than 4 mass parts, 15 mass parts are following), linking agent 1～20 mass parts is (more than preferred 2 mass parts, below 18 mass parts, more than following 3 mass parts, 15 mass parts are following), the coating composition that the black additive surpasses 3 mass parts and electroconductive stuffing 10～50 mass parts is also included within the scope of the present invention.Wherein, the preferred important document of the preferred important document of above-mentioned linking agent (preferably with respect to isocyanates linking agent 100 mass parts, containing the melamine class linking agent with the ratio of 5～80 mass parts), above-mentioned black additive and the preferred important document of electroconductive stuffing are as mentioned above.If use coating composition of the present invention, what can form thermal diffusivity, electroconductibility, erosion resistance, the adherence of filming and excellent processability does not contain filming of chromium, therefore can be with the coating that acts on electron gain instrument component coating decoration material, particularly do not contain the coating that the coating decoration material of chromium is used.
Then, the method for making coating decoration material of the present invention is described.Coating decoration material of the present invention can be coated in the coating that contains mentioned component on the surface of substrate and carry out drying and make according to known coating method.Coating method is not particularly limited, for example can enumerate in the clean surface, and impose as required and adopt rolling method, spraying method, curtain coating method to wait on the elongated metal belt surface of covering with paint, lacquer, colour wash, etc. pre-treatment (for example phosphatizing, chromate treating etc.) to apply coating, carry out exsiccant method etc. by hot-air drying stove.Take all factors into consideration homogeneity and processing cost, the covering with paint efficient etc. of coating thickness, preferred rolling method on reality is used.
And, when using resin to cover with paint, lacquer, colour wash, etc. metal sheet,,, can impose phosphatizing or chromate treating as covering with paint, lacquer, colour wash, etc. pre-treatment in order to improve adherence or the erosion resistance with resin coating as substrate.But, for the chromate treating material, the stripping property angle of chromium from the resin coating decoration material uses, the Cr adhesion amount is controlled at 35mg/m during with chromate treating 2Below for well.This be because, if in scope, with regard to may command from substrate chromate treating layer stripping chromium.And, the water-fast adherence that the existing facial ornament that is provided with the chromate treating material is as required covered with paint, lacquer, colour wash, etc. is accompanied by the stripping of 6 valency chromium, and the tendency of reduction is arranged under wet environment, but owing on above-mentioned metal sheet, suppressed stripping, therefore, the water-fast adherence of the tunicle of covering with paint does not worsen.
Perhaps, if adopt the above-mentioned bottom layer treatment that do not contain chromium of enforcement such as roller painting, spraying method, impregnating process, can access non-chromate type coating decoration material.
And the present invention is also included within the electronic instrument part of the built-in heating element of seal cavity, and promptly the whole or a part of of this its outer wall of electronic instrument part are made of with coating decoration material above-mentioned electronic instrument part.As above-mentioned electronic instrument part, can enumerate information record goods such as CD, LD, DVD, CD-ROM, CD-RAM, PDP, LCD; The goods that electrical equipment such as computer, カ-Na PVC, カ-AV, electronics, communication are correlated with; AV machines such as projector, TV, video recorder, game machine; Duplicating machine such as duplicating machine, printing press; The power supply box shell of air-conditioner outdoor unit etc., controlling box shell, vending machine, refrigerator etc.
And, in the present invention, comprise the thermal diffusivity evaluating apparatus of estimating the Board Under Test thermal diffusivity, promptly constitute by above-mentioned measured body the whole or a part of of its top, on the bottom surface of the casing that side and bottom surface are made of thermal insulation material heating element is set, and, the thermal diffusivity evaluating apparatus of temperature measuring equipment partly is set in the box house substantial middle.Above-mentioned Fig. 1 is its typical example.And, for fear of coming from the outside or the influence of the wind of air-conditioning etc. etc., obtaining stable data, the protecting component that blocking-up external conditions is set above above-mentioned measured body is preferred scheme.
Typical example such as Fig. 8 and shown in Figure 9 with this device.Wherein, Fig. 8 represent will casing the sketch of the thermal diffusivity evaluating apparatus that partly covers with protecting component of top; Fig. 9 represents the sketch of thermal diffusivity evaluating apparatus that casing is all covered with protecting component.According to Fig. 9, can block the influence that the external world brings fully, therefore useful.Certainly, these devices are typical example only, the unqualified meaning in these devices of determining.
Among the figure, 1 expression measured body (will estimate the sample of thermal diffusivity), 2 expression thermal insulation materials, 3 expression heating elements, 4 expression protecting components (cover), 5 expression temperature measuring equipments.Thermal diffusivity evaluating apparatus of the present invention has box structure, and its side and bottom surface are made of thermal insulation material 2, in the bottom surface of casing heating element 3 is set, and at box house substantial middle position temperature measuring equipment 5 is set, and the outside of device is covered by protecting component 4.And, when ambient conditions is necessarily measured, above-mentioned protecting component is not set, this scheme be illustrated as above-mentioned Fig. 1.As long as above-mentioned protecting component can be blocked extraneous, be not particularly limited, for example, can use plastics, timber, metallic substance etc.
Above-mentioned temperature measuring equipment 5 is devices of envrionment temperature that can determinator inside, in order correctly to measure this temperature, recommends suitably its position of control.Particularly, for the heating element 3 that is arranged on the bottom surface, be L with the longest straight line that draws (mm); Floorage (mm with heating element 3 2) be S; The height (mm) that arrives temperature measuring equipment 5 with heating element 3 is HT; When be H to the height (mm) of measured body 1, recommend to control it and satisfy L/H=0.7～2.8 with heating element 3; S/H 2=0.25～4; The relation of HT/H=0.3～0.7.This is because if outside these scopes, the precision of data reduces.As a reference, in Figure 10, illustrate above-mentioned L, S, H TRelation with H.
Further describe the present invention according to embodiment below, still, the following examples do not limit the present invention, in the scope that does not break away from thought of the present invention, change and implement all to comprise in the present invention.
[embodiment]
1～4 pair of first coating decoration material of the present invention/the 3rd coating decoration material of the following examples has been estimated the various characteristics based on thermal diffusivity etc.Wherein, embodiment 1～3rd, at imposing the coating of equivalent and impose that the coating decoration material of the cooling coating film of same thickness carries out on the table of substrate the inside, embodiment 4 is at having changed the kind of adding the coating in the substrate table the inside to and amount etc., and the coating decoration material that imposes the cooling coating film of different emissivities on the table the inside carries out.
Embodiment 1: to the evaluation of first coating decoration material (not adding electroconductive stuffing) thermal diffusivity
In the present embodiment, estimate the heat dissipation characteristics of first coating decoration material of the present invention.
At first, steel plate (thickness of slab 0.6mm) with electro-galvanizing is a raw sheet, on its table the inside, apply equivalent and added the coating of the carbon black (median size 25nm) of the specified rate shown in the table 1 (base resin employing vibrin, linking agent adopts melamine resin), carry out sintering afterwards, drying is made each test materials (120 * 150mm) of No.1～23.In addition, in order to compare, the raw sheet that the nothing that does not impose coating is covered with paint, lacquer, colour wash, etc. carries out same processing.
Each test materials for this preparation, adopt the device of Fig. 1, based on aforesaid method, temperature when measuring the integration emissivity of infrared rays (wavelength: 4.5～15.4 microns) and Δ T1[and adopting each test materials of No.1～32 and the temperature when adopting the test materials (not covering with paint, lacquer, colour wash, etc. raw sheet) of comparative example poor].And the infrared emission rate is put down in writing data when being heated to 100 ℃ and the data when being heated to 200 ℃ simultaneously.
In addition, Δ T1 is the bigger the better, and the expression heat dissipation characteristics is good more, carries out relative evaluation with following benchmark.First coating decoration material of the present invention with ◎ and ● coating decoration material estimate as " this coating decoration material has been brought into play good radioactivity ".
◎：3.5≤ΔT1
●：2.7≤ΔT1＜3.5
○：1.5≤ΔT1＜2.7
△：1.0≤ΔT1＜1.5
×：ΔT＜1.0
Table 1 is charged in the result's merging that obtains, simultaneously the relation of the addition (*) of graphical presentation carbon black and thickness (Y) that film in Figure 12.Among the figure, ◎, ●, zero, △ and * represent above-mentioned metewand.
[table 1]
As shown in Table 1, the heat dissipation characteristics of the coating decoration material (No.1～2) of discontented unabridged version invention key element is all poor, relative therewith, and the heat dissipation characteristics of coating decoration material (No.3～23) that satisfies key element of the present invention is all good.
Though not expression in the table, but, having surpassed preferable range of the present invention (less than 15%) at the content X of carbon black is 18% o'clock, even increase the thickness Y to 1 that films, 10,18 microns, be controlled in the scope of following formula (2) [=(X-3) * (Y-0.5) 〉=15], apply inequality significantly, be difficult to homogeneous and apply.
The evaluation of 2: the three coating decoration material (having added electroconductive stuffing) thermal diffusivities of embodiment and electroconductibility
In embodiment 1, the coating of substitution list 1 record, the coating a that use is formed below (composition of resin is identical with embodiment 1) in addition, similarly to Example 1, makes the test materials (120 * 150mm) of No.1～2 of table 2.
Coating a (having added electroconductive stuffing)
Making the resin of embodiment 1 record is 65%, and as the black additive, making the carbon black of median size 25nm is 10%, and as electroconductive stuffing, making flakey (1 micron of thickness, size are 15～20 microns) Ni is 25%.Each test materials to such preparation passes through aforesaid method, measures the integration emissivity of infrared rays (wavelength: 4.5～15.4 microns), rangeability, Δ T1 and the resistance (electroconductibility) of emissivity.
As existing steel plate, employing forms black and changes into the processing tunicle on the table the inside of the steel plate of plating Zn-Ni alloy, only from the teeth outwards, the coated steel plate (No.3 of table 2) of the transparent coating that is covered thereon again, same as described above, estimate various characteristics.When this steel plate changes into the processing tunicle at formation black, carry out the metallide processing and be prepared.
In addition, in order to compare, also the raw sheet of not covering with paint, lacquer, colour wash, etc. that does not impose coating is estimated various characteristics (No.4 of table 2) equally.
Its result puts down in writing in table 2.And, in Figure 13～16, the No.1,2 of table 2,3 and 4 Infrared wavelength and the graphic that concerns of infrared emission rate are represented.
[table 2]
By table 2 and last figure as seen, the coating decoration material (No.1～2) that satisfies key element of the present invention satisfies the rangeability of infrared emission rate, emissivity and all key elements of the present invention of Δ T1, and heat dissipation characteristics is good.
Relative therewith, No.3 is to use the example of existing black steel sheet (do not use black additive such as carbon black and impose black handle), still, owing to do not use the black additive, and do not contain conducting fibre, therefore can't obtain required heat dissipation characteristics and electroconductibility.
In addition, the long-pending of the infrared emission rate of the raw sheet of Tu Shiing (No.4) is not 0.0016, can't see heat dissipation characteristics fully.
The thermal diffusivity of 3: the-coating decoration material of embodiment/the 3rd coating decoration material, electroconductibility, anti-finger printing and anti- The evaluation of defect
In the present embodiment, in order determine to form the anti-finger printing that transparent coating causes and the raising effect of anti-defect, and the raising effect that adds the electroconductibility that electroconductive stuffing produces, test.
Particularly, (thickness of slab 0.6mm) is raw sheet with electrogalvanizing steel plate, on its table the inside, apply and added carbon black [content (X) all is 10%] with the various median sizes shown in the table 3 and 0～40% flakey Ni (1 micron of thickness as bottom-coating equivalent, 15～20 microns of width) coating (adopts vibrin as base resin, use melamine resin as linking agent), then, sintering, and dry, prepare various test materialss (120 * 150mm) (the no transparent coatings) of No.1～11 of table 3 thus.
And then, in order to confirm to form the anti-defect that transparent coating causes and the raising effect of anti-finger printing, after applying above-mentioned coating, apply transparent polyester based resin, then, carry out sintering and drying, thus, each test materials (120 * 150mm) (transparent coating is arranged) of No.12～22 of preparation table 3.Wherein, No.12～14th do not add the example as the Ni of electroconductive stuffing.
Adopt the method identical to estimate thermal diffusivity and electroconductibility to each test materials that obtains like this with embodiment 1, simultaneously, according to following main points evaluation anti-finger printing and anti-defect.Electroconductibility is carried out relative evaluation according to following benchmark.
◎: below outstanding resistance 10 Ω
Zero: good resistance 10～100 Ω
*: more than difference resistance 100 Ω
[anti-defect]
Adopting end diameter is the round shape press of 110mm, the about 50mm of punching hole diameter, and each test materials is suppressed test, and the flaw situation of the slipper that detects by an unaided eye is according to following benchmark evaluation.In addition, punching hole diameter is adjusted to gap+40 micron of mould, pressing conditions is speed 40spm, and punching R is 0.5mm.
◎: good (outward appearance does not change)
Zero: vestige is arranged slightly
*: vestige is obvious
[anti-finger printing]
On the surface of each test materials, press 1 second kind of finger, the vestige of visual assessment fingerprint.Metewand is as follows.
◎: vestige that can't see fingerprint
Zero: the vestige that fingerprint is arranged slightly
*: the vestige of fingerprint is obvious
What obtain the results are shown in table 3.In the table, "-" is meant owing to do not add electroconductive stuffing/do not form transparent coating, therefore do not estimate each characteristic.
[table 3]
Can do following research by table 3.
At first, No.1～2nd do not add electroconductive stuffing (Ni) and changes the example of the median size of black additive (carbon black), but, this median size (in 5～100nm), therefore, all can obtain good heat dissipation characteristics because being controlled at preferable range of the present invention.
In addition, the example of carbon black and Ni is contained in No.3～11st in filming, and wherein, key element of the present invention is satisfied in No.3～10, and therefore, heat dissipation characteristics and electroconductibility both sides are good.In addition, the electroconductibility of No.10 is compared with other examples (No.3～9), and reduction is arranged slightly, and this is considered to because coating thickness increases, and the resistance that causes filming increases.
Relative therewith, No.11 since the thickness of black coating film outside the preferred upper limit (below 12 microns), therefore, electroconductibility reduces.
No.12～22nd, the example of covering transparent coating on black coating film.
Wherein, the thickness of No.12～18,21～22 transparent coatings satisfies preferable range of the present invention, and therefore, anti-finger printing and anti-defect are all good.But because electroconductive stuffing is not contained in No.12～14, perhaps because the content of the electroconductive stuffing of No.21 under preferred lower limit of the present invention, therefore, is compared with 23 with the No.15 that contains electroconductive stuffing～21, electroconductibility reduces.In addition, No.22 is the many examples of addition of electroconductive stuffing, though electroconductibility is very good, can determine that processibility reduces (not record in the table).
Relative therewith, because the thickness of the transparent coating of No.19 has surpassed preferred upper limit of the present invention, therefore, electroconductibility is affected.In addition, the thickness of No.20 transparent coating outside preferred lower limit of the present invention, therefore, anti-finger printing and anti-defect reduction.
4: the first coating decoration material/thermal diffusivities of the 3rd coating decoration material of embodiment and the evaluation of electroconductibility
Present embodiment is similarly to Example 1, is determined among the embodiment 1, makes the kind of raw sheet and additive, the emissivity of table the inside carry out the heat dissipation characteristics and the electroconductibility of each test materials of various variations.
Particularly, employing is by the test materials (No.1～30) that constitutes of forming of table 4 and table 5 record.Wherein, the No.19 of table 5 uses the product that plating Zn-Ni alloy steel plate is carried out the black processing as raw sheet; The No.26 of table 5 uses Al plate (1050) as raw sheet; The No.27 of table 5 uses the Cu plate as raw sheet; Other test materialss use steel plate galvanized as raw sheet.The thickness of slab of these raw sheets all is 0.6mm.
In addition, base resin uses vibrin similarly to Example 1, and linking agent uses melamine resin, adopts method similarly to Example 1 to carry out sintering and drying, thus, obtains each test materials (120 * 150mm) of table 4 and 5.
What obtain the results are shown in table 4 and table 5.
[table 4]
[table 5]
By table 4 and table 5 as can be known, the coating decoration material (No.23 of the No.1 of table 4～15, table 5～28) that satisfies key element of the present invention all has good heat dissipation characteristics, emissivity long-pending (in the table, a * b) big more, heat dissipation characteristics is good more.And, the coating decoration material (No.2 of table 4,4,6～7,10,13 of adding Ni in filming; The No.16 of table 5～18,24～26) also has good electroconductibility.
Wherein, the No.23 of table 5～26th added carbon black inside, added additive outside the carbon black on the surface and formed the example of cooling coating film (No.23 is the example that only adds titanium oxide; No.24 mixes the example that adds titanium oxide and ferric oxide; No.25 mixes the example that adds carbon black and acrylic particles; No.26 is the example that only adds the Al scale) owing to satisfied key element of the present invention, therefore bring into play good heat dissipation characteristics.
Relative therewith, the coating decoration material (No.16 of table 5～22,29～30) of discontented unabridged version invention key element is all poor aspect heat dissipation characteristics.The example of single face is only covered with paint, lacquer, colour wash, etc. in the No.18 of table 5～20, the 29th particularly, can't obtain required heat dissipation characteristics.
The following examples 5 are based on the thermal diffusivity and the various characteristics of the property cooled off certainly to second coating decoration material of the present invention/the 3rd coating decoration material evaluation.
The thermal diffusivity of embodiment the 5: the second/the 3rd coating decoration material and the evaluation of electroconductibility
In the present embodiment, similarly to Example 1, the emissivity of measuring among the embodiment a kind to additive, table the inside carries out the heat dissipation characteristics and the electroconductibility of each test materials that various changes obtain, simultaneously by the aforesaid method evaluation from the property cooled off.
Particularly, adopt the test materials (No.1～19) of the composition formation of table 6 record.Wherein, No.17 adopts as raw sheet will plate the steel plate (thickness of slab 0.6mm) of Zn-Ni alloy steel plate black processing, in addition, use electrogalvanizing steel plate (thickness of slab 0.6mm) as raw sheet.All test materialss of base resin all adopt the vibrin identical with embodiment 1, and linking agent uses melamine resin, adopt method sintering and the drying identical with embodiment 1, thus, prepare each test materials (120 * 150mm).
Benchmark below the Δ T1 of expression heat dissipation characteristics adopts carries out relative evaluation.In second coating decoration material of the present invention, ◎, ● and zero coating decoration material is be evaluated as " the good thermal diffusivity of this coating decoration material performance ".
◎：3.5≤ΔT1
●：2.7≤ΔT1＜3.5
○：1.5≤ΔT1＜2.7
△：1.0≤ΔT1＜1.5
×：ΔT＜1.0
And expression is carried out relative evaluation from the Δ T2 of the property cooled off according to following benchmark.Δ T2 is the bigger the better, and the expression heat dissipation characteristics is good more.And in second coating decoration material of the present invention, ◎ and zero coating decoration material are be evaluated as " bringing into play good cooling certainly ".
◎：1.5≤ΔT2
○：0.5≤ΔT2＜1.5
×：ΔT2＜0.5
What obtain the results are shown in table 6 and 7.
[table 6]
[table 7]
As seen from the above table, the coating decoration material (No.1～12) that satisfies key element of the present invention has all kept good heat dissipation characteristics, and, also have good cooling certainly.Particularly, in as oneself formula (4) of the property cooled off index, the Q value (=0.9a-b) brought into play very good cooling certainly considerably beyond the No.1 more than 0.045～8, the Q value is big more, and the property cooled off is good more certainly.
And the coating decoration material (No.1～5,7～9,11～12) that adds Ni in filming also has good electroconductibility.
Wherein, the No.3 of table 6 and 7 be in surface coverage contain filming of carbon black, the film example of (not having additive) of lining only inside; No.6/No.12 is that lining contains filming of carbon black on surface/the inside, inside/and the surface-coated example of filming that contains titanium oxide; No.10 be on table the inside all coated metal transfer the example of filming of outward appearance; No.11 is covered to contain filming of Al scale from the teeth outwards, and lining inside contains the example of filming of carbon black, owing to all satisfy key element of the present invention, therefore has good cooling certainly, and heat dissipation characteristics is also good.
The No.1 of table 6 and No.11 have added the example of carbon black in the filming inside, although do not satisfy following formula (6), owing to satisfy the index [formula (4) and (5)] of the second coating decoration material defined, therefore, property cooled off and heat dissipation characteristics are all good certainly.
Relative therewith, No.13 is the single face coating decoration material that does not impose covering with paint on single face, does not obtain as basic heat dissipation characteristics.Equally, therefore No.14, does not satisfy the formula (5) as the heat dissipation characteristics index because the composition on surface (containing filming of carbon black) does not satisfy following formula (6), does not obtain required heat dissipation characteristics.No.15 does not add additive in the table the inside yet, and coating thickness is thin, therefore, does not obtain required heat dissipation characteristics.
On the other hand, No.16 is the identical example of emissivity of table the inside, does not obtain required cooling certainly.No.17 is the conventional example of adopting the black processing list the inside that uses the same method, and the emissivity of table the inside is identical, therefore, does not obtain required cooling certainly.No.18 is the big example of the inside specific surface emissivity, the property cooled off reduction certainly.
The coating decoration material that following 6 couples of the present invention of embodiment do not contain chromium serves as main research with erosion resistance, the adaptation of filming, processibility and electroconductibility.
Embodiment 6: do not contain the erosion resistance of the coating decoration material of chromium, film driving fit part, workpiece and conduction The evaluation of property
In the present embodiment, on the table the inside of the substrate of the bottom layer treatment of having carried out not containing chromium, impose the coating of equivalent, use the coating decoration material of the cooling coating film that imposes same thickness, estimate above-mentioned various characteristics.
Specifically, (amount that thickness of slab 0.8mm, single face adhere to Zn is 20g/m to use electrogalvanizing steel plate 2) as raw sheet, adopt Japanese Peint system " SarfcoatEC2000 (the Si adhesion amount 50mg/m of Co., Ltd. 2) " the bottom layer treatment that does not contain chromium.Apply the coating composition (base resin of carbon black (10%) and table 8 record as bottom-coating equivalent in its table the inside, linking agent and rust-preventive agent (using the material that forms with 8: 2 mass ratio mixing aluminium triphosphate and calcium ion-exchanged silicon-dioxide)), and (the thickness 1 μ m of flakey Ni in case of necessity, width 15～20 μ m), form cooling coating film, carry out sintering and drying then, make each test materials (120 * 150mm) (no transparent coatings) of the No.23 of table 8 thus, simultaneously, after applying above-mentioned coating, apply transparent polyester based resin, then, carry out sintering and drying, make each test materials (120 * 150mm) (transparent coating is arranged) of No.1～22 of table 8 thus.Wherein, the thickness of cooling coating film all is 8 μ m, and the thickness of transparent coating all is 1 μ m.In addition, No.21 is for adding the example as the Ni of electroconductive stuffing.
For each test materials that obtains like this, adopt the method identical to estimate thermal diffusivity and electroconductibility with embodiment 1, simultaneously, adopt method evaluation anti-finger printing and the anti-defect identical with embodiment 3.Again erosion resistance, the adaptation of filming and processibility are estimated according to following benchmark.
(erosion resistance)
Use above-mentioned each test materials, carried out the salt spray testing stipulated among the JIS-Z-2371 72 hours or 120 hours, measure the area occupation ratio that results from the outward appearance abnormal portion of planar portions on filming (rust, expand) in each elapsed time.With the area occupation ratio of the outward appearance abnormal portion measured like this is that material below 10% is as " example of the present invention ".
(processibility (fracture number))
Above-mentioned test materials is cut into 50 * 50mm, carries out driving fit bending (OT bending) test,, measure this fracture number with the crack of videoscope photo (25 times of multiplying powers) observation bend by the pliability test of regulation among the JIS K 5400.In detail, being determined at the major diameter that exists in the wide visual field of 3mm is the above fracture number of 0.1mm, will add up to the mean value of the fracture number in 10 visuals field to be evaluated as " fracture number "." fracture number " of Ce Dinging is in being be evaluated as below 5 " example of the present invention " like this.
(processibility (adaptation of filming))
After carrying out above-mentioned driving fit pliability test, twine bend, according to the extent of exfoliation of peeling off behind the band of filming, according to the following benchmark evaluation adaptation of filming with band.Evaluation object partly is the wide part of 40mm beyond the 5mm of sample two ends.
Zero: unstripped
△: have slightly and peel off (evaluation portion film peel off in 3)
*: have and peel off (evaluation portion film peel off) more than 4
The result's merging that obtains is documented in the table 8.
[table 8]
Can followingly investigate according to above-mentioned table.In addition, above-mentioned each test materials all has good thermal diffusivity, for the No.1 that has carried out transparent coating～22, confirms to have good anti-finger printing and anti-defect (not record in the table).
At first, it is all good to satisfy erosion resistance, the adaptation of filming and the processibility of coating decoration material (No.2～5,7～14,16～17,21～23) of key element of the present invention.Particularly in above-mentioned coating decoration material, be that the coating decoration material of linking agent and isocyanate-based linking agent is compared with the coating decoration material (No.8,9) of use separately to merge melamine to certainty ratio, above-mentioned characteristic is very outstanding.And, have very superior corrosion resistance at the coating decoration material that imposes transparent coating on the cooling coating film (the above-mentioned coating decoration material except that No.23).In addition, No.8 is that to use melamine separately as linking agent be linking agent (addition 5.5 quality %), and impose the example of transparent coating, but, even confirm not impose transparent coating by test, also have the very outstanding erosion resistance (area occupation ratio of the outward appearance abnormal portion of salt spray testing corrosion resistance test (120 hours) is less than 1%) (not shown in the table) of same degree.
And the electroconductibility of coating decoration material (the above-mentioned coating decoration material except that No.21) of having added electroconductive stuffing Ni is also good.
Relative therewith, the coating decoration material (No.1,6,15,18～20) of discontented unabridged version invention key element has following problem.
At first, No.1 is the example that does not use rust-preventive agent, corrosion-resistant.
No.6 is the few example of amount of resin, and the adaptation of filming and processibility reduce.
No.15,18 and 19 is with respect to the isocyanate-based linking agent, and melamine is the example of containing of linking agent proportional big (being that containing of isocyanate-based linking agent is proportional few), all is that fracture number is many, poor in processability.Particularly melamine is containing of linking agent of proportional very many No.19, can not fully obtain by adding the effect that processibility that the isocyanate-based linking agent causes improves, and it is very many that fracture number becomes, and the adaptation of filming also reduces.
No.20 is to use the example of polyester based resin, and the erosion resistance and the adaptation of filming reduce.
Coating decoration material of the present invention constitutes as mentioned above, therefore can provide and satisfy the desired original characteristic of electronic instrument part (be accompanied by water proof and dust proof etc. guarantee resistance to air loss, miniaturization, lightweight), also possess the novel electron instrument component coating decoration material that reduces this electronic instrument part internal temperature (heat dissipation characteristics) simultaneously; And then, provide and suppressed the also good electronic instrument part coating decoration material of characteristic (property cooled off certainly) that electronic instrument part rises with coating decoration material self temperature.Coating decoration material of the present invention can be used in particular for information record fields such as CD, LD, DVD, CD-ROM, CD-RAM, PDP, LCD; Electrical equipment such as computer, カ-Na PVC, カ-AV, electronics, communication association area etc.; Can be used for AV machines such as projector, TV, video recorder, game machine in addition; Duplicating machine such as duplicating machine, printing press; Various electronic instrument parts such as the power supply box shell of air-conditioner outdoor unit etc., controlling box shell, vending machine, refrigerator.
[several 1]
E ( λ ) = M ( λ , T ) A ( λ ) - K FB ( v ) - K TB ( λ , T TB ) K B ( λ , T ) - K TB ( λ , T TB )
E ( T ) = ∫ λ 1 λ 2 ϵ ( λ ) · K B ( λ , T ) · dλ ∫ λ 1 λ 2 K B ( λ , T ) · dλ
[several 2]
Figure C0212702000473
[table 1]
No. X (％) Y (μm) The P value Emissivity Thermal diffusivity
The table the inside a×b ΔT1 (℃) Relative evaluation
100℃ 200℃ 100℃ 200℃
1 0 1 -1.5 0.10 0.11 0.01 0.01 0.5 ×
2 1.5 1 -0.75 0.15 0.15 0.02 0.02 0.8 ×
3 5.0 8.0 15 0.75 0.77 0.56 0.59 3.3 ●
4 5.0 12 23 0.79 0.81 0.62 0.66 3.4 ●
5 5.0 18 35 0.78 0.81 0.61 0.66 3.4 ●
6 7.0 5.0 18 0.74 0.75 0.55 0.56 3.4 ●
7 7.0 8.0 30 0.80 0.81 0.64 0.66 3.6 ◎
8 7.0 12 46 0.81 0.83 0.66 0.69 3.7 ◎
9 7.0 18 70 0.82 0.84 0.67 0.71 3.8 ◎
10 10 3.0 17.5 0.65 0.66 0.42 0.44 2.7 ●
11 10 5.0 31.5 0.80 0.81 0.64 0.66 3.5 ◎
12 10 8.0 52.5 0.80 0.82 0.64 0.67 3.7 ◎
13 10 12 80.5 0.83 0.85 0.69 0.72 3.8 ◎
14 10 18 122.5 0.86 0.88 0.74 0.77 3.9 ◎
15 12 5.0 40.5 0.80 0.80 0.64 0.64 3.6 ◎
16 12 8.0 67.5 0.81 0.82 0.66 0.67 3.8 ◎
17 12 12 103.5 0.83 0.85 0.69 0.72 3.8 ◎
18 12 18 157.5 0.83 0.86 0.69 0.74 3.9 ◎
19 14 2.0 16.5 0.70 0.72 0.49 0.52 3.3 ●
20 14 5.0 49.5 0.80 0.81 0.64 0.66 3.8 ◎
21 14 8.0 82.5 0.81 0.84 0.66 0.71 3.8 ◎
22 14 12 126.5 0.84 0.86 0.71 0.74 3.9 ◎
23 14 18 192.5 0.86 0.88 0.74 0.77 4.0 ◎
Annotate: the addition of X=carbon black (quality %)
The Y=thickness (μ m) of filming
The P value=(X-3) * (Y-0.5)
[table 2]
No. Raw sheet Film X (％) Y (μm) The P value The infrared emission rate ΔT1 Electroconductibility (Ω)
The table the inside a×b A-H
100℃ 200℃ 100℃ 200℃ 100℃ 200℃
1 A Tu expects a 10 5 31.5 0.70 0.71 0.49 0.50 0.27 0.28 3.5 1～3
2 A Tu expects a 10 8 52.5 0.83 0.84 0.69 0.71 0.14 0.16 3.7 1～3
3 B リ ヤ-epithelium - 1.5 - 0.57 0.58 0.32 0.34 0.48 0.50 0.5 100～10 4
4 A - - - - 0.04 0.05 0.0016 0.0025 0.01 0.01 0 0.01～0.1
Annotate: the steel plate raw sheet B=of raw sheet A=electro-galvanizing will plate the steel plate that Zn-Ni alloy steel plate blackization has been handled
The addition of *=carbon black (quality %)
The Y=thickness (μ m) of filming
The P value=(X-3) * (Y-0.5)
[table 3]
No. Carbon black Y (μm) The P value Emissivity Thermal diffusivity Electroconductibility Transparent coating (μ m) The evaluation of anti-finger printing The evaluation of anti-defect
Median size (nm) X (%) The table the inside a×b △T1 (℃) Relative evaluation Ni measures (%) Electric conductivity (Ω) A face/B face Relative evaluation
100℃ 200℃ 100℃ 200℃
1 17 10 8 52.5 0.79 0.80 0.62 0.64 3.7 ○ - 10 6More than × - - -
2 55 10 8 52.5 0.79 0.80 0.62 0.64 3.7 ◎ - 10 6More than × - - -
3 25 10 5 31.5 0.80 0.81 0.64 0.66 3.5 ◎ 20 1～10 ◎ - - -
4 25 10 5 31.5 0.78 0.80 0.61 0.64 3.5 ◎ 30 1～10 ◎ - - -
5 25 10 5 31.5 0.77 0.79 0.59 0.62 3.5 ◎ 40 1～10 ◎ - - -
6 25 l2 5 40.5 0.79 0.81 0.62 0.66 3.6 ◎ 20 1～10 ◎ - - -
7 25 12 5 40.5 0.79 0.80 0.62 0.64 3.5 ◎ 30 1～10 ◎ - - -
8 25 12 5 40.5 0.79 0.80 0.62 0.64 3.5 ◎ 40 1～10 ◎ - - -
9 25 10 8 52.5 0.82 0.84 0.67 0.71 3.7 ◎ 30 1～10 ◎ - - -
10 25 10 10 66.5 0.83 0.85 0.69 0.72 3.8 ◎ 30 10～100 ○ - - -
11 25 10 20 136.5 0.85 0.87 0.72 0.76 3.9 ◎ 30 10 6More than × - - -
12 25 10 5 31.5 0.79 0.81 0.62 0.66 3.5 ◎ - 10 6More than × 1.0 ◎ ◎
13 25 10 5 31.5 0.80 0.82 0.64 0.67 3.5 ◎ - 10 6More than × 5.0 ◎ ◎
14 25 10 5 31.5 0.79 0.82 0.62 0.67 3.5 ◎ - 10 6More than × 8.0 ◎ ◎
15 25 10 5 31.5 0.80 0.82 0.64 0.67 3.5 ◎ 30 1～10 ◎ 0.3 ○ ○
16 25 10 5 31.5 0.80 0.82 0.64 0.67 3.6 ◎ 30 1～10 ◎ 1.0 ◎ ◎
17 25 10 5 31.5 0.80 0.82 0.64 0.67 3.6 ◎ 30 1～10 ◎ 1.5 ◎ ◎
18 25 10 5 31.5 0.79 0.82 0.62 0.67 3.6 ◎ 30 10～100 ○ 2.0 ◎ ◎
19 25 10 5 31.5 0.81 0.83 0.66 0.69 3.6 ◎ 30 10 6More than × 5.0 ◎ ◎
20 25 10 5 31.5 0.80 0.82 0.64 0.67 3.5 ◎ 30 1～10 ◎ 0.05 × ×
21 25 10 5 31.5 0.78 0.80 0.61 0.64 3.5 ◎ 10 10 6More than × 0.3 ○ ◎
22 25 10 5 31.5 0.77 0.79 0.59 0.62 3.5 ◎ 60 1～3 ◎ 0.3 ○ ○
Annotate: the addition of X=carbon black (quality %)
The Y=thickness (μ m) of filming
The P value=(X-3) * (Y-0.5)
[table 4]
No. The surface The inside a×b Thermal diffusivity Δ T1 (℃)
Emissivity a Additive Y μm The P value Ni ％ Electroconductibility Ω Emissivity b Additive Y μm The P value Ni ％ Electroconductibility Ω
Kind Amount % Kind Amount %
1 0.86 *1 14 18 192.5 - 10 6More than 0.86 *1 14 18 193 - 10 6More than 0.74 4.1
2 0.80 *1 10 8 52.5 30 1～10 0.84 *1 14 12 127 - 10 6More than 0.67 4.0
3 0.81 *1 7 12 46 - 10 6More than 0.80 *1 10 8 52.5 - 10 6More than 0.65 3.8
4 0.74 *1 7 5 18 30 1～10 0.87 *1 14 20 215 - 10 6More than 0.64 3.7
5 0.86 *1 10 18 122.5 - 10 6More than 0.75 *1 5 8 15 - 10 6More than 0.65 3.7
6 0.87 *1 14 20 214.5 - 10 6More than 0.65 *1 10 3 17.5 30 1～10 0.57 3.4
7 0.70 *1 14 2 16.5 30 1～10 0.80 *1 10 8 52.5 30 1～10 0.56 3.3
8 0.80 *1 10 8 52.5 - 10 6More than 0.65 *1 10 3 17.5 - 10 6More than 0.52 3.3
9 0.79 *1 5 12 23 - 10 6More than 0.70 *1 14 2 16.5 - 10 6More than 0.55 3.1
10 0.59 *1 14 1.5 11 30 1～10 0.83 *1 10 12 80.5 - 10 6More than 0.49 3.0
11 0.70 *1 12 2 13.5 - 10 6More than 0.65 *1 10 3 17.5 - 10 6More than 0.46 3.0
12 0.55 *1 10 2 10.5 - 10 6More than 0.86 *1 14 18 193 - 10 6More than 0.47 2.8
13 0.70 *1 14 2 16.5 30 1～10 0.65 *1 10 3 17.5 30 1～10 0.46 2.8
14 0.86 *1 14 18 192.5 - 10 6More than 0.52 *1 14 1.1 6.6 - 10 6More than 0.45 2.7
15 0.70 *1 12 2 13.5 - 10 6More than 0.62 *1 10 2.5 14 - 10 6More than 0.43 2.6
Annotate: (* 1: carbon black) for the kind of additive
P value=[(addition of carbon black)-3] * [Y (coating thickness)-0.5]
[table 5]
No. The surface The inside a×b Thermal diffusivity Δ T1 (℃)
Emissivity a Additive Y μm The P value Ni ％ Electroconductibility Ω Emissivity b Additive Y μm The P value Ni ％ Electroconductibility Ω
Kind Amount % Kind Amount %
16 0.12 なし なし 1 - 10 2-3 0.81 *1 7 12 46.0 30 1～10 0.10 1.5
17 0.80 *1 10 8 52.5 30 1～10 0.10 Do not have Do not have 0.5 - 0.1～1 0.08 1.5
18 0.70 *1 14 2 16.5 30 1～10 0.04 Do not cover with paint, lacquer, colour wash, etc. - 0.01-0.1 0.03 1.3
19 0.75 *1 10 2 10.5 - 10 6More than 0.45 Do not cover with paint, lacquer, colour wash, etc. - 0.01-0.1 0.34 1.0
20 0.04 Do not cover with paint, lacquer, colour wash, etc. - 0.01-0.1 0.70 *1 14 2 16.5 - 10 6More than 0.03 1.3
21 0.12 Do not have Do not have 1 - 10 2-3 0.12 Do not have Do not have 1 - 10 2-3 0.01 0.5
22 0.04 Do not cover with paint, lacquer, colour wash, etc. - 0.01-0.1 0.04 Do not cover with paint, lacquer, colour wash, etc. - 0.01-0.1 0.002 0 (standard)
23 0.80 *2 60 25 - 10 6More than 0.84 *1 14 12 127 - 10 6More than 0.67 4.0
24 0.81 *2+*3 50+5 25 - 10 6More than 0.80 *1 10 8 52.5 30 1～10 0.65 3.8
25 0.86 *1+*5 50+0.5 20 - 10 6More than 0.75 *1 5 8 15.0 30 1～10 0.65 3.7
26 0.65 *4 10 20 - 10 6More than 0.80 *1 10 8 52.5 30 1～10 0.52 3.4
27 0.86 *1+*5 14 18 - 10 6More than 0.86 *1 14 18 193 - 10 6More than 0.74 4.1
28 0.86 *1+*5 14 18 - 10 6More than 0.86 *1 14 18 193 - 10 6More than 0.74 4.1
29 0.80 *2 60 25 - 10 6More than 0.04 Do not cover with paint, lacquer, colour wash, etc. - 0.01-0.1 0.03 1.4
30 0.80 *2 60 25 - 10 6More than 0.10 Do not have Do not have 0.5 - 0.1-1 0.08 1.5
Annotate: the kind of additive (* 1: carbon black, and * 2: titanium oxide, * 3: ferric oxide, * 4:Al scale, * 5: acrylic particles)
P value=[(addition of carbon black)-3] * [Y (coating thickness)-0.5]
As raw sheet, No.19 uses will plate the steel plate that the Zn-Ni alloy steel plate carries out the black processing; No.26 uses the Al plate, and No.27 uses the Cu plate.
[table 6]
No. The surface The surface
Emissivity a Additive Y μm The P value Ni ％ Electroconductibility Ω Emissivity b Additive Y μm The P value Ni ％ Electroconductibility Ω
Kind Amount % Kind Amount %
1 0.86 *1 14 18 192.5 - 10 6More than 0.23 *1 14 0.2 -3.3 30 1～10
2 0.87 *1 14 20 214.5 - 10 6More than 0.35 *1 10 1.4 6.3 30 1～10
3 0.68 *1 10 3.5 21 30 1～10 0.27 Do not have Do not have 2.5 - 10 6More than
4 0.70 *1 14 2 16.5 30 1～10 0.38 *1 10 1.5 7 30 1～10
5 0.86 *1 14 18 192.5 - 10 6More than 0.52 *1 14 1.1 6.6 30 1～10
6 0.79 *1 5 12 23 - 10 6More than 0.48 *2 50 3 118 - 10 6More than
7 0.62 *1 10 2.5 14 30 1～10 0.35 Do not have Do not have 3 - 10 6More than
8 0.84 *1 14 12 126.5 - 10 6More than 0.55 *1 10 2 10.5 30 1～10
9 0.86 *1 14 18 192.5 - 10 6More than 0.65 *1 10 3 17.5 30 1～10
10 0.65 *4 10 20 136.5 - 10 6More than 0.50 *4 10 4 24.5 - 10 6More than
11 0.48 *4 10 6 38.5 - 10 6More than 0.36 *1 1 1.8 -2.6 30 1～10
12 0.80 *2 60 25 1397 - 10 6More than 0.65 *1 5 3.5 6 30 1～10
13 0.68 *1 10 3.5 21 - 10 6More than 0.04 Do not cover with paint, lacquer, colour wash, etc. - 0.01～0.1
14 0.40 *1 1 2 -3 - 10 6More than 0.24 Do not have Do not have 2 - 10 6More than
15 0.12 Do not have Do not have 1 30 1～10 0.12 Do not have Do not have 1 30 1～10
16 0.83 *1 10 12 80.5 - 10 6More than 0.81 *1 7 12 46 - 10 6More than
17 0.43 The black processing - 0.01～0.1 0.45 The black processing - 0.01～0.1
18 0.73 *1 7 5 18 30 1～10 0.81 *1 14 8 - 10 6More than
19 0.04 Do not cover with paint, lacquer, colour wash, etc. - 0.01～0.1 0.04 Do not cover with paint, lacquer, colour wash, etc. - 0.01-0.1
Annotate: the kind of additive (* 1: carbon black, and * 2 titanium oxide, * 3: ferric oxide, * 4:Al scale, * 5: acrylic particles)
P value=[(addition of carbon black)-3] * [Y (coating thickness)-0.5]
As raw sheet, No.17 uses will plate the steel plate that the Zn-Ni alloy steel plate carries out the black processing
[table 7]
No. Emissivity Q value 0.9a-b R value (a-0.05) * (b-0.05) From cooling property Thermal diffusivity
Surface a The inside b ΔT2 ℃ Relative evaluation ΔT1 ℃ Relative evaluation
1 0.86 0.23 0.54 0.15 2.5 ◎ 1.7 ○
2 0.87 0.35 0.43 0.25 2.3 ◎ 2.0 ○
3 0.68 0.27 0.34 0.14 2.0 ◎ 1.6 ○
4 0.70 0.38 0.25 0.21 1.9 ◎ 1.8 ○
5 0.86 0.52 0.25 0.38 1.8 ◎ 2.7 ◎
6 0.79 0.48 0.23 0.32 1.6 ◎ 2.2 ○
7 0.62 0.35 0.21 0.17 1.6 ◎ 1.7 ○
8 0.84 0.55 0.21 0.40 1.5 ◎ 2.8 ◎
9 0.86 0.65 0.12 0.49 1.1 ○ 3.4 ◎
10 0.65 0.50 0.09 0.27 0.7 ○ 2.0 ○
11 0.48 0.36 0.07 0.13 0.8 ○ 1.7 ○
12 0.80 0.65 0.07 0.45 0.7 ○ 3.1 ◎
13 0.68 0.04 0.57 -0.01 2.5 ◎ 1.2 ×
14 0.40 0.24 0.12 0.07 1.5 ◎ 1.3 ×
15 0.12 0.12 -0.01 0.005 0 × 0.5 ×
16 0.83 0.81 -0.06 0.59 0.1 × 4.0 ◎
17 0.43 0.45 -0.06 0.15 0 × 1.9 ○
18 0.73 0.81 -0.15 0.52 0.2 × 3.3 ◎
19 0.04 0.04 -0.004 0.000 0 (standard) × 0 (standard) ×
[table 8]
No. Bottom tunicle (surplus film dispels the heat) Top layer tunicle (transparent coating) thickness μ m Characteristic
Resin Linking agent Rust-preventive agent Ni Erosion resistance Processibility Electroconductibility Ω
Kind Amount % Kind Ratio ％ ％ 72 hours 120 hours Fracture number Adaptation
*14(％) *15(％) *14/*15
1 *12 57.8 1.4 5.8 0.24 - 25 1 20 40 0 ○ 1～10
2 *12 56.0 1.4 5.6 0.25 2 25 1 3 6 0 ○ 1～10
3 *12 53.4 1.3 5.3 0.25 5 25 1 Less than 1 Less than 1 0 ○ 1～10
4 *12 49.8 1.2 5.0 0.24 9 25 1 Less than 1 Less than 1 2 ○ 1～10
5 *12 41.8 1.0 4.2 0.24 18 25 1 Less than 1 Less than 1 4 ○ 1～10
6 *12 33.8 0.8 3.4 0.24 27 25 1 Less than 1 Less than 1 7 △ 1～10
7 *13 53.4 1.3 5.3 0.25 5 25 1 Less than 1 Less than 1 1 ○ 1～10
8 *12 54.5 5.5 0 - 5 25 1 Less than 1 Less than 1 5 ○ 1～10
9 *12 54.5 0 5.5 - 5 25 1 6 10 0 ○ 1～10
10 *12 54.0 0.6 5.4 0.11 5 25 1 4 7 0 ○ 1～10
11 *12 53.5 1.0 5.5 0.18 5 25 1 Less than 1 2 0 ○ 1～10
12 *12 53.4 1.3 5.3 0.25 5 25 1 Less than 1 Less than 1 0 ○ 1～10
13 *12 52.7 2.0 5.3 0.38 5 25 1 Less than 1 Less than 1 1 ○ 1～10
14 *12 51.8 3.0 5.2 0.58 5 25 1 Less than 1 Less than 1 4 ○ 1～10
15 *12 50.0 5.0 5.0 1.00 5 25 1 Less than 1 Less than 1 9 ○ 1～10
16 *12 49.0 1.2 9.8 0.12 5 25 1 Less than 1 Less than 1 1 ○ 1～10
17 *12 56.0 1.2 2.8 0.43 5 25 1 Less than 1 3 1 ○ 1～10
18 *12 53.0 5.3 1.8 2.94 5 25 1 Less than 1 Less than 1 10 ○ 1～10
19 *12 49.0 9.8 1.2 8.17 5 25 1 Less than 1 Less than 1 15 △ 1～10
20 *11 53.4 1.3 5.3 0.25 5 25 1 12 20 0 × 1～10
21 *12 53.4 1.3 5.3 0.25 5 - 1 Less than 1 Less than 1 0 ○ 10 6More than
22 *12 48.9 1.2 4.9 0.24 5 30 1 Less than 1 Less than 1 2 ○ 1～10
23 *12 53.4 1.3 5.3 0.25 5 25 - 8 13 1 ○ 1～10
Annotate: the kind=* 11 of resin: vibrin (number-average molecular weight 25.000), * 12: epoxy modified polyester resin (number-average molecular weight 25.000),
* 13: introduce bisphenol A-type vibrin (number-average molecular weight 20.000)
Kind=the * 14 of linking agent: melamine crosslinker, * 15: isocyanate crosslinking

Claims (36)

1. the electronic instrument part coating decoration material of a fine heat radiation property has the cooling coating film of thermal diffusivity in the table the inside lining of substrate, it is characterized in that the single face at least in this cooling coating film contains the black additive, and, satisfy following formula (2):
(X-3)×(Y-0.5)≥15……(2)
In the formula, X represents contained black content of additive (quality %) in the cooling coating film, and Y represents coating thickness (micron),
Also satisfy following formula (3)
4≤X＜15…(3)
In the formula, X is illustrated in the amount (quality %) of contained black additive in the cooling coating film,
In addition, also satisfy coating thickness Y＞1 micron,
Ultrared integration emissivity satisfied following formula (1) when this coating decoration material was heated to 100 ℃, wherein said Infrared wavelength: 4.5～15.4 microns,
a×b≥0.42……(1)
A: the infrared rays integration emissivity of the coating decoration material of surface-coated cooling coating film
B: the infrared rays integration emissivity of the coating decoration material of the inside lining cooling coating film.
2. as the coating decoration material of claim 1 record, satisfy a 〉=0.65 and/or b 〉=0.65.
3. as the coating decoration material of claim 1 record, in above-mentioned coating decoration material, the maximum value A of the beam split emissivity in 4.5～15.4 microns wavelength region and minimum value B poor (A-B) is below 0.35.
4. as the coating decoration material of any record in the claim 1～3, the resin that forms above-mentioned cooling coating film is non-hydrophilic resin.
5. as the coating decoration material of any record in the claim 1～3, its resistance is below 100 Ω.
6. as the coating decoration material of any record in the claim 1～3, above-mentioned cooling coating film contains electroconductive stuffing.
7. as the coating decoration material of any record in the claim 1～3, transparent coating is covered on above-mentioned cooling coating film.
8. as the coating decoration material of any record in the claim 1～3, aforesaid substrate does not contain the bottom layer treatment of chromium, and cooling coating film also contains rust-preventive agent.
9. as the coating decoration material of claim 1 record, the median size of above-mentioned black additive is 5～100nm.
10. as the coating decoration material of claim 1 record, above-mentioned black additive is a carbon black.
11. a thermal diffusivity and the electronic instrument part coating decoration material that the property cooled off is good certainly be covereds on the table of substrate the inside and film, and are covered on the surface at least of substrate and have the cooling coating film of thermal diffusivity, it is characterized in that, above-mentioned cooling coating film contains the black additive, and, satisfy following formula (6):
(X-3)×(Y-0.5)≥3……(6)
In the formula, X represents black content of additive (quality %) contained in the cooling coating film, and Y represents coating thickness (micron),
Also satisfy following formula (7)
4≤X＜15 …(7)
In the formula, X is illustrated in the amount (quality %) of contained black additive in the cooling coating film,
In addition, further satisfy coating thickness Y＞1 micron,
Ultrared integration emissivity when this coating decoration material is heated to 100 ℃ satisfies following formula (4) and (5), wherein said Infrared wavelength: 4.5～15.4 microns,
b≤0.9(a-0.05)……(4)
(a-0.05)×(b-0.05)≥0.08……(5)
A: the infrared rays integration emissivity of the coating decoration material of surface-coated cooling coating film
B: the infrared rays integration emissivity of the coating decoration material of the inside lining cooling coating film.
12. as the coating decoration material of claim 11 record, the resin that forms above-mentioned cooling coating film is non-hydrophilic resin.
13. as the coating decoration material of claim 11 record, its resistance is below 100 Ω.
14. as the coating decoration material of claim 11 record, above-mentioned cooling coating film contains electroconductive stuffing.
15. as the coating decoration material of claim 11 record, transparent coating is covered on above-mentioned cooling coating film.
16. as the coating decoration material of claim 11 record, aforesaid substrate does not contain the bottom layer treatment of chromium, and cooling coating film also contains rust-preventive agent.
17. as the coating decoration material of claim 11 record, the median size of above-mentioned black additive is 5～100nm.
18. as the coating decoration material of claim 11 record, above-mentioned black additive is a carbon black.
19. as the coating decoration material of claim 11 record, the resin that forms above-mentioned cooling coating film is a polyester based resin.
20. as the coating decoration material of claim 11 record, above-mentioned cooling coating film contains electroconductive stuffing, and above-mentioned electroconductive stuffing is Ni.
21. as the coating decoration material of claim 11 record, above-mentioned cooling coating film contains electroconductive stuffing, and the thickness of this cooling coating film is more than the 2 μ m.
22. as the coating decoration material of claim 11 record, the fracture number that satisfies under the driving fit pliability test of stipulating among the JIS K 5400 is below 5.
23. as the coating decoration material of claim 11 record, the area occupation ratio that satisfies the outward appearance abnormal portion under the salt spray testing corrosion resistance test stipulated among the JIS-Z-2371 72 hours is below 10%.
24. as the coating decoration material of claim 11 record, lining is filmed again on above-mentioned cooling coating film, the area occupation ratio that satisfies the outward appearance abnormal portion under the salt spray testing corrosion resistance test stipulated among the JIS-Z-2371 120 hours is below 10%.
25. coating composition that is used to form the electronic instrument part of claim 1 with the cooling coating film of coating decoration material, it is characterized in that, in whole film to be formed into be divided into 100 quality %, contain above black additive of 3 quality % and the electroconductive stuffing of 10～50 quality %.
26. as the composition of claim 25 record, the median size of above-mentioned black additive is 5～100nm.
27. as the composition of claim 25 record, above-mentioned black additive is a carbon black.
28. as the composition of claim 25 record, above-mentioned electroconductive stuffing is Ni.
29. film as the composition of any record in the claim 25～28 is formed.
30. coating composition that is used to form the electronic instrument part of claim 1 with the cooling coating film of coating decoration material, be applicable to and carried out the not substrate of containing chronium bottom layer treatment, it is characterized in that, contain the above epoxide modified polyester resin of 35 mass parts and/or in skeleton, introduced the electroconductive stuffing of linking agent, the black additive more than 3 mass parts and 10～50 mass parts of rust-preventive agent, 1～20 mass parts of polyester resin, 2～25 mass parts of phenol derivatives.
31. as the composition of claim 30 record, above-mentioned linking agent is with respect to 100 mass parts isocyanic ester resinoids, contains the melamine resinoid with the ratio of 5～80 mass parts.
32. as the composition of claim 30 record, the median size of above-mentioned black additive is 5～100nm.
33. as the composition of claim 30 record, above-mentioned black additive is a carbon black.
34. as the composition of claim 30 record, above-mentioned electroconductive stuffing is Ni.
35. the formed not containing chronium of composition as claim 30 record is filmed.
36. an electronic instrument part, the built-in radiator in space in sealing is characterized in that all or part of of this its outer wall of electronic instrument part is made of with coating decoration material the electronic instrument part of any record in the claim 1～25.
CNB021270201A 2001-07-25 2002-07-25 Coating decoration material with fine heat radiation property for electronic instrument part Expired - Fee Related CN1237134C (en)

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WO2008078956A1 (en) 2006-12-27 2008-07-03 Posco Excellent heat-dissipating black resin composition, method for treating a zinc coated steel sheet using the same and steel sheet treated thereby
JP5723103B2 (en) * 2009-03-27 2015-05-27 株式会社神戸製鋼所 High thermal conductivity steel sheet
KR101035011B1 (en) * 2010-01-19 2011-05-17 한국전기연구원 Heat-radiant coatings and heat-radiant plate thereby
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JP3468420B2 (en) * 2000-06-07 2003-11-17 持田商工株式会社 Heat radiating sheet and method of manufacturing the same
JP2002118202A (en) * 2000-10-05 2002-04-19 Sanyo Electric Co Ltd Heat dissipation substrate and semiconductor module

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Publication number Priority date Publication date Assignee Title
CN103081582A (en) * 2010-08-31 2013-05-01 日东电工株式会社 Heat-dissipating case and lithium battery pack using same, and semi-conducting tape for heat dissipation

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