JP6089144B1 - Copper-clad laminate and manufacturing method thereof - Google Patents

Abstract

A copper-clad laminate having high reflectivity for visible light and ultraviolet light and excellent in ultraviolet light resistance and heat resistance is provided. An organopolysiloxane having a copper-clad laminate comprising a copper layer, a white layer, an adhesive layer, and a high thermal conductivity substrate having a thermal conductivity of 200 W / m · K or higher in this order, and the white layer having a high ultraviolet light resistance. In this matrix, a composition having any one of BN, ZrO 2, SiO 2, CaF 2, and diamond having a high ultraviolet light reflectivity was used, and a white layer and an aluminum substrate were joined by a thermosetting resin. [Selection] Figure 3

Description

  The present invention relates to a copper clad laminate having high reflectivity for visible light and ultraviolet light, and excellent in ultraviolet light resistance and heat resistance. This copper clad laminate is suitable for a printed circuit board for mounting a light emitting diode (LED).

  A laminated substrate having a copper foil for forming a circuit pattern on the surface, a pattern is formed on the copper foil by means of etching or the like, and a white reflector is exposed from a portion where the copper is removed by etching or the like (hereinafter referred to as a laminated substrate) A similar laminated substrate having a copper foil on its surface is also referred to as a “copper-clad laminate”). In addition, LED devices in which light emitting elements are mounted on a copper-clad substrate are widely used in electronic devices, lighting devices, and the like. A general white reflective material can be used without any problem if it is in the visible light region, but as a reflective material for ultraviolet light, there are problems such as low reflectivity for ultraviolet light and deterioration due to ultraviolet light. there were.

  In particular, in recent years, the technological progress of LEDs has been remarkable, and the number of LED elements that generate higher-power ultraviolet light or shorter-wavelength ultraviolet light is increasing. Accordingly, the substrate side, in particular, the ultraviolet light reflecting material (hereinafter also simply referred to as “reflecting material”) is required to have excellent properties for ultraviolet light reflection and ultraviolet light resistance.

In view of such background, for example, Patent Document 1 has a high reflectance in the ultraviolet light region and the visible light region, there is little reduction in light reflectance due to heat treatment or light irradiation treatment, and the peel strength with the metal foil is low. A good resin composition, a prepreg and a copper clad laminate using the same are disclosed. These are described as being suitable for printed wiring boards for LED mounting.
Patent Document 2 has a layer containing a thermoplastic resin and a layer containing an inorganic filler in a silicone resin, and has an average reflectance of 70% or more for visible light having a wavelength of 400 to 800 nm. Proposals have been made to use a certain laminate for an LED mounting substrate.

Furthermore, Patent Document 3 discloses an LED package that is not a copper-clad laminate but excellent in reflection of ultraviolet light. As for the light reflection layer, an inorganic material formed by hydrolysis and dehydration condensation of metal alkoxide and a ceramic filler such as AlN, Al ₂ O ₃ , MgO and the like are dispersed. Since the silicone resin obtained by hydrolysis and dehydration condensation of metal alkoxide is relatively easy to reduce the number of carbon-carbon bonds that are weak against ultraviolet light, it is possible to increase the resistance to ultraviolet light among silicone resins. Further, Al ₂ O ₃ and MgO added as fillers can obtain high ultraviolet light reflection without special treatment on the surface, for example, as compared with TiO ₂ .

International Publication No. 2012/165147 JP 2010-274540 A JP 2013-004822 A

  With the use of the prepreg and the reflective layer of the copper clad laminate described in Patent Document 1, ultraviolet light resistance and ultraviolet light reflectivity with respect to general white paints and adhesives used for a reflective material for visible light Both are slightly improved. This is because titanium dioxide is used as the white filler of the white reflector exposed by removing the metal foil on the surface, and titanium dioxide has better ultraviolet light resistance than, for example, organic polymer-based white resins. It is. Moreover, the epoxy-modified silicone compound has ultraviolet light resistance superior to that of an organic polymer whose main chain is a carbon-carbon bond. However, titanium dioxide has a characteristic that it is easy to absorb ultraviolet light and hardly reflects in white ceramics. Even if the ultraviolet light reflectivity is improved by the surface treatment, the effect is limited, and it cannot be said that the ultraviolet light reflectivity is sufficiently high. In addition, the metal-clad substrate of Patent Document 1 has epoxy-modified silicone as an introduction group.

Among these, since the carbon-carbon bond portion is particularly easily broken, it cannot be said that the ultraviolet light resistance is sufficiently high. In this respect, since the same carbon-carbon bond is generated when the titanium dioxide is subjected to polyol treatment, silane coupling treatment and amine treatment, it cannot be said that sufficient ultraviolet light resistance and reflectivity are sufficient. The same applies to the isocyanurate ring contained as an essential component.

  Patent Document 2 includes two layers of a thermoplastic resin layer (A) and a layer (B) containing an inorganic filler in a silicone resin. In addition to these two layers, a copper foil is provided on the (A) side. A structure having an aluminum plate on the layer side (B) is disclosed as an example. For example, FIG. 2 illustrates this structure. Moreover, as a manufacturing method of the board | substrate for LED mounting, the method which joins an (aluminum) board | substrate after cutting into a laminated body of said (A) and said (B), a copper foil layer, and each piece (window extraction process). Is described. However, this method has a problem that it is difficult to make the thickness constant with a press. In addition, since the thermoplastic resin softens as the temperature rises, it is still difficult to use the thermoplastic resin on a substrate for mounting an ultraviolet LED that becomes high temperature during use. In particular, it cannot be used for applications where the positional accuracy of a light source or the like is severe. In Cited Document 2, the composition of the silicone resin is not particularly limited, and the form is not limited to rubber, millable, varnish, resin, elastomer, gel, and the like. Silicone resins having a silicon-oxygen bond as the main chain generally have higher ultraviolet light resistance than resins having a carbon-carbon bond as the main chain, but the form is not specified in this document. It is difficult to obtain a structure having sufficient ultraviolet light resistance in the ultraviolet region.

The insulating layer disclosed in Patent Document 3 can be expected to have a certain degree of ultraviolet light reflection and ultraviolet light resistance. However, it is technically difficult to join the insulating layer described in Patent Document 3 to both the circuit part (copper foil layer) and the heat radiating part (metal plate) on both the upper and lower surfaces without a gap. The insulating layer used in Patent Document 3 is an inorganic material in which a metal alkoxide is hydrolyzed and dehydrated and polymerized by evaporating water, a low-molecular compound, and the like during the hydrolyzing and dehydrating polymerization. Need to be released. However, when both the upper and lower surfaces are sandwiched between the copper foil layer and the metal plate, there is no water or low molecular compound release route that must be released, resulting in the problem that bubbles remain in the insulating layer itself. Arise. In order to avoid this phenomenon, when the metal foil is not joined at the time of hydrolysis and dehydration condensation (metal plate is joined), it is necessary to attach a copper foil layer again by expensive means such as sputtering thereafter. Further, when the metal plate is not joined at the time of hydrolysis and dehydration condensation (copper foil is joined), since the entire copper foil is deformed at the time of dehydration condensation and hydrolysis, it is difficult to form a flat plate. is there. Further, the insulating layer obtained by once hydrolysis and dehydration polymerization has no reactive group on the surface, and cannot be bonded to the metal plate even when heated or pressurized.
The copper clad laminate and the method for producing the same according to the present invention solve at least one of the following current technical problems.
(1) To provide a copper-clad laminate suitable for an ultraviolet LED mounting substrate or the like, in which a reflective material exposed after removing a copper layer is not easily deteriorated against ultraviolet light and has a sufficient reflectance. about.
(2) Even when the temperature of the substrate rises during LED emission, the deformation is small and can be used.
(3) Proposing a method for obtaining a copper-clad laminate having a copper layer and a metal plate on both sides in response to the above (1) and (2).
(4) Between the said copper layer and a metal plate, it is a copper clad laminated board which the reflective film which has high ultraviolet light tolerance and a high ultraviolet light reflectance exposes in the part which removed the said copper layer.

The copper clad laminate has a copper layer, a white layer, an adhesive layer, and a high thermal conductivity substrate having a thermal conductivity of 200 W / m · K or more in this order, and the white layer is in a matrix of organopolysiloxane, BN, ZrO _2, SiO 2, _{CaF 2,} have either one or two or more fillers of the diamond was the adhesive layer was solved by a thermosetting resin. This copper-clad laminate is, for example, a step of applying a white paint having one or more of BN, ZrO ₂ , SiO ₂ , CaF ₂ , and diamond in an organopolysiloxane matrix on a copper foil , A step of thermosetting a white paint on the copper foil while suppressing deformation of the copper foil, a thermosetting having a layer of the white paint and a high thermal conductive substrate having at least a thermal conductivity of 200 W / m · K or more on one side It is obtained by a manufacturing method including a step of joining the resin in a heated and pressurized state in this order.

With the copper clad laminate and the method for producing the same of the present invention, the following matters could be realized.
First, a copper-clad laminate with high resistance to ultraviolet light, particularly deep ultraviolet light, could be realized. This copper clad laminate has a copper layer such as a copper foil on the surface, and a circuit can be easily produced by etching or the like. From the portion where the copper layer is removed by etching, a reflective layer having a sufficiently high reflectance (particularly, ultraviolet light reflectance) and high ultraviolet light resistance is exposed.
Moreover, since it is a copper clad laminate in a state where the substrate material and the light reflection layer, and the light reflection layer and the copper layer (for circuit formation) are in close contact, the copper layer, the light reflection layer, and the substrate material Need not be joined after the circuit is formed. Moreover, the deformation | transformation of the board | substrate by the heat_generation | fever when LED light_emits which arises, for example, when a light reflection layer and a board | substrate material are joined using a thermoplastic resin can be decreased.
By forming a circuit on the copper-clad laminate of the present invention and mounting the LED element, an ultraviolet LED mounting substrate using it can be obtained.

  Moreover, in this invention, the manufacturing method for manufacturing the said copper clad laminated board is also disclosed collectively.

It is a schematic diagram of a 1st laminated body. It is a schematic diagram of a 2nd laminated body. It is a schematic diagram of the copper clad laminated board (3rd laminated body) of this invention which joined the 1st laminated body and the 2nd laminated body. It is a schematic diagram of a 4th laminated body. It is a schematic diagram of the copper clad laminated board (5th laminated body) of this invention which joined the 1st laminated body and the 4th laminated body. It is a schematic diagram of the copper clad laminated board in which the circuit was formed in the 3rd laminated body. It is a schematic diagram of the laminated body which joined the 1st laminated body of 2 sheets with the thermosetting prepreg (6th laminated body). It is a schematic diagram of the copper clad laminated board of this invention made into the multilayer substrate structure (7th laminated body). It is a measurement result of the ultraviolet light reflectance of various fillers. It is a measurement result of deterioration by ultraviolet light.

The copper clad laminate of the present invention can be produced by the following method.
First, the paint used for the white layer will be described.

  The paint used for the white layer has a composition in which a predetermined ceramic filler is dispersed in an organopolysiloxane matrix. The production method is described below.

First, an organoalkoxylane, water, and an acid catalyst are mixed. Organoalkoxylane is
Formula 1: R ₁ mSi (OR ₂ ) _4-m (wherein R _{1 in} Formula ₁ is an organic group having 1 carbon atom, R ₂ is an alkyl group, m is an integer of 0 to 2),
Any one or two of the compounds represented by formula (1) are used.

What applies to R ₁ (an organic group having 1 carbon atom) is either a methyl group (CH ₃ ) or a trifluoromethyl group (CF ₃ ). These are portions that become the skeleton of the matrix when it becomes an organopolysiloxane, and have no or almost no carbon-carbon bond (C—C bond) that is weak to ultraviolet light. R ₁ having a C—C bond is acceptable up to 5% of all R ₁ . If it exceeds 5%, the ultraviolet light resistance is significantly reduced.

As said R < ₂ > (alkyl group), linear alkyl groups, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl; iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso- Examples include branched alkyl groups such as pentyl, tert-pentyl, and neo-pentyl. R ₂ may contain a lot of C—C bonds because the hydroxyl group is substituted during condensation polymerization to become an alcohol and does not remain in the white layer finally.

The mixing amount of water and the acid catalyst is not particularly limited because it volatilizes later in the condensation polymerization, but it is preferably blended so that the pH value is 2-6. A mixture is thus obtained.
Next, a filler is added to the mixture. Suitable as fillers are granular particles that have a high ultraviolet light reflectance by themselves and do not deteriorate with ultraviolet light. Suitable material types include c-BN (cubic boron nitride), h-BN (hexagonal boron nitride), ZrO ₂ , SiO ₂ , CaF ₂ , diamond, etc., and one or more types should be used. Can do. All of these fillers are characterized by high ultraviolet light reflectance and ultraviolet light resistance. As an example, FIG. 9 shows reflectance data of a white body in which different fillers ZrO ₂ , SiO ₂ , Al ₂ O ₃ and TiO ₂ filler are dispersed at the same volume fraction in the same organopolysiloxane. Further, FIG. 10 shows a change in reflectance when the sample is irradiated with ultraviolet light having a wavelength of 254 nm. In FIG. 10, even when SiO ₂ , CaF ₂ and diamond were used, the same characteristics as the white body using the ZrO ₂ filler were shown. From these graphs, it can be seen that the filler has high reflectance and high ultraviolet light resistance. A filler dispersion is obtained by adding and mixing a filler to the obtained mixture. The amount of filler added is suitably such that the filler is 10 to 85% by volume when the white layer is formed. If the amount of filler is less than 10% by volume, sufficient reflectance is difficult to obtain, and if it exceeds 85% by volume, gaps are likely to occur in the matrix. What has a high reflectance and is easy to produce stably is the range which becomes especially 40 to 70 volume% of a filler.
Next, the organoalkoxysilane of the filler dispersion is subjected to condensation polymerization at about room temperature to about 70 ° C. to evaporate water and alcohol. A white paint can be obtained by adjusting the viscosity to be suitable for application. In addition, you may perform a part of said condensation polymerization reaction before filler addition. The viscosity of the white paint may be about 10 to 1000 cps when spraying, and about 1,000 to 100,000 cps when applied.

  Next, a method for forming a white paint on a copper foil will be described.

  A white paint is applied to the surface of the copper foil. As an application method, it can be applied by using a normal technique such as dipping method, casting method, spinner method, spray method, bar coating method, screen printing, metal mask, ink jet or blade. The application means is not limited to these, and any method may be used as long as it can be applied appropriately.

The copper foil to be used is not particularly limited, but it is desirable to use electrolytic copper foil (pure copper) suitable for the circuit. Moreover, about thickness, several micrometer-several mm and the thing of arbitrary thickness can be used according to a use. In addition, in order to improve adhesiveness with a white reflector, it is desirable that the surface of the copper foil is subjected to a surface roughening treatment. About the quantity to apply | coat, the quantity from which the thickness after the thermosetting process which is the next process will be 10-200 micrometers is preferable. If it is less than 10 μm, it is difficult to increase the reflectivity, and if it exceeds 200 μm, the reflectivity is not further improved, and deformation at the time of thermosetting treatment is increased, which is not preferable.
After application, the white paint is heat-cured. Curing may be performed at about 120 to 300 ° C. for 5 to 60 minutes. By performing this treatment, the polycondensation of the organoalkoxysilane is completely completed, and a solid white layer in which the filler is dispersed in the organopolysiloxane matrix is obtained. The copper layer and the white layer have high adhesiveness and are strongly bonded. The atmosphere at the time of curing can be an air atmosphere, but if possible, it is preferably performed in a non-oxidizing atmosphere. This is to prevent oxidation of the copper foil (copper layer) due to the influence of oxygen in the atmosphere. Even when oxidized, the oxidized layer on the surface of the copper layer can be removed by washing with a derusting agent or the like in a later step. In this way, the 1st laminated body which the copper layer and the white layer joined is obtained.

  In the first laminate, the laminate may warp due to condensation polymerization of the white paint in the step. In order to prevent this, it is necessary to keep the end of the copper foil part fixed at the time of thermosetting, to apply the tension to the copper foil at the time of thermosetting, or to adsorb the back side of the white paint. An effective method is to prevent the deformation by performing condensation polymerization while keeping the layer so as not to be deformed.

  The obtained first laminate has a two-layer structure having a copper layer on one side and a white layer on the other side. Among these, since the white layer is composed of an organopolysiloxane and a filler that hardly reacts with a metal or the like, it is difficult to directly bond it to a high thermal conductive substrate such as an aluminum substrate. Therefore, when joining a white layer and an aluminum substrate (high heat conductive substrate), both are joined using a thermosetting resin. As the thermosetting resin, a known thermosetting resin such as an epoxy resin, an acrylic resin, or an imide resin can be used. You may use the sheet | seat of these resin, and you may join by solidifying a liquid thing. By using the thermosetting resin, for example, a laminate with less deformation can be obtained even when the temperature becomes high during use as compared with the case where a thermoplastic resin described in the prior art document is used. When bonding, for example, the temperature may be raised to 100 to 200 ° C. in a state of being pressurized to about 0.2 to 10 MPa. Thus, a four-layer laminate (third laminate) in which the thermosetting resin layer is laminated on the white layer side of the first laminate and the aluminum substrate (high thermal conductivity substrate) is laminated on the other surface of the thermosetting resin layer. Body, the laminate of the present invention).

  The above has described the laminate with the simplest configuration. However, if the positional relationship of “copper layer-white layer-thermosetting resin-aluminum substrate (high thermal conductivity substrate)” is maintained, the other layers are replaced with these layers. It can also be sandwiched between them. As an example, an insulating resin layer can be sandwiched between a thermosetting resin and an aluminum substrate (high thermal conductivity substrate). For example, when the dielectric breakdown voltage of the white layer is not sufficient, the dielectric breakdown may occur between the copper layer and the aluminum substrate (high thermal conductivity substrate). By using the insulating resin layer, it is possible to prevent dielectric breakdown that occurs when a large current is used or when an unexpected voltage such as a lightning strike is applied.

Moreover, although the case where the white layer was one layer was described above, it is also possible to join a plurality of first laminated bodies with a thermosetting resin to form a multi-layered body.
Moreover, although the aluminum substrate was illustrated as a high heat conductive board | substrate above, as long as heat conductivity is 200 W / m * K or more, it will not be limited to an aluminum board. For example, the high thermal conductive substrate can be aluminum, copper, silver, tungsten, carbon (carbon (including graphite, carbon fiber, and carbon nanotube)), diamond alone or a mixture.

  The obtained laminate has a copper layer on the surface and a white layer inside. A circuit board can be obtained by masking a part of the surface copper layer and etching the remaining part with, for example, an acid, a hydrogen peroxide solution or a ferric chloride solution. In the obtained circuit board, a white layer excellent in ultraviolet light resistance and ultraviolet light reflectance is exposed at a portion where the copper layer is removed. Various plating is performed on the circuit, and a lead wire or an LED element is joined to the plated portion to obtain an LED mounting substrate.

Hereinafter, the present invention will be described in more detail by way of examples.
Example 1
As an organoalkoxysilane, 100 parts by mass of methyltriethoxysilane (manufactured by Kishida Chemical Co., Ltd.), 50 parts by mass of water, 25 parts by mass of acetic acid (manufactured by Kanto Chemical Co., Ltd.), and 1 part by mass of boron oxide (manufactured by Kanto Chemical Co., Ltd.) Were put into an autoclave (manufactured by Pressure Glass Industrial Co., Ltd., TAS-7-3 type reaction vessel) and stirred at 40 ° C. for 112 hours to obtain an organopolysiloxane mixture composition.
With respect to 100 parts by mass of the organopolysiloxane mixture composition, 170 parts by mass of ZrO ₂ powder having an average particle size of 2.0 μm and 55 parts by mass of butyl carbitol acetate (manufactured by Kishida Chemical Co., Ltd.) were added and mixed. For 13 hours to obtain a white paint.
The white paint is applied to a concavo-convex surface of a 35 μm thick single-sided copper foil (GTS foil, manufactured by Furukawa Electric Co., Ltd.) by a screen printing method to a thickness of about 80 μm, and baked at 260 ° C. for 30 minutes. The 1st laminated body which has a white layer on copper foil was obtained. The white layer of the first laminate has a thickness of about 50 μm, and this portion becomes an ultraviolet light reflection portion.
Then, the 2nd laminated body was heat-pressure-bonded to the said 1st laminated body. The second laminate has a two-layer structure in which a thermosetting prepreg having a thickness of 10 μm is bonded to one surface of an aluminum substrate having a thickness of 1 mm. In a state where the surface of the thermosetting prepreg of the second laminate and the white layer of the first laminate are overlapped, a pressure of 170 ° C. and 3 MPa is applied to apply heat and pressure, A laminate was obtained.
This third laminate is one form of the copper clad laminate of the present invention. The third laminate had a withstand voltage of 1.75 kV.
The third laminate has four layers of copper foil-white layer-thermosetting prepreg-aluminum substrate from the copper layer side.

(Example 2)
4 is another example using the first laminate obtained in Example 1. FIG.
In Example 1, the fourth laminate was heated and pressure-bonded to the first laminate. The fourth laminate has a three-layer structure in which a heat-dissipating insulating resin layer having a thickness of 50 μm is bonded to one side of an aluminum substrate having a thickness of 1 mm, and further, a thickness of 10 μm is provided on the back side of the heat-dissipating insulating resin layer. The heat curable prepreg has a structure adhered thereto. In a state where the surface of the thermosetting prepreg of the fourth laminate and the white layer of the first laminate are superposed, heat and pressure adhesion is applied by applying a pressure of 170 ° C. and 3 MPa, A laminate was obtained.
This fifth laminate is an embodiment of the copper clad laminate of the present invention.
The fifth laminated body has five layers of copper layer-white layer-thermosetting prepreg-heat radiation insulating resin layer-aluminum substrate from the copper foil side.
The fifth laminate has three insulating layer portions, a white layer, a thermosetting prepreg, and a heat-dissipating insulating resin layer. Both the white layer and the heat-dissipating insulating resin layer have high dielectric strength. For this reason, dielectric breakdown between the copper foil and the aluminum substrate hardly occurs. Therefore, even when applied to an ultraviolet LED mounting substrate using a very high voltage, there is no risk of dielectric breakdown. The fifth laminated body has a higher dielectric breakdown voltage than the third laminated body due to the effect of the heat-insulating insulating resin, has a dielectric breakdown voltage of 5.75 kV, and is advantageous as a large-sized LED mounting substrate that requires high dielectric strength. It had the characteristic.

(Example 3)
Two first laminates described in Example 1 were prepared, and one white layer and the other copper layer were joined with a thermosetting prepreg to obtain a sixth laminate. The fourth laminate was joined to the white layer of the sixth laminate to obtain a seventh laminate (copper-clad laminate of the present invention) having an eight-layer structure.
In the seventh laminated body, since there are two copper layers separated from the outermost surface and the inside, only a part of the circuit pattern is formed on the outermost surface, the remaining part is formed inside, and both are formed on the thickness of the copper-clad substrate. A three-dimensional circuit can be manufactured by electrically joining in the vertical direction. The area of the circuit (copper foil layer) remaining on the outermost surface after etching can be reduced, and the exposure of the white layer can be increased accordingly, so that the ultraviolet light reflectance can be improved. In addition, since the amount of Au used when Ni / Au plating (first Ni plating and Au plating on top) is performed on the outermost copper foil layer can be greatly reduced depending on the circuit shape. Cost can be reduced.

Example 4
The copper-clad laminate of the present invention obtained in Example 1 was etched in a copper etchant using a mask pattern on the copper layer side. A part of the copper foil was removed by etching, and a circuit pattern could be formed on the copper foil side of the copper clad laminate. From the etched portion, a white layer with extremely high ultraviolet light reflectivity and ultraviolet light resistance was exposed. As shown in FIG. 6, Ni / Au plating was performed on the formed circuit, and an LED element, a lead wire, and the like were joined thereon to obtain an LED mounting substrate.

1 Copper layer 2 White layer 3 Thermosetting prepreg 4 Aluminum substrate (high thermal conductivity substrate)
5 Thermal insulation resin layer 6 Circuit part (partially etched copper foil)
7 LED element 8 Lead wire 9 Ni / Au plating layer 10 1st laminated body 20 2nd laminated body 30 3rd laminated body 40 4th laminated body 50 5th laminated body 60 6th laminated body 70 6th 7 Laminate 101, 102, 103 Copper-clad laminate 101 'of the present invention Copper-clad laminate of the present invention after circuit formation

Claims (8)

It has a copper layer, a white layer, an adhesive layer and a high thermal conductivity substrate with a thermal conductivity of 200 W / m · K or higher in this order
The white layer is a composition having one or more fillers of BN, ZrO ₂ , SiO ₂ , CaF ₂ , and diamond in an organopolysiloxane matrix,
A copper-clad laminate in which the adhesive layer is a thermosetting resin. The organopolysiloxane has an organic group,
The copper clad laminate according to claim 1, wherein a ratio of the organic group having a carbon-carbon bond in the organic group is 5% or less. The organopolysiloxane has an organic group,
The copper clad laminate according to claim 1, wherein the organic group does not have a carbon-carbon bond.   The copper-clad laminate according to any one of claims 1 to 3, wherein a ratio of the filler in the white layer is 10 to 85% by volume.   The thickness of the said white layer is 10-200 micrometers, The copper clad laminated board of any one of Claims 1-4.   The copper clad laminate according to any one of claims 1 to 5, further comprising a heat-dissipating insulating resin layer between the adhesive layer and the high thermal conductive substrate.   A copper-clad laminate having a plurality of white layers, further comprising an adhesive layer, a white layer, and a copper layer in this order on the copper layer of the copper-clad laminate according to any one of claims 1 to 6. Board. at least,
Applying a white paint having one or more of BN, ZrO ₂ , SiO ₂ , CaF ₂ , and diamond in a matrix of organopolysiloxane on a copper foil;
A process of thermosetting the white paint on the copper foil while suppressing the deformation of the copper foil,
Bonding the white paint layer and a thermosetting resin having a high thermal conductivity substrate at least having a thermal conductivity of 200 W / m · K or more on one side in a heated and pressurized state;
The manufacturing method of a copper clad laminated board which contains these in this order.