阅读说明：本技术 层叠体、复合体及复合体的制造方法 (Laminate, composite, and method for producing composite ) 是由 川口顺二 于 2018-12-20 设计创作，主要内容包括：本发明提供一种色调等的外观及光透射率均优异的层叠体、复合体及复合体的制造方法。层叠体包含具有沿厚度方向贯穿的多个贯穿孔的金属箔及设置于金属箔的至少一个表面的正型感光性树脂层,金属箔的贯穿孔的平均开口直径为0.1～100μm,基于贯穿孔的平均开口率为0.1～90％。复合体具备层叠体,正型感光性树脂层具有沿厚度方向贯穿的多个贯穿孔,贯穿孔的平均开口直径为0.1～100μm,平均开口率为0.1～90％。(The invention provides a laminate, a composite and a method for producing the composite, wherein the laminate, the composite and the method are excellent in appearance such as color tone and light transmittance. The laminate comprises a metal foil having a plurality of through holes penetrating in the thickness direction and a positive photosensitive resin layer provided on at least one surface of the metal foil, wherein the average opening diameter of the through holes of the metal foil is 0.1 to 100 [ mu ] m, and the average opening ratio of the through holes is 0.1 to 90%. The composite comprises a laminate, wherein the positive photosensitive resin layer has a plurality of through holes penetrating in the thickness direction, the average opening diameter of the through holes is 0.1-100 μm, and the average opening ratio is 0.1-90%.)

1. A laminate comprising a metal foil having a plurality of through holes penetrating in a thickness direction and a positive photosensitive resin layer provided on at least one surface of the metal foil,

the average opening diameter of the through holes of the metal foil is 0.1 to 100 [ mu ] m, and the average opening ratio based on the through holes is 0.1 to 90%.

2. A laminate comprising a metal foil having a plurality of through-holes penetrating in a thickness direction, a resin layer provided on one surface of the metal foil, and a positive photosensitive resin layer provided on one surface of the metal foil on which the resin layer is not provided,

the average opening diameter of the through holes of the metal foil is 0.1 to 100 [ mu ] m, and the average opening ratio based on the through holes is 0.1 to 90%.

3. The laminate according to claim 1 or 2,

the positive photosensitive resin layer contains two compounds of (A) a phenol resin and (B) an o-naphthoquinone diazide compound or an infrared absorber.

4. The laminate according to claim 3, wherein,

the positive photosensitive resin layer contains a coloring material.

5. The laminate according to claim 4, wherein,

the coloring material includes a dye and a pigment.

6. The laminate according to any one of claims 1 to 5,

the average thickness of the metal foil is 5-1000 μm.

7. The laminate according to any one of claims 1 to 6,

the metal foil is:

a foil selected from the group consisting of aluminum foil, copper foil, silver foil, gold foil, platinum foil, stainless steel foil, titanium foil, tantalum foil, molybdenum foil, niobium foil, zirconium foil, tungsten foil, beryllium copper foil, bronze foil, brass foil, nickel silver foil, tin foil, lead foil, zinc foil, solder foil, iron foil, nickel foil, permalloy foil, nichrome foil, 42 alloy foil, kovar foil, monel foil, ukhinickel alloy foil, and hastelloy foil; or

A foil obtained by laminating the foil selected from the group and a foil of a metal different from the foil selected from the group.

8. A composite comprising the laminate according to any one of claims 1 to 7,

the positive photosensitive resin layer has a plurality of through holes penetrating in the thickness direction, the through holes having an average opening diameter of 0.1 to 100 [ mu ] m and an average opening ratio of 0.1 to 90%.

9. The complex according to claim 8,

the light transmittance is 0.1-90%.

10. A method of making a composite, wherein the composite comprises: a metal foil having a plurality of through-holes penetrating in a thickness direction, the through-holes having an average opening diameter of 0.1 to 100 μm and an average opening ratio of 0.1 to 90% based on the through-holes; and a positive photosensitive resin layer provided on at least one surface of the metal foil,

in the method for producing the composite, the positive photosensitive resin layer is exposed from the metal foil side, and the positive photosensitive resin layer after exposure is developed with an alkaline aqueous solution.

11. The method for producing a composite according to claim 10,

ultraviolet light or infrared light is used in the exposure.

Technical Field

The present invention relates to a laminate, a composite, and a method for producing a composite having a metal foil with through-holes, and more particularly, to a laminate, a composite, and a method for producing a composite, in which a positive photosensitive resin layer is formed on a metal foil with through-holes, and which has various functions while having transparency.

Background

Conventionally, it has been known that the decoration of a resin molded article is improved by evaporating a metal on the surface of the resin molded article to make it a metallic color tone or to make it a half mirror color tone.

For example, patent document 1 describes a composite for molding a metallic color decorative body, which is: a composite for molding a metallic color decorative body, which can produce a molded article having excellent appearance and light transmittance, comprises an aluminum base having a plurality of through holes in the thickness direction and a resin layer provided on at least one surface of the aluminum base, wherein the through holes have an average opening diameter of 0.1 to 100 [ mu ] m and an average opening ratio of 1 to 50% based on the through holes.

Prior art documents

Patent document

Patent document 1: international publication No. 2017/150099

Disclosure of Invention

Technical problem to be solved by the invention

The composite for molding a metallic color decorative body of patent document 1 can produce a molded article having excellent appearance and light transmittance, but further excellent appearance such as color and light transmittance are required, and such a composite is not known at present.

The invention aims to provide a laminate, a composite and a method for manufacturing the composite, wherein the laminate, the composite and the method are excellent in appearance such as color tone and light transmittance.

Means for solving the technical problem

In order to achieve the above object, the present invention provides a laminate comprising a metal foil having a plurality of through holes penetrating in a thickness direction and a positive photosensitive resin layer provided on at least one surface of the metal foil, wherein the through holes of the metal foil have an average opening diameter of 0.1 to 100 μm and an average opening ratio based on the through holes of 0.1 to 90%.

The present invention also provides a laminate comprising a metal foil having a plurality of through-holes penetrating in a thickness direction, a resin layer provided on one surface of the metal foil, and a positive photosensitive resin layer provided on one of both surfaces of the metal foil, wherein the through-holes of the metal foil have an average opening diameter of 0.1 to 100 μm and an average opening ratio based on the through-holes of 0.1 to 90%.

The positive photosensitive resin layer preferably contains two compounds of (a) a phenol resin and (B) o-naphthoquinone diazide or an infrared absorber.

Preferably, the positive photosensitive resin layer contains a coloring material.

Preferably, the coloring material comprises a dye and a pigment.

The average thickness of the metal foil is preferably 5 to 1000 μm.

Preferably, the metal foil is a foil selected from the group consisting of aluminum foil, copper foil, silver foil, gold foil, platinum foil, stainless steel foil, titanium foil, tantalum foil, molybdenum foil, niobium foil, zirconium foil, tungsten foil, beryllium copper foil, bronze foil, brass foil, nickel silver foil, tin foil, lead foil, zinc foil, solder foil, iron foil, nickel foil, permalloy foil, nichrome foil, 42 alloy foil, kovar foil, monel foil, englery nickel alloy foil, and hastelloy foil, or a foil in which a foil selected from the group and a foil of a different kind of metal from the foil selected from the group are laminated.

The present invention provides a composite comprising the laminate of the present invention, wherein the positive photosensitive resin layer has a plurality of through holes penetrating in the thickness direction, the through holes have an average opening diameter of 0.1 to 100 μm, and an average opening ratio of 0.1 to 90%.

The light transmittance is preferably 0.1 to 90%.

Also, the present invention provides a method for producing a composite body, the composite body including: a metal foil having a plurality of through holes penetrating in a thickness direction, the through holes having an average opening diameter of 0.1 to 100 μm and an average opening ratio of 0.1 to 90% based on the through holes; and a positive photosensitive resin layer provided on at least one surface of the metal foil, wherein the positive photosensitive resin layer is exposed from the metal foil side, and the positive photosensitive resin layer after exposure is developed with an alkaline aqueous solution.

Preferably, ultraviolet light or infrared light is used for the exposure.

Effects of the invention

According to the present invention, a composite excellent in appearance such as color tone and light transmittance can be provided. Further, a laminate which is a composite excellent in appearance such as color tone and light transmittance can be provided.

Further, a method for producing a composite excellent in appearance such as color tone and light transmittance can be provided.

Drawings

Fig. 1 is a schematic plan view showing a1 st example of a composite body according to an embodiment of the present invention.

Fig. 2 is a schematic cross-sectional view showing example 1 of the composite according to the embodiment of the present invention.

Fig. 3 is a cross-sectional view showing an example of a metal foil for explaining the average effective diameter of the through-holes of the composite according to the embodiment of the present invention.

Fig. 4 is a cross-sectional view showing another example of the metal foil for explaining the average effective diameter of the through-holes of the composite according to the embodiment of the present invention.

Fig. 5 is a schematic cross-sectional view showing example 2 of the composite according to the embodiment of the present invention.

Fig. 6 is a schematic cross-sectional view showing example 3 of the composite according to the embodiment of the present invention.

Fig. 7 is a schematic cross-sectional view showing a step of example 1 of the method for producing a composite according to the embodiment of the present invention.

Fig. 8 is a schematic cross-sectional view showing a step of example 1 of the method for producing a composite according to the embodiment of the present invention.

Fig. 9 is a schematic cross-sectional view showing a step of example 1 of the method for producing a composite according to the embodiment of the present invention.

Fig. 10 is a schematic cross-sectional view showing a step of example 1 of the method for producing a composite according to the embodiment of the present invention.

Fig. 11 is a schematic cross-sectional view showing a step of example 1 of the method for producing a composite according to the embodiment of the present invention.

Fig. 12 is a schematic cross-sectional view showing a step of example 2 of the method for producing a composite according to the embodiment of the present invention.

Fig. 13 is a schematic cross-sectional view showing a step of example 2 of the method for producing a composite according to the embodiment of the present invention.

Fig. 14 is a schematic cross-sectional view showing a step of example 2 of the method for producing a composite according to the embodiment of the present invention.

Fig. 15 is a schematic cross-sectional view showing a step of example 3 of the method for producing a composite according to the embodiment of the present invention.

Fig. 16 is a schematic cross-sectional view showing a step of example 3 of the method for producing a composite according to the embodiment of the present invention.

Fig. 17 is a schematic cross-sectional view showing a step of example 3 of the method for producing a composite according to the embodiment of the present invention.

Fig. 18 is a schematic cross-sectional view showing a step of example 3 of the method for producing a composite according to the embodiment of the present invention.

Fig. 19 is a schematic cross-sectional view showing a step of another example of the method for manufacturing a through-hole in a metal foil of a composite according to the embodiment of the present invention.

Fig. 20 is a schematic cross-sectional view showing a step of another example of the method for manufacturing a through-hole in a metal foil of a composite according to the embodiment of the present invention.

Fig. 21 is a schematic cross-sectional view showing a step of another example of the method for manufacturing a through-hole in a metal foil of a composite according to the embodiment of the present invention.

Fig. 22 is a schematic cross-sectional view showing a step of another example of the method for manufacturing a through-hole in a metal foil of a composite according to the embodiment of the present invention.

Detailed Description

Hereinafter, the laminate, the composite, and the method for producing the composite according to the present invention will be described in detail based on preferred embodiments shown in the drawings.

The drawings described below are exemplary drawings for describing the present invention, and the present invention is not limited to the drawings described below.

In addition, "to" which indicates a numerical range in the following includes numerical values described on both sides. For example, a range from a numerical value α to a numerical value β means a range including the numerical value α and the numerical value β, and if represented by a mathematical symbol, α ≦ β.

The terms "parallel" and "perpendicular" and the like include the error ranges that are generally allowed in the art unless otherwise specified.

[ composite body ]

The 1 st composite comprises a metal foil having a plurality of through holes penetrating in a thickness direction and a positive photosensitive resin layer provided on at least one surface of the metal foil,

the average opening diameter of the through holes of the metal foil is 0.1 to 100 μm, the average opening ratio based on the through holes is 1 to 50%,

the positive photosensitive resin layer has a plurality of through holes penetrating in the thickness direction, the average opening diameter of the through holes is 0.1 to 100 μm, and the average opening ratio is 0.1 to 90%.

A laminate comprising a metal foil having a plurality of through holes penetrating in a thickness direction and a positive photosensitive resin layer provided on at least one surface of the metal foil, wherein the average opening diameter of the through holes of the metal foil is 0.1 to 100 [ mu ] m, and the average opening ratio of the through holes is 1 to 50%. The positive photosensitive resin layer has no through-hole in the former stage when the laminate is a composite. The laminate is processed to obtain a composite.

The No. 2 composite comprises a metal foil having a plurality of through holes penetrating in a thickness direction, a resin layer provided on one surface of the metal foil, and a positive photosensitive resin layer provided on the other surface of the metal foil,

the average opening diameter of the through holes of the metal foil is 0.1 to 100 μm, the average opening ratio based on the through holes is 1 to 50%,

the positive photosensitive resin layer has a plurality of through holes penetrating in the thickness direction, the average opening diameter of the through holes is 0.1 to 100 μm, and the average opening ratio is 0.1 to 90%.

A laminate comprising a metal foil having a plurality of through holes penetrating in a thickness direction, a resin layer provided on one surface of the metal foil, and a positive photosensitive resin layer provided on the other surface of the metal foil, wherein the average opening diameter of the through holes of the metal foil is 0.1 to 100 [ mu ] m, and the average opening ratio of the through holes is 1 to 50%. The positive photosensitive resin layer has no through-hole in the former stage when the laminate is a composite. The laminate is processed to obtain a composite.

As described above, the laminate, the 1 st composite, and the 2 nd composite have the same structure, and the metal foil and the positive photosensitive resin layer have the same structure, composition, and the like, except that no through-hole is formed in the positive photosensitive resin layer.

In the present invention, the metal foil including through holes having an average opening diameter and an average opening ratio within the above ranges and the positive photosensitive resin layer provided on at least one surface of the metal foil are excellent in appearance such as color tone and light transmittance.

The details are not clear, but the inventors presume as follows.

When the average opening diameter and the average opening ratio of the through holes existing in the metal foil are within the above ranges, it is difficult to visually confirm the existence of the through holes, and it is considered that light can be transmitted without impairing the appearance such as color tone in order to make the positive photosensitive resin layer visible.

Further, the inclusion of the positive photosensitive resin layer is considered to provide excellent appearance such as color tone and light transmittance, to have various functions in addition to transmittance, and to facilitate processing of a molded article such as a metallic color decorative body used for illumination.

The average opening diameter of the through holes is calculated by taking an image of the surface of the metal foil from directly above using a magnification of 100 to 10000 times for a high resolution scanning electron microscope, extracting at least 20 through holes whose peripheries are connected in a ring shape from a photographed image obtained using the high resolution scanning electron microscope, reading the diameter of the through holes to obtain an opening diameter, and calculating the average of the diameters as the average opening diameter.

Further, the magnification in the above range can be appropriately selected so as to obtain a photographed image from which 20 or more through-holes can be extracted. Then, the maximum value of the distance between the ends of the through-hole portion was measured with respect to the opening diameter. That is, the shape of the opening portion of the through-hole is not limited to a substantially circular shape, and therefore, when the shape of the opening portion is a non-circular shape, the maximum value of the distance between the end portions of the through-hole portion is defined as the opening diameter. Therefore, for example, when the through-hole has a shape in which through-holes are integrated as 2 or more, the through-hole is regarded as 1 through-hole, and the maximum value of the distance between the ends of the through-hole portion is defined as the opening diameter.

Then, with respect to the average aperture ratio based on the through-holes, a parallel light optical element is provided on one surface side of the metal foil, parallel light is transmitted, the surface of the metal foil is photographed from the other surface of the metal foil with a magnification of 100 times for an optical microscope, and the photographed image is obtained as a photograph or digital image data. Regarding the field of view (5 portions) of 100mm × 75mm within the range of 10cm × 10cm of the obtained photographic image, a ratio (opening area/geometric area) is calculated from the total of the opening areas of the through-holes projected by the transmitted parallel light and the area (geometric area) of the field of view, and the average value in each field of view (5 portions) is calculated as the average aperture ratio.

Hereinafter, the complex will be specifically described with reference to the drawings.

Fig. 1 is a schematic plan view showing a1 st example of the composite body according to the embodiment of the present invention, and fig. 2 is a schematic cross-sectional view showing the 1 st example of the composite body according to the embodiment of the present invention.

As shown in fig. 1 and 2, the composite 10 includes a metal foil 12 having a plurality of through holes 13 penetrating in a thickness direction Dt, and a positive photosensitive resin layer 14 provided on at least one surface 12a of the metal foil 12.

The average opening diameter of the through-holes 13 of the metal foil 12 is 0.1 to 100 μm, and the average opening ratio based on the through-holes 13 is 1 to 50%.

The positive photosensitive resin layer 14 has a plurality of through holes 15 penetrating in the thickness direction Dt, the through holes 15 having an average opening diameter of 0.1 to 100 μm and an average opening ratio of 0.1 to 90%.

As shown in fig. 2, the through-holes 13 of the metal foil 12 and the through-holes 15 of the positive photosensitive resin layer 14 are arranged in a line, and 1 through-hole is formed by the through-hole 13 of the metal foil 12 and the through-hole 15 of the positive photosensitive resin layer 14.

Here, the composite 10 shown in fig. 1 and 2 has a surface in which the wall surface of the through-hole 13 is perpendicular to the surface of the metal foil 12, but as shown in fig. 3 and 4 described later, the wall surface of the through-hole 13 may have a concave-convex shape.

Fig. 3 is a cross-sectional view showing an example of a metal foil for explaining the average effective diameter of the through-holes of the composite according to the embodiment of the present invention, and fig. 4 is a cross-sectional view showing another example of a metal foil for explaining the average effective diameter of the through-holes of the composite according to the embodiment of the present invention.

The average effective diameter is the shortest distance between the wall surfaces of the through holes in the cross section taken perpendicular to the surface of the metal foil, and as shown in fig. 3 and 4, the average effective diameter is the shortest distance between the wall surfaces of the through holes in the metal foil 12 and the wall surface of the left wall surface from the reference line E₁Perpendicular line Q in point 12c having the largest distance₁From reference line E in wall surface of right hole of through hole₂Perpendicular line Q in the point 12d having the largest distance₂Is measured as the average of the distances X.

In the present invention, a parallel light optical element is provided on one surface side of the metal foil with respect to the average effective diameter, parallel light is transmitted, the surface of the metal foil is photographed from the other surface of the metal foil with a magnification of 100 times for an optical microscope, and the photographed image is obtained as photograph or digital image data. For the viewing angles (5 sites) of 100mm × 75mm in the range of 10cm × 10cm of the obtained photographic image, 20 penetrating holes projected by the transmitted parallel light were extracted at each viewing angle. The diameters of the extracted total of 100 through-holes were measured, and the average value of the diameters was calculated as an average effective diameter.

In the composite 10 shown in fig. 1 and 2, the positive photosensitive resin layer 14 is not provided on the other surface 12b of the metal foil 12, and the positive photosensitive resin layer 14 is provided only on the one surface 12 a. However, the present invention is not limited to this configuration.

For example, as shown in fig. 5, the composite 10 may have a structure in which the positive photosensitive resin layers 14 are provided on one surface 12a and the other surface 12b of the metal foil 12, respectively, that is, a structure in which the positive photosensitive resin layers 14 are provided on both surfaces of the metal foil 12. In this case, the positions of the through holes 15 of the positive photosensitive resin layer 14 provided on the surfaces 12a and 12b coincide with the positions of the through holes 13 of the metal foil 12, and 1 through hole is formed by the through hole 15 of the positive photosensitive resin layer 14 and the through hole 13 of the metal foil 12.

As shown in fig. 6, the composite 10 may have a structure in which the resin layer 16 is provided on the other surface 12b of the metal foil 12 and the positive photosensitive resin layer 14 is provided on the one surface 12 a. In the composite 10 shown in fig. 6, the resin layer 16 and the positive photosensitive resin layer 14 may be arranged in opposite positions. The resin layer 16 has a structure in which no through-hole is provided. In this case, the positions of the through holes 15 of the positive photosensitive resin layer 14 provided on the surface 12a coincide with the positions of the through holes 13 of the metal foil 12, and 1 through hole is formed by the through hole 15 of the positive photosensitive resin layer 14 and the through hole 13 of the metal foil 12.

Fig. 5 is a schematic cross-sectional view showing a 2 nd example of the composite body according to the embodiment of the present invention, and fig. 6 is a schematic cross-sectional view showing a 3 rd example of the composite body according to the embodiment of the present invention.

Hereinafter, the laminate and the composite will be described in more detail.

[ Metal foil ]

The metal foil of the laminate and the composite is not particularly limited as long as it has a through-hole. The foil is preferably a foil made of at least 1 of a metal, an alloy, and a metal compound, which can easily form the through-holes having the average opening diameter and the average opening ratio described above, and more preferably a foil made of a metal.

Further, it is also preferable that the metal foil contains metal atoms dissolved in an etchant used in a through hole forming step described later. The metal foil may be made of any one of a metal, an alloy, and a metal compound, and is referred to as a metal foil.

Specific examples of the metal foil include aluminum foil, copper foil, silver foil, gold foil, platinum foil, stainless steel foil, titanium foil, tantalum foil, molybdenum foil, niobium foil, zirconium foil, tungsten foil, beryllium copper foil, bronze foil, brass foil, nickel silver foil, tin foil, lead foil, zinc foil, solder foil, iron foil, nickel foil, permalloy foil, nichrome foil, 42 alloy foil, kovar foil, monel foil, englein alloy foil, hastelloy foil, and the like.

The metal foil may be a foil obtained by laminating a foil selected from the above-described exemplified metal group and a foil of a different kind of metal from the foil selected from the above-described group. The metal foil may be a metal foil obtained by laminating 2 or more different metal foils.

The method of laminating the metal foil is not particularly limited, and plating or a clad material is preferable. The metal used for plating is not particularly limited as long as it contains metal atoms dissolved in the etchant, and is preferably a metal. Examples of the plating material include nickel, chromium, cobalt, iron, zinc, tin, copper, silver, gold, platinum, palladium, and aluminum.

The method of plating is not particularly limited, and electroless plating, electrolytic plating, melt plating, chemical conversion treatment, and the like can be used.

The metal used for forming the cladding material on the metal foil is not particularly limited as long as it is a metal containing metal atoms dissolved in an etchant, and a metal is preferable. Examples of the metal substance include metals used for the metal foil.

< thickness of Metal foil >

The average thickness of the metal foil is preferably 5 to 1000 μm, more preferably 5 to 50 μm, and still more preferably 8 to 30 μm from the viewpoint of handling property. The average thickness of the metal foil is an average value of thicknesses measured at arbitrary 5 points using a contact type film thickness measuring instrument (digital electronic micrometer).

< aluminum foil >

When an aluminum foil is used as the metal foil, for example, 1000 types such as 1085 material, 3000 types such as 3003 material, 8000 types such as 8021 material, and the like can be used as the aluminum foil. As such an aluminum alloy, for example, aluminum alloys of alloy numbers shown in table 1 below can be used.

[ Table 1]

< through hole >

As described above, the average opening diameter of the through-holes in the metal foil is 0.1 to 100 μm, and the average opening ratio of the through-holes is 0.1 to 90%.

In view of tensile strength, transmittance, and the like, the average opening diameter of the through-holes is preferably 1 to 45 μm, more preferably 1 to 40 μm, and still more preferably 1 to 30 μm.

In addition, the average opening ratio based on the through-holes is preferably 2 to 45%, more preferably 2 to 30%, and particularly preferably 2 to 20% from the viewpoint of tensile strength, transmittance characteristics, and the like.

In the present invention, the average effective diameter of the through-holes in the cross section taken perpendicular to the surface of the metal foil is preferably 700nm or more, more preferably 800nm or more, and still more preferably 1 to 100 μm, from the viewpoint of better light transmittance.

[ Positive photosensitive resin layer ]

The positive photosensitive resin layer imparts color to the composite. The thickness of the positive photosensitive resin layer is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and most preferably 1 to 30 μm.

The thickness of the positive photosensitive resin layer was measured by cutting the composite with a microtome and measuring the average value of the thickness at any 5 points of the layer corresponding to the positive photosensitive resin layer when the cross section was observed with an electron microscope.

The positive photosensitive resin layer is not particularly limited in wavelength of exposure light as long as the through-hole can be formed by exposure and development. The positive photosensitive resin layer is exposed to, for example, infrared light or ultraviolet light and developed by an alkali aqueous solution.

The structure of the positive photosensitive resin layer is not particularly limited as long as it can be exposed to infrared light or ultraviolet light, for example, and a known positive photosensitive resin layer can be suitably used.

Specific examples of the positive photosensitive resin layer will be described below.

The positive photosensitive resin layer preferably contains two compounds of (a) a phenol resin and (B) o-naphthoquinone diazide or an infrared absorber. Also, the positive photosensitive resin layer may contain a coloring material. The coloring material may include a dye and a pigment.

[ phenol type resin ]

The phenol resin (a) includes, as the alkali-soluble polymer having a phenol group (-Ar-OH), for example, a novolac resin produced from an aldehyde such as formaldehyde and paraformaldehyde and a condensation product of pyrogallol and acetone and 1 or 2 or more types of phenols such as phenol, o-cresol, m-cresol, p-cresol, and xylenol. Further, a copolymer obtained by co-polymerizing compounds having a phenol group can be also exemplified. Examples of the compound having a phenol group include acrylamide, methacrylamide, acrylate, methacrylate, hydroxystyrene, and the like having a phenol group.

Specific examples thereof include N- (2-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl) methacrylamide, N- (3-hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxyphenylacrylic acid, m-hydroxyphenylacrylic acid, p-hydroxyphenylacrylic acid, o-hydroxyphenylmethacrylate, m-hydroxyphenylmethacrylate, p-hydroxyphenylmethacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (2-hydroxyphenyl) ethacrylic acid, 2- (3-hydroxyphenyl) ethacrylic acid, 2- (4-hydroxyphenyl) ethacrylic acid, N-hydroxyphenyl acrylamide, N- (4-hydroxyphenyl) methacrylamide, N- (3-hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) ethacrylamide, o-hydroxyphenylacrylic acid, 2- (2-hydroxyphenyl) ethyl methacrylate, 2- (3-hydroxyphenyl) ethyl methacrylate, and 2- (4-hydroxyphenyl) ethyl methacrylate.

Among these, a novolak resin or a copolymer of hydroxystyrene is preferable. Commercially available hydroxystyrene copolymers include those manufactured by Maruki Kagaku Kogyo, MARUKA LYNCUR M H-2, MARUKA LYNCUR MS-4, MARUKA LYNCUR M S-2, MARUKA LYNCUR M S-1, NIPPON SODA CO., LTD, VP-8000, and VP-15000.

The positive photosensitive resin layer may contain a polymer component, and the polymer component is preferably a homopolymer or a copolymer having a weight average molecular weight of 1.0 × 10³～2.0×10⁵The number average molecular weight of the copolymer was 5.0 × 10²～1.0×10⁵The range of (1). The polydispersity (weight average molecular weight/number average molecular weight) is preferably 1.1 to 10.

When a copolymer is used as the polymer component, the weight ratio of the minimum structural unit derived from the compound having an acidic group constituting the main chain and/or the side chain to the other minimum structural unit not containing an acidic group constituting a part of the main chain and/or the side chain is preferably 50:50 to 5:95, more preferably 40:60 to 10: 90.

The polymer component may be used alone in 1 kind, or 2 or more kinds may be used in combination, and the polymer component used is preferably in the range of 30 to 99 mass%, more preferably 40 to 95 mass%, and even more preferably 50 to 90 mass% with respect to the total solid content contained in the composition.

(surfactant)

From the viewpoint of coatability, a nonionic surfactant as described in Japanese patent application laid-open Nos. 62-251740 and/or 3-208514, and an amphoteric surfactant as described in Japanese patent application laid-open Nos. 59-121044 and/or 4-013149 may be added to the positive photosensitive resin layer.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, and/or polyoxyethylene nonylphenyl ether.

Specific examples of the amphoteric surfactant include alkylbis (aminoethyl) glycine, alkylpolyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine, and/or N-tetradecyl-N, N-betaine type (for example, product name AMOGEN K, DAIICHI KOGYO CO., LTD).

The content of the surfactant in the case of containing the surfactant is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass, based on the total solid content contained in the composition.

(solvent)

The positive photosensitive resin layer can be added with a solvent from the viewpoint of workability in forming the resin layer.

Specific examples of the solvent include dichloroethane, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N-dimethylacetamide, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ -butyrolactone, toluene, and water, and 1 kind of these may be used alone or 2 or more kinds may be used in combination.

[ O-naphthoquinone diazide Compound ]

The o-naphthoquinone diazide compound used in the present invention is preferably an ester of 1, 2-diazonaphthoquinone sulfonic acid chloride and pyrogallol-acetone resin as described in Japanese patent publication No. 43-028403. Other preferable o-quinonediazides include esters of 1, 2-diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resins described in U.S. Pat. No. 3,046,120 and U.S. Pat. No. 3,188,210. Other useful o-naphthoquinone diazide compounds are known and reported in many patents. Examples thereof include Japanese patent application laid-open Nos. Sho 47-005303, 48-063802, 48-063803, 48-096575, 49-038701, 48-013354, 37-018015, 41-11222, 45-009610, 49-017481, 2,797,213, 3,454,400, 3,544,323, 3,573,917, 3,674,495, 3,785,825, 1,227,602, 1,251,345, 48, 1,267,005, 39 1,329,888, 1,330,932 and 854,890 A compound is provided.

The o-naphthoquinone diazide compound particularly preferred in the present invention is a compound obtained by reacting a polyhydroxyl compound having a molecular weight of 1,000 or less with 1, 2-diazonaphthoquinone sulfonic acid chloride. Specific examples of such a compound include Japanese patent application laid-open Nos. 51-139402, 58-150948, 58-203434, 59-165053, 60-121445, 60-134235, 60-163043, 61-118744, 62-010645 and 62-010646, examples of the compound include those described in Japanese patent laid-open publication No. Sho 62-153950, Japanese patent laid-open publication No. Sho 62-178562, Japanese patent laid-open publication No. Hei 1-076047, U.S. Pat. No. 3,102,809, U.S. Pat. No. 3,126,281, U.S. Pat. No. 3,130,047, U.S. Pat. No. 3,148,983, U.S. Pat. No. 3,184,310, U.S. Pat. No. 3,188,210, and U.S. Pat. No. 4,639,406.

In the synthesis of these o-naphthoquinone diazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1, 2-diazonaphthoquinone sulfonic acid chloride with the hydroxyl group of the polyhydroxy compound, and it is preferable to react 0.3 to 1.0 equivalents. The obtained o-naphthoquinone diazide compound is a mixture having different positions and introduction amounts of 1, 2-diazonaphthoquinone sulfonate groups, but the proportion of the compound having all the hydroxyl groups converted by 1, 2-diazonaphthoquinone sulfonate ester groups in the mixture (the content of the completely esterified compound) is preferably 5 mol% or more, and more preferably 20 to 99 mol%. The amount of the o-naphthoquinone diazide compound in the positive photosensitive resin layer is 5 to 50 wt%, and more preferably 15 to 40 wt%.

[ Infrared absorber ]

The positive photosensitive resin layer preferably has an infrared absorber. As the infrared absorber, an infrared absorber having an onium salt type structure is preferably used from the viewpoint of being required to play a positive role between the structural units of the polymer (the unexposed portion suppresses development, and is released or disappears in the exposed portion). Specifically, dyes such as cyanine dyes and pyrylium salts can be preferably used.

Examples of the preferable dye include cyanine dyes described in, for example, Japanese patent laid-open Nos. 58-125246, 59-084356, 59-202829, and 60-078787, and cyanine dyes described in the specification of British patent No. 434,875.

Further, it is preferable to use a near-infrared absorption sensitizer described in the specification of U.S. Pat. No. 5,156,938, a substituted arylbenzo (thio) pyrylium salt described in the specification of U.S. Pat. No. 3,881,924, a trimethylthiopyrylium salt described in Japanese patent application laid-open No. 57-142645 (Specification of U.S. Pat. No. 4,327,169), a pyrylium compound described in Japanese patent application laid-open No. 58-181051, a pyrylium compound described in Japanese patent application laid-open No. 58-220143, a cyanine compound described in Japanese patent application laid-open No. 59-41363, a cyanine dye described in Japanese patent application laid-open No. 59-084248, a cyanine dye described in Japanese patent application laid-open No. 59-146061, a cyanine dye described in Japanese patent application laid-open No. 59-216146, a pentamethylthiopyrylium salt described in the specification of U.S. 4,283,475, and the like, Pyrylium compounds disclosed in Japanese patent publication No. 5-013514 and Japanese patent publication No. 5-019702.

Further, as a preferable dye, there can be also mentioned a near infrared absorbing dye represented by the formulae (c) and (II) in the specification of U.S. Pat. No. 4,756,993.

Further, the anionic infrared absorbent described in Japanese patent application No. Hei 10-079912 can also be preferably used. The anionic infrared absorbent is an infrared absorbent having an anionic structure, which is substantially free of a cationic structure in a parent nucleus of a dye that absorbs infrared light.

Examples thereof include (c1) anionic metal complexes, (c2) anionic carbon black, (c3) anionic phthalocyanines, and (c4) compounds represented by the following general formula (7). The counter cation of these anionic infrared absorbers is a monovalent cation or a higher cation containing a proton. G of the following general formula (7)_a ^-Represents an anionic substituent group, G_bRepresents a neutral substituent. X^m+Represents a cation having a valence of 1 to m including a proton, and m represents an integer of 1 to 6.

[ chemical formula 1]

[G_a ^--M-G_b]_mX^m+General formula (7)

Here, the anionic metal complex (c1) means that substantially the entire central metal and ligand in the complex portion absorbing light becomes an anion.

(c2) Examples of the anionic carbon black include carbon blacks in which an anionic group such as a sulfonic acid group, a carboxylic acid group, or a phosphonic acid group is bonded as a substituent. When these groups are introduced into carbon black, a device such as oxidation of carbon black with a predetermined acid described in page 12 of the third edition of the carbon black release (the compilation of carbon black, 4 and 5 th in 1995, and the release of carbon black in collaborated with each other) may be used.

Although the anionic infrared absorber in which an onium salt is bonded as a counter cation ion to an anionic group of the anionic carbon black is preferably used in the present invention, an adsorbate in which an onium salt is adsorbed to carbon black is not included in the anionic infrared absorber of the present invention, and the effects of the present invention cannot be obtained in a single adsorbate.

(c3) The anionic phthalocyanine is an anion in which an anionic group mentioned in the description of (c2) above is bonded as a substituent to the phthalocyanine skeleton and which is anionic as a whole.

Then, toThe compound represented by the general formula (7) (c4) will be described in detail. In the general formula (7), M represents a conjugated chain, and the conjugated chain M may have a substituent or a ring structure. The conjugated chain M can be represented by the following formula. In the following formula, R¹、R²、R³Each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group, and these groups may be linked to each other to form a ring structure. n represents an integer of 1 to 8.

[ chemical formula 2]

Among the anionic infrared absorbers represented by the above general formula (7), the following A-1 to A-19 are preferably used.

[ chemical formula 3]

[ chemical formula 4]

[ chemical formula 5]

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 8]

These dyes can be added in an amount of 0.01 to 50 wt%, preferably 0.1 to 10 wt%, and particularly preferably 0.5 to 10 wt% based on the total solid content of the positive photosensitive resin layer. If the amount of the dye added is less than 0.01% by weight, the sensitivity is lowered, while if it exceeds 50% by weight, the color tone is deteriorated.

[ coloring Material ]

The positive photosensitive resin layer may contain other dyes, pigments, and the like for the purpose of further improving sensitivity and development latitude.

As the dye, a commercially available dye and a known dye described in the literature, for example, "the passage of dyes" (edited by organic synthesis, journal of showa 45), and the like, can be used. Specific examples thereof include azo dyes, metal-complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinonimine dyes, methine dyes, squarylium pigments, and metal thiolate complexes.

As the pigment, commercially available pigments and pigments described in "recent pigment review" (edited by japan pigment technology association, journal of 1977), "recent pigment application technology" (CMC published, journal of 1986), "printing ink technology" CMC published, journal of 1984) can be used.

Examples of the type of pigment include a black pigment, a yellow pigment, an orange pigment, a brown pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a fluorescent pigment, a metal powder pigment, and other polymer-bonded pigments. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dye lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Preferred among these pigments is carbon black.

These pigments may be used without surface treatment or after surface treatment. As the method of surface treatment, there may be mentioned a method of surface coating a resin or paraffin, a method of attaching a surfactant, a method of bonding a reactive substance (e.g., a silane coupling agent, an epoxy compound, polyisocyanate, etc.) to the surface of a pigment, and the like. The above surface treatment methods are described in "the nature and application of metal soaps" (Happy Books), "printing ink technology" (CMC published, 1984) and "the latest pigment application technology" (CMC published, 1986).

The particle diameter of the pigment is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 1 μm, and particularly preferably in the range of 0.1 to 1 μm. If the particle diameter of the pigment is less than 0.01 μm, it is not preferable from the viewpoint of stability in the image recording layer coating liquid of the dispersion, and if it is more than 10 μm, it is not preferable from the viewpoint of uniformity of the image recording layer.

As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the dispersing machine include an ultrasonic disperser, a sand mill, an attritor, a bead mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a triode, a 3-roll mill, and a pressure kneader. Details are described in "recent pigment application technology" (published by CMC, journal of 1986).

The amount of the positive photosensitive resin layer added is preferably 0.01 to 50% by weight, more preferably 0.1 to 10% by weight, based on the total solid content of the dye or pigment. In addition, the dye is preferably 0.5 to 10% by weight in particular, and the pigment is preferably 1.0 to 10% by weight in particular. If the amount of the pigment or dye added is less than 0.01% by weight, the sensitivity is lowered, while if it exceeds 50% by weight, the color tone is deteriorated.

These dyes or pigments may be added to the same layer as the other components, or may be added by providing another layer. Among the above dyes or pigments, those which absorb infrared light or near-infrared light are particularly preferable. Further, 2 or more kinds of dyes and pigments may be used simultaneously.

[ resin layer ]

The resin layer is not particularly limited as long as it is a layer formed of a transparent resin material, and examples of the resin material include polyester, polyolefin, and the like.

Specific examples of the polyester include polyethylene terephthalate (PET) and polyethylene naphthalate.

Specific examples of the other resin material include polyamide, polyether, polystyrene, polyesteramide, polycarbonate, polyphenylene sulfide, polyether ester, polyvinyl chloride, polyacrylate, and polymethacrylate.

Here, "having transparency" means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

< thickness >

From the viewpoint of handling and processability, the average thickness of the resin layer is preferably 12 to 100 μm, more preferably 25 to 100 μm, and still more preferably 50 to 100 μm. The average thickness of the resin layer was measured at 5 arbitrary points using a contact type film thickness measuring instrument (digital electronic micrometer).

< transmittance >

The light transmittance of the composite is preferably 0.1-90%. The light transmittance can be adjusted by the average aperture ratio.

The light transmittance is an average value of the transmittance of light in a wavelength region of 200nm to 900nm, and is a transmittance measured in accordance with JIS (japanese industrial standards) K7361.

Hereinafter, a method for producing the composite will be described.

[ method for producing composite ]

The method for producing the composite is not particularly limited, and includes, for example, a film forming step of forming an aluminum hydroxide film on at least one surface of a metal foil, a through-hole forming step of forming a through-hole by performing a through-hole forming treatment after the film forming step, a film removing step of removing the aluminum hydroxide film after the through-hole forming step, and a positive photosensitive resin layer forming step of forming a positive photosensitive resin layer on at least one surface of the metal foil having the through-hole after the film removing step.

The method comprises a resin layer forming step of forming a resin layer on one surface of a metal foil, a film forming step of forming an aluminum hydroxide film on the surface of the metal foil on the side where the resin layer is not provided after the resin layer forming step, a through-hole forming step of forming a through-hole by performing through-hole forming treatment after the film forming step, a film removing step of removing the aluminum hydroxide film after the through-hole forming step, and a positive photosensitive resin layer forming step of forming a positive photosensitive resin layer on the surface of the metal foil on the side where the resin layer is not provided.

Hereinafter, the method for producing the composite will be described with reference to the drawings, and then each step will be described in detail.

Fig. 7 to 11 are schematic cross-sectional views showing example 1 of the method for producing a composite body according to the embodiment of the present invention in the order of steps. Example 1 of the method for producing a composite is an example of the method for producing the composite 10 shown in fig. 1 and 2. In fig. 7 to 11, the same components as those of the composite 10 shown in fig. 1 and 2 are denoted by the same reference numerals, and detailed description thereof will be omitted.

First, a metal base material 11 (see fig. 7) to be a metal foil 12 (see fig. 2) is prepared. The metal base 11 is made of aluminum, for example. Hereinafter, the metal base 11 made of aluminum will be described as an example.

Next, both surfaces 11a and 11b of the metal base material 11 are subjected to a film formation treatment to form an aluminum hydroxide film (not shown). The step of forming the aluminum hydroxide film is referred to as a film forming step.

After the film forming step, for example, electrolytic dissolution treatment is performed to form the through-hole. The step of forming the through-hole is referred to as a through-hole forming step. After the through-hole forming step, the aluminum hydroxide film is removed. The step of removing the aluminum hydroxide film is referred to as a film removal step.

Through the above steps, as shown in fig. 8, the metal foil 12 having the through-hole 13 is obtained.

Next, the positive photosensitive resin composition to be the positive photosensitive resin layer 14 (see fig. 2) is applied to the surface 12a of the metal foil 12, and as shown in fig. 9, a positive photosensitive resin film 20 is formed.

Next, as shown in fig. 10, exposure light Le is irradiated from the front surface 12b side of the metal foil 12, and the exposure light Le transmitted through the through-hole 13 is irradiated to the positive photosensitive resin film 20 using the metal foil 12 as a mask to perform exposure. Subsequently, the positive photosensitive resin film 20 is developed. By the development, as shown in fig. 11, the positive photosensitive resin layer 14 in which the through-holes 15 are formed at positions corresponding to the positions of the through-holes 13 of the metal foil 12 is formed. This provides a composite 10 in which the positive photosensitive resin layer 14 is formed on the one surface 12a of the metal foil 12. The step of forming the positive photosensitive resin layer 14 is referred to as a positive photosensitive resin layer forming step.

Fig. 12 to 14 are schematic cross-sectional views showing a method for producing a composite body according to an embodiment of the present invention, according to example 2, in the order of process steps. Example 2 of the method for producing the composite is an example of the method for producing the composite 10 shown in fig. 5. In fig. 12 to 14, the same components as those shown in fig. 7 to 11 are denoted by the same reference numerals, and detailed description thereof will be omitted.

In example 2, the steps up to the step of obtaining the metal foil 12 in which the through-holes 13 shown in fig. 8 are formed are the same as those in example 1 of the above-described composite manufacturing method.

A positive photosensitive resin composition to be a positive photosensitive resin layer 14 (see fig. 2) is applied to both surfaces of the metal foil 12 on which the through-holes 13 shown in fig. 8 are formed, and as shown in fig. 12, a positive photosensitive resin film 20 is formed. In this case, the wavelengths of light exposure are set to be different on one surface 12a of the metal foil 12 and the other surface 12b of the metal foil 12. For example, one positive photosensitive resin film 20 is exposed to infrared light, and the other positive photosensitive resin film 20 is exposed to UV light. This allows the positive photosensitive resin film 20 to be exposed in 1 step.

Then, the process of the present invention is carried out,as shown in fig. 13, the exposure light Le is irradiated from the side of one surface 12a₁Irradiating the exposure light Le from the other surface 12b side₂Exposure light Le passing through the through-hole 13 using the metal foil 12 as a mask₁、Le₂Exposure is performed.

Exposure light Le₁The light having a wavelength for exposing the positive photosensitive resin film 20 on the other surface 12b side. Exposure light Le₂The light has a wavelength for exposing the positive photosensitive resin film 20 on the one surface 12a side.

Next, each positive photosensitive resin film 20 is developed. By the development, as shown in fig. 14, through-holes 15 are formed in regions of the positive photosensitive resin film 20 where the through-holes 13 of the metal foil 12 coincide, and a positive photosensitive resin layer 14 is formed. This provides a composite 10 in which the positive photosensitive resin layers 14 are formed on the first surface 12a and the second surface 12b of the metal foil 12, respectively.

Fig. 15 to 18 are schematic cross-sectional views showing example 3 of the method for producing a composite body according to the embodiment of the present invention in the order of steps. Example 3 of the method for producing a composite is an example of the method for producing the composite 10 shown in fig. 6. In fig. 15 to 18, the same components as those shown in fig. 7 to 11 are denoted by the same reference numerals, and detailed description thereof will be omitted.

In example 3, the steps up to the step of obtaining the metal foil 12 in which the through-holes 13 shown in fig. 8 are formed are the same as those in example 1 of the above-described composite manufacturing method.

As shown in fig. 15, a resin layer 16 is formed on the surface 12b of the metal foil 12 using PET. The step of forming the grease layer 16 is referred to as a resin layer forming step.

Next, the positive photosensitive resin composition to be the positive photosensitive resin layer 14 (see fig. 2) is applied to the surface 12a of the metal foil 12, and as shown in fig. 16, a positive photosensitive resin film 20 is formed.

Next, as shown in fig. 17, exposure light Le is irradiated from the surface 12b side of the metal foil 12 on which the resin layer 16 is formed, and the exposure light Le transmitted through the through-hole 13 is irradiated to the positive photosensitive resin film 20 using the metal foil 12 as a mask to perform exposure. Subsequently, the positive photosensitive resin film 20 is developed. By the development, as shown in fig. 18, through-holes 15 are formed in regions of the positive photosensitive resin film 20 where the through-holes 13 of the metal foil 12 coincide, and a positive photosensitive resin layer 14 is formed. This provides a composite 10 in which the positive photosensitive resin layer 14 is formed on one surface 12a of the metal foil 12 and the resin layer 16 is formed on the other surface 12 b.

Hereinafter, each step of the composite production method will be described more specifically.

[ film formation Process ]

The coating forming step of the composite manufacturing method is a step of forming an aluminum hydroxide coating by applying a coating forming treatment to the surface of the metal foil.

< treatment for forming a coating >

The film forming treatment is not particularly limited, and for example, the same treatment as a conventionally known aluminum hydroxide film forming treatment can be performed.

The conditions and apparatuses described in paragraphs [0013] to [0026] of japanese patent application laid-open No. 2011-201123, for example, can be suitably employed as the film formation process.

The conditions for the film formation treatment cannot be determined in general terms because they vary depending on the electrolyte used, but the concentration of the electrolyte is usually 1 to 80 mass%, the liquid temperature is 5 to 70 ℃, and the current density is 0.5 to 60A/dm²The voltage is 1-100V, the electrolysis time is 1 second-20 minutes, and the desired amount of the film is adjusted.

In the electrolytic solution, the electrochemical treatment is preferably performed using nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, or a mixed acid of 2 or more of these acids.

In the case of performing the electrochemical treatment in an electrolytic solution containing nitric acid or hydrochloric acid, a current may be applied between the metal foil and the counter electrode, or an alternating current may be applied. When a direct current is applied to the metal foil, the current density is preferably 1 to 60A/dm²More preferably 5 to 50A/dm². When the electrochemical treatment is continuously performed, it is preferable that the metal foil is supplied with electricity through the electrolytic solutionThe formula (I) is carried out.

In the present invention, the amount of the aluminum hydroxide film formed by the film forming treatment is preferably 0.05 to 50g/m²More preferably 0.1 to 10g/m²。

[ through-hole formation Process ]

The through-hole forming step is a step of forming a through-hole by performing an electrolytic dissolution treatment after the film forming step.

< electrolytic dissolution treatment >

The electrolytic dissolution treatment is not particularly limited, and an acidic solution can be used for the electrolytic solution using a direct current or an alternating current. Among these, electrochemical treatment is preferably performed using at least one acid of nitric acid and hydrochloric acid, and more preferably electrochemical treatment is performed using a mixed acid obtained by adding at least 1 or more acids of sulfuric acid, phosphoric acid, and oxalic acid to these acids.

In the present invention, as the electrolyte solution, that is, the acidic solution, in addition to the acid, the electrolyte solutions described in the specifications of U.S. patent No. 4,671,859, U.S. patent No. 4,661,219, U.S. patent No. 4,618,405, U.S. patent No. 4,600,482, U.S. patent No. 4,566,960, U.S. patent No. 4,566,958, U.S. patent No. 4,566,959, U.S. patent No. 4,416,972, U.S. patent No. 4,374,710, U.S. patent No. 4,336,113, U.S. patent No. 4,184,932, and the like can be used.

The concentration of the acidic solution is preferably 0.1 to 2.5% by mass, and particularly preferably 0.2 to 2.0% by mass. The liquid temperature of the acidic solution is preferably 20 to 80 ℃, and more preferably 30 to 60 ℃.

The aqueous solution mainly containing the acid can be used by adding at least one of a nitroxide compound having a nitrate ion such as aluminum nitrate, sodium nitrate, or ammonium nitrate, a sulfoxide compound having a hydrochloride ion such as aluminum chloride, sodium chloride, or ammonium chloride, and a sulfate compound having a sulfate ion such as aluminum sulfate, sodium sulfate, or ammonium sulfate to an aqueous solution of the acid having a concentration of 1 to 100g/L in a range from 1g/L to saturation.

The term "mainly" means that the component mainly contained in the aqueous solution is contained in an amount of 30 mass% or more, preferably 50 mass% or more, based on the whole of the components added to the aqueous solution. Hereinafter, other components are also the same.

In the aqueous solution mainly containing the acid, a metal contained in an aluminum alloy such as iron, copper, manganese, nickel, titanium, magnesium, or silica may be dissolved. Preferably, a solution obtained by adding aluminum chloride, aluminum nitrate, aluminum sulfate or the like to an aqueous solution having an acid concentration of 0.1 to 2 mass% so that aluminum ions are 1 to 100g/L is used.

In the electrochemical dissolution treatment, a direct current is mainly used, but when an alternating current is used, the alternating current power source wave is not particularly limited, and a sine wave, a rectangular wave, a trapezoidal wave, a triangular wave, or the like can be used.

(nitric acid electrolysis)

In the present invention, through-holes having an average opening diameter of 0.1 μm or more and less than 100 μm can be easily formed by electrochemical dissolution treatment using an electrolytic solution mainly containing nitric acid (hereinafter, abbreviated as "nitric acid dissolution treatment").

Among them, the nitric acid dissolution treatment is preferably performed by using a direct current with an average current density of 5A/dm for the reason that the melting point of the through-hole formation is easily controlled²Above and setting the electric quantity to 50C/dm²Electrolytic treatment carried out under the above conditions. Further, the average current density is preferably 100A/dm²Hereinafter, the electric quantity is preferably 10000C/dm²The following.

The concentration and temperature of the electrolyte in nitric acid electrolysis are not particularly limited, and electrolysis can be performed at 30 to 60 ℃ using a nitric acid electrolyte having a high concentration, for example, a nitric acid concentration of 15 to 35 mass%, or at a high temperature, for example, 80 ℃ or higher using a nitric acid electrolyte having a nitric acid concentration of 0.7 to 2 mass%.

The electrolysis can be performed by using an electrolyte obtained by mixing at least 1 of sulfuric acid, oxalic acid, and phosphoric acid with a concentration of 0.1 to 50 mass% with the nitric acid electrolyte.

(hydrochloric acid electrolysis)

In the present invention, through-holes having an average opening diameter of 1 μm or more and less than 100 μm can be easily formed by electrochemical dissolution treatment using an electrolytic solution mainly containing hydrochloric acid (hereinafter, abbreviated as "hydrochloric acid dissolution treatment").

Among them, the hydrochloric acid dissolution treatment is preferably carried out by using a direct current so that the average current density is 5A/dm, for the reason that the melting point of the through-hole is easily controlled²Above and setting the electric quantity to 50C/dm²Electrolytic treatment carried out under the above conditions. Further, the average current density is preferably 100A/dm²Hereinafter, the electric quantity is preferably 10000C/dm²The following.

The concentration and temperature of the electrolyte in hydrochloric acid electrolysis are not particularly limited, and electrolysis can be performed at 30 to 60 ℃ using a hydrochloric acid electrolyte having a high concentration, for example, a hydrochloric acid concentration of 10 to 35% by mass, or at a high temperature, for example, 80 ℃ or higher using a hydrochloric acid electrolyte having a hydrochloric acid concentration of 0.7 to 2% by mass.

The electrolysis can be performed by using an electrolyte obtained by mixing at least 1 of sulfuric acid, oxalic acid, and phosphoric acid with a concentration of 0.1 to 50 mass% with the hydrochloric acid electrolyte.

[ Process for removing coating ]

The film removal step is a step of removing the aluminum hydroxide film by chemical dissolution treatment.

In the film removing step, the aluminum hydroxide film can be removed by, for example, performing an acid etching treatment or an alkali etching treatment, which will be described later.

< acid etching treatment >

The dissolution treatment is a treatment in which an aluminum hydroxide film is dissolved using a solution in which aluminum hydroxide is dissolved preferentially over aluminum (hereinafter, referred to as an "aluminum hydroxide solution").

Among them, the aluminum hydroxide solution is preferably an aqueous solution containing at least 1 selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, chromium compounds, zirconium compounds, titanium compounds, lithium salts, cerium salts, magnesium salts, sodium fluorosilicate, zinc fluoride, manganese compounds, molybdenum compounds, magnesium compounds, barium compounds, and simple halogen substances, for example.

Specifically, examples of the chromium compound include chromium (III) oxide and chromium (VI) anhydride.

Examples of the zirconium-based compound include ammonium zirconium fluoride, and zirconium chloride.

Examples of the titanium compound include titanium oxide and titanium sulfide.

Examples of the lithium salt include lithium fluoride and lithium chloride.

Examples of the cerium salt include cerium fluoride and cerium salt.

Examples of the magnesium salt include magnesium sulfide.

Examples of the manganese compound include sodium permanganate and calcium permanganate.

As the molybdenum compound, for example, sodium molybdate is exemplified.

Examples of the magnesium compound include magnesium fluoride-pentahydrate.

Examples of the barium compound include barium oxide, barium acetate, barium carbonate, barium chlorate, barium chloride, barium fluoride, barium iodide, barium lactate, barium oxalate, barium perchlorate, barium selenate, barium selenite, barium stearate, barium sulfite, barium titanate, barium hydroxide, barium nitrate, and hydrates thereof.

Among the above barium compounds, barium oxide, barium acetate and barium carbonate are preferable, and barium oxide is particularly preferable.

Examples of the simple halogen include chlorine, fluorine, and bromine.

Among them, the aluminum hydroxide solution is preferably an aqueous solution containing an acid, and examples of the acid include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, and the like, and may be a mixture of 2 or more acids. Among them, nitric acid is preferably used as the acid.

The acid concentration is preferably 0.01mol/L or more, more preferably 0.05mol/L or more, and still more preferably 0.1mol/L or more. The upper limit is not particularly limited, but is usually preferably 10mol/L or less, and more preferably 5mol/L or less.

The metal foil having the aluminum hydroxide film formed thereon is brought into contact with the above-mentioned solution to perform a dissolution treatment. The method of contacting is not particularly limited, and examples thereof include a dipping method and a spraying method. Among them, the dipping method is preferable.

The dipping method is a treatment of dipping the metal foil having the aluminum hydroxide film formed thereon in the above-described solution. Stirring is preferably performed during the immersion treatment because the treatment can be performed without unevenness.

The time for the immersion treatment is preferably 10 minutes or longer, more preferably 1 hour or longer, and further preferably 3 hours or longer, or 5 hours or longer.

< alkaline etching treatment >

The alkali etching treatment is a treatment of dissolving the surface layer by bringing the aluminum hydroxide film into contact with an alkali solution.

Examples of the alkali used in the alkali solution include caustic alkali and alkali metal salts. Specifically, examples of the caustic alkali include sodium hydroxide (caustic soda) and caustic potash. Examples of the alkali metal salt include alkali metal silicates such as sodium metasilicate, sodium silicate, potassium metasilicate, and potassium silicate; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal aluminates such as sodium aluminate and potassium aluminate; alkali metal aldonates such as sodium gluconate and potassium gluconate; alkali metal hydrogen phosphates such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate, and tripotassium phosphate. Among them, a caustic alkali solution and a solution containing both caustic alkali and alkali metal aluminate are preferable from the viewpoint of high etching rate and low cost. Aqueous solutions of sodium hydroxide are particularly preferred.

The concentration of the alkali solution is preferably 0.1 to 50 mass%, more preferably 0.2 to 10 mass%. When aluminum ions are dissolved in the alkali solution, the concentration of aluminum ions is preferably 0.01 to 10% by mass, more preferably 0.1 to 3% by mass. The temperature of the alkali solution is preferably 10-90 ℃. The treatment time is preferably 1 to 120 seconds.

Examples of the method of bringing the aluminum hydroxide film into contact with the alkaline solution include a method of passing the metal foil having the aluminum hydroxide film formed thereon through a bath containing the alkaline solution, a method of immersing the metal foil having the aluminum hydroxide film formed thereon in a bath containing the alkaline solution, and a method of spraying the alkaline solution onto the surface of the metal foil having the aluminum hydroxide film formed thereon (aluminum hydroxide film).

[ Positive photosensitive resin layer Forming Process ]

In the positive photosensitive resin layer forming step, the composition of the positive photosensitive resin layer is applied to the metal foil, and then the metal foil is exposed using the metal foil as a mask, and then developed to form through holes at the same positions as the through holes, thereby obtaining the positive photosensitive resin layer.

< method of formation >

The method for forming the positive photosensitive resin layer is not particularly limited, and a method for forming the positive photosensitive resin layer by coating a composition of the positive photosensitive resin layer on a metal foil is preferred.

The method of coating on the metal foil is not particularly limited, and for example, a bar coating method, a slit coating method, an ink jet method, a spray coating method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, a transfer method, and the like can be used.

< alkaline aqueous solution >

An alkaline aqueous solution is used for development. Specific examples of the alkaline aqueous solution include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alkanolamines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; cyclic amines such as pyrrole and pyridine, and these may be used alone in 1 kind or in combination with 2 or more kinds.

In addition, an appropriate amount of an alcohol or a surfactant may be added to the above-mentioned alkaline aqueous solution.

< Exposure treatment >

In the exposure of the positive photosensitive resin layer, the positive photosensitive resin layer is exposed using the metal foil as a mask. As the exposure light, light having a wavelength at which the positive photosensitive resin layer has sensitivity is used. In the exposure, exposure light is irradiated from the surface of the metal foil on the side where the positive photosensitive resin layer is not formed.

As the exposure light, for example, UV (ultraviolet) light is used, and a known light source can be used.

< development processing >

The positive photosensitive resin layer after exposure is brought into contact with, for example, the alkaline aqueous solution to develop the positive photosensitive resin layer.

The method of contact is not particularly limited, and examples thereof include a dipping method and a spraying method. Among them, the dipping method is preferable.

The time for the immersion treatment is preferably 5 seconds to 5 minutes, and more preferably 10 seconds to 2 minutes.

The alkaline aqueous solution used in the impregnation is preferably 25 to 60 ℃, more preferably 30 to 50 ℃.

[ resin layer Forming Process ]

The resin layer forming step is a step of forming a resin layer on the surface of the metal foil on the side where the positive photosensitive resin layer is not formed, out of the surfaces of the metal foil having the through-holes.

The method for forming the resin layer is not particularly limited, but examples thereof include dry lamination, wet lamination, extrusion lamination, inflation lamination, and the like.

Among these, as described above, a mode in which the average thickness of the resin layer is 25 to 100 μm and a mode in which the average thickness of the metal foil is 5 to 1000 μm are preferable, and therefore, a method of forming the resin layer by dry lamination is preferable.

For example, the conditions and apparatus described in paragraphs [0067] to [0078] of Japanese patent application laid-open Nos. 2013 and 121673 can be suitably employed for dry lamination.

[ method for Forming through-holes in Metal foil ]

The method of forming the through-hole of the metal foil is not limited to the above method. In the case of using a composite in which an aluminum foil is not used as the metal foil, a method for producing a through-hole in the metal foil will be described.

Fig. 19 to 22 are schematic cross-sectional views showing another example of a method for manufacturing a through-hole in a metal foil of a composite according to an embodiment of the present invention in order of steps. In fig. 19 to 22, the same components as those of the composite 10 shown in fig. 1 and 2 are denoted by the same reference numerals, and detailed description thereof will be omitted.

First, as shown in fig. 19, a resin layer 30 in which a plurality of metal particles 32 are embedded is formed on one surface 11a of a metal base 11 in a resin layer forming step using a composition containing a plurality of metal particles and a polymer component.

In an optional protective layer forming step using a composition containing a polymer component, as shown in fig. 20, a protective layer 33 is preferably formed on a surface 11b of the metal base 11 opposite to the surface 11a on which the resin layer 30 is formed.

Next, in a through-hole forming step of bringing the metal base 11 having the resin layer 30 into contact with an etchant to dissolve the metal particles 32 and a part of the metal base 11, as shown in fig. 21, through-holes 34 are formed in the resin layer 30 and the metal base 11.

The metal foil 12 having the plurality of through holes 13 is formed by the resin layer removing step of removing the protective layer 33 and the protective layer removing step of removing the protective layer 33. In this manner, the metal foil 12 in which the through-hole 13 is formed can be obtained.

[ Process for Forming resin layer for Forming through-hole ]

The step of forming the resin layer for forming a through hole is a step of forming a resin layer in which each part of the metal particles is embedded on one surface of the metal foil by using a composition containing a plurality of metal particles and a polymer component.

[ composition ]

The composition used in the step of forming the resin layer for forming a through-hole is a composition containing at least a plurality of metal particles and a polymer component.

< Metal particle >

The metal particles contained in the composition are not particularly limited as long as they contain metal atoms dissolved in an etchant used in a through-hole forming step described later, and are preferably particles composed of at least one of a metal and a metal compound, and more preferably particles composed of a metal.

Specific examples of the metal constituting the metal particles include aluminum, nickel, iron, copper, stainless steel, titanium, tantalum, molybdenum, niobium, zirconium, tungsten, beryllium, and alloys thereof, and 1 kind of these metals may be used alone or 2 or more kinds may be used in combination.

Among these, aluminum, nickel and copper are preferable, and aluminum and copper are more preferable.

Examples of the metal compound constituting the metal particles include oxides, complex oxides, hydroxides, carbonates, sulfates, silicates, phosphates, nitrides, carbides, sulfides, and complex compounds of at least 2 of these compounds. Specifically, copper oxide, aluminum nitride, aluminum borate, and the like can be given.

From the viewpoint of recycling the etchant to reuse the dissolved metal, it is preferable that the metal particles contain the same metal atoms as the metal foil.

The shape of the metal particles is not particularly limited, but is preferably spherical, and more preferably nearly spherical.

The average particle diameter of the metal particles is preferably 1 to 10 μm, more preferably more than 2 μm and 6 μm or less, from the viewpoint of dispersibility in the composition and the like.

Here, the average particle diameter of the metal particles means a diameter of cumulative 50% of a particle size distribution measured by a laser diffraction/scattering particle size measuring apparatus (nikkiso co., ltd., product Microtrac MT 3000).

The content of the metal particles is preferably 0.05 to 95% by mass, more preferably 1 to 50% by mass, and still more preferably 3 to 25% by mass, based on the total solid content in the composition.

< Polymer component >

The polymer component contained in the composition is not particularly limited, and conventionally known polymer components can be used.

Specific examples of the polymer component include epoxy resin, silicone resin, acrylic resin, urethane resin, ester resin, urethane acrylate resin, silicone acrylic resin, epoxy acrylate resin, ester acrylic resin, polyamide resin, polyimide resin, polycarbonate resin, and phenol resin, and these may be used alone in 1 kind or in combination with 2 or more kinds.

Among these, the polymer component is preferably a resin material selected from the group consisting of phenolic resins, acrylic resins, and polyimide resins, because of excellent acid resistance and because of the ease of obtaining a desired through-hole even when an acidic solution is used as an etchant used in the through-hole forming step described later.

From the viewpoint of facilitating removal in the resin layer removal step described later, the polymer component contained in the composition is preferably a water-insoluble and alkali-soluble polymer (hereinafter, also abbreviated as "alkali-soluble polymer"), that is, a homopolymer having an acidic group in a main chain or a side chain of the polymer, a copolymer thereof, or a mixture thereof.

The alkali-soluble polymer preferably has an acidic group in the main chain and/or side chain of the polymer, from the viewpoint of facilitating removal in the resin layer removal step described later.

Specific examples of the acidic group include a phenol group (-Ar-OH), a sulfonamide group (-SO)₂NH-R), substituted sulfonamide group (hereinafter referred to as "active imide group". ) [ (SO) is₂NHCOR、-SO₂NHSO₂R、-CONHSO₂R ], carboxyl (-CO)₂H) Sulfo (-SO)₃H) Phosphine (-OPO)₃H₂)。

Ar represents an optionally substituted 2-valent aryl linking group, and R represents an optionally substituted hydrocarbon group.

Among the alkali-soluble polymers having an acidic group, alkali-soluble polymers having a phenol group, a carboxyl group, a sulfonamide group and an active imide group are preferable, and particularly, alkali-soluble polymers having a phenol group or a carboxyl group are most preferable from the viewpoint of the balance between the strength of the formed resin layer and the removability in the resin layer removal step described later.

Examples of the alkali-soluble polymer having the acidic group include the following alkali-soluble polymers.

Examples of the alkaline water-soluble polymer having a phenol group include 1 or 2 or more types of phenols such as phenol, o-cresol, m-cresol, p-cresol, and xylenol, and novolac resins produced from aldehydes such as formaldehyde and paraformaldehyde, and condensation products of pyrogallol and acetone. Further, a copolymer obtained by co-polymerizing compounds having a phenol group can be also exemplified. Examples of the compound having a phenol group include acrylamide, methacrylamide, acrylate, methacrylate, hydroxystyrene, and the like having a phenol group.

Specific examples thereof include N- (2-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl) methacrylamide, N- (3-hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxyphenylacrylic acid, m-hydroxyphenylacrylic acid, p-hydroxyphenylacrylic acid, o-hydroxyphenylmethacrylate, m-hydroxyphenylmethacrylate, p-hydroxyphenylmethacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (2-hydroxyphenyl) ethacrylic acid, 2- (3-hydroxyphenyl) ethacrylic acid, 2- (4-hydroxyphenyl) ethacrylic acid, N-hydroxyphenyl acrylamide, N- (4-hydroxyphenyl) methacrylamide, N- (3-hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) ethacrylamide, o-hydroxyphenylacrylic acid, 2- (2-hydroxyphenyl) ethyl methacrylate, 2- (3-hydroxyphenyl) ethyl methacrylate, 2- (4-hydroxyphenyl) ethyl methacrylate, and the like.

Among these, a novolak resin or a copolymer of hydroxystyrene is preferable. Commercially available hydroxystyrene copolymers include those manufactured by Maruki Kagaku Kogyo, MARUKA LYNCUR M H-2, MARUKA LYNCUR MS-4, MARUKA LYNCUR M S-2, MARUKA LYNCUR M S-1, NIPPON SODA CO., LTD, VP-8000, and VP-15000.

Examples of the alkali-soluble polymer having a sulfonamide group include polymers having, as a main constituent, a minimum structural unit derived from a compound having a sulfonamide group. Examples of the above-mentioned compound include compounds having in the molecule thereof 1 or more sulfonamide groups each having at least one hydrogen atom bonded to a nitrogen atom, and polymerizable unsaturated groups. Among them, preferred are low molecular weight compounds having an acryloyl group, an allyl group or a vinyloxy group and a substituted or monosubstituted aminosulfonyl group or substituted sulfonimide group in the molecule.

In particular, m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like can be preferably used.

Examples of the alkali-water-soluble polymer having an active imide group include polymers having, as a main constituent, the smallest constitutional unit derived from a compound having an active imide group. Examples of the above-mentioned compounds include compounds having 1 or more active imide groups represented by the following structural formula and polymerizable unsaturated groups in the molecule.

[ chemical formula 9]

Specifically, N- (p-toluenesulfonyl) methacrylamide, N- (p-toluenesulfonyl) acrylamide, and the like can be preferably used.

Examples of the alkali-soluble polymer having a carboxyl group include polymers having, as a main constituent component, a minimum structural unit derived from a compound having 1 or more carboxyl groups and polymerizable unsaturated groups in the molecule. Specifically, there may be mentioned polymers using unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.

Examples of the alkali-soluble polymer having a sulfo group include polymers having, as a main structural unit, a minimum structural unit derived from a compound having 1 or more sulfo groups and polymerizable unsaturated groups in the molecule.

Examples of the alkali-soluble polymer having a phosphine group include polymers having, as a main constituent component, a minimum structural unit derived from a compound having 1 or more phosphine groups and polymerizable unsaturated groups in the molecule.

The minimum structural unit having an acid group constituting the alkali-soluble polymer need not be particularly 1 type, and an alkali-soluble polymer obtained by copolymerizing 2 or more types of minimum structural units having the same acid group or 2 or more types of minimum structural units having different acid groups can be used.

As a method of copolymerization, a conventionally known graft copolymerization method, a block copolymerization method, a random copolymerization method, or the like can be used.

The copolymer preferably contains 10 mol% or more, more preferably 20 mol% or more, of the compound having an acidic group copolymerized in the copolymer.

When a copolymer is formed by copolymerizing a compound, another compound not containing an acidic group may be used as the compound. Examples of the other compounds not containing an acidic group include the compounds described in the following (m1) to (m 11).

(m1) acrylates and methacrylates having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.

(m2) alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl propionate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, and N-dimethylaminoethyl acrylate.

(m3) alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate and N-dimethylaminoethyl methacrylate.

(m4) acrylamide or methacrylamide such as acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide and the like.

(m5) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.

(m6) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

(m7) styrenes such as styrene, α -methylstyrene, and chloromethylstyrene.

(m8) vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone.

(m9) olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(m10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.

(m11) unsaturated amides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide and N- (p-chlorobenzoyl) methacrylamide.

The polymer component is preferably a homopolymer or a copolymer having a weight average molecular weight of 1.0 × 10³～2.0×10⁵And a number average molecular weight of 5.0 × 10²～1.0×10⁵The range of (1). The polydispersity (weight average molecular weight/number average molecular weight) is preferably 1.1 to 10.

When a copolymer is used as the polymer component, the weight ratio of the minimum structural unit derived from the compound having an acidic group constituting the main chain and/or the side chain to the other minimum structural unit not containing an acidic group constituting a part of the main chain and/or the side chain is preferably 50:50 to 5:95, more preferably 40:60 to 10: 90.

The polymer component may be used alone in 1 kind, or 2 or more kinds may be used in combination, and the polymer component used is preferably in the range of 30 to 99 mass%, more preferably 40 to 95 mass%, and even more preferably 50 to 90 mass% with respect to the total solid content contained in the composition.

In the present invention, it is preferable that the specific gravity of the metal particles is higher than that of the polymer component for the metal particles and the polymer component, because the through-holes are easily formed in the through-hole forming step described later. Specifically, it is more preferable that the specific gravity of the metal particles is 1.5 or more and the specific gravity of the polymer component is 0.9 or more and less than 1.5.

< surfactant >

From the viewpoint of coating properties, the composition may contain a nonionic surfactant as described in Japanese patent application laid-open Nos. 62-251740 and 3-208514, or an amphoteric surfactant as described in Japanese patent application laid-open Nos. 59-121044 and 4-013149.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether, and the like.

Specific examples of the amphoteric surfactant include alkylbis (aminoethyl) glycine, alkylpolyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine, and N-tetradecyl-N, N-betaine type (for example, product name AMOGEN K, DAIICHI KOGYO CO., LTD.).

The content of the surfactant in the case of containing the surfactant is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass, based on the total solid content contained in the composition.

< solvent >

The composition may contain a solvent from the viewpoint of workability in forming the resin layer.

Specific examples of the solvent include dichloroethane, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N-dimethylacetamide, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ -butyrolactone, toluene, and water, and 1 kind of these may be used alone or 2 or more kinds may be used in combination.

< method of formation >

The method for forming the resin layer using the composition is not particularly limited, and a method for forming the resin layer by applying the composition onto a metal foil is preferable.

The method of coating on the metal foil is not particularly limited, and for example, a bar coating method, a slit coating method, an ink jet method, a spray coating method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, a transfer method, and the like can be used.

In the present invention, it is preferable to form a resin layer satisfying the following formula (1) because the formation of the through-hole is facilitated in the through-hole forming step described later.

n＜r……(1)

In formula (1), n represents the thickness of the resin layer formed, r represents the average particle diameter of the metal particles contained in the composition, and both the units of n and r represent μm.

In the present invention, the thickness of the resin layer formed in the resin layer forming step is preferably 0.5 to 4 μm, and more preferably 1 μm to 2 μm, from the viewpoints of resistance to an etchant used in the through-hole forming step described later, workability in the resin layer removing step described later, and the like.

Here, the average thickness of the resin layer means an average value of thicknesses at arbitrary 5 points measured when cut with a microtome and a cross section is observed with an electron microscope.

[ protective layer Forming Process ]

In view of workability in the through-hole forming step described later, it is preferable to have a protective layer forming step of forming a protective layer on the surface of the metal foil opposite to the surface on which the resin layer is formed, using a composition containing a polymer component, before the through-hole forming step.

Here, the polymer component may be the same as the polymer component contained in the composition used in the resin layer forming step. That is, the protective layer formed in any of the protective layer forming steps is the same as the resin layer described above except that the metal particles described above are not embedded therein, and the protective layer can be formed by the same method as the resin layer described above except that the metal particles described above are not used.

In the case where the protective layer forming step is provided, the order is not particularly limited as long as it is a step before the through-hole forming step, and the step may be performed before, after, or simultaneously with the resin layer forming step.

[ through-hole formation Process ]

The through-hole forming step included in the manufacturing method of the present invention is a step of bringing the metal foil having the resin layer into contact with an etchant after the resin layer forming step to dissolve the metal particles and a part of the metal foil and form a through-hole in the metal foil, and is a step of forming a through-hole in the metal foil by a so-called chemical etching treatment.

[ etchant ]

As the etchant, a chemical solution of an acid or an alkali, or the like can be used as long as it is a metal type etchant applied to the metal particles and the metal foil.

Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, hydrogen peroxide, and acetic acid.

Examples of the alkali include caustic soda and caustic potash.

Examples of the alkali metal salt include alkali metal silicates such as sodium metasilicate, sodium silicate, potassium metasilicate, and potassium silicate; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal aluminates such as sodium aluminate and potassium aluminate; alkali metal aldonates such as sodium gluconate and potassium gluconate; alkali metal hydrogen phosphates such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, trisodium phosphate, and tripotassium phosphate.

Further, inorganic salts such as iron (III) chloride and salified copper (II) can also be used.

These may be used in a mixture of 1 kind or 2 or more kinds.

[ treatment method ]

The process of forming the through-hole is performed by bringing the metal foil having the resin layer into contact with the etchant described above.

The method of contacting is not particularly limited, and examples thereof include a dipping method and a spraying method. Among them, the dipping method is preferable.

The time for the immersion treatment is preferably 15 seconds to 10 minutes, and more preferably 1 minute to 6 minutes.

The temperature of the etchant during immersion is preferably 25 to 70 ℃, more preferably 30 to 60 ℃.

[ resin layer removal Process ]

The resin layer removing step is a step of removing the resin layer after the through-hole forming step to produce a metal foil having a through-hole.

The method for removing the resin layer is not particularly limited, and when the alkali-water-soluble polymer described above is used as the polymer component, it is preferable to remove the resin layer by dissolving it with an alkali aqueous solution.

[ protective layer removing Process ]

The protective layer removing step is a step of removing the protective layer after the through-hole forming step to produce a metal foil having a through-hole.

The method for removing the protective layer is not particularly limited, and when the alkali-soluble polymer described above is used as the polymer component, it is preferable to remove the protective layer by dissolving it in an alkali aqueous solution. In the case where the protective layer has the same layer structure as described above except that the resin layer and the metal particles are not embedded, the protective layer can be removed in the resin layer removing step.

[ basic aqueous solution ]

Specific examples of the alkaline aqueous solution include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alkanolamines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; cyclic amines such as pyrrole and pyridine, and these may be used alone in 1 kind or in combination with 2 or more kinds.

In addition, an appropriate amount of an alcohol or a surfactant may be added to the above-mentioned alkaline aqueous solution.

[ treatment method ]

The treatment for removing the resin layer is performed by, for example, bringing the metal foil having the resin layer after the through-hole forming step into contact with the above-described alkaline aqueous solution.

The method of contacting is not particularly limited, and examples thereof include a dipping method and a spraying method. Among them, the dipping method is preferable.

The time for the immersion treatment is preferably 5 seconds to 5 minutes, and more preferably 10 seconds to 2 minutes.

The alkaline aqueous solution used in the impregnation is preferably 25 to 60 ℃, more preferably 30 to 50 ℃.

The process of removing the protective layer is not particularly limited, and may be the same as the process of removing the resin layer. For example, when the above-mentioned alkali-soluble polymer is used as a polymer component in the protective layer, a method of dissolving and removing the protective layer using an alkali aqueous solution is preferable.

[ through hole ]

The average opening diameter of the through-holes can be adjusted by, for example, the time for immersing the etchant in the through-hole forming step.

The average aperture ratio of the through-holes can be adjusted by, for example, the content of the metal particles in the composition used in the resin layer forming step.

[ antiseptic treatment ]

The method of forming the through-hole of the metal foil preferably includes a step of performing an anticorrosive treatment.

The timing of performing the corrosion prevention treatment is not particularly limited, and may be, for example, a treatment performed on a metal foil used in the resin layer forming step, a treatment in which a triazole or the like described later is added to an alkaline aqueous solution in the resin layer removing step, or a treatment performed after the resin layer removing step.

The corrosion prevention treatment includes, for example, a treatment in which a metal foil is immersed in a solution having a pH of 5 to 8.5, in which at least a triazole compound is dissolved in a solvent, to form an organic dielectric film.

Examples of the triazole include Benzotriazole (BTA) and tolyltriazole (TTA).

In addition to triazoles, various organic rust preventives, thiazoles, imidazoles, thiols, triethanolamine and the like can be used.

As the solvent used for the corrosion prevention treatment, water or an organic solvent (particularly alcohols) can be suitably used, but uniformity of the formed organic dielectric film and thickness control at the time of mass production are easily performed and are simple, and further, in consideration of influence on the environment and the like, water mainly containing deionized water is preferable.

The triazole-based dissolved concentration is appropriately determined depending on the relationship between the thickness of the organic dielectric film to be formed and the time during which the film can be processed, but is usually about 0.005 to 1 wt%.

The temperature of the solution may be room temperature, but may be heated and used as needed.

The time for immersing the metal foil in the solution is appropriately determined by the relation between the dissolution concentration of the triazole compound and the thickness of the organic dielectric film to be formed, but is usually about 0.5 to 30 seconds.

As another specific example of the anticorrosive treatment, there is a method of forming an inorganic dielectric coating film mainly containing a hydrated oxide of chromium by impregnating a metal foil with an aqueous solution in which at least 1 kind selected from the group consisting of chromium trioxide, chromate, and dichromate is dissolved in water.

Here, as the chromate, for example, potassium chromate or sodium chromate is preferable, and as the dichromate, for example, potassium dichromate or sodium dichromate is preferable. The concentration of the dissolved substance is usually set to 0.1 to 10 mass%, and the liquid temperature may be about room temperature to 60 ℃. The pH of the aqueous solution is not particularly limited from the acidic region to the alkaline region, but is usually set to 1 to 12.

The time for immersing the metal foil is appropriately selected depending on the thickness of the inorganic dielectric film to be formed.

It is preferable to perform water washing after the completion of the above-described steps of the respective treatments. For the water washing, pure water, well water, channel water, or the like can be used. In order to prevent the introduction into the next process of the treatment liquid, a clamping device may be used.

[ treatment based on roll-to-roll ]

In the manufacturing method, the treatment of each step may be performed by a so-called single sheet method using a metal foil in a cut-and-piece shape, or may be performed by a so-called Roll-to-Roll (hereinafter, also referred to as "RtoR") method in which the treatment of each step is performed while a long metal foil is conveyed in a longitudinal direction on a predetermined conveyance path.

RtoR is a manufacturing method as follows: the metal foil is fed from a roll in which a long metal foil is wound, and the metal foil is transported in the longitudinal direction and disposed in each processing apparatus on the transport path, whereby the above-described processes such as the resin layer forming process and the through-hole forming process are continuously and sequentially performed, and the metal foil (that is, the metal foil) having been subjected to the processes is wound into a roll shape again.

In the manufacturing method, the through-hole is formed by dissolving the metal particles and a part of the metal foil in the through-hole forming step as described above. Therefore, since the steps can be continuously performed without performing complicated steps, the steps can be easily performed by the RtoR method. By setting the production method to RtoR, productivity can be further improved.

The composite of the present invention can be used for applications of molded articles such as metallic tone decorative bodies for lighting applications, photocatalyst carriers, hydrogen production catalyst carriers, enzyme electrodes, carriers for noble metal absorbing materials, carriers for antibacterial agents, adsorbents, absorbents, optical filters, far infrared cut filters, sound insulating materials, sound absorbing materials, electromagnetic shields, building materials, and the like.

The present invention is basically configured as described above. Although the laminate, the composite, and the method for producing the composite of the present invention have been described above in detail, the present invention is not limited to the above embodiments, and various improvements and modifications can be made without departing from the scope of the present invention.