WO2022050360A1

WO2022050360A1 - Metal-clad laminate having protected edge, method for producing printed wiring board, and method for producing intermediate for printed wiring boards

Info

Publication number: WO2022050360A1
Application number: PCT/JP2021/032338
Authority: WO
Inventors: 徳之内田; 良一渡邊
Original assignee: 積水化学工業株式会社
Priority date: 2020-09-03
Filing date: 2021-09-02
Publication date: 2022-03-10
Also published as: CN115868254A; KR20230058589A; JPWO2022050360A1; TW202214799A

Abstract

One purpose of the present invention is to provide a metal-clad laminate having protected edge, said metal-clad laminate being able to be suppressed in breaking of the edge and being able to be suppressed in the ingress of a strong alkaline solution into the edge in cases where the metal-clad laminate is exposed to the solution. Another purpose of the present invention is to provide: a method for producing a printed wiring board; and a method for producing an intermediate for printed wiring boards. The present invention provides a metal-clad laminate having protected edge, wherein the edge of the metal-clad laminate is covered with a protective material.

Description

A method for manufacturing an end-protected metal-clad laminate, a printed wiring board, and a method for manufacturing an intermediate for a printed wiring board.

The present invention relates to a method for manufacturing an end-protected metal-clad laminate, a printed wiring board, and a method for manufacturing an intermediate for a printed wiring board.

Conventionally, adhesives and adhesive tapes have been widely used when fixing parts in electronic devices. The adhesive tape is also used as a process material in the manufacturing process of electronic devices. For example, when processing a thin member in the manufacturing process of an electronic device, the adhesive tape is used to facilitate handling and prevent damage. It is used. In addition to high adhesiveness, these adhesives and adhesive tapes are required to have functions such as heat resistance, thermal conductivity, and impact resistance depending on the environment in which they are used (for example, Patent Documents 1 to 3). ).

JP-A-2015-052050 Japanese Patent Application Laid-Open No. 2015-021067 JP-A-2015-120876

On the other hand, a substrate such as a printed wiring board used in an electronic device is manufactured by forming a circuit in a copper foil portion of a copper-clad laminate (CCL) in which a copper foil and a resin layer are laminated. In recent years, substrates such as printed wiring boards have become thinner. For example, when the thickness of a copper-clad laminate is 100 μm or less, especially around 30 to 40 μm, it is manufactured in the process of manufacturing the substrate from the copper-clad laminate. There is a problem that the end of the copper-clad laminate is damaged during the process. In particular, a strongly alkaline solution is used as the treatment liquid in the etching treatment, desmear treatment, and the like performed in the substrate manufacturing process. For this reason, there is a problem that the strong alkaline solution infiltrates the end portion of the copper-clad laminate, leading to damage to the end portion, or damage to the resin layer, causing a problem in the next process.

The present invention provides an edge-protected metal-clad laminate capable of suppressing damage to the edges of the metal-clad laminate and suppressing infiltration of the solution into the edges even when exposed to a strong alkaline solution. The purpose is. Another object of the present invention is to provide a method for manufacturing a printed wiring board and a method for manufacturing an intermediate for a printed wiring board.

The present invention is an end-protected metal-clad laminate in which the end of the metal-clad laminate is covered with a protective material. The present invention will be described in detail below.

In the metal-clad laminate with end protection of the present invention, the end of the metal-clad laminate is covered with a protective material. Such an end-protected metal-clad laminate can suppress damage to the end of the metal-clad laminate, and even when exposed to a strong alkaline solution, the solution can penetrate into the end. It can be suppressed.

The fact that the end portion of the metal-clad laminate is covered with the protective material means that at least the end face of the metal-clad laminate is covered with the protective material, and if necessary, the end face of the metal-clad laminate. The peripheral portion may also be covered with the above-mentioned protective material.
Above all, it is preferable that the end portion of the metal-clad laminate is covered with the protective material so as to extend from the front surface to the back surface of the metal-clad laminate. In such a case, since the protective material is less likely to come off, damage to the end portion of the metal-clad laminate can be further suppressed, and even when exposed to a strong alkaline solution, the end portion of the solution is exposed. Infiltration can be further suppressed. In such a case, on the front surface and the back surface of the metal-clad laminate, the width of the portion where the protective material covers the front surface and the back surface of the metal-clad laminate (the end of the protective material and the end face of the metal-clad laminate). The shortest distance) is not particularly limited, but the preferred lower limit is 1 mm, the preferred upper limit is 20 mm, the more preferred lower limit is 3 mm, and the more preferred upper limit is 10 mm.

In the metal-clad laminate with end protection of the present invention, the entire surface of one or more selected from the group consisting of the front surface and the back surface of the metal-clad laminate may be further covered with the protective material. .. In such a case, the protective material can be made more difficult to peel off.

In the metal-clad laminate with end protection of the present invention, at least a part of at least one of the four sides of the metal-clad laminate may be covered with the protective material. Above all, from the viewpoint of further suppressing damage to the end portion of the metal-clad laminate and further suppressing the infiltration of the solution into the end even when exposed to a strong alkaline solution, the metal-clad laminate has two. It is preferable that the sides and above are covered with the protective material. It is more preferable that three or more sides of the metal-clad laminate are covered with the protective material, and it is further preferable that the four sides of the metal-clad laminate are covered with the protective material. Further, it is preferable that each side of the metal-clad laminate is covered with the protective material as a whole.

In the metal-clad laminate with end protection of the present invention, the end of the metal-clad laminate may be covered with one protective material per side, or may be covered with two or more protective materials per side. It may be broken. When it is covered with two or more protective materials per side, for example, it may be covered by laminating two protective materials per side, or it may be covered by laminating three protective materials. You may.

It should be noted that the end portion of the metal-clad laminate is covered with the protective material, and the covering form thereof is that the end-protected metal-clad laminate is visually observed or a microscope (for example, KEYENCE). It can be confirmed by observing using VHX-5000) manufactured by the same company.

The metal-clad laminate is not particularly limited, and a metal-clad laminate in which a metal layer and a resin layer are laminated, which is generally used for manufacturing a substrate such as a printed wiring board, can be used. More specifically, for example, a copper-clad laminate (CCL) in which a copper foil and a resin layer are laminated, an aluminum-clad laminate in which an aluminum foil and a resin layer are laminated, and the like can be used. When such a metal-clad laminate is used, it is preferable that at least the end of the resin layer is covered with the protective material among the ends of the metal-clad laminate.

The thickness of the metal-clad laminate is not particularly limited, but may be as thin as 100 μm or less. Even with such a thin thickness, the metal-clad laminate with end protection of the present invention can suppress damage to the end of the metal-clad laminate, and when exposed to a strong alkaline solution, it can be prevented from being damaged. Can also suppress the infiltration of the solution into the end portion. The more preferable lower limit of the thickness of the metal-clad laminate is 10 μm, the more preferable upper limit is 60 μm, the particularly preferable lower limit is 30 μm, and the particularly preferable upper limit is 40 μm.

The protective material is not particularly limited, but is preferably an adhesive tape having a base material and an adhesive layer laminated on one surface of the base material. Such an adhesive tape is used by being attached so that the adhesive layer is in contact with the end portion of the metal-clad laminate. The base material is not particularly limited, and may be a metal base material or a resin base material.

When the base material is the metal base material, when the adhesive tape is attached to the end portion of the metal-clad laminate, the metal base material is exposed on the outermost surface. When metal plating is applied to such an end-protected metal-clad laminate and metal is deposited on the surfaces of the metal-clad laminate and the metal base material, the metal is well deposited. It is possible to form a metal plating layer that is difficult to peel off.
Further, when the base material is the metal base material, the metal base material is not easily damaged even when exposed to a strong alkaline solution, so that damage to the end portion of the metal-clad laminate can be further suppressed. And even when exposed to a strong alkaline solution, the infiltration of the solution into the end can be further suppressed. Further, since the base material is the metal base material, the anchoring property between the metal base material and the pressure-sensitive adhesive layer is increased without using a resin layer as described later, so that the pressure-sensitive adhesive layer is increased. It becomes difficult for a strong alkaline solution to penetrate into the inside of the. This also makes it possible to further suppress damage to the end portion of the metal-clad laminate, and further suppress the infiltration of the solution into the end portion even when exposed to a strong alkaline solution. Further, when the base material is the metal base material, the adhesive tape is folded back (bent) so as to extend from the front surface to the back surface of the metal-clad laminate and attached to the end portion of the metal-clad laminate. Even in this case, since the metal base material retains its shape, it is possible to suppress the restoring force due to the folded back metal base material. As a result, a gap is less likely to occur between the end portion of the metal-clad laminate and the adhesive layer, and peeling is less likely to occur. When the base material is the resin base material, a gap is likely to occur between the end portion of the metal-clad laminate and the pressure-sensitive adhesive layer due to the restoring force of the resin base material, and peeling is likely to occur.

The metal constituting the metal base material is not particularly limited, and examples thereof include copper, aluminum, nickel, and titanium. Further, examples of the metal constituting the metal base material include alloys such as stainless steel and monel. Of these, copper is preferable because it has a small restoring force after being folded back and is not easily torn, so that the adhesive tape is easier to handle.

When the base material is the resin base material, when the adhesive tape is attached to the metal-clad laminate, the resin base material is exposed on the outermost surface. Ra is not particularly limited at the end of the surface roughness of the resin base material, and more specifically, the surface roughness Ra of the surface opposite to the side on which the pressure-sensitive adhesive layer of the resin base material is laminated is not particularly limited, but is preferable. The lower limit is 10 nm, and the preferred upper limit is 500 nm. If the surface roughness Ra of the resin base material is within the above range, the metal-clad laminate with end-protected metal plating is subjected to metal plating treatment, and metal is applied to the surfaces of the metal-clad laminate and the resin base material. When it is deposited, the metal is well deposited and a metal plating layer that is difficult to peel off can be formed. When the base material is the resin base material, the metal plating layer is usually more easily peeled off than when the base material is the metal base material. The more preferable lower limit of the surface roughness Ra of the resin substrate is 15 nm, the more preferable upper limit is 200 nm, the further preferable lower limit is 20 nm, and the further preferable upper limit is 100 nm.
The surface roughness Ra means the arithmetic mean roughness defined in JIS B 0601-2001.

The resin base material is not particularly limited, and is, for example, a polyolefin resin film such as a polyethylene film or a polypropylene film, a polyester resin film such as a polyethylene terephthalate (PET) film, an ethylene-vinyl acetate copolymer film, or a polyvinyl chloride film. Examples thereof include a resin film and a polyurethane resin film. Further, examples of the base material include a polyethylene foam sheet, a polyolefin foam sheet such as a polypropylene foam sheet, and a polyurethane foam sheet. Of these, PET film is preferable.

The thickness of the base material is not particularly limited, but the preferred lower limit is 2 μm and the preferred upper limit is 30 μm. When the thickness of the base material is within the above range, even when the adhesive tape is folded back (bent) and attached to the end portion of the metal-clad laminate, peeling is less likely to occur. The more preferable lower limit of the thickness of the base material is 4 μm, and the more preferable upper limit is 20 μm.

The adhesive tape may further have a metal plating layer on the surface of the base material. More specifically, a metal plating layer may be further provided on the surface of the base material opposite to the side on which the pressure-sensitive adhesive layer is laminated. As described above, when the base material is the metal base material, the metal-clad laminate with end protection is subjected to metal plating treatment, and the metal is applied to the surfaces of the metal-clad laminate and the metal base material. When it is deposited, the metal is well deposited and a metal plating layer that is difficult to peel off can be formed. Even when the base material is the resin base material, if the surface roughness Ra of the resin base material is within the above range, the metal can be well deposited and a metal plating layer that is difficult to peel off can be formed. can. The metal-clad laminate with the edge treatment of the present invention may have a metal plating layer formed on the surface of the base material through such a metal plating treatment.

The pressure-sensitive adhesive layer is not particularly limited, and examples of the base polymer contained in the pressure-sensitive adhesive layer include acrylic polymers, rubber-based polymers, urethane-based polymers, and silicone-based polymers. Among them, the pressure-sensitive adhesive layer is preferably an acrylic pressure-sensitive pressure-sensitive adhesive layer or an acrylic heat-sensitive pressure-sensitive adhesive layer containing an acrylic polymer, or a rubber-based pressure-sensitive adhesive layer containing a rubber-based polymer.

The acrylic polymer usually contains an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester having an alkyl group having a carbon number in the range of 1 to 18 as a main monomer, and a monomer having a crosslinkable functional group as required. It is a (meth) acrylic acid ester copolymer obtained by copolymerizing with and by a conventional method. Further, other copolymerizable modifying monomers may be copolymerized.

The acrylic pressure-sensitive pressure-sensitive adhesive layer is relatively stable against light, heat, moisture, etc., exhibits adhesiveness at room temperature, and can be adhered to various adherends (adhesive selectivity is low). ) Also has the advantage. The acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer is not particularly limited, but it is preferable to have a structural unit derived from a monomer having a crosslinkable functional group. By having such a structural unit, it is possible to crosslink between the acrylic polymers contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer when a crosslinking agent is used in combination. By adjusting the degree of cross-linking at that time, the storage elastic modulus of the acrylic pressure-sensitive pressure-sensitive adhesive layer can be adjusted.

Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, an amide group, a nitrile group and the like. Of these, a hydroxyl group or a carboxyl group is preferable because the storage elastic modulus of the acrylic pressure-sensitive pressure-sensitive adhesive layer can be easily adjusted. Examples of the monomer having a hydroxyl group include (meth) acrylic acid esters having a hydroxyl group such as 4-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. Examples of the monomer having a carboxyl group include (meth) acrylic acid and the like. Examples of the monomer having a glycidyl group include glycidyl (meth) acrylate and the like. Examples of the monomer having an amide group include hydroxyethylacrylamide, isopropylacrylamide, dimethylaminopropylacrylamide and the like. Examples of the monomer having a nitrile group include acrylonitrile. These crosslinkable functional groups may be used alone or in combination of two or more. The content of the structural unit derived from the monomer having a crosslinkable functional group is not particularly limited, but the preferable lower limit is 0.1% by weight and the preferable upper limit is 5% by weight. When the monomer having a carboxyl group is used as the monomer having a crosslinkable functional group, the more preferable upper limit is 3% by weight, and the more preferable upper limit is 0.5% by weight from the viewpoint of further suppressing the infiltration of a strong alkaline solution. ..

The acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer preferably has a structural unit derived from a (meth) acrylate having an alkyl group having 8 or more carbon atoms. By having such a structural unit, the hydrophobicity of the acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer is increased, and the infiltration of the strong alkaline solution into the molecular chain can be further suppressed.

Examples of the (meth) acrylate having an alkyl group having 8 or more carbon atoms include n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, and isononyl (. Examples thereof include meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and isobornyl (meth) acrylate. These (meth) acrylates having an alkyl group having 8 or more carbon atoms may be used alone or in combination of two or more. Of these, 2-ethylhexyl acrylate, lauryl acrylate, and lauryl methacrylate are preferably used because the acrylic pressure-sensitive pressure-sensitive adhesive layer does not become too hard and can maintain sufficient tackiness.

The content of the structural unit derived from the (meth) acrylate having an alkyl group having 8 or more carbon atoms is not particularly limited, but the preferable lower limit is 15% by weight and the preferable upper limit is 99% by weight. When the content of the (meth) acrylate having an alkyl group having 8 or more carbon atoms is within the above range, the hydrophobicity of the acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer is increased, and the hydrophobicity is increased into the molecular chain. Infiltration of strong alkaline solution is further suppressed. The more preferable lower limit of the content of the structural unit derived from the (meth) acrylate having an alkyl group having 8 or more carbon atoms is 20% by weight, and the more preferable upper limit is 30% by weight.

The acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer may further have a structural unit derived from another monomer as long as the effect of the present invention is not impaired. Examples of the other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and ethyl carbitol (meth). ) Examples thereof include acrylate, vinyl acetate, and a fluorine-containing monomer. Further, when the acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer is prepared by an ultraviolet polymerization method, a structural unit derived from a polyfunctional monomer such as divinylbenzene or trimethylolpropane tri (meth) acrylate. It is preferable to have.

The acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer has a preferable lower limit of 250,000 and a preferable upper limit of 2 million in weight average molecular weight. When the weight average molecular weight of the acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer is within the above range, the adhesive strength of the acrylic pressure-sensitive pressure-sensitive adhesive layer is improved. The more preferable lower limit of the weight average molecular weight of the acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer is 300,000, the more preferable lower limit is 400,000, and the more preferable upper limit is 1.5 million. The weight average molecular weight (Mw) can be adjusted by the polymerization conditions (for example, the type or amount of the polymerization initiator, the polymerization temperature, the monomer concentration, etc.). Further, the weight average molecular weight (Mw) can be measured by the following method.
The acrylic polymer solution is filtered through a filter (material: polytetrafluoroethylene, pore diameter: 0.2 μm). The obtained filtrate was supplied to a gel permeation chromatograph (for example, 2690 Separations Model manufactured by Waters), and GPC measurement was performed under the conditions of a sample flow rate of 1 ml / min and a column temperature of 40 ° C. to convert an acrylic polymer into polystyrene. The molecular weight is measured to obtain the weight average molecular weight (Mw). For example, GPC KF-806L or GPC LF-804 (manufactured by Showa Denko KK) is used as the column, and a differential refractometer is used as the detector.

The method for preparing the acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer is not particularly limited, and examples thereof include a method in which the monomer from which the constituent unit is derived is radically reacted in the presence of a polymerization initiator. .. The polymerization method is not particularly limited, and a conventionally known method can be used. Examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like. Of these, solution polymerization is preferable from the viewpoint of easy synthesis and water resistance.

When solution polymerization is used as the polymerization method, examples of the reaction solvent include ethyl acetate, toluene, methyl ethyl ketone, methyl sulfoxide, ethanol, acetone, diethyl ether and the like. These reaction solvents may be used alone or in combination of two or more.

The above-mentioned polymerization initiator is not particularly limited, and examples thereof include organic peroxides and azo compounds. Examples of the organic peroxide include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5. -Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Examples thereof include isobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate and the like. Examples of the azo compound include azobisisobutyronitrile and azobiscyclohexanecarbonitrile. These polymerization initiators may be used alone or in combination of two or more.

The acrylic pressure-sensitive pressure-sensitive adhesive layer may further contain a tackifier resin. When the acrylic pressure-sensitive pressure-sensitive adhesive layer contains a tackifier resin, the adhesive strength of the acrylic pressure-sensitive pressure-sensitive adhesive layer is improved. The tackifier resin is not particularly limited, and examples thereof include kumaron resin, terpene resin, terpene phenol resin, rosin resin, rosin derivative resin, petroleum resin, alkylphenol resin, and hydrides thereof. These tackifier resins may be used alone or in combination of two or more.

The terpene phenol resin means a polymer containing a terpene residue and a phenol residue. The terpene phenol resin is a copolymer of terpene and a phenol compound (terpene-phenol copolymer resin) and a homopolymer or copolymer of terpene (terpene resin, typically an unmodified terpene resin). It is a concept including a phenol-modified terpene resin obtained by polymerizing the above, and further, a resin obtained by hydrogenating a terpene moiety in these resins.

The terpene constituting the terpene phenol resin is not particularly limited, but monoterpenes such as α-pinene, β-pinene, limonene, and camphene are preferable. Limonene includes d-form, l-form and d / l-form (dipentene).

More specifically, examples of the rosin resin include unmodified rosins (raw rosins) such as gum rosin, wood rosin, and tall oil rosin, and modified rosins obtained by modifying these unmodified rosins. Examples of the modification in the modified rosin include hydrogenation, disproportionation, polymerization and the like. More specifically, the modified rosin includes hydrogenated rosin, disproportionated rosin, polymerized rosin, and other chemically modified rosins.

As the rosin derivative resin, more specifically, for example, a rosin ester resin obtained by esterifying the rosin resin with alcohols, an unsaturated fatty acid-modified rosin resin obtained by modifying the rosin resin with an unsaturated fatty acid, and a rosin ester resin not used. Examples thereof include unsaturated fatty acid-modified rosin ester resins modified with saturated fatty acids. Examples of the rosin derivative resin include a rosin alcohol resin obtained by reducing a carboxyl group in the unsaturated fatty acid-modified rosin resin or the unsaturated fatty acid-modified rosin ester resin.
Further, examples of the rosin derivative resin include a metal salt of the rosin resin or the rosin derivative resin (particularly, a rosin ester resin), a rosin phenol resin, and the like. The rosin phenol resin can be obtained by adding phenol to the rosin resin or the rosin derivative resin under an acid catalyst and thermally polymerizing the resin.

More specifically, examples of the petroleum resin include aliphatic (C5) petroleum resin, aromatic (C9) petroleum resin, C5 / C9 copolymerized petroleum resin, and alicyclic petroleum resin. Be done.

The content of the tackifier resin is not particularly limited, but the preferable lower limit with respect to 100 parts by weight of the acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer is 3 parts by weight, and the preferable upper limit is 50 parts by weight, which is a more preferable lower limit. Is 10 parts by weight, and a more preferable upper limit is 35 parts by weight. When the content of the pressure-sensitive adhesive resin is within the above range, the adhesive strength of the acrylic pressure-sensitive pressure-sensitive adhesive layer is improved.

The acrylic pressure-sensitive pressure-sensitive adhesive layer may contain a silane coupling agent. Since the acrylic pressure-sensitive pressure-sensitive adhesive layer contains a silane coupling agent, the adhesion between the end portion of the metal-clad laminate and the acrylic pressure-sensitive adhesive layer is improved. Damage to the edge of the plate can be further suppressed, and even when exposed to a strongly alkaline solution, infiltration of the solution into the edge can be further suppressed.

The silane coupling agent is not particularly limited, and for example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. , Γ-Glysidoxypropylmethyldimethoxysilane, γ-Glysidoxypropylmethyldiethoxysilane, γ-Glysidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethylmethoxysilane, N- (2-aminoethyl) 3-aminopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyl Examples thereof include dimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptobutyltrimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane. Of these, γ-glycidoxypropyltriethoxysilane and γ-mercaptopropyltrimethoxysilane are preferable.

The content of the silane coupling agent is not particularly limited, but the preferable lower limit is 0.1 parts by weight and the preferable upper limit is 5 parts by weight with respect to 100 parts by weight of the acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer. When the content of the silane coupling agent is within this range, the adhesion between the end portion of the metal-clad laminate and the acrylic pressure-sensitive pressure-sensitive adhesive layer can be further enhanced. The more preferable lower limit of the content of the silane coupling agent is 0.5 parts by weight, and the more preferable upper limit is 3 parts by weight.

When the acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer contains a structural unit derived from the monomer having a cross-linking functional group, the acrylic pressure-sensitive pressure-sensitive adhesive layer may contain a cross-linking agent. good. The above-mentioned cross-linking agent is not particularly limited, and examples thereof include an isocyanate-based cross-linking agent, an aziridine-based cross-linking agent, an epoxy-based cross-linking agent, and a metal chelate-type cross-linking agent. Of these, isocyanate-based cross-linking agents and epoxy-based cross-linking agents are preferable.
The content of the cross-linking agent is not particularly limited, but the preferable lower limit with respect to 100 parts by weight of the acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer is 0.01 parts by weight, and the preferable upper limit is 10 parts by weight, which is more preferable. The lower limit is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.

The storage elastic modulus of the acrylic pressure-sensitive pressure-sensitive adhesive layer is not particularly limited, but the preferable upper limit of the storage elastic modulus at 23 ° C. is ² × 105 Pa. When the storage elastic modulus at 23 ° C. is ² × 105 Pa or less, the adhesion between the end portion of the metal-clad laminate and the acrylic pressure-sensitive pressure-sensitive adhesive layer is high, so that the metal-clad laminate It is possible to further suppress the damage to the end portion of the metal, and it is possible to further suppress the infiltration of the solution into the end portion even when exposed to a strong alkaline solution. A more preferable upper limit of the storage elastic modulus at 23 ° C. is 1.8 × ¹⁰⁵ Pa. The lower limit of the storage elastic modulus at 23 ° C. is not particularly limited, but from the viewpoint of maintaining the cohesive force of the acrylic pressure-sensitive pressure-sensitive adhesive layer, the preferable lower limit is 1 × 10 ⁴ Pa, and the more preferable lower limit is 3 × 10 ⁴ Pa. be.
The storage elastic modulus at 23 ° C. can be adjusted by the type, molecular weight, molecular weight distribution, type and content of the tackifier resin, type and content of the cross-linking agent, and the like. The storage elastic modulus at 23 ° C. is measured by using a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by IT Measurement Control Co., "ARES" manufactured by Leometrics Co., Ltd.). It can be obtained by measuring from −40 ° C. to 140 ° C. under the conditions of shear mode, angular frequency of 1 Hz, and speed of 5 ° C./min.

The acrylic heat-sensitive pressure-sensitive adhesive layer is relatively stable against light, heat, moisture, etc., and can be adhered to various adherends by heat-bonding. Since the acrylic heat-sensitive adhesive layer does not exhibit adhesiveness at room temperature and develops adhesiveness by heating, the pressure-sensitive adhesive layer is the acrylic heat-sensitive adhesive layer, so that the metal-clad laminate can be used. With the end portion in contact with the adhesive tape, the adhesive tape can be heat-bonded after adjusting the position and the like so that wrinkles and floating do not occur on the adhesive tape. By doing so, it is possible to further suppress the damage to the end portion of the metal-clad laminate, and further suppress the infiltration of the solution into the end portion even when exposed to a strong alkaline solution.

The acrylic heat-sensitive adhesive layer has a peak temperature of loss tangent (hereinafter, also referred to as tan δ or simply loss tangent) measured at a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device, but is not particularly limited, but is 40 ° C. The above is preferable. When the peak temperature of the loss tangent is 40 ° C. or higher, the slipperiness between the end portion of the metal-clad laminate and the adhesive tape at room temperature is improved, and the adhesive tape is less likely to wrinkle at the time of sticking. Can be done. The peak temperature of the loss tangent is more preferably 42 ° C. or higher, further preferably 45 ° C. or higher. Further, the peak temperature of the loss tangent is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and further preferably 80 ° C. or lower.
For the loss tangent, use a viscoelastic spectrometer (DVA-200 manufactured by IT Measurement Control Co., Ltd., or an equivalent product thereof) under the condition of 5 ° C./min and 1 Hz in the low-speed temperature rise shear deformation mode, -100. It can be obtained by measuring a dynamic viscoelastic spectrum at ° C to 200 ° C.

The storage elastic modulus of the acrylic heat-sensitive pressure-sensitive adhesive layer is not particularly limited, but the preferable lower limit of the storage elastic modulus at 23 ° C. is 5 × 10 ⁶ Pa, and the preferable upper limit of the storage elastic modulus at 100 ° C. is 2 × 10 ⁵ Pa. Is.
When the storage elastic modulus at 23 ° C. is 5 × 10 ⁶ Pa or more, the acrylic heat-sensitive adhesive layer does not show adhesiveness at room temperature, and the end portion of the metal-clad laminate is brought into contact with the adhesive tape. In this state, the position and the like can be adjusted so that the adhesive tape does not wrinkle or float. The more preferable lower limit of the storage elastic modulus at 23 ° C. is 8 × 10 ⁶ Pa, and the more preferable lower limit is 1 × 10 ⁷ Pa. The upper limit of the storage elastic modulus at 23 ° C. is not particularly limited, but from the viewpoint that the adhesive tape can be easily rolled, the preferable upper limit is 1 × 10 ¹⁰ Pa, and the more preferable upper limit is 1 × 10 ⁹ Pa.

When the storage elastic modulus at 100 ° C. is 2 × 10 ⁵ Pa or less, the acrylic heat-sensitive adhesive layer develops adhesiveness by heating, and the acrylic heat-sensitive adhesive layer is heat-bonded to the metal. It is possible to further suppress the breakage of the end portion of the stretched laminated plate, and further suppress the infiltration of the solution into the end portion even when exposed to a strong alkaline solution. The more preferable upper limit of the storage elastic modulus at 100 ° C. is 1 × 10 ⁵ Pa, and the more preferable upper limit is 8 × 10 ⁴ Pa. The lower limit of the storage elastic modulus at 100 ° C. is not particularly limited, but a preferable lower limit is 1 × 10 ⁴ Pa, and a more preferable lower limit is 5 × 10 ⁴ Pa from the viewpoint of suppressing exudation due to deformation of the pressure-sensitive adhesive during heat pressure bonding. be.
The storage elastic modulus at 23 ° C. or 100 ° C. can be adjusted by the type, molecular weight, molecular weight distribution, type and content of tackifier resin, type and content of cross-linking agent, and the like. Further, the storage elastic modulus at 23 ° C. or 100 ° C. is determined by using a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by IT Measurement Control Co., "ARES" manufactured by Leometrics Co., Ltd.). It can be obtained by measuring from −40 ° C. to 140 ° C. under the conditions of shear mode for elastic measurement, angular frequency of 1 Hz, and speed of 5 ° C./min.

The acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer is not particularly limited, but it is preferable to have a structural unit derived from a monomer having a crosslinkable functional group. By having such a structural unit, it is possible to crosslink between the acrylic polymers contained in the acrylic heat-sensitive pressure-sensitive adhesive layer when a crosslinking agent is used in combination. By adjusting the degree of cross-linking at that time, the storage elastic modulus of the acrylic heat-sensitive pressure-sensitive adhesive layer can be adjusted.

Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, an amide group, a nitrile group and the like. Of these, a hydroxyl group or a carboxyl group is preferable because the storage elastic modulus of the acrylic heat-sensitive pressure-sensitive adhesive layer can be easily adjusted. Examples of the monomer having a hydroxyl group include (meth) acrylic acid esters having a hydroxyl group such as 4-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. Examples of the monomer having a carboxyl group include (meth) acrylic acid and the like. Examples of the monomer having a glycidyl group include glycidyl (meth) acrylate and the like. Examples of the monomer having an amide group include hydroxyethylacrylamide, isopropylacrylamide, dimethylaminopropylacrylamide and the like. Examples of the monomer having a nitrile group include acrylonitrile. These crosslinkable functional groups may be used alone or in combination of two or more. The content of the structural unit derived from the monomer having a crosslinkable functional group is not particularly limited, but the preferable lower limit is 0.1% by weight and the preferable upper limit is 5% by weight. When the monomer having a carboxyl group is used as the monomer having a crosslinkable functional group, the more preferable upper limit is 3% by weight, and the more preferable upper limit is 0.5% by weight from the viewpoint of further suppressing the infiltration of a strong alkaline solution. ..

The acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer preferably has a structural unit derived from a (meth) acrylate having an alkyl group having 1 or more and 4 or less carbon atoms, and has 1 or more and 4 or less carbon atoms. It is more preferable to have a structural unit derived from a methacrylate having an alkyl group. Further, it is also preferable that the acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer has a structural unit derived from a (meth) acrylate having an alkyl group having a cyclic structure. When the acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer has these structural units, it becomes easy to adjust the peak temperature of the loss tangent and the storage elastic modulus to a preferable range. The acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer is a structural unit derived from a methacrylate having an alkyl group having 1 or more and 4 carbon atoms, and a structural unit derived from a methacrylate having an alkyl group having a cyclic structure. It is more preferred to have at least one selected from the group consisting of.

The (meth) acrylate having an alkyl group having 1 or more and 4 or less carbon atoms is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Can be mentioned.
The (meth) acrylate having an alkyl group having a cyclic structure is not particularly limited, and examples thereof include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate. These (meth) acrylates may be used alone or in combination of two or more. Of these, methyl methacrylate, butyl acrylate, butyl methacrylate, and isobornyl methacrylate are preferably used because the peak temperature of the loss tangent and the storage elastic modulus can be easily adjusted within a preferable range.

The total content of the structural unit derived from the (meth) acrylate having an alkyl group having 1 or more and 4 or less carbon atoms and the structural unit derived from the (meth) acrylate having an alkyl group having a cyclic structure is particularly limited. However, the preferred lower limit is 50% by weight and the preferred upper limit is 98% by weight. When the total content of the structural units is within the above range, it becomes easy to adjust the peak temperature of the loss tangent and the storage elastic modulus to the preferable ranges. A more preferable lower limit of the total content of the structural units is 60% by weight, a further preferable lower limit is 70% by weight, a more preferable upper limit is 95% by weight, a further preferable upper limit is 90% by weight, and a further preferable upper limit is 80% by weight. Is.
The total content is a structural unit derived from a (meth) acrylate having an alkyl group having 1 or more and 4 or less carbon atoms, and a structural unit derived from a (meth) acrylate having an alkyl group having a cyclic structure. The acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer may contain only one of them or both of them.
The total content of the structural unit derived from the methacrylate having an alkyl group having 1 or more and 4 or less carbon atoms and the structural unit derived from the methacrylate having an alkyl group having a cyclic structure is preferably 50% by weight. The preferred upper limit is 90% by weight, the more preferred lower limit is 60% by weight, and the more preferred upper limit is 80% by weight.

The acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer may further have a structural unit derived from another monomer as long as the effect of the present invention is not impaired. Examples of the other monomers include n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, and decyl (meth) acrylate. Examples thereof include lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, vinyl acetate, and fluorine-containing monomer. .. Further, when the acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer is prepared by an ultraviolet polymerization method, a structural unit derived from a polyfunctional monomer such as divinylbenzene or trimethylolpropane tri (meth) acrylate is further added. It is preferable to have.

The weight average molecular weight of the acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer is not particularly limited, and is the same as the weight average molecular weight of the acrylic polymer used in the acrylic pressure-sensitive pressure-sensitive adhesive layer. good.

The method for preparing the acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer is not particularly limited, and as in the case of the acrylic polymer contained in the acrylic pressure-sensitive pressure-sensitive adhesive layer, for example, the origin of the structural unit. Examples thereof include a method of radically reacting the above-mentioned monomer in the presence of a polymerization initiator.

The acrylic heat-sensitive pressure-sensitive adhesive layer may further contain a tack-imparting resin. When the acrylic heat-sensitive pressure-sensitive adhesive layer contains the tackifier resin, the adhesive strength of the acrylic heat-sensitive pressure-sensitive adhesive layer is improved. The tackifier resin is not particularly limited, and the same tackifier resin as the tackifier resin used for the acrylic pressure-sensitive pressure-sensitive adhesive layer can be used.

Among the tackifier resins, the acrylic heat-sensitive pressure-sensitive adhesive layer preferably contains a hydrogenated rosin ester resin having a hydroxyl value of 40 mgKOH / g or more. By containing the hydrogenated rosin ester resin having a hydroxyl value of 40 mgKOH / g or more in the acrylic heat-sensitive adhesive layer, the interfacial adhesion between the end portion of the metal-clad laminate and the adhesive tape is further improved. Even when exposed to a strong alkaline solution, the infiltration of the solution into the end portion of the metal-clad laminate can be further suppressed. The upper limit of the hydroxyl value of the hydrogenated rosin ester resin having a hydroxyl value of 40 mgKOH / g or more is not particularly limited, but is usually about 80 mgKOH / g, preferably 50 mgKOH / g or less.

The content of the tackifier resin is not particularly limited, but the preferable lower limit is 5 parts by weight, the preferable upper limit is 50 parts by weight, and the more preferable lower limit is 50 parts by weight with respect to 100 parts by weight of the acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer. 10 parts by weight, more preferably 35 parts by weight. When the content of the tackifier resin is within the above range, the adhesive strength of the acrylic pressure-sensitive adhesive layer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer is improved.

The acrylic heat-sensitive adhesive layer may contain a silane coupling agent. Since the acrylic heat-sensitive adhesive layer contains a silane coupling agent, the adhesion between the end portion of the metal-clad laminate and the acrylic heat-sensitive adhesive layer is improved. The damage to the end portion can be further suppressed, and the infiltration of the solution into the end portion can be further suppressed even when exposed to a strong alkaline solution.
The silane coupling agent is not particularly limited, and the same silane coupling agent as the silane coupling agent used for the acrylic pressure-sensitive pressure-sensitive adhesive layer can be used. The content of the silane coupling agent is not particularly limited, and the same content as the content in the acrylic pressure-sensitive pressure-sensitive adhesive layer can be adopted.

When the acrylic polymer contained in the acrylic heat-sensitive pressure-sensitive adhesive layer contains a structural unit derived from the monomer having a cross-linking functional group, the acrylic heat-sensitive pressure-sensitive adhesive layer may contain a cross-linking agent. The cross-linking agent is not particularly limited, and the same cross-linking agent as the cross-linking agent used for the acrylic pressure-sensitive pressure-sensitive adhesive layer can be used. The content of the cross-linking agent is not particularly limited, and the same content as the content in the acrylic pressure-sensitive pressure-sensitive adhesive layer can be adopted.

Since the rubber-based polymer has a relatively low polarity, the fact that the base polymer is the rubber-based polymer makes it difficult for the strong alkaline solution to penetrate into the inside of the rubber-based pressure-sensitive adhesive layer. As a result, damage to the end portion of the metal-clad laminate can be further suppressed, and even when exposed to a strong alkaline solution, infiltration of the solution into the end portion can be further suppressed. The rubber-based polymer is a block copolymer having at least a block derived from an aromatic vinyl monomer and a block derived from a conjugated diene monomer, or a hydrogenated product thereof (hereinafter, also simply referred to as "block copolymer"). Is preferable.

The aromatic vinyl monomer is not particularly limited, and is, for example, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4 -T-butylstyrene, 5-t-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether , N, N-dimethylaminoethylstyrene, N, N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4- Examples thereof include t-butylstyrene, vinylxylene, vinylnaphthalene, vinylpyridine, diphenylethylene, tertiary amino group-containing diphenylethylene and the like. The tertiary amino group-containing diphenylethylene is not particularly limited, and examples thereof include 1- (4-N, N-dimethylaminophenyl) -1-phenylethylene. These aromatic vinyl monomers may be used alone or in combination of two or more.

The conjugated diene monomer is not particularly limited, and for example, isoprene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, and the like. Examples thereof include 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene and 2-chloro-1,3-butadiene. These conjugated diene monomers may be used alone or in combination of two or more.

The block copolymer is not particularly limited, and may be any block copolymer having rubber elasticity at room temperature and having a hard segment portion and a soft segment portion. The block derived from the aromatic vinyl monomer is the hard segment portion, and the block derived from the conjugated diene monomer is the soft segment portion.
Specific examples of the block copolymer include styrene-isoprene-styrene (SIS) block copolymer, styrene-butadiene-styrene (SBS) block copolymer, and styrene-chloroprene-styrene block copolymer. Can be mentioned. Further, examples of the block copolymer include a hydrogenated product, and more specifically, for example, a styrene-ethylene-butylene-styrene (SEBS) block copolymer and a styrene-ethylene-propylene-styrene (SEPS) block. Examples include polymers, styrene-ethylene-ethylene-propylene-styrene (SEEPS) and the like. Further, as the block copolymer, for example, a styrene-isobutylene-styrene (SIBS) block copolymer and the like can be mentioned. Among them, SIS block copolymers and SBS block copolymers are preferable, and SIS block copolymers are more preferable, from the viewpoint of easily exhibiting high adhesive strength. These block copolymers may be used alone or in combination of two or more.

The block copolymer includes a triblock copolymer of a block derived from the aromatic vinyl monomer and a block derived from the conjugated diene monomer, and a block derived from the aromatic vinyl monomer and the conjugated diene monomer. It may contain a diblock copolymer with a block derived from. The content of the diblock copolymer in the block copolymer (hereinafter, also referred to as “diblock ratio”) is not particularly limited, but a preferable lower limit is 50% by weight, and a more preferable lower limit is 70% by weight. When the diblock ratio is within the above range, the adhesion between the end portion of the metal-clad laminate and the rubber-based adhesive layer is high, so that the end portion of the metal-clad laminate is further suppressed from being damaged. And even when exposed to a strong alkaline solution, the infiltration of the solution into the end portion can be further suppressed. The upper limit of the diblock ratio is not particularly limited, but is preferably 90% by weight from the viewpoint of maintaining the cohesive force of the rubber-based pressure-sensitive adhesive layer. The diblock ratio can be calculated from the peak area ratio of each copolymer measured by the gel permeation chromatography (GPC) method.

The content of the block derived from the aromatic vinyl monomer in the block copolymer (also referred to as "styrene content" when the aromatic vinyl monomer is styrene) is not particularly limited, but a preferable upper limit is 20% by weight. A more preferred upper limit is 16% by weight. When the content of the block derived from the aromatic vinyl monomer is within the above range, the rubber-based pressure-sensitive adhesive layer does not become too hard, and the adhesion to the end portion of the metal-clad laminate becomes high. It is possible to further suppress damage to the end portion of the metal-clad laminate, and it is possible to further suppress the infiltration of the solution into the end portion even when exposed to a strong alkaline solution. The lower limit of the content of the block derived from the aromatic vinyl monomer is not particularly limited, but the preferable lower limit is 8% by weight from the viewpoint of maintaining the cohesive force of the rubber-based pressure-sensitive adhesive layer.
The content of the blocks derived from the aromatic vinyl monomer can be calculated from the peak area ratio of each block measured by 1H-NMR.

The weight average molecular weight of the block copolymer is not particularly limited, but the preferred lower limit is 50,000 and the preferred upper limit is 600,000. When the weight average molecular weight of the block copolymer is 50,000 or more, the heat resistance of the rubber-based pressure-sensitive adhesive layer becomes higher. When the weight average molecular weight of the block copolymer is 600,000 or less, it is possible to prevent the compatibility between the block copolymer and other components from being excessively lowered. The more preferable lower limit of the weight average molecular weight is 100,000, and the more preferable upper limit is 500,000.

The rubber-based pressure-sensitive adhesive layer preferably further contains a terpene phenol resin (T1) having a hydroxyl value of 20 mgKOH / g or more and 140 mgKOH / g or less. When the rubber-based pressure-sensitive adhesive layer contains the tack-imparting resin, the adhesive strength of the rubber-based pressure-sensitive adhesive layer is improved. In particular, when the rubber-based pressure-sensitive adhesive layer contains the terpene phenol resin (T1), the strong alkaline solution is less likely to penetrate into the inside of the rubber-based pressure-sensitive adhesive layer.

The hydroxyl value of the terpene phenol resin (T1) has a lower limit of 20 mgKOH / g and an upper limit of 140 mgKOH / g. When the hydroxyl value of the terpene phenol resin (T1) is within the above range, the polarity of the terpene phenol resin (T1) is within an appropriate range, so that a strong alkaline solution is formed inside the rubber-based pressure-sensitive adhesive layer. It becomes difficult to infiltrate. The preferable lower limit of the hydroxyl value of the terpene phenol resin (T1) is 40 mgKOH / g, the preferable upper limit is 100 mgKOH / g, the more preferable lower limit is 50 mgKOH / g, and the more preferable upper limit is 80 mgKOH / g.
The hydroxyl value of the tackifier resin is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to the hydroxyl group when 1 g of the tackifier resin is acetylated, and is specified in JIS K 0070: 1992. It is defined as a value measured based on the potential difference titration method.

The softening point of the terpene phenol resin (T1) is not particularly limited, but the preferable lower limit is 150 ° C. When the softening point of the terpene phenol resin (T1) is 150 ° C. or higher, the molecular weight of the terpene phenol resin becomes large and the solubility in a strong alkaline solution becomes low, so that the inside of the rubber-based pressure-sensitive adhesive layer is formed. Strongly alkaline solutions are less likely to penetrate. Further, when the softening point of the terpene phenol resin (T1) is 150 ° C. or higher, the heat resistance of the rubber-based pressure-sensitive adhesive layer becomes higher. A more preferable lower limit of the softening point of the terpene phenol resin (T1) is 160 ° C. The upper limit of the softening point of the terpene phenol resin (T1) is not particularly limited, but the practical upper limit is about 180 ° C.
The softening point of the tackifier resin is the temperature at which the solid resin softens and begins to deform, and was measured based on the softening point test method (ring ball method) specified in JIS K 5902 and JIS K 2207. Defined as a value.

The content of the terpene phenol resin (T1) is not particularly limited, but the preferable lower limit is 3 parts by weight and the preferable upper limit is 80 parts by weight with respect to 100 parts by weight of the rubber-based polymer. When the content of the terpene phenol resin (T1) is 3 parts by weight or more, the strong alkaline solution is less likely to penetrate into the rubber-based pressure-sensitive adhesive layer. When the content of the terpene phenol resin (T1) is 80 parts by weight or less, the rubber-based pressure-sensitive adhesive layer does not become too hard and the adhesion to the end of the metal-clad laminate becomes high. It is possible to further suppress damage to the end portion of the metal-clad laminate, and it is possible to further suppress the infiltration of the solution into the end portion even when exposed to a strong alkaline solution. The more preferable lower limit of the content of the terpene phenol resin (T1) is 10 parts by weight, and the more preferable upper limit is 60 parts by weight.

The rubber-based pressure-sensitive adhesive layer may contain a pressure-imparting resin other than the terpene phenol resin (T1). However, in the rubber-based pressure-sensitive adhesive layer, the total content of the terpene phenol resin (T2) having a hydroxyl value of more than 140 mgKOH / g and the rosin ester resin (T3) is 100 parts by weight of the rubber-based polymer. It is preferably 5 parts by weight or less. When the total content of the terpene phenol resin (T2) and the rosin ester resin (T3) is 5 parts by weight or less, the strong alkaline solution is less likely to penetrate into the rubber-based pressure-sensitive adhesive layer. .. Since the terpene phenol resin (T2) has a higher hydroxyl value and higher polarity than the terpene phenol resin (T1), if the content of the terpene phenol resin (T2) is too large, the inside of the rubber-based pressure-sensitive adhesive layer It becomes easy for a strong alkaline solution to infiltrate. Further, since the rosin ester resin (T3) has functional groups such as an ester group, a hydroxyl group, and a carboxyl group, even if the content of the rosin ester resin (T3) is too large, the inside of the rubber-based pressure-sensitive adhesive layer It becomes easy for a strong alkaline solution to infiltrate into the rosin. The total content of the terpene phenol resin (T2) and the rosin ester resin (T3) is preferably 2 parts by weight or less, and more preferably 0 part by weight.

The pressure-sensitive adhesive layer may contain additives such as plasticizers, emulsifiers, softeners, fillers, pigments, dyes, and other resins, if necessary. It was

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably thicker than 1/2 the thickness of the metal-clad laminate. In such a case, even when the adhesive tape is attached to the end portion of the metal-clad laminate so as to extend from the front surface to the back surface of the metal-clad laminate, the end portion of the metal-clad laminate may be used. A gap is less likely to occur between the adhesive layer and the adhesive layer, and peeling is less likely to occur. As a result, damage to the end portion of the metal-clad laminate can be further suppressed, and even when exposed to a strong alkaline solution, infiltration of the solution into the end portion can be further suppressed. The thickness of the pressure-sensitive adhesive layer is more preferably thicker than 2/3 of the thickness of the metal-clad laminate. Specifically, the thickness of the pressure-sensitive adhesive layer has a preferable lower limit of 5 μm, a preferable upper limit of 100 μm, a more preferable lower limit of 10 μm, and a more preferable upper limit of 50 μm.

When the pressure-sensitive adhesive layer is the acrylic heat-sensitive pressure-sensitive adhesive layer, it is preferable that the pressure-sensitive adhesive tape further has a pressure-sensitive pressure-sensitive pressure-sensitive adhesive layer between the base material and the acrylic heat-sensitive pressure-sensitive adhesive layer. That is, it is preferable that the pressure-sensitive adhesive tape has the base material, the pressure-sensitive pressure-sensitive adhesive layer, and the acrylic heat-sensitive pressure-sensitive adhesive layer in this order. By having the pressure-sensitive pressure-sensitive adhesive layer between the base material and the acrylic heat-sensitive adhesive layer, the adhesive tape increases the anchoring property between the base material and the acrylic heat-sensitive adhesive layer. Therefore, even when exposed to a strong alkaline solution, peeling between the base material and the acrylic heat-sensitive adhesive layer is less likely to occur. As a result, damage to the end portion of the metal-clad laminate can be further suppressed, and even when exposed to a strong alkaline solution, infiltration of the solution into the end portion can be further suppressed.
As the pressure-sensitive pressure-sensitive adhesive layer, for example, the acrylic pressure-sensitive pressure-sensitive adhesive layer described above can be used, but the pressure-sensitive pressure-sensitive pressure-sensitive adhesive layer is not limited thereto.

When the pressure-sensitive adhesive layer has the pressure-sensitive pressure-sensitive adhesive layer between the base material and the acrylic heat-sensitive pressure-sensitive adhesive layer, the thickness of the pressure-sensitive pressure-sensitive adhesive layer is not particularly limited, but the preferable lower limit is 0.1 μm. The preferred upper limit is 30 μm. When the thickness of the pressure-sensitive pressure-sensitive adhesive layer is within the above range, the anchoring property between the base material and the acrylic heat-sensitive pressure-sensitive adhesive layer is further improved. The more preferable lower limit of the thickness of the pressure-sensitive pressure-sensitive adhesive layer is 5 μm, and the more preferable upper limit is 20 μm.

The pressure-sensitive adhesive tape preferably further has a resin layer between the base material and the pressure-sensitive adhesive layer, and the resin layer preferably contains a resin having a polar functional group. Since the pressure-sensitive adhesive tape has the resin layer, the anchoring property between the base material and the pressure-sensitive adhesive layer is increased, so that the strong alkaline solution is less likely to penetrate into the pressure-sensitive adhesive layer. As a result, damage to the end portion of the metal-clad laminate can be further suppressed, and even when exposed to a strong alkaline solution, infiltration of the solution into the end portion can be further suppressed.

The polar functional group is not particularly limited, but at least one selected from the group consisting of a nitrile group, a carbonyl group, a carboxyl group and an amino group is preferable because it is excellent in adhesion to the metal base material and the resin base material. Of these, a nitrile group and a carbonyl group are more preferable.

Specific examples of the resin having the polar functional group include acrylonitrile butadiene rubber (NBR), maleic anhydride-modified styrene-ethylene-butylene-styrene (maleic anhydride-modified SEBS), and amine-modified styrene-ethylene-butylene-styrene. (Amin-modified SEBS) and the like. Among them, NBR and maleic anhydride-modified SEBS are preferable because they are excellent in adhesion to the resin base material and also in adhesion to the pressure-sensitive adhesive layer.

The thickness of the resin layer is not particularly limited, but a preferable lower limit is 0.1 μm and a preferable upper limit is 3 μm. When the thickness of the resin layer is within the above range, the anchoring property between the base material and the pressure-sensitive adhesive layer is further improved. The more preferable lower limit of the thickness of the resin layer is 0.5 μm, and the more preferable upper limit is 2 μm.

The resin layer may contain additives such as plasticizers, emulsifiers, softeners, fillers, pigments and dyes, and other resins, if necessary.

FIGS. 1 to 8 show sectional views schematically showing an example of a region covered with a protective material in the metal-clad laminate with end protection of the present invention.
In the metal-clad laminate 1 whose edges are protected as shown in FIGS. 1 to 4, an adhesive tape 30 having a base material 31 and an adhesive layer 32 is used as a protective material. That is, the end portion of the metal-clad laminate 2 is covered with one adhesive tape 30 per side. In FIGS. 1 to 4, the adhesive tape 30 is folded back (bent) so as to extend from the front surface to the back surface of the metal-clad laminate 2, and is attached to the end of the metal-clad laminate 2. Further, in FIG. 4, the entire back surface of the metal-clad laminate 2 is covered with the adhesive tape 30.

In the metal-clad laminate 1 whose edges are protected as shown in FIGS. 5 to 7, the adhesive tape 30 having the base material 31 and the pressure-sensitive adhesive layer 32 as the protective material, and the pressure-sensitive adhesive having the base material 31'and the pressure-sensitive adhesive layer 32' Tape 30'and is used. That is, the end portion of the metal-clad laminate 2 is covered with two adhesive tapes 30 and 30'on each side. In FIGS. 5 to 7, the adhesive tapes 30 and 30'are attached to the ends of the metal-clad laminate 2 so as to extend from the front surface to the back surface of the metal-clad laminate 2.

In the metal-clad laminate 1 whose end is protected as shown in FIG. 8, the adhesive tape 30 having the base material 31 and the pressure-sensitive adhesive layer 32 as the protective material, and the pressure-sensitive adhesive tape 30 having the base material 31'and the pressure-sensitive adhesive layer 32' 'And an adhesive tape 30'' having a base material 31'' and an adhesive layer 32'' are used. That is, the end portion of the metal-clad laminate 2 is covered with three

adhesive tapes

30, 30 ′ and 30 ″ per side. In FIG. 8,

adhesive tapes

30, 30 ′ and 30 ″ are attached to the ends of the metal-clad laminate 2 so as to extend from the front surface to the back surface of the metal-clad laminate 2.

In FIGS. 2 to 8, 3a shows the interface between the pressure-sensitive adhesive layers, and by making the interface 3a as small as possible, damage to the end portion of the metal-clad laminate 2 can be further suppressed. Even when exposed to a strong alkaline solution, the infiltration of the solution into the end portion can be further suppressed.

The use of the metal-clad laminate with end protection of the present invention is not particularly limited, but it can be particularly preferably used when manufacturing a printed wiring board. A method for manufacturing a printed wiring board using a metal-clad laminate, the printing having a protection step of covering the end of the metal-clad laminate with a protective material to obtain the end-protected metal-clad laminate of the present invention. A method for manufacturing a wiring board is also one of the present inventions.

In the protection step, the method of covering the end portion of the metal-clad laminate with a protective material to obtain the end-protected metal-clad laminate of the present invention is not particularly limited. For example, when the adhesive tape as described above is used as the protective material, a method of attaching the adhesive tape to the end of the metal-clad laminate using a tape laminator, or a method of attaching the adhesive tape to the metal by using a press machine. Examples thereof include a method of crimping to the end portion of the laminated laminated plate, a method of manually attaching the adhesive tape to the metal laminated laminated plate, and the like. In these methods, when the adhesive tape is attached to the square of the metal-clad laminate, the adhesive tape may be attached in duplicate or may be attached so as not to overlap.

In the method for manufacturing a printed wiring substrate of the present invention, after the above-mentioned protection step, the metal-clad laminate whose end is protected according to the present invention is further subjected to metal plating treatment to obtain the above-mentioned metal-clad laminate and the above-mentioned protective material. A metal plating step of precipitating metal on the surface may be performed. In the metal plating step, the method of metal plating treatment is not particularly limited, and conventionally known methods such as electroless plating adopted when manufacturing a printed wiring board can be used. In the metal plating step, by using the metal-clad laminate with the end protection of the present invention, it is possible to suppress damage to the end of the metal-clad laminate. Further, when the adhesive tape as described above is used as the protective material and the base material is the metal base material, the metal can be well deposited and a metal plating layer that is difficult to peel off can be formed. Even when the base material is the resin base material, if the surface roughness Ra of the resin base material is within the above range, the metal can be well deposited and a metal plating layer that is difficult to peel off can be formed. can.

In the method for manufacturing a printed wiring substrate of the present invention, after the above-mentioned protection step, a circuit forming step of etching or desmearing the end-protected metal-clad laminate of the present invention may be further performed. In the circuit forming step, the method of etching treatment or desmear treatment is not particularly limited, and a conventionally known method adopted when manufacturing a printed wiring board can be used. In the circuit forming step, by using the metal-clad laminate with the end protection of the present invention, damage to the end of the metal-clad laminate can be suppressed, and when exposed to a strong alkaline solution, the metal-clad laminate can be prevented from being damaged. Can also suppress the infiltration of the solution into the end portion.

The metal plating step and the circuit forming step may be performed first as long as they are performed after the protection step. Further, the metal plating step and the circuit forming step may be repeated as long as they are performed after the protection step.

In the method for manufacturing a printed wiring board of the present invention, a trimming step for separating a region covered with a protective material in the metal-clad laminate with end protection of the present invention may be further performed. As a result, the region covered with the protective material can be separated, and a printed wiring board after circuit formation can be obtained. In the trimming step, the method for separating the region covered with the protective material in the metal-clad laminate with the end protection of the present invention is not particularly limited, and examples thereof include a method of cutting with a slitter.

A method for manufacturing an intermediate used for a printed wiring board, for a printed wiring board having a protection step of covering the end portion of the metal-clad laminate with a protective material to obtain the edge-protected metal-clad laminate of the present invention. A method for producing an intermediate is also one of the present inventions.

According to the present invention, an end-protected metal-clad laminate capable of suppressing damage to the end of the metal-clad laminate and suppressing infiltration of the solution into the end even when exposed to a strong alkaline solution can be provided. Can be provided. Further, according to the present invention, it is possible to provide a method for manufacturing a printed wiring board and a method for manufacturing an intermediate for a printed wiring board.

It is sectional drawing which shows typically an example of the area covered with the protective material in the metal-clad laminated board which protected the edge of this invention. It is sectional drawing which shows typically an example of the area covered with the protective material in the metal-clad laminated board which protected the edge of this invention. It is sectional drawing which shows typically an example of the area covered with the protective material in the metal-clad laminated board which protected the edge of this invention. It is sectional drawing which shows typically an example of the area covered with the protective material in the metal-clad laminated board which protected the edge of this invention. It is sectional drawing which shows typically an example of the area covered with the protective material in the metal-clad laminated board which protected the edge of this invention. It is sectional drawing which shows typically an example of the area covered with the protective material in the metal-clad laminated board which protected the edge of this invention. It is sectional drawing which shows typically an example of the area covered with the protective material in the metal-clad laminated board which protected the edge of this invention. It is sectional drawing which shows typically an example of the area covered with the protective material in the metal-clad laminated board which protected the edge of this invention.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Preparation of acrylic polymer 1)
Ethyl acetate was added as a polymerization solvent to the reaction vessel, and after bubbling with nitrogen, the reaction vessel was heated while flowing nitrogen to start reflux. Subsequently, a polymerization initiator solution obtained by diluting 0.3 parts by weight of azobisisobutyronitrile 10-fold with ethyl acetate as a polymerization initiator was put into a reaction vessel, and 47 parts by weight of butyl acrylate and 50 parts by weight of 2-ethylhexyl acrylate were added. Parts, 2.8 parts by weight of acrylic acid and 0.2 parts by weight of 2-hydroxyethyl acrylate were added dropwise over 2 hours. After completion of the dropping, the polymerization initiator solution obtained by diluting 0.3 part by weight of azobisisobutyronitrile as a polymerization initiator with ethyl acetate 10-fold was put into the reaction vessel again, and the polymerization reaction was carried out for 4 hours to carry out an acrylic polymer. 1 Containing solution was obtained.
The weight average molecular weight (Mw) of the obtained acrylic polymer 1 was 450,000 in terms of polystyrene by gel permeation chromatography using GPC LF-804 (manufactured by Showa Denko KK) as a column. rice field.

(Preparation of acrylic polymer 2)
Acrylic polymer 1 except that the monomers used were changed to 33 parts by weight of butyl acrylate, 32 parts by weight of butyl methacrylate, 32 parts by weight of methyl methacrylate, 2.8 parts by weight of acrylic acid and 0.2 parts by weight of 2-hydroxyethyl acrylate. Similarly, a solution containing acrylic polymer 2 was obtained.
Regarding the obtained acrylic polymer 2, the weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography using GPC LF-804 (manufactured by Showa Denko KK) as a column, and it was 330,000. rice field.

(Preparation of acrylic polymer 3)
Acrylic polymer except that the monomer used was changed to 33 parts by weight of butyl acrylate, 32 parts by weight of butyl methacrylate, 32 parts by weight of isobornyl acrylate, 2.8 parts by weight of acrylic acid and 0.2 parts by weight of 2-hydroxyethyl acrylate. In the same manner as in No. 1, a solution containing acrylic polymer 3 was obtained.
The weight average molecular weight (Mw) of the obtained acrylic polymer 3 was 350,000 in terms of polystyrene by gel permeation chromatography using GPC LF-804 (manufactured by Showa Denko KK) as a column. rice field.

(Preparation of rubber polymer)
As the rubber-based polymer, a styrene-isoprene-styrene block copolymer (SIS) (Zeon Corporation, Quintac 3520, diblock ratio 78% by weight, styrene content 15% by weight) was used.

(Preparation of adhesive A)
To 100 parts by weight of the obtained acrylic polymer 1-containing solution, 15 parts by weight of a polymerized rosin ester resin (Pencel D160, hydroxyl value 42 mgKOH / g, manufactured by Arakawa Chemical Industries, Ltd.) was added to 100 parts by weight. Further, 1 part by weight of a silane coupling agent (KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 1 part by weight (solid component ratio) of an isocyanate-based cross-linking agent (Coronate L, manufactured by Tosoh Co., Ltd.) are added to prepare a solution of the pressure-sensitive adhesive A. did.

(Preparation of adhesive B)
As a tackifying resin, 25 parts by weight of a polymerized rosin ester resin (manufactured by Arakawa Chemical Industry Co., Ltd., Pencel D160, hydroxyl value 42 mgKOH / g) and a terpene phenol resin (manufactured by Yasuhara Chemical Co., Ltd., YS Polystar G150, hydroxyl value 130 mgKOH / g, softening point 150 ° C.) ) A solution of the pressure-sensitive adhesive B was prepared in the same manner as the pressure-sensitive adhesive A except that 10 parts by weight was used.

(Preparation of adhesive C)
The solution concentration of the rubber polymer and 10 parts by weight of terpenphenol resin (YShara Chemical Co., Ltd., YS Polystar T160, hydroxyl value 60 mgKOH / g, softening point 160 ° C) with respect to 100 parts by weight of the rubber polymer is in the solvent (toluene). A solution of the pressure-sensitive adhesive C was prepared by adding and stirring so as to be 30% by weight.

(Preparation of adhesive D)
A solution of the pressure-sensitive adhesive D was prepared in the same manner as the pressure-sensitive adhesive C except that 10 parts by weight of Polyterpen (manufactured by Yasuhara Chemical Co., Ltd., YS resin PX-1250, hydroxyl value 0 mgKOH / g, softening point 125 ° C.) was used as the pressure-sensitive adhesive resin. Prepared.

(Adhesive E adjustment)
As a tackifying resin, 15 parts by weight of a polymerized rosin ester resin (manufactured by Arakawa Chemical Industry Co., Ltd., Pencel D160, hydroxyl value 42 mgKOH / g) and a terpene phenol resin (manufactured by Yasuhara Chemical Co., Ltd., YS Polystar G150, hydroxyl value 130 mgKOH / g, softening point 150 ° C.) ) A solution of the pressure-sensitive adhesive E was prepared in the same manner as the pressure-sensitive adhesive A except that 10 parts by weight was used.

(Adhesive F adjustment)
The pressure-sensitive adhesive F was the same as the pressure-sensitive adhesive C except that 10 parts by weight of a terpene phenol resin (manufactured by Yasuhara Chemical Co., Ltd., YS Polystar U-115, hydroxyl value 20 mgKOH / g, softening point 115 ° C.) was used as the pressure-sensitive adhesive resin. A solution was prepared.

(Adhesive G adjustment)
Similar to the pressure-sensitive adhesive C, the pressure-sensitive adhesive G was used as the pressure-sensitive adhesive resin except that 10 parts by weight of a terpene phenol resin (manufactured by Yasuhara Chemical Co., Ltd., YS Polystar G-125, hydroxyl value 130 mgKOH / g, softening point 125 ° C.) was used. A solution was prepared.

(Adjustment of thermal adhesive H)
In the obtained solution containing acrylic polymer 2, hydrogenated rosin ester resin (manufactured by Arakawa Chemical Industry Co., Ltd., pine crystal KE-359, hydroxyl value 42 mgKOH / g) was added as an adhesive resin to 100 parts by weight of the acrylic polymer 2. 25 parts by weight was added. An epoxy-based cross-linking agent (Tetrad C manufactured by Mitsubishi Gas Chemical Company, Inc.) was added in an amount of 0.2 parts by weight (solid component ratio) to prepare a solution of the heat-sensitive adhesive H.

(Adjustment of thermal adhesive I)
A solution of the thermal pressure-sensitive adhesive I was prepared in the same manner as the heat-sensitive pressure-sensitive adhesive H except that the acrylic polymer 2-containing solution was changed to the acrylic polymer 3-containing solution.

(Adjustment of thermal adhesive J)
A solution of the heat-sensitive pressure-sensitive adhesive J was prepared in the same manner as the heat-sensitive pressure-sensitive adhesive H except that the pressure-sensitive adhesive resin was changed to a hydrogenated rosin ester resin (Arakawa Chemical Industry Co., Ltd., ester gum H, hydroxyl value 29 mgKOH / g).

(Examples 1 to 13)
(1) Production of Pressure Sensitive Adhesive Tape The obtained adhesive solution was applied onto a PET film having a thickness of 75 μm and subjected to a mold release treatment so that the thickness of the adhesive layer 1 after drying would be the thickness shown in Table 2. Then, it was dried at 110 ° C. for 5 minutes to form the pressure-sensitive adhesive layer 1. The pressure-sensitive adhesive layer 1 was transferred to the substrate shown in Table 2 and cured at 40 ° C. for 48 hours to obtain a pressure-sensitive adhesive tape.
In addition, a measurement sample composed of only the pressure-sensitive adhesive layer 1 having a thickness of 10 mm × 6 mm and a thickness of 1 mm was prepared by the same method. The obtained measurement sample was subjected to a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Measurement Control Co., Ltd.) under the conditions of a shear mode for dynamic viscoelasticity measurement, an angular frequency of 1 Hz, and a speed of 5 ° C./min. Dynamic viscoelasticity was measured from −40 ° C. to 140 ° C., and the storage elastic modulus at 23 ° C. was measured. The measurement results are shown in Table 1.

(2) Manufacture of copper-clad laminate with end-protected edges The obtained pressure-sensitive adhesive tape is cut into 7 mm × 80 mm, and the pressure-sensitive adhesive tape is applied to the copper-clad laminate (CCL) so as to have the coating form shown in Table 2. ) (Manufactured by Panasonic, R1515E, resin layer thickness 40 μm, copper foil thickness 2 μm) was manually attached to the end to obtain a copper-clad laminate with the end protected.
More specifically, in Examples 1, 3 to 7, 9 to 13, the pressure-sensitive adhesive tape was attached so as to have the covering form shown in FIG. First, place the pressure-sensitive adhesive tape on one side of one side of the copper-clad laminate so that the end of the long side of the pressure-sensitive adhesive tape comes at a position 3.5 mm from the end of the copper-clad laminate, and 2 kg. The pressure was applied at a speed of 300 mm / min using a roller. After that, while pressing the base material surface of the pressure-sensitive adhesive tape that has not been attached with a stainless steel plate, the pressure-sensitive adhesive tape is bent so that no gap is formed toward the other surface of the copper-clad laminate, and the copper-clad laminate is laminated. It was affixed to the other side of the plate and crimped at a speed of 300 mm / min using a 2 kg roller. The same operation was carried out on the side of the copper-clad laminate facing the side facing the pressure-sensitive adhesive tape, and the pressure-sensitive adhesive tape was attached to obtain a copper-clad laminate with end protection.
In Example 2, the pressure-sensitive adhesive tape was attached so as to have the covering form shown in FIG. First, place the pressure-sensitive adhesive tape on one side of one side of the copper-clad laminate so that the end of the long side of the pressure-sensitive adhesive tape comes at a position 3.5 mm from the end of the copper-clad laminate, and 2 kg. The pressure was applied at a speed of 300 mm / min using a roller. Then, another pressure-sensitive adhesive tape was similarly pressure-bonded to the other surface of the copper-clad laminate at a speed of 300 mm / min using a 2 kg roller. The same operation was carried out on the side of the copper-clad laminate facing the side facing the pressure-sensitive adhesive tape, and the pressure-sensitive adhesive tape was attached to obtain a copper-clad laminate with end protection.
In Example 8, the pressure-sensitive adhesive tape was attached so as to have the covering form shown in FIG. First, place the pressure-sensitive adhesive tape on one side of one side of the copper-clad laminate so that the end of the long side of the pressure-sensitive adhesive tape comes to the position 3.3 mm from the end of the copper-clad laminate, and 2 kg. The pressure was applied at a speed of 300 mm / min using a roller. After that, while pressing the base material surface of the pressure-sensitive adhesive tape that has not been attached with a stainless steel plate, the pressure-sensitive adhesive tape is bent toward the other surface of the copper-clad laminate, and the other surface of the copper-clad laminate is bent. It was attached to a copper-clad laminate at a position 3.3 mm from the end, and crimped at a speed of 300 mm / min using a 2 kg roller. The same operation was carried out on the side of the copper-clad laminate facing the side facing the pressure-sensitive adhesive tape, and the pressure-sensitive adhesive tape was attached to obtain a copper-clad laminate with end protection.

(Example 14)
(1) Production of Thermal Adhesive Tape After the obtained adhesive solution is applied onto a PET film having a thickness of 75 μm and subjected to mold release treatment so that the thickness of the adhesive layer 1 after drying becomes the thickness shown in Table 2. , 110 ° C. for 5 minutes to form the pressure-sensitive adhesive layer 1. The pressure-sensitive adhesive layer 1 was transferred to the substrate shown in Table 2 under 100 ° C. conditions and cured at 40 ° C. for 48 hours to obtain a heat-sensitive adhesive tape.
In addition, a measurement sample composed of only the pressure-sensitive adhesive layer 1 having a thickness of 10 mm × 6 mm and a thickness of 1 mm was prepared by the same method. The obtained measurement sample was subjected to a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Measurement Control Co., Ltd.) under the conditions of a shear mode for dynamic viscoelasticity measurement, an angular frequency of 1 Hz, and a speed of 5 ° C./min. Dynamic viscoelasticity was measured from −40 ° C. to 140 ° C., and the storage elastic modulus at 23 ° C. and 100 ° C. was measured. Furthermore, using a viscoelasticity measuring device (DVA-200, manufactured by IT Measurement Control Co., Ltd.), a dynamic viscoelasticity spectrum of -100 ° C to 200 ° C under the conditions of 5 ° C / min and 1 Hz in the low-speed temperature rise shear deformation mode. The peak temperature of the loss tangent was measured by measuring. The measurement results are shown in Table 1.

(2) Manufacturing of Copper-clad Laminated Plate with End-Protected Edge-Protected Copper-clad Laminated Plate was obtained in the same manner as in Examples 1 to 13. However, instead of crimping the pressure-sensitive adhesive tape with a 2 kg roller, the heat-sensitive adhesive tape was attached by thermocompression bonding at a pressure of 0.3 MPa for 30 seconds under 100 ° C. conditions.

(Examples 15 to 19)
(1) Production of Heat-Sensitive Adhesive Tape The thickness of the pressure-sensitive adhesive layer 1 after drying is the thickness shown in Table 2 on a PET film obtained by mold-releasing the obtained pressure-sensitive adhesive solution for forming the pressure-sensitive adhesive layer 1 with a thickness of 75 μm. After coating so as to be, it was dried at 110 ° C. for 5 minutes to form the pressure-sensitive adhesive layer 1 (pressure-sensitive pressure-sensitive adhesive layer). The pressure-sensitive adhesive layer 1 was transferred to the substrate shown in Table 2 and the release-treated PET film was peeled off. Then, the pressure-sensitive adhesive solution for forming the pressure-sensitive adhesive layer 2 was applied onto a PET film having a thickness of 75 μm and subjected to a mold release treatment so that the thickness of the pressure-sensitive adhesive layer 2 after drying would be the thickness shown in Table 2, and then 110. The adhesive layer 2 (heat-sensitive adhesive layer) was formed by drying at ° C. for 5 minutes. The pressure-sensitive adhesive layer 2 is transferred to the pressure-sensitive adhesive layer 1 under 100 ° C. conditions and cured at 40 ° C. for 48 hours. A heat-sensitive adhesive tape in which the mold adhesive layer) and the release-treated PET film were laminated in this order was obtained.
In addition, a measurement sample composed of only the pressure-sensitive adhesive layer 2 having a thickness of 10 mm × 6 mm and a thickness of 1 mm was prepared by the same method. The obtained measurement sample was subjected to a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Measurement Control Co., Ltd.) under the conditions of a shear mode for dynamic viscoelasticity measurement, an angular frequency of 1 Hz, and a speed of 5 ° C./min. Dynamic viscoelasticity was measured from −40 ° C. to 140 ° C., and the storage elastic modulus at 23 ° C. and 100 ° C. was measured. Furthermore, using a viscoelasticity measuring device (DVA-200, manufactured by IT Measurement Control Co., Ltd.), a dynamic viscoelasticity spectrum of -100 ° C to 200 ° C can be obtained under the conditions of 5 ° C / min and 1 Hz in the low-speed temperature rise shear deformation mode. By measuring, the peak temperature of the loss tangent was measured. The measurement results are shown in Table 1.

<Evaluation>
The following evaluation was performed on the copper-clad laminate with end protection obtained in the examples. The results are shown in Table 2.

(1) Evaluation of the number of wrinkles on the adhesive tape The attached adhesive tape was visually confirmed, and the number of wrinkled locations was counted. The case where there was no wrinkle was marked with ⊚, the case where there was one wrinkle was marked with ◯, the case where there were two or three wrinkles was marked with Δ, and the case where there were four or more wrinkles was marked with ×.

(2) Electroless plating process Electroless plating was performed on the copper-clad laminate with the end protected under the conditions shown in Table 3. The appearance of the copper-clad laminate with end-protected copper-clad laminates was observed at a magnification of 50 times using a microscope (VHX-5000, manufactured by KEYENCE CORPORATION) to confirm the presence or absence of plating precipitation. The case where the plating was well deposited was evaluated as 〇.
In addition, the presence or absence of plating peeling was confirmed by attaching a commercially available cellophane tape to the plated portion deposited on the surface of the base material of the adhesive tape and conducting a peeling test. The case where the plating was not transferred to the cellophane tape was evaluated as ◯, and the case where the plating was partially transferred was evaluated as Δ.

(3) Desmear process The copper-clad laminate with end-protected copper-clad laminates is subjected to desmear treatment under the conditions shown in Table 4, and then the desmear-treated liquid is removed from the end-protected copper-clad laminate to remove 30. It was left at room temperature for a minute. After leaving it at room temperature for 30 minutes, the appearance of the adhesive tape was observed with a microscope (manufactured by KEYENCE, VHX-5000) at a magnification of 20 times to confirm the presence or absence of peeling of the adhesive tape. The case where no peeling was observed was evaluated as 〇.
Then, the adhesive tape was peeled off from the copper-clad laminate, and the discoloration of the copper in the portion where the adhesive tape of the copper-clad laminate was attached was confirmed to evaluate the protective property (presence or absence of wetting). ◎ when no discoloration of copper was observed, 〇 when discoloration of copper was observed within 2 mm from the end of the part where the adhesive tape was attached, and 〇 when discoloration of copper was observed more than that. It was marked as x.

(4) Edge protection of the copper-clad laminate The desmear step and the electroless plating step are performed in this order on the copper-clad laminate whose end is protected, and then the adhesive tape is applied from the copper-clad laminate. It peeled off. The end of the copper-clad laminate was observed with a microscope (manufactured by KEYENCE, VHX-5000) at a magnification of 50 times, and the case where there was no defect was evaluated as ◯, and the case where the defect occurred was evaluated as ×. A copper-clad laminate not covered with a protective material was used as a comparison target (Comparative Example 1).

1 Metal-clad laminate with end protection 2 Metal-clad laminate 30, 30', 30'' Adhesive tape 31, 31', 31'' Base material 32, 32', 32'' Adhesive layer 3a Adhesive layer Interface between each other

Claims

An edge-protected metal-clad laminate, characterized in that the edges of the metal-clad laminate are covered with a protective material.
The first aspect of the present invention, wherein the protective material is an adhesive tape having a base material and an adhesive layer laminated on one surface of the base material, and the base material is a metal base material. Metal-clad laminate with protected edges.
The metal-clad laminate with end protection according to claim 2, wherein the metal base material is exposed on the outermost surface.
The first aspect of the present invention, wherein the protective material is an adhesive tape having a base material and an adhesive layer laminated on one surface of the base material, and the base material is a resin base material. Edge-protected metal-clad laminate.
The metal-clad laminate with end protection according to claim 4, wherein the resin base material has a surface roughness Ra of 10 nm or more and 500 nm or less.
The end-protected metal-clad laminate according to claim 1, 2, 3, 4 or 5, wherein the end portion of the metal-clad laminate is covered with two or more of the protective materials per side. Board.
The metal-clad laminate according to claim 1, 2, 3, 4 or 5, wherein the end portion of the metal-clad laminate is covered with one protective material per side.
Claims 1, 2, 3, 4, 5, 6 are characterized in that the end portion of the metal-clad laminate is covered with the protective material so as to extend from the front surface to the back surface of the metal-clad laminate. Or the metal-clad laminate with end protection according to 7.
Further, claims 1, 2, 3, 4, 5, characterized in that the entire surface of one or more selected from the group consisting of the front surface and the back surface of the metal-clad laminate is covered with the protective material. 6, 7 or 8 end-protected metal-clad laminate.
The metal-clad laminate according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein the metal-clad laminate has a thickness of 100 μm or less.
The end-protected metal-clad laminate according to claim 2, 3, 4 or 5, wherein the thickness of the adhesive layer of the adhesive tape is thicker than ½ of the thickness of the metal-clad laminate. ..
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape is an acrylic pressure-sensitive pressure-sensitive adhesive layer, and the acrylic pressure-sensitive pressure-sensitive adhesive layer has a storage elastic modulus of 2 × 105 Pa or less at 23 ° C. Item 2. The end-protected metal-clad laminate according to Item 2, 3, 4, 5 or 11.
2. 4, 5 or 11 The end-protected metal-clad laminate.
The metal-clad laminate with end protection according to claim 2, 3, 4, 5 or 11, wherein the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape is an acrylic heat-sensitive pressure-sensitive adhesive layer.
The end of the acrylic heat-sensitive adhesive layer is protected at the end according to claim 14, wherein the peak temperature of the loss tangent measured at a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device is 40 ° C. or higher. Metal-clad laminate.
The acrylic heat-sensitive pressure-sensitive adhesive layer has a storage elastic modulus of 5 × 10 6 Pa or more at 23 ° C. and a storage elastic modulus of 2 × 10 5 Pa or less at 100 ° C. The described end-protected metal-clad laminate.
The end-protected metal-clad laminate according to claim 14, 15 or 16, wherein the adhesive tape further has a pressure-sensitive adhesive layer between the base material and the acrylic heat-sensitive adhesive layer. Board.
The end protection according to claim 2, 3, 4, 5, 11, 12, 13, 14, 15, 16 or 17, wherein the adhesive tape further has a metal plating layer on the surface of the base material. Metal-clad laminate.
It is a method of manufacturing a printed wiring board using a metal-clad laminate.
The end of the metal-clad laminate is covered with a protective material, and claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 A method for manufacturing a printed wiring board, which comprises a protection step for obtaining the described end-protected metal-clad laminate.
Further, claim 19. The method for manufacturing a printed wiring board according to the description.
The method for manufacturing a printed wiring board according to claim 19 or 20, further comprising a circuit forming step of performing an etching treatment or a desmear treatment on the metal-clad laminate whose end is protected.
The method for manufacturing a printed wiring board according to claim 19, 20, or 21, further comprising a trimming step for separating a region covered with the protective material in the end-protected metal-clad laminate.
A method for manufacturing intermediates used for printed wiring boards.
The end of the metal-clad laminate is covered with a protective material, and claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 A method for manufacturing an intermediate for a printed wiring board, which comprises a protection step for obtaining the described end-protected metal-clad laminate.