KR20230058589A - End-protected metal-clad laminate, method for manufacturing printed wiring boards, and method for manufacturing intermediates for printed wiring boards - Google Patents

Abstract

An object of the present invention is to provide an edge-protected metal-clad laminate capable of suppressing breakage of the end portion of the metal-clad laminate and suppressing penetration of the solution to the end portion even when exposed to a strong alkaline solution. . Moreover, this invention aims at providing the manufacturing method of a printed wiring board, and the manufacturing method of the intermediate body for printed wiring boards. The present invention is an end-protected metal-clad laminate in which an edge of the metal-clad laminate is covered with a protective material.

Description

End-protected metal-clad laminate, method for manufacturing printed wiring boards, and method for manufacturing intermediates for printed wiring boards

The present invention relates to a method for manufacturing a metal-clad laminate with edge protection, a printed wiring board, and a method for manufacturing an intermediate for printed wiring boards.

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

Japanese Unexamined Patent Publication No. 2015-052050 Japanese Unexamined Patent Publication No. 2015-021067 Japanese Unexamined Patent Publication No. 2015-120876

On the other hand, board|substrates, such as a printed wiring board used for electronic equipment, are manufactured by forming a circuit in the copper foil part of the copper clad laminated board (CCL) in which copper foil and the resin layer were laminated|stacked. In recent years, thinning of substrates such as printed wiring boards has progressed, and for example, when the thickness of the copper clad laminate is 100 μm or less, especially around 30 to 40 μm, manufacturing a substrate from the copper clad laminate In the process, there is a problem that the end portion of the copper clad laminate is damaged during the manufacturing process. In particular, in etching treatment, desmear treatment, etc. performed in the substrate manufacturing process, a strong alkaline solution is used as a treatment solution. For this reason, problems such as penetration of the strong alkaline solution into the ends of the copper-clad laminate, leading to breakage of the ends, or damage to the resin layer to cause defects in the next step have occurred.

An object of the present invention is to provide an edge-protected metal-clad laminate capable of suppressing breakage of the end portion of the metal-clad laminate and suppressing penetration of the solution to the end portion even when exposed to a strong alkaline solution. . Moreover, this invention aims at providing the manufacturing method of a printed wiring board, and the manufacturing method of the intermediate body for printed wiring boards.

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

The end-protected metal-clad laminate of the present invention is one in which the end of the metal-clad laminate is covered with a protective material. Such an end-protected metal-clad laminate can suppress breakage of the end of the metal-clad laminate, and even when exposed to a strong alkaline solution, can suppress penetration of the solution to the end.

That the edge 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, a peripheral portion of the end face may also be covered with the protective material. .

Especially, it is preferable that the end part of the said metal-clad laminated board is covered with the said protective material so that it may extend from the front surface to the back surface of the said metal-clad laminated board. In such a case, since the protective material becomes difficult to peel off, breakage of the end portion of the metal-clad laminate can be further suppressed, and penetration of the solution into the end portion can be further suppressed even when exposed to a strong alkaline solution. In this case, in the front and rear surfaces of the metal-clad laminate, the width of the portion where the protective material covers the front and rear surfaces of the metal-clad laminate (the shortest distance between the edge of the protective material and the cross section of the metal-clad laminate) is particularly limited However, a preferable lower limit is 1 mm and a preferable upper limit is 20 mm, a more preferable lower limit is 3 mm, and a more preferable upper limit is 10 mm.

In the edge-protected metal-clad laminate of the present invention, the whole of one or more surfaces selected from the group consisting of the front and back surfaces of the metal-clad laminate may be covered with the protective material. In such a case, it is possible to make the reliance material more resistant to peeling.

As for the metal-clad laminate of this invention edge protection, at least one part in at least 1 of 4 sides of the said metal-clad laminate should just be covered with the said protective material. Among others, from the viewpoint of further suppressing breakage of the end portion of the metal-clad laminate and further suppressing permeation of the solution to the end portion even when exposed to a strong alkaline solution, at least two sides of the metal-clad laminate are used as the protective material. Preferably covered. More preferably, three or more sides of the metal-clad laminate are covered with the protective material, and more preferably, four sides of the metal-clad laminate are covered with the protective material. Moreover, it is preferable that each side of the said metal-clad laminated board is covered with the said protective material over the whole.

In the edge-protected metal-clad laminate of the present invention, the ends 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. When covered with two or more protective materials per side, for example, you may be covered by bonding two protective materials per side, or you may be covered by bonding three protective materials together.

In addition, the edge of the metal-clad laminate is covered with the protective material, and the form of the cover is determined by visually observing the edge-protected metal-clad laminate or using a microscope (e.g., VHX-5000 manufactured by Keyence Corporation). It can be confirmed by observing using .

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 substrates such as printed wiring boards, may be used. More specifically, for example, a copper clad laminate (CCL) in which copper foil and a resin layer are laminated, an aluminum clad laminate in which aluminum foil and a resin layer are laminated, and the like can be used. In the case of using such a metal-clad laminate, it is preferable that at least an 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 small thickness, the end-protected metal-clad laminate of the present invention can suppress breakage of the end portion of the metal-clad laminate, and even when exposed to a strong alkaline solution, can suppress penetration of the solution to the end portion. there is. A more preferable lower limit of the thickness of the metal-clad laminate is 10 μm, a more preferable upper limit is 60 μm, a particularly preferable lower limit is 30 μm, and a particularly preferable upper limit is 40 μm.

Although the said reliance material is not specifically limited, It is preferable that it is an adhesive tape which has a base material and the adhesive layer laminated|stacked on one surface of the said base material. Such an adhesive tape is used by sticking it so that the said adhesive layer is in contact with the edge part of the said metal clad laminated board. The substrate is not particularly limited, and may be a metal substrate or a resin substrate.

In the case where the substrate is the metal substrate, when the adhesive tape is attached to an end portion of the metal clad laminate, the metal substrate is exposed to the outermost surface. When a metal plating treatment is performed on such an edge-protected metal-clad laminate and metal is deposited on the surfaces of the metal-clad laminate and the metal substrate, the metal precipitates favorably and the metal plating layer does not peel off easily. can form.

In addition, when the substrate is the metal substrate, since the metal substrate is not easily damaged even when exposed to a strong alkaline solution, breakage of the end portion of the metal-clad laminate can be more suppressed, and when exposed to a strong alkaline solution Even in this case, penetration of the solution to the end portion can be further suppressed. In addition, since the base material is the metal base material, since the anchoring property between the metal base material and the pressure-sensitive adhesive layer is increased even without interposing a resin layer as described later, a strong alkaline solution is prevented from entering the inside of the pressure-sensitive adhesive layer. It gets difficult. Also by this, breakage of the edge part of the said metal-clad laminated board can be more suppressed, and penetration into the edge part of the solution can be suppressed more even when it is exposed to strong alkaline solution. In addition, when the substrate is the metal substrate, even when the adhesive tape is folded (folded) and attached to an 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 metal substrate has a shape , it is possible to suppress the restoring force caused by folding the metal substrate. Accordingly, it is difficult to create a gap between the end portion of the metal-clad laminate and the pressure-sensitive adhesive layer, and peeling is less likely to occur. When the base material is the resin base material, a gap is easily formed 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 substrate is not particularly limited, and examples thereof include copper, aluminum, nickel, and titanium. Moreover, alloys, such as stainless steel and Monel, are also mentioned as a metal which comprises the said metal base material. Among them, copper is preferable because the restoring force after folding is small and it is difficult to tear, so that the handleability of the adhesive tape becomes better.

When the base material is the resin base material, when the adhesive tape is applied to the metal clad laminate, the resin base material is exposed on the outermost surface. The surface roughness Ra of the resin substrate, more specifically, the surface roughness Ra of the surface of the surface of the resin substrate opposite to the side on which the pressure-sensitive adhesive layer is laminated is not particularly limited, but a preferable lower limit is 10 nm, and a preferable upper limit is 500 nm. . When the surface roughness Ra of the resin substrate is within the above range, metal plating is performed on the edge-protected metal-clad laminate and metal is deposited on the surface of the metal-clad laminate and the resin substrate, the metal is favorably Along with precipitation, a metal plating layer that is difficult to peel can be formed. Moreover, compared with the case where the said base material is the said resin base material, peeling of a metal plating layer becomes easy normally compared with the case of the said metal base material. A more preferable lower limit of the surface roughness Ra of the resin substrate is 15 nm, a more preferable upper limit is 200 nm, a still more preferable lower limit is 20 nm, and a still more preferable upper limit is 100 nm.

In addition, surface roughness Ra means the arithmetic average roughness prescribed|regulated by JISB 0601-2001.

The resin substrate is not particularly limited, and examples thereof include polyolefin resin films such as polyethylene films and polypropylene films, polyester resin films such as polyethylene terephthalate (PET) films, ethylene-vinyl acetate copolymer films, poly A vinyl chloride type resin film and a polyurethane type resin film are mentioned. Moreover, as said base material, polyolefin foam sheets, such as a polyethylene foam sheet and a polypropylene foam sheet, a polyurethane foam sheet, etc. are mentioned. Especially, a PET film is preferable.

The thickness of the substrate is not particularly limited, but a preferable lower limit is 2 μm and a preferable upper limit is 30 μm. When the thickness of the substrate is within the above range, peeling is less likely to occur even when the adhesive tape is folded back (folded) and attached to an end portion of the metal clad laminate. A more preferable lower limit of the thickness of the substrate is 4 μm, and a 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, you may further have a metal plating layer on the surface of the side opposite to the side on which the said adhesive layer was laminated|stacked of the said base material. As described above, when the substrate is the metal substrate, metal plating is performed on the edge-protected metal-clad laminate, and metal is deposited on the surface of the metal-clad laminate and the metal substrate, the metal While favorably precipitating, it is possible to form a metal plating layer that is difficult to peel off. Even when the base material is the resin base material, as long as the surface roughness Ra of the resin base material is within the above range, a metal plating layer that does not peel easily can be formed while metal precipitates satisfactorily. The metal-clad laminate subjected to end treatment of the present invention may be one in which a metal plating layer is formed on the surface of the base material by passing through such a metal plating treatment.

The pressure-sensitive adhesive layer is not particularly limited, and examples of the base polymer included in the pressure-sensitive adhesive layer include acrylic polymers, rubber-based polymers, urethane-based polymers, and silicone-based polymers. Especially, it is preferable that the said adhesive layer is an acrylic pressure-sensitive adhesive layer or an acrylic heat-sensitive adhesive layer containing an acrylic polymer, or a rubber-type adhesive layer containing a rubber-type polymer.

The acrylic polymer is usually made of an acrylic acid alkyl ester and/or a methacrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms as a main monomer, and a monomer having a crosslinkable functional group as necessary with this as the main monomer. It is a (meth)acrylic acid ester copolymer obtained by copolymerizing by a method. In addition, you may copolymerize other modifying monomers that can be copolymerized.

The acrylic pressure-sensitive adhesive layer also has advantages such as being relatively stable against light, heat, moisture, etc., exhibiting adhesiveness at room temperature, and being able to adhere to various adherends (low adherend selectivity). The acrylic polymer contained in the acrylic pressure-sensitive adhesive layer is not particularly limited, but preferably has a structural unit derived from a monomer having a crosslinkable functional group. By having such a structural unit, when a crosslinking agent is used in combination, the acrylic polymers contained in the acrylic pressure-sensitive adhesive layer can be crosslinked. The storage elastic modulus of the acrylic pressure-sensitive adhesive layer can be adjusted by adjusting the degree of crosslinking at that time.

As said crosslinkable functional group, a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, an amide group, a nitrile group etc. are mentioned, for example. Especially, a hydroxyl group or a carboxyl group is preferable from the viewpoint of easy adjustment of the storage elastic modulus of the acrylic pressure-sensitive adhesive layer. As a monomer which has the said hydroxyl group, (meth)acrylic acid ester which has a hydroxyl group, such as 4-hydroxybutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate, is mentioned, for example. As a monomer which has the said carboxyl group, (meth)acrylic acid etc. are mentioned, for example. As a monomer which has the said glycidyl group, glycidyl (meth)acrylate etc. are mentioned, for example. As a monomer which has the said amide group, hydroxyethyl acrylamide, isopropyl acrylamide, dimethylaminopropyl acrylamide etc. are mentioned, for example. As a monomer which has the said nitrile group, acrylonitrile etc. are mentioned, for example. The monomers which have these crosslinkable functional groups may be used independently or may use 2 or more types together. The content of the structural unit derived from the monomer having the crosslinkable functional group is not particularly limited, but a preferable lower limit is 0.1% by weight and a preferable upper limit is 5% by weight. When using the monomer having the carboxyl group as the monomer having the crosslinkable functional group, a more preferable upper limit is 3% by weight, and a still more preferable upper limit is 0.5% by weight from the viewpoint of further suppressing penetration of the strong alkaline solution.

It is preferable that the acrylic polymer contained in the acrylic pressure-sensitive adhesive layer 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 adhesive layer increases, and penetration of the strong alkaline solution into the molecular chain can be further suppressed.

As the (meth)acrylate having an alkyl group having 8 or more carbon atoms, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate Late, isononyl(meth)acrylate, decyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, isostearyl(meth)acrylate, isobornyl(meth)acrylate etc. can be mentioned. These (meth)acrylates which have an alkyl group with 8 or more carbon atoms may be used independently or may use 2 or more types together. Among them, it is preferable to use 2-ethylhexyl acrylate, lauryl acrylate, and lauryl methacrylate in that the acrylic pressure-sensitive adhesive layer does not become too hard and can maintain sufficient tackiness.

Although content of the structural unit derived from the (meth)acrylate which has the said C8 or more alkyl group is not specifically limited, A preferable lower limit is 15 weight% and a preferable upper limit is 99 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 adhesive layer increases, and penetration of the strong alkaline solution into the molecular chain is further suppressed. A more preferable lower limit of the content of the structural unit derived from (meth)acrylate having an alkyl group having 8 or more carbon atoms is 20% by weight, and a more preferable upper limit is 30% by weight.

The acrylic polymer contained in the acrylic pressure-sensitive adhesive layer may further have structural units derived from other monomers within a range that does not impair the effects of the present invention. As the other monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) Acrylate, ethyl carbitol (meth)acrylate, vinyl acetate, a fluorine-containing monomer, etc. are mentioned. In addition, when the acrylic polymer contained in the acrylic pressure-sensitive adhesive layer is prepared by ultraviolet polymerization, further, structural units derived from polyfunctional monomers such as divinylbenzene and trimethylolpropane tri(meth)acrylate it is desirable to have

The acrylic polymer contained in the acrylic pressure-sensitive adhesive layer has a preferable lower limit of 250,000 and a preferable upper limit of 2,000,000 of the weight average molecular weight. When the weight average molecular weight of the acrylic polymer contained in the acrylic pressure-sensitive adhesive layer is within the above range, the adhesive strength of the acrylic pressure-sensitive adhesive layer is improved. A more preferable lower limit of the weight average molecular weight of the acrylic polymer contained in the acrylic pressure-sensitive adhesive layer is 300,000, a still more preferable lower limit is 400,000, and a more preferable upper limit is 1,500,000. In addition, the weight average molecular weight (Mw) can be adjusted according to polymerization conditions (eg, type or amount of polymerization initiator, polymerization temperature, monomer concentration, etc.). In addition, the weight average molecular weight (Mw) can be measured by the following method.

The acrylic polymer solution is filtered with a filter (material: polytetrafluoroethylene, pore diameter: 0.2 mu m). The obtained filtrate is supplied to a gel permeation chromatograph (eg, 2690 Separations Model, manufactured by Waters), and GPC measurement is performed under the conditions of a sample flow rate of 1 milliliter/min and a column temperature of 40 ° C., and polystyrene conversion of acrylic polymer Molecular weight is measured to determine the weight average molecular weight (Mw). As a column, for example, GPC KF-806L or GPC LF-804 (manufactured by Showa Denko) is used, and a differential refractometer is used as a detector.

The method of preparing the acrylic polymer contained in the acrylic pressure-sensitive adhesive layer is not particularly limited, and a method of radically reacting a monomer derived from the structural unit in the presence of a polymerization initiator is exemplified. The polymerization method is not particularly limited, and conventionally known methods can be used. For example, solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, block polymerization, etc. are mentioned. Among them, solution polymerization is preferred from the viewpoints 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, and diethyl ether. These reaction solvents may be used independently or may use 2 or more types together.

The polymerization initiator is not particularly limited, and examples thereof include organic peroxides and azo compounds. As the organic peroxide, for example, 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-butylper Oxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, etc. are mentioned. As said azo compound, azobisisobutyronitrile, azobiscyclohexane carbonitrile, etc. are mentioned, for example. These polymerization initiators may be used independently or may use 2 or more types together.

The acrylic pressure-sensitive adhesive layer may further contain a tackifying resin. When the acrylic pressure-sensitive adhesive layer contains a tackifying resin, the adhesive force of the acrylic pressure-sensitive adhesive layer is improved. The tackifying resin is not particularly limited, and examples thereof include coumarone resins, terpene resins, terpene phenol resins, rosin resins, rosin derivative resins, petroleum resins, alkylphenol resins, and hydrides thereof. These tackifying resins may be used independently and may use 2 or more types together.

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

Although the terpene constituting the terpene phenol resin is not particularly limited, monoterpenes such as α-pinene, β-pinene, limonene, and camphene are preferred. In addition, limonene includes d-isomer, l-isomer and d/l-isomer (dipentene).

As said rosin resin, more specifically, undenatured rosin (raw rosin), such as gum rosin, wood rosin, tall oil rosin, etc., modified rosin obtained by modifying these unmodified rosins, etc. are mentioned. As modification in the said modified rosin, hydrogenation, disproportionation, polymerization, etc. are mentioned, for example. More specific examples of the modified rosin include hydrogenated rosin, disproportionated rosin, polymerized rosin, and other chemically modified rosin.

As the rosin derivative resin, more specifically, for example, a rosin ester resin obtained by esterifying the rosin resin with an alcohol, an unsaturated fatty acid-modified rosin resin obtained by modifying the rosin resin with an unsaturated fatty acid, and an unsaturated rosin ester resin and unsaturated fatty acid-modified rosin ester resins modified with fatty acids. Moreover, as said rosin derivative resin, the rosin alcohol resin etc. which carried out the reduction process of the carboxyl group in the said unsaturated fatty acid modified rosin resin or unsaturated fatty acid modified rosin ester resin are mentioned, for example.

Moreover, as said rosin derivative resin, the metal salt of the said rosin resin or rosin derivative resin (especially rosin ester resin), rosin phenol resin, etc. are mentioned. Further, the rosin phenol resin is obtained by thermal polymerization by adding phenol to the above rosin resin or rosin derivative resin under an acid catalyst.

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

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

The acrylic pressure-sensitive adhesive layer may contain a silane coupling agent. When the acrylic pressure-sensitive adhesive layer contains a silane coupling agent, adhesion between the end portion of the metal-clad laminate and the acrylic pressure-sensitive adhesive layer increases, so that breakage of the end portion of the metal-clad laminate can be further suppressed, and in a strong alkaline solution Even when exposed, penetration of the solution to the end portion can be further suppressed.

The silane coupling agent is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, 2-(3,4-epoxy Cyclohexyl)ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethylmethoxysilane, N-(2-aminoethyl)3-aminopropyltrie Toxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptobutyltrimethoxysilane, γ- Mercaptopropyl methyldimethoxysilane etc. are mentioned. Especially, γ-glycidoxypropyltriethoxysilane and γ-mercaptopropyltrimethoxysilane are preferable.

The content of the silane coupling agent is not particularly limited, but a preferable lower limit is 0.1 parts by weight and a preferable upper limit is 5 parts by weight based on 100 parts by weight of the acrylic polymer contained in the acrylic 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 adhesive layer can be further improved. A more preferable lower limit of the content of the silane coupling agent is 0.5 parts by weight, and a more preferable upper limit is 3 parts by weight.

When the acrylic polymer contained in the acrylic pressure-sensitive adhesive layer contains a structural unit derived from the monomer having the crosslinkable functional group, the acrylic pressure-sensitive adhesive layer may contain a crosslinking agent. The crosslinking agent is not particularly limited, and examples thereof include an isocyanate-based crosslinking agent, an aziridine-based crosslinking agent, an epoxy-based crosslinking agent, and a metal chelate-type crosslinking agent. Especially, an isocyanate-type crosslinking agent and an epoxy-type crosslinking agent are preferable.

The content of the crosslinking agent is not particularly limited, but the lower limit is preferably 0.01 part by weight, the upper limit is 10 parts by weight, and the lower limit is 0.1 part by weight, more preferably 100 parts by weight of the acrylic polymer contained in the acrylic pressure-sensitive adhesive layer. The upper limit is 5 parts by weight.

The storage modulus of the acrylic pressure-sensitive adhesive layer is not particularly limited, but a preferable upper limit of the storage modulus at 23°C is 2×10 ⁵ Pa. When the storage modulus at 23 ° C. is 2 × 10 ⁵ Pa or less, the adhesion between the end portion of the metal-clad laminate and the acrylic pressure-sensitive adhesive layer increases, so that breakage of the end portion of the metal-clad laminate can be further suppressed, Even when exposed to a strong alkaline solution, penetration of the solution to the end portion can be further suppressed. A more preferable upper limit of the storage elastic modulus at 23°C is 1.8×10 ⁵ Pa. The lower limit of the storage modulus at 23°C is not particularly limited, but from the viewpoint of maintaining the cohesive force of the acrylic pressure-sensitive adhesive layer, a preferable lower limit is 1×10 ⁴ Pa, and a more preferable lower limit is 3×10 ⁴ Pa.

In addition, the storage elastic modulus at 23°C can be adjusted according to the type, molecular weight, molecular weight distribution, type and content of the tackifying resin, type and content of the crosslinking agent, and the like of the acrylic polymer. In addition, the storage elastic modulus at 23 ° C. is measured in the shear mode of dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by Haiti Measurement & Control Co., Ltd., "ARES" manufactured by Rheometrics Corporation, etc.) , can be obtained by measuring from -40 °C to 140 °C under conditions of angular frequency of 1 Hz and speed of 5 °C/min.

The acrylic heat-sensitive adhesive layer is relatively stable against light, heat, moisture, and the like, and can be adhered to various adherends by heat compression. Since the acrylic thermal-sensitive adhesive layer does not exhibit adhesiveness at room temperature and develops adhesiveness when heated, since the adhesive layer is the acrylic thermal-sensitive adhesive layer, the edge of the metal-clad laminate and the adhesive tape are in contact with each other, After adjusting the position and the like so that wrinkles and lifting do not occur on the adhesive tape, it can be heat-compressed. By doing in this way, breakage of the edge of the metal-clad laminate can be further suppressed, and intrusion into the edge of the solution can be further suppressed even when exposed to a strong alkaline solution.

The peak temperature of the loss tangent (hereinafter also referred to as tanδ or simply loss tangent) of the acrylic thermosensitive adhesive layer measured at a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device is not particularly limited, but is preferably 40°C or higher. . When the peak temperature of the loss tangent is 40° C. or higher, the sliding property between the edge of the metal-clad laminate and the adhesive tape at room temperature is improved, and the adhesive tape is less prone to wrinkles during application. The peak temperature of the loss tangent is more preferably 42°C or higher, and more preferably 45°C or higher. The peak temperature of the loss tangent is preferably 100°C or less, more preferably 90°C or less, and still more preferably 80°C or less.

In addition, the loss tangent was measured using a viscoelastic spectrometer (DVA-200, manufactured by Haiti Measurement & Control Co., Ltd., or an equivalent thereof) under the condition of 5°C/min, 1 Hz in the low-speed heating shear deformation mode, -100°C. It can be obtained by measuring the dynamic viscoelasticity spectrum at -200°C.

The storage modulus of the acrylic heat-sensitive adhesive layer is not particularly limited, but a preferable lower limit of the storage modulus at 23°C is 5×10 ⁶ Pa, and a preferable upper limit of the storage modulus at 100°C is 2×10 ⁵ Pa.

If the storage elastic modulus at 23°C is 5×10 ⁶ Pa or more, the acrylic thermosensitive adhesive layer does not exhibit tackiness at room temperature, and the end portion of the metal-clad laminate and the adhesive tape are in contact with the adhesive tape. The position, etc. can be adjusted so that wrinkles and lifting do not occur. A more preferable lower limit of the storage elastic modulus at 23°C is 8×10 ⁶ Pa, and a still 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 of easily forming the adhesive tape into a roll shape, a preferable upper limit is 1×10 ¹⁰ Pa, and a 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 thermal-sensitive adhesive layer develops adhesiveness by heating, and the acrylic thermal-sensitive adhesive layer is heat-compressed to prevent breakage of the end portion of the metal-clad laminate. It is more suppressed, and penetration into the edge of the solution can be further suppressed even when exposed to a strong alkaline solution. A more preferable upper limit of the storage elastic modulus at 100°C is 1×10 ⁵ Pa, and a still 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 from the viewpoint of suppressing exudation due to deformation of the pressure-sensitive adhesive during heat compression, a preferable lower limit is 1×10 ⁴ Pa, and a more preferable lower limit is 5×10 ⁴ is Pa.

In addition, the storage elastic modulus at 23°C or 100°C can be adjusted according to the type, molecular weight, molecular weight distribution of the acrylic polymer, the type and content of the tackifying resin, the type and content of the crosslinking agent, and the like. In addition, the storage elastic modulus at 23 ° C. or 100 ° C. is determined by measuring dynamic viscoelasticity using a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by Haiti Measurement & Control Co., Ltd., "ARES" manufactured by Rheometrics Corporation, etc.) It can be obtained by measuring from -40 ° C to 140 ° C under the conditions of the shear mode, angular frequency of 1 Hz and speed of 5 ° C / min.

The acrylic polymer included in the acrylic thermal pressure-sensitive adhesive layer is not particularly limited, but preferably has a structural unit derived from a monomer having a crosslinkable functional group. By having such a structural unit, when a crosslinking agent is used in combination, the acrylic polymers contained in the acrylic heat-sensitive adhesive layer can be crosslinked. By adjusting the degree of crosslinking at that time, the storage elastic modulus of the acrylic thermosensitive adhesive layer can be adjusted.

As said crosslinkable functional group, a hydroxyl group, a carboxyl group, a glycidyl group, an amino group, an amide group, a nitrile group etc. are mentioned, for example. Especially, a hydroxyl group or a carboxyl group is preferable from the viewpoint of easy adjustment of the storage modulus of the acrylic heat-sensitive adhesive layer. As a monomer which has the said hydroxyl group, (meth)acrylic acid ester which has a hydroxyl group, such as 4-hydroxybutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate, is mentioned, for example. As a monomer which has the said carboxyl group, (meth)acrylic acid etc. are mentioned, for example. As a monomer which has the said glycidyl group, glycidyl (meth)acrylate etc. are mentioned, for example. As a monomer which has the said amide group, hydroxyethyl acrylamide, isopropyl acrylamide, dimethylaminopropyl acrylamide etc. are mentioned, for example. As a monomer which has the said nitrile group, acrylonitrile etc. are mentioned, for example. The monomers which have these crosslinkable functional groups may be used independently or may use 2 or more types together. The content of the structural unit derived from the monomer having the crosslinkable functional group is not particularly limited, but a preferable lower limit is 0.1% by weight and a preferable upper limit is 5% by weight. When using the monomer having the carboxyl group as the monomer having the crosslinkable functional group, a more preferable upper limit is 3% by weight, and a still more preferable upper limit is 0.5% by weight from the viewpoint of further suppressing penetration of the strong alkaline solution.

The acrylic polymer contained in the acrylic thermosensitive adhesive layer preferably has a structural unit derived from a (meth)acrylate having an alkyl group having 1 to 4 carbon atoms, and a methacrylate having an alkyl group having 1 to 4 carbon atoms. It is more preferable to have a structural unit derived from it. It is also preferable that the acrylic polymer contained in the acrylic heat-sensitive adhesive layer has a structural unit derived from a (meth)acrylate having an alkyl group having a cyclic structure. The peak temperature of the loss tangent and the storage elastic modulus can be easily adjusted within preferred ranges when the acrylic polymer contained in the acrylic thermosensitive adhesive layer has these structural units. The acrylic polymer included in the acrylic thermal-sensitive adhesive layer is composed of a structural unit derived from a methacrylate having an alkyl group having 1 or more and 4 or less carbon atoms, and a structural unit derived from a methacrylate having an alkyl group having a cyclic structure. It is more preferable to have at least one selected from the group.

The (meth)acrylate having an alkyl group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Acrylates etc. are mentioned.

The (meth)acrylate having an alkyl group having the above cyclic structure is not particularly limited, and examples thereof include cyclohexyl (meth)acrylate and isobornyl (meth)acrylate. These (meth)acrylates may be used independently or may use 2 or more types together. Among them, it is preferable to use methyl methacrylate, butyl acrylate, butyl methacrylate, or isobornyl methacrylate from the viewpoint that the peak temperature of the loss tangent and the storage modulus can be easily adjusted to a preferred range. .

The total content of structural units derived from (meth)acrylate having an alkyl group having 1 to 4 carbon atoms and (meth)acrylate having an alkyl group having a cyclic structure is not particularly limited. , the preferred lower limit is 50% by weight, and the preferred upper limit is 98% by weight. When the total content of the constituent units is within the above range, it is easy to adjust the peak temperature of the loss tangent and the storage elastic modulus to a preferred range. A more preferable lower limit of the total content of the constituent units is 60 wt%, a still more preferable lower limit is 70 wt%, a more preferable upper limit is 95 wt%, a still more preferable upper limit is 90 wt%, and an even more preferable upper limit is 80 wt%.

In addition, the said total content is the sum of the structural unit derived from the (meth)acrylate which has the said C1 or more and 4 or less alkyl group, and the structural unit derived from the (meth)acrylate which has the said alkyl group which has a cyclic structure. Although the content is shown, the acrylic polymer contained in the acrylic thermosensitive adhesive layer may contain either one or both.

In addition, the total content of the structural unit derived from the methacrylate having an alkyl group having 1 to 4 carbon atoms and the methacrylate having an alkyl group having the cyclic structure has a preferable lower limit of 50% by weight, A preferable upper limit is 90 wt%, a more preferable lower limit is 60 wt%, and a more preferable upper limit is 80 wt%.

The acrylic polymer contained in the acrylic heat-sensitive adhesive layer may further have structural units derived from other monomers within a range that does not impair the effects of the present invention. As the other monomers, for example, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate Acrylate, Decyl (meth)acrylate, Lauryl (meth)acrylate, Stearyl (meth)acrylate, Isostearyl (meth)acrylate, Benzyl (meth)acrylate, Phenoxyethyl (meth)acrylate , ethyl carbitol (meth)acrylate, vinyl acetate, fluorine-containing monomers, and the like. In addition, when the acrylic polymer contained in the acrylic thermosensitive adhesive layer is prepared by ultraviolet polymerization, further, a structural unit derived from a polyfunctional monomer such as divinylbenzene or trimethylolpropane tri(meth)acrylate it is desirable to have

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

The method for preparing the acrylic polymer contained in the acrylic heat-sensitive adhesive layer is not particularly limited, and as in the case of the acrylic polymer contained in the acrylic pressure-sensitive adhesive layer, for example, a monomer derived from the structural unit is polymerized A method of carrying out a radical reaction in the presence of an initiator, and the like are exemplified.

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

It is preferable that the said acrylic heat-sensitive adhesive layer contains hydrogenated rosin ester resin whose hydroxyl value is 40 mgKOH/g or more among the said tackifying resins. When the acrylic heat-sensitive adhesive layer contains a hydrogenated rosin ester resin having a hydroxyl value of 40 mgKOH/g or more, the interfacial adhesion between the edge of the metal-clad laminate and the adhesive tape is further improved, even when exposed to a strong alkaline solution. Penetration of the solution to the edge 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, and preferably 50 mgKOH/g or less.

The content of the tackifying resin is not particularly limited, but a preferable lower limit is 5 parts by weight, a preferable upper limit is 50 parts by weight, and a more preferable lower limit is 10 parts by weight, A more preferable upper limit is 35 parts by weight. When the content of the tackifying resin is within the above range, the adhesive strength of the acrylic pressure-sensitive adhesive layer included in the acrylic heat-sensitive adhesive layer is improved.

The acrylic heat-sensitive adhesive layer may contain a silane coupling agent. When the acrylic thermal adhesive layer contains a silane coupling agent, adhesion between the end portion of the metal-clad laminate and the acrylic thermal adhesive layer increases, so that breakage of the end portion of the metal-clad laminate can be further suppressed, and in a strong alkaline solution Even when exposed, penetration of the solution to the end portion can be further suppressed.

The silane coupling agent is not particularly limited, and the same silane coupling agent as the silane coupling agent used in the acrylic pressure-sensitive adhesive layer may be used. Content of the said silane coupling agent is not specifically limited, either, The same content as the content in the said acrylic pressure-sensitive adhesive layer is employable.

When the acrylic polymer contained in the acrylic thermal-sensitive adhesive layer contains a structural unit derived from the monomer having the cross-linkable functional group, the acrylic thermal-sensitive adhesive layer may contain a crosslinking agent. The crosslinking agent is not particularly limited, and the same crosslinking agent as the crosslinking agent used in the acrylic pressure-sensitive adhesive layer may be used. Content of the said crosslinking agent is not specifically limited, either, The same content as the content in the said acrylic pressure-sensitive adhesive layer can be employ|adopted.

Since the rubber-based polymer has relatively low polarity, when the base polymer is the rubber-based polymer, it is difficult for a strong alkaline solution to penetrate into the rubber-based pressure-sensitive adhesive layer. Accordingly, breakage of the end portion of the metal-clad laminate can be further suppressed, and penetration of the solution to the end portion can be further suppressed even when exposed to a strong alkaline solution. The rubber-based polymer is preferably 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, simply referred to as "block copolymer").

The aromatic vinyl monomer is not particularly limited, and examples thereof include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, and 2,4-diisopropyl. Styrene, 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-butyl styrene, 4-t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, diphenyl ethylene, tertiary amino group-containing diphenyl ethylene, 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 independently or may use 2 or more types together.

The conjugated diene monomer is not particularly limited, and examples thereof include isoprene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1, 3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene and the like. These conjugated diene monomers may be used independently or may use 2 or more types together.

The block copolymer is not particularly limited, and may be a block copolymer having rubber elasticity at room temperature and having a hard segment portion and a soft segment portion. Moreover, the block derived from the said aromatic vinyl monomer is a hard segment part, and the block derived from the said conjugated diene monomer is a soft segment part.

Specific examples of the block copolymer include styrene-isoprene-styrene (SIS) block copolymers, styrene-butadiene-styrene (SBS) block copolymers, and styrene-chloroprene-styrene block copolymers. . Moreover, a hydrogenated compound is also mentioned as said block copolymer, More specifically, for example, a styrene-ethylene-butylene-styrene (SEBS) block copolymer and a styrene-ethylene-propylene-styrene (SEPS) block copolymer , styrene-ethylene-ethylene-propylene-styrene (SEEPS), and the like. Moreover, as said block copolymer, a styrene-isobutylene-styrene (SIBS) block copolymer etc. are mentioned, for example. Especially, from a viewpoint of being easy to exhibit high adhesive force, SIS block copolymer and SBS block copolymer are preferable, and SIS block copolymer is more preferable. These block copolymers may be used independently or may use 2 or more types together.

In addition to the triblock copolymer of a block derived from the aromatic vinyl monomer and a block derived from the conjugated diene monomer, the block copolymer includes a block derived from the aromatic vinyl monomer and a block derived from the conjugated diene monomer. You may contain a block copolymer. 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, since the adhesion between the edge of the metal-clad laminate and the rubber-based pressure-sensitive adhesive layer increases, breakage of the edge of the metal-clad laminate can be further suppressed, even when exposed to a strong alkaline solution. Penetration of the solution to the end portion can be further suppressed. The upper limit of the diblock ratio is not particularly limited, but from the viewpoint of maintaining the cohesive force of the rubber-based pressure-sensitive adhesive layer, the upper limit is preferably 90% by weight. In addition, the diblock ratio is computable 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 (when the aromatic vinyl monomer is styrene, it is also referred to as "styrene content") is not particularly limited, but a preferable upper limit is 20% by weight, a more preferable 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 of the end portion of the metal-clad laminate increases, so that breakage of the end portion of the metal-clad laminate can be further suppressed. and even when exposed to a strong alkaline solution, penetration into the end of the solution can be further suppressed. The lower limit of the content of the block derived from the aromatic vinyl monomer is not particularly limited, but from the viewpoint of maintaining the cohesive force of the rubber-based pressure-sensitive adhesive layer, the lower limit is preferably 8% by weight.

In addition, content of the block derived from an aromatic vinyl monomer is computable 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 a preferable lower limit is 50,000 and a preferable 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, compatibility between the block copolymer and other components can be prevented from being excessively lowered. A more preferable lower limit of the weight average molecular weight is 100,000, and a 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 a tackifying resin, the adhesive strength of the rubber-based pressure-sensitive adhesive layer is improved. Especially, when the said rubber-type adhesive layer contains the said terpene phenol resin (T1), it becomes more difficult for a strong alkaline solution to penetrate into the inside of the said rubber-type 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) falls within an appropriate range, making it more difficult for a strong alkaline solution to penetrate into the rubber-based pressure-sensitive adhesive layer. A preferable lower limit of the hydroxyl value of the terpene phenol resin (T1) is 40 mgKOH/g, a preferable upper limit is 100 mgKOH/g, a more preferable lower limit is 50 mgKOH/g, and a more preferable upper limit is 80 mgKOH/g.

In addition, the hydroxyl value of the tackifying resin is the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when acetylating 1 g of the tackifying resin, based on the potentiometric titration method specified in JIS K 0070: 1992 is defined as the measured value.

The softening point of the terpene phenol resin (T1) is not particularly limited, but a 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 is increased and the solubility in the strong alkaline solution is lowered, so that the strong alkaline solution is more difficult to penetrate into the rubber-based pressure-sensitive adhesive layer. . Moreover, if the softening point of the said terpene phenol resin (T1) is 150 degreeC or more, the heat resistance of the said rubber-type adhesive layer will become higher. A more preferable lower limit of the softening point of the terpene phenol resin (T1) is 160°C. Although the upper limit of the softening point of the said terpene phenol resin (T1) is not specifically limited, The practical upper limit is about 180 degreeC.

In addition, the softening point of the tackifying resin is the temperature at which the solid resin begins to soften and deform, and is defined as a value measured based on the softening point test method (ring and ball method) specified in JIS K 5902 and JIS K 2207.

The content of the terpene phenol resin (T1) is not particularly limited, but a preferable lower limit is 3 parts by weight and a 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, it becomes more difficult for the strong alkaline solution to penetrate into the inside of 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 of the end portion of the metal-clad laminate increases, so that breakage of the end portion of the metal-clad laminate can be further suppressed. and even when exposed to a strong alkaline solution, penetration into the end of the solution can be further suppressed. A more preferable lower limit of the content of the terpene phenol resin (T1) is 10 parts by weight, and a more preferable upper limit is 60 parts by weight.

The rubber-based pressure-sensitive adhesive layer may contain a tackifying 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 5 parts by weight based on 100 parts by weight of the rubber-based polymer It is preferable that it is below. When the total content of the terpene phenol resin (T2) and the rosin ester resin (T3) is 5 parts by weight or less, penetration of the strong alkaline solution into the rubber-based pressure-sensitive adhesive layer becomes more difficult. 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, a strong alkaline solution penetrates into the rubber-based pressure-sensitive adhesive layer. it becomes easier to do In addition, since the rosin ester resin (T3) has a functional group such as an ester group, a hydroxyl group, or a carboxyl group, even if the content of the rosin ester resin (T3) is too large, a strong alkaline solution easily penetrates into the inside of the rubber-based pressure-sensitive adhesive layer. lose The total amount of the terpene phenol resin (T2) and the rosin ester resin (T3) is preferably 2 parts by weight or less, more preferably 0 part by weight.

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

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably thicker than 1/2 of 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 span from the front surface to the back surface of the metal clad laminate, it is difficult to form a gap between the end portion of the metal clad laminate and the pressure-sensitive adhesive layer, Peeling does not occur easily. Accordingly, breakage of the end portion of the metal-clad laminate can be further suppressed, and penetration of the solution into the end portion can be further suppressed even when exposed to a strong alkaline solution. 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 and a preferable upper limit of 100 μm, and 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 adhesive layer, it is preferable that the pressure-sensitive adhesive tape further has a pressure-sensitive adhesive layer between the substrate and the acrylic heat-sensitive pressure-sensitive adhesive layer. That is, it is preferable that the adhesive tape has the base material, the pressure-sensitive adhesive layer, and the acrylic heat-sensitive adhesive layer in this order. Since the adhesive tape has the pressure-sensitive adhesive layer between the base material and the acrylic heat-sensitive adhesive layer, anchorage between the base material and the acrylic heat-sensitive adhesive layer is increased, even when exposed to a strong alkaline solution. Peeling between the base material and the acrylic heat-sensitive adhesive layer becomes more difficult to occur. Accordingly, breakage of the end portion of the metal-clad laminate can be further suppressed, and penetration of the solution to the end portion can be further suppressed even when exposed to a strong alkaline solution.

As said pressure-sensitive adhesive layer, although the acrylic pressure-sensitive adhesive layer mentioned above can be used, for example, it is not limited to this.

When the pressure-sensitive adhesive tape has the pressure-sensitive adhesive layer between the substrate and the acrylic heat-sensitive adhesive layer, the thickness of the pressure-sensitive adhesive layer is not particularly limited, but preferably has a lower limit of 0.1 μm and a preferable upper limit of 30 μm. When the thickness of the pressure-sensitive adhesive layer is within the above range, anchorage between the base material and the acrylic heat-sensitive adhesive layer is further improved. A more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 5 μm, and a more preferable upper limit is 20 μm.

It is preferable that the said adhesive tape further has a resin layer between the said base material and the said adhesive layer, and it is preferable that the said resin layer contains resin which has a polar functional group. Since the anchoring property between the base material and the pressure-sensitive adhesive layer increases when the pressure-sensitive adhesive tape has the resin layer, it is difficult for a strong alkaline solution to penetrate into the pressure-sensitive adhesive layer. Accordingly, breakage of the end portion of the metal-clad laminate can be further suppressed, and penetration of the solution to the end portion can be further suppressed even when exposed to a strong alkaline solution.

The polar functional group is not particularly limited, but is preferably at least one selected from the group consisting of a nitrile group, a carbonyl group, a carboxyl group, and an amino group in view of excellent adhesion to the metal substrate and the resin substrate. Especially, a nitrile group and a carbonyl group are more preferable.

As the resin having the polar functional group, specifically, for example, acrylonitrile butadiene rubber (NBR), maleic anhydride-modified styrene-ethylene-butylene-styrene (maleic anhydride-modified SEBS), amine-modified styrene-ethylene- butylene-styrene (amine-modified SEBS); and the like. Among them, NBR and maleic anhydride-modified SEBS are preferable in terms of excellent adhesion to the resin substrate and also excellent 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. If the thickness of the said resin layer is within the said range, the anchor property between the said base material and the said adhesive layer will improve more. A more preferable lower limit of the thickness of the resin layer is 0.5 μm, and a more preferable upper limit is 2 μm.

The said resin layer may contain additives, such as a plasticizer, an emulsifier, a softener, a filler, a pigment, dye, etc., other resin, etc. as needed.

1 to 8 are cross-sectional views schematically showing an example of a region covered with a protective material in the metal-clad laminate having edge protection according to the present invention.

In the metal-clad laminate 1 with edge protection shown in FIGS. 1-4, the adhesive tape 30 which has the base material 31 and the adhesive layer 32 as a protective material is used. That is, the end of the metal-clad laminate 2 is covered with one adhesive tape 30 per side. 1-4, the adhesive tape 30 is folded back (folded) and attached to the edge part of the metal-clad laminate 2 so that it may span from the front surface of the metal-clad laminate 2 to the back surface. In addition, in FIG. 4, the whole back surface of the metal-clad laminated board 2 is covered with the adhesive tape 30. As shown in FIG.

In the metal-clad laminate 1 with edge protection shown in FIGS. 5-7, the adhesive tape 30 which has the base material 31 and the adhesive layer 32 as a protective material, the base material 31', and the adhesive layer 32' ) is used. That is, the edge of the metal-clad laminate 2 is covered with two adhesive tapes 30 and 30' per side. 5-7, adhesive tapes 30 and 30' are affixed to the edge part of the metal-clad laminate 2 so that it may extend from the front surface of the metal-clad laminate 2 to the back surface.

In the metal-clad laminate 1 with edge protection shown in FIG. 8, the adhesive tape 30 which has the base material 31 and the adhesive layer 32 as a protective material, the base material 31', and the adhesive layer 32' The adhesive tape 30'' which has it, and the adhesive tape 30'' which has the base material 31'' and the adhesive layer 32'' are used. That is, the end 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.

2 to 8, 3a indicates the interface between the pressure-sensitive adhesive layers, and by not generating a gap at the interface 3a as much as possible, breakage of the end portion of the metal-clad laminate 2 can be further suppressed. And, even when exposed to a strong alkaline solution, penetration of the solution to the end portion can be further suppressed.

Although the use of the edge-protected metal-clad laminate of this invention is not specifically limited, It can be used especially suitably when manufacturing a printed wiring board. As a method for manufacturing a printed wiring board using a metal-clad laminate, a method for manufacturing a printed wiring board having a protective step of covering an end portion of the metal-clad laminate with a protective material and obtaining the end-protected metal-clad laminate of the present invention is also provided. one of the inventions.

In the protection step, the method of covering the edge of the metal-clad laminate with a protective material to obtain the metal-clad laminate with edge protection of the present invention is not particularly limited. For example, in the case of using the above-described adhesive tape as the protective material, a method of sticking the adhesive tape to the end of the metal-clad laminate using a tape laminator, a method of attaching the adhesive tape to the metal-clad using a press machine A method of pressure-bonding to an end portion of a laminated sheet, a method of bonding the above-mentioned adhesive tape to the above-mentioned metal-clad laminated sheet by hand, and the like are exemplified. In addition, in these methods, when the adhesive tape is affixed to the four corners of the metal-clad laminate, the adhesive tape may be applied overlapping or not overlapping.

In the manufacturing method of the printed wiring board of the present invention, after the protection step, a metal plating treatment is further performed on the end-protected metal clad laminate of the present invention, and metal is deposited on the surface of the metal clad laminate and the protective material. A metal plating step may be performed. In the above metal plating step, the method of metal plating treatment is not particularly limited, and a conventionally known method such as electroless plating employed when manufacturing a printed wiring board can be used. In the said metal plating process, the breakage of the edge part of the said metal clad laminated board can be suppressed by using the metal clad laminated board with edge protection of this invention. Moreover, when the above-mentioned adhesive tape is used as the said reliance material, and the said base material is the said metal base material, while the metal precipitates favorably, the metal plating layer which does not peel easily can be formed. Even when the base material is the resin base material, as long as the surface roughness Ra of the resin base material is within the above range, a metal plating layer that does not peel easily can be formed while metal precipitates satisfactorily.

In the manufacturing method of the printed wiring board of this invention, after the said protection process, you may further implement the circuit formation process of giving an etching process or a desmear process with respect to the metal clad laminated board with edge protection of this invention. In the above circuit formation step, the method of etching treatment or desmear treatment is not particularly limited, and a conventionally known method employed when manufacturing a printed wiring board can be used. In the circuit formation process, by using the end-protected metal-clad laminate of the present invention, breakage of the end portion of the metal-clad laminate can be suppressed, and even when exposed to a strong alkaline solution, penetration into the end portion of the solution is prevented. can be suppressed

As long as the metal plating process and the circuit formation process are performed after the protection process, either one may be performed first. Further, the metal plating step and the circuit formation step may be repeatedly performed as long as they are performed after the protection step.

In the manufacturing method of the printed wiring board of this invention, you may further implement the trimming process of isolate|separating the area|region covered with the protective material in the edge-protected metal-clad laminate of this invention. In this way, the area covered with the protective material is separated, and a printed wiring board after circuit formation can be obtained. In the trimming step, the method of separating the region covered with the protective material in the end-protected metal-clad laminate of the present invention is not particularly limited, and examples thereof include a method of cutting with a slitter.

As a method for producing an intermediate used for a printed wiring board, a method for producing an intermediate for a printed wiring board having a protective step of covering an edge of a metal-clad laminate with a protective material and obtaining the edge-protected metal-clad laminate of the present invention is also one of the inventions.

According to the present invention, breakage of the ends of the metal-clad laminate can be suppressed, and even when exposed to a strong alkaline solution, penetration of the solution into the ends can be suppressed. It is possible to provide an end-protected metal-clad laminate. Moreover, according to this invention, the manufacturing method of a printed wiring board and the manufacturing method of the intermediate body for printed wiring boards can be provided.

1 is a cross-sectional view schematically showing an example of a region covered with a protective material in a metal-clad laminate having edge protection according to the present invention.
Fig. 2 is a cross-sectional view schematically showing an example of a region covered with a protective material in a metal-clad laminate having edge protection according to the present invention.
Fig. 3 is a cross-sectional view schematically showing an example of a region covered with a protective material in a metal-clad laminate having edge protection according to the present invention.
Fig. 4 is a cross-sectional view schematically showing an example of a region covered with a protective material in a metal-clad laminate having edge protection according to the present invention.
Fig. 5 is a cross-sectional view schematically showing an example of a region covered with a protective material in the end-protected metal-clad laminate of the present invention.
Fig. 6 is a cross-sectional view schematically showing an example of a region covered with a protective material in the end-protected metal-clad laminate of the present invention.
Fig. 7 is a cross-sectional view schematically showing an example of a region covered with a protective material in a metal-clad laminate having edge protection according to the present invention.
Fig. 8 is a cross-sectional view schematically showing an example of a region covered with a protective material in the end-protected metal-clad laminate of the present invention.

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

(Preparation of acrylic polymer 1)

After adding ethyl acetate as a polymerization solvent into the reaction vessel and bubbling with nitrogen, the reaction vessel was heated to initiate reflux while introducing nitrogen. Subsequently, as a polymerization initiator, a polymerization initiator solution obtained by diluting 0.3 parts by weight of azobisisobutyronitrile 10 times with ethyl acetate was introduced into the reaction vessel, and 47 parts by weight of butyl acrylate, 50 parts by weight of 2-ethylhexyl acrylate, and acrylic acid were added. 2.8 parts by weight and 0.2 parts by weight of 2-hydroxyethyl acrylate were added dropwise over 2 hours. After completion of the dropwise addition, a polymerization initiator solution obtained by diluting 0.3 parts by weight of azobisisobutyronitrile 10 times with ethyl acetate as a polymerization initiator was put into the reaction container again, and a polymerization reaction was carried out for 4 hours to obtain a solution containing acrylic polymer 1.

About the obtained acrylic polymer 1, it was 450,000 when the weight average molecular weight (Mw) by polystyrene conversion was calculated|required by the gel permeation chromatography method using GPC LF-804 (made by Showa Denko) as a column.

(Preparation of acrylic polymer 2)

33 parts by weight of butyl acrylate, 32 parts by weight of butyl methacrylate, 32 parts by weight of methyl methacrylate, acrylic polymer 1 and In the same way, a solution containing acrylic polymer 2 was obtained.

About the obtained acrylic polymer 2, it was 330,000 when the weight average molecular weight (Mw) by polystyrene conversion was calculated|required by the gel permeation chromatography method using GPC LF-804 (made by Showa Denko) as a column.

(Preparation of acrylic polymer 3)

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 isobornyl acrylate, 2.8 parts by weight of acrylic acid and 0.2 part by weight of 2-hydroxyethyl acrylate. In the same manner as above, a solution containing acrylic polymer 3 was obtained.

About the obtained acrylic polymer 3, it was 350,000 when the weight average molecular weight (Mw) by polystyrene conversion was calculated|required by the gel permeation chromatography method using GPC LF-804 (made by Showa Denko) as a column.

(Preparation of rubber-based polymer)

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

(Preparation of adhesive A)

To the obtained acrylic polymer 1-containing solution, 15 parts by weight of polymerized rosin ester resin (Pensel D160, hydroxyl value 42 mgKOH/g, manufactured by Arakawa Chemical Industry Co., Ltd.) was added to 100 parts by weight of acrylic polymer 1. Furthermore, 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 crosslinking agent (Colonate L, manufactured by Tosoh Corporation) were added to prepare a solution of adhesive A. .

(Preparation of adhesive B)

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

(Preparation of adhesive C)

A rubber-based polymer and 10 parts by weight of a terpene phenol resin (YS Polystar T160, manufactured by Yasuhara Chemical Co., Ltd., hydroxyl value 60 mgKOH/g, softening point 160 ° C.) based on 100 parts by weight of the rubber-based polymer were mixed in a solvent (toluene) at a solution concentration of 30 weight % and stirred to prepare a solution of the adhesive C.

(Preparation of adhesive D)

A solution of adhesive D was prepared in the same manner as in adhesive C except that 10 parts by weight of polyterpene (YS Resin PX-1250, hydroxyl value: 0 mgKOH/g, softening point: 125°C) was used as the tackifying resin. .

(adjustment of adhesive E)

As the tackifying resin, 15 parts by weight of a polymerized rosin ester resin (manufactured by Arakawa Chemical Industries, Ltd., Pencil D160, hydroxyl value 42 mgKOH/g) and a terpene phenol resin (manufactured by Yasuhara Chemical, YS Polystar G150, hydroxyl value 130 mgKOH/g, 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 (softening point: 150°C) was used.

(adjustment of adhesive F)

A solution of adhesive F was prepared in the same manner as in adhesive C except that 10 parts by weight of 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 tackifying resin. prepared.

(adjustment of adhesive G)

A solution of adhesive G was prepared in the same manner as in adhesive C, except that 10 parts by weight of terpene phenol resin (Yasuhara Chemical Co., Ltd., YS Polystar G-125, hydroxyl value 130 mgKOH/g, softening point 125 ° C.) was used as the tackifying resin. prepared.

(Adjustment of thermal adhesive H)

To the obtained acrylic polymer 2-containing solution, 25 parts by weight of a hydrogenated rosin ester resin (Fine Crystal KE-359, hydroxyl value 42 mgKOH/g, manufactured by Arakawa Chemical Industry Co., Ltd.) as a tackifying resin based on 100 parts by weight of acrylic polymer 2 was added. 0.2 parts by weight (solid component ratio) of an epoxy-based crosslinking agent (Tetrad C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to prepare a solution of the thermosensitive adhesive H.

(Adjustment of Thermal Adhesive I)

A solution of the thermal adhesive I was prepared in the same manner as in the thermal adhesive H, except that the solution containing the acrylic polymer 2 was changed to the solution containing the acrylic polymer 3.

(Adjustment of thermal adhesive J)

A solution of thermal adhesive J was prepared in the same manner as in thermal adhesive H, except that the tackifying resin was changed to hydrogenated rosin ester resin (manufactured by Arakawa Chemical Industry, ester gum H, hydroxyl value: 29 mgKOH/g).

(Examples 1 to 13)

(1) Manufacture of pressure-sensitive adhesive tape

The obtained adhesive solution was coated onto a PET film having a thickness of 75 μm subjected to release treatment so that the thickness of the adhesive layer 1 after drying became the thickness shown in Table 2, and then dried at 110° C. for 5 minutes to form an adhesive layer 1. This pressure-sensitive adhesive layer 1 was electrodeposited on the base material shown in Table 2, cured at 40°C for 48 hours, and a pressure-sensitive adhesive tape was obtained.

Further, a measurement sample consisting of only the pressure-sensitive adhesive layer 1 having a size of 10 mm x 6 mm and a thickness of 1 mm was prepared in the same manner. With respect to the obtained measurement sample, using a dynamic viscoelasticity measuring device (DVA-200 manufactured by Haiti Measurement & Control Co., Ltd.), the shear mode of dynamic viscoelasticity measurement, an angular frequency of 1 Hz, and a speed of 5 °C/min were carried out at -40 °C to 140 °C. The dynamic viscoelasticity was measured up to °C, and the storage modulus at 23 °C was measured. Table 1 shows the measurement results.

(2) Manufacture of end-protected copper-clad laminates

The obtained pressure-sensitive adhesive tape was cut into 7 mm × 80 mm, and the pressure-sensitive adhesive tape was formed into a copper clad laminate (CCL) (manufactured by Panasonic, R1515E, resin layer thickness 40 μm, copper foil thickness 2 μm) so as to have the coating form shown in Table 2. It was attached by hand to the edge of the edge to obtain a copper-clad laminate with edge protection.

More specifically, in Examples 1, 3 to 7, and 9 to 13, pressure-sensitive adhesive tapes were affixed so as to have the covering form shown in FIG. 1 . First, a pressure-sensitive adhesive tape is placed 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 is at a position of 3.5 mm from the end of the copper-clad laminate, and a pressure-sensitive adhesive tape is applied at 300 mm/min using a 2 kg roller. squeezed at speed. After that, while pressing the base material surface of the unattached pressure-sensitive adhesive tape with a stainless steel plate, the pressure-sensitive adhesive tape is bent toward the other surface of the copper-clad laminate so as not to form a gap, and attached to the other surface of the copper-clad laminate and compressed at a speed of 300 mm/min using a 2 kg roller. The same operation was also performed on the side opposite to the side to which the pressure-sensitive adhesive tape was attached of the copper-clad laminate, the pressure-sensitive adhesive tape was affixed to obtain a copper-clad laminate with edge protection.

In Example 2, a pressure-sensitive adhesive tape was affixed so as to have the covering form shown in FIG. 6 . First, a pressure-sensitive adhesive tape is placed 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 is at a position of 3.5 mm from the end of the copper-clad laminate, and a pressure-sensitive adhesive tape is applied at 300 mm/min using a 2 kg roller. squeezed at speed. Thereafter, another pressure-sensitive adhesive tape was similarly applied 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 also performed on the side opposite to the side to which the pressure-sensitive adhesive tape was attached of the copper-clad laminate, the pressure-sensitive adhesive tape was affixed to obtain a copper-clad laminate with edge protection.

In Example 8, a pressure-sensitive adhesive tape was affixed so as to have the covering form shown in FIG. 2 . First, the pressure-sensitive adhesive tape is placed 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 is at a position of 3.3 mm from the end of the copper-clad laminate, and a pressure-sensitive adhesive tape is applied at 300 mm/min using a 2 kg roller. squeezed at speed. After that, while pressing the substrate side of the unattached pressure-sensitive adhesive tape with a stainless steel plate, the pressure-sensitive adhesive tape is folded and bent toward the other surface of the copper-clad laminate, and the copper-clad laminate is applied to the other surface of the copper-clad laminate. It was attached to the position of 3.3 mm from the end and crimped at a speed of 300 mm/min using a 2 kg roller. The same operation was also performed on the side opposite to the side to which the pressure-sensitive adhesive tape was attached of the copper-clad laminate, the pressure-sensitive adhesive tape was affixed to obtain a copper-clad laminate with edge protection.

(Example 14)

(1) Manufacture of thermal adhesive tape

The obtained adhesive solution was coated onto a PET film having a thickness of 75 μm subjected to release treatment so that the thickness of the adhesive layer 1 after drying became the thickness shown in Table 2, and then dried at 110° C. for 5 minutes to form an adhesive layer 1. This pressure-sensitive adhesive layer 1 was electrodeposited on the base material shown in Table 2 under conditions of 100°C, cured at 40°C for 48 hours, and a heat-sensitive adhesive tape was obtained.

Further, a measurement sample consisting of only the pressure-sensitive adhesive layer 1 having a size of 10 mm x 6 mm and a thickness of 1 mm was prepared in the same manner. With respect to the obtained measurement sample, using a dynamic viscoelasticity measuring device (DVA-200 manufactured by Haiti Measurement & Control Co., Ltd.), the shear mode of dynamic viscoelasticity measurement, an angular frequency of 1 Hz, and a speed of 5 °C/min were carried out at -40 °C to 140 °C. The dynamic viscoelasticity was measured up to °C, and the storage modulus at 23 °C and 100 °C was measured. Further, using a viscoelasticity measuring device (DVA-200, manufactured by Haiti Measurement & Control Co., Ltd.), a dynamic viscoelasticity spectrum of -100°C to 200°C was measured under conditions of 5°C/min and 1 Hz in a low-speed heating shear deformation mode. The peak temperature of the loss tangent was measured. Table 1 shows the measurement results.

(2) Manufacture of end-protected copper-clad laminates

In the same manner as in Examples 1 to 13, copper clad laminates with edge protection were obtained. However, instead of crimping of the pressure-sensitive adhesive tape with a 2-kg roller, the heat-sensitive adhesive tape was affixed by thermal compression bonding at a pressure of 0.3 MPa for 30 seconds under conditions of 100°C.

(Examples 15 to 19)

(1) Manufacture of thermal adhesive tape

After coating the obtained pressure-sensitive adhesive solution for forming the pressure-sensitive adhesive layer 1 onto a PET film subjected to release treatment with a thickness of 75 μm so that the thickness of the pressure-sensitive adhesive layer 1 after drying becomes the thickness shown in Table 2, it was dried at 110 ° C. for 5 minutes, and the pressure-sensitive adhesive layer 1 (pressure-sensitive adhesive layer) was formed. This pressure-sensitive adhesive layer 1 was electrodeposited to the base material shown in Table 2, and the PET film subjected to the release treatment was peeled off. After that, the pressure-sensitive adhesive solution for forming the pressure-sensitive adhesive layer 2 was coated on a PET film having a thickness of 75 μm subjected to release treatment so that the thickness of the pressure-sensitive adhesive layer 2 after drying became the thickness shown in Table 2, and then dried at 110° C. for 5 minutes An adhesive layer 2 (thermal-sensitive adhesive layer) was formed. This pressure-sensitive adhesive layer 2 was electrodeposited on the pressure-sensitive adhesive layer 1 under conditions of 100 ° C., cured at 40 ° C. for 48 hours, and the base material, pressure-sensitive adhesive layer 1 (pressure-sensitive adhesive layer), pressure-sensitive adhesive layer 2 (thermal-sensitive adhesive layer), and release treatment were performed. A heat-sensitive adhesive tape in which PET films were laminated in this order was obtained.

Further, a measurement sample consisting of only the pressure-sensitive adhesive layer 2 having a size of 10 mm x 6 mm and a thickness of 1 mm was prepared in the same manner. With respect to the obtained measurement sample, using a dynamic viscoelasticity measuring device (DVA-200 manufactured by Haiti Measurement & Control Co., Ltd.), the shear mode of dynamic viscoelasticity measurement, an angular frequency of 1 Hz, and a speed of 5 °C/min were carried out at -40 °C to 140 °C. The dynamic viscoelasticity was measured up to °C, and the storage modulus at 23 °C and 100 °C was measured. Further, by using a viscoelasticity measuring device (DVA-200, manufactured by Haiti Measurement & Control Co., Ltd.), a dynamic viscoelasticity spectrum of -100 ° C to 200 ° C. was measured under the conditions of 5 ° C. / min, 1 Hz in the low-speed heating shear deformation mode The peak temperature of the loss tangent was measured. Table 1 shows the measurement results.

(2) Manufacture of end-protected copper-clad laminates

In the same manner as in Examples 1 to 13, copper clad laminates with edge protection were obtained. However, instead of crimping of the pressure-sensitive adhesive tape with a 2-kg roller, the heat-sensitive adhesive tape was affixed by thermal compression bonding at a pressure of 0.3 MPa for 30 seconds under conditions of 100°C.

＜Evaluation＞

The following evaluation was performed about the edge-protected copper clad laminated board obtained in the Example. The results are shown in Table 2.

(1) Evaluation of the number of wrinkles of adhesive tape

The attached adhesive tape was visually confirmed, and the number of wrinkle occurrence points was counted. A case with no wrinkles was rated as ◎, a case with one wrinkle was marked as ○, a case with two or three wrinkles was marked as △, and a case with four or more wrinkles was marked as ×.

(2) Electroless plating process

Electroless plating was performed on the edge-protected copper-clad laminate under the conditions shown in Table 3. The appearance of the edge-protected copper-clad laminate was observed at a magnification of 50 times using a microscope (VHX-5000, manufactured by Keyence Corporation), and the presence or absence of plating precipitation was confirmed. The case where plating was deposited favorably was made into (circle).

Moreover, the presence or absence of plating peeling was confirmed by carrying out the test of attaching and removing a commercially available cellophane tape to the plating part precipitated on the base material surface of the adhesive tape. The case where the plating was not transferred to the cellophane tape was marked as ○, and the case where the plating partially transferred was marked as △.

(3) Desmear process

After performing a desmear treatment on the edge-protected copper-clad laminate under the conditions shown in Table 4, the desmear treatment liquid was removed from the edge-protected copper-clad laminate and left to stand at room temperature for 30 minutes. After being allowed to stand at room temperature for 30 minutes, the appearance of the adhesive tape was observed at a magnification of 20 times using a microscope (VHX-5000, manufactured by Keyence Corporation), and the presence or absence of peeling of the adhesive tape was confirmed. The case where peeling was not seen was made into (circle).

After that, the adhesive tape was peeled off from the copper clad laminate, discoloration of copper in the portion of the copper clad laminate to which the adhesive tape had been affixed was confirmed, and protection (absence or absence of wetting) was evaluated. The case where no discoloration of copper was observed was rated as ◎, the case where discoloration of copper was observed at 2 mm or less from the end of the portion where the adhesive tape was attached was rated as ○, and the case where discoloration of copper was observed more than that was rated as ×.

(4) End protection of copper clad laminate

After carrying out the said desmear process and the said electroless plating process in this order with respect to the edge-protected copper clad laminated board, the adhesive tape was peeled from the copper clad laminated board. The end of the copper-clad laminate was observed at a magnification of 50 times using a microscope (VHX-5000, manufactured by Keyence Corporation), and the case where there was no defect was designated as ○, and the case where defect occurred was designated as ×. In addition, a copper-clad laminate not covered with a protective material was used as a comparison object (Comparative Example 1).

According to the present invention, breakage of the ends of the metal-clad laminate can be suppressed, and even when exposed to a strong alkaline solution, penetration of the solution into the ends can be suppressed. It is possible to provide an end-protected metal-clad laminate. Moreover, according to this invention, the manufacturing method of a printed wiring board and the manufacturing method of the intermediate body for printed wiring boards can be provided.

1: end-protected metal-clad laminate
2: metal clad laminate
30, 30', 30'' : adhesive tape
31, 31', 31'': description
32, 32', 32'': adhesive layer
3a: Interface between pressure-sensitive adhesive layers

Claims (23)

An end-protected metal-clad laminate, characterized in that ends of the metal-clad laminate are covered with a protective material. According to claim 1,
The protection material is an adhesive tape having a base material and an adhesive layer laminated on one side of the base material, and the base material is a metal base material. According to claim 2,
An end-protected metal-clad laminate, characterized in that the metal substrate is exposed on the outermost surface. According to claim 1,
The protective material is an adhesive tape having a base material and an adhesive layer laminated on one side of the base material, and the base material is a resin base material. According to claim 4,
The end-protected metal-clad laminate, characterized in that the resin substrate has a surface roughness Ra of 10 nm or more and 500 nm or less. The method of claim 1, 2, 3, 4 or 5,
An end portion of the metal-clad laminate is covered with two or more of the protective materials per side. The method of claim 1, 2, 3, 4 or 5,
An end portion of the metal-clad laminate is covered with one protective material per side. The method of claim 1, 2, 3, 4, 5, 6 or 7,
An edge 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. The method of claim 1, 2, 3, 4, 5, 6, 7 or 8,
Further, the end-protected metal-clad laminate is characterized in that the whole of at least one surface selected from the group consisting of the front and back surfaces of the metal-clad laminate is covered with the protective material. The method of claim 1, 2, 3, 4, 5, 6, 7, 8 or 9,
The end-protected metal-clad laminate, characterized in that the metal-clad laminate has a thickness of 100 μm or less. The method of claim 2, 3, 4 or 5,
The end-protected metal-clad laminate, characterized in that the thickness of the pressure-sensitive adhesive layer of the adhesive tape is thicker than 1/2 of the thickness of the metal-clad laminate. The method of claim 2, 3, 4, 5 or 11,
The adhesive layer of the adhesive tape is an acrylic pressure-sensitive adhesive layer, and the acrylic pressure-sensitive adhesive layer has a storage elastic modulus at 23°C of 2 × 10 ⁵ Pa or less. The method of claim 2, 3, 4, 5 or 11,
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape is a rubber-based pressure-sensitive adhesive layer, and includes a rubber-based polymer and a terpene phenol resin having a hydroxyl value of 20 mgKOH / g or more and 140 mgKOH / g or less. End-protected metal-clad laminate. The method of claim 2, 3, 4, 5 or 11,
The end-protected metal-clad laminate, characterized in that the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape is an acrylic heat-sensitive adhesive layer. 15. The method of claim 14,
The end-protected metal-clad laminate, characterized in that the acrylic heat-sensitive adhesive layer has a peak temperature of a loss tangent measured at a measurement frequency of 1 Hz using a dynamic viscoelasticity measuring device of 40 ° C. or higher. The method of claim 14 or 15,
The acrylic heat-sensitive adhesive layer has a storage modulus at 23°C of 5×10 ⁶ Pa or more and a storage modulus at 100° C. of 2×10 ⁵ Pa or less. The method of claim 14, 15 or 16,
The end-protected metal-clad laminate, characterized in that the adhesive tape further has a pressure-sensitive adhesive layer between the substrate and the acrylic heat-sensitive adhesive layer. The method of claim 2, 3, 4, 5, 11, 12, 13, 14, 15, 16 or 17,
The end-protected metal-clad laminate, characterized in that the adhesive tape further has a metal plating layer on the surface of the base material. A method for manufacturing a printed wiring board using a metal clad laminate, comprising:
An edge of the metal clad laminate is covered with a protective material, and claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, A print characterized by having a protection step for obtaining the end-protected metal clad laminate according to claim 11, claim 12, claim 13, claim 14, claim 15, claim 16, claim 17 or claim 18 A method for manufacturing a wiring board. According to claim 19,
Further, the manufacturing method of the printed wiring board characterized by including a metal plating step of performing a metal plating treatment on the end-protected metal clad laminate and depositing a metal on the surface of the metal clad laminate and the protective material. According to claim 19 or 20,
Further, the manufacturing method of the printed wiring board characterized by having a circuit formation step of subjecting the metal-clad laminate having edge protection to an etching treatment or a desmear treatment. According to claim 19, 20 or 21,
Further, the method for manufacturing a printed wiring board characterized by including a trimming step of separating a region covered with the protective material in the metal-clad laminate having edge protection. As a method for producing an intermediate used for a printed wiring board,
An edge of the metal clad laminate is covered with a protective material, and claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, A print characterized by having a protection step for obtaining the end-protected metal clad laminate according to claim 11, claim 12, claim 13, claim 14, claim 15, claim 16, claim 17 or claim 18 A method for producing an intermediate for a wiring board.

Images