WO2016208730A1 - 片面金属張積層板の製造方法および製造装置 - Google Patents
片面金属張積層板の製造方法および製造装置 Download PDFInfo
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- WO2016208730A1 WO2016208730A1 PCT/JP2016/068861 JP2016068861W WO2016208730A1 WO 2016208730 A1 WO2016208730 A1 WO 2016208730A1 JP 2016068861 W JP2016068861 W JP 2016068861W WO 2016208730 A1 WO2016208730 A1 WO 2016208730A1
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- WO
- WIPO (PCT)
- Prior art keywords
- clad laminate
- sided metal
- protective material
- peeling
- metal
- Prior art date
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- B29C65/40—Applying molten plastics, e.g. hot melt
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- H—ELECTRICITY
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Definitions
- the present invention relates to a method for producing a single-sided metal-clad laminate suitably used for a flexible printed circuit board (hereinafter also referred to as FPC). More specifically, the present invention relates to a method and an apparatus for manufacturing a single-sided metal-clad laminate using a heat-resistant film having a thermoplastic resin layer on both sides for producing a double-sided metal-clad laminate.
- FPC flexible printed circuit board
- a metal-clad laminate suitable as a printed circuit board for electronic and electrical equipment a structure in which a metal foil is laminated on both front and back sides of a polyimide film, a structure in which a metal foil is laminated on only one side and a double-sided metal-clad laminate
- a single-sided metal-clad laminate which is a flexible laminate.
- thermocompression bonding (hereinafter also referred to as thermal lamination)
- the thermoplastic polyimide layer present on the surface on which the metal foil is not laminated is fused to a metal roll or a protective film, which makes it difficult to produce a single-sided metal-clad laminate.
- the technique which uses the polyimide of a specific structure for the thermoplastic polyimide layer of the side which does not affix a metal foil is disclosed (for example, patent document 1).
- positions a protective film to at least one between a metal roll and a laminated material is disclosed (for example, patent document 2).
- a single-sided metal-clad laminate can be obtained by etching only a single-sided metal foil using a double-sided metal-clad laminate.
- the manufacturing process is increased by one because of the etching process.
- the present invention has been made in view of the above-mentioned problems, and its purpose is that the metal foil is not laminated even though a thermoplastic resin layer is provided on both surfaces of the heat-resistant film as the core layer.
- a single-sided metal plate that can efficiently produce a single-sided metal-clad laminate without fusing the thermoplastic resin layer surface to a metal roll or protective film, and can easily and inexpensively obtain a single-sided metal-laminated plate with reduced warpage. It is providing the manufacturing method and manufacturing apparatus of a metal-clad laminated board.
- the present inventors have found that the above-mentioned problems can be solved by the following method to obtain the target single-sided metal-clad laminate (E), and the present invention has been completed. It came to do.
- the method for producing a single-sided metal-clad laminate (E) uses an adhesive sheet (C) having a thermoplastic resin layer (B) on both sides of a heat-resistant film (A), and an adhesive sheet (C).
- the metal foil (D) is laminated on one side of the adhesive sheet via the thermoplastic resin layer (B), and the adhesive sheet (C) is protected on the side where the metal foil (D) is not laminated via the thermoplastic resin layer (B).
- a method for producing a single-sided metal-clad laminate (E) comprising a step of laminating a material (G), further comprising a step of peeling off the protective material (G), and the single-sided metal before peeling off the protective material (G)
- the angle ⁇ formed by the tension laminate (E) and the peeled protective material (G) is greater than 0 and less than 90 °.
- the manufacturing apparatus of the single-sided metal-clad laminate (E) includes an adhesive sheet (C) having a thermoplastic resin layer (B) on both sides of a heat-resistant film (A), and a thermoplastic resin on one side.
- Protective material disposed via the thermoplastic resin layer (B) on the side where the metal foil (D) disposed via the layer (B) and the metal foil (D) of the adhesive sheet (C) are not laminated (G) is a one-sided metal-stretching part including a heat-laminating part for heat-laminating and a protective material peeling part for peeling the protective material (G) from the single-sided metal-clad laminate (E).
- the said protective material peeling part makes
- the angle ⁇ is configured to be greater than 0 and less than 90 °. .
- the present invention it is possible to easily produce a single-sided metal-clad laminate using the conventionally produced materials and apparatuses for double-sided metal-clad laminates and to etch a single-sided metal foil Therefore, productivity can be improved at low cost.
- the production method of the present invention exhibits a remarkable effect particularly when a single-sided metal-clad laminate is continuously produced by a thermal lamination method.
- a to B representing a numerical range means “A or more (including A and greater than A)” and “B or less (including B and less than B)”.
- heat resistant film (A) ⁇ Heat resistant film (A)>
- “heat resistance” means that it can withstand use at a heating temperature during thermal lamination.
- the heat resistant film (A) is not particularly limited as long as it satisfies the above properties, and various known films such as polyimide film and polyethylene naphthalate can be used.
- a heat resistant film (A) is a heat resistant polyimide film from the point which is excellent not only in heat resistance but in physical properties, such as an electrical property.
- the “heat-resistant polyimide film” may be formed by containing 90% by weight or more of non-thermoplastic polyimide, and the molecular structure and thickness of non-thermoplastic polyimide are not particularly limited.
- the non-thermoplastic polyimide used for forming the heat-resistant polyimide film is generally manufactured using polyamic acid (also referred to as polyamic acid) as a precursor, but the non-thermoplastic polyimide is completely imidized. Alternatively, a precursor that is not imidized, that is, a polyamic acid may be included in part.
- the non-thermoplastic polyimide generally refers to a polyimide that does not soften or show adhesiveness even when heated.
- the present invention refers to a polyimide that is heated in a film state at 450 ° C. for 2 minutes, does not wrinkle or stretch, and maintains its shape, or has substantially no glass transition temperature.
- the glass transition temperature can be obtained from the value of the inflection point of the storage elastic modulus measured by a dynamic viscoelasticity measuring device (DMA). Further, “substantially has no glass transition temperature” means that thermal decomposition starts before the glass transition state is reached.
- a polyimide film can be manufactured using polyamic acid as a precursor. Any known method can be used as a method for producing the polyamic acid.
- the aromatic tetracarboxylic dianhydride and the aromatic diamine are dissolved in a substantially equimolar amount of an organic solvent to control the temperature. It can be produced by stirring until the polymerization of the aromatic tetracarboxylic dianhydride and the aromatic diamine is completed under the conditions.
- These polyamic acid solutions are usually obtained at a concentration of 5% to 35% by weight, preferably 10% to 30% by weight. When the concentration is in this range, a suitable molecular weight and solution viscosity can be obtained.
- any known method and a combination thereof can be used.
- the characteristic of the polymerization method in the polymerization of polyamic acid is the order of addition of the monomers, and the physical properties of the polyimide obtained can be controlled by controlling the order of addition of the monomers. Therefore, in the present invention, any method of adding monomers may be used for the polymerization of polyamic acid.
- the following method is mentioned as a typical polymerization method. That is, 1) A method in which an aromatic diamine is dissolved in an organic polar solvent and this is reacted with a substantially equimolar amount of an aromatic tetracarboxylic dianhydride for polymerization.
- An aromatic tetracarboxylic dianhydride is reacted with a small molar amount of an aromatic diamine compound in an organic polar solvent to obtain a prepolymer having acid anhydride groups at both ends. Then, the method of superposing
- An aromatic tetracarboxylic dianhydride and an excess molar amount of the aromatic diamine compound are reacted in an organic polar solvent to obtain a prepolymer having amino groups at both ends.
- the polyamic acid obtained by using any of the above polymerization methods may be used, and the polymerization method is not particularly limited.
- aromatic diamine examples include, but are not limited to, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 2,2-bis ⁇ 4 -(4-aminophenoxy) phenyl ⁇ propane, 2,2-bis ⁇ 4- (4-aminophenoxy) phenyl ⁇ hexafluoropropane, bis ⁇ 4- (3-aminophenoxy) phenyl ⁇ sulfone, bis ⁇ 4- ( 4-aminophenoxy) phenyl ⁇ sulfone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3, 3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-dichlorobenzidine,
- aromatic tetracarboxylic dianhydride is not limited to this, but for example, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3 , 3'-Benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,4'-oxyphthalic dianhydride, ethylene bis (trimellitic acid monoester acid anhydride), bisphenol A bis (Trimellitic acid monoester anhydride), pyromellitic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydr
- aromatic diamine and the aromatic tetracarboxylic dianhydride may be reacted so as to have a substantially equimolar amount, and the order of addition, the combination of monomers, and the composition are not particularly limited. Absent.
- the organic solvent used as a polymerization solvent for producing the polyamic acid is not particularly limited as long as it dissolves the aromatic diamine, the aromatic tetracarboxylic dianhydride, and the resulting polyamic acid.
- the polymerization solvent for example, amide solvents such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone are preferable.
- the resin solution can be prepared using the obtained organic solvent solution of polyamic acid (polyamic acid solution) as it is.
- the reaction temperature for producing the polyamic acid is preferably ⁇ 10 ° C. to 50 ° C. Controlling within this temperature range is preferable because the reaction proceeds at a good reaction rate and is excellent in productivity. Further, the reaction time is not particularly limited, but is usually from several minutes to several hours.
- the curing agent includes at least one of a dehydrating agent and a catalyst.
- the dehydrating agent is not particularly limited as long as the polyamic acid can be dehydrated by dehydration and cyclization, but for example, aliphatic acid anhydride, aromatic acid anhydride, N, N′-dialkylcarbodiimide, lower aliphatic Listed are halides, halogenated lower aliphatic acid anhydrides, aryl sulfonic acid dihalides, thionyl halides, and the like. These may be used alone or in combination of two or more. Among these, aliphatic acid anhydrides and aromatic acid anhydrides can be particularly preferably used.
- the catalyst is not particularly limited as long as it is a component having an effect of promoting the dehydration ring-closing action of the dehydrating agent on the polyamic acid.
- a component having an effect of promoting the dehydration ring-closing action of the dehydrating agent on the polyamic acid Specifically, for example, an aliphatic tertiary amine, an aromatic tertiary amine, and the like. And heterocyclic tertiary amines.
- a filler can be added to the heat resistant film (A).
- Any filler may be used, but preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica and the like.
- thermoplastic resin layer (B) examples include polycarbonate resins, acrylonitrile / styrene copolymer resins, thermoplastic polyimide resins, and the like. Can be preferably used. If the thermoplastic polyimide resin exhibits desired properties such as a significant adhesive force with a metal foil and a suitable linear expansion coefficient, the content, molecular structure, and thickness of the thermoplastic polyimide resin contained in the layer are as follows. It is not particularly limited. However, in order to develop desired properties such as significant adhesive strength and a suitable linear expansion coefficient, it is practical that the thermoplastic resin layer (B) contains 50% by weight or more of the thermoplastic polyimide resin. preferable. Furthermore, the thermoplastic polyimide resin contained in the thermoplastic resin layer (B) facing through the heat-resistant film is the same kind from the viewpoint of balancing the linear expansion coefficient in the entire adhesive sheet and simplifying the manufacturing process. It is preferable that
- thermoplastic polyimide resin contained in the thermoplastic resin layer (B) for example, thermoplastic polyamideimide, thermoplastic polyetherimide, thermoplastic polyesterimide and the like can be suitably used.
- thermoplastic polyimide contained in the thermoplastic resin layer (B) can be obtained by a conversion reaction from the precursor polyamic acid.
- any known method can be used as with the precursor of the non-thermoplastic polyimide resin that can be used for the heat-resistant film (A).
- the thermoplastic polyimide resin used in the present invention is 150 ° C. It preferably has a glass transition temperature (Tg) in the range of ⁇ 300 ° C.
- Tg can be calculated
- the polyamic acid precursor of the thermoplastic polyimide that can be used in the present invention is not particularly limited, and any known polyamic acid can be used.
- the raw materials exemplified above and the production conditions can be selected as appropriate and used in the same manner.
- Thermoplastic polyimides can be adjusted in various characteristics by combining various raw materials such as aromatic tetracarboxylic dianhydride and aromatic diamine, but generally use ratio of rigid structure aromatic diamine is large. In this case, the glass transition temperature becomes high, the storage elastic modulus at the time of heating increases, and the adhesion and workability may decrease.
- the use ratio of the aromatic diamine having a rigid structure is preferably 40 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less with respect to the total amount of the aromatic diamine.
- aromatic diamines and aromatic tetracarboxylic dianhydrides used in preferred thermoplastic polyimide resins include aromatic diamines and aromatic tetracarboxylic dianhydrides that can be used in the aforementioned heat-resistant polyimide film. Can be used. More preferably, an aromatic diamine having an aminophenoxy group and an acid dianhydride such as benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, or biphenyl sulfone tetracarboxylic dianhydride. Examples include those obtained by polymerization reaction.
- an inorganic or organic filler, and other resins may be added as necessary.
- thermoplastic resin layer is used for the heat resistant film (A) used as a core layer.
- a method of forming (B) on each side or simultaneously on both sides, a method of forming the thermoplastic resin layer (B) into a sheet shape, and bonding this to the surface of the heat-resistant film (A) serving as the core layer, etc. can be mentioned.
- the heat-resistant film (A) and the thermoplastic resin layer (B) to be the core layer are co-extruded to produce an adhesive sheet (C) that substantially forms a laminate in one step. Also good.
- thermoplastic polyimide resin when used for the thermoplastic resin layer (B), a resin solution obtained by dissolving or dispersing the thermoplastic polyimide resin or a resin composition containing the thermoplastic polyimide resin in an organic solvent is used as a heat resistant film.
- the conditions for synthesis of polyamic acid and imidization of polyamic acid at this time are not particularly limited, but conventionally known raw materials and conditions can be used.
- the polyamic acid solution may contain, for example, a coupling agent depending on the application.
- each layer which concerns on the adhesive sheet (C) in this invention, what is necessary is just to adjust suitably so that it may become the total thickness according to a use, but a warp does not arise in the state of an adhesive sheet (C).
- the thickness balance of each thermoplastic resin layer (B) is preferably adjusted in consideration of the linear expansion coefficient of each layer. When the difference in linear expansion coefficient between the heat-resistant film (A) and the thermoplastic resin layer (B) opposed via the heat-resistant film (A) is small, it becomes easy to balance the thickness.
- the total thickness of the adhesive sheet (C) is preferably 5 ⁇ m to 50 ⁇ m, more preferably 7 ⁇ m to 30 ⁇ m. If it exists in this range, it can be conveniently used as a base material of FPC.
- PIXIO registered trademark
- the metal foil (D) is not particularly limited, but when the single-sided metal-clad laminate (E) of the present invention is used for electronic equipment / electric equipment, for example, copper or copper alloy And foil made of stainless steel or its alloy, nickel or nickel alloy (including 42 alloy), aluminum or aluminum alloy.
- copper foils such as rolled copper foil and electrolytic copper foil are frequently used.
- these copper foils can be preferably used as the metal foil (D).
- the antirust layer, the heat-resistant layer, or the contact bonding layer may be apply
- the thickness of the metal foil (D) is preferably, for example, 3 ⁇ m to 30 ⁇ m, more preferably 5 ⁇ m to 20 ⁇ m.
- the surface roughness (Rz) of the metal foil (D) is preferably 0.01 ⁇ m to 1 ⁇ m. When the surface roughness (Rz) of the metal foil (D) is outside this range, the adhesiveness with the thermoplastic resin layer (B) may be inferior.
- ⁇ Protective film (F)> in order to improve the appearance of the obtained single-sided metal-clad laminate (E), the side on which the metal foil (D) is laminated is placed on the metal foil (B) via the thermoplastic resin layer (B). It is preferable to laminate D) and further laminate the protective film (F) in contact with the metal foil (D).
- a protective film (F) is laminated
- the protective film (F) is laminated between the pressing surface (for example, metal roll) and the metal foil (D).
- the protective film (F) is not particularly limited as long as it can withstand the heating temperature in the thermocompression bonding step, heat resistant plastic such as non-thermoplastic polyimide film, metal foil such as copper foil, aluminum foil, SUS foil, etc. Can be suitably used.
- heat resistant plastic such as non-thermoplastic polyimide film, metal foil such as copper foil, aluminum foil, SUS foil, etc.
- a non-thermoplastic polyimide film is more preferably used from the viewpoint of excellent balance between heat resistance and recyclability.
- Various known films can be used as the non-thermoplastic polyimide film.
- Apical registered trademark
- Upilex registered trademark
- Ube Industries, Ltd. Kapton manufactured by Toray DuPont Co., Ltd. Registered trademark
- the protective film (F) is particularly limited as long as the protective film (F) can have a thickness such that the single-sided metal-clad laminate (E) does not peel off from the protective film (F) in the process of peeling the protective material (G). Not.
- the thickness is preferably 25 ⁇ m to 300 ⁇ m, more preferably 50 ⁇ m to 250 ⁇ m.
- ⁇ Protective material (G)> the side which does not laminate
- the protective material (G) is not particularly limited as long as it can withstand the heating temperature in the thermocompression bonding step, heat resistant plastic such as non-thermoplastic polyimide film, metal foil such as copper foil, aluminum foil, and SUS foil. Can be suitably used. Among these, a non-thermoplastic polyimide film is more preferably used from the viewpoint of excellent balance between heat resistance and recyclability.
- the protective material (G) is not particularly limited as long as it can have a thickness that does not cause a problem such that the single-sided metal-clad laminate (E) peels from the protective material (G) in the step of peeling the protective film (F). Not.
- the thickness is preferably 10 ⁇ m to 300 ⁇ m, more preferably 25 ⁇ m to 300 ⁇ m, and still more preferably 50 ⁇ m to 250 ⁇ m.
- non-thermoplastic polyimide film Various known films can be used as the non-thermoplastic polyimide film.
- Apical (registered trademark) manufactured by Kaneka Corporation, Upilex (registered trademark) manufactured by Ube Industries, Ltd., Kapton manufactured by Toray DuPont Co., Ltd., Etc. are exemplified.
- ⁇ Linear expansion coefficient of protective material (G)> when the linear expansion coefficient of the adhesive sheet (C) is X1 and the linear expansion coefficient of the protective material (G) is X2, the protective material (G) satisfying
- X1-X2 is more preferably 4.5 ppm / ° C. to 8.5 ppm / ° C., particularly preferably 5 ppm / ° C. to 8 ppm / ° C. If it is in this range, it is possible to suppress warpage of the obtained single-sided metal-clad laminate (E), and it is also possible to reduce the dimensional change rate.
- the surface roughness of the protective material (G) is preferably in the range of 0.01 ⁇ m to 3 ⁇ m, and more preferably in the range of 0.01 ⁇ m to 1 ⁇ m.
- the protective material (G) having a surface roughness within this range is used, it becomes easy to peel the adhesive sheet (C) from the protective material (G), and the obtained single-sided metal-clad laminate (E) is curled. Can be suppressed.
- the surface roughness of the protective material (G) refers to the surface roughness of the surface of the protective material (G) on the side in contact with the adhesive sheet (C).
- thermoplastic resin layer (B) 2 will be provided on both surfaces of the heat resistant film (A) 1.
- the side on which the metal foil (D) 4 is laminated is laminated with the metal foil (D) 4 via the thermoplastic resin layer (B) 2, and the side on which the metal foil (D) 4 is not laminated is the thermoplastic resin layer ( B) A protective material (G) 7 is directly laminated on 2.
- the metal foil (D) 4 is laminated via the thermoplastic resin layer (B) 2, and the protective film (F) 6 is further in contact with the metal foil (D) 4. It is also possible to laminate.
- thermocompression bonding method obtained by laminating the above-mentioned layers by thermocompression bonding is preferable from the viewpoint that wrinkles and the like of the single-sided metal-clad laminate (E) can be suppressed.
- the method for bonding the adhesive sheet (C) and the metal foil (D) include a thermocompression bonding method by batch processing using a single plate press, a hot roll laminating apparatus (also referred to as a thermal laminating apparatus), or a double belt press (DBP) apparatus.
- the thermocompression bonding method using a hot roll laminating apparatus having a pair of metal rolls is preferable from the viewpoint of the equipment cost including productivity and maintenance cost.
- the “heat roll laminating apparatus having a pair of metal rolls” herein may be an apparatus having a metal roll for heating and pressurizing a material, and the specific apparatus configuration is particularly limited. It is not a thing.
- the method for producing a single-sided metal-clad laminate (E) according to the present invention may include a step of heating the adhesive sheet (C) before laminating the above-described layers.
- the method of heating an adhesive sheet (C) is not specifically limited, For example, the method of using a heater can be mentioned.
- the heater used for the heating is more preferably installed on the side of the adhesive sheet (C) where the protective material (G) is laminated. This is preferable because the peel strength is appropriate and the peeling behavior is improved.
- the said adhesive sheet (C) is heated at the temperature of 250 degreeC or more, More preferably, it is 300 degreeC or more, More preferably, it is 400 degreeC or more.
- an upper limit becomes like this.
- the adhesive sheet (C) is 550 or less, More preferably, it is 500 degrees C or less.
- the protective material (G) can be peeled off more easily, and the single-sided metal-clad laminate (E) may sag or wrinkle. This can be avoided more preferably.
- the heating time is not particularly limited, but is, for example, 0.1 minute to 1 minute.
- At least one of the protective film (F) or the protective material (G) can be used in the next step while being laminated on the single-sided metal-clad laminate (E).
- the protective film (F) or the protective material (G) can be used in the next step while being laminated on the single-sided metal-clad laminate (E).
- a preferred embodiment of the method for producing a single-sided metal-clad laminate (E) according to the present invention is an adhesive having a thermoplastic resin layer (B) on both sides of a heat-resistant film (A) as shown in FIG.
- the sheet (C) 3 only the metal foil (D) 4 is laminated on one side of the adhesive sheet (C) 3 via the thermoplastic resin layer (B), and the metal foil (D) of the adhesive sheet (C) 3.
- 4 includes a step of laminating the protective material (G) 7 via the thermoplastic resin layer (B) on the side where the 4 is not laminated, and further a step of peeling the protective material (G) 7.
- another preferred embodiment of the method for producing a single-sided metal-clad laminate (E) according to the present invention includes a thermoplastic resin layer (B) on both sides of a heat-resistant film (A) as shown in FIG.
- the adhesive sheet (C) 3 is used, and the metal foil (D) 4 is laminated on one side of the adhesive sheet (C) 3 via the thermoplastic resin layer (B), and further protected by contacting the metal foil (D) 4 Including the step of laminating the protective material (G) 7 via the thermoplastic resin layer (B) on the side of the adhesive sheet (C) 3 on which the metal foil (D) 4 is not laminated, the film (F) 6 being laminated. And a step of peeling the protective material (G) 7 and the protective film (F) 6.
- the frequency with which wrinkles or warpage occurs in the single-sided metal-clad laminate (E) is high. Very few and preferable.
- the single-sided metal-clad laminate (E) is formed in order to obtain a laminated state of the protective material (G) and the single-sided metal-clad laminate (E) that have poor film rigidity. ) Wrinkles and warpage easily occur.
- the peeling angle that is, the protective material (G) and the single-sided metal-clad laminate (E) are made.
- the angle, or the angle formed by the protective film (F) and the single-sided metal-clad laminate (E) is also the quality of the single-sided metal-clad laminate (E) from which the protective material (G) and the protective film (F) have been peeled. And found to have a great effect on warping.
- the angle ⁇ formed by the single-sided metal-clad laminate (E) before peeling off the protective material (G) and the peeled protective material (G) is preferably greater than 0 and less than 90 °.
- ⁇ is a single-sided metal-clad laminate (E) just before the protective material (G) is peeled off and the peeled protective material (G ).
- peel strength peel strength
- the protective material (G) is suitable for the single-sided metal-clad laminate. It is possible to peel appropriately from (E).
- ⁇ is more preferably 10 ° or more and less than 80 °, further preferably 10 ° or more and less than 70 °, and particularly preferably 10 ° or more and less than 60 °.
- the peel strength (peel strength) between the protective material (G) and the single-sided metal-clad laminate (E) is the angle ⁇ described above with respect to the single-sided metal-clad laminate (E) before peeling off the protective material (G).
- it is preferably 0.01 N / cm to 1.8 N / cm, more preferably 0.05 N / cm to 0.2 N / cm.
- the single-sided metal-clad laminate (E), specifically, the laminate of the adhesive sheet (C) and the metal foil (D) is bonded to the protective material (G) before peeling (180 ° - ⁇ ) Is preferably 0.01 N / cm to 2.0 N / cm, more preferably 0.05 N / cm to 0.2 N / cm. .
- peel strength (peel strength) between the protective material (G) and the single-sided metal-clad laminate (E) is less than or equal to the above-described upper limit, a part of the protective material (G) is a single-sided metal-clad laminate (E)
- the peeling strength (peel strength) between the protective material (G) and the single-sided metal-clad laminate (E) is not described above. If it is more than the lower limit, the protective material (G) is preferably peeled off from the single-sided metal-clad laminate (E) in the process, or floats to cause wrinkles, which is preferable.
- (beta) is the single-sided metal-clad laminated board (E) just before peeling a protective film (F), and the peeled protective film (F ).
- ⁇ is within this range, peeling during the process of the protective film (F) does not occur even after the protective material (G) is peeled off. Further, the protective film (F) does not remain on the single-sided metal-clad laminate (E) when the protective film (F) is peeled off.
- ⁇ is more preferably an acute angle because warpage of the obtained single-sided metal-clad laminate (E) is less likely to occur.
- ⁇ is more preferably 10 ° or more and less than 80 °, further preferably 10 ° or more and less than 70 °, and particularly preferably 10 ° or more and less than 60 °.
- the peel strength (peel strength) between the protective film (F) and the single-sided metal-clad laminate (E) is the angle ⁇ described above with respect to the single-sided metal-clad laminate (E) before peeling the protective film (F). In the case of pulling and peeling (I method described later), it is preferably 0.01 N / cm to 1.8 N / cm, more preferably 0.05 N / cm to 0.2 N / cm.
- the single-sided metal-clad laminate (E) specifically, the laminate of the adhesive sheet (C) and the metal foil (D) is applied to the protective film (F) before peeling (180 ° - ⁇ ) Is preferably 0.01 N / cm to 2.0 N / cm, more preferably 0.05 N / cm to 0.2 N / cm. .
- peel strength (peel strength) between the protective film (F) and the single-sided metal-clad laminate (E) is not more than the above-mentioned upper limit, a part of the protective film (F) is a single-sided metal-clad laminate (E).
- the peeling strength (peel strength) between the protective film (F) and the single-sided metal-clad laminate (E) is not described above. If it is more than the lower limit, the protective film (F) is preferably peeled off from the single-sided metal-clad laminate (E) in the process, or floats to cause wrinkles, which is preferable.
- the occurrence of wrinkles and warpage in the single-sided metal-clad laminate (E) may be affected by the type and thickness of the copper foil.
- ⁇ is preferably in the range of 10 ° to 80 °.
- the rolled copper foil is generally more flexible than the electrolytic copper foil having the same thickness, the rolled copper foil is affected by the stress when the protective material (G) and the protective film (F) are peeled due to the flexibility. This is probably because of this.
- thermocompression bonding apparatus various suitable configurations can be adopted as the way of passing each film (also referred to as a pass line) in the thermocompression bonding apparatus. For example, as shown in FIGS. 3 and 5, after the rolled adhesive sheet (C) 3 is unwound from the roll, the metal foil (D) 4 and the protective material (G) 7 are applied to the adhesive sheet (C) 3.
- the protective film (F) 6 is bonded together as needed, and the laminated material to be laminated is then thermocompression bonded through a pair of metal rolls 9 and further passed through a pair of peeling rolls 10 to provide a protective material (G ) 7 and if necessary, the protective film (F) 6 is peeled off to form the single-sided metal-clad laminate (E) 5, and the adhesive sheet (C) 3, the thermocompression-bonded material, and one side
- the metal-clad laminate (E) 5 may be in a straight line and passes while meandering between various rolls provided in a thermocompression bonding apparatus including a pair of or more metal rolls 9 and a pair of or more peeling rolls 10. May be.
- the straight line means that the adhesive sheet (C) 3, the thermocompression-bonded material, and the single-sided metal-clad laminate (E) 5 move on a single plane without meandering.
- the adhesive sheet (C) 3, the thermocompression-bonded laminated material, and the single-sided metal-clad laminate (E) 5 are straight in part of the pass line and meander in other parts. Good.
- the radius of the pair of peeling rolls for peeling the protective material (G) from the single-sided metal-clad laminate (E) is the same as that of the peeling roll on the side of the protective material (G). It is preferably smaller than the radius rb of the peeling roll on the (E) side (that is, the metal foil (D) side or the protective film (F) side).
- the radius of the pair of peeling rolls for peeling the protective film (F) from the single-sided metal-clad laminate (E) is the same as that of the peeling roll on the side of the protective film (F). It is preferably smaller than the radius rb of the peeling roll on the laminate (E) side (that is, the adhesive sheet (C) side or the protective material (G) side).
- the curvature at the time of peeling of the protective material (G) or protective film (F) to be peeled is smaller as the radius ra of the peeling roll on the side of the protective material (G) to be peeled or the protective film (F) to be peeled is smaller.
- the radius ra of the peeling roll on the side of the protective material (G) to be peeled off or the side of the protective film (F) to be peeled off, and the radius rb of the peeling roll on the side of the single-sided metal-clad laminate (E) on the opposite side It is preferable that the radius ratio ra / rb is less than 1. Thereby, the single-sided metal-clad laminated board (E) without a wrinkle and a curvature can be obtained.
- ra / rb is more preferably less than 0.75, and even more preferably less than 0.4.
- the speed at which the protective material (G) and the protective film (F) are peeled from the single-sided metal-clad laminate (E), that is, the conveyance speed of the metal-clad laminate is preferably 3.5 m / min or less, more preferably 2 m. / Min.
- a peeling speed of 3.5 m / min or less is preferable because uniformity during peeling can be maintained.
- the heating method of the material to be laminated in the thermocompression bonding method is not particularly limited. For example, heating using a conventionally known method capable of heating at a predetermined temperature, such as a heat circulation method, a hot air heating method, an induction heating method, or the like. The method can be used.
- the method for pressurizing the material to be laminated in the thermocompression bonding method is not particularly limited. For example, a conventionally known method capable of applying a predetermined pressure such as a hydraulic method, a pneumatic method, a gap pressure method, or the like. The pressurizing method which employ
- the heating temperature in the thermocompression bonding step that is, the pressure bonding temperature (laminating temperature) T1 (° C.) is 20 ° C. from the glass transition temperature (Tg) T2 (° C.) of the thermoplastic resin layer (B) of the adhesive sheet (C) to be used.
- the temperature is preferably higher by ⁇ 90 ° C., more preferably by 50 ° C. to 80 ° C. higher than the Tg of the thermoplastic resin layer (B) of the adhesive sheet (C). If T1-T2 is within this range, the adhesive sheet (C) and the protective material (G) can be peeled well.
- the laminating speed in the thermocompression bonding step is preferably 0.5 m / min or more, and more preferably 1.0 m / min or more. If it is 0.5 m / min or more, sufficient thermocompression bonding is possible, and if it is 1.0 m / min or more, productivity can be further improved.
- the higher the pressure in the thermocompression bonding step that is, the laminating pressure
- the higher the laminating temperature can be lowered and the laminating speed can be increased.
- the lamination pressure is too high, the dimensional change of the obtained single-sided metal-clad laminate (E) tends to deteriorate.
- the lamination pressure is too low, the adhesive strength of the metal foil of the single-sided metal-clad laminate (E) obtained tends to be low.
- the lamination pressure is preferably in the range of 49 N / cm to 490 N / cm (5 kgf / cm to 50 kgf / cm), and in the range of 98 N / cm to 294 N / cm (10 kgf / cm to 30 kgf / cm). More preferably. Within this range, the three conditions of the lamination temperature, the lamination speed and the lamination pressure can be made favorable, and the productivity can be further improved.
- ⁇ Manufacturing apparatus for single-sided metal-clad laminate (E)> In order to obtain a single-sided metal-clad laminate (E) by the method for producing a single-sided metal-clad laminate (E) according to the present invention, a metal foil (D), a protective film (F), a protective film is applied to the adhesive sheet (C). It is preferable to use a hot roll laminating apparatus that press-bonds the laminated material to be laminated obtained by laminating the material (G) and the like while continuously heating. In this thermal laminating apparatus, the protective material (G) and, if necessary, the protective film (F) are peeled off from the single-sided metal-clad laminate (E) after the thermal laminating section where thermal lamination is performed.
- a laminated material feeding portion for feeding out the laminated material may be provided in the preceding stage of the thermal laminating portion for performing thermal lamination, or a laminated material in which the laminated material is wound up in the subsequent stage of the thermal laminating portion.
- a material winding unit may be provided.
- the apparatus for producing a single-sided metal-clad laminate (E) is an adhesive sheet having thermoplastic resin layers (B) on both sides of a heat-resistant film (A) as shown in FIG. C) 3, the metal foil (D) 4 disposed on one side of the thermoplastic resin layer (B), and the thermoplastic resin layer on the side of the adhesive sheet (C) where the metal foil (D) is not laminated
- the protective material (G) 7 disposed via (B) is thermally laminated with the thermal laminate 9 and the protective material (G) 7 provided on the subsequent stage is laminated on the single-sided metal-clad laminate (E And a protective material peeling part which peels from 5.
- the angle (alpha) which the single-sided metal-clad laminated board (E) before peeling protective material (G) and the peeled protective material (G) makes is larger than 0, and less than 90 degrees It is comprised so that it may become.
- the peeling strength (peel strength) of a protective material (G) and a single-sided metal-clad laminate (E) becomes small, it is suitable, and a protective material (G) is a single-sided metal-clad laminate (E). Can be appropriately peeled off.
- production of curvature was further suppressed can be obtained.
- the apparatus for producing a single-sided metal-clad laminate (E) has thermoplastic resin layers (B) on both sides of a heat-resistant film (A) as shown in FIG.
- Adhesive sheet (C) 3 having, metal foil (D) 4 disposed on one side of the thermoplastic resin layer (B), and protective film disposed in contact with the metal foil (D) 4 ( F) 6 and heat for laminating the protective material (G) 7 disposed on the side of the adhesive sheet (C) 3 where the metal foil (D) 4 is not laminated via the thermoplastic resin layer (B).
- Laminating portion 9 protective material peeling portion for peeling protective material (G) 7 from single-sided metal-clad laminate (E) 5 and protective film (F) 6 provided on the subsequent stage, and single-sided metal-clad laminate (E)
- the protective film peeling part peeled from 5 is included.
- an angle ⁇ formed by the single-sided metal-clad laminate (E) 5 before peeling the protective material (G) 7 and the peeled protective material (G) 7 is larger than 0.
- the protective film peeling portion is formed by the single-sided metal-clad laminate (E) before peeling the protective film (F) and the peeled protective film (F). The angle ⁇ is greater than 0 and less than 90 °.
- the peeling strength (peel strength) of a protective material (G) and a protective film (F), and a single-sided metal-clad laminate (E) becomes small, it is suitable, and a protective material (G) and protection It is possible to appropriately peel the film (F) from the single-sided metal-clad laminate (E). Moreover, the single-sided metal laminated sheet in which generation
- the protective film peeling part is provided in the subsequent stage of the protective material peeling part.
- a heater for heating the adhesive sheet (C) is provided before the thermal laminate part.
- the protective material peeling portion, or the protective material peeling portion and the protective film peeling portion, respectively, are provided with a single-sided metal-clad protective material (G) or a protective material (G) and a protective film (F) via a pair of peeling rolls. More preferably, the laminate is peeled off from the laminate (E). By being passed through a pair of peeling rolls, for example, compared to a case where a single peeling roll is passed, it is not pulled by the single-sided metal-clad laminate (E), the protective material (G) or the protective film (F). , Stable peeling becomes possible.
- the radius ra between the peeling roll on the protective material (G) side to be peeled off or the protective film (F) side to be peeled off, and the radius rb of the peeling roll on the opposite side of the single-sided metal-clad laminate (E) side The ratio ra / rb is preferably less than 1 as described above.
- a winding unit for winding the peeled protective material (G) and a peeled protective film (F) and a feeding unit for feeding it out is also preferable to provide If these take-up portions and feeding portions are provided, the protective material (G) and the protective film (F) once used in the thermocompression bonding step are taken up and installed again on the feeding side, so that the protective material ( G) and the protective film (F) can be reused.
- the protective material (G) and the protective film (F) once used in the thermocompression bonding step are taken up and installed again on the feeding side, so that the protective material ( G) and the protective film (F) can be reused.
- winding unit the feeding unit, the end position detection unit, and the winding position correction unit are not particularly limited, and various conventionally known devices can be used.
- the warpage of the obtained single-sided metal-clad laminate (E) by controlling the linear expansion coefficient of the entire adhesive sheet (C) described above. Specifically, when a rectangular single-sided metal-clad laminate (E) having a size of 7 cm wide ⁇ 20 cm long is produced, 20 ° C., 60% R.D. H. It is preferable that the warping of the four corners after leaving for 12 hours in this environment is 1.0 mm or less. If the warpage of the single-sided metal-clad laminate (E) is within the above range, it is possible to suppress warpage during conveyance in the process and warpage of the FPC after circuit formation by etching.
- the present invention has the following configuration.
- An adhesive sheet (C) having a thermoplastic resin layer (B) on both sides of the heat resistant film (A) is used, and a metal foil (on one side of the adhesive sheet (C) is interposed via the thermoplastic resin layer (B).
- D) In the method for producing a single-sided metal-clad laminate (E) including a step of laminating a protective material (G) via a thermoplastic resin layer (B) on the side of the adhesive sheet (C) where the metal foil (D) is not laminated. And an angle ⁇ formed between the single-sided metal-clad laminate (E) before peeling off the protective material (G) and the peeled protective material (G), further comprising a step of peeling off the protective material (G).
- An adhesive sheet (C) having a thermoplastic resin layer (B) on both sides of the heat resistant film (A) is used, and a metal foil (with a thermoplastic resin layer (B) on one side of the adhesive sheet (C) ( D) is laminated, and further a protective film (F) is laminated in contact with the metal foil (D), and the thermoplastic resin layer (B) is interposed on the side of the adhesive sheet (C) where the metal foil (D) is not laminated.
- a method for producing a single-sided metal-clad laminate (E) comprising a step of laminating a protective material (G), further comprising a step of peeling off the protective material (G) and the protective film (F),
- the angle ⁇ formed by the single-sided metal-clad laminate (E) before peeling off) and the peeled protective material (G) is larger than 0 and less than 90 °, and before peeling the protective film (F)
- the angle ⁇ formed by the single-sided metal-clad laminate (E) and the peeled protective film (F) is Is larger than 90 °, the manufacturing method of the single-sided metal-clad laminate according (E) [1].
- thermocompression bonding method uses a thermal laminating apparatus having a pair of metal rolls.
- thermoplastic resin layer (B) contains a thermoplastic polyimide resin
- the protective material (G) or the protective material (G) and the protective film (F) are peeled from the single-sided metal-clad laminate (E) at a speed of 3.5 m / min or less, [1] to [11] The manufacturing method of the single-sided metal-clad laminated board (E) in any one of.
- the protective material (G) or the protective material (G) and the protective film (F) are each peeled off from the single-sided metal-clad laminate (E) via a pair of peeling rolls (peeling material ( The radius ratio ra / rb between the radius ra of the peeling roll on the G) side or the protective film (F) side to be peeled and the radius rb of the peeling roll on the opposite single-sided metal-clad laminate (E) side is less than 1.
- the method for producing a single-sided metal-clad laminate (E) according to any one of [1] to [12].
- An apparatus for producing a single-sided metal-clad laminate (E), comprising:
- (F) It is a manufacturing apparatus of a single-sided metal-clad laminate (E) including a protective film peeling part for peeling off the single-sided metal-clad laminate (E), wherein the protective material peeling part is a protective material (G) Single-sided metal-clad laminate (E) before peeling off and the protective material peeled off ( ) Is formed so that the angle ⁇ is greater than 0 and less than 90 °, and the protective film peeling portion is a single-sided metal-clad laminate (E) before peeling the protective film (F),
- the apparatus for producing a single-sided metal-clad laminate (E) according to [14], wherein an angle ⁇ formed by the peeled protective film (F) is greater than 0 and less than 90 °.
- thermoplastic resin layer (B) contains a thermoplastic polyimide resin
- the protective material peeling portion, or the protective material peeling portion and the protective film peeling portion are respectively provided with the protective material (G) or the protective material (G) and the protective film (F) via a pair of peeling rolls. It is designed to peel from the single-sided metal-clad laminate (E), the radius ra of the peeling roll on the protective material (G) side to be peeled off or the protective film (F) side to be peeled off, and the single-sided metal tension on the opposite side
- the linear expansion coefficient was measured by using a TMA120C manufactured by Seiko Electronics Co., Ltd. (sample size width 3 mm, length 10 mm), and once raising the temperature from 10 ° C. to 400 ° C. at 10 ° C./min with a load of 3 g. After cooling to 10 ° C., the temperature was further increased at 10 ° C./min, and the average value was calculated from the coefficient of thermal expansion from 100 ° C. to 200 ° C. during the second temperature increase.
- test piece was cut into a 10 mm ⁇ 100 mm strip. Produced.
- a double-sided tape G9052 (double-sided tape 13 in the figure) manufactured by Sony Chemical Corporation is applied to the opposite side of the surface to be pulled of the test piece, The test piece was laminated on the substrate 14.
- the peel angles ⁇ 1, ⁇ 2, and ⁇ 1, ⁇ 2 were set to the angles shown in Table 1, peeled according to JIS C6471 “8.1 peel strength”, and the load was measured at 50 mm / min. .
- Peel strength measurement (I method) was used to peel the protective material 7 from the single-sided metal-clad laminate (A) for evaluation of peel strength and peel strength at a peel angle ⁇ 1.
- Peel strength measurement (Method I) for peeling the protective film 6 at a peel angle ⁇ 1 from the strength measurement (Method II) and the single-sided metal-clad laminate (B) for peeling strength evaluation was used.
- thermoplastic polyimide layer after peeling can be peeled in the same state as before thermal lamination, ⁇ , peelable and the thermoplastic polyimide layer after peeling before thermal lamination
- gloss is slightly lower, but is in a state where there is no problem in use, is in a state where it can be peeled off and the thermoplastic polyimide layer after the peeling is partially micro scratched, but there is no problem in use
- ⁇ was evaluated as x when the thermoplastic polyimide layer after peeling was in a state of undulating even if it was difficult to peel and could be peeled off.
- Example 1 Rolled copper foil with a thickness of 12 ⁇ m, which is a metal foil, on a heat-resistant double-sided adhesive sheet having a linear expansion coefficient of 20 ppm / ° C. and a thermoplastic resin layer having a Tg of 290 ° C. (Pixio FRS manufactured by Kaneka Corporation) GHY5-82F-HA (Metal Co., Ltd., width 270 mm) is laminated, and a protective film (Apical (registered trademark) 125 NPI manufactured by Kaneka Co., Ltd.) is placed so that the metal foil is sandwiched between the adhesive sheets.
- a polyimide film having a linear expansion coefficient of 16 ppm / ° C.
- Rz 2.2 ⁇ m as a protective material (Apical (registered trademark) 75 NPI manufactured by Kaneka Corporation) and passing between a pair of metal rolls of a hot roll laminator.
- Thermal lamination was performed under conditions of 1 m / min.
- the adhesive sheet was heated at a heater temperature of 300 ° C. from the protective material side before heat lamination.
- the length of the heater used was 300 mm, and the heating time was 0.3 minutes.
- the single-sided metal-clad laminate (E) according to the present invention was manufactured by peeling in order. In the peeling process, ⁇ was 55 ° and ⁇ was 30 °.
- the protective film was peeled off without peeling off the protective material, and a single-sided metal-clad laminate (A) for peeling strength evaluation composed of the protective material, a heat-resistant double-sided adhesive sheet, and copper foil was produced. Furthermore, the protective material was peeled off, and without removing the protective film, a single-sided metal-clad laminate (B) for peeling strength evaluation composed of a heat-resistant double-sided adhesive sheet, copper foil and protective film was produced. The peel strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 1.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 1.
- a polyimide film Aral (registered trademark) 12.5AH manufactured by Kaneka Corporation
- Rz 2.1 ⁇ m
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 1.
- Example 4 A single-sided metal-clad laminate (E) was produced in the same manner as in Example 1 except that an electrolytic copper foil having a thickness of 12 ⁇ m (Mitsui Metals 3EC-M3S-HTE) was used as the metal foil.
- an electrolytic copper foil having a thickness of 12 ⁇ m Mitsubishi Metals 3EC-M3S-HTE
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 1.
- Example 5 In Example 1, a pair of release rolls each having a radius ratio (ra / rb) of two release rolls of 0.5 (50 mm / 100 mm) was used for peeling off the protective material and the protective film. Other than that, a single-sided metal-clad laminate (E) was produced in the same manner as in Example 1.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 1.
- Example 6 a single-sided metal-clad laminate (E) was produced in the same manner as in Example 1 except that thermal lamination was performed at a lamination speed (conveying speed of the metal-clad laminate) of 3 m / min. did.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 1.
- Example 7 a single-sided metal-clad laminate (E) was produced in the same manner as in Example 1 except that ⁇ was 85 ° C. in the step of peeling the protective material.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 1.
- Example 8 a single-sided metal-clad laminate (E) was produced in the same manner as in Example 1 except that the adhesive sheet was heated from the protective material side at a heater temperature of 500 ° C. before heat lamination.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 1.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 2.
- the single-sided metal-clad laminate (E) In the manufacturing process of the single-sided metal-clad laminate (E), there was no adhesion of the thermoplastic resin of the adhesive sheet to the transport roll or the like. Although the obtained single-sided metal-clad laminate (E) was slightly warped, it was in an acceptable range. Moreover, although the adhesive force of the adhesive sheet (single-sided metal-clad laminate) and the protective material was larger than that of Example 1 and difficult to peel, it was in a peelable range.
- Example 10 In Example 1, except that a pair of peeling rolls having a radius ratio (ra / rb) of two peeling rolls of 1 (100 mm / 100 mm) was used for peeling the protective material and peeling the protective film, respectively. Other than that, a single-sided metal-clad laminate (E) was produced in the same manner as in Example 1.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 2.
- the single-sided metal-clad laminate (E) In the manufacturing process of the single-sided metal-clad laminate (E), there was no adhesion of the thermoplastic resin of the adhesive sheet to the transport roll or the like. Although the obtained single-sided metal-clad laminate (E) was slightly warped, it was in an acceptable range. Moreover, although the peeling condition of the protective material and the protective film was inferior to Example 1, it was the range which can be peeled.
- Example 11 the single-sided metal-clad laminate (E) was prepared in the same manner as in Example 1 except that thermal lamination was performed under the condition that the lamination speed (conveying speed of the metal-clad laminate) was 4 m / min. Manufactured.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 2.
- the single-sided metal-clad laminate (E) In the manufacturing process of the single-sided metal-clad laminate (E), there was no adhesion of the thermoplastic resin of the adhesive sheet to the transport roll or the like. Although the obtained single-sided metal-clad laminate (E) was slightly warped, it was in an acceptable range. Moreover, although the peeling condition of the protective material and the protective film was inferior to Example 1, it was the range which can be peeled.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 2.
- the single-sided metal-clad laminate (E) In the manufacturing process of the single-sided metal-clad laminate (E), there was no adhesion of the thermoplastic resin of the adhesive sheet to the transport roll or the like. Although the obtained single-sided metal-clad laminate (E) was slightly warped, it was in an acceptable range. Moreover, although the peeling condition of the protective material and the protective film was inferior to Example 1, it was the range which can be peeled.
- Example 13 In Example 1, a single-sided metal-clad laminate (E) was produced in the same manner as in Example 1 except that the adhesive sheet was not heated before heat lamination.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 2.
- Example 1 As shown in FIG. 6, in Example 1, except that the angle ⁇ formed by the protective material (G) before peeling and the single-sided metal-clad laminate (E) was set to 165 °, the same as in Example 1 Thus, a single-sided metal-clad laminate (E) was produced.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 2.
- Example 2 As shown in FIG. 7, in Example 1, except that the angle ⁇ formed by the protective film (F) before peeling and the single-sided metal-clad laminate (E) was 165 °, the same as in Example 1 Thus, a single-sided metal-clad laminate (E) was produced.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 2.
- the adhesive force between the copper foil (single-sided metal-clad laminate (E)) and the protective film was greater than that of Example 1 and was difficult to peel off, although there was no sticking to the transport roll or the like. Further, warpage occurred in the obtained single-sided metal-clad laminate (E).
- Example 3 As shown in FIG. 9, the angle ⁇ for peeling the protective material is 90 °, the angle ⁇ for peeling the protective film is 90 °, and only one peeling roll 12 is used on each of the protective material side and the protective film side.
- a single-sided metal-clad laminate (E) was produced in the same manner as in Example 1 except for.
- the peeling state of the protective material and the protective film and the warpage of the single-sided metal-clad laminate (E) were evaluated. Moreover, the peeling strength was measured using the single-sided metal-clad laminate (A) and the single-sided metal-clad laminate (B). The results are shown in Table 2.
- the method and apparatus for producing a single-sided metal-clad laminate according to the present invention uses a conventionally produced material and apparatus for a double-sided metal laminate, and the surface of the thermoplastic resin layer on the side where no metal foil is laminated is As a printed circuit board for electronic and electrical equipment, a single-sided metal-clad laminate can be produced without fusing to a metal roll or a protective film, and a single-sided metal laminate with reduced warpage can be obtained inexpensively and easily. It can use suitably for manufacture of a suitable single-sided metal-clad laminate.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Description
本発明において「耐熱性」とは、熱ラミネート時の加熱温度での使用に耐え得ることを意味する。従って、耐熱性フィルム(A)としては、上記性質を満たすフィルムであれば特に制限はなく、例えば、ポリイミドフィルムやポリエチレンナフタレートなどの公知の各種フィルムを用いることができる。中でも、耐熱性のみならず電気特性等の物性にも優れている点から、耐熱性フィルム(A)は耐熱性ポリイミドフィルムであることが好ましい。
1)芳香族ジアミンを有機極性溶媒中に溶解し、これと実質的に等モルの芳香族テトラカルボン酸二無水物を反応させて重合する方法。
2)芳香族テトラカルボン酸二無水物とこれに対し過小モル量の芳香族ジアミン化合物とを有機極性溶媒中で反応させ、両末端に酸無水物基を有するプレポリマーを得る。続いて、全工程において芳香族テトラカルボン酸二無水物と芳香族ジアミン化合物が実質的に等モルとなるように芳香族ジアミン化合物を用いて重合させる方法。
3)芳香族テトラカルボン酸二無水物とこれに対し過剰モル量の芳香族ジアミン化合物とを有機極性溶媒中で反応させ、両末端にアミノ基を有するプレポリマーを得る。続いて、全工程において芳香族テトラカルボン酸二無水物と芳香族ジアミン化合物が実質的に等モルとなるように芳香族テトラカルボン酸二無水物を用いて重合する方法。
4)芳香族テトラカルボン酸二無水物を有機極性溶媒中に溶解および/または分散させた後、実質的に等モルとなるように芳香族ジアミン化合物を用いて重合させる方法。
5)実質的に等モルの芳香族テトラカルボン酸二無水物と芳香族ジアミンの混合物を有機極性溶媒中で反応させて重合する方法。
などのような方法である。これら方法を単独で用いても良いし、部分的に組み合わせて用いることもできる。
本発明において、熱可塑性樹脂層(B)としては、例えば、ポリカーボネート系樹脂、アクリロニトリル・スチレン共重合樹脂、熱可塑性ポリイミド系樹脂等が例示されるが、耐熱性の点から、特に熱可塑性ポリイミド樹脂が好ましく用いられうる。前記熱可塑性ポリイミド樹脂は、金属箔との有意な接着力や好適な線膨張係数など、所望の特性が発現されれば、当該層に含まれる熱可塑性ポリイミド樹脂の含有量、分子構造、厚みは特に限定されるものではない。しかしながら、有意な接着力や好適な線膨張係数などの所望の特性の発現のためには、実質的には熱可塑性ポリイミド樹脂を熱可塑性樹脂層(B)中に50重量%以上含有することが好ましい。更に、耐熱性フィルムを介して対向する熱可塑性樹脂層(B)に含まれる熱可塑性ポリイミド樹脂は、接着シート全体での線膨張係数のバランスや、製造工程を簡略化する等の観点から、同種であることが好ましい。
本発明にかかる接着シート(C)の製造方法については特に限定されるものではないが、三層構造の接着シート(C)の場合、コア層となる耐熱性フィルム(A)に熱可塑性樹脂層(B)を片面毎に、もしくは両面同時に形成する方法、熱可塑性樹脂層(B)をシート状に成形し、これを上記コア層となる耐熱性フィルム(A)の表面に貼り合わせる方法等が挙げられる。あるいは、コア層となる耐熱性フィルム(A)と熱可塑性樹脂層(B)を共押出しして、実質的に一工程で積層体を製膜する接着シート(C)を作製する方法であってもよい。
本発明において、金属箔(D)としては特に限定されるものではないが、電子機器・電気機器用途に本発明の片面金属張積層板(E)を用いる場合には、例えば、銅または銅合金、ステンレス鋼またはその合金、ニッケルまたはニッケル合金(42合金も含む)、アルミニウムまたはアルミニウム合金からなる箔を挙げることができる。一般的な金属張積層板では、圧延銅箔、電解銅箔といった銅箔が多用されるが、本発明においてもこれらの銅箔を金属箔(D)として好ましく用いることができる。なお、これらの金属箔(D)の表面には、防錆層や耐熱層あるいは接着層が塗布されていてもよい。また、上記金属箔(D)の厚みについては特に限定されるものではなく、その用途に応じて、十分な機能が発揮できる厚みであればよい。金属箔(D)の厚みは、例えば、3μm~30μmが好ましく、より好ましくは5μm~20μmである。金属箔(D)の表面粗度(Rz)は0.01μm~1μmであることが好ましい。金属箔(D)の表面粗度(Rz)がこの範囲外の場合は熱可塑性樹脂層(B)との接着性が劣る場合などがある。
本発明においては、得られる片面金属張積層板(E)の外観を良好なものとするために、金属箔(D)を積層する側は、熱可塑性樹脂層(B)を介して金属箔(D)を積層し、さらに金属箔(D)に接して保護フィルム(F)を積層することが好ましい。熱圧着方法を用いる場合は、具体的には、加圧面(例えば、金属ロール)と、接着シート(C)および金属箔(D)と、の間に保護フィルム(F)を積層する。言い換えれば、加圧面(例えば、金属ロール)と金属箔(D)との間に保護フィルム(F)を積層する。
本発明においては、接着シート(C)の金属箔(D)を積層しない側は、熱可塑性樹脂層(B)に直接保護材料(G)を積層する。具体的には、加圧面(例えば、金属ロール)と接着シート(C)との間に保護材料(G)を積層する。
本発明においては、接着シート(C)の線膨張係数をX1、保護材料(G)の線膨張係数をX2とするとき、|X1-X2|≧3ppm/℃である保護材料(G)を使用することが好ましい。保護材料(G)の線膨張係数X2が当該関係式を満たす範囲にあれば、巻取工程において保護材料(G)を剥離した後や、必要に応じて行うエッチング工程後の接着シート(C)のカールを抑制できる。|X1-X2|は好ましくは3ppm/℃~15ppm/℃、より好ましくは4ppm/℃~12ppm/℃である。接着シート(C)全体の線膨張係数制御により、得られる片面金属張積層板(E)の反りの発生を抑制することが可能となる。|X1-X2|はさらに好ましくは4.5ppm/℃~8.5ppm/℃、特に好ましくは5ppm/℃~8ppm/℃である。この範囲内であれば、得られる片面金属張積層板(E)の反りを抑制することが可能であり、さらに寸法変化率も小さくすることが可能となる。
本発明においては、保護材料(G)の表面粗度が0.01μm~3μmの範囲内であることが好ましく、0.01μm~1μmの範囲内であることがより好ましい。表面粗度がこの範囲内の保護材料(G)を用いる場合は、接着シート(C)と保護材料(G)を剥離させることが容易となり、得られた片面金属張積層板(E)がカールすることを抑制できる。なお、ここで、保護材料(G)の表面粗度とは、保護材料(G)の接着シート(C)と接する側の表面の表面粗度をいう。
本発明に係る片面金属張積層板(E)の製造方法は、例えば図1及び図2を参照して説明すれば、耐熱性フィルム(A)1の両面に熱可塑性樹脂層(B)2を有する接着シート(C)3を用い、接着シート(C)3の片面に熱可塑性樹脂層(B)2を介して金属箔(D)4を積層することによる片面金属張積層板(E)5の製造方法である。金属箔(D)4を積層する側は、熱可塑性樹脂層(B)2を介して金属箔(D)4を積層し、金属箔(D)4を積層しない側は、熱可塑性樹脂層(B)2に直接保護材料(G)7を積層することを特徴とする。金属箔(D)4を積層する側は、熱可塑性樹脂層(B)2を介して金属箔(D)4を積層し、さらに金属箔(D)4に接して保護フィルム(F)6を積層することも可能である。
上記熱圧着の工程における加熱温度、すなわち圧着温度(ラミネート温度)T1(℃)は、用いる接着シート(C)の熱可塑性樹脂層(B)のガラス転移温度(Tg)T2(℃)より20℃~90℃高い温度であることが好ましく、接着シート(C)の熱可塑性樹脂層(B)のTgより50℃~80℃高い温度であることがより好ましい。T1-T2がこの範囲であれば、接着シート(C)と保護材料(G)とを良好に剥離させることができる。
本発明にかかる片面金属張積層板(E)の製造方法によって片面金属張積層板(E)を得るためには、接着シート(C)に、金属箔(D)、保護フィルム(F)、保護材料(G)などを貼り合わせて得られる、貼り合わされた被積層材料を連続的に加熱しながら圧着する熱ロールラミネート装置を用いることが好ましい。この熱ラミネート装置では、熱ラミネートを行う熱ラミネート部の後段に、保護材料(G)および必要に応じて保護フィルム(F)を、片面金属張積層板(E)から剥離する、保護材料等剥離部が設けられている。この熱ロールラミネート装置では、熱ラミネートを行う熱ラミネート部の前段に、被積層材料を繰り出す被積層材料繰出部を設けてもよいし、熱ラミネート部の後段に、被積層材料を巻き取る被積層材料巻取部を設けてもよい。これらの各部を設けることで、上記熱ロールラミネート装置の生産性をより一層向上させることができる。上記被積層材料繰出部および被積層材料巻取部の具体的な構成は特に限定されるものではなく、例えば、接着シート(C)や金属箔(D)、あるいは得られる片面金属張積層板(E)を巻き取ることのできる公知のロール状巻取機等を挙げることができる。
接着シート(C)の金属箔(D)を積層しない側に、熱可塑性樹脂層(B)を介して保護材料(G)を積層する工程を含む片面金属張積層板(E)の製造方法であって、さらに保護材料(G)を剥離する工程を含み、保護材料(G)を剥離する前の片面金属張積層板(E)と、剥離された保護材料(G)とがなす角度αが0より大きく90°未満であることを特徴とする、片面金属張積層板(E)の製造方法。
線膨張係数の測定は、セイコー電子(株)社製TMA120Cを用いて(サンプルサイズ 幅3mm、長さ10mm)、荷重3gで10℃/minで10℃~400℃まで一旦昇温させた後、10℃まで冷却し、更に10℃/minで昇温させて、2回目の昇温時の100℃から200℃における熱膨張率から平均値として計算した。
フィルムの表面粗度(Rz)の測定は、株式会社キーエンス社製VK-X200を用いて、JIS B 0601 1994に準拠して測定した。
実施例および比較例で得られた引き剥がし強度評価用の片面金属張積層板(A)および片面金属張積層板(B)を用いて、10mm×100mmの短冊状にカットして、試験片を作製した。
保護材料の剥離状況を観察し、剥離後の熱可塑性ポリイミド層が熱ラミネート前と同じ状態である状態に剥離できた場合を◎、剥離可能であって剥離後の熱可塑性ポリイミド層が熱ラミネート前より若干光沢が低下したものの使用上は問題ない状態である場合を○、剥離可能であって剥離後の熱可塑性ポリイミド層に部分的にミクロ的なキズが生じているものの使用上は問題ない状態である場合を△、剥離困難であって剥離できたとしても剥離後の熱可塑性ポリイミド層が全体的に波打つような状態である場合を×と評価した。
保護フィルムの剥離状況を観察し、保護材料の剥離状況の評価と同様の基準で評価を行った。
得られた片面金属張積層板(E)から、7cm幅×20cm長サイズの評価用試料を切り出した。この試料を20℃、60%R.H.の環境下に、12時間放置した後、試料の四隅の反りを測定した。四隅の反りがいずれも1.0mm以下で反りが無い場合を◎、四隅の反りがいずれも3.0mm以下の場合を○、四隅の反りがいずれも5.0mm以下である場合を△、少なくとも1つの隅の反りが5.0mm以上であり明確に反りがある場合を×と評価した。
線膨張係数20ppm/℃、熱可塑性樹脂層のTg290℃の耐熱性両面接着シート(株式会社カネカ製ピクシオFRS、幅255mm)に対して、金属箔である厚み12μmの圧延銅箔(JX日鉱日石金属株式会社製GHY5-82F-HA、幅270mm)を積層させ、更にこの金属箔を接着シートと挟むようにして保護フィルム(株式会社カネカ製アピカル(登録商標)125NPI)を配し、接着シートの逆面に保護材料として線膨張係数16ppm/℃、Rz=2.2μmのポリイミドフィルム(株式会社カネカ製アピカル(登録商標)75NPI)を配して、熱ロールラミネート装置の一対の金属ロール間を通すことにより、ラミネート温度360℃、ラミネート圧力245N/cm、ラミネート速度(金属張積層板の搬送スピード)1m/minの条件で熱ラミネートを行った。なお、接着シートは熱ラミネート前に保護材料側から300℃のヒーター温度で加熱した。用いたヒーターの長さは300mmであり、加熱時間は0.3分であった。その後、図5の方法で、それぞれ、2本の剥離ロールの半径の比(ra/rb)が0.32(40mm/125mm)である、一対の剥離ロール間を通して、保護材料および保護フィルムをこの順に剥離することにより、本発明に係る片面金属張積層板(E)を製造した。剥離する工程でのαは55°、βは30°であった。
実施例1において、保護材料として線膨張係数12ppm/℃、Rz=0.3μmのポリイミドフィルム(宇部興産株式会社製ユーピレックス(登録商標)25S)を使用したことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
実施例1において、保護材料として線膨張係数32ppm/℃、Rz=2.1μmのポリイミドフィルム(株式会社カネカ製アピカル(登録商標)12.5AH)を使用したことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
金属箔として、厚み12μmの電解銅箔(三井金属製3EC-M3S―HTE)を使用したことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
実施例1において、保護材料および保護フィルムの剥離に、それぞれ2本の剥離ロールの半径の比(ra/rb)が0.5(50mm/100mm)である一対の剥離ロールを用いたことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
実施例1において、ラミネート速度(金属張積層板の搬送スピード)3m/minの条件で熱ラミネートを行ったことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
実施例1において、保護材料を剥離する工程におけるαを85℃としたことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
実施例1において、接着シートを熱ラミネート前に保護材料側から500℃のヒーター温度で加熱したことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
実施例1において、保護材料として線膨張係数20ppm/℃、Rz=0.5μmのポリイミドフィルム(宇部興産株式会社製ユーピレックス(登録商標)50S)を使用したことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
実施例1において、2本の剥離ロールの半径の比(ra/rb)が1(100mm/100mm)である一対の剥離ロールを、保護材料の剥離および保護フィルムの剥離にそれぞれ用いたことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
実施例1において、ラミネート速度(金属張積層板の搬送スピード)を4m/minの条件で熱ラミネートを行ったことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
実施例1において、保護材料として線膨張係数20ppm/℃、Rz=3.5μmのポリイミドフィルム(サンドブラスト処理をしたカネカ製ポリイミドフィルムアピカル)を使用したことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
実施例1において、接着シートを熱ラミネート前に加熱しなかったことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
図6に示すように、実施例1において、剥離前の保護材料(G)と片面金属張積層板(E)がなす角度αを、165°としたことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
図7に示すように、実施例1において、剥離前の保護フィルム(F)と片面金属張積層板(E)がなす角度βを、165°としたことを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
図9に示すように、保護材料を剥離する角度αを90°、保護フィルムを剥離する角度βを90°とし、保護材料側および保護フィルム側にそれぞれ1個の剥離ロール12のみを使用することを除き、他は実施例1と同様にして片面金属張積層板(E)を製造した。
2 熱可塑性樹脂層(B)
3 接着シート(C)
4 金属箔(D)
5 片面金属張積層板(E)
6 保護フィルム(F)
7 保護材料(G)
8 両面金属張積層板
9 一対の金属ロール
10 一対の剥離ロール
11 ヒーター
12 剥離ロール
13 両面テープ
14 基板
15 台座
Claims (20)
- 耐熱性フィルム(A)の両面に熱可塑性樹脂層(B)を有する接着シート(C)を用い、接着シート(C)の片面に熱可塑性樹脂層(B)を介して金属箔(D)を積層し、
接着シート(C)の金属箔(D)を積層しない側に、熱可塑性樹脂層(B)を介して保護材料(G)を積層する工程を含む片面金属張積層板(E)の製造方法であって、
さらに保護材料(G)を剥離する工程を含み、
保護材料(G)を剥離する前の片面金属張積層板(E)と、剥離された保護材料(G)とがなす角度αが0より大きく90°未満であることを特徴とする、片面金属張積層板(E)の製造方法。 - 耐熱性フィルム(A)の両面に熱可塑性樹脂層(B)を有する接着シート(C)を用い、接着シート(C)の片面に熱可塑性樹脂層(B)を介して金属箔(D)を積層し、さらに金属箔(D)に接して保護フィルム(F)を積層し、
接着シート(C)の金属箔(D)を積層しない側に、熱可塑性樹脂層(B)を介して保護材料(G)を積層する工程を含む片面金属張積層板(E)の製造方法であって、
さらに保護材料(G)および保護フィルム(F)を剥離する工程を含み、
保護材料(G)を剥離する前の片面金属張積層板(E)と、剥離された保護材料(G)とがなす角度αが0より大きく90°未満であるとともに、保護フィルム(F)を剥離する前の片面金属張積層板(E)と、剥離された保護フィルム(F)とがなす角度βが0より大きく90°未満であることを特徴とする、請求項1に記載の片面金属張積層板(E)の製造方法。 - 保護材料(G)および保護フィルム(F)を片面金属張積層板(E)から剥離する際、保護材料(G)、その後保護フィルム(F)の順に剥離することを特徴とする、請求項2に記載の片面金属張積層板(E)の製造方法。
- 熱圧着方法を用いることを特徴とする、請求項1~3のいずれか1項に記載の片面金属張積層板(E)の製造方法。
- 熱圧着方法が、一対以上の金属ロールを有する熱ラミネート装置を用いることを特徴とする、請求項4に記載の片面金属張積層板(E)の製造方法。
- 熱圧着する際の圧着温度T1が、接着シート(C)の熱可塑性樹脂層(B)のガラス転移温度T2より20~90℃高いことを特徴とする、請求項4または5に記載の片面金属張積層板(E)の製造方法。
- 熱圧着前に、接着シート(C)を250~550℃の温度で加熱することを特徴とする、請求項4~6のいずれか1項に記載の片面金属張積層板(E)の製造方法。
- 接着シート(C)の線膨張係数をX1、保護材料(G)の線膨張係数をX2とするとき、|X1-X2|≧3ppm/℃である保護材料(G)を使用することを特徴とする、請求項1~7のいずれか1項に記載の片面金属張積層板(E)の製造方法。
- 表面粗度が0.01μm~3μmである保護材料(G)を使用することを特徴とする、請求項1~8のいずれか1項に記載の片面金属張積層板(E)の製造方法。
- 耐熱性フィルム(A)が、非熱可塑性ポリイミドフィルムであることを特徴とする、請求項1~9のいずれか1項に記載の片面金属張積層板(E)の製造方法。
- 熱可塑性樹脂層(B)が熱可塑性ポリイミド樹脂を含むことを特徴とする、請求項1~10のいずれか1項に記載の片面金属張積層板(E)の製造方法。
- 保護材料(G)または保護材料(G)および保護フィルム(F)を片面金属張積層板(E)から剥離する速度が3.5m/min以下であることを特徴とする、請求項1~11のいずれか1項に記載の片面金属張積層板(E)の製造方法。
- 保護材料(G)または保護材料(G)および保護フィルム(F)は、それぞれ、一対の剥離ロールを介して、片面金属張積層板(E)から剥離され、剥離される保護材料(G)側または剥離される保護フィルム(F)側の剥離ロールの半径raと、反対側の片面金属張積層板(E)側の剥離ロールの半径rbとの半径比ra/rbが、1未満であることを特徴とする、請求項1~12のいずれか1項に記載の片面金属張積層板(E)の製造方法。
- 耐熱性フィルム(A)の両面に熱可塑性樹脂層(B)を有する接着シート(C)と、その片面に熱可塑性樹脂層(B)を介して配置されている金属箔(D)と、接着シート(C)の金属箔(D)を積層しない側に熱可塑性樹脂層(B)を介して配置されている保護材料(G)とを、熱ラミネートする熱ラミネート部と、
その後段に設けられている、保護材料(G)を片面金属張積層板(E)から剥離する保護材料剥離部とを含む、片面金属張積層板(E)の製造装置であって、
前記保護材料剥離部は、保護材料(G)を剥離する前の片面金属張積層板(E)と、剥離された保護材料(G)とがなす角度αが0より大きく90°未満となるように構成されていることを特徴とする、片面金属張積層板(E)の製造装置。 - 耐熱性フィルム(A)の両面に熱可塑性樹脂層(B)を有する接着シート(C)と、その片面に熱可塑性樹脂層(B)を介して配置されている金属箔(D)と、金属箔(D)に接して配置されている保護フィルム(F)と、接着シート(C)の金属箔(D)を積層しない側に熱可塑性樹脂層(B)を介して配置されている保護材料(G)とを、熱ラミネートする熱ラミネート部と、
その後段に設けられている、保護材料(G)を片面金属張積層板(E)から剥離する保護材料剥離部と、保護フィルム(F)を片面金属張積層板(E)から剥離する保護フィルム剥離部とを含む、片面金属張積層板(E)の製造装置であって、
前記保護材料剥離部は、保護材料(G)を剥離する前の片面金属張積層板(E)と、剥離された保護材料(G)とがなす角度αが0より大きく90°未満となるように構成されているとともに、保護フィルム(F)を剥離する前の片面金属張積層板(E)と、剥離された保護フィルム(F)とがなす角度βが0より大きく90°未満となるように構成されていることを特徴とする、請求項14に記載の片面金属張積層板(E)の製造装置。 - 前記保護材料剥離部の後段に、保護フィルム剥離部が設けられていることを特徴とする、請求項15に記載の片面金属張積層板(E)の製造装置。
- 前記熱ラミネート部の前段に、接着シート(C)を加熱するためのヒーターが備えられていることを特徴とする、請求項14~16のいずれか1項に記載の片面金属張積層板(E)の製造装置。
- 耐熱性フィルム(A)が、非熱可塑性ポリイミドフィルムであることを特徴とする、請求項14~17のいずれか1項に記載の片面金属張積層板(E)の製造装置。
- 熱可塑性樹脂層(B)が熱可塑性ポリイミド樹脂を含むことを特徴とする、請求項14~18のいずれか1項に記載の片面金属張積層板(E)の製造装置。
- 前記保護材料剥離部、または前記保護材料剥離部および保護フィルム剥離部は、それぞれ、一対の剥離ロールを介して、保護材料(G)または保護材料(G)および保護フィルム(F)を片面金属張積層板(E)から剥離するようになっており、剥離される保護材料(G)側または剥離される保護フィルム(F)側の剥離ロールの半径raと、反対側の片面金属張積層板(E)側の剥離ロールの半径rbとの半径比ra/rbが、1未満であることを特徴とする、請求項14~19のいずれか1項に記載の片面金属張積層板(E)の製造装置。
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